DE2711522A1 - POLYMER-POLYBLEND PREPARATIONS WITH IMPROVED TOUGHNESS AND THE PROCESS FOR THEIR PRODUCTION - Google Patents

Description

DR. BERG DIPL.-ING. SlAPF DIPL.-ING. SCHWABE DR. DR. SANDMAIR

PATENTANWÄLTE Ftatbch 860245.8000 Munich 86 /. f \ \ O / C.

Dr. leej D ^ Lb «. You can do it. P.Ol lac IMl «. IMO guards H " IhrZekkai UeerZekfcea 27 911 I MÖNCHEN »

Yo «*. Omni '* M-erti.chersu.ee 45 1 6. MfIZ. 1977

Lawyer file no. : 27 911

MONSANTO COMPANY St. L o u i s, Missouri / USA

Polymer-polyblend preparations with improved toughness and processes for their production

It is known that toughness properties such as Impact resistance, elongation and overall toughness of polyalkenyl aromatic Polymers such as polystyrene and styrene / acrylic

° nitrile polymers (SAN) by incorporating commercial

rr \ len diene rubbers with a molecular weight of 30,000

^ ₁ to 250,000 in amounts of 2 to 36% by weight.

oJ, HIPS and ABS are commercially available as tough engineering plastics

materials for pressed parts and sheet or film products that x / R 709838/09? 8 -2-

((W) 911272 Name: Buken: 911273 BERGSTAPF PATENT Munich Bavarian VerarubMk Munich 453100 911274 TELEX: Hypo-Buik Manchen 3890002624 913310 05245 «BERG d Posticheck Manchen 65343-Mt

have considerable technical usefulness, used.

The technical properties of rubber-reinforced HIPS and ABS polymer polyblends require another Improvement to meet the ever faster increasing industrial demands on such plastics. In particular it has been found that elongation at break without deterioration in tensile strength is a critical property the toughness, which alone is adequate in known HIPS and ABS polyblends.

It is known to improve the elongation at break of such polyblends lubricants, such as mineral oil and Wax, add. However, such additives degrade tensile strength and porosity temperature and do not exhibit improved overall toughness.

The present invention provides HIPS and ABS polyblends with improved elongation at break without deterioration in tensile strength, which was improved by mixing liquid polymers of conjugated diene monomers into the polyblend Overall toughness, and they can be made by polymerization processes in which the Incorporating a liquid polymer of a conjugated diene monomer into the polymerizing preparation

709838/0920 - 3 -

Λ-

Polymerization process is not inhibited and an additive is created that is compatible with the rubber phase of the polyblend, that the elongation at break and the low temperature properties without deterioration of the tensile strength or the heat distortion temperature of the polymer -! - polyblend improved.

It has been found that the above and related objects can be easily and largely accomplished by a polymer-polyblend formulation can be dissolved, which is the polymerization product of

(A) 13 to 97 parts by weight of at least one monoalkenyl aromatic Monomers,

(B) 0 to 85 parts by weight of at least one monoalkenylnitrile monomer,

(C) 2 to 36 parts by weight of a diene rubber, and about

(D) 0.2 to 20 parts by weight of a liquid polymer of a conjugated diene monomer

contains, the entire polyblend consists of 100 parts by weight.

The invention is broadly based on improved polymer-polyblend formulations of the HIPS and ABS classes of polyblends and their production can be used, with the polyblends by incorporating 0.2 to 20 parts by weight of a liquid polymer of a conjugated diene monomer into the

709838/0928 " ⁴ "

Polyblend, based on 100 parts by weight of polyblend, an improved Have elongation at break without deterioration in tensile strength.

It is known to those skilled in the art that the term "polyblend", as used herein, is a mixture of polymers means that are essentially incompatible. HIPS polyblends are mixtures of polystyrene as the base material phase having a diene rubber phase dispersed therein, wherein the rubber phase has been grafted with polystyrene to its to support particulate dispersion in the polystyrene phase. ABS polyblends are mixtures of diene rubbers, dispersed in a SAN polymer matrix phase, the rubber phase being grafted with SAN to their To aid dispersion as particles. The polyblends can be produced by:

(1) mechanically mixing the melt of the two phases;

(2) Polymerize in bulk a solution of the diene rubbers dissolved in the monomers with stirring, either batch or continuous;

(3) Combination of polymerization in bulk and suspension polymerization, whereby a monomer / rubber solution is polymerized in bulk with stirring to a degree of conversion of 10 to 50 % , with subsequent suspension of the polymerization mixture in an inert

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-S-

th liquid (e.g. water) and completion of the polymerization, and

(4) Emulsion polymerization of the monomers, the monomers being added to a rubber latex emulsion with emulsified in the rubber and polymerized as a monomer / rubber mixture.

These methods are known to the person skilled in the art. U.S. Patent 3,488,743 teaches bulk / suspension polymerization of HIPS polybiends and the melt blending of HIPS polyblends in Example 1. U.S. Patent 3,509,237 teaches emulsion polymerization, polymerization in Mass / suspension and the melt mixing of ABS polyblends in example 1, parts A, B and C. Continuous polymerization bulk HIPS and ABS polyblends are taught in U.S. Patent 3,511,895.

The polyblend formulations of the present invention are HIPS and ABS polyblends that can be prepared by adding about 0.2 to 20 parts by weight of a liquid polymer of a conjugated diene monomer during melt blending or the Polymerization of the polyblend gives an improved elongation at break and still a high tensile strength.

The polyblend preparation of the present invention can 709838/0921 - 6 -

* 40 '
as the polymerization product of processes (2), (3) and, the product being improved by adding about 0.2 to 20 parts of a liquid polymer of a conjugated diene monomer to the polymerizing mixture of monomers and rubber. The liquid polymer can be added as part of the feed formulation or at any stage of the polymerization. The liquid polymer has not been found to adversely affect the polymerization, for example the rate of polymerization, and it can therefore be added at any point in the conversion. Most economically, it is preferably added as part of the feed formulation for bulk and bulk / suspension polymerization processes. In the emulsion process, it is particularly economical to add it to the rubber latex as a solution in the monomers prior to polymerization. However, if the rubber latex has agglomerated to form larger particles, it is preferred to add the liquid polymer with the monomers. It is known to coagulate the rubber latex, separate the rubber and disperse it in the monomers, followed by bulk polymerization. In such processes, it is preferred to add the liquid polymers with the rubber to the monomers in bulk before or during the polymerization. It is known that the polyblend preparations in solution or in

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To polymerize mass with 5 to 20 % of a diluent to control the heat of polymerization. In such processes, it is preferred to add the liquid polymers to the initial polymerization formulation, although if desired they can be added at any stage of the polymerization.

Melt blending of polymers to produce polyblends is known to the person skilled in the art. Such melt blending can be done in commercial extruders, Banbury mixers or any high-shear mixers or in a device for colloidal division, wherein the mixing and conversion to the colloidal state of the matrix polymers, rubbers and the liquid Polymers is done by uniform mixing and blending at the melting temperature of the matrix phase. HIPS polyblends can be mixed in the melt at temperatures from 150.degree. C. to 260.degree. C., preferably at 200.degree. C. to 240.degree whereas ABS polyblends in the melt at temperatures from 215 ° C to 260 ° C, preferably at 235 ° C to 250 ° C.

The alkeny! Aromatic polymer of the poly blend contains at least a monoalkenyl aromatic monomer of the general formula

709838/0928 " ⁸ "

χ I C = CH ₂

Ar

in which Ar is phenyl, halophenyl, alkylphenyl and / or Is alkylhalophenyl and X is selected from the group consisting of hydrogen and an alkyl radical of less than three carbon atoms.

Examples of monomers that can be used in the polymerization are styrene; α-alkyl monovinylidene monoaromatic compounds, for example α-methylstyrene, α-ethylstyrene, α-methylvinyltoluene, etc .; Ring-substituted alkyl styrenes, for example vinyl toluene, o-ethyl styrene, p-ethyl styrene, 2, ¹ * -dimethyl styrene, etc .; Ring-substituted halostyrenes, for example o-chlorostyrene, p-chlorostyrene, o-bromostyrene, 2, I-dichlorostyrene, etc .; Ring-alkyl-, ring-halogen-substituted styrenes, for example 2-chloro-i-methylstyrene, 2,6-dichloro-1-methylstyrene, etc. If desired, mixtures of such monovinylidene aromatic monomers can also be used. The average molecular weight of the monoalkenyl aromatic polymers can be in the range from 20,000 to 100,000, preferably in the range from 10,000 to 60,000 Staudinger.

In the HIPS polyblends, the monoalkeny! Aromatic monomers in amounts of about 13 to 98 parts by weight, preferably

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in amounts of about 60 to 97 parts by weight and particularly preferably in amounts of about 80 to 97 parts by weight on the polyblend of 100 parts by weight.

The diene rubbers of the polyblend are any rubber polymer (a rubber-like polymer with a Freezing temperature not above 0 ° C, preferably not higher than -20 ° C, as determined by the ASTM test D-7 ^ 6-52T) of one or more of the conjugated 1,3-dienes, e.g. butadiene, isoprene, 2-chloro-1,3-butadiene, 1-chloro-1,3-butadiene, Piperylene, etc., and also cyclopentadiene. Such rubbers include copolymers and block copolymers of conjugated 1,3-dienes with up to an equal amount by weight of one or more copolymerizable ones monoethylenically unsaturated monomers, such as monovinylidene aromatic hydrocarbons (e.g. styrene; an aralkylstyrene, the ar-ethyl-styrenes, p-tert.-butylstyrene, etc.j an a-methylstyrene, a-ethylstyrene, a-methyl-p-methylstyrene, Etc.; Vinyl naphthalene, etc.); Arhalo-monovinylidene aromatic Hydrocarbons (e.g. 3. o-, m- and p-chlorostyrene, 2,4-dibromostyrene, 2-methyl-4-chlorostyrene, Etc.); Acrylonitrile; Methacrylonitrile; Alkyl acrylates (e.g. Methyl acrylate, butyl acrylate, 2-xthylhexyl acrylate, etc.), the corresponding alkyl methacrylates; Acrylamides (e.g. acrylamide, Methacrylamide, n-butyl acrylamide, etc.); unsaturated

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Ketones (e.g. vinyl methyl ketone, methyl isopropenyl ketone, etc.); α-olefins (e.g. ethylene, propylene, etc.); Pyridines; Vinyl ester (e.g. vinyl acetate, vinyl stearate, etc.); Vinyl and vinylidene halides (e.g. the vinyl and vinylidene chlorides and vinylidene chlorides and bromides, etc.); and the same.

Although the rubber can contain up to about 2.0 percent, based on the weight of the rubber-forming monomer or monomers, of a crosslinking agent, crosslinking can pose problems in dissolving the rubber in the monomers for the graft polymerization reaction. In addition, excessive crosslinking can lead to a loss of rubber properties.

A preferred group of rubbers are the stereospecific polybutadiene rubbers produced by the polymerization of 1,3-butadiene. These rubbers have a cis isomer content of about 30 to 98 percent and a trans isomer content of about 70 to 2 percent, and usually contain at least about 85 percent polybutadiene formed by 1,1 addition, with no more than about 15 percent % polybutadiene formed by 1,2-addition. The Mooney viscosities of the rubber (ML-J *, 100 ° C) can range from about 20 to 70 with a glass transition temperature in the range from about -50 ° C to -105 ° C, as determined by ASTM test 0- 7 ^ 6-52T lie.

709838/0928 -ii-

The diene rubber can be used in the HIPS polyblends in quantities of about 2 to 36 parts by weight, preferably in amounts of about 2 to 20 parts by weight, based on the polyblend to 100 parts by weight, be present.

In the ABS polyblends, the diene rubber can be used in quantities in In the range from about 2 to 60 parts by weight, preferably in the range from about 2 to 36 parts by weight, based on the polyblend to 100 parts by weight, may be present.

Examples of monoalkenyl nitrile monomers are those of the general formula

C = CH ₂

CN

wherein R is selected from the group consisting of hydrogen and alkenyl radicals having 1 to 4 carbon atoms. the Monoalkenyl nitrile monomers can be acrylonitrile, methacrylonitrile and / or xthacrylonitrile.

In the ABS polyblends, the polymerizable monomers contain at least 13 parts by weight of monoalkenyl aromatic monomer and preferably from about 13 to 97 parts by weight, particularly preferably from about 50 to 75 parts by weight. the

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Monoalkenyl monomers can be used in amounts ranging from about 5 to 85 parts by weight, particularly preferably in amounts of 20 to 50 parts by weight, based on the polyblend to 100 Parts by weight, be present.

Examples of the monomers that are compatible with the monoalkenyl aromatic and monoalkenyl nitrile monomers can be copolymerized, are conjugated 1,3-dienes, e.g. butadiene, Isoprene, etc.; α- or ß-unsaturated monobasic acids and derivatives thereof, e.g., acrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, methacrylic acid and the corresponding esters thereof, acrylamide, methacrylamide; Vinyl halides, such as vinyl chloride, Vinyl bromide, etc .; Vinylidene chloride, vinylidene bromide, etc .; Vinyl esters, such as vinyl acetate, vinyl propionate, Etc.; Dialkyl maleates or fumarates, such as dimethyl maleate, diethyl maleate, dibutyl maleate, the corresponding fumarates, etc. Small amounts of the above monomers can improve the properties in HIPS and ABS polyblends can be used, preferably in Quantities from 1 to 25 parts by weight, particularly preferably from 5 to 15 parts by weight, based on the polyblend to 100 parts by weight. Such monomers can be used with the matrix monomers or the diene rubber monomers as copolymer monomers be used.

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The liquid polymers of a conjugated diene monomer can be prepared in bulk, suspension, emulsion, or solution. The liquid polymer can be a homopolymer of a conjugated diene (diolefin) - monomer of 4 to 6 carbon atoms, e.g. 1,3-butadiene, 1- or 2-chlorobutadiene (chloroprene), isoprene, piperylene, cyclopentadiene, 2,3- Dimethylbutadiene or copolymers of the monomers mentioned. Such conjugated diene monomer liquid polymers also include copolymers of diene monomers with monoalkenyl aromatic and / or monoalkenyl nitrile monomers such as styrene, α-methylstyrene, acrylonitrile, methacrylonitrile, and the like. The liquid polymer of a copolymer of a conjugated diene monomer can contain up to about 50% by weight, preferably up to about 20% by weight , of the above comonomers. A process for the preparation of liquid polymers from conjugated diene monomers is described in US Pat. No. 3,462,516 using alkali metal catalysis, particularly sodium catalysis. The liquid polymers have molecular weights in the range from 300 to 20,000, preferably in the range from 500 to 10,000. These polymers are normally liquid and have no measurable large rotor Mooney value at 212 ° C and are therefore not considered rubbers. The liquid polymers can have xanthate, mercaptan, hydroxyl or carboxy1 end groups. Other

709838/0921 " ¹ ^"

End groups such as SOH, SO ₂ H, S0, H, SeO ₃ H, SeO ₃ H, LiO ₃ H, SnO ₂ H, SbO ₂ H, SbOH, SbO ₃ H, TeO ₃ H, and the like can be used.

Another commonly used method involves solution polymerization in the presence of the alkali metal catalyst Lithium as described in U.S. Patent 3,462,516. The general response may be by the following equations

MRM + X (C ₄ H ₆ ) -► MR (C ₄ Hg) _x -M

^M - <Wn- ^R - ⁽ Wx-n- ^M

or combinations of these equations where M-R-M is an organoalkali metal compound. A specific one Example is the following:

Li- (CH ₂ ) jj-Li + X (CH ₂ = CH-CH = CH ₂ ) * ■ Li- (CH ₂ -CH = CH-CH ₂ ) _n - (CH ₂ ) ₄ - (CH ₂ - CH = CH-CH ₂ ) _x _ _n -Li

In the specific example, a 1,4 addition of Butadiene shown; however, it should be noted that 1,2-addition and combinations of 1,4- and 1,2-addition can also occur.

The treatment of this resulting polymer with carbon dioxide and a mineral acid leads to the replacement of the lithium

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atoms through a carboxy group, with the lithium as a salt the acid is separated off. Such treatment results in a carboxy-terminated polymer. A polymer hydroxy terminated containing reactive hydroxy terminated can be obtained by using the polymer reacts with the terminal lithium atoms with an epoxy compound at elevated temperatures, with subsequent Treatment with a mineral acid to replace the lithium atoms with hydrogen atoms.

Liquid rubbers are used in the temperature range between -100 ° C and + 150 ° C, preferably in the range between -75 ° C and + 75 ° C. The respective temperatures used will depend on both the monomers used and the initiators used for the preparation of the polymers are used and one skilled in the art will have no difficulty in selecting the particular initiator and of the particular pressures and temperatures necessary to achieve a particular result. Such Processes therefore do not present any problems to the person skilled in the art. The amount of catalyst used can vary, however it is preferably in the range of between about 1 and about 30 millimoles per 100 grams of the monomer. It is preferred that the polymerization in the presence of a suitable diluent, such as benzene, toluene,

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Cyclohexane, xylene, η-butane or the like. Typically, the diluent is selected from hydrocarbons, such as paraffins, cycloparaffins and aromatics, which contain ¹ J to 10 carbon atoms per molecule selected.

The above liquid polybutadienes have only functional end groups. A preferred class of liquid diene polymers are those which have other than functional groups as end groups and which are classified as telomeres will. U.S. Patent 3,760,025 describes such telomeres having telogen or end groups which complete the polymers from diene monomers (or taxogens).

The telogens used are aromatic compounds, especially aromatic hydrocarbon compounds, which contain at least one hydrogen atom capable of being replaced by a lithium atom, but which are free of any other substituents such as hydroxyl, chlorine, bromine, iodine, carboxyl and nitro are there these substituents react with the organolithium compounds or complexes used as catalysts. Illustrative examples of such telogens are benzene, C 1-4 mono-, di- and trialkylbenzenes such as, for example

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Toluene, ethylbenzene, n-propylbenzene, isopropylbenzene, o-, m- and p-xylenes; 1,3,5-trimethylbenzene, n-, sec- and tert-butylbenzenes; Cyclohexylbenzene; Alkyl, very particularly with 1 to 4 carbon atoms, and cycloalkyl-substituted polycyclic aromatic compounds, such as, for example, 1,2,3,4-tetrahydronaphthalene, 1-methylnaphthalene, 1-isopropylnaphthalene, 1,3-isobutylnaphthalene and 1-cyclohexylnaphthalene; alkoxy aromatic compounds such as anisole; 1,3-dimethoxybenzene; Monopropoxybenzene; 1-methoxynaphthalene and 1,3-dimethoxynaphthalene; dialkylaminoaromatic compounds, very particularly those in which the alkyl radical has 1 to k carbon atoms, for example dimethylaminobenzene; 1,3-bis (diisopropylaminobenzene) and 1-dimethylaminonaphthalene. Toluene is particularly satisfactory. The telogens mentioned usually provide one terminal phenyl group per diene polymer chain, the other end group being the organo group of the organometallic initiator, for example a lower alkyl.

U.S. Patents 3,678,121 and 3,751,501 describe other liquid diene polymers with various microstructures of the diene moiety. Such liquid diene polymers can have an unsaturation in the range of 75 to 95 %, a polybutadiene microstructure with about 5 to 40 % trans-1,4, about 5 to 35 % cis-1,4 and about 35 to 90 % 1, 2-vinyl,

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a molecular weight of preferably about 500 to 3000 and 3 to 10 wt. have terminal aralkyl groups. The polybutadiene microstructure can also contain about 5 to 25 percent cyclized 1,2 structure. The terminal lithium group can be removed with aralkyl or with acids, such as, for example, hydrochloric acid, to introduce a hydrogen atom to terminate the chain.

Such liquid polymers of a conjugated diene monomer, which contain terminally non-reactive polymers can be obtained from the following companies:

(1) Lithium Corporation of America, 2 Pennsylvania Plaza, New York, N.Y., under the tradename "Lithene";

(2) The Richardson Company of Melrose Park, Illinois, under the tradename "Ricon", or

(3) The Dynachem Corporation, Sante Fe Springs, California, under the tradename "Hystel".

The invention is broadly based on improved polymer-polyblend formulations of the HIPS and ABS classes of polyblends and their production can be used, with those mentioned Polyblends provide improved elongation at break without deteriorating tensile strength by incorporating 0.2 to 20 parts by weight, based on 100 parts by weight of poly

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blend, a liquid polymer of a conjugated diene monomer have in the polyblend. It can be about 5 to 50, preferably 10 to 30 percent by weight, on a weight percent basis, of the diene rubber in the polymer polyblend by the above-described liquid polymer of a diene monomer to create a polymer-polyblend with improved elongation at break and overall toughness.

In summary, according to the present invention, the elongation at break and the toughness of rubber-reinforced Polystyrene and polymer-polyblends of the ABS type without deterioration of the tensile strength due to the addition of any one liquid polymers of conjugated diene monomer having a molecular weight of about 1,000 to 10,000. The liquid polymers can be used during any stage of the process for making the polymer-polyblend be incorporated.

The following examples serve to explain the principle of the invention without, however, restricting it.

example 1

Manufacture of HIPS polybiends

In a reaction vessel, a total of 8.0 parts of a butadiene homopolymer with a molecular weight of about

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94,000 and 92.0 parts of styrene monomer stirred. The mixture also contained 0.1 part di-tert-butyl peroxide, 0.05 Parts of tertiary dodecyl mercaptan and minor amounts of an antioxidant and mineral oil.

The polymerization in bulk was carried out to a degree of conversion of approximately 30.0 % and the syrup produced in this way then with 425 parts of water and a suspending agent formulation which is marketed by RT Vanderbilt under the trade name DARVAN, and which consists of 0.5 part of a copolymer of 95.5 Μοί-ί acrylic acid and 4.5 mol-55 2-ethylhexyl acrylate, 0.3 part of calcium chloride and 1.0 part of a condensation product of naphthalenesulfonic acid and aldehyde, mixed. The suspension was stirred and initially heated to about 100 ° C. This was followed by heating with stirring to about 155 ° C. over a polymerization cycle rate of about 4 hours and at a pressure of about 6.3 to 7.4 kg / cm. The batch was then cooled, centrifuged, washed and dried, whereby the polymerized product was obtained in the form of small spherical beads. The beads recovered from the polymerization process contained about 8.0 weight percent rubber grafted to a superstrate: substrate ratio of 170: 100 with the rubber particles 0.4 to 2.0 microns in diameter

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at an average size of about 0.8 microns.

Then 62.5 parts of the beads produced in this way were in the melt with 37 »5 parts of polystyrene homopolymer, 0.3 part of an alkylated phenol as an antioxidant and 0.2 part of a stearate soap to provide a HIPS polybiend preparation with 5 wt. Rubber mixed. For an extruded sample made therefrom, a

ρ
Yield strength of 205 kg / cm and a tensile strength of

25 ¹ * kg / cm ² with an elongation at break of 22 % according to ASTM D-638 test specification.

Example 2

Production of ABS polyblend part A.

To 250 parts of a latex of butadiene / acrylonitrile copolymer (93: 7) containing 50.0 % solids and approximately 1.0 part of rubber reserve soap as an emulsifier were 70.0 parts of water, 1.0 part of rubber reserve soap and 1.0 part of potassium persulfate was added.

This emulsion was heated to 65 ° C. with stirring and then 140.0 parts of styrene, 60.0 parts of acrylonitrile and 3> 0 parts of terpinolene were added over the course of about 6 hours. The emulsion was stirred for one hour thereafter

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kept at the temperature, cooled, coagulated by adding magnesium sulfate and the coagulate then washed and dried. The resulting graft copolymer had a superstrate: substrate ratio of about 0.9: 1.0 and a number average particle size of about 0.14 microns.

part B

14 parts of a soluble butadiene rubber were dissolved in 26.0 parts of acrylonitrile and 60.0 parts of styrene. Then 0.07 part of a mixture of tert-butyl peracetate, 0.05 part of di-tert-butyl peroxide and stabilizers were added admitted. The mixture was heated to 100 ° C. with stirring. Terpinolene became over the course of approximately 5 hours as a chain transfer agent, and at the end of this period an additional 0.4 part was added.

At a 30.0 / J conversion of the monomers, the polymerized syrup dispersed in 120.0 parts of water, 2.0 parts of styrene, and, as a suspending agent, 0.3 part of a copolymer of 95.5 mol% acrylic acid and 4.5 Mol% 2-ethylhexyl acrylate, one in a 1, above solution had a specific viscosity of about 4.0 determined in water at 25 ° C. The suspension obtained was stirred and heated, cooled, centrifuged, washed and dried to polymerize the remaining monomers,

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thereby making the graft copolymer in the form of small spherical Pearls received. The superstrate: substrate ratio was about 0.9 to 1.0: 1.0 and the particle size was about 0.9 microns.

Part C.

The graft copolymer of Part A (21.4 parts) was disclosed in US Pat Melt with 78.6 parts of a SAN copolymer to produce a polyblend with about 7.47 parts of diene rubber

6 mixed and examined. The yield point was 4.6 χ 10 kg / m,

6? the tensile strength 4.2 10 kg / m and the elongation at break

25 % (ASTM D-638).

Part D.

The graft copolymer from Part B (51.0 parts) was mixed with 47.5 parts of SAN copolymer and 1.5 parts of Carbowax mixed, resulting in 7.21 parts by weight of diene rubber in the polyblend

6 2 targets. The yield strength was 4.2 10 kg / m, the

6?
Tensile strength 3.9 x 10 kg / m 2, and one was obtained

Elongation at break of about 20 % (ASTM D-638).

Example 3

HIPS polybiend with liquid polymers

Example 1 was repeated, using 95 parts of styrene monomer, 4 parts of a homopolymer of butadiene (with a

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Mooney viscosity of 35) and 1 part of a liquid polymer of a butadiene monomer (Lithene QH, 35 % vinyl, molecular weight 3000). The polymerization product containing ¹ J parts of a diene rubber and 1 part of liquid polymers, comparable to the final mixed product of Example 1 with 5 parts of 5 wt .-% of a

f \ ? Diene rubber. The yield strength was 2.1 χ 10 kg / m, the

r ρ

Tensile strength 2.5 10 kg / m and the elongation at break 46 % (ASTM D-638). It can be seen that the polyblend in which 1 part by weight (20% by weight) of a diene rubber was replaced by a liquid polymer of a butadiene monomer, unexpectedly an approximately 100% increase in elongation at break without a deterioration in the yield point which provided superior overall toughness.

Example k

ABS polyblends with liquid polymers

Part A and Part C of Example 2 were made using of 25.0 parts or 20 parts by weight? of a liquid polymer of a butadiene monomer Lithene QH as 25.0 parts of the Butadiene / acrylonitrile diene rubber repeated in Part A.

The value for the yield point of the polyblend was 4.2 10 kg / m ² and the tensile strength 4.6 10 kg / m, b <an elongation at break of about 51 % (ASTM D-638).

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Part B and Part D of Example 2 were repeated, 2.8 parts by weight of the diene rubber being replaced by 2. U parts (20% by weight) of liquid polymer in Part B. The yield point of the polyblend was 4.6 × 10 kg / m, the tensile strength 4.9 × 10 kg / m and the elongation at break about 45 % (ASTM D-638). It was unexpectedly found that the ABS polyblends had about a 100 # increase in elongation at break with no deterioration in tensile strength, thus giving improved overall toughness.

Example 5 In the melt with liquid polymer

mixed HIPS polybiends

Example 1 was repeated, whereby an HTPS polyblend with about 8.0 wt. Diene rubber received. Then 50.0 parts by weight of the beads produced in this way were mixed in the melt with 1.0 part of a liquid polymer of a butadiene monomer (Lithene QH) and 49.0 parts of a polystyrene homopolymer, whereby a polyblend with 4 wt . Parts of diene rubber, 1 part by weight (20 parts by weight) of a liquid polymer and 95 parts by weight of a homopolymer obtained. An extruded sample produced therefrom gave a yield point of 2.1 10 kg / m, a tensile strength of 2.6 10 kg / m and an elongation at break of about 42 % (ASTM D-63Ö). It has been found that the HIPS

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Polyblend products of mixing in the melt from HIPS polyblend with a liquid polymer of a butadiene monomer, unexpectedly, a significantly improved one Create elongation at break without impairing the strength properties, v / o by means of a polyblend with improved Overall toughness is obtained.

Example 6 With liquid polymers in the melt

mixed ABS polyblends

Example 5 was repeated using the ABS poly blend prepared in Example 2D with 7.21 parts by weight (% by weight ) of diene rubber in the ABS poly blend. About 66.0 parts of the polyblend were melt blended with 1.44 parts of liquid polymer (Lithene QH) and 27.8 parts of SAN PoIymerem, yielding a polyblend having ¹ 1.77 parts by weight of diene rubber, 1.44 Parts by weight (20% by weight ) of liquid polymer obtained. An extruded one made from it

f \ ? Sample had a yield strength of 4.4 10 kg / m, one

6 2 Tensile strength of 4.6 10 kg / m and an elongation at break of about 43 %>

Examples 7 to 18

HIPS and ABS polyblends were made in the melt with varying amounts of liquid polymer as in the examples

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len 5 and 6 mixed. The proportions of the formulations are in the following table together with the test results.

It can be seen from the test results that the elongation at break of the HIPS Polybiends produced for comparison purposes (Example 7) with an elongation at break of 22 %, and the ABS polyblend (Example 11) with an elongation at break of 25 % by incorporating a liquid polymer conjugated diene monomers, with about 10 to 50% by weight of the diene rubber being replaced by the liquid polymer, can improve considerably.

709838/0928 " ²⁸ "

Examples 7-18

co co UJ 00

co NJ

example Polymer-
Polyblend Service
rubber
(Parts) Liquid
Polymers
(Parts) Stretch limit
(kg / m ² ) Tensile strength
(kg / m ² ) Elongation at break 7th HIPS 5.0 0.0 * 2.04 2.54 22nd 8th HIPS 4.5 0.5 2.25 2.74 36 9 HIPS 4.0 1.0 · 2.10 2. ht, · '-; -' JO HIPS 2.5 2.5 · 1.97 2.23 84 11 SECTION 7.2 O ₃ O * ά ₃ ή4 4.20 2 ^u 12th SECTION 4.8 1.4 * 4.42 4.64 43 13th SECTION 3.6 3.6 * 4.30 4.42 79 14th SECTION 18.0 0.0 * 3.60 3.16 40 15th SECTION 14.4 3.6 " 3.73 3.38 75 16 HIPS 4.0 ι, ο ·· 2.10 2.60 42 17th HIPS 4.0 ι, ο ··· 1.97 2.60 38 18th HIPS 4.0 i, o ···· 2.18 2.80 37

• Lithene QH (35 % vinyl, molecular weight 3000) · ♦ Hystel B-2000 (90 % vinyl, molecular weight
2000) * ♦ · Ricon 150 (70 % vinyl, molecular weight 2000) ···· Lithene AH (55 % vinyl, molecular weight 1800)

cn ro ro

IV

r \ j

Claims (6)

Claims 1. Rubber-reinforced polymer-polyblend preparation with improved elongation and strength properties, characterized by the polymerisation product from (A) 13 to 97 parts by weight of at least one monoalkenyl aromatic Monomers, (B) 0 to 85 parts by weight of at least one monoalkenyl nitrile monomer, (C) 2 to 36 parts by weight of a diene rubber, and about (D) 0.2 to 20 parts by weight of a liquid polymer of a conjugated diene monomer, whereby the entire polyblend consists of 100 parts by weight. 2. Preparation according to claim 1, characterized in that the monoalkenyl aromatic monomer is styrene, aralkylstyrene, α-alkylstyrene and / or α-arhalostyrene, the diene rubber is polybutadiene, butadiene / styrene copolymer, butadiene / acrylonitrile copolymer of polypentenamer or mixtures thereof, the polybutadiene rubber having a cis isomer content of 30 to 98 % and a T range of -5O ⁰ C to -105 ° C has, the copolymeric butadiene rubbers have a T range from -20 ° C to -70 ⁰ C and the liquid ORIGINAL INSPECTED - yi - - ι. Polymers of a conjugated diene monomer, a polybutadiene, a butadiene / styrene copolymer or a butadiene / acrylonitrile copolymer, or mixtures thereof. 3. Polymer-polyblend preparation, characterized in that the preparation is the polymerization product from (A) 13 to 97 parts by weight of styrene, (B) 0 to 98 parts by weight of acrylonitrile, (C) 2 to 36 parts by weight of polybutadiene rubber, and (D) 0.2 to 20 parts by weight of a liquid polymer of a conjugated diene having a molecular weight in the range from 1,000 to 10,000, 4. Process for the production of an improved polymer-polyblend preparation, characterized in that a liquid polymer of a conjugated diene monomer is mixed with the polymerization product from (A) 13 to 97 parts by weight of at least one monoalkenyl aromatic Monomers, (B) 0 to 85 parts by weight of at least one monoalkenyl nitrile monomer, and (C) 2 to 36 parts by weight of a diene rubber mixes, the liquid polymer with the polyblend in 709838/0928 an amount of 0.2 to 20 parts by weight is mixed, the entire polyblend consists of 100 parts by weight. 5. The method according to claim 4, characterized in that the monoalkenyl aromatic monomer is styrene, aralkylstyrene, α-alkylstyrene and / or o-arhalostyrene, the diene rubber is polybutadiene, butadiene / styrene copolymer, butadiene / acrylonitrile copolymer of polypentenamer or mixtures thereof , the polybutadiene rubber having a cis isomer content of 30 to 98 % and a T range from -50 ° C to -105 ° C, the copolymeric butadiene rubbers a T range from -20 ° C to - 70 ° C and the liquid polymer of a conjugated diene monomer is a polybutadiene, a butadiene / styrene copolymer and / or a butadiene / acrylonitrile copolymer. 6. The method according to claim 4, characterized that a liquid polymer of a conjugated diene monomer with the polymerization product from (A) 13 to 97 parts by weight of styrene, (B) 0 to 98 parts by weight of acrylonitrile, (C) 2 to 36 parts by weight of polybutadiene rubber mixes, the polymer being a conjugated monomer - 32 709838/09? » -M- Has a molecular weight of 500 to 10,000 and mixed with the polyblend in an amount of 0.2 to 20 parts by weight where the entire polyblend consists of 100 parts by weight. 709838/0928