CA1112394A - Non-ionic, water-dispersible polyurethanes - Google Patents
Non-ionic, water-dispersible polyurethanesInfo
- Publication number
- CA1112394A CA1112394A CA265,660A CA265660A CA1112394A CA 1112394 A CA1112394 A CA 1112394A CA 265660 A CA265660 A CA 265660A CA 1112394 A CA1112394 A CA 1112394A
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- CA
- Canada
- Prior art keywords
- oxide units
- oxide
- radical
- isocyanate
- difunctional
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/80—Masked polyisocyanates
- C08G18/8061—Masked polyisocyanates masked with compounds having only one group containing active hydrogen
- C08G18/8064—Masked polyisocyanates masked with compounds having only one group containing active hydrogen with monohydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4833—Polyethers containing oxyethylene units
- C08G18/4837—Polyethers containing oxyethylene units and other oxyalkylene units
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/50—Polyethers having heteroatoms other than oxygen
- C08G18/5021—Polyethers having heteroatoms other than oxygen having nitrogen
- C08G18/5036—Polyethers having heteroatoms other than oxygen having nitrogen containing -N-C=O groups
- C08G18/5042—Polyethers having heteroatoms other than oxygen having nitrogen containing -N-C=O groups containing ureum groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/78—Nitrogen
- C08G18/7806—Nitrogen containing -N-C=0 groups
- C08G18/7818—Nitrogen containing -N-C=0 groups containing ureum or ureum derivative groups
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Paper (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
Abstract of the Invention The present invention relates to non-ionic, water-dispersible polyurethanes having a substantially linear molecular structure and lateral polyalkylene oxide poly-ether chains containing ethylene oxide units characterized in that from about 40 to 95% of the alkylene oxide units of the lateral polyalkylene oxide polyether chains consist of ethylene oxide units and from about 5 to 60% consist of propylene oxide, butylene oxide or styrene oxide, to aqueous dispersions of these non-ionic, water-dispersible polyurethanes and to processes for producing these non-ionic, water-dispersible polyurethanes.
Description
WATER-DISP _ IBLE POLYURETEIANES
Background of the Invention Aqueous dispersions of polyurethanes or polyurethane ureas have long been known (cf~, for examlple, Anyewandete Chemie, S2, (1970) pages 53 to 63, DT-OS Nos. 2,314l512,
Background of the Invention Aqueous dispersions of polyurethanes or polyurethane ureas have long been known (cf~, for examlple, Anyewandete Chemie, S2, (1970) pages 53 to 63, DT-OS Nos. 2,314l512,
2,314,513 or 2,320,719 and U.S. Patent Nos. 3,920,598,
3,935,146 and 3 905 929~ and have a high quality level.
Not least -the fact that many of these dispersions are free from emulsifiers contributes towards this high level. They contain chemically incorporated hydrophilic centers which impart self-emulsifiability to the otherwise hydrophobic elastomers. q'his method of producing sel~-emulsi~iability has two principal advantages o~er the use of emulsifiers:
1) less hydrophilic centers are required.
2) ~he emulsifier incorporated is unable to migrate ~xom shaped articles produced from elastomer dispersions of this type. As a rule, behavior of this type has a con-siderable efEect upon the propex~-y spectrum.
The firs~ feature in particular considerably reduces the sensitivity to water o~ shaped articles produced from self-emulsified polyurethanes. The hydrophilic centers incorporated into known water-dispersible polyure~hanes and polyurethane ureas may represent both salt-like, i.e. ionic groups and also hydrophilic non-ionic groups.
The above-mentioned non-ionic,water-disper~ible polyurethanes include, in particular, -the polyurethanes and LeA 16,869 polyurethane ureas containing lateral polyethylene oxide chain~ accordirlg to DT~OS Nos. 2,314,512; 2,314,513 and 2,320,719 and U.S. Patent Nos. 3,920,598,3 935 146 arld 3 905 929 The non-ionic polyurethane dispers:ions described in these prior publications are eminently suitable for the production of mechanically strong, highly elastic coatings.
Both non-flexible substrates, such as wood and metals, and also flexible substra-tes, such as textiles or leather may be coated with the dispersions. One preferred field of application is the coating o~ textiles. Xowever, it has been found that in certain cases, especially in cases where high-gloss transfer papers are used, coated texti]es pro-duced using these polyurethanes show a phenomenon which may seriously restrict their commercial value. This phenomenon is the appearance oE a coating which becomes increasingly dull in the event of prolonged storage. High-gloss, dark-pigmented or colored coatings in particuIar show a speckled, matt-grey appearance after from 3 to 6 weeks which seriously - affec~s the optical appearance of the sheet-form material.
Although this undesira~le phenomenon may be eliminated by wiping with a damp cloth, it reappears after a certain time.
Accordingly, an object of the present invention is to provide non-ionic, water-dispersible polyurethanes which may be used for the production of textile coatings which do not show the unfavorable phenomenon referred to above.
Acrording to the present invention, this object may sur~
prisingly be achieved by incorporating certain quantities of other alkylene oxide units in addition to ethylene oxide units into the polyether side chains which are responsihle for the dispersibility of the polyurethanes~
LeA 16~869 -2=
Summary of the Invention Accordingly, the present invention rela-tes to non~
ionic, water~dispersible polyurethanes having a su~stantially linear molecular structure and lateral ]?olyalkylene oxide polyether chains containing ethylene ox:ide units which are responsible for dispersibility, d.istinguished by the fact that, based on the number of alkylene oxide units, from about 40 to 95% of the alkylene oxide units of the lateral poly-alkylene oxide polyether chains consist of ethylene oxide units and from about 5 to 60% of propylene oxide, butylene oxide or styrene oxide units.
The present invention also relates to aqueous dis-persions of these polyurethanes.
E'urthermore, the present invention also relates to the preerred process or producins these water-dispersible polyurethanes by reacting organic diisocyanates with difunc-tional organic compounds ("difunctional" in the context of the isocyanate polyaddition reaction~ containing terminal isocyanate-reactive hydrogen atoms and having a molecular weight of from about 300 to 6000 in the presence of synthe-sis components containing hydrophilic groups which guarantee the dispersibility of the polyurethanes, and optionally in the presence of the chain extenders known in polyurethane ; chemistry having a molecular weight below about 300 and optionally in the presence of the additives and aids normally used in polyurethane chemistry, distinguished by the act that the synthesis components containing hydrophil.ic groups are diQls corresponding to the following general :Eormula:
LeA 16,859 -3-, , : :
3~!~
R' R' HO`-CH-CH -N-C~I -CH-OII
CO-NH-R-MH-CO-O-X-Y-R"
and/or diisocyanates corresponding to -the following geneLal :Eormula:
OCN-R-N-CO-NH-R-NCO
CO
Z-X-Y-R"
wherein R represents a difunctional radical of the -type obtained by removing the isocyanate groups from a diisocyanate having a molecular weigh-t of from about 112 to 1000, R' represents a hydrogen a-tom or a monofunc-tional hydrocarbon radical having from 1 to 8 carbon atoms, X represents a difunctional radical obtained by removing the terminal oxygen atom from a polyalkylene oxide radical having :Erom about 5 to 90 al]cylene oxide unlts of which, based on their number, from about 40 to 95% consist oE ethylene oxide units and from about 5 to 60% of propylene oxicle, butylene oxide or styrene oxide uni-ts, Y represents oxygen or -NR'''- and 0 R" and R~ , which may be the same or different, each represent monofunctional hydrocarbon radicals having Erom 1 to 12 carbon atoms, Z represents a radical which has the same definition as Y.
LeA 16~6~9 Detailed Description of the Invention Organic diisocyanates suitable for use in the pre:Eerred process described above for producing the polyure-thane elastomers according to the present invention are organic diisocyanates coxresponding to the general Eormula:
R(NCO)2 wherein R represents an organic radical of the type obtained by removin~ the isocyanate groups from an organic diisocyanate having a molecular weight of from aboùt 112 to 1000 and preferably from a~out 140 to 400.
Diisocyanates particularly preferred Eor the process according to the present invention are those corresponding to the above general formula, wherein R represents a difunctional aliphatic hydrocarbon radical having from 4 to 18 carbon atoms, a difunctional cycloaliphatic hydrocarbon radical -~- having from 5 to 15 carbon atoms, a difunctional aromatic hydrocarbon radical having from 6 to 15 carbon atoms or an araliphatic hydrocarbon radical having from 7 to 15 carbon atoms.
Typical xepresentati.~es of organic diisocyanates preferably used for the process according ko the present invention are, for example, tetramethylene diisocyanate, : hexamethylene diisocyanate, ~odecamethylene diisocyanate, cyclohexane 1,3 and 1,4-diisocyanate, 1-isocyanato-3-isocyanatomethyl-355,5-trimethyl cyclohexane, 4,4'-diisocya-na~o dicyclohexyl methane, aromatic diisocyanates, such as 2~4-diisocyanato toluene, 2,6-diisocyanato toluene, mixtures LeA 16,869 -5-of these isomers, 4,4'-diisocyanato diphenyl methane, 1~5-diisocyanato naphthalene or ~-xylylene diisocyanate.
Difunctional compounds (in the conte~t oE the i.socy-anate polyaddition reaction) containing terminal isocyanate-reactive groups and having a molecular ~eight of from about 300 to 6000, preferably from about 500 to :3000, which are suitable for use in accordance with the present invention are, in particular:
(1) The dihydroxy polyesters, known in polyurethane chemistry, of dicarboxylic acids, such as succinic acid~ adipic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, etc., and diols, such as ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, diethyl.ene glycol., 1/4 butane diol, 1,6-hexane diolj 1,8-octane diol, neopentyl glycol, 2-methyl-1,3-propane diol, or the various isomeric bis-hydroxy methyl cyclo-hexanes;
- (2~ The polylactones known in polyurethane chemistry such as the polymers of s-caprolactone started on the above-mentioned dihydric alcohols;
(3) The polycarbonates known in polyure~lane chemis-try of the type which may be obtained by reacting the above-mentioned diols 9 for example, wi~h diaryl carbonates or phosgene;
(~I) rThe polyethers known in polyurethane chemistry, such as the polymers and copolymers of styrene oxide, propylene oxide, tetrahydrofuran, butylene oxide or epichlorhydrin, produced with difunctional starter molecules, such as water, the above-mentioned diols or amines containing 2 N~H-bonds.
LeA 16,869 -6-It is also po~sible to use ethylene oxide, provided that the polye~her used contains a maximum of about 10~, by weight, of ethylene oxide~ In general, however, polye-thers obtalned without ethylene oxide are used;
5(5) The polythioethers, polyt:hio mixed ethers, poly-thio ether esters known in polyurethane chemi~try;
(6) The polyacetals known in polyurethane chemistry, for example of the above-mentioned diols and formaldehyde; and (7) ~ifunctional polyether esters containing terminal isocyanate-reactive groups;
(8) Polyamides and polyes~er amides containing terminal hydroxyl and/or primary or secondary amino groups of the type described in DT-OS No. 2,320,719.
Dihydroxy polyesters, dihydroxy~polylactones, di-hydroxy polyethexs and dihydroxy polycarbonates are preferablyused in the process according to the present invention.
Basically, however, the compounds according to the present invention could also be produced without the use of relatively high molec~llar weight polyhydroxyl compounds, i.e.
501ely fox diisocyanates and low molecular weight reactants (molecular weight <300).
Chain extenders having a molecular weight below about 300 suitable for use in the process according to the present invention for producing the self-dispersible polyurethanes are~ for example, the low molecular weight diols described with reference to the production o~ the dihydroxy polyesters or even diamines, such as diaminoe-thane, 1,6-diaminohexane, pipera~ine, 2,5-dimethyl pipera~ine, 1-amino-3-aminomethyl-3~5/5 trimethyl cyclohexane, 4,4'-diaminodicyclohexyl methane, LeA 16,~69 7-1,4-diaminocyclohexane, 1,2-propylene diamine ox eve.n hydrazine, amino acid hydrazides, hydrazides of semicarbazido carboxyli.c acids~ bis-hydrazides and bis-semicarba~ides.
In addi-tion to the above-mentiolled difunctional synthesis components ("di:Eunctional" in ~he context of the isocyanate polyaddition reaction), it is a:Lso possible in certain cases, i.e. where weak branching of the polyurethanes is required, to use small proportions o~ the txifunctional and higher functional synthesis components known in poly-urethane chemistry, such as for example tris~(isocyanathe~yl~
biuret, triphenylmethane-triisocyanate, glycerol~ trimethylol~
propane or pentaerythritol~
Hydrophllic synthesls components having lateral hydrophilic chains containing ethylene oxide units correspond-ing to the following general formula:
R' R' O-NH-P~-NH-CO-O-X-Y-R" ~I~
and/or to the general formula:
- OCN-R-N-CO-NH R-NCO
(II) Z-X-Y-R"
are used in the process according to the present invention.
Particularly preferred synthesis componen~s are those corresponding to general formula (I) above.
In general formula (X) and (II) above, R represents a difunctional radical of the type obta.ined by removing the isocyanate groups from a diisocyanate corresponding to the general formula R(NCO)2 of the type mentioned above, LeA 16,869 -8-R' represents a hydrogen atom or a rnonofunctlonal hydro-carbon radical having from 1 to 8 carbon atoms, pre-ferably a hydrogen a-tom or a methyl groupl R" represents a monofunctional hydrocarbon radical having from 1 to 12 carbon atoms, preferably an unsubstituted alkyl radical having :Erom 1 to 4 carbon atoms, X represents a difuncti.onal radical obtainecl by removing the terminal oxygen atom from a polyalkylene oxide radical having from about 5 to 90 and preferably from about 20 to 70 chain members~ of which from about 40 to 95% and preferably from about 60 to 90% consists of ethylene oxide units and from about 5 -to 60%, preferably from about 10 to 40%, of propylene oxide, butylene oxide or styrene oxide units, of which propylene oxide units are preferred, Y represents oxygen or -NR"'- wherein R"' has the same definition as R", X represents a radical which has the same definition as Y.
The compounds corresponding to general formula (I) and (II) above may be producecl by ~he methods according to DT-OS Nos. 2,314,512 and 2,314,513 and U.S. Patent Numbers 3,935,146, 3,920,598 and 3,905,929. In addition to the disclosures of these two Offenlegungsschrifts and the U.S.
Patents, it is pointed out that, instead of using the monofunctional polyether alcohols mentioned therein as starting materials, it is a1so possible to use those of the type, only from about 40 to 95% and preferably from about 60 to 90~ of whose polyether segment consists oF ethylene oxide units and from about 5 to 60%, preferably from about 10 to 40%, of propylene oxide, butylene LeA 16,689 _9_ .~
' ~
~2~
oxide or styxene oxide units, of which the propylene oxide UIlitS are preferred.
The process according to the present invention for producing the self dispersible polyurethanes may be carried out in accordance with the methods known in polyurethane chemistry both by the one-stage process and also by the two-stage process ~prepolymer process~.
For producing the self-dispersible polyurethanes, the reactants are used in an equivalent ratio of isocyanate groups to isocyana-te-xeactive groups of from about 0.8:1 to 2.5:1, preferably from about 0.95:1 to 1.5:1. The use of an NCO-excess naturally results in the formation o compounds containing NCO-groups which, when converted into an aqueous dispersion, react further with the water, accompanied by chai.n extension, to form the dispersed end product. According-ly, the a~ove equivalent ratio embodies all the components involved in the synthesis of the polyurethanes according to the present invention, including the amino-group-containing -~ chain extender optionally used in the form of aqueous solutions r but not the proportion of water used for dispersing the polyurethanes which reacts with any NCQ-grouprcontaining compounds present in a chain-extending reacti.on.
; Both the one~stage process and the two-stage process may be carried out in the presence or absence of solvents.
Suitable solvents, especially if, as described below, it is intended to convert the polyurethanes into an aqueous dispersion during or after their production/ are, fox example, water-miscible solvents that are inert with .respect to i~ocyanate groups and which boil a~ temperatures below about 100C, such as acetone or methyl ethyl ketone~
L~A 16l869 -10-For carrying ou-t the one-stage process, the di-functional compounds containing terminal isocyana-te-reactive groups and having molecular weights of fxom about 300 to 6000 mentioned under (1) to (8) above are optionally mixed with the hydrophilic synthesis component (I) and with the chain extender used, if any, having a molecular w~ight below about 300. The diisocyanate component which contains the above~
mentioned d.iisocyanates without hydrophilic groups and, optionally hydrophilic diisocyanates (II), in the absence of solvents, is then added to the above obtained mixture, after which the reaction mixture is reacted, preferably at temperatures oE from about 50 to 150C, and optionally after the addition of catalys-ts known in polyurethane chemistry, such as ~or example tin~II-octoa-te, di.bu-tyltindilaura-te or triethylene diamine~ The quantity in which the diisocyanate components are used is such tha-t an NCO:OH ratio of from about 0.8 to 1.05 prevails. During the reaction, the viscosity of the reaction mixture increases so that one of the above-mentioned solvents is gradually added to the mixture. Finally, an organic solution of the fully reacted polyurethane is obtained, its concentration . preferably being adjusted to from about 10 to 70%, by weight, and more especially to from about 15 to 55%, by weight, expressed as solids.
2~In that case, the dissolved polyurethane elastomers are best converted in-to an aqueous dispersion by adding water to the stirred solution. In many cases, the solution passes through the phase oE a water-in-oil emulsion, after which it changes into an oil-in-water emulsion, simultaneously over~
coming a viscosity maximum. Removal of the solvent by distillation leaves behind a puxe aqueous stable dispersion.
For carrying out the two-stage process, an NCO-prepolymer is preferahly initially prepared in the melt :Erom Le~ 16,869 3~
excess diisocyana-te, rela-tively high molecular weight compounds with isocyanate-reactive groups of the type rnentioned by way of example in (1) to (8) above and hydrophilic synthesis component (I), maintaining an NCO/OH ratio of from about 1.1:1 to 3.5:1, preferably from about 1.2:1 to 2.5:1, in the absence of solvents or even in the presence of sol.vents. Where :Lt is prepared in the absence o solvents, the NCO-prepolymer thus prepared is subsequently dissolved for example in a suitable solvent.
The solution of -the prepolymer thus obtained may then be re-acted in known manner with the chain extender having a mol.ecular weight below about 500 of the type mentioned by way of example above.
To prepare the polyurethane dispersions according to the present invention, it is particularly recorNmended to adopt a particular variant of the two-stage process in which water or a water/solvent mixture is added in small quantities to the described solution of the NCO-prepolymer with the solution of the chain extender (in this case the above-mentioned diamines and hydrazine derivatives are preferably used as chain extenders) in such a way that the NCO:NH ratio is from about 2.5 to 1.05. This reaction may be carried out at room temperature or even J preferably, at temperatures of from about 25 to 60C~ By subsequently adding the rest of the water and removing the solvent, the polyurethane dispersion is finally obtained. However, it is also possible in this embodiment of the process to dissolve the chain extender in the total quantity of the water finally present in the dispersion (from about 50 to 200%, by weight, based on solid polyurethane).
However, the two-stage process described above rnay also be carried out in the absence of solvents without any LeA 16,869 -12-real difficulties by preparing the described NCO-prepolymer in solvent-free form and stir-iny i-t as a melt into -the water. In this case, too, the above-mentioned chain ex-tenders containing amino groups may be used in solution in the water.
The water-dispe~sible polyurethane elas-tomers according to the present invention are of predominantly linear molecular structure and are characteri.zed by a content of ethylene o~ide incorporated laterally within a polyalkylene oxide chain of from about 3 to 30%, by weight, preferably from about 4 to 20~ by wei.ght, from about 40 to 95% and preferably from about 60 to 90% of the alkylene oxide segments of the lateral polyalkylene oxide polyether chain, based on the number of alkylene oxide units, consisting of ethylene oxide units, and from about 5 to 60%, preferably from about 10 to 40% of propylene oxide, butylene o~ide or styrene oxide units, preferably propylene oxide units. Accordingly, when the process according to the present invention as described above is carried out in practice, the type and quantity of hydrophilic synthesis components ~I) and (II) are selected in such a way that the end product satlsfies these require-ments. It does not ma-tter whether the lateral polyether chain is a mixed polyether chain having statis-tical distri-bution of the alkylene oxide segments or a block polyether chain.
The lateral polyalkylene oxide chain which contains the ethylene oxide units essential to the present invention is preferably attached through yroups:
(i) corresponding to the following general formul.a:
-N
~O-NH-R-NH-CO-O-X-Y-R"
L~A 16,869 . ~13-o~
(ii) corresponding -to khe following general Eormula:
CO-Z-X-Y-R"
wherein R, R", R"', X, Y and Z are as defined abo~e.
The process according to the present invention as described above merely represents the preferred method, but by no means the only method of obtaining the polyure~hanes according to the present invention. Ano-ther method of obtaining the polyurethanes according to the present invention is, for example, to introduce the non-ionic lateral hydrophilic groups into a preferably linear polyurethane elastomer by reacting thls elastomer with hydrophilic mono-isocyanates corresponding to the Eollowing general formula:
OCN-R-NH-CO-O-X-Y-R"
wherein R, X, Y, R" and R"' are as defined above.
Hydrophilic monoisocyanates of this type may be produced by an analogous process to that described in DT-OS
No. 2,314,512, although it is pointed out in addition to the disclosure of that Offenlegungsschrift that, instead o:E using the monofunctional polyether alcohols mentioned there as starting materials, it is also possible to use those oE
which the polyether segment, in addition to ethylene oxide units, also contains up to about 60%,by weight/ and preferably up to about 40%, by weightr of propylene oxide units, butyl oxide units or styrene oxide units, preEerably propylene oxide units.
LeA 16,869 -14-~2~'~4 In cases where the polyurethanes according to the present. invention are produced using these hydrophilic mono-isocyanates, a linear polyurethane is preferably prepared from the above-mentioned starting materials preferab].y using an equivalent ratio of isocyanate groups to isocyanate-reactive groups o:E about 1:1, the linear polyurethane thus prepared containing no lateral hydrophilic polyether segments.
This linear polyurethane elastomer is then reacted in the nlelt or in a suitable solvent, for example of the type men-tioned above, with the hydrophilic monoisocyanates at fromabout 50 to 150C, producing an addition of the isocyanate group of the hydrophilic monoisocyanate to the active hydrogen atoms of the ure~hane and/or urea groups present in the linear polyurethane.
The polyurethane according to the present invention thus obtained, either in the form of a melt or in the form of a solution, may then be converted into an aqueous dispersion by mixing with water and distilling off the auxiliary solvent used, if any.
Generally, the polyurethanes according to the present invention may be converted into aqueous dispersions by any methods including~ for example, dispersion in the absence of solvents, for example by mixing the polyurethane melt wi-th water in an apparatus which is able to generate high shear gradients, and the use of very small quantities of solvent for plasticization during processing in the same apparatus, and also the use of non-mechanical dispers.ion aids, such as soundwaves of extremely high frequency. Finally, in the case of polyurethane ureas too, chain extension may be carried LeA 16,869 -15-ou-t after the prepolymex has been converted into an aqueous emulsion. Ilowever, it is also possible to use simple mixers, for example, s-tirrer equipped vessels or so~called "flow mixers", because the polyurethanes accord:ing to the present invention are self~dispersible.
The polyurethanes dispersed in accordance with the present invention have an average particle size of from about 10 m~ to 5 ~, preferably from about 200 to 800 m~l. Naturally, the optical dispersion or Tyndall effect begins to appear in the case of dispersions having particle sizes below about 500 m~. If the lateral polyethylene oxide segment content of the polyurethane solid is below about 5%, it is also possible to obtain average particle diameters of from about 5 to approximately S0 ~. Dispersions of this type are of lnterest, for example, for the production of polyurethane powders~
The flow behavior of the dispersions, which it is not intended to discuss in detail here, is govered by particle size and concentration. In the case of relatively small particles, viscosity increases, in addition to which an in-creasingly higher flow limit occurs below a particle size ofapproximately 100 m~ (Bingham substance). Irrespective of this dependence, viscosity increases with increasing con-centration which, with this class of dispersions, may amount to as much as 70~, in some cases up to a level of 50P.
The dispersions are not sensitive to electrolytes.
I'his provides, for example, for the acid-catalyzed cross-linking of the latex particles with formaldehyde or formalde-hyde derivatives; similarly they may be pigmented wi-th electrolyte-active pigments or dyes. ~nother property of the dispersions according to the present invention is t:he LeA 16,869 -16-3~
fact that they ma~ be coagula-ted under heat which :[nakes them suitable for processing ln_o films permeable -to wa-ter vapor simply by heating.
The dispersions may be blendecl with o-ther dispersions, for example with polyvinyl acetate, polyetl1ylene, polystyrene polybutadiene, polyvinyl chloride, polyacrylate and copolymer plastics dispersions. The addition of known chemically non-fixed, preferably ionic emulsifiers is also possi~le, but, of course, not essential.
Finally, fillers, plasticizers, pigments, carbon black and silica sols, aluminum, clay and asbestos dispersions may also be incorporated into the dispersions.
The dispersions of the polyurethane compositions in water are generally stable~ storable and transportable and may be processed a-t any later stage, for example by ~orming.
In general, they dry directly into dimensionally stable plastics coatings, although forming of the end products may also be carried out in the presence of known crosslinking agents. Polyurethanes having different properties may be obtained according to the chemical composition selected and to the urethane group content. Thus, it is possible to obtain soft tacky compositions and thermoplastic and elastomeric products having a variety of different hardnesses up to glass~hard duroplasts. The hydrophilicity of the products may also vary within certain limits. The elastic products may be thermoplastically processed at elevated temperatures, for example at from about lOO to l80~C, providing they are not chemically crosslinked.
The end products of the process are su.itab.1.e for coating and impregnating woven and non-woverl textiles, LeA 16/869 -17-leather, paper, wood, metals, ceramics, stone, concrete, hitumen, rigid Ei~ers, straw, cJlass, porcelain, plastics of a variety of different types, glass fibers, ~or anti-static and crease-resistant finishing, as binders for non-wovens, adhesives, adhesion promoters, laminating agents,hydrophobizing agents, plasticizers, binders, for example for cork powderor sawdust; glass fibers, asbestos, paper-like materials, plastics or rubber waste, ceramic materials~ as auxiliaries in textile printing and in the paper industry, as additives to polymers; as sizing agents, for example for glass fibers; and for finishing leather.
The dispersions or pastes are preferably applied to a porous substrate which subsequently remains bonded to the end product, such as woven or non-woven textile structures and fiber mats, felts or non-wovens, also paper web~, foam sheets or split leather which, by virtue of their absorbi~g action, cause the coating to harden immediately. This is followed by drying and, optionally, pressing at elevated temperature. However, drying may also be carried out on smooth porous or non-porous materials, for example, metal glass, paper, cardboard, ceramic materials, sheet steel, silicone rubber, aluminum Eoil, the end sheet structure subse~uently being lifted off and used as such or applied to a substrate using the reversal process by bonding, flame lamination or calendering. Application by the reversal process may be carried out at any time.
The properties of the end products may be modified by using vinyl polymers or active or inactive fillers. It is possible to usel for example, polyethylene, polypropylene, polyvinyl acetate 9 ethylene-vinyl aceta~e copolymers, which LeA 16,869 ~18-3~
may optionally be (partially) hydrolyzed and/or yraEted with vinyl chloride, styrene-butadiene copolymers, ethylene (graft) copolymers, polyacrylates, carbon black, silica, asbestos, talcum, kaolin, titanium dioxide and glass in -the -Eorm of powder or in the form of ~ibers or cellulose. Depending upon the required property spectrum and the application envisaged for the end products, up to about 70%, based on total dry substance~ of these fillers may be present in the end product.
Dyes, pigments, plastici~ers or additives which lG influence the flow properties may, of course, also be added.
Drying of the products obtained by various application techniques may be carried out either at room temperature or at elevated temperature. The drying temperature to be selected in each individual case, which is governed not only by the chemical composition o-f the material, but above all by moisture content, the drying time and -the layer thickness, is readily determined by a preliminary test. For a given heating time, the drying temperature must always be below the solidification temperature.
The sheet structures may then be coated with a finish in order to increase their surface resistivity. ~queous dispersions or solutions are again preferably used for this purpose.
Extremely ri~id polyurethanes obtained from finely divided dispersions and sols are suitable for use as stoving lacquers and, in some cases, even as air-drying lacquers.
They combine extreme hardness and elasticity with high gloss and, in cases where aliphatic diisocyanates are used, favorable light stability and weather resistance.
LeA 16,869 -19-... . . .. . .. . . .
3~
The polyurethanes according to the present inventiondiffer from the polyurethanes according to DT~OS No. 2r31~,512 in the surprising fact that text.ile coatings which have been produced from aqueous dispersions thereof do not show any tendency to form a dull surface, even in the event oE pro-longed storage.
Le~ 16,869 -20 3~
EXAMPI,ES
(A) 840 parts of 1,6-hexane diisocyanate are added to 1800 parts of a polyether having an OH number oE 31, produced in the conventional way from n-butanol cmd ethylene oxide and propylene oxide in a molar ratio of 83:17~ followed by stirring for 3 hours at 100C. The reaction mixture -then has an NCO content of 14.3%, by weight~ 670 parts of 1,6-hexane diisocyanate are recovered by distillat:ion in a vacuum of from 0.05 to 0.1 Torr at a temperature of 120C.
105 parts of bis-(2-h droxyethyl)-amine are then introduced~
after which the entire quantity of the isocyanate preadduct is stirred in slowly at a temperature of from 25 to 30C.
On completion of the addition, the mixture is stirred for another 30 minutes. On cooling the reaction product remains liquid. After standing for 2 months, a slight haze is formed, although it may readily be eliminated by gentle heating.
The product has an OH number of 55.
, (B) 1~40 parts of a 1,6-hexane diol polycarbonate having an OH number of 56 are dehydrated for 30 minutes at 100C/
14 Torr. After cooling to approximately 70C, followed by the addition of 160 parts of the adduct described in (A), a mixture of 244 parts of 3-isocyanatomethyl-3,5,5-trimethyl cyclohexyl isocyanate and 185 parts of l/~-hexane diisocyanate is added, the tempera-ture again increased with stirring to 100~C and maintained at that level for about 3 hours. r~he mixture then has an NCO-content of 4.14%, ~y weight. After cooling to 60C, 4000 parts of anhydrous acetone are stixred in.
LeA 16,869 ~21-102 parts of 3-aminomethyl-3,5,5-trimethyl cyclo~
- hexyl amine are dissolved in 200 parts of water and the result-ing solution slowly added wlth thorough stirring to the pre-polymer solution cooled to room temperature. After stirring for 10 minutes, 15 parts of hydrazine monohyclrate are added all at once, followed by stirring for another 15 minutes.
2345 pa.rts of water are then introduced into the mixture with vigorous stirring. A dispersion of the solid in a water/acetone mixture is formed. The acetone present in this mixture is removed by distillation, leaving behind a bluish-white aqueous dispersion of the solid in a concentration of about 50%. The solid contains about 4.96~, by weight, of ethylene oxide incorporated within lateral polyether chains.
EXAMPLE 2 (Comparision Example) Following the procedure described in Example 1 (B), an aqueous dispersion of a polyurethane urea is prepared from : the following starting materials:
1880 parts of the hexane diol polycarbonate according to Example 1, 135 parts of an adduct according to Example 1~) of 1 mole of an n-butanol~started polyethylene oxide poly-ether having an OH number of 28, 1 mole of 1,6-hexane diisocyanate and 1 mole of bis-(2-hydroxy~
ethyl)-amine, - 25 244 parts of 3-isocyanato methyl-3,5,5-trimethyl cyclohexyl isocyanate, 185 parts of 1,6-hexane di:isocyanate, 102 parts of 3-aminomethyl-3,5,5-trimethyl cyclohexyl amine, 15 parts of hydrazine monohydrate, LeA 16,869 -22-2561 parts of water.
The dispersion has a solids conten-t of about 50~.
The solid contains about 4.63%, by weight, of ethylene oxide incorporated within lateral polyether chains.
The dispersions according to Examples 1 and 2 are poured into metal molds so that, following evaporation of the water and heating for 30 minutes to 120C, clear sheet structures measureing 25 x 25 x 0O5 cm are obtained. After storage for 3 weeks at room temperature, the surface of the molding produced from the dispersion of Example 2 is dull and speckled, while the other molding has a glossy surface.
If the Example 2 molding is heated Eor 10 minutes to 50C, the haze disappears, but reappears after storage for 24 hours at room temperature. If its surface is wipped with a moist sponge and dried, it has a smooth glossy appearance like the molding according to Example 1. However, the cloudy surface haze reappears after storage for 3 weeks at room temperature.
-EXA~PLE 3 (A) 1165 parts of 2,4--diisocyanato toluene are added to 1500 parts of a polyether haviny an OH number of 25, produced in the conventional way from n-butanol and ethylene oxide and propylene oxide in a molar ratio of 71:29, followed by heating for 5 hours to 100C i.n the presence o:E 2.7 parts 2S of 4-toluene sulphonic acid methyl ester and 0.13 parts of - zinc acetyl acetonateO Following the addition of 0~7 parts of benæoyl chloride, 26~5 parts of a solution of an allopha-nate diisocyanate in 2,4-diisocyanato toluene having an NCO
: LRA 16,869 ~23-~J~
con-tent of 17.8~ are obtained. The polyethylene oxide conten-t amounts to about 35O5%l by weight.
(B) 2000 parts of a polyester diol of ethylene glycol and adipic acid haviny an OH number of 56 are dehydrated or 30 minutes at 100C/14 Torr. After cooling to 70C, 472 parts of the solution described in (A) and 174 par-ts of 2,4-diiso-cyanatotoluene are added and the mixture stirred for 3 hours at that temperature. Thereafter the mixture has an NCO-content of 3.17%, by weight. After cooling to 60C, 4170 parts of anhydrous acetone are stirred in. 39 parts of diaminoethane are dlssolved in 127 parts of water and the resulting solution slowly added with thorough stirring to the prepolymer solution cooled to room temperature. Arter stirring or 10 minutes, 4000 parts of water are added with vigorous stirring. A dispersion of the solid in a water/
acetone mixture is formed. The acetone is removed by distillation, leaving behind a bluish-white, aqueous dispersion of the solid in a concentration of about 40%. The solid contains about 6.14%, by weight, oE ethylene oxide incorporated within lateral polyether chains.
EXaMPLE ~ (Comparison Example) (A) 1305 parts of 2,4-diisocyanatotoluene are added to 1500 parts of an n butanol-started polyethylene o~ide alcohol having an OH number of 28, followed by heating for 5 hours to 100C in the presence of 2.7 parts of 4-toluene sulphonic acid methyl ester and 0.13 part of zinc acetyl acetonate.
Following the addition of 0.7 part o-f benzoyl chloride, 2805 parts of a solution of an allophanate diisocyanate in 2,4-diisocyanatotoluene having an NCO-content of 20% is obtained.
LeA 16,869 -24-3~
The polyethylene oxide content amounts to about 68.6%~
(B) Following the procedure of Example 3(B) a.n aqueous dispersion is prepared from the following starting materials:
2000 parts oE a polyester diol of ethyleIIe glycol and adipic acid having an OH number of 56, 251 parts of -the allophanate diisocyanate solution accordin.g to Example 4(A) 243 parts of 2,4-diisocyanatotoluene 39 parts of diaminoethane 3800 parts of water.
The dispersion thus obtained has a solids content of about 406 . The solid contains about 6.73% of ethylene oxide incorporated within lateral polyether chains.
Followiny the procedure of Example 2, moldings are produced from the dispersions according to Examples 3 and 4 and subjected to the conditions and tests described therein.
The molding according to Example 3 behaves in the same way as the molding according to Example 1, iOe.~ does not show any surface coating, whereas the molding according to Example
Not least -the fact that many of these dispersions are free from emulsifiers contributes towards this high level. They contain chemically incorporated hydrophilic centers which impart self-emulsifiability to the otherwise hydrophobic elastomers. q'his method of producing sel~-emulsi~iability has two principal advantages o~er the use of emulsifiers:
1) less hydrophilic centers are required.
2) ~he emulsifier incorporated is unable to migrate ~xom shaped articles produced from elastomer dispersions of this type. As a rule, behavior of this type has a con-siderable efEect upon the propex~-y spectrum.
The firs~ feature in particular considerably reduces the sensitivity to water o~ shaped articles produced from self-emulsified polyurethanes. The hydrophilic centers incorporated into known water-dispersible polyure~hanes and polyurethane ureas may represent both salt-like, i.e. ionic groups and also hydrophilic non-ionic groups.
The above-mentioned non-ionic,water-disper~ible polyurethanes include, in particular, -the polyurethanes and LeA 16,869 polyurethane ureas containing lateral polyethylene oxide chain~ accordirlg to DT~OS Nos. 2,314,512; 2,314,513 and 2,320,719 and U.S. Patent Nos. 3,920,598,3 935 146 arld 3 905 929 The non-ionic polyurethane dispers:ions described in these prior publications are eminently suitable for the production of mechanically strong, highly elastic coatings.
Both non-flexible substrates, such as wood and metals, and also flexible substra-tes, such as textiles or leather may be coated with the dispersions. One preferred field of application is the coating o~ textiles. Xowever, it has been found that in certain cases, especially in cases where high-gloss transfer papers are used, coated texti]es pro-duced using these polyurethanes show a phenomenon which may seriously restrict their commercial value. This phenomenon is the appearance oE a coating which becomes increasingly dull in the event of prolonged storage. High-gloss, dark-pigmented or colored coatings in particuIar show a speckled, matt-grey appearance after from 3 to 6 weeks which seriously - affec~s the optical appearance of the sheet-form material.
Although this undesira~le phenomenon may be eliminated by wiping with a damp cloth, it reappears after a certain time.
Accordingly, an object of the present invention is to provide non-ionic, water-dispersible polyurethanes which may be used for the production of textile coatings which do not show the unfavorable phenomenon referred to above.
Acrording to the present invention, this object may sur~
prisingly be achieved by incorporating certain quantities of other alkylene oxide units in addition to ethylene oxide units into the polyether side chains which are responsihle for the dispersibility of the polyurethanes~
LeA 16~869 -2=
Summary of the Invention Accordingly, the present invention rela-tes to non~
ionic, water~dispersible polyurethanes having a su~stantially linear molecular structure and lateral ]?olyalkylene oxide polyether chains containing ethylene ox:ide units which are responsible for dispersibility, d.istinguished by the fact that, based on the number of alkylene oxide units, from about 40 to 95% of the alkylene oxide units of the lateral poly-alkylene oxide polyether chains consist of ethylene oxide units and from about 5 to 60% of propylene oxide, butylene oxide or styrene oxide units.
The present invention also relates to aqueous dis-persions of these polyurethanes.
E'urthermore, the present invention also relates to the preerred process or producins these water-dispersible polyurethanes by reacting organic diisocyanates with difunc-tional organic compounds ("difunctional" in the context of the isocyanate polyaddition reaction~ containing terminal isocyanate-reactive hydrogen atoms and having a molecular weight of from about 300 to 6000 in the presence of synthe-sis components containing hydrophilic groups which guarantee the dispersibility of the polyurethanes, and optionally in the presence of the chain extenders known in polyurethane ; chemistry having a molecular weight below about 300 and optionally in the presence of the additives and aids normally used in polyurethane chemistry, distinguished by the act that the synthesis components containing hydrophil.ic groups are diQls corresponding to the following general :Eormula:
LeA 16,859 -3-, , : :
3~!~
R' R' HO`-CH-CH -N-C~I -CH-OII
CO-NH-R-MH-CO-O-X-Y-R"
and/or diisocyanates corresponding to -the following geneLal :Eormula:
OCN-R-N-CO-NH-R-NCO
CO
Z-X-Y-R"
wherein R represents a difunctional radical of the -type obtained by removing the isocyanate groups from a diisocyanate having a molecular weigh-t of from about 112 to 1000, R' represents a hydrogen a-tom or a monofunc-tional hydrocarbon radical having from 1 to 8 carbon atoms, X represents a difunctional radical obtained by removing the terminal oxygen atom from a polyalkylene oxide radical having :Erom about 5 to 90 al]cylene oxide unlts of which, based on their number, from about 40 to 95% consist oE ethylene oxide units and from about 5 to 60% of propylene oxicle, butylene oxide or styrene oxide uni-ts, Y represents oxygen or -NR'''- and 0 R" and R~ , which may be the same or different, each represent monofunctional hydrocarbon radicals having Erom 1 to 12 carbon atoms, Z represents a radical which has the same definition as Y.
LeA 16~6~9 Detailed Description of the Invention Organic diisocyanates suitable for use in the pre:Eerred process described above for producing the polyure-thane elastomers according to the present invention are organic diisocyanates coxresponding to the general Eormula:
R(NCO)2 wherein R represents an organic radical of the type obtained by removin~ the isocyanate groups from an organic diisocyanate having a molecular weight of from aboùt 112 to 1000 and preferably from a~out 140 to 400.
Diisocyanates particularly preferred Eor the process according to the present invention are those corresponding to the above general formula, wherein R represents a difunctional aliphatic hydrocarbon radical having from 4 to 18 carbon atoms, a difunctional cycloaliphatic hydrocarbon radical -~- having from 5 to 15 carbon atoms, a difunctional aromatic hydrocarbon radical having from 6 to 15 carbon atoms or an araliphatic hydrocarbon radical having from 7 to 15 carbon atoms.
Typical xepresentati.~es of organic diisocyanates preferably used for the process according ko the present invention are, for example, tetramethylene diisocyanate, : hexamethylene diisocyanate, ~odecamethylene diisocyanate, cyclohexane 1,3 and 1,4-diisocyanate, 1-isocyanato-3-isocyanatomethyl-355,5-trimethyl cyclohexane, 4,4'-diisocya-na~o dicyclohexyl methane, aromatic diisocyanates, such as 2~4-diisocyanato toluene, 2,6-diisocyanato toluene, mixtures LeA 16,869 -5-of these isomers, 4,4'-diisocyanato diphenyl methane, 1~5-diisocyanato naphthalene or ~-xylylene diisocyanate.
Difunctional compounds (in the conte~t oE the i.socy-anate polyaddition reaction) containing terminal isocyanate-reactive groups and having a molecular ~eight of from about 300 to 6000, preferably from about 500 to :3000, which are suitable for use in accordance with the present invention are, in particular:
(1) The dihydroxy polyesters, known in polyurethane chemistry, of dicarboxylic acids, such as succinic acid~ adipic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, etc., and diols, such as ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, diethyl.ene glycol., 1/4 butane diol, 1,6-hexane diolj 1,8-octane diol, neopentyl glycol, 2-methyl-1,3-propane diol, or the various isomeric bis-hydroxy methyl cyclo-hexanes;
- (2~ The polylactones known in polyurethane chemistry such as the polymers of s-caprolactone started on the above-mentioned dihydric alcohols;
(3) The polycarbonates known in polyure~lane chemis-try of the type which may be obtained by reacting the above-mentioned diols 9 for example, wi~h diaryl carbonates or phosgene;
(~I) rThe polyethers known in polyurethane chemistry, such as the polymers and copolymers of styrene oxide, propylene oxide, tetrahydrofuran, butylene oxide or epichlorhydrin, produced with difunctional starter molecules, such as water, the above-mentioned diols or amines containing 2 N~H-bonds.
LeA 16,869 -6-It is also po~sible to use ethylene oxide, provided that the polye~her used contains a maximum of about 10~, by weight, of ethylene oxide~ In general, however, polye-thers obtalned without ethylene oxide are used;
5(5) The polythioethers, polyt:hio mixed ethers, poly-thio ether esters known in polyurethane chemi~try;
(6) The polyacetals known in polyurethane chemistry, for example of the above-mentioned diols and formaldehyde; and (7) ~ifunctional polyether esters containing terminal isocyanate-reactive groups;
(8) Polyamides and polyes~er amides containing terminal hydroxyl and/or primary or secondary amino groups of the type described in DT-OS No. 2,320,719.
Dihydroxy polyesters, dihydroxy~polylactones, di-hydroxy polyethexs and dihydroxy polycarbonates are preferablyused in the process according to the present invention.
Basically, however, the compounds according to the present invention could also be produced without the use of relatively high molec~llar weight polyhydroxyl compounds, i.e.
501ely fox diisocyanates and low molecular weight reactants (molecular weight <300).
Chain extenders having a molecular weight below about 300 suitable for use in the process according to the present invention for producing the self-dispersible polyurethanes are~ for example, the low molecular weight diols described with reference to the production o~ the dihydroxy polyesters or even diamines, such as diaminoe-thane, 1,6-diaminohexane, pipera~ine, 2,5-dimethyl pipera~ine, 1-amino-3-aminomethyl-3~5/5 trimethyl cyclohexane, 4,4'-diaminodicyclohexyl methane, LeA 16,~69 7-1,4-diaminocyclohexane, 1,2-propylene diamine ox eve.n hydrazine, amino acid hydrazides, hydrazides of semicarbazido carboxyli.c acids~ bis-hydrazides and bis-semicarba~ides.
In addi-tion to the above-mentiolled difunctional synthesis components ("di:Eunctional" in ~he context of the isocyanate polyaddition reaction), it is a:Lso possible in certain cases, i.e. where weak branching of the polyurethanes is required, to use small proportions o~ the txifunctional and higher functional synthesis components known in poly-urethane chemistry, such as for example tris~(isocyanathe~yl~
biuret, triphenylmethane-triisocyanate, glycerol~ trimethylol~
propane or pentaerythritol~
Hydrophllic synthesls components having lateral hydrophilic chains containing ethylene oxide units correspond-ing to the following general formula:
R' R' O-NH-P~-NH-CO-O-X-Y-R" ~I~
and/or to the general formula:
- OCN-R-N-CO-NH R-NCO
(II) Z-X-Y-R"
are used in the process according to the present invention.
Particularly preferred synthesis componen~s are those corresponding to general formula (I) above.
In general formula (X) and (II) above, R represents a difunctional radical of the type obta.ined by removing the isocyanate groups from a diisocyanate corresponding to the general formula R(NCO)2 of the type mentioned above, LeA 16,869 -8-R' represents a hydrogen atom or a rnonofunctlonal hydro-carbon radical having from 1 to 8 carbon atoms, pre-ferably a hydrogen a-tom or a methyl groupl R" represents a monofunctional hydrocarbon radical having from 1 to 12 carbon atoms, preferably an unsubstituted alkyl radical having :Erom 1 to 4 carbon atoms, X represents a difuncti.onal radical obtainecl by removing the terminal oxygen atom from a polyalkylene oxide radical having from about 5 to 90 and preferably from about 20 to 70 chain members~ of which from about 40 to 95% and preferably from about 60 to 90% consists of ethylene oxide units and from about 5 -to 60%, preferably from about 10 to 40%, of propylene oxide, butylene oxide or styrene oxide units, of which propylene oxide units are preferred, Y represents oxygen or -NR"'- wherein R"' has the same definition as R", X represents a radical which has the same definition as Y.
The compounds corresponding to general formula (I) and (II) above may be producecl by ~he methods according to DT-OS Nos. 2,314,512 and 2,314,513 and U.S. Patent Numbers 3,935,146, 3,920,598 and 3,905,929. In addition to the disclosures of these two Offenlegungsschrifts and the U.S.
Patents, it is pointed out that, instead of using the monofunctional polyether alcohols mentioned therein as starting materials, it is a1so possible to use those of the type, only from about 40 to 95% and preferably from about 60 to 90~ of whose polyether segment consists oF ethylene oxide units and from about 5 to 60%, preferably from about 10 to 40%, of propylene oxide, butylene LeA 16,689 _9_ .~
' ~
~2~
oxide or styxene oxide units, of which the propylene oxide UIlitS are preferred.
The process according to the present invention for producing the self dispersible polyurethanes may be carried out in accordance with the methods known in polyurethane chemistry both by the one-stage process and also by the two-stage process ~prepolymer process~.
For producing the self-dispersible polyurethanes, the reactants are used in an equivalent ratio of isocyanate groups to isocyana-te-xeactive groups of from about 0.8:1 to 2.5:1, preferably from about 0.95:1 to 1.5:1. The use of an NCO-excess naturally results in the formation o compounds containing NCO-groups which, when converted into an aqueous dispersion, react further with the water, accompanied by chai.n extension, to form the dispersed end product. According-ly, the a~ove equivalent ratio embodies all the components involved in the synthesis of the polyurethanes according to the present invention, including the amino-group-containing -~ chain extender optionally used in the form of aqueous solutions r but not the proportion of water used for dispersing the polyurethanes which reacts with any NCQ-grouprcontaining compounds present in a chain-extending reacti.on.
; Both the one~stage process and the two-stage process may be carried out in the presence or absence of solvents.
Suitable solvents, especially if, as described below, it is intended to convert the polyurethanes into an aqueous dispersion during or after their production/ are, fox example, water-miscible solvents that are inert with .respect to i~ocyanate groups and which boil a~ temperatures below about 100C, such as acetone or methyl ethyl ketone~
L~A 16l869 -10-For carrying ou-t the one-stage process, the di-functional compounds containing terminal isocyana-te-reactive groups and having molecular weights of fxom about 300 to 6000 mentioned under (1) to (8) above are optionally mixed with the hydrophilic synthesis component (I) and with the chain extender used, if any, having a molecular w~ight below about 300. The diisocyanate component which contains the above~
mentioned d.iisocyanates without hydrophilic groups and, optionally hydrophilic diisocyanates (II), in the absence of solvents, is then added to the above obtained mixture, after which the reaction mixture is reacted, preferably at temperatures oE from about 50 to 150C, and optionally after the addition of catalys-ts known in polyurethane chemistry, such as ~or example tin~II-octoa-te, di.bu-tyltindilaura-te or triethylene diamine~ The quantity in which the diisocyanate components are used is such tha-t an NCO:OH ratio of from about 0.8 to 1.05 prevails. During the reaction, the viscosity of the reaction mixture increases so that one of the above-mentioned solvents is gradually added to the mixture. Finally, an organic solution of the fully reacted polyurethane is obtained, its concentration . preferably being adjusted to from about 10 to 70%, by weight, and more especially to from about 15 to 55%, by weight, expressed as solids.
2~In that case, the dissolved polyurethane elastomers are best converted in-to an aqueous dispersion by adding water to the stirred solution. In many cases, the solution passes through the phase oE a water-in-oil emulsion, after which it changes into an oil-in-water emulsion, simultaneously over~
coming a viscosity maximum. Removal of the solvent by distillation leaves behind a puxe aqueous stable dispersion.
For carrying out the two-stage process, an NCO-prepolymer is preferahly initially prepared in the melt :Erom Le~ 16,869 3~
excess diisocyana-te, rela-tively high molecular weight compounds with isocyanate-reactive groups of the type rnentioned by way of example in (1) to (8) above and hydrophilic synthesis component (I), maintaining an NCO/OH ratio of from about 1.1:1 to 3.5:1, preferably from about 1.2:1 to 2.5:1, in the absence of solvents or even in the presence of sol.vents. Where :Lt is prepared in the absence o solvents, the NCO-prepolymer thus prepared is subsequently dissolved for example in a suitable solvent.
The solution of -the prepolymer thus obtained may then be re-acted in known manner with the chain extender having a mol.ecular weight below about 500 of the type mentioned by way of example above.
To prepare the polyurethane dispersions according to the present invention, it is particularly recorNmended to adopt a particular variant of the two-stage process in which water or a water/solvent mixture is added in small quantities to the described solution of the NCO-prepolymer with the solution of the chain extender (in this case the above-mentioned diamines and hydrazine derivatives are preferably used as chain extenders) in such a way that the NCO:NH ratio is from about 2.5 to 1.05. This reaction may be carried out at room temperature or even J preferably, at temperatures of from about 25 to 60C~ By subsequently adding the rest of the water and removing the solvent, the polyurethane dispersion is finally obtained. However, it is also possible in this embodiment of the process to dissolve the chain extender in the total quantity of the water finally present in the dispersion (from about 50 to 200%, by weight, based on solid polyurethane).
However, the two-stage process described above rnay also be carried out in the absence of solvents without any LeA 16,869 -12-real difficulties by preparing the described NCO-prepolymer in solvent-free form and stir-iny i-t as a melt into -the water. In this case, too, the above-mentioned chain ex-tenders containing amino groups may be used in solution in the water.
The water-dispe~sible polyurethane elas-tomers according to the present invention are of predominantly linear molecular structure and are characteri.zed by a content of ethylene o~ide incorporated laterally within a polyalkylene oxide chain of from about 3 to 30%, by weight, preferably from about 4 to 20~ by wei.ght, from about 40 to 95% and preferably from about 60 to 90% of the alkylene oxide segments of the lateral polyalkylene oxide polyether chain, based on the number of alkylene oxide units, consisting of ethylene oxide units, and from about 5 to 60%, preferably from about 10 to 40% of propylene oxide, butylene o~ide or styrene oxide units, preferably propylene oxide units. Accordingly, when the process according to the present invention as described above is carried out in practice, the type and quantity of hydrophilic synthesis components ~I) and (II) are selected in such a way that the end product satlsfies these require-ments. It does not ma-tter whether the lateral polyether chain is a mixed polyether chain having statis-tical distri-bution of the alkylene oxide segments or a block polyether chain.
The lateral polyalkylene oxide chain which contains the ethylene oxide units essential to the present invention is preferably attached through yroups:
(i) corresponding to the following general formul.a:
-N
~O-NH-R-NH-CO-O-X-Y-R"
L~A 16,869 . ~13-o~
(ii) corresponding -to khe following general Eormula:
CO-Z-X-Y-R"
wherein R, R", R"', X, Y and Z are as defined abo~e.
The process according to the present invention as described above merely represents the preferred method, but by no means the only method of obtaining the polyure~hanes according to the present invention. Ano-ther method of obtaining the polyurethanes according to the present invention is, for example, to introduce the non-ionic lateral hydrophilic groups into a preferably linear polyurethane elastomer by reacting thls elastomer with hydrophilic mono-isocyanates corresponding to the Eollowing general formula:
OCN-R-NH-CO-O-X-Y-R"
wherein R, X, Y, R" and R"' are as defined above.
Hydrophilic monoisocyanates of this type may be produced by an analogous process to that described in DT-OS
No. 2,314,512, although it is pointed out in addition to the disclosure of that Offenlegungsschrift that, instead o:E using the monofunctional polyether alcohols mentioned there as starting materials, it is also possible to use those oE
which the polyether segment, in addition to ethylene oxide units, also contains up to about 60%,by weight/ and preferably up to about 40%, by weightr of propylene oxide units, butyl oxide units or styrene oxide units, preEerably propylene oxide units.
LeA 16,869 -14-~2~'~4 In cases where the polyurethanes according to the present. invention are produced using these hydrophilic mono-isocyanates, a linear polyurethane is preferably prepared from the above-mentioned starting materials preferab].y using an equivalent ratio of isocyanate groups to isocyanate-reactive groups o:E about 1:1, the linear polyurethane thus prepared containing no lateral hydrophilic polyether segments.
This linear polyurethane elastomer is then reacted in the nlelt or in a suitable solvent, for example of the type men-tioned above, with the hydrophilic monoisocyanates at fromabout 50 to 150C, producing an addition of the isocyanate group of the hydrophilic monoisocyanate to the active hydrogen atoms of the ure~hane and/or urea groups present in the linear polyurethane.
The polyurethane according to the present invention thus obtained, either in the form of a melt or in the form of a solution, may then be converted into an aqueous dispersion by mixing with water and distilling off the auxiliary solvent used, if any.
Generally, the polyurethanes according to the present invention may be converted into aqueous dispersions by any methods including~ for example, dispersion in the absence of solvents, for example by mixing the polyurethane melt wi-th water in an apparatus which is able to generate high shear gradients, and the use of very small quantities of solvent for plasticization during processing in the same apparatus, and also the use of non-mechanical dispers.ion aids, such as soundwaves of extremely high frequency. Finally, in the case of polyurethane ureas too, chain extension may be carried LeA 16,869 -15-ou-t after the prepolymex has been converted into an aqueous emulsion. Ilowever, it is also possible to use simple mixers, for example, s-tirrer equipped vessels or so~called "flow mixers", because the polyurethanes accord:ing to the present invention are self~dispersible.
The polyurethanes dispersed in accordance with the present invention have an average particle size of from about 10 m~ to 5 ~, preferably from about 200 to 800 m~l. Naturally, the optical dispersion or Tyndall effect begins to appear in the case of dispersions having particle sizes below about 500 m~. If the lateral polyethylene oxide segment content of the polyurethane solid is below about 5%, it is also possible to obtain average particle diameters of from about 5 to approximately S0 ~. Dispersions of this type are of lnterest, for example, for the production of polyurethane powders~
The flow behavior of the dispersions, which it is not intended to discuss in detail here, is govered by particle size and concentration. In the case of relatively small particles, viscosity increases, in addition to which an in-creasingly higher flow limit occurs below a particle size ofapproximately 100 m~ (Bingham substance). Irrespective of this dependence, viscosity increases with increasing con-centration which, with this class of dispersions, may amount to as much as 70~, in some cases up to a level of 50P.
The dispersions are not sensitive to electrolytes.
I'his provides, for example, for the acid-catalyzed cross-linking of the latex particles with formaldehyde or formalde-hyde derivatives; similarly they may be pigmented wi-th electrolyte-active pigments or dyes. ~nother property of the dispersions according to the present invention is t:he LeA 16,869 -16-3~
fact that they ma~ be coagula-ted under heat which :[nakes them suitable for processing ln_o films permeable -to wa-ter vapor simply by heating.
The dispersions may be blendecl with o-ther dispersions, for example with polyvinyl acetate, polyetl1ylene, polystyrene polybutadiene, polyvinyl chloride, polyacrylate and copolymer plastics dispersions. The addition of known chemically non-fixed, preferably ionic emulsifiers is also possi~le, but, of course, not essential.
Finally, fillers, plasticizers, pigments, carbon black and silica sols, aluminum, clay and asbestos dispersions may also be incorporated into the dispersions.
The dispersions of the polyurethane compositions in water are generally stable~ storable and transportable and may be processed a-t any later stage, for example by ~orming.
In general, they dry directly into dimensionally stable plastics coatings, although forming of the end products may also be carried out in the presence of known crosslinking agents. Polyurethanes having different properties may be obtained according to the chemical composition selected and to the urethane group content. Thus, it is possible to obtain soft tacky compositions and thermoplastic and elastomeric products having a variety of different hardnesses up to glass~hard duroplasts. The hydrophilicity of the products may also vary within certain limits. The elastic products may be thermoplastically processed at elevated temperatures, for example at from about lOO to l80~C, providing they are not chemically crosslinked.
The end products of the process are su.itab.1.e for coating and impregnating woven and non-woverl textiles, LeA 16/869 -17-leather, paper, wood, metals, ceramics, stone, concrete, hitumen, rigid Ei~ers, straw, cJlass, porcelain, plastics of a variety of different types, glass fibers, ~or anti-static and crease-resistant finishing, as binders for non-wovens, adhesives, adhesion promoters, laminating agents,hydrophobizing agents, plasticizers, binders, for example for cork powderor sawdust; glass fibers, asbestos, paper-like materials, plastics or rubber waste, ceramic materials~ as auxiliaries in textile printing and in the paper industry, as additives to polymers; as sizing agents, for example for glass fibers; and for finishing leather.
The dispersions or pastes are preferably applied to a porous substrate which subsequently remains bonded to the end product, such as woven or non-woven textile structures and fiber mats, felts or non-wovens, also paper web~, foam sheets or split leather which, by virtue of their absorbi~g action, cause the coating to harden immediately. This is followed by drying and, optionally, pressing at elevated temperature. However, drying may also be carried out on smooth porous or non-porous materials, for example, metal glass, paper, cardboard, ceramic materials, sheet steel, silicone rubber, aluminum Eoil, the end sheet structure subse~uently being lifted off and used as such or applied to a substrate using the reversal process by bonding, flame lamination or calendering. Application by the reversal process may be carried out at any time.
The properties of the end products may be modified by using vinyl polymers or active or inactive fillers. It is possible to usel for example, polyethylene, polypropylene, polyvinyl acetate 9 ethylene-vinyl aceta~e copolymers, which LeA 16,869 ~18-3~
may optionally be (partially) hydrolyzed and/or yraEted with vinyl chloride, styrene-butadiene copolymers, ethylene (graft) copolymers, polyacrylates, carbon black, silica, asbestos, talcum, kaolin, titanium dioxide and glass in -the -Eorm of powder or in the form of ~ibers or cellulose. Depending upon the required property spectrum and the application envisaged for the end products, up to about 70%, based on total dry substance~ of these fillers may be present in the end product.
Dyes, pigments, plastici~ers or additives which lG influence the flow properties may, of course, also be added.
Drying of the products obtained by various application techniques may be carried out either at room temperature or at elevated temperature. The drying temperature to be selected in each individual case, which is governed not only by the chemical composition o-f the material, but above all by moisture content, the drying time and -the layer thickness, is readily determined by a preliminary test. For a given heating time, the drying temperature must always be below the solidification temperature.
The sheet structures may then be coated with a finish in order to increase their surface resistivity. ~queous dispersions or solutions are again preferably used for this purpose.
Extremely ri~id polyurethanes obtained from finely divided dispersions and sols are suitable for use as stoving lacquers and, in some cases, even as air-drying lacquers.
They combine extreme hardness and elasticity with high gloss and, in cases where aliphatic diisocyanates are used, favorable light stability and weather resistance.
LeA 16,869 -19-... . . .. . .. . . .
3~
The polyurethanes according to the present inventiondiffer from the polyurethanes according to DT~OS No. 2r31~,512 in the surprising fact that text.ile coatings which have been produced from aqueous dispersions thereof do not show any tendency to form a dull surface, even in the event oE pro-longed storage.
Le~ 16,869 -20 3~
EXAMPI,ES
(A) 840 parts of 1,6-hexane diisocyanate are added to 1800 parts of a polyether having an OH number oE 31, produced in the conventional way from n-butanol cmd ethylene oxide and propylene oxide in a molar ratio of 83:17~ followed by stirring for 3 hours at 100C. The reaction mixture -then has an NCO content of 14.3%, by weight~ 670 parts of 1,6-hexane diisocyanate are recovered by distillat:ion in a vacuum of from 0.05 to 0.1 Torr at a temperature of 120C.
105 parts of bis-(2-h droxyethyl)-amine are then introduced~
after which the entire quantity of the isocyanate preadduct is stirred in slowly at a temperature of from 25 to 30C.
On completion of the addition, the mixture is stirred for another 30 minutes. On cooling the reaction product remains liquid. After standing for 2 months, a slight haze is formed, although it may readily be eliminated by gentle heating.
The product has an OH number of 55.
, (B) 1~40 parts of a 1,6-hexane diol polycarbonate having an OH number of 56 are dehydrated for 30 minutes at 100C/
14 Torr. After cooling to approximately 70C, followed by the addition of 160 parts of the adduct described in (A), a mixture of 244 parts of 3-isocyanatomethyl-3,5,5-trimethyl cyclohexyl isocyanate and 185 parts of l/~-hexane diisocyanate is added, the tempera-ture again increased with stirring to 100~C and maintained at that level for about 3 hours. r~he mixture then has an NCO-content of 4.14%, ~y weight. After cooling to 60C, 4000 parts of anhydrous acetone are stixred in.
LeA 16,869 ~21-102 parts of 3-aminomethyl-3,5,5-trimethyl cyclo~
- hexyl amine are dissolved in 200 parts of water and the result-ing solution slowly added wlth thorough stirring to the pre-polymer solution cooled to room temperature. After stirring for 10 minutes, 15 parts of hydrazine monohyclrate are added all at once, followed by stirring for another 15 minutes.
2345 pa.rts of water are then introduced into the mixture with vigorous stirring. A dispersion of the solid in a water/acetone mixture is formed. The acetone present in this mixture is removed by distillation, leaving behind a bluish-white aqueous dispersion of the solid in a concentration of about 50%. The solid contains about 4.96~, by weight, of ethylene oxide incorporated within lateral polyether chains.
EXAMPLE 2 (Comparision Example) Following the procedure described in Example 1 (B), an aqueous dispersion of a polyurethane urea is prepared from : the following starting materials:
1880 parts of the hexane diol polycarbonate according to Example 1, 135 parts of an adduct according to Example 1~) of 1 mole of an n-butanol~started polyethylene oxide poly-ether having an OH number of 28, 1 mole of 1,6-hexane diisocyanate and 1 mole of bis-(2-hydroxy~
ethyl)-amine, - 25 244 parts of 3-isocyanato methyl-3,5,5-trimethyl cyclohexyl isocyanate, 185 parts of 1,6-hexane di:isocyanate, 102 parts of 3-aminomethyl-3,5,5-trimethyl cyclohexyl amine, 15 parts of hydrazine monohydrate, LeA 16,869 -22-2561 parts of water.
The dispersion has a solids conten-t of about 50~.
The solid contains about 4.63%, by weight, of ethylene oxide incorporated within lateral polyether chains.
The dispersions according to Examples 1 and 2 are poured into metal molds so that, following evaporation of the water and heating for 30 minutes to 120C, clear sheet structures measureing 25 x 25 x 0O5 cm are obtained. After storage for 3 weeks at room temperature, the surface of the molding produced from the dispersion of Example 2 is dull and speckled, while the other molding has a glossy surface.
If the Example 2 molding is heated Eor 10 minutes to 50C, the haze disappears, but reappears after storage for 24 hours at room temperature. If its surface is wipped with a moist sponge and dried, it has a smooth glossy appearance like the molding according to Example 1. However, the cloudy surface haze reappears after storage for 3 weeks at room temperature.
-EXA~PLE 3 (A) 1165 parts of 2,4--diisocyanato toluene are added to 1500 parts of a polyether haviny an OH number of 25, produced in the conventional way from n-butanol and ethylene oxide and propylene oxide in a molar ratio of 71:29, followed by heating for 5 hours to 100C i.n the presence o:E 2.7 parts 2S of 4-toluene sulphonic acid methyl ester and 0.13 parts of - zinc acetyl acetonateO Following the addition of 0~7 parts of benæoyl chloride, 26~5 parts of a solution of an allopha-nate diisocyanate in 2,4-diisocyanato toluene having an NCO
: LRA 16,869 ~23-~J~
con-tent of 17.8~ are obtained. The polyethylene oxide conten-t amounts to about 35O5%l by weight.
(B) 2000 parts of a polyester diol of ethylene glycol and adipic acid haviny an OH number of 56 are dehydrated or 30 minutes at 100C/14 Torr. After cooling to 70C, 472 parts of the solution described in (A) and 174 par-ts of 2,4-diiso-cyanatotoluene are added and the mixture stirred for 3 hours at that temperature. Thereafter the mixture has an NCO-content of 3.17%, by weight. After cooling to 60C, 4170 parts of anhydrous acetone are stirred in. 39 parts of diaminoethane are dlssolved in 127 parts of water and the resulting solution slowly added with thorough stirring to the prepolymer solution cooled to room temperature. Arter stirring or 10 minutes, 4000 parts of water are added with vigorous stirring. A dispersion of the solid in a water/
acetone mixture is formed. The acetone is removed by distillation, leaving behind a bluish-white, aqueous dispersion of the solid in a concentration of about 40%. The solid contains about 6.14%, by weight, oE ethylene oxide incorporated within lateral polyether chains.
EXaMPLE ~ (Comparison Example) (A) 1305 parts of 2,4-diisocyanatotoluene are added to 1500 parts of an n butanol-started polyethylene o~ide alcohol having an OH number of 28, followed by heating for 5 hours to 100C in the presence of 2.7 parts of 4-toluene sulphonic acid methyl ester and 0.13 part of zinc acetyl acetonate.
Following the addition of 0.7 part o-f benzoyl chloride, 2805 parts of a solution of an allophanate diisocyanate in 2,4-diisocyanatotoluene having an NCO-content of 20% is obtained.
LeA 16,869 -24-3~
The polyethylene oxide content amounts to about 68.6%~
(B) Following the procedure of Example 3(B) a.n aqueous dispersion is prepared from the following starting materials:
2000 parts oE a polyester diol of ethyleIIe glycol and adipic acid having an OH number of 56, 251 parts of -the allophanate diisocyanate solution accordin.g to Example 4(A) 243 parts of 2,4-diisocyanatotoluene 39 parts of diaminoethane 3800 parts of water.
The dispersion thus obtained has a solids content of about 406 . The solid contains about 6.73% of ethylene oxide incorporated within lateral polyether chains.
Followiny the procedure of Example 2, moldings are produced from the dispersions according to Examples 3 and 4 and subjected to the conditions and tests described therein.
The molding according to Example 3 behaves in the same way as the molding according to Example 1, iOe.~ does not show any surface coating, whereas the molding according to Example
4 undergoes the same surface changes as the molding according to Example 2.
Although the inventic~n has been described in detail for the purpose of illustration, it is to ~e understood ~hat such detail is solely for that purpose and that variations can be made therein by those skilled in the art without de-parting from the spirit and scope of the invention except as it may be limited by the clalms.
LeA 16/869 -25-
Although the inventic~n has been described in detail for the purpose of illustration, it is to ~e understood ~hat such detail is solely for that purpose and that variations can be made therein by those skilled in the art without de-parting from the spirit and scope of the invention except as it may be limited by the clalms.
LeA 16/869 -25-
Claims (13)
1. Non-ionic water-dispersible polyurethanes having a substantially linear molecular structure and lateral polyalkylene oxide polyether chains containing ethylene oxide units which are responsible for dispersibility, wherein from about 40 to 95% of the alkylene oxide units of the lateral polyalkylene oxide polyether chains, based on the number of alkylene oxide units, consist of ethylene oxide units and from about 5 to 60% are selected from the group consisting of propylene oxide, butylene oxide and styrene oxide units.
2. Aqueous dispersions of the polyurethanes claimed in Claim 1.
3. A process for producing non-ionic water-dispersible polyurethanes having a substantially linear molecular structure by reacting organic diisocyanates with difunctional organic compounds ("difunctional" in the context of the isocyanate polyaddition reaction) containing terminal isocyanate-reactive hydrogen atoms and having a molecular weight of from about 300 to 6000 in the presence of synthesis components containing hydrophilic groups which guarantee the dispersibility of the polyurethanes and optionally in the presence of chain extenders having a molecular weight below about 300 known in polyurethane chemistry and optionally in the presence of the aids and additives commonly used in polyurethane chemistry, wherein the synthesis components containing hydrophilic groups are diols corresponding to the following general formula:
LeA 16,689 and/or diisocyanates corresponding to the following general formula:
wherein R represents a difunctional radical of the type obtained by removing the isocyanate groups from a diisocyanate having a molecular weight of from about 112 to 1000.
R' represents a hydrogen atom or a monofunctional hydro-carbon radical having from 1 to 8 carbon atoms, X represents a difunctional radical obtained by removing the terminal oxygen atom from a polyalkylene oxide radical having from about 5 to 90 alkylene oxide units, of which, based on the number thereof, from about 40 to 95% consist of ethylene oxide units and from about 5 to 60% are selected from the group consisting of propylene oxide, butylene oxide and styrene oxide units, Y represents oxygen or -NR'''- and R" and R"' which may be the same or different, each represent monofunctional hydrocarbon radicals having from 1 to 12 carbon atoms, Z represents a radical which has the same definition as Y.
LeA 16,689 and/or diisocyanates corresponding to the following general formula:
wherein R represents a difunctional radical of the type obtained by removing the isocyanate groups from a diisocyanate having a molecular weight of from about 112 to 1000.
R' represents a hydrogen atom or a monofunctional hydro-carbon radical having from 1 to 8 carbon atoms, X represents a difunctional radical obtained by removing the terminal oxygen atom from a polyalkylene oxide radical having from about 5 to 90 alkylene oxide units, of which, based on the number thereof, from about 40 to 95% consist of ethylene oxide units and from about 5 to 60% are selected from the group consisting of propylene oxide, butylene oxide and styrene oxide units, Y represents oxygen or -NR'''- and R" and R"' which may be the same or different, each represent monofunctional hydrocarbon radicals having from 1 to 12 carbon atoms, Z represents a radical which has the same definition as Y.
4. The non-ionic water-dispersible polyurethanes of Claim 1 wherein the lateral polyalkylene oxide polyether chains are present in from about 3 to 30% by weight based on the weight of the polyurethane.
LeA 16,869
LeA 16,869
5. A process for the production of a non-ionic water dispersible polyurethane having a substantially linear molecular structure comprising reacting:
(a) organic diisocyanates, (b) organic difunctional compounds having isocyanate-reactive end groups and having a molecular weight of from about 300 to 6000, and (c) synthesis components containing hydrophilic groups which are responsible for the dispersibil-ity of the polyurethane, said synthesis components selected from the groups consisting of diols of the formula and diisocyanates of the formula wherein R represents a difunctional radical of the type obtained by removing the isocyanate groups from a diisocyanate having a molecular weight of from about 112 to 1000.
R' represents a hydrogen atom or a mono-functional hydrocarbon radical having from 1 to 8 carbon atoms, X represents a difunctional radical obtained by removing the terminal oxygen atom from a polyalkylene oxide radical having from about 5 to 90 alkylene oxide units, of which, based on the number thereof, LeA 16,869 from about 40 to 95% consist of ethylene oxide units and from about 5 to 60% consist of the alkylene oxide units selected from the group consisting of propylene oxide, buty-lene oxide and styrene oxide units Y represents oxygen or -NR"'- and R" and R"', which may be the same or different, each represent monofunctional hydrocarbon radicals having from 1 to 12 carbon atoms, Z represents a radical which has the same definition as Y, so as to produce a polyurethane which contains from about 3 to 30% by weight of lateral polyalkylene polyether chains.
(a) organic diisocyanates, (b) organic difunctional compounds having isocyanate-reactive end groups and having a molecular weight of from about 300 to 6000, and (c) synthesis components containing hydrophilic groups which are responsible for the dispersibil-ity of the polyurethane, said synthesis components selected from the groups consisting of diols of the formula and diisocyanates of the formula wherein R represents a difunctional radical of the type obtained by removing the isocyanate groups from a diisocyanate having a molecular weight of from about 112 to 1000.
R' represents a hydrogen atom or a mono-functional hydrocarbon radical having from 1 to 8 carbon atoms, X represents a difunctional radical obtained by removing the terminal oxygen atom from a polyalkylene oxide radical having from about 5 to 90 alkylene oxide units, of which, based on the number thereof, LeA 16,869 from about 40 to 95% consist of ethylene oxide units and from about 5 to 60% consist of the alkylene oxide units selected from the group consisting of propylene oxide, buty-lene oxide and styrene oxide units Y represents oxygen or -NR"'- and R" and R"', which may be the same or different, each represent monofunctional hydrocarbon radicals having from 1 to 12 carbon atoms, Z represents a radical which has the same definition as Y, so as to produce a polyurethane which contains from about 3 to 30% by weight of lateral polyalkylene polyether chains.
6. The process of Claim 5 wherein X represents a difunctional polyalkylene oxide radical having from about 20 to 70 alkylene oxide units, of which, based on the number thereof, from about 60 to 90% consist of ethylene oxide units and from about 10 to 40% consist of alkylene oxide units selected from the group consisting of propylene oxide, butylene oxide and styrene oxide units.
7. The process of Claim S wherein chain extenders having a molecular weight below about 300 are used.
8. The process of Claim 5 wherein the reactants are used in an equivalent ratio of isocyanate groups to isocy-anate-reactive groups of from about 0.8.1 to 2.5:1.
9. The process of Claim 5 wherein the organic difunctional compounds having isocyanate-reactive end groups are selected from the group of compounds consisting of dihydroxy polyesters, dihydroxy polylactones, dihydroxy polyethers and LeA 16,869 dihydroxy polycarbonates.
10. The aqueous dispersions of Claim 2 wherein the average particle size is from about 10 mµ to 5 µ.
11. The process according to Claim 3 wherein the lateral polyalkylene oxide polyether chains are present in from about 3 to 30% by weight based on the weight of the polyurethane.
12. The process according to Claim 1 or 3 wherein the reactants are used in an equivalent ratio of isocyanate groups to isocyanate-reactive groups of from about 0.8:1 to 2.5:1.
13. Non-ionic,water dispersible polyurethanes produced using an isocyanate group to isocyanate-reactive group equivalent ratio of from about 0.95:1 to 1.5:1 having a substantially linear molecular structure and about 3 to 30%
by weight, based on the weight of the polyurethane, of lateral polyalkylene oxide polyether chains containing ethylene oxide units which are responsible for dispersibility, wherein from about 40 to 95% of the alkylene oxide unites of the lateral polyalkylene oxide polyether chains, based on the number of alkylene oxide units,consist of ethylene oxide units and from about 5 to 60% are selected from the group consisting of propylene oxide, butylene oxide and styrene oxide units, said alkylene oxide unites contributed by synthesis components selected from the group consisting of diols of the formula and diisocyanates of the formula LeA 16,689-Ca wherein R - represents a difunctional radical of the type obtained by removing the isocyanate groups from a diisocyanate having a molecular weight of from about 112 to 1000, R'- represents a hydrogen atom or a monofunctional hydro-carbon radical having from 1 to 8 carbon atoms, X - represents a difunctional radical obtained by removing the terminal oxygen atom from a polyalkylene oxide radical having from about 5 to 90% alkylene oxide units, of which, based on the number thereof, from about 40 to 95% consist of ethylene oxide and from about 5 to 60% consist of the alkylene oxide units selected from the group consisting of propylene oxide, butylene oxide and styrene oxide units, Y - represents oxygen or -NR"' -, R' and R"', which may be the same or different, each represent monofunctional hydrocarbon radicals having from 1 to 12 carbon atoms, and Z - represents a radical which has the same definition as Y.
LeA 16,689-Ca
by weight, based on the weight of the polyurethane, of lateral polyalkylene oxide polyether chains containing ethylene oxide units which are responsible for dispersibility, wherein from about 40 to 95% of the alkylene oxide unites of the lateral polyalkylene oxide polyether chains, based on the number of alkylene oxide units,consist of ethylene oxide units and from about 5 to 60% are selected from the group consisting of propylene oxide, butylene oxide and styrene oxide units, said alkylene oxide unites contributed by synthesis components selected from the group consisting of diols of the formula and diisocyanates of the formula LeA 16,689-Ca wherein R - represents a difunctional radical of the type obtained by removing the isocyanate groups from a diisocyanate having a molecular weight of from about 112 to 1000, R'- represents a hydrogen atom or a monofunctional hydro-carbon radical having from 1 to 8 carbon atoms, X - represents a difunctional radical obtained by removing the terminal oxygen atom from a polyalkylene oxide radical having from about 5 to 90% alkylene oxide units, of which, based on the number thereof, from about 40 to 95% consist of ethylene oxide and from about 5 to 60% consist of the alkylene oxide units selected from the group consisting of propylene oxide, butylene oxide and styrene oxide units, Y - represents oxygen or -NR"' -, R' and R"', which may be the same or different, each represent monofunctional hydrocarbon radicals having from 1 to 12 carbon atoms, and Z - represents a radical which has the same definition as Y.
LeA 16,689-Ca
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP2555534.4 | 1975-12-10 | ||
| DE2555534A DE2555534C3 (en) | 1975-12-10 | 1975-12-10 | Polyurethanes dispersible in water |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1112394A true CA1112394A (en) | 1981-11-10 |
Family
ID=5963989
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA265,660A Expired CA1112394A (en) | 1975-12-10 | 1976-11-15 | Non-ionic, water-dispersible polyurethanes |
Country Status (16)
| Country | Link |
|---|---|
| US (1) | US4190566A (en) |
| JP (1) | JPS5271598A (en) |
| AT (1) | AT350268B (en) |
| AU (1) | AU503071B2 (en) |
| BE (1) | BE849218A (en) |
| BR (1) | BR7608223A (en) |
| CA (1) | CA1112394A (en) |
| DE (1) | DE2555534C3 (en) |
| DK (1) | DK552976A (en) |
| ES (1) | ES454071A1 (en) |
| FR (1) | FR2334699A1 (en) |
| GB (1) | GB1516018A (en) |
| IT (1) | IT1066799B (en) |
| NL (1) | NL182481C (en) |
| NO (1) | NO764053L (en) |
| SE (1) | SE7613831L (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4946910A (en) * | 1987-07-24 | 1990-08-07 | Basf Corporation, Inmont Division | Novel non-ionic polyurethane resins having polyether backbones in water-dilutable basecoats |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2816815A1 (en) * | 1978-04-18 | 1979-10-31 | Bayer Ag | WATER DISPERSIBLE OR SOLUBLE POLYURETHANES AND A METHOD FOR THEIR MANUFACTURING |
| DE2843790A1 (en) | 1978-10-06 | 1980-04-17 | Bayer Ag | METHOD FOR THE PRODUCTION OF AQUEOUS DISPERSIONS OR SOLUTIONS OF POLYURETHANE-POLYHURANE, THE DISPERSIONS OR SOLUTIONS AVAILABLE BY THIS METHOD, AND THEIR USE |
| DE2900574A1 (en) | 1979-01-09 | 1980-07-17 | Bayer Ag | USE OF WATER-SOLUBLE ELECTROLYTES AS ADDITIVES IN AQUEOUS PLASTIC DISPERSIONS AND AN AQUEOUS PLASTIC DISPERSION CONTAINING A WATER-SOLUBLE ELECTROLYTE |
| JPS56819A (en) * | 1979-05-17 | 1981-01-07 | Mitui Toatsu Chem Inc | Thermosetting polyurethane resin and coating agent |
| DE2930410A1 (en) | 1979-07-26 | 1981-02-12 | Bayer Ag | PROCESS FOR THE PRODUCTION OF STABLE Aqueous DISPERSIONS OF OLIGO- OR POLYURETHANES, AND THEIR USE AS A COATING AGENT FOR FLEXIBLE OR NON-FLEXIBLE SUBSTRATES |
| US4686137A (en) * | 1980-02-29 | 1987-08-11 | Thoratec Laboratories Corp. | Moisture vapor permeable materials |
| US5120813A (en) * | 1980-02-29 | 1992-06-09 | Th. Goldschmidt Ag | Moisture vapor permeable materials |
| DE3027198A1 (en) * | 1980-07-18 | 1982-02-11 | Bayer Ag, 5090 Leverkusen | SOLID, PRE-DISPERSABLE WATER-DISPERSIBLE, ISOCYANATE GROUPS, A METHOD FOR THE PRODUCTION OF AQUEOUS PLASTIC DISPERSIONS USING THESE PRE-PLASTICS, AND THEIR IMPROVERS |
| US4408008A (en) * | 1981-07-24 | 1983-10-04 | Mobay Chemical Corporation | Stable, colloidal, aqueous dispersions of cross-linked urea-urethane polymers and their method of production |
| US4567228A (en) * | 1984-05-21 | 1986-01-28 | Ppg Industries, Inc. | Aqueous dispersion, internally silylated and dispersed polyurethane resins, and surfaces containing same |
| US4582873A (en) * | 1984-05-21 | 1986-04-15 | Ppg Industries, Inc. | Process for producing aqueous dispersions, internally silylated and dispersed polyurethane resins, and surfaces containing same |
| US4542065A (en) * | 1984-05-21 | 1985-09-17 | Ppg Industries, Inc. | Chemically treated glass fibers and strands and dispersed products thereof |
| JPS6164271U (en) * | 1984-09-29 | 1986-05-01 | ||
| US4950423A (en) * | 1986-01-22 | 1990-08-21 | The B. F. Goodrich Company | Coating of EMI shielding and method therefor |
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|---|---|---|---|---|
| US3988278A (en) * | 1970-08-17 | 1976-10-26 | Minnesota Mining And Manufacturing Company | Stable polymer latex and process for making same |
| US3796678A (en) * | 1970-08-17 | 1974-03-12 | Minnesota Mining & Mfg | Highly branched,capped polyurethanes for pressure sensitive adhesives |
| US3894131A (en) * | 1972-05-18 | 1975-07-08 | Minnesota Mining & Mfg | Poly(urethane-urea) sealants and sealing underground structures therewith |
| DE2314512C3 (en) * | 1973-03-23 | 1980-10-09 | Bayer Ag, 5090 Leverkusen | Thermoplastic, nonionic, water dispersible substantially linear polyurethane elastomers |
| DE2314513C3 (en) * | 1973-03-23 | 1980-08-28 | Bayer Ag, 5090 Leverkusen | Process for the preparation of aqueous polyurethane dispersions |
| DE2320719C2 (en) * | 1973-04-25 | 1983-04-14 | Bayer Ag, 5090 Leverkusen | Thermoplastic, emulsifier-free, non-ionic, water-dispersible, essentially linear polyurethane-amide elastomers, processes for their production and use |
-
1975
- 1975-12-10 DE DE2555534A patent/DE2555534C3/en not_active Expired
-
1976
- 1976-11-15 CA CA265,660A patent/CA1112394A/en not_active Expired
- 1976-11-26 NO NO764053A patent/NO764053L/no unknown
- 1976-12-02 US US05/746,919 patent/US4190566A/en not_active Expired - Lifetime
- 1976-12-07 IT IT52496/76A patent/IT1066799B/en active
- 1976-12-07 AU AU20327/76A patent/AU503071B2/en not_active Expired
- 1976-12-08 JP JP51146672A patent/JPS5271598A/en active Granted
- 1976-12-08 BR BR7608223A patent/BR7608223A/en unknown
- 1976-12-08 GB GB51180/76A patent/GB1516018A/en not_active Expired
- 1976-12-09 BE BE173095A patent/BE849218A/en not_active IP Right Cessation
- 1976-12-09 SE SE7613831A patent/SE7613831L/en unknown
- 1976-12-09 DK DK552976A patent/DK552976A/en unknown
- 1976-12-09 ES ES454071A patent/ES454071A1/en not_active Expired
- 1976-12-09 NL NLAANVRAGE7613716,A patent/NL182481C/en not_active IP Right Cessation
- 1976-12-10 FR FR7637362A patent/FR2334699A1/en active Granted
- 1976-12-10 AT AT914676A patent/AT350268B/en not_active IP Right Cessation
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4946910A (en) * | 1987-07-24 | 1990-08-07 | Basf Corporation, Inmont Division | Novel non-ionic polyurethane resins having polyether backbones in water-dilutable basecoats |
Also Published As
| Publication number | Publication date |
|---|---|
| DE2555534A1 (en) | 1977-06-16 |
| JPS565454B2 (en) | 1981-02-05 |
| BR7608223A (en) | 1977-11-22 |
| ATA914676A (en) | 1978-10-15 |
| JPS5271598A (en) | 1977-06-15 |
| AT350268B (en) | 1979-05-25 |
| NL182481C (en) | 1988-03-16 |
| NO764053L (en) | 1977-06-13 |
| BE849218A (en) | 1977-06-09 |
| AU2032776A (en) | 1978-06-15 |
| DK552976A (en) | 1977-06-11 |
| NL7613716A (en) | 1977-06-14 |
| AU503071B2 (en) | 1979-08-23 |
| SE7613831L (en) | 1977-06-11 |
| ES454071A1 (en) | 1977-11-16 |
| NL182481B (en) | 1987-10-16 |
| GB1516018A (en) | 1978-06-28 |
| DE2555534C3 (en) | 1981-01-08 |
| US4190566A (en) | 1980-02-26 |
| FR2334699B1 (en) | 1982-11-12 |
| FR2334699A1 (en) | 1977-07-08 |
| DE2555534B2 (en) | 1980-04-30 |
| IT1066799B (en) | 1985-03-12 |
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