DE1745097A1 - Polymeric compositions and processes for their preparation - Google Patents

Description

17450 & 7

March 20, 1967

Monsanto Company, 66 St. Louis, Missouri, P.T.A.

Polymeric compositions and methods of making them

The present invention relates to new polymeric compositions and especially new polyblende from nepfropftta Rubbers with copolymers, which at least mainly consist of an aromatic monovinylidene hydrocarbon and an unsaturated nitrile, and the process for their preparation.

It is known that bolyblends of rubbers with copolymers from etyrol / acrylonitrile Irp. advantageous in the Creation of additional sets with desired EigenachaX » where toughness and cheap resistance are "owl", good malleability. In general, increasing the rubber content is beneficial in increasing toughness but in general there are certain losses in other properties, such as the Glani »

2OS0U / 12U

It is an object of the present invention to provide a new polyblend of rubber old a HieohpolyBerlsat eu so the sum at least mainly from an arooatie without monovinylidene carbon hydrogen and an unsaturated nitrile, which tends to have an unreasonable balance of properties.

It is also an object of the invention to provide a polyblend ohciffen, which formulates relatively simply and economically and offers the opportunity, starting from the usual, easily available components properties easily "according to KaB" hire.

Another goal is to create a polyblend, .the high impact strength, good Qlanε and good strength properties has and a large extent more versatile Uses.

It is also an object of the invention; a simple · and relatively economical process offered production of such Rubber-Miechpolynerisat-Polyblends eu eohaffen that the Using a ready-made asset · and already present methods eur making the grafted Kautsohukkoaponenten allowed.

Other related objects and advantages will become apparent from the following detailed description and the accompanying one

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easier to understand. Debt! let:

Pig. 1 a drawing showing the effect of the increase the amount of chewable graft components according to the invention indicates the bottom viscosity of the composition, and

Tig. Figure 2 is a drawing in which the effect of the monomer feed during the grafting of the low graft Component on the impact strength and the quality of the invention-based composition is shown.

It has now been found that the above-mentioned and related objects and advantages can be readily achieved with a composition comprising a polyblend of

i) a basic substance oiaes copolymer that at least mainly of an aromatic mono-vinyl chloride water and an unsaturated ffitrile,

B) a first graft copolymer with a chewing ' • base and a layer of a copolymer, at least mainly of an aromatic mono-Tliiylldeiücohlenwasserstoff and an unsaturated nitrile, and

C) a «wide graft copolymer with a LautschukgrundlAge and a layer made of a copolymer contains, the mindeetene mainly from one aromatic honovylidane hydrocarbon \ uid one

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unsaturated nitrile. One of the raw graft polymers has a ratio of layer to base of 5 to 35: 100 and the other graft copolymer has a ratio of layer to base of 50 to 250: 100. Represent the two combined Pfropfiniaohpolymerieate 1 _f 0 to 70.0 wt .-- ff represents the ßesamtmjschung and dae niedriggepfropfte copolymer constitutes about 20 _T 0 bie 97.0 i "of the total weight of the combined graft copolymers of.

The method of operation is not entirely clear in theory, but it is believed that the low-grafted particles Sun balls tend to constrict and relatively large particles pretend, creating a high degree of numeracy which is then carried by the highly grafted rubber particles, which do not show this sweetness is expanded. With suitable Combination, the two grafted components act in such a way that the luster and firmness properties of the mass on a desired one Height can be maintained.

The Mischpolyme r isate

The invented copolymers of both the The basic substance as well as the grafts consist at least mainly of e.lneia aroserttieoben Monovicyliden-

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hydrocarbon and an unsaturated Nltril _f that is, dieee monomers at least 50.0 wt. -i> wnd preferably at least 75.0 wt .- ^ make the copolymers. Ee is ata most desirable "ilaö diose monomers" indeatene * jO, O G-ew .- # the mixed polymer data and the usual, commercially available indigenous proportions consist practically entirely of these monomers, albeit in smaller amounts, i. That is, less than 5tO% by weight of other components, such as chain transfer agents, modifiers and the like, may be included.

Since the fcliuohpolymerisat © used for Pfropfauflegen oit the copolymer dor Qrundaubetana should be compatible _r sru give good properties to, lsi ieloht ereichtlioh that this requires the Anweeenheit of Bhnliciitn monomers. It is most desirable that the Auflngeruleoh- * polyaerlaate come close to the chemical composition of the copolymers of the basic substance, in order to achieve an adaptation of the chemical properties, and therefore it is desired that the requirements of both graft polmerlaate closely approximate each other. In addition, it is assumed that there is an increased chemical bond with a correspondingly large amount of chemical properties, moreover, that there is an adaptation of the relevant mixed polymers, which ends in the basic substance and in the structure been, beiepJ elsweia »? if fiJe

2 0 9 8 U / U 1 6

Containing aorylate, possible to obtain a high degree of clarity and practical transparency « Ea is clear, however, (IbB deviations in the composition the copolymers of the basic substance and the conditions, for example, different monomers and / or different ratios, may be desirable for some areas of application and that certain deviations from even the result of process variables can occur.

Examples of aromatic monovinylidene hydrocarbons, which are used in the misoh polymers can, are styrene, raonoaromatic a-alkyltnonovinylidene compounds, for example ot-methylB tyrol, <x ~ itbyls tyrol, Qt-methylvinyltoluene, a-methyldialkylstyrenes and the like, ring-substituted alkylstyrenes, for example vinyltoluene, o-Ethylstyrene, p-Xthyl3tyrcI, 2,4-dimethylstyrene and the like, ring-substituted haloetyrenes, for example o-chlorostyrene, p-chlorostyrene, o-brometyrene, 2,4-dichlorosiyrene and the like, ring-alkyl- and -halogen-substituted styrenes, for example 2-chloro-4-methylstyrene, 2,6-dichloro-4-ethylstyrene and the like, vinyl naphthalene, vinyl anthraea and the like. The alkyl substituents generally have 1 to 4 carbon atoms and can be isopropyl and isobutyl groups. If necessary, can Mixtures of such aromatic monovinylidene monomers can be used.

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Examples of unsaturated nitriles that can be used in the polyacrylates, and acrylonitrile, methacrylonitrile, Ϊ thacrylonitrile and mixtures thereof.

Examples of monomers compatible with the monovinylidene aromatic hydrocarbons and the unsaturated nitriles can be copolymerized, aind conjugated 1,3-dienes, for example butadiene, isoprene, etc., ot ~ cder fl-unsaturated monobasic acids and derivatives thereof, for example acrylic acid, ethyl aorylate, ethyl aorylate, Acrylic acid butyl ester, acrylic acid-2 ~ ethyl ~ hexyl ester, methacrylic acid and the corresponding esters thereof, acrylamide, methacrylamide, vinyl halides, such as vinyl chloride, Vinyl bromide and the like, vinylidene chloride, vinylidene bromide and the like, vinyl esters such as vinyl acetate, vinyl propionate and the like, dialcylnaleates or diimarates, such as methyl maleate, Diethyl maleate, dibutyl maleate, the corresponding fumarates and the like, as known to those skilled in the art, the amounts will vary these Coaonooeren, which are incorporated into the copolymer can be, depending on various factors.

The Monomerforaiulierure can the time of polymerization also a preformed polymer or a partially polymerisiertea material contained _s beiBpielsJ "a Õîä

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partially polymerized monovinylidene aromatic hydrocarbon or a copolymer thereof.

The polyraeriöierbaren monomeric mixtures contain at least 20 wt .- ^, preferably at least 50 wt. ~ # _F of the aromatic Monovinylidenraonoraeren "They also contain at least 5 wt .- # preferably _f ^ least 10 wt .-, of the unsaturated nitriles. From the standpoint of highly advantageous economic practice, the monomer formulations contain 20 to 95 percent by weight, preferably 60 to 85 percent by weight , of the aromatic vinylidene cobalt substance and 80 to 5 percent by weight, preferably 40 to 15 percent % By weight of the unsaturated uritrile.

Ji e _a Grima ^ subfltanz Jjjffa trijc }

As is known to those skilled in the art, the Polybleüd is produced by preforming the monomers in the presence of the Chewable chukfl can be polymerized. Ee will in general assumed that / 3 part of the polymer on dera preformed rubber grafts as it forms in general it is not possible to use the Kautaohuk aue of the poly merized mass with usual chewing agents extract; even if a certain amount of the rubber polymers are not calibrated in an actual chemical bond can be located with the polymer.

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As base may be approached below about 0.3 t 1 eu at a Pfropfwirkeamkeit 100 i "normal proof β only at ratios of monomers, at least • is in part of the monomers which are polymerized in the presence of the preformed rubber not cheraiaoh bound thereto so that a basic eubβ cans for the Pfropf mis ob. polymerissate is created. This part can, depending on the ratio of monomers to rubber, dor specific monomers "formulation _for the type of rubber and the Polyraerieationebedingüngen increased or ver-Bindert be. In general, copolymers that have been produced without the inclusion of rubber are coapounded with material from the graft polymerisation reactions in order to obtain the desired approximation,

All Ubliohen Polymerisationsverfehren can be used Performing the polymerization of the ungrafted pad, d. H. it can be in hate, suspension ■ and polymerized celiac ion or combinations thereof will. Such processes are known and will also be described below with regard to the graft copolymer leation reactions besohrieben.

The K

It einä veTHchie'lene Kautechuke, on dia dae MLsnhpclymariöat, during the Polymerieafcion in their opposite

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wart can be grafted, as the basis of the graft copolymers usable »that you belong to rienkautschulte, Ethylene / propylene rubber, acrylate rubbers, polyisoprene rubbers and mixtures thereof, eowia mixed poly ■ meriaate thereof with one another or with other aisohpolymerisbaren Monomers.

The preferred rubbers are Men-Kautnchuke or mixtures of diene Kauteohuken, ie all kautsohukartigen Polymerieate (Polymericate with a glass transition temperature not over ⁰ ° C, preferably nioht about -2O ⁰ C ₁ determined governed according to ASTM Test D-746-52T) of one or more conjugated 1,3-dienes, for example butadiene, isoprene, piperylene, chloroprene, and the like. Such rubbers include homopolymers of conjugated 1,3-dienes with up to an equal amount of one or more miso-polymerizable monoethylene-unsaturated monomers Monomers, such as aromatic monovinylidene hydrocarbons, for example styrene, an aralkylstyrene such as o-, ra · and p-methylstyrenes, 2,4-dimethylstyrene, the arylethylstyrene, p-t-butyletyrene and the like, an α-alkylstyrene such as «-methylstyrene, α -Xthylstyrene, ou-lieth.yl-p-Hnothylstyrene and the like, vinylnaphthalene and the like, aromatic aryl halide, monovinylidbrichydrocarbons, for example the o-, m- and p-chlorostyrene ,, 2, 4-ülbromskyroJ _f

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^ß AD ORIG / _NAl

17A5097 H.

2-methyl-4-chloro-retyrene and the like. Acrylonitrile, methacrylonitrile, Aoryleic acid alkyl esters, for example acrylic acid ethyl ester, Acrylaauretnitylester, Acrylaäure-2 Ethylhoxylaater and the like, the corresponding Methaorylaäurealkyleeter, Acrylamides, sometimes acrylamide, methacrylamide, N-butylncrylamide and the like, unsaturated ketones, atapieleweiee vinyl ethyl ketone, methyl propenyl acetone and the like "" - olefins, for example "ethylene, propylene, etc." like., pyridines, vinyl esters, in some cases vinyl acetate, Vinyl etearate and the like, and vinyl and vinylidene halides, beiepialeweiee dia vinyl and vinylidanoles and vinylidene chlorides and bromides and the like.

When also the rubber can contain about 2 i * of an offset, based on the weight of the dee or the chewing on the honey, the network can probably be based on the rubber in the Mcnonprcr; ii \ r cancel the graft polymerization reaction. In addition, overflowing networking can lead to loss of chewing owls. The crosslinking agent can be any of the agents conventionally used for crosslinking diene chews, for example divinylbenzene, diallylraaleet, di-. allyl furarate, diR13yl adipate. _t Aorylaäureal.lyieatar, Moth aorylaäux'eallylester, Dircü * ylate and Dinüljii'iurylate vou PolyhydroxyaTVoho3en _{f for} example Dimelhoorvieäureäthyleneglyfeolester and the like.

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A preferred group of rubbers and chews sohuke, which consists essentially of 75 to 100 wt. 56 butadiene and / or Iooprene and up to 25 Oew.-Jt of a monomer bo stand, which is selected from aromatic Honovjjiylidenkohlwaasstoff, for example styrene, and unsaturated nitriles, for example acrylonitrile, or Mlsohungen of that. Butadiene homopolymers are particularly advantageous bases or a copolymer of 90 to 95 percent by weight Butadiene and 5 to 10% by weight of acrylonitrile or styrene.

Pur the polymerization of Kauteohukmonomeren usually be applied different methods wobu polymerization in Maeie _f in suspension and are in emulsion. The emulsion polymerization can be used to produce a latex emulsion which can be used as a basis for the emulsion polymerization of the graft copolymer.

Graft polymerization process

The graft copolymers are prepared by adding the monomers of the copolymer in the presence of the preformed Rubber base are polymerized, generally in accordance with Ubliohen graft polymerization methods, wosu polymerisation in suspension, in emulsion or in Include mass or combinations thereof. In such a graft polymerization, the pre-

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Kautsohukgrundlage formed dissolved or dispersed in the monomers and this mixture is polymerized _f to at least a portion dea Mischpolyicarisate on the KautBohukgrundlage cheraieoh to tie or graft. Depending on the ratio of the monomers to the rubber base and the polyaerieation conditions, it is possible to obtain both the desired degree of grafting of the copolymers on the rubber base and the polymerization of the ungrafted copolymers, including a filing of the base sub-structures below eohaw.

As will be explained in more detail below, the ratio of the monomers is aura rubber, such as ee In, in the graft polymerization reaction is introduced, the main determining factor for the ratio of the layer to the basis in the case of the calibrated graft copolymer. Anyway, the polymerization conditions can also apply to the ohemical nature of the rubber and the Teilohengrüße, the Oil rates of addition of monomers, chain transfer agents and the like exert an effect.

Bs can therefore use the same polymerization process eur creation of the low-grafted and the high-grafted Rubbers can be used by varying the conditions. However, if necessary, but preparation of the two different chewing grafts different

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Polymerisationβverfahren can be used, whereby it is the respective characteristics »dee procedures allow the To facilitate deviation.

Polymer laallonarer in Maeae / Suapengion In an advantageous combined mass / Suspenalona · »polymerisation process, the monomers, the rubber base and the catalyst (oowle other optional components) are filled into a conventional reactor and then polymerised in mass by in the course of about 1 to 48 hours at a pressure of 0.07 to 7.03 kg / cm (1 to 100 pai) is ^{heated to a temperature of about 75 to 125 0} C until some of the monomer, la generally about 15.0 to 50 , 0% by weight thereof are polymerized, and stirring is carried out in the usual manner to assist the heat transfer during the reaction. The time for this partial polymerization will vary depending on the catalyst, the pressures and temperatures used, and the particular monomers and their proportions. In general, it is preferred to carry out such a prepolymerization process to the conversion of about 20.0 to 55.0 weight percent of the monomer.

Any catalyst that generates free radicals can can be used in the practice of the present invention, including active radiation. It is

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/ ς

preferred, a suitable catalyst system for the polymerization of the monomer, for example the customary peroxy compounds which are soluble in the monomers. Examples of KataXyeatoren aind di-t-butyl peroxide, beneoyl peroxide, Lauroyl peroxide, olyl peroxide, toluyl peroxide, Di-t-butyldiperphthalate, t-butyl peracetate, t-butyl perbeneoate, Diouayl peroxide, t-butyl peroxide isopropyl carbonate, 2,5-dinethyl-2,5-di- (t-butylperoxy) -hexane, 2,5-dimethyl-2,5-di- (t-butylperoxy) -hexln-3t t-butyl hydroperoxide, cumor hydroperoxide, p-lethane hydroperoxide, cyclopentane hydroperoxide, Isopropylbene sol hydroperoxide, p-t-butylouaol hydroperoxide, Pinane hydroperoxide, 2,5-dine t hy lhexane-2,5-di hydroperoxide and « the like, as well as mixtures thereof.

The catalyst is generally in the range of 0.001 to 1.0% by weight and vorxu ^ aweiee in the order of magnitude of 0.005 to 0.5 wt. 5t of the polymer soluble material before «in Dependence on the monomers and the desired polyoleationioneolue.

ti "known, it is often desirable for the molecular weight regulators such as mercaptans, halides and terpenes in relatively small wt .- ^ quantities in the order of 0.001 to 2.5 wt ~ _# £ eineuarbelten of the polymerizable material. On the other hand, it can also be necessary, relatively

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small amounts of AnMoxydouiien and stabilizers in the usual spielsweiee rOkylierten Piieiio? o, Ginzuarbei th, although these may be added during or after zn 3 polymerization.

The syrup, from which the partially polymerized formulation is obtained, is then in the presence of a suspension agent, such as the aoryleic acid / Acrylaii-Miochpolyni; rieaten <Jer USA-Fatenteohrift 2 945 013 and the USA-Patent 3 051 68 ?, ground with waeeer. Subordinate dieporting auxiliaries can also be added in order to obtain the desired suspension de "syrup" in faaaer bu. The suspending agent is given as little as possible, even if it can also be acetate of the monomers from the beginning or during the initial polymerization. The suspension is stirred and heated to a temperature of about 75 to 200.degree. C. for 48 hours in order to obtain an essentially complete polymerization of the monomers contained therein. Voraugsweiae this is further · Polymerisatlon at a temperature of about 100 to HO ⁰ O 1 bit 20 hours wae from the catalyst and the amount thereof used is dependent durohgefUhrt. When the polymerization reaction is essentially complete, unreacted monomers and volatiles are stripped off and the polymer beads are centrifuged, washed and dried.

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Alternatively, the monomers and the Kautaohulcgrun llf.g initially in water auopendlBiofc and ββ can dia entire Polymerisa fcionsrealci; ion can be carried out in suspension, In each case infalIu aiuia & zlj.cho Mono mere, catalyst and p.rulcre Korans en fcen tu d) .e polymer! - Formulation of satlons at various Gtui'on üöb Polymeric »- tionβverfahren8 should be introduced.

BmulBlonBpol ymeriBatione process

In the emulsion polymerization process, the monomers and the chewing base are emulsified in Waoeer, indene suitable emulsifying agents are used, for example petta acid soaps, alkali metal or amaontum soap of alkyl or alkylene sulfonates and sulfonates with higher molecular weight, inorganic sulfonates, aliphatic acids, salified sulfonates, inorganic acids. ,. Emulsifiers, which eioh to be particularly advantageous; have been shown to be WatrluinoIeate _; In general, the building agent is provided in quantities of about 0.1 to 15 parts by weight per 100 parts by weight of monomers and ffasaar is provided in an amount of about 4 parts per part of monomers and the same larger proportions are provided if greater dilution is required.

In certain cases, an aqueous layer formed in the emulsion polymerization of the chewing owl base may be ex dus when dge

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Create a medium in which the monomers with or without additives Borrowed emulsifiers, water and the like can be incorporated. However, the rubber can be dissolved in the monomers and the mixture can be emulsified or a latex can be separated therefrom getting produced.

There are usually various water-soluble polymerization initiators, which form free radicals, used for EbuI sionspolymerieation the Xautechukmonoineren, woau traditional peroxy and azo catalysts belong, and the The resulting latex can be used as the aqueous medium be, with which dlo Mlsohpolymerisatntonomeren are used, In this way, the catalyst for rubber polymerization act entirely or partially as a catalyst for the graft polymerization. However, at the time of the Graft polymerisation of a suitable catalyst was also given. Examples of suitable peroxy catalysts are the alkali metal peroxides, -persulfates, -perborates, -perasetates and -percarbonate and hydrogen peroxide. If necessary, can the catalysts are activated with the formation of redox systems will you. It can also be advantageous to use an oil solution Incorporate a catalyst, for example a Catalyst as identified above for bulk / emulsion polymerization processes. However, auoh other free radical generating catalysts can be used, such as current irradiation.

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/ 3

Chain transfer agents and other polymoriaaticne Modifying agents can be used if necessary and ee is generally advantageous, a higher one Alley line roa ρ tan, like tert. ~ Dodecyl mercaptan, to be incorporated, Both all promoters and all regulation are carried out works. Antioxidants and stabilizers, such as the alkylated phenols, can also be added.

The Emulslonsnischung is then polymerleiert in an inert Atmesphäre at temperatures in the range of 20 to 1OQ ⁰ C with stirring. Druoke τοη 0.07 ble 7.03 kg / oaa (1 ble 100 pel) can be used and the memorization and / or further catalyst can be added proportionally or continuously over the course of part of the reaction cycle. The polymerization continues until practically all monomers, ie more than 90%, have reacted. The remaining monomers and other volatile components are then distilled off from the latex, which is then drained, washed and dried.

Effect of TellohengrflBe and Vera et sung

In general, the particle size is Keutecbuke in the polymerizable monomers during dos Pfiopfpolymerieationsreaktionwi an effect on the optimal graft ratio for the low graft to Mi aohpolyrnerleat.

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As can be readily seen, a given weight percent of smaller sized rubber particles provides a considerably greater surface area for grafting than the equivalent weight of larger chewable rubber particles. Accordingly, the graft density can be varied depending on the size of the chewy particles. In general, the smaller rubber particles allow a higher degree of grafting than the larger particles in order to generally give comparable results.

However, the particle size de; Imuteohukpfropfmiachpolymerieate in the polyblend also an important effect on the oil and strength properties, i.e. increasing Particle size of the graft copolymer tends to reduce this Adversely affecting properties.

Accordingly, the particle size of the graft polymerizate can be varied from 0.01 / i up to 2.0 ^ and more, what of the final properties of the composition depends. In the preferred compositions are graft copolymers with a particle size of about 0.05 ^ to 0.30 / t and desirably from 0.08 to 0.15 / *. used. When determining the average particle size becomes a dispersion of the graft copolymer particles and a photomicrograph made in front of it.

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Then the size of about 200 to 1000 particles is measured and taken the average, with an average Particle size is obtained which is on a number average based. Alternatively, other MeSaethodrn be used, belspieleweiee lichtstrduur.getnethoden, as long as there is an acceptably close relationship between the actual OrUBe and the method used.

Although the rubber can be crosslinked, this can above Calibrated point of the dissolution or dispersion of the rubber create problems for a SuepeneiocBpoly & arieationrrsrfahren. For emileion polymerization processes, rubber has However, a significant degree of networking is required.

With regard to the graft misohpolya «rieate iet au say» that during the graft polymerization process »indeatens in some degree of networking occurs »if desired by adding networking agents or regulating the polymerisation conditions can wtrdtn more. By doing • Obtained in highly networked, high-grafted copolymer is, the drink will be part of the graft polymerizate borrowed upright, ao dA0 calibrated this results in optimal effectiveness.

Graft ratio of the MiechpolynerlBat.c Ex-wähui; prepared as above, has the low; g * grafted &

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3t

Mixed polymer a ratio of edition to basis, which can vary in the range from 5.0 to 35.0 to 100.0. When the graft ratio decreases, an apparent one occurs Tendency of particles to agglomerate and effectiveness reduce the process of the invention, as well as a notable deterioration in other properties. If the graft ratio exceeds 35.0 ι 100.0, there is a notable reduction in impact strength and with other properties of the Zueaimaensetungen on. In the case of exercises before Bug ten Zusarameneet, there is a graft ratio from 10.0 to 20.0: 100.0 used.

Graft ratio in the case of the highly grafted copolymers can vary from 50.0 t 100.0 to below 250.0: 100.0. In the preferred mummy sets, a graft ratio is used from about 60.0 to 150.0 ι 100.0 used. The lowering of the graft ratio in the case of highly grafted polymers less than about 50 t 100 leads to deterioration of various physical properties. The upper Orense of 250-100 is essentially due to the degree of grafting determined, which was available in conventional processes, if also possible, i.e. a higher degree of grafting works satisfactorily.

It has been found in various tests that the degree of grafting of the low-grafted component is literal

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for determining Acr properties the Zv settlement is. Figures _# 2 of the accompanying drawing veraiT-Bchaulicht the effect of d "r variation of Pfrop / verhöltni" eee the niedriggepfropften component in cinerr. Polyblend, in which the total content of gum base is 16.0 aew, -5 »of the composition, and in which the graft ratio of the highly grafted component is kept consistent. In a number of compositions, equal amounts of the two graft copolymers are used. As can be seen, the Istod value of the impact strength for the compounds produced in this way falls rapidly at a graft ratio in the range from about 0.10 to 0.20, while the Hunter Glla value is sunimat Contain ratio »which maintains a favorably high impact value while making good clans.

Making the Mix

The white graft polymer can be incorporated into the ungrafted Mlsohpolymerisat basic substance according to different Methods are mixed in. In the preferred methods, the dl graft polymers are mixed by extrusion or poured through a roller mill, with or without additives of further ungrafted copolymer, wae from the Amount of ungrafted copolymer in the

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_{Loading trolleys that deliver the caoutchouc grafts f} and dea in the mixture depends on the desired gummed rubber graft content. Alternatively, a mixed latex aua the graft products having different particle size fcftnn prepared and are coagulated, provide au to beads containing the Kautsohukpfropfproduktβ the desired ewei Teilohengrööenbereiche in the desired Ieengen.

In general, the mixtures may contain 1 _r 0 to 70.0 of the two combined Kautschukpfropfprodukte. The increase in the total amount of rubber graft product increases if the ratio of the low SIaS grafted product to the total graft product is kept constant, but generally the Izod bottom viscosity of the composition, increases the viscosity of the mixture rapidly and reduces the tensile stress on yielding and breaking and the tension module. Accordingly, preferred blends contain about 10.0 to 50.0 weight percent, and most desirably about 20.0 to 40.0 weight percent, of the combined rubber graft product.

The effect of varying the rubber content of the composition can be seen from Figure 1 of the drawing, according to which a number of compositions are prepared become “the high-grafted and low-grafted component” r.

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is

in a ratio of 60 ι 40 en thai th, the content of rubber base in the composition being varied by adding increased amounts of the two grafted components. As can be seen, the laod value increases and the impact strength falls relatively quickly as the amount of chewing material is increased.

In general, the properties achieved according to the invention are create most of the degree of grafting of the low-grafted ones Coaponents and their percentage in the Getsarätpfropfaiechpolyraerieatea addicted. Accordingly, the feed compositions desirably contain the low-grafted one Kieohpolymerie & t in small quantities, if the AurjaaS there Grafting is increased. The desired supply of additional seeds range for varying · graft ratios oind mis der Table I below,

Table I.

^ der Q eeamt graft f misch polymer i sat β_

5 to 10 t to 100 20 to 40

10 to 15 ι 100 40 to 60

15 to 20 ι 100 50 to 80

20 to 25 t 100 60 to 85

25 to 30 t 100 75 to 95

30 to »35 ι 100 85 to 97

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Let it be clear that there are optional components, such as fillers, antioxidants, stabilizers and the like, can be added depending on the intended application and its type.

The following examples are intended to illustrate the present invention further without restricting it. All parts and sewing parts, unless otherwise stated.

example 1
hot At

To 1200.0 parts of a latex made from Inen Butadiene / Aorylnitrll-Mieohpolymerisat (93: 7), which contain 50.0 + solids and about 1.0 part of rubber reeerve eoap as emulsifier, 476.0 parts Waceer and 52.0 parts of a 2. Above aqueous Calluapereulfatieaung given. Dl "emulsion is erhitst with stirring to 60 ⁰ C and then la course be sugegehen of about 6 hours 80.0 parts of styrene and 42.0 parts of acrylonitrile. The Emuleion is stirred for an hour at the

- · ■ temperature kept, cooled, coagulated and the won The copolymer is then washed and dried. The resultant Ffropfmisohpolyncrie & t has a ratio τοη edition iu basis of about 0.2 to 1.0

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rf

and a particle size (numbers du :: cheohaitt) of st about 0.09 ^ «.

To 900 parts of a latex of a butadiene / aeryl nitrile copolymers (95: 7), which contain 50.0 $> solids and about 1.0 part of rubber substitute soap as an emulsifying agent, 1055.0 parts of water and 2.0 parts of Iautechuk treatment soap are added given together with 240.0 parts of a 2.0% aqueous potassium persulfate solution.

The emulsion is heated with stirring to about 65 ⁰ O, then 155.0 parts of styrene, 235.0 parts acrylonitrile and 4.8 parts of terpinolene will result ale chain transfer agent DAEU the course of about 6 hours. The emuleion is then kept at that temperature for one hour with stirring, cooled, coagulated and the graft copolymer is then washed and dried. The resulting graft copolymer has a coating / base ratio of about 1.0 1 1.0 and the average particle size, based on the number average, is about 0.14 / *.

Tell Cx

In an extrusion mixer, 200.0 parts of Ffropfaischpolynerlsat prepared according to Part A, 424.0 Parts of all Part B are made from a graft mix polymer 1>

- 27 - 2098U / 1216

BATH

eat and 304.0 parts of styrene / aorylnitrile Miechpolrmerieaf. (70: 30} given. On this week a Zuoemaienoetü is given obtained which contains about 16.0% by weight of the caulchuk base.

The loot of the composition is found to be 22.6 <m kg / am (4.2 loot, pounds) and the shrinkage is 42.0 pounds. Me pellets have a Hunter Glane value of 23.

Example 2
Part Ai

The procedure of Part A of Example 1 is essentially repeated with only 16.0 parts of the aqueous Potassium pereulfate solution, 40.0 parts styrene and 21.0 parts Acrylonitrile can be used. The amount of water added to the rubber latex is 403.0 parts. The resulting Graft copolymer has a ratio of ffropfauflage bu basis of about 10.0 ι 100.0.

Part Bt

200 parts of the graft copolymers prepared in Part A above are in the extrusion mixer with 456.0 Parts of the copolymers prepared according to Part B of Example 1 and 347.0 parts of raw styrene / acrylonitrile polymer mixed to form a polyblend.

2098U / 1216

BAD CHiGiNAL

Ea is found that from the above composition compacts made 29 »5 on kg / cm (5.5 foot pounds) and have a iRod value of the impact resistance \ on a Hunter Glanzweri of 43rd IUe shrinkage is 45.0 £.

B e yes ρ ie 1 £

Part A ;

The operation of Part B of Example 1 is iai essential repeated, with the exception of the 800.0 parts Rubber latex, 500.0 parts styrene, 263.0 parts acrylonitrile, 51-3 parts of terpinolene, 265.0 parts of the aqueous Potassium sulfate solution and 1097.0 parts of water are used will.

Part bi

A poly blend is produced by adding 515.0 parts of the graft copolymers of Part A above, 287.0 parts Styrene / aorylnitrile misoh polymer and 200.0 parts of dee Pfropfaiechpolymsrlaate prepared according to Part A of Example 2 be mixed by extrusion.

It is found that "pellets produced from the compound have an Issod value of 8 impact" ability of 28.5 ca kg / on (5.3 foot pounds) and a Hunter oil value of 45. The shrinkage is 42.0 %.

- 29 ■
209814/1218

Example 4

A third composition is produced using a single graft polymer with a Verhol tr »La from edition eu basis of 50: 100. The basic substance and the overlay polyesters are styrene / aorylnitrile mixed polyols (70:30) and the rubber layer represents about 16.0% by weight of the total amount of water, and it is found that the sole capacity of this composition is 36.6 kg /of. (6.8 foot pounds) and the Hunter Olance value is 0.

horny bi

Ss will have a similar ZusasunenaetEtmg

the one single FfropdTmisch polymerisat with a ratio of edition eu basis of 200; 100 contains _r made. It is found that the Iaod value of the impact ability of this composition is 3.22 ob kg / oB (0.6 foot paunds) and the Hunter value is 97.

part Oi

Bs is a mixture of equal proportions of the graft ■ iaohpolymerisatβ of the above parts A and B into one Polyblend made of 16.0 Sew .- ^ Oesaratkaut-Bohuk ι contains. The compacts from it have an Izod value the weight of 30 cn kg / oa (5 "6 foot pounds) and

ν 30 -

209814/1216

BATH ORIGINAL

a Hunter Glane value of 67. So let it be seen that the mixture containing the highly grafted component and the low grafted component in combination exhibits a highly desirable balance of properties,

Aue the foregoing detailed description and the It is clear from examples that the present invention provides a new rubber-coated polyblend which is highly acclaimed Shows the balance of the properties and offers the possibility of varying the relative amount of x two grafted components, the degree of grafting · des low-grafted copolymer and the total amount of the grafted components combined in the aggregate easily deliver properties "naoh measure" tu. If the optimal values are selected, the compositions have a extraordinary and highly desired balance of inheritance.

It can be seen that the present invention dl Opportunity provides dl · components »u deliver to each other and with ungrafted copolymer, which is the basic substance represents, can be mixed to eo a wide range of clay coexistence with the desired Blgeneohhaften do surrender. YIe leloht erelohtlioh, can be an existing one Equipment for manufacturing the Kauteohuk graft components and the basic polymeric material used

- 31 2098U / 1216

will. Accordingly, the methods and compositions of the present invention are relatively economical and easy to use.

It will be appreciated that many variations of the methods described can be made without the To leave the scope of the invention.

- 32

2098U / 1216

BATH ORIGINAL

Claims (30)

Claim β 1, polyblend composition, characterized in that that they are out A) a basic substance of a copolymer that at least haupteächlioh from an aromatic monovinylidene hydrocarbon and an unsaturated! citril, B) a first graft copolymer with a rubber base and a layer made of elastic copolymer, that at least mainly of a monovinylidene aromatic hydrocarbon and one consists of unsaturated bititrile, this first graft copolymer has an edition to base ratio of 5.0 to 35.0: 100.0 and Cf) a wide graft copolymer bit of a rubber base and a pad made of a misoh polymer consists, at least mainly, of an aromatic Monoirlnylidtnkohltnwasstretoff and ink unsaturated litrile, vobti the swtitt PfropfttisohpQlymerisat a ratio of edition eu basis tone 50.0 to 250.0 ι 100.0 and wherein - 33
2098 H / 121 the erate and sweite Pfropfmisohpolyaerieat 1.0 to 7O O ₉ wt .- * · de polyblends and the first Pfropfmlaohpolymerisat about 20.0 to 97.0 wt .- * represent the GesamtsgewiohtB of the combined graft copolymers, 2. Composition according to Claim 1, characterized in that that the aromatic monovinylidene hydrocarbon the copolymers of the base substance and the graft ■ isohpolymsrlsatauflagen Styrene is. 3. Supplement according to claim 1, characterized in that that the unsaturated iltrile of the copolymer of the Basic substance and the graft polymeric layers acrylonitrile let. 4. Zueaeaeneeteung naoh claim 1, characterized gekennseiohnet, that the Kautachuk base of the non-graft polymers at least about 7% by weight of conjugated diene contains "selected from diene rubbers, HoBiopolymerieates and rubber-like Copolymers, which are at least 75 wt .- * sines conjugated dian · included. 5. Zueaanensetaung according to claim 1, characterized It pays that the aromatic mono-tloylidene carbon hydrogen and the unsaturated litrile at least 75.0 wt .- * the copolymers dsr graft polymerizate conditions - 34 2098U / 121 » BATH ORIGINAL and make up the basic substance. 6. The composition according to claim 1, characterized in that the Ffropfwiοcnpolymerisate about 10.0 to Make up 50.0% by weight of the polyblenda " 7. Composition according to claim 1, characterized in that that the first graft copolymer has a ratio from edition see below basis of about 10 to 20.0: and the second graft polymer has a ratio of about 60.0 to 150 t 100. 8 «together * et * ung according to claim 1, daduroh marked, dm3 the graft copolymers have an average particle size, based on the number average of have about 0.08 to 0.15 m « 9. Composition according to claim 1, characterized by that the first graft copolymer has a ratio by edition has a basis and is present in quantities in the composition «as indicated below} 17 * 5087 16 Ratio # dar Qeaaatpfropfalschpol.ycerlsat ■ 5 to 10t100 20 to 40 to 15 * 100 4 ° to ⁶⁰ up to 2CH00 ^{50 to 80} piB 251100 ^{60 ble 85} to 3Oi100 75 to 95 from 35 to 100 85 to 97 10. Polyblends ueanne wetting, characterized in that there is no A) a basic substance ae copolymers, daa eumindeat Mainly made of an aromatic monovinylid carbon water and an unsaturated hitrile, B) a first graft of a bake polymer made from a chewing base and a support aue a mixed polymeriaa-t, dae lumlndeet haupteäohlioh from an aroaatlachen lionovinylldenkohlenwaeeeretoff and an unsaturated nitrile, which is a graft polyacrylate Ratio of circulation to the basis of 10 to 20.0: 100.0 has, and C) a "wide graft polyyeerieat with a chewy owl base and an overlay consists of a copolymer, the main thing being that there is also one aromatic monovalent carbon and one unsaturated nitrile, whereby the awnite graft - 36 2098U / 1216 BAD ORiGiNAL Misobpolymerisat a ratio of Auflag «to basis of 60.0 to 150 t 100.0 and wherein the first and the second graft polymer 10 bit 50 GeW ₄ - ^ of the polyblend and the first graft polymer about 40 * 0 to 85.0 wt. - make up? t of the total weight of the combined graft copolymers, 11, composition according to claim 10, dadaroh §skenn ~ Rewards that the aromatic monovinylidene carbonaceous fiber - material of the copolymers of the basic substances and the PfrcpfsiBchpolymerisatauflagen Styrene iet. 12 «Sueaamensetsung n * oh Ancpruob 10» thereby obtained * nnaelaid *, AeJ dae uns & ktlgt · nitrile of the ÄioohpolyiMrieate the Grimdsub & tane and the Pfropfalschpolyaei / isatauflagea Is acrylonitrile. 13 »Combination according to claim 10, characterized in that dad the Eauteohuk base de ?. ' Pfropfmiechpolyaerieate Contains at least about 75% conjugated diene, selected from rubber honopolyers and Chewable MisohpolyBerieaten, the "at least 75 wt .- ^ contain a conjugated diene, 14. Summary according to claim 10, characterized in that the aromatic Monovinylidsnkohlenwmseer- ^209814/1216 substance and the unsaturated nitrile at least 75-0 wt of the copolymers of the graft polymer supports and make up the basic substance. 15. Composition according to claim 10, characterized in that the first graft mixed polymer is a ratio from edition su basis asked and in quantities in the composition exists, as indicated below} Ratio % of total graft polymers 5 to 10: 100 20 to 40 10 to 15 »100 40 to 60 15 to 20: 100 50 to 80 20 to 25: 100 60 to 85 - 25 to 30: 100 75 to 95 30 to 35s100 85 to 97 16. Composition according to claim 10, characterized in that that the aromatic Monovinylidenkohlenwasaeratoff the mispolymerization of the basic substrate and the Pfropfraiaoh polymerizat support styrene and the unsaturated Nitrile is the copolymers acrylonitrile and 8 Styrene and acrylonitrile at least 75.0% by weight of the Mi β oh polymers dar Pfropfmiachpolyaeriaatauflagan and dar Make up the basic substance. 17. Method of manufacturing a polyblende, thereby marked that one 2098U / 1216 17 * 50§7 33 A) a first polymerizable mixture that is a monomer formulation and a prepolymerized rubber contains, polymerized to at least a portion of the polymerizing monomers on the rubber graft on and a first graft polymer au create, with the monaural formulation at least mainly from a monovinylidene aromatic hydrocarbon and an unsaturated nitrile and the first graft polymer a 7erhSltnie from edition to basic from 5.0 to 35.0: 100.0 shows B) a eweite polymerizable mixture containing a monomer formulation and a vorpolymerieierten rubber polymerized to graft at least a portion of the polymerizing monomers onto ά * η rubber and tu provide a second graft copolymer, wherein the monomer formulation aua at least mainly an aromatic Monovlnylldenkohlenwaeserstoff 'and a consists of unsaturated nitrile and the second graft copolymer has a ratio of coating on the basis of 50.0 to 250.0 ι 100.0, and C) the first and the second Pfropfmisohpolyraerieat under Creation of a polyblend mixes in which the graft copolymers 1.0 to 70.0 wt. And wherein the first PfropfiBiaehpo'j- meriBat about 20.0 to 97.0 wt .- # the total weight of the combined: graft copolymers ouch. 39 - 209814/1218 18. Method according to claim 17, characterized in that « that the aromatic Monovinylidenkohlenwasaeratoff der Monomer formulations styrene iat. 19. The method naoh claim 17, characterized in ~ notwithstanding that the unsaturated nitrile of the monomer formulations Is acrylonitrile. 20. Method according to claim 17, characterized in that the rubber of the first and the “ride” Misohung is selected from diene rubber homopolymer seeds and chewable copolymers containing at least 75.0% by weight of a conjugated diene. 21. The method according to claim 17, characterized in that the aromatic monovinylidene hydrocarbon and the unsaturated nitrile is at least 75.0% by weight of the monomer formulations of the first and second Make a mix. 22. The method according to claim 17, characterized-rewarded, that the first graft polymer is a ratio From edition to base of about 10 to 20.0 ι and the "wide Pfropfaisohtjolynerieat a ratio of \> ■ ■ about 60.0 to 150 t 100 ^ - 40 - 209814/121 $ bad original 23 »Method according to claim 17, characterized in that the first graft polymer has a ratio of coating to base and is present in the polyblend in amounts as follows: ratio " 4 > of the Isaiah graft mixed polymers 5 to 10: 100 20 to 40 10 to 15 * 100 40 to 60 15 to 20: 100 50 to 80 20 to 25 t 100 60 to 85 25 to 30 »100 75 to 95 30 to 35x100. 85 to 97 24. Method of manufacturing a polyblend, thereby marked that one A) a first polymerizable mixture which is a monomer formulation and contains a prepolymerized rubber, polymerized, including grafting and grafting at least a portion of the polymer-sizing monomers onto the rubber to create the first graft copolymer, the Mono mer formulation at least mainly from an aromatic mono vinyl id eiikohlenwasserat off and an unsaturated one liitrile and the first graft with polymer has a ratio of circulation to base of 10.0 to 20.0 J tOO, B) a second polymerizable mixture which is a monomer formulation and a prepolymerized chewing gum «. 41 2098U / 1216 contains, polymerized to at least part of the poly * grafting merging monomers onto the rubber and create a second graft copolymer au, the Bumiuderst monomer formulation mainly from an aromatic one HonoYinylidenkohl watered off and an unsaturated There is hitrile and the second graft copolymer has a ratio of edition on the basis of 60.0 to 150: 100.0 and C) mixing the first and eweite graft copolymer to create a polyblends, from which the graft copolymers of 10.0 to 50 0 weight _f £ and wherein the first graft copolymer from about 40.0 to 80.0 parts by weight jf the total weight of combined graft copolymers turn off. 25. Procedure according to Anepruoh 24 "daduroh marked" that the monovinylidene aromatic hydrocarbon of the monomer formulations Styrene ieb. 26. The method according to Anepruoh 24, thereby marked, that the unsaturated nitrile of the ifonomer formulations is acrylonitrile is, 27. The method according to claim 24, because that the rubber of the first and the second mixture is selected is made from Uienkeuteohuk-Homopolymerieaten. and rubber-like Copolymers containing at least 75.0% by weight * - 42 - bad original; 2098U / 121S contain conjugated diene, 28. The method according to claim 24, characterized in that the aromatic Monovinylidenkohlenwasseratoff and as "unsaturated Kitril constitute at least 75.0 wt. -I" the monomer formulations of the first and second mixture, 29. The method according to claim 24, characterized in that that the aromatic Monovinyliöe-Ucchlenwaeaerstoff der Monora formulations styrene and the unsaturated nitrile of the formulations is acrylonitrile and that styrene and acrylonitrile are at least 75.0% by weight of the polymerizate remove the graft layers of the graft polynerieate. 30. The method according to claim 24, characterized in that that the graft copolymers have an average particle size, based on the number average, of about 0.08 to 0.15ft. 31 «Method according to claim 24, characterized in that that the polymerizable mixture of the polymerization steps an emulsion of the prepolymerized rubber and the Mononserforraulierung is. - 43 - 2098U / 1218 bad original Blank page