DE3030804A1 - POLYMERISAT MIXTURE - Google Patents

Description

The invention relates to a polymer mixture the good Has impact resistance, is flexible and at the same time hard and good crush resistance on v / eist. In addition, the polymers in the mixture are compatible with one another.

The above physical properties are all important for many applications. For example these properties are used in automotive bumpers high level required. The same applies to the materials used in the manufacture of footwear, especially sports boots, be used. In addition, there are numerous other types of endings for a material, the one mentioned Has a combination of properties.

Almost all of them are currently used for the stated purposes Substances are expensive, so there is a great need to provide a substitute. Polyurethanes are a typical raw material for the manufacture of ski boots, for example. However, these polyurethanes are proportionate expensive. However, they have the stiffness of plastics and the elasticity of rubber and are therefore very well suited for these areas of application.

The recent development of copolymers from monomers, such as styrene and conjugated dienes has made a valuable raw material available for numerous fields of application. In many cases such copolymers have elastomeric properties at ambient temperature and are thermoplastic at elevated temperatures. They have the general properties of vulcanized rubbers that require however, no vulcanization to achieve these properties. Depending on the composition of the monomers, i.e. the

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The proportions of styrene in the block copolymer are the same Properties of the polymer are those of vulcanized rubber, which means "with a high content of conjugated Dien is the case. If the styrene content is high, the polymers are the same on the other hand, more of a thermoplastic material, such as polystyrene with high impact resistance. The realm of possibilities desirable properties is evident, and these block copolymers have a wide field of application found.

Nevertheless, such block copolymers are not completely satisfactory for some purposes. Some of the required properties as a material for sports boots, for example, hardness and step resistance. The currently available block copolymers do not have these properties to the desired extent.

The combination of a polyphenylene oxide, a block copolymer from an aromatic vinyl compound with a conjugated diene and a graft copolymer of a monomeric acrylic compound with a diene rubber is in U.S. Patent 3,833,687. A similar combination, at which the graft copolymer is one of a diene rubber and a styrene monomer, is the subject of U.S. Patent 3,835,200. A Process for Polymerizing a Mixture of styrene and acrylonitrile in the presence of a block copolymer of an ethylene-propylene copolymer and a diene rubber, is described in U.S. Patent 3,719,731. From the Shell Chemicals Technical Bulletin RBX / 76/3 is the combination of styrene-butadiene-styrene block copolymers known with polystyrene, with polyethylene and polypropylene.

The combination of a graft copolymer is disclosed in US Pat. No. 3,04-9,5Q5 of polybutadiene, styrene and acrylonitrile and a polyurethane. The combination of one Block copolymers made from styrene and butadiene and a poly- ' EsterWethane is known from US Pat. No. 3,562,355. In the end

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is the polymerization of styrene in the presence of a styrene-butadiene copolymer Subject of Uo-PS 3 062 777

The invention relates to a polymer mixture composed of a block copolymer composed of styrene and a conjugated one Diolefin with 4 to 6 carbon atoms and a graft copolymer, in which a styrene polymer and Ms to 4-0 parts, "based on the mass of the graft copolymer, acrylonitrile and / or diethyl methacrylate on a rubbery substrate made of polybutadiene or a copolymer of butadiene, styrene and up to 10? ό (based on the substrate) Acrylonitrile are grafted on.

The polymer mixture can also be a styrene polymer or a thermoplastic, elastomeric polyurethane, the relatively high molecular weight polyester segments contains, included.

The polymer mixture according to the invention is distinguished by good flexibility, hardness, impact resistance, gloss, wear strength and crush resistance. Also lie its costs are significantly below those of the substances currently in use which it can replace on the market. the unexpected compatibility of these polymers enables formulations with a wide range of compositions, which have a corresponding range of the aforementioned favorable properties.

The block copolymer

The conjugated diolefin is generally butadiene or Isoprene, preferably butadiene, is used. 2,3-Dimethylbutadiene can also be used. The block copolymer is through terminal styrene blocks with elastomeric diolefin middle blocks marked. It therefore has an ABA structure, where B is an elastomeric diolefin polymer unit means. A preferred embodiment is a

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Styrene-butadiene-styrene block copolymer.

The block copolymers are linear and can be carried out batchwise anionic polymerization of styrene, conjugated diolefin and finally styrene again. For example, styrene is in the presence of an alkyllithium 'catalyst polymerized to a so-called "living polymer". Butadiene is then added to this, the polymerization with the formation of an intermediate product A-B-Li progresses, which is also a living polymer. Then again styrene is added to one Form styrene polymer block. Eventually it becomes a chain terminator admitted. The A-B-Li "living polymer" can also be coupled to itself. In both cases a block copolymer with the structure ABA is obtained. The polystyrene blocks each have a molecular weight from about 10,000 to 45,000 and the polyolefin block has a molecular weight from et v / a 35,000 to 150,000. Details on processes by which these block copolymers can be produced are given in U3-P3en 3 231 635, 3,239 4-73 and 3,265,755 and in Allport and Jones, "Block Copolymers ", K. 3 (pp. 31-37), Applied Science Publishers, London (1974-), included.

The graft copolymer

The graft copolymer used according to the invention can be prepared by known processes, for example - (1) through. Production of a polymer latex (substrate) by

Polymerization (in aqueous emulsion) of butadiene or a mixture of butadiene, styrene and up to 10 / έ (based on the monomer content of the latex) acrylonitrile,
(2) adding a mixture of styrene and up to 40% acrylonitrile and / or methyl methacrylate (based on the monomer content of the added mixture) to the latex, and

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(3) Polymerize the mixture according to (2).

Accordingly, the polymer latex according to (1) can be poly "butadiene Copolymer of butadiene and styrene or a copolymer be made of butadiene, styrene and acrylonitrile. The graft copolymer can be 15 "to 70p styrene, based on the total mass of the monomers. The mixture according to (2) can consist of styrene and acrylonitrile, styrene and methyl methacrylate or of styrene, acrylonitrile and methyl methacrylate ". The butadiene content of the graft copolymer is in the range of about 10 to about 60%.

Crosslinkers can be used in the above process as required can be used. You can at the latex production stage and in step (3) ″ in the preparation of the side chains. Specific examples of suitable crosslinkers are diviny! benzene, dimethacrylates, such as mono-, di-, tri- and tetra-ethylene glycol dimethacrylate and 1,5-butylene glycol dimethacrylate, Trially! Phosphate, triallyl cyanurate, Tetraallylsilane, diallyl itaconate and diethylene glycol diacrylate.

Processes for the preparation of the graft copolymers are known. Methods for making ABS resins are, for example known from U.S. Patents 2,082,80S and 2,994,683. The MBS resins and other graft copolymers are in made in a similar way.

The graft copolymers in which the side chains (graft) consist of a copolymer are particularly preferred of styrene and acrylonitrile and the main chain (substrate) consist of a butadiene polymer. Another preferred one Graft copolymer is the MABS resin, i.e. a polymer in which the side chains consist of a graft copolymer consist of acrylonitrile, methyl methacrylate and styrene. Another preferred graft copolymer (MBS) is finally made by copolymerizing styrene and

130013/1129

Methyl methacrylate prepared in the presence of a butadiene polymer as a substrate.

It is also possible to use mixtures of Pfr op f copolymers will. For example, two different ABS resins or a mixture of an ABS resin and a MABS resin, a mixture of an MBS resin and a MÄBS resin Mixture of two different MBS resins or a mixture of one ABS resin and two different MABS resins are used will.

Particularly "preferred is a graft copolymer isate in which a copolymer of about 70 to 90 parts of styrene and about 10 to 30 parts of methyl methacrylate on a butadiene polymer is grafted as a substrate.

The Sty ROLP o lymer isat

As a styrene polymer, the usual all-purpose polystyrene, i.e. the homopolymer used. It has a semi-linear Structure and is not crystalline. Although it is one of the most widely used thermoplastics, As such, it is characterized by limited weather resistance and relatively low impact resistance.

The polyurethane

The polyurethane component of the polymer mixture according to the invention is derived from polyesters, more precisely from polyesters with terminal hydroxyl groups. These Polyesters, for their part, can either be produced by condensation from approximately equivalent amounts of a glycol and a dicarboxylic acid or their anhydride, or by reacting a lactone with at least 6 carbon atoms in the lactone ring a small amount of a functional initiator, such as a glycol, an amino alcohol or a diamine. In both cases is the molecular weight of the polyester relatively high, for example in the range of

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about 1000 to 3000.

.. 'hen the polyester by condensation of a G-Iy ko Is and a dicarboxylic acid is produced, then a G-Iykol with 2 to 6 carbon atoms are used, for example ethylene, trimethylene, tetramethylene, hexylene and propylene glycol. The dicarboxylic acid is aliphatic and contains 2 to 8 carbon atoms, for example succinic acid, glutaric acid, Adipic acid, pimelic acid and suberic acid. The condensation polymerization is carried out according to known methods .

The polyester can also be obtained by polymerization from a lactone such as caprolactone. The polymerization is "for example, about 120 to 200 ⁰ G, effected by simple mixing of the lactone with a bifunctional initiator at elevated temperature. Preferably, a catalyst at a concentration of about 0.001 to 0.5 ?? used There is a huge. Number of catalysts, basic and neutral esterification catalysts being preferred. Details of the processes for the production of lactone polyesters of the type in question are described in US Pat. Nos. 2,933,477 and 2,933,473.

Be the above-mentioned linear dihydroxy polyesters can be with an excess of an aromatic diisocyanate such as 4,4'-diphenylmethane diisocyanate (MDI) or toluene diisocyanate (TDI) at 80 to 120 ⁰ C converted to a prepolymer, which is a G-emic from the represents excess, unreacted diisocyanate and a polymeric diol with diisocyanate end groups. This mixture can then be reacted with a chain extender in such a stoichiometric amount that just all free isocyanate groups react. Glycols with a lower molecular weight with 2 to 10 carbon atoms, for example ethylene glycol, 1,4-butanediol, 1,4 bis (2-hydroxy-

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ethoxy) benzene and 1,6-hexamethylene glycol can be used. A specific example of a polyurethane suitable according to the invention can consist of 1 molar equivalent of a dihydroxypolyester, 6 molar equivalents of a diisocyanate and 5 molar equivalents of a chain extender are prepared. Usually it is advantageous to use 2 to 6 moles of diisocyanate per mole of dihydroxy polyester.

The polyurethanes used in the present invention are preferred cross-linked. The cross-linking can simply go through Use of a slight excess of diisocyanate can be achieved.

The stages in the preparation of the prepolymer mixture.es and The manufacture of the final polyurethane can be combined and carried out as a single step.

Further details can be found in Allport and Jones, "Block Copolymers", pp. 227-234, Applied Science Publishers, London, (1973).

The polymer mixtures

The relative proportions of the polymers contained in the mixtures according to the invention are about 20 to 90 parts of block copolymer and about 10 to 80 parts of graft copolymer. The mixtures preferably contain about 30 to 80 parts of block copolymer and about 20 to 70 parts of graft copolymer. If the polymer mixtures contain a styrene polymer, the relative proportions of the polymers are about J> 0 to 80 parts of block copolymer, about 10 to 40 parts of graft copolymer and about 10 to 40 parts of styrene polymer. If the polymer mixtures contain a polyurethane, the relative proportions of the polymers are about 25 to 80 parts of block copolymer, about 10 to 50 parts of graft copolymer and about 5 "to 50 parts of polyurethane.

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The properties of the mixtures depend of course on theirs Composition.

The polymer mixtures according to the invention can by Melting and mixing of two or more of the specified polymers are produced. Usually one will Intensive blending device, such as a Banbury blender or a two roll mill, or any of the various single or multiple screw extruders are used. 10

The example illustrates the invention.

example

It is the processability and compatibility of the polymer mixtures tested on the basis of the actual processing, which was carried out with mixtures of the following table I specified composition can be carried out.

The tests include mixing in a Banbury mixer at 160 ⁰ C, injection molding and milling on a two roll mill. The test pieces are rated on a scale from 1 to Ί0 (based on the ease and speed with which the mixture produces a smooth, homogeneous mass), where 1 means very good and 10 means very bad. These test results are shown in Table II, which also contains the evaluations for the compatibility on a scale from 1 to 10, where 1 means poor (incompatible) and 10 means good (compatible). Compatibility ratings are based on whether the specimen delaminates or breaks upon bending and the general homogeneity of the specimen appearance. Table II also contains the values for the Taber Abrasion Test (ASTM D 1044-73).

ABS-1, ABS-2, ABS-3 and ABS-4 are ABS resins where the The substrate is a butadiene polymer, and the following

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The proportions of the monomers have:

Butadiene Styrene Acrylonitrile AB3-1 50 32 18th ABS-2 20th 51 29 ABS-3 29 46 25th ABS-4 45 40 15th

MABS-1, MAB3-2 and MBS are graft copolymers in which
the substrate is a 25-75 copolymer of styrene and butadiene, and the proportions of the monomers are as follows:

Butadiene styrene acrylonitrile methyl methacrylate

lat

MABS-1 57 19 4 20

MAB8-2 49 31 2 18

MBS 50 30 - 20

The designation SBS relates to a styrene-butadiene-styrene block copolymer which contains 0.5 percent by weight of 1076 (n-octadecyl-3- (3 ^ 5'-di-tert-butyl-4-hydroxyphenyl) propionate) as a stabilizer. Sas block copolymer has a
Shore A hardness of 62, a tensile strength of about 320 bar, a molecular weight (GPC) of 150,000 to 200,000, a styrene content of 20/3 and a solution viscosity (25% in toluene)
from 1/22 Pa.s.

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10

15th

20 25 30

ABS-1 ABS-2 - 16 - ABS-4 MABS-1 3030804 Table I. Pr ooe 20th ABS-3 MABS-2 MBS SBS 1 50 100 2 50 80 3 20th 50 4th 20th 50 5 50 80 6th 30th 80 7th 30th 50 8th 30th 70 9 10 70 10 70 * 11 10 20th 20th 70 * 12th 20th 30th 20th 70 * 13th 30th 10 70 14th 20th 10 60 15th 20th 30th 60 16 30th 20th 70 17th 40 50 18th 70 50- 19th 15th 15th 60 20th 10 20th 30th 21st 40 10 70 22nd 10 40 70 23 70 50 24 50 25th 50 30th 26th 70 50 50 27 50 50 28 40 30 ** 29 40 50 ** 30th 50 50 ** 31 40 60 32 25th 25th 50 '** 33 60 34 50 ** 35 50 50 50 ** 36 70 30 ** 37 50 38 50 50

* Contains about 30% of a lower aromatic naphthenic oil as a calibrant; Shore Α rating: 4-6. Higher molecular weight, contains about 30? Έ of a lower aromatic naphthenic oil as a calibrant.

35

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- 17 Table II

sample

1 2 3 4 5

10 11 12 13

Banbury misher

2 1 1 1

Y er workability

2-roll oOrit mill güß. ,

1 2 2 2 1

2 2 2 2

Tolerability visible Taber

10 9 9 9 9

10 8 8 8

200 80

6th 1 1 8th 7th 1 1 8th 8th 1 1 9

14 15 16 17 18 8 8 8 8 8

131

19 20 21 22 23

2 2 1 1 1

2 2 1 1 1

6 9 8 8 7

117

24 25 26 27 28

1 1 1

2-3 1

1 1 1

2-3 1

8 9 9 9 9

145

29 30 31 32 33 9 8 4 4 4

200

34 35 36 37 38

1 1 1 1

2 1 1 1

8-9 8-9

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The compatibility (1) of the polymer components, the mixtures containing a styrene polymer, is shown in Table III. Ratings are based on whether a sample (a pressed or injection molded panel) delaminates or breaks when bent, and the general homogeneity of the sample's appearance. The samples are evaluated on a scale from 1 to 10, with 1 meaning poor (incompatible) and 10 good (tolerable). Reviews addition are also shown (2) (mixing in a Banbury at 160 Miseher ⁰ G and then grinding in a two roll mill) and for the crush resistance for the processability. These reviews

are based on a scale from 1 to 10, with 1 meaning good and 10 bad.

20th SECTION PS Tabel III SBS-3 (D (2) (3) 15th 20th SBS-1 SBS-2 8th 1 2 ProbeMABS 25th 25th 60 8th 1 3 1 . 25th 25th 60 50 5.5 3 2.5 2. 20th 25th 8th 1 4th 3. 10 30th 50 9.5 1 4.5 4th 20th 20th 50 8th 1 4th 5. 10 70 8th 1 3.5 6th 25th 25th 70 - 9 - 7th 15th 25th 50 8th 1 3.5 8th. 19th 19th 60 8th 1 4th 9. 25th 25th 62 8th 1 4th 10. 15th 25th 50 8th 1 4th 11. 19th 19th 60 8th 3 4th 12th 19th 19th 62 62 9 1 - 13th 25th 25th 50 8th 1 6th 14th 15th

In the table above, PS means a styrene polymer.

The compatibility of the polymer components of the invention Mixtures containing a polyurethane are shown in Table IV. The ratings are based on whether a sample (a pressed or injection molded plate) delaminated or breaks during bending, and on the general

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mean homogeneity of the appearance of the sample. The samples are rated on a scale from 1 to 10, where 1 means poor (incompatible) and 10 means good (tolerable).

Table IV

1. 20th 2. 27 3. 22nd 4th .14 5. 20th 6th 7th -30 8th. -30

· SECTION' '^; PU-I '' PU-2 SBS-I SKS-Z valuation

10 70 6.5

18 55 6.5

3. 22 11 67 6.5

43 43 6.5

40 40 -9.5

30 35. 35 9.0

35 35 9.0

8. -30 35 35 9.0

In Table IV above:

PTJ-1: A slightly cross-linked polyurethane made from polycaprolactone with an ohore D hardness of 53

PU-2: A lightly cross-linked polyurethane from one lower alkylene adipate with a Shore D hardness of 53.

The values in the tables show that the invention Mixtures are all well tolerated, some of which are even very well tolerated. These mixtures are as already explained by their good crush resistance, gloss, hardness, abrasion resistance, flexibility and impact resistance marked. They are also relatively cheap compared to polyurethane itself.

All parts and percentages are based on weight, unless otherwise stated. 35

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Claims (1)

VOSSIUSVO SS IUS-TA U CHNER · HEUNEMANN · RAUH PATENTANWÄLTE 303080A SIEBERTSTRASSE A ■ 8OOO MUNICH 86 ■ PHONE: (O8 9) 47 4O75 CABLE: BENZOLPATENT MUNICH · TELEX 5-29453 VOPAT D u.Z. : P 74Λ (Ra / H) Case: O73I6I-M BORG-WARNER CORPORATION Chicago, Illinois, V.3t.A. "Polymer mixture." Priority: August 15, 1979, V.St.A., No. 66 717 August 15, 1979, V.St.A., No. 66 7I8 August 15, 1979, V.St.A., No. 66 719 Claims 1. Polymer mixture, marked thereby net that it is a block copolymer of styrene and contains a conjugated diolefin with 4 to 6 carbon atoms and a graft copolymer in which a styrene polymer and up to 4-0 parts based on mass of the graft copolymer, acrylonitrile and / or methyl methacrylate on a rubber-like substrate made of a ButsE diene polymer or a copolymer of butadiene, styrene and up to 1Ο? ό acrylonitrile are grafted on. 2. Polymer mixture according to claim 1, characterized in that the block copolymer is a copolymer Is styrene and butadiene. 3. Polymer mixture according to claim 1, characterized in that net that the block copolymer is a styrene-butadiene Is styrene block copolymer.
L 130013/1129 j r _ -π 4-, polymer IS at mixture according to. Claim, i, characterized, that the rubbery substrate of the graft copolymer is a butadiene polymer. 5 polymer mixture according to claim 1, characterized in that that the graft copolymer by grafting a copolymer of styrene and acrylonitrile onto a rubber-like one Substrate has been made. 6. polymer mixture according to claim 1, characterized in that the graft copolymer by grafting one Copolymer of styrene and methyl methacrylate has been produced on a rubber-like substrate. 7. polymer mixture according to claim 1, characterized in that the graft copolymer by grafting one Copolymer of styrene and about 10 to 30 parts Methyl methacrylate on a rubbery substrate. δ. Polymer mixture, characterized in that it 1) a block copolymer of styrene and a conjugated one Diolefin with 4-6 carbon atoms, 2) a graft copolymer in which a styrene polymer and up to 40 parts, based on the mass of the graft copolymer, acrylonitrile and / or Methyl methacrylate on a rubbery substrate from a butadiene polymer or a copolymer are grafted from butadiene, styrene and up to 10% acrylonitrile, and 3) Contains polystyrene. 9. polymer mixture according to claim S, characterized in that that the block copolymer is a copolymer of butadiene and styrene. ^L 130013/1129 10. Polymer mixture. according to claim 8, characterized in that that the block copolymer is a styrene-butadiene-styrene block copolymer is. 11. polymer mixture according to claim 8, characterized in that that the rubbery substrate of the graft copolymer is a butadiene polymer. 12. polymer mixture according to claim 8, characterized in that the graft copolymer by grafting one Copolymers of styrene and acrylonitrile on a rubber-like one Substrate has been made. 13 polymer mixture according to claim 8, characterized in that that the graft copolymer by grafting a copolymer of styrene and methyl methacrylate on rubbery substrate has been produced. 14. Polymer mixture according to .Anspruch 8, characterized in that that the graft copolymer by grafting a Copolymer of about 7O to 90 parts of styrene and about 10 to 30 parts of methyl methacrylate on a rubbery one Substrate has been made. 15 · polymer mixture, characterized in that it 1) a block copolymer of styrene and a conjugated diolefin with 4-6 carbon atoms, 2) a graft copolymer in which a styrene polymer and up to 40 parts, based on the mass of the graft copolymer, acrylonitrile and / or Methyl methacrylate on a rubbery substrate a butadiene polymer or a copolymer of butadiene, Styrene and up to 10% acrylonitrile are grafted on, and 3) contains a thermoplastic, elastomeric polyurethane, the polyester segments with relatively. has high molecular weight. L 130013/1129 -J Γ. Π 16. Polymer mixture according to. Claim. 15, characterized in that da8 the block copolymer from a copolymer Is butadiene and otyrol. 17 polymer mixture according to claim 15, characterized in that that the block copolymer is a styrene-butadiene-styrene block copolymer is. 18. Polymer mixture according to claim 15, characterized in that that the rubbery substrate of the graft copolymer isats is a butadiene polymer. 19 · polymer mixture according to claim 15, characterized in that the graft copolymer by grafting one Copolymer of styrene and acrylonitrile on a rubber-like Substrate has been made. 20. Polymer mixture according to claim 15, characterized in that the graft copolymer by grafting one Copolymer of styrene and methyl methacrylate has been produced on a rubber-like substrate. 21. Polymer mixture. according to claim 15, characterized in that that the graft copolymer by grafting a copolymer of etxira 70 to 90 parts of styrene and etx-ra. 10 to 30 parts of methyl methacrylate on a rubbery one Substrate has been made. 22. Polymer mixture according to claim 15, characterized in that that the polyester segment of the polyurethane is a caprolactone polymer. 23. Polymer mixture according to claim 15, characterized in that that the polyester segment of the polyurethane is a lower alkylene adipate polymer is. ^L 130013/1 129 1 24. Polymer mixture. according to claim 15, characterized in that that the polyurethane is cross-linked. L 13 0013/1129 'J.