CA1110379A

CA1110379A - Compositions containing hydrogenated block copolymers and polyamides

Info

Publication number: CA1110379A
Application number: CA277,869A
Authority: CA
Inventors: William P. Gergen; Sol Davison
Original assignee: Shell Canada Ltd
Current assignee: Shell Canada Ltd
Priority date: 1976-06-07
Filing date: 1977-05-06
Publication date: 1981-10-06
Also published as: AU2585577A; BE855420A; GB1562338A; FR2354367A1; SE418299B; JPS6011941B2; CH633817A5; AU509014B2; DE2725664A1; FR2354367B1; ES459526A1; NL7706195A; SE7706572L; US4041103A; IT1081813B; NL183197C; DE2725664C2; JPS52150457A; NL183197B; BR7703666A

Abstract

A B S T R A C T
An interpenetrating network is obtained by mixing a selectively hydrogenated block copolymer comprising at least two terminal polymer blocks of a monoalkenyl arene and at least one intermediate polymer block of a conjugated diene, in which the terminal polymer blocks constitute between 8 and 55% by weight of the block copolymer with a polyamide.

Description

.73'7~3

- 2 - .

The invention relates to a composition on the basis of a partially hydrogenated block copolymer comprising at least two termir..al polymer blocks A
of a monoalkenyl arene having an average molecular weight of from 5,000 to 125~000, and at least one :~
intermediate pcly~er block B of a con,jugated diene having an average molecular weight of from 10,000 -to 300,000, in whioh the proportion of the terminal polymer blo~.ks A is between 8 and 55% by weight of :
the block copolymer~ and no more than 25% of the arene double bonds of the~polymer blocks A and at least 80% of -:.
the aliphatic double bonds of the polymer blocks B have .
; been reduced by hydrogenation.
Block copolymers comprising at least two terminal ~ -polymer blocks of a monoalkenyl arene and at least one intermediate polymer block of a conjugated diene are ~ :
known. A block copolymer of this type is representedjby the structure polystyrene-polybutadiene-polystyrene (SBS).
When the monoalkenyl arene blocks comprise less than 55%
: 20 b~ weight o~ the block copolymer, the product can be referred to as a thermoplastic elastomer. .By this is meant ,a polymer which in the melt state is ~rocessable in an ordinary equipment for processing thermoplastics but in .
the solid state behaves like a c,hemically vulcanized rubber :
without chemical vulcanization having been effected.

3~7 - 3 ~

Such block copolymer.s are not compatible with polar polymers, such as polyamides. According to British patent specification 1,l90~049 this shortcoming is removed by mixing the block copolymer with the polyamide in the presence of a salt of a metal from groups II A, III A, IV A, I B, II B, III B, IV B, V B, ~TI B, VII B or VIII
of the Periodic System with an aliphatic carboxylic acid, hydrofluoric acid or phosphoric acid. Example 8 of the patent specification discloses a composition containing `
75 parts of a three~block copolymer of butadiene and 30%
by weight of styrene (1,2-vinyl content 10%, 1,4~cis content 35%), 25 parts of polycaprolactam and 2 parts of lanthanum (III) fluoride.
It has been found that an interpenetrating network can i5 be obtained by mixing a partially hydrogenated block copolymer~ -~
and a polyamide. An interpenetrating network of two polymers is a blend in which one polymer would be thought of as fillin~ the voids of a form of the second polymer. The interpenetrating network is not a blend in which there , ~
is molecular mixing.iAlthough the polymers form separate and :
dist~inct phases, they are not in a form which can lead to gross phase separation causing delamination.
Now, the invention provides a composition on the basis of a partially hydrogenated block copolymer comprising at least two terminal polymer blocks A of a monoalkenyl arene having an average molecular weight of from 53000 to 125,00?
' , . ;. :.:

and at least one intermediate polymer block B of a conjugated : diene having an average molecular weight of from 10,000 to 300,000 ~;
in which the proportion of the terminal polymer blocks A is between 8 and 55~ by weight of the block copolymer, and no more than 25% of the diene double bonds of -the polymer blocks A and at least 80% of the aliphatic double bonds of the polymer blocks B have been reduced by hydrogenation, which composition is char~
acterized in that it comprises :: , (a~ 100 parts by weight of the partially hydrogenated block 10 copolymer and ~1 (b) 5 to 200 parts by weight of a polyamide having the formula (I) or (II) CH2)a NH- ~ or (II) t ~ CH2 ~ C NH - -~CH2~c---NH ~

wherein a, b and c each vary from 4 to 12 and n and m are integers corresponding to a number average molecular weight of between 10,000 and 30,000.
The block copolymer may be linear, radial or branched.
Methods for the preparation of such polymers are known ~ :
in the art. The structure of the block copolymers 3~7`~9 is determined by the methods of polymerization. ~or e~ampleg linear polymers result by se~uen~ial intro-duction of the desired monomers into the reaction vessel when using such initiators as lithium-alkyls or dilithiostilbene, or by coupling a two segment block copolymer with a difunctional couplln~ agent. Branched structures, on the other hand, may be obtained by the use of suitable coupling agents havlng a functionality with respect to the precursor polymers of three or more.
Coupling may be effected with multifunctional coupling agents such as dihalo-alkanes or - alkenes as well as certain polar co~pounds such as silicon halides, siloxanes or esters of monohydric alcohols with carboxylic acids. The presence of any coupling residues in the p01ymer may be ignored for an adequate description of the polymers forming a part of the compositions of this invention. Likewise~ in the generic sense, the specific structures also may be ignored. The invention applies especially to the use of selectively hydrogenated polymers having the configuration before hydrogenation of the following typical species~
polystyrene-polybutadiene-polystyrene (SBS) polystyrene-polyisoprene-polystyre~e (SIS) poly(alpha-methylstyrene)-polybutadiene-poly(alpha-methylstyrene) (-MeSB~-MeS) and poly(alpha-methylstyrene)-polyisoprene-poly(alpha-methylstyrene)(~-MeSI-MeS) : . ' ~ . !

Both polymer blocks A and B may be either homopolymer or random copolymer blocks as long as each block predominates in at least one class of the monomers - ;~
characterizing the blocks as defined hereinbefore. Thus, blocks A may comprlse styrene/alpha-methylstyrene copolymer blocks or styrene/butadiene random copolymer blocks as long as the blocks individually predominate in monoalkenyl arenes. The term "monoalkenyl arene" will be taken to include styrene and its analogs and homologs includirg alpha-methylstyrene and ring-substituted styrenes, particularly ring-methylated styrenes. The preferred monoalkenyl arenes are styrene and alpha-methylstyrene, and styrene is particularly preferred.
The blocks B may comprise homopolymers of butadiene or isoprene, copolymers of butadiene with isoprene an~ copolymers of one of these two dienes with a monoalkenyl arene as long as the blocks B predomi-nate in conjugated diene units. When the monomer employed is butadiene, it is preferred that between 2~ 35 and 55 mol percent of the condensed butadiene units in the butadiene polymer block have 1,2 configuration. Thus, when such a block is hydrogenated, the resulting product is, or resembles, a regular copolymer block of ethylene and butene-1 (EB). If the conJugated diene employed is isoprene, the resulting hydrogenated product is or resembles a regular copolymer block of alter-nating ethylene and propylene (EP).

3'7~

Hydrogenation of the precursor block copolymers is preferably effected by use of catalyst comprising the reaction products of an aluminium alkyl compound with nickel or cobalt carboxylates or alkoxides under such conditions as to substantially completely hydrogenate at least 80% of the aliphatic double bonds while hydrogenating no more than about 25% of the alkenyl arene aromatic double bonds. Preferred block copolymers are those where at least 99% of aliphatic double bonds are hydrogenated and less than 5% of the aromatic double bonds are hydrogenated.
The average mo~ecular weights of the individual blocks may vary within certain limits. The block copolymer present in the composition according to the invention h~s at least two terminal pclymer blocks A of a monoalkenyl arene having an average molecular , weight of from 5J000 to 125,000 and at least one intermediate polymer block B of a conjugated diene having an average -molecular weight of from 10~000 to 300,000. These molecular weights are most accu~ately determined by tritium counting methods or osmotic pressure measurements. The proportion of the polymer blocks A of the monoalkenyl arene should be bet~een 8 and 55% by weight of the block copolymer, preferably between 10 and 30% by weight. ~ ;
The polyamide being present in the composition according to the invention herein referred to as nylons are represented by the following formulas:

.

~ ~ ~ CH2- ~ NH ~ or ~ C ~ CH2) b ----t ~ 2 ~ MH ~ m where a, b and c each vary from 4 to 12 incluslve. The nylons can be those having pendant hydrocarbon groups in place of a hydrcgen attached to the nitrogen or the methylene carbons of the polymer backbone. The molecular wei~hts (Mn - number average molecular wei~ht) of the polya~ides used in the invention are between 10,000 and 30,0QO, 1preferably between 15,000 and 25,000.
Preferred nylons are nylon 6 (polymer of epsilon amino caprolactam), nylon 6,6 (polymer of hexamethylene diamine and adipic acid), nylon 6glO (polymer of hexamethylene diamine and sebacic acid), nylon 11 (polymer of ~-amlno undecanoic acid), nylon 4 (polymer of pyrrolidone), nylon 7 (polymer of amino heptanoic acid), nylon 9 (polymer of 9-amino nonanoic acid). rTylon 6 and nylon 6,6 are particularly preferred.
The amount of polyamide employed varies from 5 to 200 phr, preferably 5 to 75 phr, more preferably 10 to 40 phr. "Phr~' means parts by wei~ht per 100 parts by wei~ht of the partially hydrogenated block copolymer.
There are at least two means (more positive than the observance of the absence of delamination) by which -~

i,3~,9 g the presence of an interpenetrating network can be shown. In one method~ an interpenetrating network is shown when moulded or extruded objects made from the blends of this invention are placed in a solvent that dissolves away the block copolymer, and the re-maining polymer structure (coMpriSing the polyamide) ~
still has the c'hape lf the moulded or extruded object -If the remaining ~tructure has the appearance of ^~
continuity then an~interpenetrating network has been formed.
The second method of detecting the presence of ;~
an interpenetrating network is by measuring the tensile strength at break of the blen~. This follows simply from the fact that an applied tensile stress is ;
distributed over the avàilable network elements. The number of elements supporting a force is decreased in the presence of a noncontributing filler. At low concentrations of the secondary heterophase (the polyamide) where an interpenetrating network is absent, islands of polyamide crystallites dilute the number of block copolymer elements bearing stress.
If the concentration of polyamide is increased to a point where a continuous crystalline structure occurs `
throughout the block copolymer network, the second network is then capable of bearing a portion of the tensile strength and the presence of interpenetrating network is shown by increased tensile modulus and strength.

3L~ 3t7~ ~ ~

The nylon and the hydrogenated block copolymer may be blended in any manner that produces the interpe~etrating net~ork. ~or example, the two polymers may be dissolved in a solvent common for 5 both and coagulated by admixing in a solvent in which neither polymer is soluble. But more preferably, a particularly useful procedure is to intimately mix the two polymers as mel s o~ nibs and/or powder in a device which provides shear. In the case of nylon 0 113 milling on a 5 cm mill at 195-215C for 10-15 minutes was Eufficient to achieve a compatible blend, but was not sufficient for blending nylon 6 or nylon 66. However, good results were obtained l~ith nylon 6 using a Banbury Laboratory Model B mixer. In order to achieve the mixing necessary for an interpenetrating network with nylon 66 it was necessary to use both the mixing obtained with a Banbury Laboratory P~odel B
and a pass through an Ankerwerk 3-ounce reciprocating screw injection moulder. A practical way to ensure the interpenetratlng network, is to blend the polymers as nibs and/or powders on a Banbury at a temperature of 10-30C above the melting point of the highest melting polymer, followed by a processing step, i.e., extruding on a twin screw extruder, or injection moulding on a reciprocating screw machine 3t~

- 11 ~
, The mixing or processing temperature employed varies from 200C to 300C.
The blend of ~ylon with the partially hydrogenated block copolymer may be compounded with an extending oil ordinarily uséd in the processing of rubber and plastics. Especially preferred are the types of oil that are compatible with the elastomeric blocks of the blocks copolymer. While oils of higher aromatics content are satisfactory, those petroleum-based while oils having low volatility and less than 50%
aromatics content as determined by the clay ~el method ~-(tentative ASTM method D 2007) are particularly preferred. ;~
The oils should additionally have low volatility, preferably havin~ an initial boiling point above 260C.
The amount of oil employed may vary from 0 to 50 phr (phr = parts by weight per hundred parts by weight of block copolymer), preferably from 5 to 30 phr.
The blend of nylon with the partially hydrogenated block copolymer may be further compounded with a resin.
The additional resin may be a polymeric alpha-ole~in or a ~low promoting resin such as an alpha-methylstyrene resin, a vinyl toluene/alpha-methylstyrene resin and an end-block plasticizing resin. The polymers of alpha-olefins include both high and low density polyethylene, isotactic and atactic polypropylene and poly~
butene-1. The preferred poly-alpha-ole~in is iso-tactic polypropylene, which is a crystalline polypropylene.

3~

.
The amount of the additional resin may vary from 0 to 100 phr, preferably' from 5 to 25 phr.
Further the co~position may contain fillers, antîoxi~dants, stabilizers and other compounding ingred:ients.
I Elastomeric compositions prepared in accordance ; with this invention are suitable for most purposes - ;
where rubbers and flexible thermoplastics such as polyurethanes are employed, such as in mechanical --goods, thermoformed articles, insulations, etc. The compositions may be inJection moulded, blow moulded, or extruded. Other moulded articles as well as films, sheets, and textile coatings may be produced. The compositions may be cast from solvents to form films 15~ or spun into fibers or coated on other objects. Moulding compositions having the usual plastic end uses may be prepared, particularly when the monoalkenyl arene polymer blocks oonstitute a high percentage of the weight of the block polymer. Contemplated plastic end uses encompass mouldings, mechanical goods, extruded objects such as films, sheets, and fibers. The present invention is especially useful in applications where fabricated articles are subjected to high temperature oxidative ; environments such as automotive under-the-hood applications or electrical power applications.

To illustrate the ;nstant invention, the following illustrative ex;~mpl~s are given.
~ ' '~ .
The followi~g two tables set out blends of polystyrjene/hydrogenated polybutadiene/polystyrene block copolymer with low and medium viscosity nylon 6 and low viscosity nylon 66. These blends are prepared by mixing the components on a Banbury Model "B" Laboratory mixer at approximately 400C for seven minwtes, until a smooth blend was obtained, followed by injection ~;
moulding in a reciprocating screw Ankerwerk injection moulding mach-ne at 260C.
Block copolymer A has block molecular weights of 255000-100,000-25,000; block copolymer B has block molecular wei~hts of 9,000 47,000-9,000; and block copolymer C has block molecular weights of 65000- ~.
35,000-6,000.
The formulations and results are presented below in Tables 1, 2 and 3.

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OO 1::4 F o o o o o I a~ h r1 VO ~ ~1 ~ ~1 ~1 ~ bOE~ X P~ O
.
a) ~ ~~, i,_,r1 4~
r-l ~ X ~ O ~ E ( O
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~d ~ ~ ~ ~ ~ ~ ~ , ~ _` ^
~ æ ~ :

3t79 Exam~le II
A 112.5 kg sample of a nylon 6, polystyrene/
hydrogenated polybutadiene/polystyrene block copolymer ~ -blend having the following composition and properties was made by blending on a Werner-Pfleiderer twin screw extruder, model ZSK 83/700, at zone temperatures ranging ~ !
from 200-240C then inJection moulding test parts on `
a Stokes reciprocating screw injection moulding machine at 230-275C.
~P~ ~, ~, .
~ ~hr Block Copolymer 1) 50 :
Block Copolymer 2) 50 Nylon 6 Resin 3) 30 Polypropylene 4) 10 Carbon Black Concentrate 5) 5 Antioxidants 6) UV Stabilizers 7) 1) Nominal molecular weight 65m, approximately 28% w polystyrene. ;~
2) Nominal molecular weight 47m, approximately 28% w polystyrene.
3) Low viscosity nylon 6 resin

4) Medium melt flow polypropylene nibs.

5) 1/1 dispersion of SRF black in EVA.

6) Equal amounts of a hindered phenol and dilaurylthio-dipropionate.

7) Equal amounts of a benzotriazole and a hydroxybenzoate. -h3 7 ASTM Result Method Specific Gravity - 0.96 Tensile and Hardness Properties Hardness, Shore A Points - 91 Hardness, Shore D Points - 36 Tensile Strength at Break, D-412 155 kg/cm 23C
Elongation at Break, % D-412 350 ~

Modulus at 100% Elongation, kg/cm2 23C D-412 91 Modulus at 300% Elongation, kg/cm2 23C D-412 141 -Flexural Properties Modulus of Elasticity, kg/cm2 23C D-790 1266 ~5 i70C 352 Tinius-Olson Stiffness~
kg/cm2/rad D-747 422-562 Tear Strength Die Angle Tear, kg/linear 2.5cm D 624 144-247.5 Abrasion Resistance Tabor H-18, cc/1000 rev. D-1O44 1.90 Gardner 50 cm/0.45 kg - good 125cm/0.45 kg good 200cm/0.45 kg fair-good (-30C) 5O cm/0.45 kg fair-good P3'Y~ ;
- 25 - .
i A,STM
~ Method Result E :t:~ N~b.re Tensile Hysteresis, 100%

Elongation - -First cycle loss, % 7 Equilibrium loss, % 40 ::;

.
1) Properties were measured on ASTM plaques or Ross Flex bars which were injection moulded on a Stokes reciproc~ting screw machine at 7.2 - 274C.
Example III
100 parts of a hydrogenated ~S resin having ~ `
polystyrene blocks with a number average molecular weight ~f 10,000 and a hydrogenated butadiene block with a number!average molecular weight of 50,000 with 0.2 phr IONO ~ were blended with 50 parts of a nylon 11, (Rilson BMNO from Aquitaine Chemical) on a 2"

Farrell mill for 10-15 minutes at 195-215C. The blend processed well on the mill, and compression ~ ;
moulded tensile bars dld not show delamination. A
satisfactory interpentrating blend is obtained. The physical properties were:

Tensile at break 74.5 k~/cm2 Elongation at break 400%
Modulus at 300% elong. 54.8 k~/cm .Set at break 15~

:

r .
,;' . . , ~E~
Example II is repeated but a poly(alpha-methyl-styrene)/hydrogenated butadiene/pol~(alpha-methylstyrene) block copolymer is used in place of the SEBS. A satis-factory interpenetrating blend is obtained.
xample V
:
Example II is repeated except a polystyrene/
hydrogenated polyisoprene/polystyrene block copolymer is substituted f~ the SRBS. A satisfactory i.nterpene-trating blend is dbtained.
Exam~le VI . .
Example II is repeated except a poly(alpha-methylstyrene)/hydrogenated polyisoprene~poly(alpha~
methylstyrene) block copolymer is substituted for the SEBS. A satisfactory interpenetrating bIend is obt,ained.
The Examples show that impact st:rength, elasticity ;
and flexibility are greatly reduced at nylon contents substantially over 50%, based on total blend, and that nylon~hydrogenated ABA blends are vastly superior in resistance to heat distortion at high temperatures in comparison to the neat selectivity hydrogenated ABA-type block copolymers.

Claims

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A composition on the basis of a partially hydrogenated block copolymer comprising at least two terminal polymer blocks A of a monoalkenyl arene having an average molecular weight of from 5,000 to 125,000 and at least one intermediate polymer block B of a conjugated diene having an average molecular weight of from 10,000 to 300,000, in which the proportion of the terminal polymer blocks A is between 8 and 55% by weight of the block copolymer, and no more than 25% of the arene double bonds of the polymer blocks A and at least 80% of the aliphatic double bonds of the polymer blocks B have been reduced by hydrogenation, characterized in that the composition comprises (a) 100 parts by weight of the partially hydrogenated block copolymer and (b) 5 to 200 parts by weight of a polyamide having the formula (I) or (II):

(I) or (II) wherein a, b and c each vary from 4 to 12 and n and m are inte-gers corresponding to a number average molecular weight of between 10,000 and 30,000.

2. A composition as claimed in claim 1, in which the pro-portion of the terminal polymer blocks A of the monoalkenyl arene is between 10 and 30% by weight of the block copolymer.

3. A composition as claimed in claim 1, in which the polyamide has a number average molecular weight of between 15,000 and 25,000.

4. A composition as claimed in claim 1, in which the poly-amide is present in an amount of from 5 to 75 parts by weight on 100 parts by weight of the block copolymer.

5. A composition as claimed in claim 4, in which the composi-tion contains from 10 to 40 parts by weight of the polyamide on 100 parts by weight of the block copolymer.

6. A composition as claimed in claim 1, in which the composi-tion contains an extending oil in an amount of no more than 50 parts by weight on 100 parts by weight of the block copolymer.

7. A composition as claimed in claim 6, in which the composi-tion contains an extending oil in an amount of from 5 to 30 parts by weight on 100 parts by weight of the block copolymer.

8. Articles prepared by using a composition as claimed in

claim 1.