IL23759A - Preparation of high impact copolymers - Google Patents

Description

The preparation of Impact copolymera EDISON 22833 This invention relates to the preparation of impact copolymers from vinyl monomers by polymerizing these monomers in which rubber is More especially the invention relates to a process for the preparation of ne and acrylonitrile type copolymers having good acrylonitrile and butadiene copolymers can be prepared by mechanical mixing of a resinuous component consisting of a and of a rub ber component consistin of a synthetic Such a method of preparation has the that it requires a very thorough mechanical mixing in order to obtain a homogeneous distribution of the resin ous and rubber Also products prepared this way do not have any particularly good properties as regards resistance to heat and and the products are difficult to Further only some types of synthetic are suitable for use in the preparation of these copolymers can also be prepared by graft polymerization of an acrylonitrile and styrene mixture onto a latex prepared from a synthetic or tural Such a even if compared to the cal mixing has appreciable because the obtained product has better properties in relation to its polymer the method is not economical since it involves high costs in the drying of the as it is an emulsion polymerization the polymerization tives can only be eliminated with difficulty from the mer which is formed and this may in degradation of the prepared according to this the elastic properties of the natural or synthetic ber can not be completely Lastly it is also noted that considerable difficulties may ar in the paration of the copolymer from the emulsion and in the drying of the eventually separated According to the invention there is provided a process for the preparation of high impact copolymers prising polymerizing a monomers mixture of a styrene type monomer arid an acrylonitrile type monomer in which has been dissolved a synthetic or natural rubber until the conversion degree of the monomers to copolymer is from 10 to by and then completing the polymerization of the mixtu re in aqueous Polymers prepared in accordance with the invention have good impact properties even at low have a good surface appearance and high resistance to heat and These polymers may be used either on their own or in admixture with other thermoplastic materials so as to give moulded articles having good mechanical properties even at low temperatures surface It will be seen that a process in accordance with the invention is carried out in two The initial merization of the monomers mixture is effected either in the presence of water or in Before the second polymerization a suspension system is added and the polymerization is completed in an aqueous suspension and the conversion degree of the monomers to copolymer reaches a value of to 99 Then the polymerized mixture can be steam distilled to remove unreacted monomers and other The autoclave in which the po lymerization is effected may then be cooled and discharged off and the copolymer is left in the form of which can be washed and dried with hot The dried beads may then be extruded under vacuum to eliminate any traces of remaining volatile impu rities and thereafter the obtained product is ready to be either as it is or mixed with other thermoplastic pro ducts in order to obtain moulded bodies having desirable such as a high resistance to heat and impact even at low a high resistance to hydrocarbon vents and with good light The monomer mixture in which the synthetic or tural rubber is dissolved consists generally of a styrene type monomer and an acryloni trile type The ne type monomer is preferably one or more of styrene or a styrene and but alkylstyrenes such as halo gen styrenes such as mono and dichlorostyrene may be The acryloni trile type monomer is acryloni but methacryloni trile trile and acrylic and metha crylic esters may also be used in admixture with or in tial or total substitution of the acryloni trile The quantitative composition of the monomers mixtu re will vary according to the nature of the monomers forming good results are obtained by using from to 80 by weight of the styrene type monomer and from by weight of the acryloni trile type The best results are obtained by using mixtures consisting of from 20 to parts by weight of acryloni trile together with from 80 to 60 parte by weight of styrene The synthetic or natural rubbers which may be used in the process according to the invention will consist ly of products containing at least by of a dienic conjugated hydrocarbon chemically and may include up to of substances able to polymerize with dienic hydrocarbon Good results are obtained by employing dried synthetic elastomers obtained by polymerization o a dienic such as butadiene isoprene and may also contain small amounts of monomers able to polymerize with the dienic hydrocarbon itself such styrene for and the like Very good results have been achieved using some synthetic elastomers consisting of 1 of chemically bined 1 such as for the polybutadiene types commercially known as of the Firestone average contents of a cis 1 EUROPRENE CIS of content of a cis and PLIOFLEX 5OOO of the Goodyear low contents of 1 cis The use of such instead of the usual GRS type of synthetic rubber allows one to obtain copolymers having good mechanical properties even at low The synthetic or natural rubber will generally be added with the normal and when it is ved in the monomers a stabilising agent may be ded to avoid degradation which can occur during the successive stages of the The quantity of rubber used will generally range from 5 to parts by weight per 00 parts of the monomers containing the rubber dissolved Best are obtained by using from 4 to 1 6 parts by weight of the rubber per 00 parts by weight of monomers containing the rubber dissolved During the polymerization in the aqueous sion the ratio by weight of may vary within wide Good results are obtainable with a ratio of from 0 to 10 1 The polymerization of the monomers mixture taining the dissolved is preferably but not neces carried out in the presence of Preferred catalysts are organic peroxide which will decom pose at the polymerization temperature of about 7 1 Particularly suitable catalysts for butylperoxide amylhydroperoxide cumene tetralinhydroperoxide tertiary butylperacetate tertia ry butylperbenzoate tiary benzoil peroxide and The quantity of catalyst used will vary according to its Usually from 0 to 0 5 parts by weight of catalyst will be used per 100 parts by weight of monomers Best results are obtained by using butyl peroxide in amounts of from 01 to 2 part by weight per 100 parts of monomers If the first polymerization step is carried out in when the mixture reaches a certain conversion degree it may be discharged into an autoclave containing water for the successive suspension polymerization whether the first polymerization step is carried out in bulk or in the presence of at a conversion degree of the monomers mixture to polymer which is preferably from 20 to by a suspension system is consisting preferably of a mixture of partially hydrolized acrylic methacrylic and polyvinyl alcohol or the like and aventually an inorganic acid salt which is strongly dissociatable in aqueous A particularly good polymer may be obtained using as the suspensio system a mixture of polyvinyl cohol and the product of the partial alkaline hydrolysis of polymethylmethacrylate having a hydrolysis grade and having in a aqueous solution a viscosity of 200 tipoise at a temperature of in amounts of from to 1 part by weight and of from to 5 parts by per 100 parts by weight of the monomers During the polymerization the molecular weight of the copolymer can be controlled by adding small amounts of a chaintransfer For the same purpose a process has been applied described in our Israelian patent tion which consists in increasing the temperature with the conversion of the monomers to polymer so as to obtain a copolymer having a substantially constant and prefixed molecular In this way it is possible to eliminate the gel effect by which the cular weight of the during their would thend to increase during the polymerization It is therefore possible to obtain a having a desired molecular weight and a desired moulding without changing the excellent properties of stability to solvents and the high impact the impact characteristics being dependent essentially upon the qualitative and quantitative composition of the starting monomers and to the type and amount of the rubber dissolved in the monomers The graft copolymers prepared in accordance with the invention have physical and chemical ties which depend on the quality and amount of the mono and rubber used and on the type of the tion thermic cycle The following list shows the general type of properties of polymers which are obtained by a process in accordance with the a resilience with notch at measu red according to of from 3 7 to kg a resilience Izod with notch at measured according to ASTMD of from 3 8 to 20 kg a resilience Izod with notch at red according to ASTMD 25 of from 2 5 to 1 2 kg an MOT measured accordind to ASTM D 6 8 of from 77 to a breaking load under traction measured 2 cording to ASTM D 638 of from 300 to 0 an elongation measured according to D of from 1 0 to a modulus of elasticity under red according to ASTM D 638 of from 20000 to 30000 a rockwell hardness scale L measured according to ASTM D of from 88 to 96 a maximum stress under flection measured cording to ASTM D 78Ο of from 500 to 920 a modulus of elasticity under flection measured 2 according to ASTM D 790 of from 18000 to 29000 and a light stability measured on a such a for traction sed for 500 hours maintains practically unchanged its lours and mechanical whereas prior products show a decay in their properties after only 200 hours of According to a preferred process the synthetic rubber consisting of chemically combined butadiene with a high content of cis structure stabilized and finely ground and dissolved in or in a styrene and mixture keeping the mixtu re stirred for a certain time at a temperature of about During the dissolution the rubber may be further stabilized by adding small amounts of a suitable stabilizer such for example as a trialkylarylphosphite The thus obtained tion is then filtered to remove the undissolved cles and acrylonitrile is Thereafter a catalyst and a agent for the control of the molecular weight may be At this stage two methods can be whether one intends to carry out the initial in the presence of water or in If the initial polymerization is carried out in the presence of water the solution of the monomers is transferred to a polymerization autoclave containing a certain amount of preferably freed from Then the polymeriza tion is started by subjecting the autoclave content to a mic cycle specifically studied in relation to the ristics of the copolymer to be When the conversion degree of the monomer reaches a value of from 20 to by weight a suspension system consisting of a mixture a polymethylmethacrylate partially hydrolized and vinyl is then If the initial polymerization is carried out in bulk the solution of monomers containing is kept for a certain time with stirring in order to reach a conver sion degree of the monomers into copolymers of 20 to by At this the mixture is transfer red into a polymerization autoclave containing water ferably previously freed from the suspension system is and the mixture is subjected to a suitable thermic cycle under the same conditions as just described in connection with the polymerization in the presence of At the end of either of the polymerizations just described the autoclave contents are steam distilled in order to eliminate the last traces of unconverted mono The autoclave contents are thereafter washed and dried with hot The obtained polymers which is usually form of small is extruded under vacuum at temperatures of from to in order to eliminate the traces of volatile impurities still remaining in the The obtained copolymer product is then ready to be with the addition of normal additives generally the moulding of articles having excellent physical and chemical properties and an excellent The copolymer products may also be mixed in substantially all ratios wit other thermoplastics materials such for example as polymers copolymers from styrene methylmethacrylate and the like so as to provide moulding compositions which produce moulded bodies having excellent physical and chemical properties and very good The invention will now be illustrated with reference to the following in which all parts are given by weight EXAMPLE 1 6 parts of polybutadiene rubber of polybutadiene with an average content of a cis structure and as sold FIRESTONE under the name 35 ground to very fine were ded with stirring to 59 parts of monomeric con taining also the rubber stabiliser which is an alkyl arylphosphite produced by the Rubber The mixture was continuously stirred and brought to a temperature of and kept for hours under these the solution the rubber ved in the was filtered in order to te any particles of undissolved At this stage 35 parts of acrylonitrile monomer were added together with a polymerization talyst consisting of parts of ditertiary peroxide together with part of a agent consisting of tertiary dodecylmercaptan and the mixture was transferred to a pressure polymerization autoclave containing 100 parts of water previously freed from The mixture was gradually heated so that in an hour the temperature had been raised to The contents of the autoclave were kept at this temperature for even and a half thereafter the temperature was increased to over a period of two hours and this temperature was maintained for another During the when the conversion degree of the monomers had reached a suspension system was added consisting of 0 parts of partially hydrolised polymethylmethacrilate consisting of tially hydrolised with lisis grade and having in a aqueous solution a viscosity of 200 centipoise at a temperature of and 1 parts of polyvinyl The reaction mixture was then cooled to a temperature of and the contents of the autoclave were steam distilled to eliminate The contents of the autoclave thereafter cooled to a temperature lower than the melting point of the resulting polymer which formed as beads which were centrifuged and dried with hot at a temperature of The polymer product was extruded under vacuum at the temperature of and has the properties shown in Table 1 EXAMPLES These Examples followed according to Example 1 but used different amounts of monomers and agent and added the suspension system at different conversion degrees of the E Styrene Acr lo Rubber Type o Conversion No ni trile Transfer rubber at which suspension 2 57 33 0 0 20 1 0 37 3 53 5 31 5 0 1 5 DIENE 37 k 66 2S 0 6 DIENE 2k 5 57 0 33 0 0 10 37 The properties of the products are shown on Table EXAMPLE 6 parts of polybutadiene similar to that used in Examples 1 to k were added with ring to a mixture consisting of 28 parts of styrene and parts of 1styrene Stirring was continued and the mixture was brought to a temperature of and kept under these conditions for a period of Afterward the solution was filtered in order to eliminate any undis solved rubber Then parts of acrylonitrile the polymerization catalyst consisting of 1 5 parts of butylperoxide and 0 1 parts of an sing agent consisting of butylparacresol were added to filtered and the mixture was transferred into a polymerization autoclave which tained 100 parts of water previously freed from The contents of the autoclave were gradually heated and after an hour the temperature of the mixture had been brought up to 1 1 The contents of the autoclave were heated uniformly for a further 8 hours talcing care that during this period the temperature increased regularly from to Once the conversion degree had reached a value of 25 suspension system similar to the one used in Example 1 was and once the conversion degree was 3 parts of styrene monomer were At the end of the 8 hours the contents of the autoclave steam distilled under pressure to remove residual unconverted and then the contents of the autoclave were and the ting polymer product was centrifuged and hot air at a temperature of The polymer product was extruded vacuum at the temperature of and it had the properties shown in Table EXAMPLE 7 Example 6 was repeated as far as the lution of the rubber in the monomers and the filtering of the Then the acrylonitrile the catalyst and the antioxidizing agent were added as before and the mixture was heated for about 3 hours at a perature of to reach a conversion degree of The partially converted monomers mixture was thereafter transferred into a polymerization clave containing parts of water previously freed from oxygen and was heated at a temperature of a suspension system similar of 1 was added and the polymerization was continued by submitting the whole mixture a gradual heating from during a period of hours and ding parts of styrene when the conversion degree steam reached The autoclave contents were to remove the unconverted Thereafter the Example was operated as previously The properties of the obtained polymer product are shown in Table 1 EXAMPLE 8 6 parts of polybutadiene rubber were added with stirring to parts of hylstyrene The stirred mixture was brought to a temperature of and kept for hours under these After filtration to remove any undissolved rubber 33 parts of acrylonixjtile a polymerization catalyst consisting of parts of butylperoxide and 1 part of a added agent consisting of tertiary dodecylmercaptan the The mixture was then gradually heated for an hour so that the temperature reached the end of the Thereafter the mixture was maintained at for 12 At this the mixture was transferred to a polymerization autoclave containing 100 parts of water which had been previously freed from oxygen and the autoclave contents were brought to a temperature of The contents were kept at this temperature for the temperature was then increased to and kept under conditions for the temperature was increased to 1 arid this rature was kept for three and then during the next hour the temperature was increased to ly the mixture was steam distilled to remove the ted The autoclave contents were with hot air at obtained polymer product was extruded under vacuum at a temperature of The properties of the polymer product are shown in Table 80 parts of a copolymer prepared as in Example 1 intimately with 20 parts of a copolymer containing styrene and 26o le chemically The properties of this latter copolymer are listed in the following Table II in which the methods of testing were the same as se indicated in Table TABLE II Resilience at 2 Heat distortion temperature 95 Breaking load under traction 750 Elongation 2 5 Modulus of elasticity under Hardness scale L 0 2 Maximum stress under flection Modulus of elasticity under flection 35 000 Light stability after 500 hours very good The properties of the product obtained by extrusion mixing extruder with a mm at the temperature of are summarized the following Table III in which the methods of testing were the same as those indicated in Table TABLE III Resilience Izod at Resilience Izod at Resilience Izod at Heat distortion temperature 2 Breaking load under traction Elongation Modulus of elasticity under traction Maximum stress under fleotion 850 Modulus of elasticity under fleotion The produo also had a high stability to light and 80 parts by weight of a oopolymer prepared according to Example were closely mixed with 20 parts by weight of a polymer containing b weigh of by weight of and weight of chemically The properties of this latter are listed on the Table hereinafter TABLE IV Resilience at j x t Heat distortion temperature ASTM 648 Breaking load traction ASTM 750 Elongation ASTM D 638 Modulus of elasticity under traction 638 kg cm2 stress lection 790 Modulus of elasticity under fleotion ASTM 790 She properties of the product obtained extrusion mixing extruder with a 30 at the temperature of are summarised in Sable Resilience at Heat distortion temperature 91 Breaking under traction 490 Elongation Modulus of elasticity under traction stress under flection Modulus of elasticity under flection She determination of these propertied had been effected by the usual standard measuring methods indicated in the preceding product was also characterised by a high stability to light and Example 1 1 70 parts by weight of a copolymer prepared according to Example were closely mixed with 30 parts by weight of a copolymer containing weight of by weight of acrylonitrile chemically She properties of latter copolymer are listed on the Sable VI hereinafter Resilience at x D 256 2 Heat distortion temperature 648 Breaking load under traction 750 Elongation Modulus of elasticity under traction 658 Rockwell Hardness D 785 110 under flection 790 1100 Modulus of elasticity under flection TO Resilience at at at Heat temperature Breaking load 500 Elongation Modulus of elasticity under Maximum stress unde flection 650 of elasticity unde flection The determination of t ese properties had teen effected the usual measuring methods indicated in the preceding product was also characterised by a high stability to light and 80 parts of prepared as in Example 4 closely mixed 20 parts of the acrylonitrile copolymer whose properties are shown on Sable 3 operating described a product the properties shown in following in which the methods of testing were the same as those indicated in Resilience at fiesilieace at Eesilienoe at Heat distortion temperature Breaking load under traotlon Elongation Modulus of elasticity under traction The product had a high stability light and 15 of a terpolymer parts of chemically combined parts of chemically combined and parts of chemically combined and the properties in Table were mixed with 25 of copolymer prepared as in Example Resilience at Heat distortion thermic 102 Breaking load under traction Elongation of elasticity traction Maximum stress under flection of elasticity under flection The polymers were mixed under the conditions specified in the preceding and a product was obtained whose properties are shown in Table i which the of testing were the same as those indicated in X at Heat distortion thermic W Breaking load under traction 700 Elongatio of elasticity under traction stress under flection Modulus of elasticity under flection The product had high stability to light and Instead of using 25 parts of the copolymer prepared as in 25 parts of the copolymer prepared according to Example 1 were used and a product was obtained whose properties are listed in the following Sable in which the methods of testing were the same as those indicated in Table Resilience at Heat distortion thermio Breaking under traction Modulus of elasticity under traotion stress under flection Modulus of elasticity under flection The product also was highly stable to light and Instead of mixing 75 parts of the styrene terpolymer and 25 parts of the copolymer prepared as in 1 or a mixture was prepared 50 parts of terpolymer and 50 parts of the copolymer prepared as in Example a produet was obtained properties are summarized in Table in the methods of testing were the same as those indicated in Table XII Resilience laod at distortion thermic 100 Elongation 16 Modulus of elaetioity Maximum stress under flection Modulus of elaetioity under flection product was also highly stable to and 50 parts of a containing methylstyrene of acrylonitrilo chemically combined the properties listed in XXXI vera intimately mixed with 50 parts of a copolymer prepared as in Example 8s Izod at 2 Heat distortion temperature thermic 104 Breaking load under traction 720 Elongation 2 of elaetioity under traotion stress under flection Modulus of elasticity under fleotion The product obtained from this mixture has the properties summarized in Table i which the methods of testing the same as those indicated in Table p XIV Resilience at Heat distortion temperature Breaking load under traction 600 Elongation 7 Modulus elasticity under traotion stress under flection Modulus elaetioity under flection product also a high stability to light and Example 80 parte by weight of a copolymer according to Example 1 but having the following starting composition by weight of at by Weight of aorylonitrlle and by weight of polybutadiene 35 and furthe characterised by the following Resilience at 5 Kg Heat distortion temperature Breaking load tinder traction 33 Elongation 9 Modulus of elasticity under traction Maximum stress under flection 655 Modulus of of elasticity unde flection were olosely mixed with 20 parts by weight of a copolymer taining by weight of by weight of acr lonitri le chemically properties of latter copolymer are listed on the TABLE XV Resilience Izod at 256 Heat distortion temperature ASTM Breaking load under traction ASTM D 638 750 Elongation ASTM D 638 Modulus of elasticity under traction D 638 Rockwell Hardness scale L ASTM D Maximum atrees flection ASTM D 7 Ο 1 100 Modulus of elasticity under flection ASTM D stability o very good a ter 50 hours properties of the product obtained by extrusion mixin extruder a 30 at the tempera ture of summarised in Table XVI TABLE XVI Resilience at at at Heat distortion temperature Breaking load under traction 350 Elongation 11 2 Modulus of elasticity unde traction Maximum stress under flection 680 Kg Modulus of elasticity under determination of these properties had been effected by the standard measuring methods indicated in the preceding This product was also characterised by a high stability to light and Elongation D 638 Modulus elastic ty traction ASTM D Rockwell Hardness scale ASTM D Maximum stress unde ASTM Kg Modulus elasticity flection ASTM P 790 Light stability Fade Meter very afte 500 hours The properties of product obtained by extrusion extruder with a 30 at ture of are summarised in Table XVIII TABLE XVIII Resilience at at 3 at 3 distortion temperature B load unde traction 420 Elongation 1 1 Modulus of elasticity under traction 2 Maximum stress under flection 820 Modulus of elasticity under flection determination of these properties had by usual standard measuring methods indicated in preceding This product was also characterised by a high stability to light and solventso Elongation 2 ASTM Modulus of elasticity under traction Hardness scale L ASTM D 110 Maximum stress under flection 790 Modulus of elasticity under flection ASTM D 790 Light stability o very good a ter 500 hours The properties of the product by extrusion mixing extruder a 30 mm at the temperature of are summarised in Table XX hereinafterβ TABLE XX Resilience at 17 at at Heat distortion temperature Breaking load under tractio 0 Elongation Modulus of elasticity under traction 500 Maximum stress under 590 Modulus of elasticity under flection 21 The determination of these properties had been effected by the usual standard measuring methods indicated in the preceding This product vas also characterised by a high stability to light and solvents Example parts by weight of a copolymer prepared aooording to Example 1 but having the following starting composition 56 by weight of by weight of by weight of polybutadlene NF 35 and furtherly racterized by the following ReeUience at 2 26 Heat distortion temperature 76 load under traction 285 Elongation Modulus of elasticity under traction 2 Maximum stress under flectio 505 2 Modulus of elasticity under flection 17 were olosely mixed with 60 parts by weigh of a copolymer taining 7 by weight of by weight of aorylonitri chemically The properties of this latter copolymer listed on the Table XXI hereinafter TABLE XXI at ASTM 256 2 cm cm Heat distortio temperature ASTM D Breaking load under traction ASTM D 638 Kg cm2 2 ASTM D 638 Modulus of elasticity under traction ASTM D 638 Rockwell Hardness scale L 110 Maximum stress under flection ASTM D 1100 Modulus of elasticity under flection ASTM 790 Light stability o very good a ter 500 hours The properties of the product obtained by extrusion ing extruder with a 30 mm at the ture of are in Table XXII TABLE Resilience at at C at 5 Heat distortion temperature Breaking load traction 435 Kg cm 2 Elongation 7 Modulus of elasticity traction Maximum stress under flection Modulus of elasticity under flection 27 The determination of these properties had been effected by the usual standard measuring methods indicated the preceding examplese This product characterised a high stability to and Example 19 37 parts b weight of a copolymer prepared aooording to ple 1 but having the following composition by weight of by weight of by weight of polybutadiene stone 35 und furthedy eharactarized by the following properties Resilience Izod at II Heat distortion temperature Breaking load under traction 495 Elongation Modulus of elasticity under traction Maximum stress flection 910 Modulus of elasticity under flection were closely mixed with parts by weight of a copolymer containing weight of styrene9 by weight of acrylonitrile and by weight of methylstyrene chemically The properties of this latter oopolymer are listed on the Tuble XXIII hereinafter indicated XXIII Resilience Izod at x ASTM 4 Heat distortion temperature ASTM D 48 Modulue of elasticity under flection The properties of the produot obtained by exstrusion mixing tory extruder with a mm at the temperature of are summarised in TABLE XXIV Resilience zod at at 1 at 1 Heat distortion temperature Breaking load under traotion 555 Elongation Modulus of elasticity under traotion Maximum stress under flection 1075 Modulue of elasticity under flection The determination of these properties had been effected by the usual standard measuring methods indicated in the preceding This product was also characterised by a high stability to light and Example 20 75 parts by of a oopolymer prepared according ta 1 but hawing composition by weight of by weight of by weight of polybutadiene and characterized by the following properties Resilienoe at C M distortion temperature Breaking load under traotion 495 Elongation Modulus of elasticity under traotion Maximum stress under 910 Modulus of elasticity flection were closely mixed with 25 parts by weight of a copolymer containing 33 by weight of by weight of acrylonitrile and by weight of methyletyrene chemioally combinede The properties of this latter copolymer are listed on the Table XXV hereinafter TABLE XXV Izod at D 256 1 Heat distortion temperature ASTM D 648 Breaking load under traotion ASTM D 638 750 Elongation 2 5 63Θ Breaking load under traotion Elongation 15 Modulus of elasticity under traction 500 Maximum stress under flection 960 Modulus of elasticity under flectio 32 rt The determinatfion of these properties had been effeoted by the usual standard measuring methods Indicated in the preceding This product was also characterised by a high stability to light and solvents 25 parte by copolymer prepared according to pie closely with by weight of cr The properties of this latter polymer are listed on the Table hereinafter TABLE XXVII Resilience at ASTM D ortion temperature ASTM D 648 Breaking load under traction Elongation ASTM 638 Modulus of elasticity under traction Rockwell Hardness scale L ASTM D Maximum stress under flection Modulus of elasticity under flection D 790 The properties of the produot obtained by extrusion mixing extruder with a 30 mm at the temperature of are summa rised in Table XXVIII XXVIII Resilience at at V at Heat distortion temperature 91 Breaking load under traction Elongation Modulus of elasticity under traction 500 Maximum stress under fleotion Modulus of elasticity under fleotion 600 The determination of these properties had been effected by the usual standard measuring methods indicated the preceding exampleso This product was also characterised by a high stability to light and solventSo 75 parte weight of a copolymer to Example 6 were closely mixed with 25 parts by weight polymethylmetaorylatea The properties of this latter polymer are listed on the Table XXIX reinafter indi TABLE XXIX Resilience at 1 AST B 256 2 1 Heat distortion temperature ASTM D 648 Breaking under traction 6 ASTM B Modulus of elasticity under traction ell Hardness scale 1 2 B 785 Modulus of elasticity under flection Light stability o very good after 500 hours The properties of the product obtained by extrusion mixing extruder with a mm at the temperature of 1 C are marised in Table XXX hereinafter TABLE XXX Reeilience Izod at 5 at at II II Heat distorsion temperature Breaking load under traction Elongation Modulus of elasticity under traction Maximum ess under flection 780 II r Modulus of elasticity under flection 22 90 II The determination of these properties had been effected by the usual standard measuring methods indicated in the preceding This product was also characterised by a high stability to light and solve Example 80 b weight of a copolymer prepared according to Example 1 but having the following starting by weight of styrene by weight of by weight of polybutadiene NF 35 and furtherly charac terized by the following Resilience at 26 Heat distortion temperature Brea ing load under traction 285 Elongation Modulus of elasticity under Maximum stress under flection Modulus of elasticity under flection were closely mixed with 20 parts by weight of a The properties pf this latter polymer are listed on the Table hereinafter TABLE XXXI Resilience Izod at ASTM D 256 Hea distortion temperature ASTM D 648 Breaking load under traction ASTM D 638 775 Elongation ASTM D Modulus of elasticity under traction ASTM D 638 Hardness scale L 112 D Maximum stress under flection ASTM D 79P Modulus of elasticity flection ASTM D 790 Light stability o very good after 500 hours The properties of the product obtained by extrusion mixing extruder with a 30 mm at the ture o are summarised in Table XXXII TABLE XXXII Resilience at at at Heat distortion temperature 2 Breakin load under traction 350 Elongation 2 Modulus of elasticity under traction Maximum stress under flection 620 Modulus flection The determination of these properties had effected by the usual stazxdard measuring methods indicated in the precedin This product was also characterised by a high stability to light and insufficientOCRQuality

Claims (1)

1. described and ascertained the nature of our said invention and in what manner the same is to declare that what A process for the preparation of high impac copolymers comprising polymerising a mixture of type monomer an type monomer in which dissolved a synthetic or natural rubber until the conversion degree of monomer to copolymer from 10 by and then completing the polymerization of the mixture in aqueous A process as claimed in Claim in which the initial polymerization of the monomers mixture is effeoted in the presence of process as claimed in in which the initial polymerisation of monomers mixture is effected in A process as claimed any of Olalms 1 to in which the monomers mixture contains one or of s an such as or halostyrene such as mono or and one or more of and A process as claimed in any preceding in which the monomers mixture contains from 50 to by weight of the styrene type monomer 50 to by of the aorylonitrile type A process as claimed Claim in which the monomers mixtures contain from 60 to by weight of styrene and from 40 to by Weight A claimed any preceding the synthetic or natural rubber contains at least by weight Of a chemically combined conjugated process as claimed Claim in whioh the or natural rubber contains up to by weight of a substance with the A process as in in which synthetic or natural rubber is a synthetic elastomer containing of chemically combined butadiene A process as claimed in any preceding in which from to parts by weight of synthetic or natural rubber are present in 100 parts by weight of the monomers A process as claimed in Olaim in which from 4 to 16 parts by weight of the synthetic or natural rubber are present in 100 parts by weight of monomers containing the rubber dissolved A process as claimed in any preceding in which the molecular weight of the copolymer is controlled during the polymerisation by polymerizing in the presenoe of transfer agents and adopting a thermic cycle of polymerization to give the molecular weight of the desired Λ process as claimed in Olaim which copolymer having a substantially constant and predetermined molecular weight is obtained by increasing the polymerisation temperature simultaneously with the conversion of the monoaere to A process as claimed in any preceding claim9 which is carried out in the presence of a polymerization Α as claimed in Claim in which the polymerization catalyst is a oleosoluble peroxide decomposable at the polymerization the peroxide being present in amount of from to part by weight per 00 parts by weight of the monomers containing the rubber dissolved A process as claimed in Claim in which the peroxide present in an amount of from to part by weight per 100 parts by weight of the monomers mixture containing the rubber dissolved A process as claimed in any preceding which the polymerization stage effected in aqueous suspension oarried out the of a suspension system consisting of a mixture of an acrylic methacrylic partially ester of polyvinyl alcohol and eventually of an Inorganic acid salt which strongly dissociates in aqueous A process as claimed in in which the suspension system consists of a mixture of polyvinyl alcohol and the product of the partial alkaline hydrolysis of polymethylmethacrylate having a hydrolysis grade and having in a aqueous solution a viscosity of 200 at a temperature of the components of the system being present in amounts of from to part by weight and of from to parts by pe 100 parts by weight of the monomers mixture containing the rubber dissolved process as claimed in any preceding in which the ratio by weight between water and the monomers A process for the preparation of high copolymers in accordance Claim and substantially as herein A process the preparation of high impact copolymers substantially as described with reference to any Examples 1 to A impact copolymer prepared by a process as claimed in any preceding A polymeric composition containing from 1 to by weight of at least copolymer prepared by the process according to an of Olalma 1 to 21 and 99 to by weight of thermoplastic polymeric material selected from polymers and copolymers of and A composition as claimed in Claim in which the thermoplastic polymeric material is a eopolyaerization product containing om 50 to 80 partB by weight of styrene and from 50 to 20 parts by weight of acrylonitrile chemically A composition as claimed in Claim in which the polymeric material is a styrene and acrylonitrile copolymer prepared according to Israel Patent Application A composition as claimed in Claim in which the thermoplastic polymer material is a copolymerization product containing 65 parts by weight of and 35 parts by weight of acrylonitrile chemically A composition as claimed in Claim 23 which the polymer material is A polymeric composition in accordance with Oloim and substantially as herein with reference to any of Examples 9 to A moulded o when prepared from a copolymer as claimed in Claim 22 or a composition as claimed in any of Claims 23 to insufficientOCRQuality