DE2406334A1 - FIRE-RESISTANT THERMOPLASTIC MIXED POLYMERIZED CONCENTRATE - Google Patents

Description

DR. BERG DIPL.-ING STAPF

PATENT LAWYERS 8 MUNICH 8O. MAUERKIRCHERSTR. 45

Attorney's file 24 774 1 1st FEu. TJh

Be / Sch

Monsanto Company St. Louis, Missouri / USA

"Fire-retardant thermoplastic polymer concentrate"

This invention relates to a fire retardant for polymeric grafted rubber Mischpolymerisatkonzentrat PoIyblends containing a grafted chloroprene rubber and a polymer of at least one Monovinylidenkohlenwasserstoffmonomeren and 0 to 90 wt. ° / o of an ethylenically unsaturated nitrile, wherein the chloroprene rubber is grafted with the monomers. By the

08-12-0236A. -2-

409833/0981

(0611) 9 * 8272 987043 983310 telegram *. BERGSTAPF PATENT MOndiM TELEX 05 24 MO BEUG d Banki Bayarifdi Vaniiubank MOndwn 453100 Pottidiacki MOndiwi 653 43

Copolymer concentrate is obtained after formation of a Polyblends with the styrene polymers, the styrene polymer with high impact resistance and fire retardancy. A metal connection can optionally be added to the polyblend to give the polyblend self-extinguishing properties to rent.

Styrene group polymeric materials including polystyrene and its copolymers, impact-resistant polystyrene, the dispersed rubber phases as polyblends contains and recently impact-resistant copolymers and terpolymers of styrene have been considered tough, for technical Synthetic materials suitable for the purposes of this have gained great commercial importance. Such plastics occur as components of equipment, automobiles and building construction.

Legal regulations require that such plastics are fire retardant and self-extinguishing. The industry has developed many improved grades of such materials, but with the ever increasing demand for high-performance plastics most self-extinguishing types of insufficient physical properties, vie suffer from a lack of toughness and impact resistance.

So far, self-extinguishing plastics have been made with different Formulated additives which, if added in sufficient quantity to form self-extinguishing properties,

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will give cause that in the polymer the physical properties are severely affected. Fire retardancy enhancing materials such as halogenated ones aliphatic and aromatic compounds that are compatible with the plastics of the styrene polymer group are, often act as plasticizers and lower the modulus, whereby they reduce the tensile or tear strength.

Certain inorganic compounds, in particular metal oxide compounds, appear to be theirs when used together with the halogenated organic compound Catalyze decay or enter the reaction chain with formation of metal halides, which are effective fire retardants Means are. The effect of these systems cannot be foreseen to the extent that there are many such combinations lower the melting point of the polymer, causing it to pyrolyze faster, so actually his Increase flammability. In addition to flammability, such combinations have caused polymer systems degrade during heat processing or when exposed to calibration.

Attempts have been made to remove polymeric plasticizers containing halogens, such as polyvinyl chloride and chlorinated olefins, to overcome the disadvantages of halogenated low molecular weight organic compounds. Such polymeric However, materials decrease when used with plastics

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the styrene group their thermal stability during processing and provide lower physical properties, in particular lower modulus, heat deformation and impact resistance. "

The above-mentioned problems can be overcome by using impact-resistant polymeric polyblends within the styrene group that one is a special new type of fire-retardant grafted chloroprene rubber copolymer concentrate of the present invention incorporates, by virtue of being both fire retardant and superior physical properties such as impact resistance and toughness, are formed. It was also found that the novel grafted chloroprene rubber mixed polymer concentrates, if they are used together with certain metal oxides in the polyblends, the polyblend ^ elbe-extinguishing Can impart properties.

It is therefore the fire-retardant grafted rubber copolymer concentrates of the present invention has great utility for the production of polyblends. The polymer processors can polymerize or buy rigid styrene polymers, along with the mixed polymer concentrate Fire retardants according to the present invention polymerize and tough polyblends with self-extinguishing properties Kompounden, whereby the compound processor greater processing freedom receives.

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The grafted chloroprene rubber copolymer concentrate of the present invention is a product of the polymerization in which the monomers are copolymerized in the presence of the chloroprene rubber, the monomers being grafted onto the rubber and polymerization also taking place to form polymers of these monomers. The extent of grafting can be controlled with regard to the rubber which is to be grafted with 10 to 100% by weight of these monomers, based on the weight of the rubber, the percentage of polymer formed generally being from 1 to 82 % on the copolymer, can be varied. The term "grafted rubber Mischpolymerisatkonzentrat" refers to a copolymer containing a high percentage of rubber in the copolymer is preferably 40 to 60 wt.% Generally 15 to 75. These concentrates can also contain other additives, such as dyes, pigments, antioxidants, UV absorbers, fillers, lubricants, plasticizers, fibers, etc., as described, these concentrates containing brittle styrene polymers to improve their toughness and other physical properties than Polyblend can be processed.

The grafted chloroprene rubber copolymer concentrates of the present invention have over their use in polyblends large custom made

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availability. The polymerization products of rubbers with monomers are generally obtained from polymerization processes obtained by coagulation, filtration, washing and drying. The copolymer generally lies in such processes in a finely divided state with large effective surfaces to support drying. However, are Such copolymers of the butadiene rubber type are very flammable in the usual rotary or fluid bed dryer. It was found that the grafted polychloroprene copolymer concentrate of the present invention is fire retardant and does not easily undermine combustion, supports, making such concentrates much safer to dry, handle, process and store.

It has also been found that the grafted chloroprene mixed polymer concentrates have antistatic properties, which improves or facilitates safety and handling in dryers and material handling systems. Possibilities of explosions are reduced because the concentrate particles do not develop high electrostatic charges that can be the formation of explosions and ^T yours, discharged in the processing of finely divided rubber particles as the Butadienkautschukarten.

The present invention relates to a thermoplastic Mixed polymer concentrate with fire retardancy for polymeric polyblends, the mixed polymer concentrate preparation

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contains:

(A) 1 to 82 Gew.fi of a polymer of at least one Monovinylidene aromatic hydrocarbon monomers and an ethylenically unsaturated nitrile monomer, where the ethylenically unsaturated nitrile monomer content 0 to 90 wt. ^, based on the weight of the polymer, is and

(B) 18 to 99 wt. # Of a grafted chloroprene rubber copolymer, where the rubber is grafted with:

(1) at least one monovinylidene aromatic hydrocarbon off monomer en and

(2) an ethylenically unsaturated nitrile monomer, wherein the ethylenically unsaturated nitrile monomer portion from 0 to 90 wt. ^, based on the weight ■ of the total grafted monomers, furthermore a proportion of chloroprene rubber in an amount of 15 to 75 wt., Based on the weight of the copolymer concentrate, is present and polymer (A) and copolymer (B) as this copolymer concentrate by polymerizing at least one of the monomers was obtained in the presence of the chloroprene rubber.

As used herein, the term "polyblend" means a mechanical mixture of incompatible polymers, the mixing being carried out in the melt phase

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2408334

is, the one polymer phase evenly distributed in another polymer phase in the melt and cooled State is dispersed.

The grafted chloroprene rubber copolymer concentrate of the present invention can be dispersed in the polystyrene or polystyrene copolymer phase by means of conventional melt processing of a mechanical mixture of the two or processed into a polyblend. The melt processing and mixing is conventionally as known in the art, by extrusion, or Banbury mixers Mahlen- treatment performed reaches a melting temperature of 204- to 232 ⁰ C in the example, the Styrolpolymerisatphase. Other additives can be present in the melt, such as antioxidants, lubricants, and pigments.

Such polystyrene polyblends have the stiffness and modulus of the outer polystyrene or polystyrene copolymer phase. The internal grafted chloroprene rubber phase is only present in the form of small rubber particles, which are responsible for it ensure that the polyblend has a much higher impact resistance than it can be formed as a single phase by the rigid outer polymeric phase. It is believed, that such rubber particles stress- or load-compensating Centers are formed which give the polyblend high impact resistance, greater elongation until breakage under stress

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and impart greater toughness without serious loss of modulus or stiffness in the outer phase.

The grafted chloroprene rubber copolymer concentrate with self-extinguishing properties of the present Invention is a product of the polymerization in which at least one monovinylidene aromatic monomer and / or Ethylenically unsaturated nitrile monomers are polymerized in the presence of chloroprene rubber. The polymerization reaction causes the monomers to polymerize as homopolymers or copolymers and as homopolymer or interpolymer chains linked to the rubber molecule to form a grafted one Polychloroprene rubber copolymer concentrate.

The monovinylidene aromatic monomers used in the polymers for the preparation of the concentrates * of this invention used include styrene, aralkylstyrenes, for Example o-, m- and p-methylstyrenes, ethylstyrenes, isopropylstyrenes, -Butylstyrenes, -tertiary butylstyrenes, various alpha-alkylstyrenes, for example methylstyrenes, Ethylstyrenes, various arylhalostyrenes, for example o-, m- and p-chlorostyrenes, bromostyrenes, fluorostyrenes, various di-, tri-, tetra- and penta-substituted. Chlorostyrenes, bromostyrenes and fluorostyrenes and various alpha- and beta-halogen-substituted styrenes, for example alpha-chlorostyrenes, alpha-bromostyrenes, beta-halogen-substituted and the same.

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The ethylenically unsaturated nitrile monomers used in the copolymer concentrates used include, for example, acrylonitrile, methacrylonitrile, ethacrylonitrile, Methyl methacrylonitrile and the like, with acrylonitrile and methacrylonitrile and the like being particularly preferred will.

Both the vinylidene aromatic monomer and the ethylenically unsaturated nitrile monomer can be larger Proportion in relation to the other can be used in the interpolymerization or in the grafting. For example you can copolymerize styrene and acrylonitrile, the preferred ratio of styrene to acrylonitrile (S / AN) 75 $ S to 25 $ AN is or you can use the azeotropic mixture of the use both, which gives a uniform copolymer. These ratios can range from 95/1 to 1/95 S / AN can be varied in certain polymerization processes, making polymers with great utility receives.

For purposes where the properties of gas impermeability, When light stability, toughness, etc. are needed, it is preferred to use the nitrile monomer in larger sizes To have proportions, for example up to 90 wt. ^, Available. For other purposes where the finished part must have greater plasticity, a preparation is preferred that contains a larger proportion of the monovinylidene aromatic monomer, for example up to 90 wt. #. The monovinyl

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aromatic monomers can be halogen substituted to form a fire retardant halogen source and can be used in the present invention in larger proportions, for example 20 to 80 wt.

The rubber component of the copolymer concentrate can be polychloroprene or copolymers of chloroprene and other monomers, for example butadiene, acrylonitrile, methacrylonitrile, styrene, arylhalostyrene, alpha-halostyrenes, Arylalkylstyrenes, alpha-alkylstyrenes, vinyl chloride or mixtures of polychloroprene and other synthetic or natural rubber types, for example polybutadiene, Butadiene-styrene copolymers, isoprene, types of nitrile rubbers, acrylate rubber, butadiene-styrene-acrylonitrile terpolymers, Chloroprene-butadiene-styrene terpolymers, chloroprene-butadiene-acrylonitrile terpolymers, halogenates Rubbers and the like. ·

Other monomers can be copolymerized with the monovinylidene aromatic monomers and the ethylenic unsaturated nitriles of the copolymer concentrate phase, as already described. The monomers described can by such other monomers, for example 1 to 25 wt. replaces v / earths that are suitable for maintaining the properties of the polyblend, as already described. Examples such other monomers are conjugated 1,3-dienes, for example butadiene, isoprene, etc., alpha- or beta-unsaturation monobasic acids or derivatives thereof,

409833/0981 ~ ¹² ~

for example acrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, methacrylic acid and the corresponding Esters thereof, acrylamide, methacrylamide, 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. The other monomers described above can continue to be used with the chloroprene Rubber phase either as comonomers or grafted Monomers copolymerized on the polychloroprene rubber will.

The chloroprene rubbers are commercially available as solid rubbers or available as rubbers contained in emulsions. The generally preferred solid Rubbers are such that they do not contain an antioxidant, are colorless and have good heat stability for processing and in the monovinylidene-aromatic and ethylenically unsaturated nitrile monomers are soluble or dispersible either together or individually. A polymerisation mixture of polychloroprene, Styrene and acrylonitrile, etc., wherein the rubber is in solution or dispersed in the intended for reaction Monomers present will polymerize in such a way that the monomers are grafted onto the polychloroprene rubber molecules Chains caused to form a copolymer or grafted chloroprene rubber to graft

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will. As the polymerization proceeds, a copolymer of styrene and acrylonitrile also becomes (SAN) formed in the reaction mixture. When the SAN phase becomes larger than the graft phase, it becomes the rubber phase inverts and becomes the inner phase of a dispersed grafted rubber particle in SAN. While stirring this dispersion becomes a uniform dispersion of grafted chloroprene rubber in SAN polymer, whereby a grafted chloroprene copolymer concentrate is formed. Polyblends have greater impact resistance than the stiff SAN phase alone. In the present invention, the grafted chloroprene forms the new combination not only by improving the impact resistance of the larger SAN phase, but also by the fact that the SAN polymers are fire retardant and self-extinguishing.

The chloroprene rubbers contained in emulsions are easily grafted by the fact that the ones to be reacted are grafted Monomers dispersed in the emulsion and such monomers on the rubber roughly as in the case of the 'solution polymerization system grafted on.

The percentage of grafting is measured in terms of extent controlled and can be from about 10 to 100 #, depending on the particle size of the rubber, based on the average weight, and the desired properties can be varied.

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The percentage grafting is defined as the weight percent of the monomers, based on the rubber particle the weight of the rubber, are grafted, for example 10 ounces Rubber grafted with 100 grams of monomers has a percentage of $ 100 based on the weight of the monomers grafted.

The particle size of the rubber, based on the average weight, is selected ao that a balance of good physical properties, such as impact resistance and gloss, is achieved. In emulsion polymerization systems, the rubber particles have sizes in the range from 0.01 to 0.35 µm, with about 0.05 to 0.20 µm being particularly preferred, thereby producing polyblends with desirable impact resistance and high gloss. If the particle size is small, the surface gloss of injection-molded objects is not reduced. Rubber particles of this size are grafted in the range of 10 to 100% by weight, with up to 65% being preferred to ensure compatibility and good gloss. Rubber particles with a larger size, based on the average weight, of 0.4-0 to 1.5 / µm and preferably 0.50 to 1.0 µm are processed with small kai ischuk particles in polyblends in order to further increase the impact resistance. The larger rubber particles are grafted in the range from 5 to 40% by weight , with 10 to 30% being particularly preferred in order to ensure compatibility and the integrity and particulate matter

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.tat of the rubber particle.

In general, polyblends made from the concentrate contain 50 to 97 and preferably 70 to 90 $> ■ of the total weight of the grafted rubber in the polyblend, in the form of smaller grafted rubber particles, and accordingly 3 to 50, preferably 10 to 30 $ larger grafted rubber particles, which ensure a balance between good gloss and impact resistance.

The polyblends prepared from the concentrate is a 15 to 40 wt.% Of chloroprene rubber, based on the Gesamtpolyblend to the self-expiring properties for the combination ensured. The grafted rubber must be present in the polyblend in an amount of 16.5 to 80, preferably 16.5 to 70 wt. , based on the weight of the chloroprene rubber.

Polyblends using the grafted chloroprene rubber concentrate can also be produced with good gloss and impact resistance by preferring grafted ones Selects rubber particles with an optimum of a size, based on the average weight, · as a mixture of small and large rubber particles. Man

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this can be achieved by using rubber particles with a particle size, based on the average weight, from about 0.4 to 1.0 µm, preferably 0.5 "to 0.8 µm and with a higher amount in the range from 10 to and in particular 15 to 65 wt., Based on the weight of rubber, grafts.

A further improvement to the polyblend system is used to ensure good physical properties such as gloss and impact resistance. The degree of grafting stabilizes the rubber particles, thereby maintaining their particulate character so that they remain dispersed in the polyblend and do not agglomerate under the heat and shear forces of melt colloidation and processing. The chloroprene rubber is preferably chemically crosslinked so that it retains this particulate property. The particularly preferred types of chloroprene rubber used in the emulsion graft systems are crosslinked and have a medium to high gel content, being extremely viscous with a Mooney viscosity of at least 200 (MS 2 1/2 min. 100 ^° C.) these rubber latices are commercially available.

It was further found that the physical properties of the grafted chloroprene rubber mixed polymer concentrates can be further improved by using small amounts of grafted polybutadiene rubber

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mixed in to increase the low-temperature impact properties. Chloroprene rubbers have a transition temperature of the second order (Tg according to ASTM Test D-74-6-52T) of about -4-OoC. and become brittle when this temperature is reached when using. The polyblends lose their impact resistance when the polyblend exceeds this temperature range achieved because the grafted rubber particles of the polyblend become brittle and no longer tension or Can absorb stress. Polybutadiene rubbers with a lower Tg, in particular the high cis-type polybutadiene rubbers, have a Tg range - from about -50 to -1O5 ° C, with a preferred range about -75 to -95 ° G. Such rubbers are aromatic with monovinylidene Monomers (for example styrene) and / or ethylenically unsaturated nitrile monomers, for example Acrylonitrile or methacrylonitrile grafted and are then functional and compatible with the concentrates of this invention.

It has been found that a small amount of grafted polybutadiene rubber, wherein the rubber is 50% crosslinked to 150 wt. # of the specified monomers is grafted and 5 to 40, preferably 10 to 30 wt. ^, based on the The weight of the rubber, which forms the total concentrate, provides an impact strength of 8.2 to 38.2 kg / cm / cm notch, if this rubber with the grafted polychloroprene copolymer polyblend with a highly grafted chloro-

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pre-rubber is mixed with a small particle size. ' The grafted polybutadiene rubber particles generally have an average weight size of about 0.7 to 4.0 µm, preferably 0.8 to 1.2 µm, wherein the polychloroprene rubber particles have an average weight size of 0.01 to 0.35 µm. Have such mixtures a high gloss, in the range of 50 to 70 according to the Hunter Gloss Meter.

In order to produce self-extinguishing polyblends, it is necessary to include at least about 1% by weight in the polyblend based on the weight of the polyblend, having an inorganic compound and generally not more than $ 15, with the preferred amount ranging from $ 5 to $ 10.

The preferred inorganic compounds are certain metal oxides, for example Sb ₂ O ₃ ,, BioO ^, MoO ₃ ,, SnOp ₅ WO ₅ , and the like. SbpO, is particularly preferred.

The following examples serve to illustrate the invention without restricting the scope of the invention.

Investigation procedures;

"Underwriter's Laboratory Subject No. 94 Test" The self-extinguishing (SE) properties were measured using the "Underwriter's Laboratory Subject No. 94 Test" which was tested on a test sample of 15.24 × 1.27 × 0.32 cm as was carried out as follows:

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The test sample was attached to the top with its longest vertical dimension by a clamp on a ring attached so that the lower end of the sample is 0.4-5 cm located above the top of the burner. The burner is then removed from the sample, ignited and adjusted to that a 1.9 cm high blue flame is formed.

The test flame is now placed centrally under the lower end of the test sample and left there for 10 seconds. The test flame is then withdrawn and the duration of the flame or glow combustion of the sample is recorded. If the flame or glow combustion of the sample ceases within JO seconds after removing the test flame, the flame is placed under the sample again for 10 seconds immediately after the flame or glow combustion the rehearsal stops. The examination flame is withdrawn again and the duration of the Hamm or glow combustion of the Sample held.

If the sample burns particles or drops during the Burning drops during this investigation, these drops are dropped on a horizontal surface of cotton fibers (untreated Bandage cotton), with this cotton being placed 0.30 m below the test sample. As a significant Flame particles are considered to be those which are suitable for igniting the cotton fibers.

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The duration of the flame or glow combustion of the vertical Samples after attaching the test flame should be on average of three samples (6 flame applications) exceed 25 seconds (maximum not more than 30 seconds) and the Part of the sample that is outside the clamp should not burn completely during the test.

Materials that meet the above requirements and that do not contain burning particles or droplets during after the burning test are called "self-extinguishing, class I".

Materials that meet the above requirements, but from which burning particles or droplets drip off, which burn only for a short time during the experiment are referred to as "self-extinguishing, class II".

In the class SE-O those materials are classified, for which the duration of the flame or glow combustion is below is less than 5 seconds under the conditions given above.

To determine the flammability of plastics, the oxygen index method ASTM Test D-2863 was used with the "General Electric Flammability Index Tester Model A-499O-A" used. A trial bar, 0.32 1.27 χ 12.7 cm, is inserted injection molded and placed in the test device indicated above. On the test device is an oxygen and a

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Nitrogen tank attached. By means of control valves An atmosphere can be formed within the test device which has any desired nitrogen to oxygen ratio contains. The lower the concentration of oxygen that supports combustion, the higher the level the flammability of the test sample. It will in general assumed that the oxygen content should be at least $ 20 to keep the combustion going, thus a material is regarded as sufficiently fire retardant can be. However, the higher the values, the better it is. The flame of the propane burner is on one end attached to the test sample in the testing device. If the sample burns for at least three minutes, the oxygen concentration is reduced. As part of the bei The limit of the oxygen concentration is determined by several specimens in tests with the usual error limits which just burns the test sample for at least three minutes, but does not burn at a 1 $ lower oxygen concentration preserved. This limited concentration is then referred to as the "Limiting Oxygen Index (LOI)".

The particle size, based on the average weight, is determined in such a way that the polyblend rubber dispersed in dimethylformamide, for which purpose 2 g of polyblend in 98 g of solvent are used. The dispersion is then on a ratio of 3: 1 diluted with methyl ethyl ketone and

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using the method of Groves, M.J., Kaye, B.H., Scarlett, B., in "Size Analysis of Subsieve Powders Using A Centrifugal Photosedimentometer", British Chemical Engineering, Volume 9: 742-744 (1964). A "Particle Size Analyzer Model 5000 "from the Martin Sweets Company, Louisville, Kentucky used.

Impact strength was determined using the ASTM Test D-256 method A, commonly known as the "Izod Test". The impact or notch toughness values are a benchmark _ for toughness and for technical purposes are high values, preferably higher than 8.2 kg cm / cm notch required.

The heat distortion temperature under load was determined according to ASTM

ρ Test D-648 determined using a load of 18.56 kg / cm. The test values should remain high enough that the polyblend is used at high temperatures for technical purposes, for example in automotive engineering and for equipment, is functional.

To investigate the extent of the graft or the amount of graft 1 g of grafted resin was added to 20 ml of 50/50 dimethylformamide / methyl ethyl ketone solvent dispersed. Dabe ;, the matrix polymer will dissolve. Centrifuge and decant the solvent off. The procedure is repeated three times and the grafted rubber is dried under vacuum, after which the weight is determined.

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Weight of the grafted rubber

_{n /} _ "" - weight of rubber _____ -v inn ° / o grafting = x IUU

Weight of rubber

For the investigation, samples of the plastic were usually made in a comminuted form. A part of the plastic particles is pressverformrat at 166 to 182 ⁰ C and

ρ
506 kg / cm of pressure to form a plate about 0.32 cm thick. Test bars with dimensions of 0.32 × 1.27 × 15 × 2 cm were then cut from this shaped plate.

Samples of the polyblend polymers were used made of ungrafted and grafted chloroprene rubber to explain the properties of the / two types and it became their suitability in terms of self-extinguishing properties and impact resistance in polymers investigated the styrene group. Furthermore, related physical properties were measured, like heat distortion under load and gloss.

example 1 control

A typical polyblend of styrene-acrylonitrile copolymer (SAN) with a content of about 25? Ö AN and one grafted Polybutadiene rubber grafted with a 75/25 S / AN ratio of the monomers was used.

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The polyblend rubber, which contained about 2½% rubber and about $ 77 SAN by weight, is marketed by the Monsanto Company of St. Louis, Missouri under the trademark "Lustran ^ ABS 740". The impact strength is 27.25 kg cm / cm notch at 2J ⁰ C; the percentage of oxygen that just barely supports combustion is 18 # (LOI), although it does not meet the UL 94 test. The person skilled in the art recognizes that this polyblend rubber has a desirable high impact strength, but too little fire retardancy for the purposes of use. The grafted rubber then has the necessary compatibility to reinforce the polyblend rubber with the formation of high toughness.

Example 2 control

_iin polyblend rubber with SAN copolymer, marketed by the Monaanto Company of St. Louis, Missouri under the trademark "Lustran ^ ^ SAN 21" is made using 65 parts of SAN polymer, 30 parts of a commercially available solid, soluble non -Crosslinked chloroprene rubber and 5 parts SbpO ^ produced. The polyblend rubber is colloid-processed on a Bolling roller mill using a steam pressure of 9.14 kg / cm, whereby a melting temperature of 204 to 232 ^° C. is reached during 5 limits, after which the polyblend rubber is removed from the mill, cooled and crushed.

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Test samples were made. Received in the UL 94 test one fourth of SE-O, from which it follows that the Polyblendkautscb.uk is self-extinguishing. Investigations of the impact strength according to Izod show a lower value than 2.73 kg cm / cm notch, from which it follows that the chloroprene rubber, which is both a non-crosslinked and ungrafted rubber, the necessary interfacial compatibility with the stiff phase of the SAN copolymer for the formation of a tough polyblend rubber is missing.

Example 3 control

A polyblend rubber was produced in such a way that you first an emulsion of a SAN copolymer with an emulsion of a crosslinked, commercially available Chloroprene rubber mixes and with an aluminum sulfate allowed to coagulate to form a friable mass with a content of $ 40 rubber and $ 60 SAN. The emulsion of the SAN copolymer is prepared using the following formulation, parts per 100 parts total monomers:

Styrene 70

Acrylonitrile 30

Water 116

Kai iump er sulfate 0.0 * 05

Terpinolene 0.003

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Protective rubber soap

(Rubber Reserve Soap, in stores

available sodium salt of

Olein, stearin and palmitin

acids). 0.013

(Commercially available sodium salt of formaldehyde naphthalene sulfonate) '0.005

The ionomers are dispersed in the water that makes the soap and Darvan and at 95 ° C under reflux for 3 hours and 4-5 minutes in the presence of the potassium persulfate and des Catalyst and the terpinoline modifier under Stirring polymerizes. The emulsion contains 46.3?> SAIT polymer in the emulsion.

The average particle size of the rubber particles in the chloroprene rubber latex and the polyblend is about 0.12 , um, (based on the average weight after the centrifuge photo-sedimentation method) .

The crumbly cash register is mechanically mixed with a SAH copolymer Lustran ^v ' SAN 21 from Monsanto Company of St. Louis, Missouri and tested as in Example 2, the mixture being 10 parts of chloroprene rubber, 65 parts of 3AE polymer and 5 parts of Sb-C ** contains. The Izod values are 8.2 kg cm / cm notch. The UL-94 test provides SE-0 values. The percentage of oxygen required to sustain the combustion is 25.1 "? (LOI) and the V / arm deformation under load at 18.6 kg / cm ² is 91 ° C. It results

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that the polyblend is self-extinguishing, Feuerhemnunp; has a high heat distortion temperature and a higher degree of toughness because the rubber is networked. The jimulsion mixing gives a better one Polyblend rubber than that of Example 2 with an impact strength of 8.2 kg cm / cm notch versus 2.73 kg cm / cm Notch for a mixture of chloroprene rubber and mixed polymer in which the rubber is not crosslinked.

Example 4

The grafted chloroprene rubber polymer concentrate is made from the following components:

Parts:

Chloroprene rubber ($ 50 solids) 100

Styrene monomer 28

Acrylonitrile monomer 12

Emulsifier (sodium salt of an alkyl

diphenyl oxide sulfonate) 1

Potassium persulfate initiator 1

Terpinolene Modifier 0.5

Water 260

The chloroprene latex, water, Dowfax and terpinolene are added with stirring in a reaction vessel and brought to 85 ⁰ C. The monomers and the initiator to the reaction mixture for 2 hours, added, the Endzu ^ö abe after 1 1/2 hours is carried out to give a latex

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with a solids content of 35? 4 is obtained. The average particle size of the rubber particles in the. Latex is about 0.12 µm (based on average weight as determined by the centrifuge photo-sedimentation method). A grafted chloroprene rubber is formed along with the SAK copolymer to give the copolymer concentrate of the present invention. The mixed polymer concentrate contains about 1.5% by weight of chloroprene rubber, 10.3% by weight of SAN copolymer as a graft copolymer on the rubber and 18.2% by weight of SA! II-! Ischpolyrnerisat as a free copolymer. The chloroprene rubber has 14.4% by weight of grafted SAH copolymer, it being assumed that the weight ratio of the graft copolymer to the rubber is 10.3: 71.5 or 14.4% by weight based on the chloroprene rubber. The latex obtained is further mixed with the SAIT latex from Example 3 and coagulated using aluminum sulfate to form the solid polyblend rubber. The analysis of the polyblend rubber shows a mixture of 3C? ' Polychloroprene at 14.4 wt .; SAK grafted onto rubber; &% (, SAiT polymer, including the grafted SAC. The mixture is further melt-colloidized on a cooler as in Example 2 with 5fi Sb 0 and the comminuted polyblend is tested. The Izod impact strength is 23.98 kg cm / cm notch; the ^T 7 heat deformation temperature under load is 88 ⁰ C; the UL-94 test value is SE-O and the percentage of oxygen to sustain the combustion is 25.6? i (LOI).

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that the grafted chloroprene copolymer concentrate a polyblend rubber with high impact resistance or Provides toughness, self-extinguishing properties and high fire retardancy without undermining the heat distortion temperature is lost for functional technical purposes.

Example 5

Example 4 was repeated with the result of an overall lower conversion of 75 / · ', the SAN graft proportion on the chloroprene rubber of the mixed polymer concentrate being 11.4% by weight, based on the rubber. The 3nd polyblend mixture contains 30 ^ chloroprene , 65, '' ■ SAN polymer and 5 $ Sb £ _O: z as in example 4. the mixture was schmelzkolloidiert as in example 2 and it was checked the crushed Polyblendkautschuk the Izod impact strength was 12.5 kg · cm / cm. Notch, from which it follows that the toughness is lower when the amount of graft is lower and there is thus less interaction with the rigid or hard SAN phase, but higher than with the ungrafted chloroprene rubbers of Examples 1 and 2. The UL-94 test gives values of SE-O, which indicates that the polyblend rubber is highly self-extinguishing.The percentage of oxygen to maintain the combustion is 25.3 μi (LOI), which results in a high fire retardancy ibt and the heat distortion temperature under load is 92 ⁰ G, from which it follows that the polyblend rubber is self-extinguishing and tough without the heat "

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Deformation temperature for technical purposes suffers.

Example 6

A higher grafted chloroprene was prepared by using the following formulation, wherein the parts are based on 100 parts of total monomers:

Styrene 70

Acrylonitrile 30

Chloroprene rubber

^ solids) 100

Terpinolene 1

Commercially available ITetriuia salt a formaldehyde naphthalene sulfonate. 1

Potassium persulfate 1

Protective rubber soap

(Rubber Reserve Soap) 1

Water 270

The sodium salt of a formaldehyde naphthalenesulfonate is added to water and the carbonoprene rubber latex is then dispersed, after which the monomers and the catalyst are added. The ionomers and the catalyst are added at 25 parts per hour in a ratio of 70/30 with corresponding amounts of catalyst over the course of 4 hours. The protective rubber soap is added after half of the corn has been added. The polymerization is carried out at 85 ⁰ C under stirring, thereby obtaining a latex having about 35 ndfeststoffen / i £. A grafted chloroprene

409833/0981

Rubber is formed together with the SAiT copolymer, resulting in a copolymer concentrate of the present invention. The solids of the copolymer concentrate of the latex contain, according to analysis, 50% by weight of chloroprene rubber, 24% by weight of SAN-I copolymer as a graft copolymer and 26% by weight of SAN as a free copolymer, based on the total weight of the copolymer concentrate. The chloroprene rubber contains 48 μg of grafted SAH copolymer, based on the weight of the rubber. The latex obtained is further mixed with the SAN latex from Example 3 and coagulated using aluminum sulfate to obtain the solid polyblend rubber the polyblend is about 0.12 μm (based on the average weight). The SAN grafting on the chloroprene rubber is 48.0% by weight , based on "ouch". The final polyblend mixture contains 30% chloroprene, 65/4 SAiT polymer and ^ ήό Sb-O ^, v / ie in Example M-. The mixture is melt-colloidized as in Example 2 and the comminuted polyblend rubber is tinted. The Izod impact strength is 4.36 kg cm / cm notch, which results in low values with regard to the impact resistance and toughness; the UL-94 Q? est is ^ t values of SE-O, from which it follows that the material is self-extinguishing and the thermal deformation under load is 77 0, before a loss of heat distortion is evident. It can be seen that too high a graft height on the small chloroprene rubber particles

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Toughness lowers.

Examples 7,6, 9 and 10

Latex mixtures of low and high grafted polychloroprene rubber were prepared, for which purpose the grafted rubber mixed polymer concentrates of Examples M and 6 were used as low or high grafted, with the formation of mixtures which had a chloroprene rubber content of 30% by weight. These mixed polymer concentrate mixtures were in turn processed with SAH latex as in Example 3 to form a polyblend. The final mixtures were processed into polyblend rubbers according to the compositions given in the table below, the table also showing the physical tests for each composition. The "Peak Hunter Gloss Values" were measured by measuring the gloss of an injection molded sample on a Hunter Laboratory Model D-36 Glassmeter from Eunter Associates of McLean, Virginia.

7th Examples
8th 9 IC Grafted down
rubber 30th 15th 9 0 Highly grafted
rubber 0 15th 21 30th SAIT polymer at 65 65 65 65 Ant imonoxid 5 5 5 5

Izod impact strength

(kg cm / crn notch '24.0 16.9 14.7 M-, M-

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- 33 -
Table (continued) 7th Examples
8th 2406334 10 88 83 2 80 HDTUL ⁺ (kg / cm ² ) ( ⁰ G) SE-O SE-O 83 SE-O UL-94 0 4th SE-O 64 Peak Hunter Gloss 23

⁺ (Deformation temperature under load)

From the test values it can be seen that the chloroprene rubber mixed polymer concentrates grafted down increase the highly grafted chloroprene rubber copolymer concentrates to a high degree of toughness, They can go from about 4.4 kg cm / cm notch to toughness values of over 8.2 kg cm / cm notch, a value that is general is recognized for impact-resistant polyblends · can bring.

it can also be seen that the gloss of highly grafted rubbers is higher than that of low-grafted rubbers Rubbers.

Examples 11-15 Rubber Particle Size Parameters

j-Js it was found that the chloroprene latex (50 ^ solids) had an average rubber particle size of about -0.12 µm (based on weight average). Of the Latex is partially agglomerated, so that larger particles than in Examples 4 to 10 can be used for the investigation Has available. The agglomeration was according to the

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following procedures using:

Chloroprene rubber latex

(25 # solids) 1GO parts

Emulsifier 0.045 parts

Acetic anhydride 6 parts

Water 300 parts

carried out.

6 parts of acetic anhydride are dissolved in 60 ml of water and
adds it to the rubber latex that contains the emulsifier. The mixture is stirred 30 seconds after the addition and left to stand for 30 minutes, then 2 parts of emulsifier are added to the emulsion in order to stabilize the emulsion. An average particle size of the rubber particle of about
0.50 µm (based on the average weight). the
Particle size of the agglomerated rubber can be varied using codifications of the method given above. The L; acetic anhydride is subject to the
Hydrolysis and reacts with the rubber emulsifier, making the emulsion less stable and agglomeration of the
Rubber particles is effected. Larger particles can therefore be obtained by increasing the length of the acid anhydride used while maintaining a stable emulsion for subsequent handling, washing and
Grafting reactions. The chloroprene rubber latex contains a sodium resin soap as an emulsifier, which is protonated by the anhydride to enable agglomeration. That

-35-409833 / 0981

Emulsifier is then added in large quantities stabilize the larger particles to form a stable emulsion. Agglomerated particles of a size of 1.5 / ils can easily be made using the above Procedure received.

The emulsion identified above is then grafted according to the procedure of Example 6 using varying amounts of terpinolene and catalyst to vary the conversion and percentage grafting. The grafted rubber copolymer concentrate latex is then in a polyblend with a SAIJ polymer latex, as in Example 6 described, processed. For examples 11 to 15, the following details are given:

11 Examples 21 21 21 1.0 £ 1 1.5 1.0 1.0 catalyst 1.0 1.0 0.0 0.0 0.5 ferpinolen. (Parts) 2.5 0.5 15.0 21.9 27.3 Amount of graft
(Weight; -;) 64- 8.9 85 99 82.0 f. ' conversion 30th 77 30th 30th 30th Ge; v. ^ Rubber 65 30th 65 65. 65 Wt. ^ SAIf 5 65 5 5 5 Gew.fi Sb ₀ D-, 12.5 5 12.5 15.8 8.2 Iz od impact resistant
speed (kg cm / cm
Score) 23 12.5 ^ 9 50 __ Hunter Gloss 41

-36-409833 / 0981

- * 36 Examples Tabel (Continuation) 12th 82 H HDTUL ⁰ G + 84

13 14 "5

85 85 81

UL-94 SE-O SE-O SE-O SE-O SE-O

⁺ (Deformation temperature under load)

The values show that the percentage grafting of the mixed • polymer concentrate from about $ 2.5 to about $ 30 with an average chloroprene rubber particle size of about 0.5 / µm (based on the average weight) can be varied can before the impact strength begins to drop, while the gloss improves as the weight percentage improves Grafting is increased. It can also be seen that the rubber types grafted down with an average particle size of about 0.50 to be reasonable have high gloss compared to the low-grafted chloroprene rubbers of Examples 4 to 5, which has an average rubber particle size of about 0.12 / µm. It could be concluded from this that the smaller particle size rubbers are rubbers with much greater effective surface area for grafting and therefore actually less grafted v / can ground and agglomerate to form large particles, which increases the impact resistance, but the gloss is lowered. Regardless of theoretical considerations, the percentage grafting of the mixed polymer concentrate should

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409833/0981

Trats in proportion to the particle size can be adjusted to have both good impact resistance and gloss within of the parameters given above. It can also be observed that the heat deformation is high and the Polyblend rubbers have excellent self-extinguishing properties.

Examples 16 and 17

Examples 7 b'is 10 were repeated using a mixture of highly grafted rubber Mischpolymerisatkonzentrats of Example 6 with an average particle size of about 0.12 microns and a% degree of grafting of 48.0 wt. And the low-grafted rubber-Mischpolymerisatkonzentrat of Example 13 with an average rubber particle size of about 0.5 µm and a degree of grafting of about 15.0 wt. The test results are:

Weight? O Low-grafted rubber

Wt. ^C / o Highly grafted rubber Wt. # SAN polymerisate Wt. ^ Sb 0 Izod impact strength (kg cm / cm2) Hunter Gloss IiDTUL ( ⁰ C) UL-94

example
16 example
17th 3 6th 27 24 65 65 5 5 11.4 13.1 45 60 80 81 ss-o ■ SE-O
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409833/098 1

The test results show that polyblend rubbers with high impact resistance can be produced if 10 to 20% by weight of low-grafted chloroprene rubber having a particle size in the range of about 0.50 / µm with 80 to 90 % of highly grafted chloroprene rubber with rubber particles in the range of about 0.12 um mixes. Furthermore, the gloss of such mixtures gives high values together with other good heat distortion temperatures and excellent self-extinguishing properties.

Example 1H

Part A

14 parts of a soluble butadiene rubber were dissolved in 26.0 parts of acrylonitrile and 60.0 parts of styrene. For this was added 0.07 part of a mixture of terbutyl peracetate, 0.05 parts of di-tert-butyl peroxide and stabilizers. The mixture the mixture is heated to 100 ° C. with stirring. Terpinolen was at a rate of about 0.1 parts per hour for about 5 hours added as chain transfer agent, after this time a further 10.4 parts were added.

At 30, the above conversion of the monomers became partially polymerized Dispersed syrup in 120.0 parts V / water, to which 2.0 parts of styrene and, as a suspending agent, 0.3 parts a copolymer of 95.5 mol. ^ acrylic acid and 4.5 mol. ^ J 2-ethylhexyl acrylate added, the suspending agent a specific viscosity of about 4.0,

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- 59 -

was correct as 1, C; .- ice solution in water at 25 ° C. the obtained suspension was stirred and allowed to polymerize of the remaining monomer heated, cooled, centrifuged, washed and dried, whereby the grafted rubber copolymer concentrate received in the form of small spherical pearls. The ratio of superstrate to substrate is about 0.9 to 1.0: 1.0 and the particle size of the grafted rubber is about 0.9 µm. The analysis of the mixed polymer concentrate gives 14% by weight of rubber, 14% by weight grafted SAN copolymer and 72% by weight SAN.

70 g of the beads from Part A were ground and, as described in Example 2, melt-colloidized with 930 g of the final polyblend mixture from Example 6. The final polyblend rubber now contains about Ύρ polybutadiene rubber. The ground polyblend rubber is crushed and tested.

Part C.

Using the procedure outlined above, 210 grams of Part A was added with 790 grams of the final polyblend from Example 6 colloid. The achieved end polyblend chew contains now about 3? j polybutadiene rubber. The ground polyblend rubber is finely crushed and checked. The test results for the two types of polyblend rubber B and C are given below.

409833/0981

UIi-94-
test Impact resistant
ability test EDTUL
Test ⁰ G 2406334 Polyblend SE-C 13.6 k £ cm / cm
score 86 shine
test Part E. SE-O ' 33.2 kg cm / cm
score oil 70 Part 0

The soluble rubber Arben used in Example 18 are commercially available diene rubbers, such as high cis-Polybutadienkautschukarten having a cis-isomer content of about 30 to 98 $ and with a phase transition of the second order (glass transition temperature) Tg of about -50 ⁰ G to -105 ° C, determined according to ASTM test method D-74-6-52T. Other soluble diene rubbers include copolymers of conjugated 1,3-butadiene with up to equal amounts by weight of one or more copolymerizable monoethylenically unsaturated monomers, such as monovinylidene aromatic monomers, for example styrene, and monoäthylcn-'fjcl. unsaturated nitriles, for example acrylonitrile. The preferred Dienmischpolymerisatkautschukarten have a transition temperature of the second order, Tg, in the range of -20 ° to -70 ⁰ C.

The types of polychloroprene rubbers contained in an emulsion and used to make the concentrates of the present invention are readily available in the form of latices. These latices have a rubber solids content of about 3 ^; + ₅ $ 5 to $ 60, a p "value of about 9 to 13, a latex-specific gravity of about 1.10 to 1.15,

409833/0981

a rubber specific gravity of 1.23 to 1.42, a latex viscosity of 16 to 400 cps. (Erookfield "viscosity) and they are stabilized by anionic or cationic emulsifying agents. Three types of rubbers contained in the latices are crosslinked and are medium or high types of gels, viscous, have a Mooney viscosity of at least about 200 (MS-2-1 / 2 min 100 ^° C.) The rubber particle size distribution of such latices can be different, so that the selected particle size range, based on the average weight, can be obtained.

Examples 19-23 Tested polyblend ratios

The grafted chloroprene latex of Example 6 at about 35% solids was coagulated with aluminum sulfate and the solid recovered as a friable copolymer concentrate and dried. Analysis of the solid showed 74 $ grafted rubber and 26 $ SAN polymerizate as a tough phase. The crumbly rubber copolymer concentrate contains 50 $ chloroprene rubber and 48 wt. ?? grafted SAN, making 24 # SAN copolymer in the Relationship to the crumbly mass received. The rubber ■ has a particle size of 0.12 μm. The grafted rubber latex of Example 13, which has a rubber particle size of 0.5 / µm, is coagulated with aluminum sulfate, Obtained as a crumbly mixed polymer concentrate and dried. Analysis of the solids gives a content

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of 5% by weight of rubber with a degree of grafting of 15 $ SAU, corresponding to 7.5% by weight of SAU to the crumbly raw mass that together with 42> 5 # SAN copolymer as a stiff phase be.

The SAN latex from Example 3 is coagulated with aluminum sulfate and recovers the solids as SAU powder Polymer with good flowability. The grafted The friable copolymer concentrate of Examples 6 and 13 and the SAN polymer from Example 3 are dry mixed with SbpO ^ to form mixtures and at 218 ° C melt-mixed to form a uniform polyblend rubber. The polyblends are injection molded into test pieces and examined for their self-extinguishing properties and impact strength. The proportions of the above Materials for spring polyblend rubber are given below in addition to the test results.

mixture

Example 6 concentrate
Example 6 rubber
Example 6 Graft SAU
Example 6 SAN
Example 13 concentrate

Examples Weight ^ i 22nd 23 G Shares in 64.0 64, 0 19th 20th 36.8 32.0 32, 4- 24.0 32.0 18.4 15, ^ 15, 6th 12.0 16, c 6.3 16.6 16, 16, c
-43- 5.8 7.7 11.6 16.0 6.2 3.3 9.2 6.0 3.0

409833/0981

19 20 21 22 23

Example 13 rubber 3.0 4.0 4.6 8.0 8.0

Example 13 Graft SAN 0.5 0.6 0.7 1.2 1.2

Example 13 SAN 2.5 3.4 3.9 6.8 6.8

Ex. 3 SAIi 55.0 51.0 44.0 16.0 19.0

Total rubber 15.0 20.0 23.0 40.0 40.0

Total SAH 70.0 71.0 67.0 56.0 59.0

Sb ₂ O ₃ 15.0 9.0 10.0 4.0 1.0

UL 94 test SE-O ¹ SS-O ¹ SE-O ² SE-O SE-O ⁵

Izod 5.45 8.2 9.8 17.4 19.6

(1) UL 94 with 0.32 cm thick test sample

(2) UL 94 with 0.18 cm thick test sample

(3) UL 94 with a 0.64 cm thick sample

From the test values given above and the previous ones Examples described, it is clear that the grafted chloroprene rubber copolymer concentrate when it is with Polyblends are processed, good impact resistance over then Range from 15 to 40 wt. J and self-extinguishing properties associated with SbgO ^ over a range of up to 15 wt.

-Pat ent claims-

40 9833/0981

Claims (24)

Patent claims: 1. Thermoplastic mixed polymer concentrate with fire prevention, characterized by the salary from: (A) 1 to 82 wt. ^C / o of a polymer of at least one monovinylidene aromatic hydrocarbon and an ethylenically unsaturated nitrile monomers, wherein the proportion of the ethylenically unsaturated nitrile is O to 90 wt.% Of the polymer and (B) 18 to 99 wt. ^ Of a grafted chloroprene rubber copolymer, where the rubber is grafted with: (1) at least one monovinylidene aromatic hydrocarbon monomer and (2) an ethylenically unsaturated nitrile monomer, wherein the proportion of the ethylenically unsaturated nitrile monomer 0 to 90 wt.% Based on the weight of total monomers grafted, wherein a chloroprene rubber content of 15 to 75 Weight; 3, based on the weight of the copolymer concentrate, is present, the polymer (A) and the copolymer (B) as a copolymer concentrate was obtained by polymer 409833/0981 sation of at least one of the monomers in the presence of the chloroprene rubber. 2. mixed polymer concentrate according to claim 1, characterized in that the monovinylidene-aromatic Monomers made from styrene, aralkylstyrenes, alpha-alkylstyrenes, alpha-halostyrenes, arylhalostyrenes and their mixtures is selected. 3. mixed polymer concentrate according to claim 1, characterized in that at least one of the monovinylidene aromatic hydrocarbon monomers Styrene is. 4. mixed polymer concentrate according to claim 1, characterized in that at least one of the monovinylidene aromatic hydrocarbon monomers is alpha-methylstyrene. 5 · I''i'ischpolymerisat concentrate according to claim 1, characterized in that at least one of the monovinylidene aromatic hydrocarbon monomers is monochlorostyrene. 6. mixed polymer concentrate according to claim 1, characterized in that at least one of the ilonovinylidene aromatic hydrocarbon -46- 409833/0981 monomeric monobromostyrene is. 7 · mixed polymer concentrate according to claim 1, characterized in that the ethylenic unsaturated nitrile is acrylonitrile, methacrylonitrile, and / or ethacrylonitrile. 8. mixed polymer concentrate according to claim 1, characterized in that the ethylenic unsaturated nitrile is acrylonitrile. 9 · mixed polymer concentrate according to claim 1, d a through marked that the ethylenically unsaturated nitrile is methacrylonitrile. 10. mixed polymer concentrate according to claim 1, characterized in that the grafted Chloroprene rubber in an amount of about 18.0 to 99 weight fi, based on the weight of the copolymer concentrate, is present, making 15 to 75 wt. ^ Chloroprene rubber are present in the copolymer concentrate. 11. mixed polymer concentrate according to claim 1 with the content of a first grafted chloroprene rubber an average graft rubber particle size, based on the average weight, of 0.01 to 0.35 µm, one second grafted chloroprene rubber with a through -47-409833 / 0981 cut rubber particle size, by weight average, of 0.40 to 1.5 µm, the first grafted rubber being present in an amount of 50.0 to 97.0% based on the total weight of the first and second grafted rubbers; the first grafted rubber is grafted to about 10 to 100 wt.% with the monomers and, grafted $ of the monomers of the second grafted rubber having from about 5 to 50 wt. 12. Mischpolymerisatkonzentrat according to claim 1, characterized in that a grafted chloroprene rubber having a rubber particle size, based on the average weight of 0.4 to 1.0 / um about 10 to 100 wt.% Of the monomers based on the weight of the chloroprene rubber, is grafted. 13. Copolymer concentrate according to claim 1, characterized in that the grafted chicory rubber is crosslinked and has a Mooney viscosity of about at least 200 (MS-2-1 / 2 min. 100 ^° C). 14. mixed polymer concentrate according to claim 1, characterized in that the grafted ^; Chloroprene rubber has an ionic rubber component which contains a chloroprene which is copolymerized with at least one ionomer which can be polymerized with the chloroprene. -48-409833 / 0981 15 · mixed polymer concentrate according to claim 14, characterized in that the grafted Chloroprene rubber has a rubber component which contains a chloroprene which is mixed with at least one monomer, namely Styrene, acrylonitrile, methacrylonitrile, butadiene and / or isoprene is copolymerized. 16. mixed polymer concentrate according to claim 15, characterized in that the monomer Styrene is. 17. mixed polymer concentrate according to claim 1, characterized in that the mixed polymer concentrate is mixed with a monomer of acrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, methacrylic acid, methyl methacrylate, Ethyl ethacrylate, butyl methacrylate and / or 2-ethylhexyl methacrylate. 18. I-Iischpolymerisatzentrat according to claim 1, characterized in that about 10 to 30 Gew.ρ of the chloroprene rubber part by a diene rubber of polybutadiene, butadiene-styrene, butadiene-acrylonitrile, butadiene-methacrylonitrile and / or eutadiene-styrene-acrylonitrile is replaced, where the diene rubber is grafted with: (1) at least one monovinylidene aromatic monomer 409833/0981 and (2) an ethylenically unsaturated nitrile monomer, wherein the ethylenically unsaturated nitrile monomer has a share from 0 to about 90 weight percent based on weight of the total grafted monomers and wherein the grafted diene rubber having a rubber particle size based on the average weight, from 0.7 to 1.5 μm, with 50 to 150% by weight of the monomer is grafted and the grafted chloroprene rubber has a rubber particle size based on the average weight, from about 0.05 to 0.20 / µm, with about 10 to 100 wt. # of the monomers is grafted. 19 · mixed polymer concentrate according to claim 18, characterized in that the monovinylidene aromatic Monomer is styrene. 20. mixed polymer concentrate according to claim 18, characterized in that the ethylenic unsaturated nitrile monomers is acrylonitrile. 21. mixed polymer concentrate according to claim 18, characterized in that the polybutadiene rubber has a cis isomer content of 30 to 98 $ and a Tg range of -50 to -105 ⁰ G and the butadiene copolymer rubber types have a Tg range of -20 to - 70 ⁰ C. -50- 409833/0981 22. copolymer concentrate according to claim 18, characterized in that it is copolymerized a monomer. Acrylic acid, methyl acrylate, Ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, methacrylic acid, Methyl methacrylate, ethyl methacrylate, butyl methacrylate and / or 2-ethylhexyl methacrylate. 23- Thermoplastic fire-retardant polymer concentrate, marked by (A) 1 to 82 wt. ^ Of a polymer of at least one Monovinylidene aromatic monomers and an ethylenically unsaturated nitrile monomer, the ethylenic unsaturated nitrile monomers in a proportion of 0 to 90 wt. ^, based on the weight of the polymer, forms, mixed with (B) 18 to 99% by weight of a grafted chloroprene rubber copolymer, wherein the rubber is grafted with (1) at least one monovinylidene aromatic monomer and (2) an ethylenically unsaturated nitrile monomer, wherein the ethylenically unsaturated nitrile monomer has a proportion of 0 to 90 wt. ^, based on the grafted total monomers, forms and the grafted Chloroprene rubber a first graft -51- 409833/0981 The second chloroprene rubber wherein the grafted rubber has an average particle size based on the average weight of 0.01 to 0.35 µm in terms of v / e, and a second chloroprene graft rubber wherein the average rubber particle size based on the average weight is 0 40 to i, 50 / µm, the first grafted rubber is about 10 to 100% by weight grafted with the specified monomers, in an amount of 50.0 to 97 * 0% by weight, based on the total weight of the first and second grafted rubbers is present, the second grafted rubber is grafted with 5 to Μ-0 ', ό of the monomers, the grafted rubbers 15 to 75 wt. ^ a, based on the weight of the chloroprene rubber, are present in the copolymer concentrate, the Grafted chloroprene rubber is crosslinked with a Mooney viscosity of at least 200 (MS-2-1 / 2 min., 100 ° C), in which the polymer (A) and the mixed polymer (B) as mixed polymer concentrate t was obtained by polymerizing at least one of the monomers in the presence of the ChI or opren rubber. 24. mixed polymer concentrate according to claim 23, characterized in that the polymer (A) SAN and the polymer (B) is grafted with styrene and acrylonitrile. 409833/0981 ORIGINAL INSPECTED