CN102453245B - Polyester and preparation method thereof - Google Patents
Polyester and preparation method thereof Download PDFInfo
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- CN102453245B CN102453245B CN201010530778.5A CN201010530778A CN102453245B CN 102453245 B CN102453245 B CN 102453245B CN 201010530778 A CN201010530778 A CN 201010530778A CN 102453245 B CN102453245 B CN 102453245B
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Abstract
The invention provides a novel polyester and a preparation method thereof. The novel polyester is formed by self-condensation of a monomer having a structure of a formula 1, wherein in the formula 1, R1 is C1-C20 alkyl or C6-C20 aryl. The polyester provided by the invention is good in heat resistance and crystallinity, and the content of carbon derived from a biological source can reach more than 35%.
Description
Technical field
The present invention relates to a kind of new polyester and preparation method thereof.
Background technology
Along with current industrial development, be that the polyester material of Material synthesis is ubiquitous in the life of the mankind with oil, also increasing to the demand of polyester material, cause petroleum-based energy gradually exhausted thus, demand and oil price continue to rise; Use simultaneously oil as in the production process of raw material and final discarded in a large amount of CO
2discharge result in global warming, the series of environmental problems such as white pollution, environmental stress is day by day heavy, directly threatens the existence of the mankind.Therefore under the demand of the whole world towards Green Chemistry, low-carbon economy, bioenergy is shown one's talent, and how to utilize organism-based raw material to research and develop low toxicity, the oligosaprobic novel material that can reduce destruction to environment, is one of important research problem of facing of people.
Current people have utilized renewable biological source to have developed multiple polymers raw materials for production product and various new polymkeric substance.Such as E.I.Du Pont Company, by fermenting to corn, through biological and chemical process, prepares 1,3-PDO, and have developed the Poly(Trimethylene Terephthalate) (PPT) deriving from biomaterial and non-petroleum material containing the 36wt% that has an appointment.Natureworks company is raw material equally with farm crop, through biological and chemical process, has produced pure biogenetic derivation and has been easy to biodegradable poly(lactic acid) (PLA) polymkeric substance.The terephthalic acid 1,2-propylene glycol ester of high molecular that utilized 1,2-PD and terephthalic acid to synthesize in Chinese patent CN101643946A, the distribution of this molecular weight of polyesters is little, and color and luster is good, and catalyst levels is few, but 1,2-PD used is petroleum resources.And this polyester exists unstable, make goods there is many problems, such as: thermotolerance is bad, crystallinity is poor, so this kind polyester all receives restriction to a certain degree in range of application.
Summary of the invention
The object of the present invention is to provide one to have better thermotolerance and crystalline polyester, be further to provide a kind of polyester with better thermotolerance and crystalline biogenetic derivation; On the one hand there is good thermotolerance, crystallinity, expand its range of application; Adopt biogenetic derivation composition in polymer raw material on the other hand, reduce cost, and solve the environmental problems such as white pollution.
Technical solution of the present invention is:
A kind of polyester of the present invention, is characterized in that: this polyester is formed from condensation by the monomer of structure as shown in Equation 1,
formula 1
Wherein R
1for C
1~ C
20alkyl or C
6~ C
20aromatic base.
Polyester of the present invention, is characterized in that: the R in formula 1
1for C
6~ C
20aromatic base.
The intrinsic viscosity of polyester of the present invention is 0.50 ~ 1.0dl/g.
The preferred biogenetic derivation carbon content of polyester of the present invention is greater than 35%.Polymer biological source carbon content is determined by the mensuration of C14.This is because carbonic acid gas contains C14 element in air, in upper atmosphere, itself and nitrogen occur to clash into and generate C14 element, not containing C14 element in oil, this is because the transformation period of C14 element is 5370, this and oil form the required time and compare little, thus can by determining its biological content to the mensuration of carbon in sample 14 element.
The preparation method of described polyester comprises the steps:
(1) reacted in the basic conditions by the compound of 1,2-PD with structure as shown in Equation 2, then carry out hydrogenation or hydrolysis, acidifying, obtain intermediate product, intermediate product structure is for shown in formula 1:
formula 2
formula 1
Wherein R
1c
1~ C
20alkyl or C
6~ C
20aromatic base, R
2for C
1~ C
5alkyl, X is halogen;
(2) intermediate product that step (1) obtains is carried out vacuum polycondensation, obtain polyester; Polymeric reaction temperature is 210 ~ 290 DEG C.
Described alkaline condition refers to the existence of one or more mixtures in sodium hydride, hydrolith, sodium sulphite, sodium hydroxide, potassium hydroxide, hydrated barta, calcium hydroxide.This reaction is carried out in a solvent, and solvent is DMF (DMF), DMSO (dimethyl sulfoxide (DMSO)) etc.
Acetate, the carbonate such as zinc, manganese, magnesium can be used in polycondensation process, or the organometallic compounds such as the metal oxides such as zinc, manganese, magnesium and tin, zinc, titanium are as catalyzer, the mixture having in tetrabutyl titanate, isopropyl titanate, n-butylstannoic acid, manganese acetate, Cobaltous diacetate, magnesium acetate one or more specifically can enumerated.Stablizer phosphorus compound is also used in this step, can be trivalent or phosphoric organic compound and inorganic phosphorous compound, that can simply enumerate has trimethyl phosphite 99, triphenylphosphate, phosphoric acid etc., can be the commercially available trivalent of phosphorus system and the antioxidant of pentavalent, as commercially available PEP36, AP1500, AX-71.
The compound of structure can be 4-bromomethyl-benzoic acid methyl ester, 8-bromine ethyl octylate, 6-chlorine isopropyl hexylate, 11-bromoundecane acetoacetic ester, 10-bromo-decane acetoacetic ester, the acid of 5-chloropentane methyl esters, 2-isobutyl ethyl bromide, 2 bromopropionic acid ethyl ester, 2-bromine ethyl butyrate, bromo-acetic acid tert-butyl etc. as shown in Equation 2.Preferred 4-bromomethyl-benzoic acid methyl ester in the present invention, structural formula is:
Introduce because in macromolecular chain the thermotolerance that aromatic ring structure can improve polyester material, but aromatic ring can make molecular chain rigidity too large too much, loses the plasticity of material more, even can not machine-shaping.
Institute's raw material 1,2-PD is R-type structure and/or S-type structure.
1,2-PD used is obtained by biogenetic derivation.Biogenetic derivation can be glycerine (i.e. glycerol), also can be the stalk of corn, sugarcane, wheat or other farm crop.
In production of biodiesel process, often produce 1t biofuel with regard to by-product 0.1t glycerine.Biofuel (Biodiesel), i.e. fatty acid methyl ester is the recyclability fuel of a kind of clean, the environmental protection utilizing rapeseed oil, soybean oil, recovery culinary art oil, animal wet goods renewable oils fat to be prepared by esterification and transesterification reaction for raw material.
Adopt novel non-noble metal nano-copper base catalytic material the glycerin by-products selective hydrogenation in production of biodiesel can be prepared 1,2-PD.Relevant glycerine prepares 1 at present, 2-propylene glycol, mostly under high pressure hydrogen (5 ~ 10MPa) condition, use Pt, the non-precious metal catalysts such as noble metal catalyst and Cu and Ni such as Rh and Ru, in intermittent high-pressure reactor, catalysis hydrocracking glycyl alcohol prepares 1,2-PD. and this reaction comprises means of dehydration of glycerol generation hydroxyacetone intermediate and hydroxyacetone hydrogenation obtains 1,2-PD two processes.This not only forms cheap product technology of producing 1,2-PD, and the synthesis for polyester monocase 1,2-PD provides a low cost and the non-petrochemical industry synthetic route of environmental protection.
The 1,2-PD used in the present invention is the stalk utilizing corn, wheat, sugarcane and other farm crop, through biological fermentation and/or the chemical industry course of processing obtained.Such as corn is through bioprocess separating starch, the sugar of 5 carbon and 6 carbon is obtained through processing, these sugars can prepare multicomponent binary alcohol through the technique of hydrogenation catalyst, after purifies and separates general procedure, then to being separated obtain 1,2-propylene glycol carries out heat treated, the temperature wherein heated is 150 ~ 200 DEG C, and the time of heating is 2 ~ 10 hours, after cooling again with activated carbon contacts process, just can obtain raw material 1,2-PD component of the present invention.
The following describes the evaluation method of the physical property in the present invention.
(1) by carrying out the shared proportion of biogenetic derivation in deterministic compound to the mensuration of radiocarbon C14 element (C14).
Mainly by acceleration machine mass spectrometer (AMS), sample is carried out to the mensuration of C14 content, this is because carbonic acid gas contains C14 element in air, this is due in upper atmosphere, itself and nitrogen occur to clash into and generate C14 element, not containing C14 element in oil, this is because the transformation period of C14 element is 5370, this and oil form the required time and compare little, thus can by determining its biological content to the mensuration of C14 element in sample.
Namely can be originated by the biological content of following formulae discovery:
In biogenetic derivation C element content %=sample C14 content/sample in total C content.
(2) DSC test:
Constant temperature 3 minutes after differential scanning calorimeter DSC (TA, Q100) is warmed up to 280 DEG C from 40 DEG C with 16 DEG C/min, eliminates thermal history; Then rapid cool to room temperature, then constant temperature 3 minutes after being warmed up to 320 DEG C from 40 DEG C with 16 DEG C/min, then cool to 40 DEG C with 16 DEG C/min, terminate.The melt temperature (Tm) obtained in heating up according to second time and melting enthalpy carry out thermotolerance and crystalline evaluation.
(3) measurement of intrinsic viscosity:
Take 1.6 grams polyester slice in test tube, at 100 DEG C dry 20 minutes, then add 20ml ortho chloro phenol and make it heating for dissolving.Sample solution is joined in capillary(tube)viscometer and automatically measures, by calculating intrinsic viscosity.
Embodiment
The present invention is further illustrated for following embodiment.
Embodiment 1:
(1) 1,2-PD of biogenetic derivation obtained by corn (R-type structure) and sodium hydride are dissolved in DMF (DMF), temperature of reaction is 0 DEG C, after reaction 5min, is progressively warmed up to room temperature 26 DEG C, 4-bromomethyl-benzoic acid methyl ester (structure is in table 1) is added after in 20min, react after 2 hours and extract, dry, be separated by chromatographic column, again by its hydrogenation, acidifying, obtains intermediate product, and the structure of intermediate product is:
(2) be 290 DEG C by intermediate product obtained above in temperature, vacuum polymerization, obtains polyester product; Polyester product is the polyester product (n=200) that coincidence unit structure is following.
Embodiment 2:
(1) 1,2-PD of biogenetic derivation obtained by glycerine (R-type structure) and sodium hydride are dissolved in DMF (DMF), temperature of reaction is 0 DEG C, after reaction 5min, is progressively warmed up to room temperature 26 DEG C, 4-bromomethyl-benzoic acid methyl ester (structure is in table 1) is added after in 20min, react after 2 hours and extract, dry, be separated by chromatographic column, again by its hydrogenation, acidifying, obtains intermediate product, and the structure of intermediate product is:
(2) be 290 DEG C by product obtained above in temperature, vacuum polymerization, obtains polyester product; Polyester product is the polyester product (n=200) that coincidence unit structure is following.
Embodiment 3:
(1) by the 1,2-PD of biogenetic derivation obtained by corn (R-type structure) with and sodium hydride be dissolved in DMF (DMF), temperature of reaction is 0 DEG C, after reaction 5min, is progressively warmed up to room temperature 26 DEG C, 2-isobutyl ethyl bromide (structure is in table 1) is added after in 20min, react after 2 hours and extract, dry, be separated by chromatographic column, again by its hydrogenation, acidifying, obtains intermediate product, and the structure of intermediate product is:
(2) be 290 DEG C by product obtained above in temperature, vacuum polymerization, obtains polyester product; Polyester product is the polyester product (n=200) that coincidence unit structure is following.
Embodiment 4:
(1) by the 1,2-PD of biogenetic derivation obtained by corn (S-type structure) with and sodium hydride be dissolved in DMF (DMF), temperature of reaction is 0 DEG C, after reaction 5min, is progressively warmed up to room temperature 26 DEG C, 8-bromine ethyl octylate (structure is in table 1) is added after in 20min, react after 2 hours and extract, dry, be separated by chromatographic column, again by its hydrogenation, acidifying, obtains intermediate product, and the structure of intermediate product is:
(2) be 290 DEG C by product obtained above in temperature, vacuum polymerization, obtains polyester product; Polyester product is the polyester product (n=200) that coincidence unit structure is following.
Embodiment 5:
(1) by biogenetic derivation obtained by corn 1,2-propylene glycol (racemic modification) is dissolved in DMF (N with sodium hydride, dinethylformamide) in, temperature of reaction is 0 DEG C, after reaction 5min, progressively be warmed up to room temperature 26 DEG C, 6-chlorine isopropyl hexylate (structure is in table 1) is added after in 20min, react after 2 hours and extract, dry, be separated by chromatographic column, again by its hydrogenation, acidifying, obtains intermediate product, and the structure of intermediate product is: (racemic modification is the mixture of R-type structure and S-type structure)
(2) be 290 DEG C by product obtained above in temperature, vacuum polymerization, obtains polyester product; Polyester product is the polyester product (n=200) that coincidence unit structure is following.
Comparative example 1:
By terephthalic acid, petroleum resources 1, 2-propylene glycol (R-type structure) is put in esterifying kettle, esterification is carried out at temperature 225 DEG C and condition of normal pressure, esterification is terminated when no longer gold-plating goes out water, esterification products is moved into poly-unit, add catalyzer tetrabutyl titanate conventional used again, stablizer phosphoric acid, antioxidant 1010 (four [methyl-β-(3, 5-di-tert-butyl-hydroxy phenyl) propionic ester] pentaerythritol ester), stir, with the polycondensation method of routine at below vacuum 200Pa, carry out polycondensation under 265 DEG C of conditions and obtain Poly(Trimethylene Terephthalate).
Terephthalic acid structural formula:
Comparative example 2:
By terephthalic acid, petroleum resources 1, 2-propylene glycol (S-type structure) is put in esterifying kettle, esterification is carried out at temperature 225 DEG C and condition of normal pressure, esterification is terminated when no longer gold-plating goes out water, esterification products is moved into poly-unit, add catalyzer tetrabutyl titanate conventional used again, stablizer phosphoric acid, antioxidant 1010 (four [methyl-β-(3, 5-di-tert-butyl-hydroxy phenyl) propionic ester] pentaerythritol ester), stir, with the polycondensation method of routine at below vacuum 200Pa, carry out polycondensation under 265 DEG C of conditions and obtain Poly(Trimethylene Terephthalate).
Comparative example 3:
By terephthalic acid, petroleum resources 1, 2-propylene glycol (racemic modification) is put in esterifying kettle, esterification is carried out at temperature 225 DEG C and condition of normal pressure, esterification is terminated when no longer gold-plating goes out water, esterification products is moved into poly-unit, add catalyzer tetrabutyl titanate conventional used again, stablizer phosphoric acid, antioxidant 1010 (four [methyl-β-(3, 5-di-tert-butyl-hydroxy phenyl) propionic ester] pentaerythritol ester), stir, with the polycondensation method of routine at below vacuum 200Pa, carry out polycondensation under 265 DEG C of conditions and obtain Poly(Trimethylene Terephthalate).
Each data of embodiment and comparative example are specifically in table 1.
Table 1
Claims (6)
1. a preparation method for polyester, is characterized in that: comprise following steps:
(1) reacted in the basic conditions by the compound of 1,2-PD with structure as shown in Equation 2, then carry out hydrogenation or hydrolysis, acidifying, obtain intermediate product, intermediate product structure is for shown in formula 1:
Wherein R
1c
6~ C
20aromatic base, R
2for C
1~ C
5alkyl, X is halogen;
(2) intermediate product that step (1) obtains is carried out vacuum polycondensation, obtain polyester; Polymeric reaction temperature is 210 DEG C ~ 290 DEG C.
2. the preparation method of polyester according to claim 1, is characterized in that: described raw material 1,2-PD is R-type structure and/or S-type structure.
3. the preparation method of polyester according to claim 1 and 2, is characterized in that: described raw material 1,2-PD is obtained by biogenetic derivation.
4. the polyester prepared by method described in claim 1, is characterized in that: this polyester is formed from condensation by the monomer of structure as shown in Equation 1,
Wherein R
1for C
6~ C
20aromatic base.
5. polyester according to claim 4, is characterized in that: the intrinsic viscosity of this polyester is 0.50 ~ 1.0dl/g.
6. polyester according to claim 4, is characterized in that: the biogenetic derivation carbon content of this polyester is greater than 35%.
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| CN201010530778.5A CN102453245B (en) | 2010-10-25 | 2010-10-25 | Polyester and preparation method thereof |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5607687A (en) * | 1995-03-06 | 1997-03-04 | Ethicon, Inc. | Polymer blends containing absorbable polyoxaesters |
| US5618552A (en) * | 1995-03-06 | 1997-04-08 | Ethicon, Inc. | Absorbable polyoxaesters |
| CN101525419A (en) * | 2008-03-04 | 2009-09-09 | 东丽纤维研究所（中国）有限公司 | Polyester made of raw material of 1,2-propylene glycol |
| CN102190782A (en) * | 2010-03-17 | 2011-09-21 | 东丽纤维研究所（中国）有限公司 | Copolyester compound and method for preparing same |
-
2010
- 2010-10-25 CN CN201010530778.5A patent/CN102453245B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5607687A (en) * | 1995-03-06 | 1997-03-04 | Ethicon, Inc. | Polymer blends containing absorbable polyoxaesters |
| US5618552A (en) * | 1995-03-06 | 1997-04-08 | Ethicon, Inc. | Absorbable polyoxaesters |
| CN101525419A (en) * | 2008-03-04 | 2009-09-09 | 东丽纤维研究所（中国）有限公司 | Polyester made of raw material of 1,2-propylene glycol |
| CN102190782A (en) * | 2010-03-17 | 2011-09-21 | 东丽纤维研究所（中国）有限公司 | Copolyester compound and method for preparing same |
Non-Patent Citations (2)
| Title |
|---|
| 4-Substituted 1,7-dioxacycloalkan-8-ones.;Kraft, Philip and Cadalbert, Riccardo;《Synthesis》;19981130(第11期);1662-1669 * |
| Synthesis of 17 membered-ring oxalactonesand its odor characteristics;Kurata, Takeo and Kurita, Nozomi;《Fain Kemikaru》;20080229;第37卷(第2期);43-49 * |
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