DE1937298A1 - Polymer mass with high impact strength - Google Patents

Description

The present invention relates to a polymeric mass with a high notch base which is obtained by mixing two together precisely defined types of Aorylon / Tril-Butadiene-Styreneharaen (hereinafter abbreviated as ABS resins) and the sioh in characterized particularly advantageously by improved physical properties. The one from the specified mixture In particular, existing polymeric mass exhibits a synergistic effect in relation to the Izod notch base ability on, that is, that determined by the Izod method Impact strength value is the notched Iaod impact value fttr exceeds the resin components forming the mixture.

The aorylonitrile-butadiene-styrene resins, which are also referred to as fluramiplastikoaterialien, comprise chewing-modified thermoplastic resins, which also include graft copolymers of chew-like materials with acrylonitrile and styrene monomers. The expression ⁿ graft copolymer ^H is known (reference is made to Journal of Polymer Soience, Volume 3, 1962, page 260) and denotes resins produced by a process in which a substrate, for example a rubber-like β diene material having unsaturations, undergoes polymerization with a monomer or a Vi

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0 6AÖ 0RS61NM.

miBoh is subjected, with chains protruding from the substrate (so-called Pfrepfketten) are formed. You molecules of the graft copolymers formed in this way hence from two or more polymeric ropes »those from the indicated polymerization of a rubber-like substrate result with monomeric materials. As a rule, the rubber plastic materials have also been used in the form of polystyrene high notch counting denoted polymer in which it is a chewy-like diene that interacts with styrene monomers is graft polymerized.

They known ABS-haters don't just include such polymers Kassen »made by direct graft polymerisation of monomers Components on a chewable diene substrate but also those polymeric masses which are derived from clay, that is, meohanic Oeaisohe made of polymeric materials such as Nitrilteutsohuk with resinous styrene-Aorylonitrilmieohpolyaerieaten. Tertality plays a role in the production of such mixtures the individual components play an extremely important role and it happened that when mixing elastomers with one thermoplastic resin with maximum compatibility of the components results in a mixture whose properties are in the Are usually also of maximum effect.

Bas technological field of aorylonitrile-butadiene-styrene resins has become very complex in the meantime and systems that are as simple as those made by polymerisation, for example, are no longer sufficient of styrene and acrylonitrile on a chewy diene substrate with the formation of the interpolymers known as ABS resins, »but they are becoming permanent for them today Expanding areas of application ABS resins with a wide range of different properties are required. So can For example a resin with regard to certain properties, for example notched impact strength and tensile strength, meet the requirements, but with regard to others, for a particular one Purpose of use particularly important properties,

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for example gloss or hardness, prove to be insufficient. Further the trade is also placing ever higher demands on the properties of such resins and the industry is keen to meet these requirements. In a corresponding manner can also the case that a resin with satisfactory Shine and sufficient hardness are not the best for a particular one Sohmelsfluss required high notch toughness. Furthermore, ABS resins must also have sufficient properties of their own in the soil corresponding requirements in terms of notch resistance and hardness, which has the consequence that the technology of such ABS Harse has become very complex due to the need for coordinated properties.

How different the properties of ABS polymers are can be, is indicated by the following, where it If the information is based on the American system of measurement, more detailed information illustrated. For example, the tensile strength can be coherent depending on the ASTM test methods used by a minimum of 2000 to a maximum of 12,000; the Rockwell hardness, as determined on the R scale, can range from 30 or below that, up to 123, the Isod notched impact strength can be from 0.5 to 15 and the heat distortion temperature can, for example, from 60 ° 0 up to values as high as 113 ° above sea level row. Tone of particular interest are the tensile strengths, which, in combination with a high gloss, determine the suitability of a material for injection molding processes. For ABS resins suitable for extrusion processes must have a medium Izod notch base, However, they have high tensile strength values, whereas they are suitable for calender or web material processes ABS Harse high properties and medium Izod kerbing counts Require tensile strength properties.

One. Discussion of ABS resins and their technology therefore leads to the need for further improvements in manufacture and mixing such masses are required to be versatile

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usable polymer masses with improved, by corresponding Selection of the components of the mixture to create properties that can be influenced.

The object of the invention is therefore to specify polymeric materials, those by mixing aorylonitrile-butadiene-styrene resins obtained and can be supplied to an independent use, further by mixing two ABS components represent obtained polymeric masses which have surprising synergistic properties with regard to the Izod-Kerbsohlagzählgkeit, that is, a higher notched impact strength than the sum of the core impact strength values of the one-core components have, further due to the fact that au their manufacture at least one ABS component from a cheap ABS system is used in significant quantities, can be produced in particularly economical catfish and the Aich also, if two ABS components manufactured according to different processes with different Particle size of the chewy ingredients used are »characterized by a high notch soleplate.

The polymer cash register according to the invention is characterized by an intimate mixture of (a) a graft polymer a chewy diene and a mixture of a vinyl cyanide and vinyl aromatic hydrocarbons, the rubbery diene component thereof present in the final composition has a particle size of about 0.8 to 25 microns, and (b) a rubbery diene polymer with grafted vinyl cyanide and aromatic vinyl hydrocarbon monomers, its rubber-like diene component predominantly consists of particles with a particle size from 0.005 to about 1 micron.

Components (a) and (b) are preferably in that specified Mixture in a ratio of 25175 to 75 * 25 before, and component (a) is derived from a thermoset using a rubber-like linear polydiene material

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ten blook suBpeneionapolyerisation, whereas component (b) is a latex-based polymer, that is to say, in a graft polymer obtained by emulsion polymerisation from a butadiene chewing pebble substrate with styrene and aorylonitrile. As already erwannt, each of these components can be cited an independent use, as both certain desirable characteristics of the broad spectrum of advantageous properties _t by 'which such ABS resins are characterized »comprise ·

! The synergistic effect in relation to Izod notched curd » when mixing the specified components with different particle sizes in the polymer obtained Mass occurs according to the invention is completely surprising and not easily explainable. This synergistic effect results in a surprisingly high value for the Isod notch sole viscosity the polymer cash register consisting of the mixture "which is higher than the values for the Isod-Kerbschleg" capacity of the individual ABS components before mixing. This synergistic effect is in fact so pronounced that the Isod notch bottom values in some polymeric compounds are different Mixing up the two, sram used ABS components almost add. This Xatsaohe is completely surprising because of the missing a component with an Isod-Kerbsohlagzänlgkelt Clay for example 6 (determined according to the usual known ASTM test methods) with a component with a notch base count of 2 in the ratio of 50 to 50 are expected, that is a polymeric compound with an iBOd-notch resistance ▼ on about 4 »but of more than 6, as shown in the received- polymeric masses according to the invention actually lall is «is received.

To produce the polymeric compositions according to the invention, as already mentioned, about 25 to 75 parts of one by Bloek-Sttspenslonspolymerisation ABS Haraea obtained with a rope sofa size that extends over the entire styrene-Aorylonitrilaatrix from 1 to about 25 microns, preferably from 1 to 10

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Microns (also known as the "large ** particle size") mixed with a polymeric material obtained by various processes, including one Latex, that is to say, obtained by emulsion polymerization Polybutadiene substrate styrene and aorylonltrile grafted on A polymer based on SBR, polyisoprene or natural rubber can also be used as the latex. Sas used as the second component polymer Material has a chewy-like substrate old "small" particle size, i.e. the rubbery ones Most of the particles have a particle size of 0.005 to 1 micron, preferably from 0.05 to 0.3 micron.

It is known that in the latex material used according to a preferred embodiment, hereinafter referred to as ABS resin based on latex, the particle size of the chewy ingredient can be controlled by Changing the type and amount of emulsifier, stirring, and rate of final conversion and polymerization. the Particle size can be in latex or emulsion polymerizations can be controlled in such a way that, depending on the polymerization conditions, either small or large particle sizes are obtained will.

Advantageous servant chewing owls can, for example, naoh dem following process can be produced * First, in a reactionary holds a reaction mixture made from an alkali metal fatty acid, for example kallua oleate and Kalinapersttlfat as a catalyst, a mercaptan for control the molecular weight and a small amount of a base, for example potassium hydroxide, optionally in combination with a buffer compound (for example sodium phosphate) to keep the pH at a level that allows the formation of free Fatty acid is avoided, as is finally the case with butadiene and water. The reaction mixture of the specified type is as a "hot" Polyaerisatlonsrezept referred to as the difference from a so-called "cold" recipe where another

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Catalyst system, which is usually a peroxide activator, is used. The "hot ^8" polymerization is then carried out for about ten to twenty hours at about 50 ° C. with stirring, a latex being obtained in which 60 to 90% or more of the butadienes are converted into kauteohuk Unreacted butadiene can be removed by a wide variety of customary known processes by so-called flash distillation or by stripping.

In the "hot" polymerization reaction of the type indicated, soap can also be added during or after the polymerization in order to further stabilize the rubber parts formed. In the reaction mixture given, soaps such as dodecylamine hydrochloride can be used, in which case the pH of the mixture is kept below 7 by using water-soluble acids. Furthermore, non-ionic soaps can also be used in any pH range. As a rule, acrylonitrile and styrene monomers are added to the ώ-. ·, ^ Th latex to form an ABS resin.

Reben the specified polybutadiene latex also has the use of SBR, Hitrll and natural rubber as proven useful. The usable SBR (a styrene-butadiene iso polymer) can be obtained in latex form and have a styrene content of 5 to 40 percent by weight. Of the Usable nitrile rubber has an aorylonitrile content from 10 to 50 percent by weight.

Raise the manufacture of the ABS Maasen according to the invention Usable acrylonitrile and styrene monomers have also been found to be useful, for example Methaorylonitrile in combination with styrene or alpha-methylstyrene, also with vinyl toluene and substituted styrenes

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or mixtures of the specified compounds, i.e. Gemlaohe from vinyl cyanide and aromatic vinyl compounds.

To carry out the polymerization, butadiene is generally emulsified in an aqueous mixture containing suitable soaps and an initiator *, for example potassium or ammonium sulfate, is used. The polymerization can be carried out up to a solids content of 30 to 65, if necessary also lower or higher values, and as a rule, as already mentioned, the particle size of the chewing material particles can be adjusted by varying the type and amount of emulsifier, the stirring and the Final conversion and polymerization rates are controlled. In the manner indicated, either chewing material particles having a particle size of predominantly about 0.005 to 0.25 microns or with an IEe ¹ l size of about 0.1 to 0.8 microns can be obtained.

The polymeric compositions according to the invention have their Completion of a total amount of rubber is lower than the chew content that is required for after Hardened products obtained directly from the latex process in is generally considered sufficient. So include an example the most diverse, by mixing the specified Both components obtained polymeric compositions according to the invention usually 10 to 15 # rubber, whereas comparable known polymers obtained directly from latex Masses must contain at least $ 15 to $ 25 rubber. Of the Chewable content in the finished polymeric compositions of the invention can be $ 5 to $ 25, preferably $ 10 to $ 25 be.

The emulsion polymerization processes of the type indicated therefore usually lead eu ABS products with an in the AorylonitrII-butadiene matrix disperse chewy chewable Basic structure, the rubber particles of which are predominantly rope have a partial height which lies in the range »the the resin your use in the polymer masses after the er · »

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Fladung makes suitable, nSmlloh in the range of 0.05 to 0.3 Micron·

The polyhutadiene latices produced according to the specified process may have about 30 to 60Ji or more solid particles of the desired particle size.

In order to produce the ABS hare with a large particle size of the chewy-like component dispersed in the aorylon / tril-styrene matrix by means of a bloeksuepenslon process, the chewing-material-like component can be a diene hydrocarbon, for example linear polybutadiene or linear SBR, the initial process step being a polypropylene step using prepolymerization with stirring. To carry out this prepolymerization step, the polymerization is initiated after dissolving the rubber in the monomers and then continued until a phase inversion occurs.After the phase inversion occurs, stirring is continued until the particle size of the rubber is about 1 to 25 microns, preferably 1 to 10 microns If »Danaoh the Polymerisatlonsgemlsoh or the prepolymer either transferred into an aqueous suspension or left in a resting zone, the first-mentioned process step is prevented to ABS pearl material with 5 to 25 £» preferably 5 to 1596 rubber in the form of individual particles dispersed over the entire harem matrix are obtained. In the suspension stage, peroxide initiators can be used and the prepolymerization can be carried out either thermally or in the presence of one or more peroxides.

It is a preventive embodiment of the invention used as latex-based polybutadiene in which Butadiene represents the polymer-producing monomer and in which the solids in a total concentration of 30 to with the particle size of the polybutadiene ranging from 0.05 to 0.3 microns.

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Styrene can be used in the manufacture of polybutylene latex and the aorylonitrile in which catfish are polymerized »that 5 to 35 weight percent aorylonitrile, added to the existing styrene plus polybutadiene, and 30 to 80 weight percent Styrene, based on the weight of the polybutadienes present and acrylonitrile, which can be added Polybutadiene obtained.

To carry out the polymerization, the polybutadiene latex, which, for example, has a test substance content of τοπ 30 ^, is baked into a reaction vessel, whereupon 25 parts by weight of aorylonitrile and 45 parts of styrene are added, as are various customary known polymerization initiators and chain transfer agents. The polymerization is carried out for about six hours at a temperature of about 65 to 85 ° 0, after which the mixture obtained is coagulated with dilute saline solution and sulfuric acid. Optionally, the latex can also be pre-grafted with aorylonitrile-styrene, whereby a pre-grafted latex with about 30% rubber and 20 pounds of styrene-aorylonitrile is obtained.

To carry out such a peat grafting process, 8u a »latex, see example a la commercially available latex old about 44 * solid content (polybutadiene rubber) and AU soap content, the rubber has a particle size of 0.05 to 0.5 microns, as much styrene Aorylonitrile is added to a content of styrene aorylonitrile of 72128, which gives a mass containing about 80% of rubber and 20% of styrene-aerylonitrile grafted onto it by grafting. To carry out the stated experience, aaaoniu aereulphate is used as the initiator and tertiary Sodeoylaarcaptan is used as the chain transfer agent. The polymerization should take place at 66 ° 0 within swel hours

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proceed with stirring »with 50 # of the styrene-aoryionitrile Half an hour at the beginning and the remaining 506 Added after reaching the intended temperature of 66 ° C will. The Qeeamt solids content in the poly. merization is 40j6 and the pre-grafted latex obtained of the specified type is then in a suspension polymerisation system with a styrene-aorylonitrile monomer mixture, the styrene-aorylonitrile ratio of which is 72/28, applied »being the suspension polymerization system during the polymerization with small amounts of mineral oil and Additives »for example ethylenediaminetetraacetic acid (ΒΟΙΑ) is moved. In the suspension stage, the ratio of water used to polymer is 3 * 1 and as a suspending agent is Hydrozyäthyloelluloee in amounts from 0.2 to £ 0.6 based on the total amount of water used. KDlA is used in amounts of 0.4 #, based on the existing Styrene, and the chain transfer agents are used in amounts of 0.2 to 2 percent by weight, also based on handenee styrene is used.

In the specified suspension stage of muddled EUR "/ ■ -> - position of ABS resins are used as initiators t-bui; ^ *» * - bensoat and di-t-butyl peroxide used in compliance with the following PolymerisatlonstemperaturzylcluB!

1.5 hours at 71 to 104 ° 0 for 2.5 hours at 104 ⁰ C * 1 5 hours at 104 to 13O ⁰ G for 0.5 hours at 130 ° C

For the production of ABS harnesses with large tube sizes, as already mentioned, in the bloosuspension process as Kautsohuk is a diene hydrocarbon of the specified Type are used, wherein the first process stage is a graft copolymerization, in which a stirring Prepolymerization is carried out · In this prepolymerization, as already mentioned, after the rubber has been blown

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The polymerization is initiated in the monomers and then continued until a phase inversion has taken place, whereupon stirring is continued until the particle size of the precipitated chewing gum particles is so much reduced that the predominant portion of chewing gum particles is a part size of 1 to about 25 Mitron, preferably 1 to 10 microns, particularly advantageously 0.8 to 4 microns. As already mentioned, the polymerization mixture or the prepolymer is either transferred to an aqueous suspension or kept in a quiescent zone, the transfer to an aqueous suspension being preferred in order to remove ABS particles with a chewing content of 5 to 25%. preferably obtained from 5 to 15 # »bu. A preferred polymerization process of the type indicated is described, for example, in British patent specification 1,020,176, which is why particular reference is made to the specified patent specification in the context of the present invention. The polybutadiene is preferably one with a predominant ois-1,4-content of sum example 30 to 98 and a Mooney viscosity of 30 to 120, preferably from 35 to 90 (ML4 at 44 ⁰ O (112 °?)) used·

For the production of the polymeric composition according to the invention the ABS powder and pearls with suitable stabilizers, Lubricants and other additives combined * for intimate mixing of the various components in mixing drums dry blended and melt blended by extrusion in a ventilated single-ear screw extruder. That dry mixing of the components can be effected, for example, in a Hensohel-type mixer and the subsequent mixing by melting can be in a continuously operating Banbury-Tarrell mixer or, preferably, though not necessarily in a twin-eared owl rudder take place.

The following examples are intended to explain the invention in more detail

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The properties of the polymers described in the examples Masses were determined using the following test methods, test conditions, and units

properties Sohselsflufi

Izod *

Kerbstohlst

sänigiceit

Tensile strength measurement

Tensile strength reagent

strain

Rockwell '
R hardness

Hit bending temperature no

Dvuok expansion
Measurement value and
fail

ASPt method JM236-62f

D-256

Test rod divided, with the blind end values and not communicates the final values

units

conditions

become part of it

D-638-64I

D-630-64T D-735-62

D-643-56 D-790-66

Oraaaa / 10 Hin. 230 ° 0/500 ° Graaa weight

0.3048 m. Spritsgudprttf-0.4536 leg / linge of the Anenafl · 2.54 on notch 1/2 "ml 1/8» times (rt.Lb/In.) 5 "terform

ACCORDING TO ASTM METHOD

D-647

Icg / oa ² (p8i)

Tensile strength testlings made recovered

ASTM method D-638

To carry out the procedure described in Example 1 the reused ABS-Hars “it was big part size after of the procedure outlined above, which is described in the British Patent 1,020,176. In the examples, the weight data refer to the chewable component used, the mineral oil, de * Trienonylphenylphosphite, des t-Dodeoxomercaptane and de Initiator to 100 parts by weight of the chemical. The weight information of the used high-temperature catalyst and possibly susatslioh of the used mercaptans related to each other 100 Oewloht parts of the Torhandenen prepolymer. The weights of the hydroxyethyl cellulose used in the aqueous

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Suspenaionsbad insist on the custom of the existing Waters

In the examples given in Table I, linear polybutadienes with a medium and high ois content were also used applies that after the »ur production of graft isohpolymers The method used has been obtained and good physical properties in terms of impact resistance have, as seen in the XBod-notch bracing mounts »· oranges, which on molded test specimens genie the ASTM-Teet method D-256 results. It needs to be highlighted The fact that test specimens deformed by the Spritsgufl method usually have higher notch base counting values are expressed in 0.3048 m. 0.4536 kg / 2.54 om notch.

example 1

The components and process requirements listed in Table I below were used to manufacture polymeric cash registers used. The physical properties of the polymeric compositions obtained were determined. The results obtained are also listed in Table I.

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- 15 B. 1937298 £ 75 I. 25th Components Table Z 75 Weight parts 75 - 60 25th S. 25th 8th* 25th Pre-Olympic degree A. - - - 15th Styrene 4 * # 75 0 ** 0.1 8th" Aorylonitrile 75 0.1 25th 0.1 110 _ t * -methyl styrene 25th 0.1 0.1 30.0 0.1 Polybutadiene « 75-85 8th* 75-85 120 Benaoyl peroxide 4 * 31.0 0.1 43.0 33.5 t-dodeoylmeroaptan 0.1 0.1 Polymerization at ⁰ C 0.1 75-85 0.2 total solids 75-85 33.5 100 salary, γο 31.0 0.2 0.2 165 0.2 Sueveneion level 100 100 0.25 100 Addition of catalyst 3 133 100 - 165 t-butyl perbenzoate 0.33 0.2 0.25 0.25 Prepolymer 0.2 - 100 0.1 - water 100 100 Hydroxyethyloellulose 133 0.25 t-dodeoylmeroaptan 0.33 0.1 Physical own societies

1.6 2.5 0.03 0.4

3.7 4.2 2.4 0.11 0.1 1.4 95

Iaod fillet count - 1.0 Ice it (2) (compression molded)

Soha elefluS (3) at 0.1 190OC (grams / 10 minutes)

Bending temperature ° G (18.5 lrg / cm ^z 264 psi)

A) Thermal prepolymerization 2) ASTM D-256-56
; 3) ASTM IM233-67T

* linear polybutadiene with 35 $ 18-1.4 oil content (Mooney viscosity

* ♦ linear polybutadiene with 95 cis-1,4-oil content (Hooney viscous

sity about 50)

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It was agreed that during the suspension stage the specified Polymerization no agglomeration occurred. The particles obtained were placed in a simple vacuum oven 65 ° 0 completely dried before they were used to prepare the mixtures according to the invention. The received ABS polymers, near completion, exhibited carbon fiber particles with an average particle size of 1 to 4 microns on.

Example 2

This example illustrates one convenient process for making latex-based ABS polymers.

A small particle size polybutadiene (the majority of the particles had a particle size of 0.05 to 0.3 microns) was filtered and then placed in a reaction vessel equipped with a stirring, nitrogen inlet, ventilation, heating and cooling device as well as temperature and pressure measuring devices. The stirrer was then put into operation at low rotational speeds (about 50 rpm) in order to keep foaming as low as possible. A measured amount of demineralized water and an aqueous initiator solution (ammonium persulfate) were then introduced into the reaction vessel. A monomer mixture consisting of styrene and aorylonltrile in a ratio of 72/28 and a modifier (t-dodeoyl mercaptan) were weighed, mixed and flushed with nitrogen . According to a process feature of the process used, half of the required amount of monomer was fed into the reactor, whereupon the reaction vessel was closed and the contents of the vessel were flushed with nitrogen and finally a nitrogen pressure of 0.35 atmospheres was maintained in the vessel. The reaction vessel was then heated to the polymerization ^{temperature of about 66 °} C. and left at this temperature for six hours.

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Measured the special process feature of the specified process, the reaction mixture was continuously added within 1 ₍ 5 hours with the second half of the monomer mixture a. Thereafter, the polymerization temperature was increased for about one hour, including the heating time, to about 77 ^° C. The polymerization was continued for this time until the desired solids content of about $ 40 was reached. The feed mass for carrying out the specified process had the following composition:

Styrene about 18.1 kg Aerylonitrile about 7t3 kg Latex (sth & 40 / MHoUtUjhuk) about 227 to 240 kg

Ammonia urea sulfate about 130g ($ 0.5 based on
Styrene-acrylonitrile)

t-dodocylraercaptan about 800 g (3.2% based on styrene-acrylonitrile)

Demineralized water about 79.4 feg

In the pre-grafted latex obtained, the ratio was from rubber to styrene-acrylonitrile 80:20 $ and the obtained Polymer can be used for the production of ABS-Maseen with any percentage rubber content can be used.

The pre-grafted latex prepared in the manner indicated was used to make a concentrate containing 40 pounds of rubber as well used in further experiments in a simple manner for the production of polymeric hats with rubber contents of 5 to 80 pounds. To prepare the concentrate, a stirrer, nitrogen supply, aeration device, heating and Cooling device as well as temperature and pressure measuring devices Reaction vessel (378.5 l) demineralized water introduced in a measured amount with stirring at 170 rpm. The amount of water used was determined by the desired Ratio of the total amount of water to the total amount of polymer, which in the present Pail was 3.0 / 1.0. then

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a suspending agent, for example Hydroxya / thyloellulose in an amount of up to 0.365t, based on the total water present, was sieved into the Realrtionagefäß. An aqueous solution of the trisodium salt of ethylenediaminetetraacetic acid (about 0.2 pounds, based on the total polymer) was then added to the reaction vessel (0.20? ^ Based on the entire polymer), mineral oil as lubricant C0.5 ^, based on the entire polymer) and antioxidants sun example trisnonylphenylphOBphite and 2,6-di-tertiary-bntyl-4-ynethylphenol (known under the Designation "Polygar £ HR", 0.2 #, based on the total polymer, and under the designation "Ionol", 0.05%, based on the total monomer), weighed, mixed and flushed with nitrogen in a storage vessel. The reactor was then sealed, purged with nitrogen and heated to a transition temperature of 7O ⁰ C. Then, the _r Monomerengemlsoh added followed by InittatorltSsung (t-Butylperpenzoat, 0.15 ^ # at; sgen dae on total polymer, as well as di-t-butyl peroxide, 01 ojt, based on the geemmta polymer ") was added with styrene as the solvent . The initiator solution was given within 13 minutes in order to ensure complete mixing. It showed that the initiator solution given can also be present as a component of the monomer mixture and can be added with it. The pre-grafted latex was then added over the course of 1/2 hour. The polymer leation cycle was then started. The reactor contents were then cooled and dehydrated for better handling. The process product was obtained in the form of willow spherical Perlon.

The feed for making the specified concentrate with 40Jt I & utsohuk content showed the following guwwmimeetiiing:

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Water "Batrosol HR" (liydroxyäthyloelluloße)

1937298 178 5 lrg 882 S. 720 ml 28.3 fcg 11.1 kg 163 2 β 408 e 163 €

Styrene

Aerylonitrile

t-Bodecylme ^ captan

"PrlÄOl 355" (mineral oil) "Polygard HIt"

■ lonol "40.8 g

The polymer. lonssyklue scam:

1.5 hours a at 71 to 104 ⁰ O

2.5 hours at 104 ^° C

1.5 hours at 104 to 13o ⁰ G

0.5 Stnnflen at 130 ⁰ C

Example 3

This example shows the "Manufacture!"!;. ^ Y "a palpsiere ^ Hassen after fler Ecfindtmg by mixing a Bloel £ suspensl <ms ~ ABS polyaeren of the specified type with a suspension ABS on latex base of the specified type. Hit These ootnlsohen the production of extruded webs with the following properties was sought: Melt flow of about 1. Izoa inheritance toughness, expressed in 0.3048 m. 0.4536 kg / 2.54 cm notch, of about 8 to 3.5 _t tensile strength values of 21 , 3 (43 psi) and ^{above and hardness values of the n} R ⁿ scale of 90 and higher.

For the production of the ABS polyamide on a latex base, a pre-grafted polybutadiene latex used and styrene / Aorylenltrile polymerized in suspension in a ratio of 72/28 « Older pre-grafted latex was prepared according to the method described in Example 2 Process described in a simple manner by the fact that a folybatadiene latex from a small particle size (as Kauteolrak) »it styrene / aorylonitrile in the ratio τοη 72/28

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was polymerized in emulsion, finally an au 8055 made of rubber and $ 20 styrene-aorylonitrile Graft polymeriBate was obtained. The polymerization was carried out according to the procedure given above. The received pre-grafted latex was then transformed into a second reaction » Vessel introduced, whereupon this further styrene and aorylonitrile in a ratio of 72/28 augeftthrt and hydroxyethyl cellulose as a suspending agent and t-butyl perbenaate as an initiator was used. The polymerization was carried out according to the procedure described in Example 2, using an ABS polymer with a rubber content of 18 # was obtained «The composition of the mixtures obtained and their physical properties are listed in Table II below.

table II

Properties of polymer wet from two different ABS polymers with different particle sizes of the rubber particles

_{Blook suspension -} 100 75 j> 0 2 £ O - ABS *

ABS based on Ietex * »0_ 21 52 31 122 Sohmel flow g / 10 min 0.6 1.0 2.1 2.9 0.0 Tensile strength 310.5 339.4 371.7 367.5 367.5 value kg / em ² (psi) (4420) (4830) 6280) (5220) (5220) tensile strength 357.6 353.4 356.2 319.0 304.9 ^ say kg / cm ² (psi) (5080) (5020) ( 5060) (4540) (4340)

Elongation f> 57.2 56.8 62.0 23.5 9.5 Iitod-KerbBOhlagi-capable
in O, 3O43kO, 4536
kg / 2.54 cm notch 4.3 8.3 8.9 8.0 5.1 Rockwell R hardness 87 87 88 88 91 Heat deformation ⁰ C 97.3 - 97.3 98.5 - Pall notch impact resistant
speed of the railway; bolt Mr.
Radius in inches 30th 43 58 55 Notched Izod impact strength
the train ü'Jj / ID 5.3 /
4.7 6.1 /
5.8

* contains 11 # linear polybutadiene (see example 1) ** contains 18 # rubber.

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The results shown in Table II show the pronounced Synergistic pool effect of the obtained polymers Measures close to the invention in relation to the notched Izod impact strength.

Example 4

This example shows the manufacture of conduit-suitable polymeric hats by bonding two together different ABS ears with different particle sizes the chewing material using similar ABS · « Polymers such as those described in Example 3 for carrying out the procedure Procedure were used.

Although it is known that carbon black is the main ingredient in ABS polvaeren degraded, it turned out that by mixing in the same high quality »for the production of pipes suitable resins can be produced. It was found that natural mixtures of blook suspension polymers with ABS resins latex-based isod notched invert toughness values of 8.0 to 8.9. Decreased by ingesting $ 0.8 RuB the notch bottom viscosity is about 6 to 7, however, it is nooh internally a matter of higher hoards than they are considered appropriate for pipelines. The results obtained by mixing with 3 # carbon black concentrate are listed in Table III below.

909885/1630

8AD ORIGINAL

co ο CD 00 00 cn

co co

Table III
Polymer · masses made of Blook-SnapenalonB-ABS-Harg with ABS-Harg on Latexbaaia

Bloclc-SuflpeneionB-ABS * latexgeaiaoh ABS * "Melt flow g / 10 min. At 23O ⁰ O Iz! Od" -Carbole strength in _Λ 0.304 · ^ ra. 04536 kg / 2.54 cm; 1.3 ° test tab

Tensile strength increased kg / om ² (pel) Tensile strength predictions kg / o »2 (Del) Elongation ji hardness« R · Hiteed formation temperature ⁰ C iall notch flexibility 3810/4.) Pipeline 0.3048 m - 0.4536 kg 1 "Bolsen

“Legs

100 (Hatural) 75 50

(Hatural) 100 25 50

0.6 0.8 0.9 1.0

4.5 / 5.0 / 5.9 6.9

50 50 75 67 45 45 50 50 25th 33 55 55 1.1 0.9 0.9 1.0 0.9 0.8 6.7 6.1 5.3 5.8 6.8 7 ₉ 3

5.4

309.0 366.0 349.2 371.0 366.8 356.9 335.8 364.0 359.0 366.8 (4400) (5200) (4970) (5270) (5210) (5070) (4780) (5170) (4860) (5210)

302.0 335.1 333.0 328.1 345.0 340.1 361.1 341.5 337.0 (4300) (4770) (4740) (4670) (4900) (4840) (5130) (4860) (4800)

36.9 30.5 34.4 37.5 43.6 59.3 48.6 50.3 97 92 97 95 94 98 96 97 95.3-95.2 95

9.5
91

120

90

110

omitted 11? 6 "diene 55" (linear polybutadiene - see example 1) contains 18 * polybutadiene caustic (see example 2)

- 22 -

The results outweigh the synergistic effects in the ger obtained; sjohen, being in solohea. polymer masses, whose Is ^ -Rär'aschlagaöhigkeitswerte are reduced by the incorporation of carbon black} nooh will always get such high KerbaehlagABigkeitswert that they exceed those of known polymer masses more or even ^{better, and furthermore the T} ^ oS-insole toughness are better than all those of the internal components. The found? All-Kerbsofe! Agz & higIceita value of 120, given in 0.3043 m. 0.4536 kg and measured on a pipe of 3j inches, is more than twice the value considered appropriate for a 4-inch pipe, the 5 ^ --- jnnuicM ^

example $

This example shows the production of a polymeric material suitable for extrusion in glossy webs using a mixture of 505C ordinary blook-3uepensions ABS with 50% ABS based on latex using a white pigment -Prtiflingon results obtained compared with those of commercially available JLBS polymers «rare · The results obtained are in the following T & bell © I? aw'gaf ^? thrt.

t commercial product according to the invention Ρ ^ο1 Τ » ^β * ^β Η * ⁸⁸ ·

Block suspension ABS * 50 ABS on latex play ** 50 SohmelsfliiB g / 10 Hin. 2.3 3.9 Izoa notch tough Tceit 4.9 4.7

in 0.3043 m. 0.4536 kg / 2.54 cm

Tensile strength measured value kg / cm ² 414 « G (5890) AOi, 2 (5700)

(psl)

L kg / O!

(psi)

Tensile strength failure kg / cm ² 335.1 (4770) 33? _f 2 (4800)

9.0 19.2

Hardness 93 103

♦ contains 91 * "diene

** contains I85S rubber

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8AD ORIGINAL

In addition, preliminary sheet properties (Izod kerbsohlagsähkeit and dart value) on 2794/1 thick sheets obtained by extruding the obtained polymeric Hassen certainly. The results obtained are shown below:

Notched Izod impact strength in 0.3048 m. 0.4536 kg / 2.54 cm notch

Room temperature MD 3 * 3

TD 2,

Drop bolt value in 0.3048 m - 0.4536 kg (£ "R-6 * oil)

Room temperature 36

* shows the joint fracture in the Izodteat

Example 6

This example shows the production of foranlings for east river suitable polymeric hating by blending common block suspension ABS polymers with ABS polymers latex base. The results obtained are in the following tables Y and YI listed.

909865/1630

Blook-Ststspensions-ABS ⁴ ABS on latez-based ABS *** Sohnel & fluS g / 10 Hin.

Isod notch bottom impact strength in 0.3042 a * 0.4536 kg / 2 ₍ tensile strength measured value kg / o "* ² (p _Bi )

Eyes ability to react kg / oa ² (pel)

Elongation jt

Heard "R"
HDT

* contains 9 * "Diene 55" polybutadiene. ** contains 18) 1 rubber.

- 25 - 7th 100 1937298 Tabel 6.9 4.1 Bigenso
ten of the poly
meren masses 100 386.5 _BC
(5490) 65 328.8
(4580) 35 7.6 10.1 8.8 1.5
5 4 οι » 96 4.7 484.6
(6890) - 457.9
(6510) 399.8
(5680) 387.9 _BC
(5510) 8.8 14.0 110 106 - 93.0

Table 71

properties of the flooring materials

Blook suspension ABS * ABS on latex basls * ♦ SoheelBflufl g / 10 Hin.

XflOd notch pad & hlgkelt DE in 0.3048 a. 0.4536 kg / 2.54 on

Eye candy kg / om2 (psi)

failure failure on2 (pei)

100

Shepherd
HDT

* as in table 7. * ♦ wi · in table 7.

100 4.9 7.6 1.8 1.5 372.4 484.6 _%
(6890) (5290) 399.8
(5680) 314.0
(4470) 8.8 10.4 110 96

Properties of the polymeric hates

65
35
6.4
5.4

34.7 ^ 6180)

365.4 _% (5190)

9.6
106

909085/1630

6AD LOCATION

The results listed in Tables 7 and TI »own the surprising eynergy properties in Besing on Iaod-Kerbeohlageahigkeit the polymer masses obtained according to the invention.

Example 7

This example shows the production of polymer cash registers duroh Termieohen a blook suepenaiona ABS polymer with Xautsohukpartikdln an average particle size ron 1 to 4 microns with a commercially available ABS polyamide latex base with BJautsohnkpartikel an average Partial height from less than 1 micron. The results obtained are listed in the following table TII.

909885/1630

BATH ORIGINAL

Table TII

100 * himdela-I SECTION

75 * hÄOdtüI 5OJt haaitXe- 25 * haadel · - 100 * Block · Ubliohee ABS «fcUofct« ASS üblioh * · ASS _κ Sucp.ABS Block-Sue. (2 $) Blook ~ St «p, (50) Bloek-Sejp« (7i3)

co O (O OO OO cn

σ> ca ο

g / 10 mn.

(230 * 0/5000 g)

Iasod-Eerbeohlagzähigkelt in 0.3048 m. 0.4536 kg / 2.54 approx. Notch 1/8 · Test β tab, room temperature

Zttgf © quality measurement value kg / oa? (pm)

0.1 0.2

0.3

0.6

0.9

Service agencies kg / cnr (psi)

Tensile elongation at break Zttgaoaul kg / cm ² (pel)

7.2h

347.8 (4950)

309, β (4410)

41.2

19700 (2.8) 7.9h

375, 2
(5530)

314.0
(4470)

31.1

17600 (2.5)

7.6h

338.7,
(4820)

27.4
19700 (2.8)

7.0

4th
(

03.3 _%

5730)

(5110)
34.6
20400 (2.9)

4.5

387.0 (5500)

373.7 (5.80)

36.9

21100

Hardness (Rockwell "R" -

Slcftla) 84.6

Hitssed eformierungateape-

temperature ⁰ C 96.5

84.3

99.5

90
98.3

96
99.0

100

93.8

KJ CO OO

The results show "that" the dimensions according to the invention also using common commercially available ABS resins based on latex polybutadiene or SBR elastomers are known that with the help of the Blookauspenaionspolyjaerization ABS resins in a very economical way Wise divisible aind »whereas latex processes are more expensive.

909885/1630

JAWOlXG QAB SAD ORlGiHAL

Example 3

Beast's example tends to make one for foralinge old High level of flow suitable polymeric cash register duroh Veraisohen of a blook-Suflpenfli <mfl-AB8-Hs.r «« 8 «it a bans« of latexbaais. The results obtained are shown in the following. belle TOI listed.

Blook-Suepenelone-ABS, % -Iate *. * **

SJabeil · YfII

ICG

Sohaelsflue g / 10 Hin * 4s9 18.0 12.2 10 ₉ 7 Xsod notch sole layer i
0 _# 3048 a «0.4536% g / 2, f4 ο S 1.3
M. 1.0 3.5 1Ö4 SogfeatigkeitesieS ^ rt
kg / om {psi) ψ2Λ 441.O ₁₁
(5290) <6270) • 418.8
(5950) 97 2ng £ setigk # it8Y63? $ Agen
kg / onK (pei) 535 * 1 ^ 39Ö, 7 _V 347.8 _t
(5550) (4950) Behntmg? Ί 10 _s 4 10.7 Harder* 96 111 HitsedeforBiertmge «
tea temperature ⁰ C «

♦ contains 89S "diene ♦♦ contains 18y £

Be m & emphasized wise, &«& ee blen @ s? difficult i ^ enn nioht nn »auglläh VKSt Poljaere a @ K high SeluselsfluS as well as a high Xssod-Serbsohlageability enfspz ^ ehend de.», given polymer wet after the invention Merssustellem »

Example 9

Is was "in concentrated A3S" £ oXyüer _for that heidt a polymer with a "Ka-itaohu & gebtli rom. 44 ^ _for the na @ hd @ si in Example 2 1>" sohriebeiien Terfahr # n produced before "ar," with a block -Stispensiona ABS bollard with a Sautsehukge 'stop tone 11 ^, because @ near the one described in Example 1

909885 / 1S3Ö

8AD ORIGINAL

drive has been made "ar" made. You received Results are shown in Table IX below.

Table IX Bleck-Suspension-ABS * 90 (20.4 Irg)

Latex ABS % 10 (2.27 kg)

Son's flow rate g / 10 min. 1.0 0.9

Isod-Notch-Bänigke it 3, 6 ^h 5.0 in 0.3048 a. 0.4536 kg / 2.54 om

strength measurement value kg / om ² (pel) 349.2 (4970) 345.0 (4900)

eye strength reagent kg / o » ² (psi) 371.2 (5280) 359.0 <5100)

. Elongation % 70

"Htote" R 91

Example 10

A polymeric mass was produced using the Zet «x-ABS-Keasentrat® described in Example 9, but which in this case was a bloom suspension ABS polymer with a content of 9% lisearea ^ olybutadienkaittsohnk
"Bee 35" was veraiaoht. The results obtained are shown in Table Z below.

Table X

BlQok-Svspenelons-ABS t 100 90 latex ABS 10

SohjMlsflue 6.2 3 * 4

! ■ od bottom load capacity 2.1 7.6 ^h

Tensile strength measurement value kg / oa ² (psi) 5O2.5 (7150) 427 * 6 (6080)

mounting bracket kg / cxa ² (psi) 411.1 (5840) 392.8 (5580)

Elongation + 15.2 43.6

Shepherd 109 101

909885/1 630

SAO ORiGINAL

The results obtained in the examples clearly indicate the considerable parts of the gate achieved according to the invention.

909885/1630

. ^ timiö OMi BAD OfilöWAL

Claims (7)

Claims 1. Polysere mass of old high kerbsohlatfEftigkeit, marked by a content of a Qemisoh aue (a) one Graft isohpolymer leate made from a rubbery diene and a weslsoh made of a vinyloyanide and an aromatic one Ylnyl hydrocarbon, its chewy-gum-like Dlenkosponente bus predominantly from particles with particle size from 1 to about 25 microns; and (b) a chewed eohukartite grafted diene Yinyloyanid and aromatic Ylnylkohlenwaeseretoff, des- sen chewy-stick-like diene components bus predominantly of particles with a particle size of 0.005 to about 1 micron. 2. Polymer Hasse with a higher notched Izod layer all of those of components (a) or (b), characterized by a content of a mixture consisting of (a) BU 25 to 75 percent by weight of a plug! Sohpolyserisat aue a chewing diene as well as aorylonitrile and styrene, the chewing diene component of which consists predominantly of particles with a particle size of 1 to about 10 microns, and (b) au 25 to 75. wiohtsprozent from a Pfropfsileohpolymerleat from a diene * kautsohukartigen on latezbasls and Aorylonitril and styrene whose kautacbukartlge Dlenkosponente over · predominantly of particles sit a particle size of 0.05 to less than about 1 micron is made · 3 · Polysere mass on ABS base with a higher laod notch resistance than that of the coaponemts (a) or 00 »characterized by« a content of an Oeslsoh consisting of (a) 25 to 75 percent by weight of a graft polymer cracked from a chewing material-like polybutadiene as well as aorylonitrile and styrene, the polybutadiene component of which is predominantly composed of particles 909885/163 Ö The liver particle size is about 1 to 10 microns and is present in an amount of 5 to about 25 percent by weight, depending on the grafted polymer, and (b) 75 to 25 percent by weight of a graft polyolefin grafted onto an emulsion-polymerized butadiene polymer grafted on Aorylonitril and styrene "whose Butadienpolynerkomponente sun predominant cable consists of particles having a Teilohengröfle Q of about ₉ 05 to 1 micron and in the Pfropfmiochpolymerisat in an amount of about 10 to 60 weight percent, beisogen on Pfropfmisohpolyraerisat that is present. 4 · polymeric mass according to claim 3 »characterized that the Dienkautochuk is component (a) from one linear polybutadiene. 5 · Polymeric mass according to claim 3 »thereby gokennseiohne-c, dad the rubber-like polybutadiene of component ia) from a linear polybutadiene with an ois-1,4-content Clay at least 30 and up to about 98 and a quantity of 5 to 15 sprouts by weight, based on the Graft copolymer is present, and that the butadiene polymer of component (b) in an amount of 20 to 45 CtoviohteproBent, drawn on the graft polymer » is present. 6. Polymeric mass naoh claim 3 »known by this, dad the rubber-like material of the two components (a) and (b) in a fraction of 10 to 25 percent by weight is present. 7. Polymeric composition according to claim 3, characterized in that the chewing material of the two components (a) and (b) in a total concentration of 10 to 20 percent is present. 909885/1630 ORiOINAL