DE1569418A1 - Molding compounds, consisting of an elasticizing graft polymer and a thermoplastic copolymer - Google Patents

Description

Our No. 11 615 Aug 8, 1969

Montecatini EDISON S, ρ, A, Milan / Italy

Formia masses, ordering from an elasticizing plug— polymer and a thermoplastic copolymer

iie _o 'e.:iDtand present. Invention are molding compounds consisting of 8

1o 1 to 99 3öW _e -> an elasticizing graft polymer and

2o 99 to 1; (lev;. .- ^ o-a thermoplastic copolymer of 20 to 50 wt »- ^ one monomer of 'the Jlyp Aorylnitrils and 50 to 80 wt ^c / o of a monomer from the lyp Ütyro.ls,

where the eleventh-stiffening graft polymer 1 is made up of a graft polymer and a graft compound, it can be verified that the graft polymer renders through suspension or mixture suspension of 50 - 80 wt -. ⁰ Jo Monurioren styrene type and 20 - 50 wt .- ^ monomers and acrylonitrile in-.Gegenwart from 0.5 to 50 wt .- ^ butadiene

009816/1864 _{QAn a}

BAD ORIGINAL documents (Art. 7 g I Abe. A No. I UaU 3 de * Anderunoifl · ·. Ν. 4, %

polymer, "based on the total composition of monomers and butadiene polymer.

The rubber-like material of the molding compositions according to the invention represents a copolymer of styrene and / or o ^ -Methylstyrene-Acrylonitril-Butadiene and / or isoprene and gives the molding compositions high impact strength properties.

The production of deformable hats with the properties mentioned above is known per se, namely the production takes place in the alli ^; ; a du -: * ch mechanical mixing of a resinous styrene-acrylonitrile copolymer with a styrene-acrylonitrile-butartiene mixture, the latter by graft polymerization of a mixture of acrylonitrile and styrene on a synthetic latex or natural rubber is obtained «,

This known method has considerable advantages, in particular However, with regard to the properties that can be achieved in the end product (partial formation of an ierpolymeren), is because of the considerable costs that result from the necessary drying of the latex, uneconomical .. Since it is sent out! If it is an emulsion polymerization, the removal of the polymerization additives prepares the natural polymerizate certain? * difficulties; partial degradation of the polymer therefore cannot always be avoided. The elastic properties of the natural and synthetic g-ummls dissolve

• not always optimally exploit the separation d s interpolymer -ßei from the emulsion and drying - * - as already mentioned - there are further J3chwierigkei1 | §ö and ^ extra cost.

In contrast, the present invention relates to alien and a process for their production which do not have the disadvantages mentioned above. The polymers of the invention have high impact strength properties

ORIGINAL

1569A18

even "at low! Demperaturen to exhibit a high resistance to hydrocarbon solvents and Lichteinwirkunc and τοπ relatively high. l ^l eiaper-itiiren are not attacked or destroyed. This erfindungsgeinässen molding compositions are prepared by mechanically blending the following components, namely

a) a resinous polymeric material which is polyneses and high polymers of styrene, o-ethylstyrene, Acrylonitrile, acts,

b) a rubber-like graft polymer, which through Polymerization of a monomer mixture of styrene and ■ Acrylonitrile on a synthetic or natural rubber which is present in a homogeneous solution, is won,

produced ·· The polymers produced under a) are produced in a known manner.

The copolymers defined in b) are processed in a two-stage process. -Procedure made; First, a monomer mixture is prepared in which the synthetic or natural rubber is present in a homogeneous solution and subjected to a laser polymerisation or a polymerisation in the presence of water up to the equivalent degree of conversion, which is generally between and 50 ρ. Then the mixture of the partially un ~ ev; Ji ^; i lter. Monomers in aqueous suspension continue to polymerize until a degree of conversion of 98 to 99 ° is reached. At the beginning of the second polymerization stage, the suspension medium is added.

As soon as the degree of conversion of the monomers has reached the required level ( $ 90 to $ 99), the polymerization mixture is reduced to three levels of distillation to remove traces of non-converted steu! Onomers and other impurities present, • / u remove the criterion. The polymerization autoclave is then cooled down

009816/1864

- BAD ORlGiNAL

and emptied. "J) ac thus obtained styrene-acrylonitrile-butf'äienliioclipolyiiierisat, which is in i-'orm von liügelchen, v.'ij. · > Ebfc-separated, washed and with hot air, ^ c-trocl-net, Die. ' dried granules are extruded under vacuum to remove traces of residual volatile contaminants to remove ■ ■ /. ".". /) Ii e ser cleaning is the j-roduct for the 'ieiterverarbeituniv ej is, wherein ■■ as Product A ^ s such or in rodukten ii .ellung with other thermoplastic ^x are used,.

The monomers, in which the synthetic or natural rubber is dissolved, generally consists of a ii ^ er: .- ', ^ of styrene or. otyrene derivatives and acrylonitrile or acrylonitrile derivatives. To the Gtyroiderivateu, the oyster styrene used in the present invention seltnt v; to earth ground, are a-ilethylsty oil, ^r lstyrole other ALK3, including -.etl'.yläthylstyrol, halo styrenes such -eriiorte. 3, mono- and dichlorostyrene, among other things . or oc'er in Ili.-chunc; riit styrene itself uses \. 'r-; raen.

The acrylonitrile derivatives which, in addition to acr; / nitrile itself, v ··. _ ■ -turns will köj-iien, /-. include: - jethacr3'lnitril, Chlcraci-ylr.itril, Acrylic and methacrylic acid esters and similar terb ^ iiurj / e!:, Öie likewise either alone odor in i-i chun (. with acrylonitrile even verv.'ei: d..t can be.

The iuenver-ver-iiäitnisse of the various ionomers; in the.; iachuiig can vci. ! Yes, it will be quite different from everyone, but the results will be preserved to whom '. Styrene or styrene derivatives in - c- ^ ren from 550 to 60 percent by weight and acrylonitrile oner Acryliiiitrilivate in -! Narrow of 2l to 50 'JevicJitsproze.'. Iv: Particularly good results can be achieved. c if the ii .chunc- ^ -C bis. Contains iewiciitsteile acrylonitrile to ⁿ hl to βυ parts of styrene and / or ^{a-luethylstyrol:} 40th

The synthetic or natural ^ ouch, ke, the eriinuur.,; .. _; emäso uses v.'crden, umi'assei '. im all. ■ · (. ■■. .oiiie. ¹ , ι ι \ · .uJct.t ^, the vc-

r. 70 '■' Ki 'iloiiv-'asje ^ oicfi'e with:. ·.], Jugiert e'j 'Jiei: t i

009816/1864

1589418

ι, "possibly in connection with 0 to 30 ° j other Sa1v, -3taa; 3en, aie are polymerizable with the Dieri_Kohlenwasserstoff iclie elastomers used by .Volynierisation ο lues ..'.- i-ji-.s, z.'ß, jutr-.diene and / or isoprene and / or Jul ..- r.-prt-η, ^ e ^ ibid otherwise in the presence of smaller, poly-aerisable monomers, e.g. styrene, acrylic

nitrile H.ii. ^ ewcnuen been oind.

JiG ^T -'urle ^ ei-Zundeii that certain synthetic ^ lastonere the to 100 ■ '} from ci'C; ^r ii ': ch bonded 1,3-butadiene molecules exist, for' the rJwecir.e of the previous invention particularly -.eaignet sin ¹¹ DIEIiE 35 / ITi ¹ A "äer Pirma Firestone Go ₀ (with through->,;: iijiittliciiGn content of cis-1.4-structure)," BUROPKÖHE CIS of Α1 ·: "Ι0» (with a certain content of oris-1, 4 structure) and "PLIOi ¹ LSX 50uj" dor '-. "Irina Goodyear Co ₀ (with a low content of ice-1,4-structure.' Ur). The use of such elastomers instead of der ünlij. "-.-; n GPLO-kautochuktypes allow the production of mixed-pol.

The milled synthetic or natural rubber is used together with the normal additives. At the moment of the solution: -, a stabilizer is added to the honeycomb preparation to prevent the degradation that occurs in the various treatment stages _; .; on to work. The amount of rubber can be between 0.5 νάνι%) parts by weight, preferably 4 and 16 parts by weight, to 100 parts of the amount consisting of lionoin and the rubber dissolved in it.

jJis ... ^ Ij; "-; rirjatioii dor containing the rubber in solution j-iOaon ^ ri'iioCMi.inü 'is carried out according to the invention in two stages. The o -.- TJth stage can be in the i-iasse or in the presence of water clu ..: 'o.-i /.-'..'.uhrt v / earth. The next stage is an ionization in 'v'ysyri ^ or Guspension dar, D.;. s Uewiolrtsverliältnis Wasser:

Ö098 16/1 884 bad original

i-icmcrner is variable within wide limits, regardless of which method is ne.cii worked Favorable results are generally ersielt when the ^u ewichtsverhältnis' water / ϊ-ϊοηο-mer (containing the dissolved rubber) zwijchen 0.5 5 1 and 10: 1 lie. ^ T.

The lolymerisation the ^T "onomermiechung in which the; -aut ..;. Is dissolved chuk, is preferably, but not necessarily necessarily, carried out in the presence of catalysts If the polymerization be carried out in the presence of catalysts, so the use has öllüslicher organic feroxides which decompose at polymerization temperatures between 70 ° and 170 ° C. The following compounds are particularly suitable as catalysts: di-tert-butyl poroxide, butyl hydroperoxide, tert-amyl hydroperoxide, di-tert-hexyl peroxide, Acetylbenzene peroxide, cumene hydroperoxide, tetralin hydroperoxide, phenylcyclohexyl hydroperoxide, tert-butyl peracetate, 13rt -butyl perbenzoate, di-tert-butyl perphthalate, di-tert-butyl peradipate, tert-butyl peroxide, benzoyl peroxide and others

Such catalysts are generally used in amounts of from 0.001 to 0.5 parts by weight per 100 parts by weight of monomer mixture with rubber dissolved therein. Particularly favorable results can be achieved when using di-tert-butyl peroxide in amounts of 0.01 to 0.2 parts by weight per 100 parts of a monomer mixture with rubber dissolved therein. If the first stage of polymerisation is carried out in bulk, the prepolymer becomes after the desired degree of conversion has been achieved. s placed in an autoclave in which ^w ater for the subsequent suspension polymerization stage is contained. Regardless of whether the first polymerization stage is carried out in bulk or in the presence of water, the emulsifier must be added during the second polymerization stage when the degree of conversion of the monomers into the polymer has reached a certain degree of conversion, which is preferably between 20 and 40 ' which consists of a

ÖÖ9816 / 1864 BAD ORIGINAL

iier i; i .'hung of partially hydrolysed acrylic acid and / or iuctiifior ^ l acid estersi], polyvinyl alcohol and other compounds and possibly strongly dissociated inorganic salts in aqueous solution. s by partially alkaline hydrolysis of ioly ^ ethyl methacrylate (75% degree of hydrolysis), which in aqueous solution has a viscosity of 200 centipoise at 20 ° C. and which is also mixed with i-olyvinyl alcohol, the amount of which is between 0.01 and 5 Parts or 0.001 to 1 part by weight per 100 parts of monomer dispersion with the rubber dissolved therein. To regulate the molecular weight, a small amount of a conventional chain transfer agent is used to work the method described in Italian patent application 40 079/63, according to which the Polyuerisatio The temperature is increased in coincidence with the conversion of the ionomers into polyners, so that an iJi.ychpolymerisat with a constant and predetermined molecular weight is obtained. In this way it is possible to switch off the so-called Tromsdorf effect, according to which the molecular weight of the copolymers continues to rise over the entire duration of the polymerization.

As a result, it is! Calibrated., When working according to the procedure subject to the present invention and simultaneous application of a chain transmission means and corresponding control of the Heat supply in the sense mentioned above! To produce copolymers, which has a molecular weight within well-defined Grenaen and thus have good deformability and the outside through light stability, temperature and solvent resistance as well as excellent impact propertieseii award. The impact strength properties depend on the as far as I am concerned, the composition (so.'ohl qualitative as well as quantitative) of the fees used as starting material such as a: .I of the type and amount of what is dissolved in the monomers s clml '. s off.

16/1864

The graft copolymers are notable for their physical properties and chemical properties, which on the one hand V021 type and Amount of monomers or rubber used and also depend on the type of polymerization process. The following table shows the properties of -i-'products, which result from the method according to the present invention get, compiled,

Notched impact strength at +23 ⁰ O, according to ASTM D 256:

3.7 to 25 kg cm / cm

Notch; impact toughness at O ⁰ O, according to n;, ch ASTM D 256:

3.8 to 20 kg cm / cm

Notched impact strength at -29 ° C, according to ASTM D 256;

2.5 to 12 kg cm / cm

*)
HDT measured according to ASTM D 648:

77 to 102 ⁰ O

Breaking load under tension , measured according to ASTM D 638:

300 to 51o kg / cm ²

# Elongation at break , measured according to ASTM D 638:

$ 10 to $ 48>

Modulus of elasticity under tension , measured according to ASTM D 638:

20,000 to 30,000 kg / cm ²

Rockwell hardness scale L. measured according to ASTM D 785 t

88 to 96

Maximum load under bending , measured according to ASTM D 790 t

500 to 920 kg / cm ²

Modulus of elasticity under bending , measured according to ASTM D 790:

18,000 to 29,000 kg / cm ²

Idchstabilität , eaten in a ⁽¹ ade-O-rleter (xenon 6KW lamp), the 'J-'est sample was practically unchanged in color and mechanical properties even after 50 hours, while corresponding irortuhte of the known type already after 200 hours . * Eiir; ir]: rr a ^-;. - r-hlasser: the pieckanifachen properties showed.

009016/1864 tunnel

BATH ORIGINAL

The synthetic rubber made up of 100 ρ from 1,3-butadiene moleculeGf. 'breathed and has a hone retention of 1,4-cis-addition, is in finely ground state and with the use of a stabilizer in styrene or α-methylstyrene or in a Mi. ¹ ClHUi;':; released from styrene and a-Metiiylstyrol, wherein the Kiscliuij, -. '* is maintained under -itühren "at a Toiiperatur of about 70 V. C ^r ai> rend of Losens of the rubber may optionally v / urther stabilizers are added, for example Trialkylarylphosphite The solution obtained in this way is filtered, if necessary, in order to remove undissolved rubber particles, and then mixed with xicrylonitrile. Subsequently, the catalyst and the transfer agent for molecular weight control are added. From here it is possible to continue working in two different ways, depending on whether the first stage of polymerization is to be carried out in the Hasse or in the presence of water.

a) Carrying out the first polymerization stage in the presence of water »

The Kozioraerlösung, in which the rubber, the Jolymerisationskata-Iysator, the chain transfer agent and optionally others

are,

Dissolved sediments are transferred into an olymmerization autoclave which contains a certain amount of water, which has previously been freed from the oxygen it contains As soon as 20 to 40 % of the monomers have been converted, the emulsifier is added, which preferably consists of a mixture of partially hydrolyzed methyl methacrylate and polyvinyl alcohol. Subjected to amine distillation to remove traces of unconverted monomers. Thereafter, the contents of the autoclave are cooled, centrifuged, washed and dried with hot air. After this treatment, the product is in i'orm small particles and is under

008616/1064 bad original

Vacuum "extruded at temperatures of 1HO to 22O ⁰ G in order to remove further traces of volatile" impurities that may still be present in the dom ui chpolymerisat,

b) Carrying out the second polymerization stage in the + mass.

The nonoi.iermochung, in which the rubber, the catalyst, the chain transfer agent and other additives are dissolved, is stirred for a while until a degree of conversion of the I-iononere of 2 to 40 per cent is reached. At this time, the --Iischling obtained is transferred to a Polynerisationsautoklaven which contains sow _erg toffreies water; then add: aan the emulsifier and heat in the manner already indicated j then proceed with the procedure indicated under a).

The resinous polymer material, which according to a) in ili ^ chung with the rubber-like compound polymers are used> :. ann, consists of Miüchpolymevisaten from styrene and / or α-methylstyrene with acrylonitrile et al. "Compounds, preferably used a copolymer containing 50 to 80 parts by weight of styrene and / or α-methylstyrene in addition to 20 to 50 parts by weight of acrylonitrile contains.

example 1

6 parts Polybutedien- ^ autschuk (100 fo polybutadiene with an average content of 1,4-cis-structure, which is marketed by the company. Firestone under the trade designation "SERVE 35 HF / A", is finely ground and with stirring, in 59 ' ! 'rush styrene monomer introduced containing the rubber stabilizer "Poligard" (This stabilizer is an alkyl aryl phosphite and from the US rubber Co. under the specified ^ andelsbez ^ Lhriiig distributed) ervärmt. the iMinchung is under constant stirring to 70 ⁰ C. and kept under these conditions for 5 hours, followed by "The solution of rubber in styrene is filtered to remove particles of undissolved rubber

0Öfli1S / i664 BADORIQINAL

remove «ί <·· ^ replace the solution with 35! 'eilen rioriorierera acrylonitrile, O, O15' ^ yilen di-tert.-bv / fcylperoxjra as polymerization catalyst as _3-u ct eiiubertrd £;!. iuigS "edium" Anschliesseiid is introduced the solution in a polymer ion-pressure autoclave 100 'feile previously deoxygenated "water contains the contents of the autoclave is gradually heated so that the temperature of the reaches 120 ⁰ G l-iiüchunc in one hour.. After keeping the autoclave contents 7 .1 / 2 hrs. at this Te.nper & tur, ie 120 ⁰ C ₀ Subsequently, the temperature in-the course of 2 hrs. at 145 ° C increases, whereupon this higher temperature is maintained for another St -;. Udo ". As soon as the ilmw.mdlimgsgrad the lionomer has reached $ 24, the emulsifier is to ^ es ^ ett. This ilmulg agent consists of

Ό, 5 parts of partially hydrolyzed polymethyl meth-

acrylate

0.1 part polyvinyl alcohol,

liaoh 3e end of lolyi'ieris ^ tion cools ι _; ; ε »η the autoclave inlet down to 105 ° G and subjects it to steam distillation in order to remove any non-modified monomers:!. The product obtained in this way is cooled down to such an extent that the temperature falls below the climelspunLt of the roller. The polymer lie _L; t in the form of ICügelcheij which a ^ gentrifuriert un ^. > ei RO ⁰ ^ ^ra i "t neissluft be dried ^ anach the product is vacuum extruded at a temperature of 180 C. The properties of the l-roduktes are i: i. i'abel3.e I 3U3aimaeiigestellt.

Example 2

! • lan works "- as in example 1 on ^ egeoeii and uses 6 parts rolybutylene rubber of the type given in Example 1, 66 Parts of btyrol, 2S parts of acrylonitrile uii-J. 0.05 parts of the

'IM ε -'rcaukt consisted of partially hydrolyzed *? !!! Polymethyl - * - laet'i ^ cx-vlfit (Ausuass der Hydrolysis =: 75 '/ j)', which in "5; U.-er viä3sri; 5-3r Lö3u: u. ·; at 20 C a viscosity of 2Gü Gentipoise

' ^rj - ^w . ^{oia + '00 9816/186} U

called chain transfer agents. The properties of the thus obtained Product are also given in Table I.

'Example 3

6 parts of the P0lybutadien-Kaut3cb.uk in Example 1 Art were stirring a mixture of 28 '^' θIlen styrene and 34 parts of α-methylstyrene were added. Still stirring the mixture was heated to 70 ° O and 5 hours under these conditions held. The solution obtained in this way was filtered in order to remove any undissolved chewing paste. Then it was added '29 ^ eIIe monomerep acrylonitrile, the polymerization catalyst,

consisting of 0.15 parts of di ~ tert "-Butylperoxyd and 0.1 ^TEI: (2,6-di-tert, -butylparacresol) Ie an antioxidant to back \ ■. Kan transferred the solution to a polymerization autoclave which contained 100 parts of oxygen-free water. The contents of the autoplave were gradually heated so that the temperature; the mixture after 1 hour was 110 Ω. Thereafter, the contents of the autoclave was uniformly. Further heated for 8 hours in length, with care taken, the temperature that gradually and uniformly from 110 ° to 140 ⁰ O increased. Thereafter, the contents of the autoclave were subjected to steam distillation under pressure to remove unreacted monomers.

j As soon as the degree of conversion of the monomers ert ven ^w a 25 ° ^C J] had been reached, an emulsifying agent was the reasonable in Example 1! given species. Once the Umwandlungagrad $ 34 constituted were 3 ■ '■ parts of styrene monomer was added, ^ annoh "the contents of the autoclave was cooled, the polymer was removed by centrifugation and with hot air at 8ö ° ö dried The product thus ^obtained;!. In vacuo at Einei ? Temperature of 190 ⁰ O extz? Udlei * t. The properties of the product '■ * IM listed in Table I.

Example 4 '

6 parts of tOlybutadiön-Kautechuk in Example 1 fc & öö & rl ^ benen

Art were under RUhrea # 1ΐιϊΐ3τ increase of 28 S # il »iit '# | fs? ^{Ol lS} " ^w

000616/1664

it i -. ti.

ItI t

it ir »ι *

* 6 t I t II Ϊ

'· ■ ι t

and 34 parts of α-methylstyrene were added. Still stirring, the mixture was heated to 70 ° C. and kept under these conditions for 5 hours. The rubber cement was then filtered to remove undissolved rubber particles. 29 1 part of monomeric acrylonitrile, the polymerization catalyst, namely 0.15 part of di-tert-butyl peroxide, and 0.1 part of an antioxidant which consisted of 2,6-di-tert-butylparacresol were then added solution are added. The mixture was 3 hours "to a temperature of 110 0 heated, wherein a Umwand- development degree was achieved of 26 fo. The partially converted mono] ierini ;; churig was introduced subsequently ■ autoclaves in a Polymerisationsauto- containing 100 ' ^ rush to 118 ⁰ ^ heated oxygen Reies water contained ^ to used an emulsifier of the type indicated in üeispiel. 1 After the addition of the emulsifier, the polymerization of the i-iischung was continued by gradually over a period of 5 h., the temperature of 115 ° increased to 140 g and 3 parts of styrene added after the Unwaiidluii ^ sgrad 34 had reached fi. the contents of the autoclave was subjected ^ estillation finally, the steam to non-Ulrikes- en ~ did monomers remove. The product obtained in this way was further worked up as indicated in the preceding examples. The properties of the product are summarized in Table I.

Example 5

6 parts of polybutadiene Eautschuk of the type specified in Example 1 were added with stirring in 61 parts of ct-methyl styrene introduced limber still under stirring, the mixture to 70 ⁰ C and was heated for 5 hours. Kept under these conditions. After filtering to remove undissolved rubber particles, 33 parts of monomeric acrylonitrile, the polymerization catalyst (0.2 part of di-tert-butyl peroxide) and a chain transfer agent (0.1 part of di-tert-dodecyl mercaptan) were added. The mixture was gradually heated so that the temperature reached ^{95 0 O within 1 hour.} The mixture was then kept at 95 ° C for 12 hours,

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At this point the mixture was transferred to a polymerization autoclave containing 100 parts of oxygen-free water. The contents of the autoclave were first ^{heated to 100 0} and kept at this temperature for 5 hours; then the temperature was increased to 105 0 and held at this level for 4 hours; the temperature was then increased to 115 and 3 hours , maintained at this height; achllesslich the mixture within 1 hour until raised to 140 ⁰ C Thereafter, the above-emic was subjected to steam distillation to remove non-umgeeet ^ te monomers to remove the contents of the autoclave was cooled finally centrifuged.. and dried at 80 ⁰ O with hot air, and the product thus obtained was extruded in a vacuum at a i'emperatur 190 ⁰ O the properties of the product thus obtained are shown in Table I..

009816/1864

Table I.

!Properties

Measurement methods

Notched impact 2 capable · 1/2 «χ 1/4 ·" at +23 C

1/2 * χ 1/4 "at O ⁰ C

1/2 "X 1/4 * at

-29 ⁰ O

Dimensional stability (HDT

Breaking load under tension

$> Elongation at break Young's modulus under tension.

Röckwell hardness scale L.

Maximum load under bending Modulus of elasticity under bending Most ability

ASTM D 256/56

Example 1 Example 2 Example 3 Example 4 Example 5

9 kg cm / cm 7 kg cm / cm 6.5 kg cm / cm 6 kg cm / cm 3.3 kg era / cm 7 _t 5 ti η 6 ft ti _5> 5 η it 5 ti π 3.7 "»

It Il

"D 648/56

5 "90 ⁰ C

95 ⁰ C

4.5

99 ⁰ C

2.6 »

102 ⁰ C

450 kg / cm '

² 460 kg / cm ² 450 kg / cm ² 510 kg / cm ² _f

8-15 ^ 8- $ 15 48 55 '30 # 14 ^ "ft.

■ *

D 638/58 28,000 kg / an ² 27,000 kg / cm ² 23,000 kg / cm ² 25,000 kg / 6m ² 30,000 kg / cm ²

D 638/56 D 638/56

410 kg / cm * 8 -

785 790/58

88

93

96

740 kg / cm ² 780 kg / cm ² 710 kg / cm ² 640 kg / cm ² 920 kg / cm ²

»D 790/58 27,000 kg / cm ² 27,000 kg / cm ² 22,000 kg / tm ² 25,000 kg / an ² 29,000 kg / cm ²

Fade-O-Meter after 500 hours after 500 hours after 500 hours after 500 hours after 500 hours, very good . very good very good very good very good '

Example 6

80% of the i-Tifjch inerisates produced according to tieiapiol 1 are intimately mixed with 20% by weight of a copolymer of 74% by weight of styrene and 26% by weight of acrylonitrile. The properties of the product thus obtained are shown in Table II. The various dates were licc \ x o.en ASTIl- ^ ethods listed on p. 7/8 be.; Tiüi. t.

Table II

Hitting capacity at + 23 ° G I ¹ 'ο rmb est and i ^ L eit
Breaking load under tension ia elongation at break

Modulus of elasticity in tension Rockv / ell hardness scale Li-iHximalbelastun _o · under ^ ie ^ ung modulus under ^ iei; un _£: Lichstebilität in Zj e.de-0-meter

The ügensci: aften of a product, v / elches through I-ii.'jchc /. de: " both component :! in the extruder (laboratory extruder with 30 mm diameter) at a temperature of 1 y0 ° 0 horrx-i-itei Lt wurdo are summarized in Table III.

Table III

2.0 kg cm / cjii 95 ⁰ C 750 kg / cm 2.5 34 COO !! I! 110 1 100 Il It 35 000 Il Il very good after 500 hours

Notched impact strength at +23 ⁰ C

Π Il

, ο.

ι »" -29 ⁰ C

Dimensional stability
Breaking load under tension / o elongation at break

Modulus of elasticity under tension i 'maximum load under ^^ ie ^ ung Elaoti:; j t.ti i-.sinodul under ie, -un ;:

5, 6th kg cm / cm kg / cm fl 5, 1 Il H ti 5, 0 Il Il Il Il 88 5 ⁰ C It 450 ti 23, 5Si 31,000 850 2 P 000

^009816/1864 BADOR ₁ G ₁ NAL

Duu · * ■ roäukt also distinguished aioh by a low light stability and a ^ u tu -υ st hardness -jo ^ en solvent.

^χ 'ϋΐ.; μΐο1 7

30 Cl.jv ions great ο ine α according to Example 2 Kischpolyrierisates are produced with 2.0 ^ weight parts of a -.ioclipolyi.-iorisates μ us styrene and. Acrylonitrile, whose i-agenschaiten are given in -L ¹ Mi) VjIIe II, intimately mixed. If you work like iiii vorliergelienaGii example, you get a product, its. Ui ^ enachaften are shown in Table IY.

table IV

Curved toughness at +23 G π ir O ⁰ G

ir Ii -29 ⁰ G

j'orj.ibe stiiii'iiiyke it
• breaking load under tension _f '·; , ^! j * $ .;. ·· 11 ο: ι de hnun ^;

■ ^ lr, .sti ", itütsniodul under tension

i; among youngsters under "bend

^ roduct also showed high light stability and a ü Resistance to solvents.

5.5 kg cm / 'cm 4.7 Il 11 3.6 Il Il 9O ⁰ G 425 kg / cm 29 000 Il Il 800 Il Il 27 500 1 »Il

Voile of a '-L'erpolyrriuren τοη the following composition

33.5 Grewic parts styrene

37.5. "Alpha-methyl styrene

?. ') "Acrylonitrile

; i (;; i given in 'L'abolle V' Eigeriscliaften

009816/1864

- 1ö -

Tabel

ICe / bsehl; - £ zälii _t -: i - .: oit at +23 0 'Oi ¹ I oeötäruLJ. Le; it
':;πιοϊι1:'..'- ΐ under opnr.üun ^ , '■> - cloth; .ehnun,

üjl-isticity modulus under Spa.r.uiu .; Maximum ooluütun_ with .. '. · R-i'jrun; · ül-.stizitätsnüdul turner J3ie ^ _ur. _O

1.5

ια: ° ο

36 CcO 1 UO 34 OCO

lc £ c:; / c il cm ^

Il Il Il Il Il Il

v / urdoii with 25 Ge'-iic '-. parts of the ^. "G ^ äss' .oiapiel 4 presented Iiischpolyi..erisates vori; .ii.: cnt,.!''leads: .ian do.s VerlU' tcx · don in the Yor-ILV: 3hor: .. ion -oispielon anrc- -> jrj.i. -.? ^ i ^ L ^eii duroli so ei "huh .t r.an a - ^ cc: \ u: .t : · ϊΐ ori in 'i-'obolla VI nr _: orebe f, i. - ^ ϊ ^^ ·: ,,; ΰ:. ^. ΐton.

Table VI

Kei-b.jclilPisähi ^ i'.eit at +? 3 ° G ΐ'ο rmb e π t and i ^ k e i t

100 '700 5

34 500 1 100 33 ol.:;

kg Ο ", .:, / cm ² It Il Il It Il Il

Modulus of elasticity under span: .un {; i'iaximal stressuria; under üie ^ ung iilastizitcitsmodul under IUe; Lin _f; ·;

Ground V / instead of 25 parts of α tu _(, buäss üeirsj iel 4 made /-.isohpolyi-ierisatee 25 parts of the Example 1 ^ eiiiss Hischpolynerisates prepared vei- "., ^J jt end, we obtain ein.troduict with the in χοbelle VII indicated JSi ^

Table VII

Notch toughness at + 23 ° C dimensionally stable
■ örcJuhliJst under tension $ elongation at break

Modulus of elasticity under tension Maximum load under iiie ;; unj Young's modulus under bending

009816/1864

2.5 kg cm / cm

96 ⁰ C kg / cm 600 12? B With 35 000 Il K 1 ObO Il H 34 000 BATH ORIGINAL

"Ve LV;, -". Et: .. aii compartments of 75 parts of the heated Toj: iU: J '; ^! : i share the, ii.je ^ xDolyi: ieri ^r jatcG according to example 1 or 4 [j ;, vie'A'iciitsteile des T-vrpolyueren uud 50 ^u e \. 'ic'.rbsteile des ι,;, ο- j-olyr-ieriaats gomJLas -'eispiol 4, so get "; aan a product Ii ₁ It de; j in ^ a ^ elle VIII.

Table YIII

Basket sleepiness at +2 I ¹ O Γι · / · * e 8t and igkc- it ■ ^ rac ^ -l'-is under o

. 4.4 kg / ^ cra ² '100 ⁰ C 530 ti Il 16 ^c / o M. Il 30th 000 Il Il 1 000 29 000

Jilliat iniii'tsrucual with or Α-Γ :: ϋ .. · 'albeluötui!.,' Under

El "rr'i ^ itr.tsmodul under g

All _i:; dieoen Jeiapiel liei \; estell " ^f en - ^ rcuiuite zeicliiien du.-'-: ^1. '." Ι: ο · μ3 LichstaiDility and good - "estänai ^ lceit i'e _t ^- er. Losiiii _fe 's i'iittt'l from,

5 ^ --eile eir.ee iiochpolymerisates from Gö ^l t ° o '- ^ eth ^' lstyrene and 35 / J Ac: -: ;; lnitril nix the properties given in Table IX

abelle IX

iorb; ohla _e sähi _; _lceit bei ίο rn ο est ändi _o ']'. eit -irunhlast u ^ ter tension

104 ⁰ C leg cm / cm 720 UOO kg / cn ² 37 100 Il It 1 000 ti It 37 ti Il

Jl-3 st i Kitat sinoi-iil nut or Spa il; .ixi.'i.albel: i3tu. T under bending Elo-sti £ -it.äts: no-üul uat Jr. lJie _f '-ung

vru '-. i-.n nit 5 ^r ''-': icLtöteile des, _c -.... iss .- «iripiel 4 her _: " -G3telteii- --i: '. ··. ,, VlyireVis ^ toG ixi :: ig veri ';i;.: o.it. Jic ". create. '· the Hiiiciiai ^; .er; "- / igtο v / io ii» fjiijyiel 5 mige. -ben; daü ^x roni., kt vies die Li, Tr-j j. Io X avj; t "■ '.-". -öi. - ! - «if O] JHc! 'L · ..' ^! <I; ίιιι,

0 0 9 8 1 6 /1.8 6

bad original

Table X

Notched impact strength at +23 C S ¹ O rmb est änd i; ; speed
Breaking load under tension ^c / o elongation at break

Modulus of elasticity under tension i-ir.xiii: al loadingui .r under bending Young's modulus under bending

Lichtstabilitä ^"1; and Lösungsroittelbeständi ': ness well

Example 10

2 , 5 kg cn / cm 101 ⁰ C 600 kg / cm ' ¹ ' 7th 33 000 Il If 1 000 11 Il 32 000 Il Il

80 G-ewichtsteile a genäss prepared in Example 1 ^ iuchpolyme.L'iGtites v.'ui-20 with the weight of a te ilen ■ erpolymerisetes from 33 [5 weight percent styrene, 29 ^C, S trei.'ichtsprczent Acr3'lnitril and 37 , 5 percent by weight of α-ί-iethylstyrene inni '_-; vcrmi-jcht. The üigerischa-ften des Terpcl ^ nncrisates si) Λ in T-nbo XI together.

Table XI

iilG ^ ity at +23 ⁰ O 1.5 kg cn / or

Forrabost ar. rligke it
üruchrst under .tension ° / ό- elongation at break

Modulus of elasticity under tension Maximum load under bending Modulus of elasticity under bending

The properties of the missing with the help of a laboratory extruder with a diameter of 30 mm with an i'emj

102 ^C G kg / Il 750 Il 2 , 5 It Il 36 000 Il 1 100 Il 34 000

of 190 ° ^ preserved ^x roductes are listed in 'table XII susami-ien.

BATH ORIGINAL

009816/1864

Table XII

K BV υ 3 ο.h toughness was +23 G it ti Q ⁰ G

II it -29 ⁰ G

under chip

.Jlf. & ■ ti; \ i power module under tension

o under .bending

l under

1 kg cn / approx 5, 8th Il Il 4, 3 . M. Il 91 5 ⁰ O 490 / C2; l ~ 39 β 28 500 Il Il 810 It Il 25,000 Il Il

LicL'tGtp.'bility and solution Liii; tolbc3täinli: -; keit '

70 u) ioate parts .ies' according to example 1 liertestelle i> Ii., Chpolymeri sateo with 30 parts by weight of a l'.ischpolymerisates from 74% styrene and 26% by weight acrylonitrile inni missJht, Die Eir; en3,; 'aaften des styrene-acrylonitrile-rliscli - /.' crcisc-tes are compiled in 'fabeile XIII.

Table XIII

ICerbß -iila-jzäliigkeit at +23 G i ^{| l} or in be G t and i glce it
; ji "iici.l -, / jt under tension; j: J γα oh de] ix ιυη; _ \

aily-.tiaitatsmodul 'under tension Rocicv / ell-.iärt-3kfila L ^ ■ Hxii'ialL ^ lastunfr under riveting -Sla.j "- 'icity: .iodul under curvature

Licht3 ⁺ ..tbielität in the ^ ade-O-raeter after 50u hours

very good.

2 kg cm/ 95 ° C 750 leg / 2
cm 2.5 34 000 Il Il 110 1 100 Il Il 35 000 Il Il

. · .Oni ". Door of 19O ⁰ G of the product obtained are in

j ton of the with iiiife of the laboratory Ji'xtruder at t
'L'fVh'jllo iCIV a

009816/1864 bad original

Table XIV

4th » 7th __ If G cm / era 90 3 Il K 500 » 3 Il 26th t 5 ⁰ G 5CU cm ² 850 7th Il 30th 600 Il Il Il Il 27 ft

Toughness at +23 ⁰ G Ii ti Q ⁰ G

ι. ι, _29 ° c

Pο rmbe u t andigke it
'- ■ ruciilaüt under Sp; / j - ^ ruchdehr-ung

Modulus of elasticity uncer ops.nrr i-.rjs: ii.ial load under ^v jiegun; ·; Young's modulus below 23 ie gun

Light stability and solvent resistance Well

Example 12

hau represents in the v / eioe described in.-ei ;; j.iel 1, however using 59.4 percent by weight St7 / rol, 30.6 percent by weight Acrylonitrile and 10 Gev.'ichtsproaent Polybutr.iien (Firestone IF 35 A) produced a first copolymer, v / elches has the following properties:

Notched impact strength at +23 G dimensional stability
Breaking load under tension ^c / o elongation at break

Electric modulus under tension axial loading under bending Young's modulus below ".-Iiegun ;;

30 parts by weight of this first polymer are mixed with 20 parts of an Iochpolyraerisates of 74 percent by weight styrene and 26 percent by weight acrylonitrile ini.a _{ö the} properties of this last Hi,.; Chpolyriex * isates are given above in table ZIII.

Di'e EigonfjCiiaften by the Ve MiiJoiien using a Labora- r.oriums ro-Extruiers with. '.'; an iairchuesser of 30 mi: i at a

009816/1864 bad or, g. _N al

14.5 kg cm / cm 82 ⁰ G 335 ρ
kg / cm 9 25th 500 It It 655 Il ti 23 400 Il If

Temperature of 19O ⁰ O obtained. "^ roduktes are susam; in Table XV;, '. set _β-

■■ "... Table XV

Notched impact strength at + 23 ° G it ti qOq

it ir _29 ° G

Dimensional stability
3inichlast under tension

IJlaDtiaitätsmoditl under tension ilaxii ^ al burden under Pieguivr Modulus of elasticity under "Bieguiit;

Liquid stability and solvent resistance ' Well

3.4 kg ; ciTi / cm / cm 6.7 Il η 5.2 Il Il Il 85 ° G Il • 350 ke Il 11 27 500 Il 680 Il 26,400 If

40 (each of the first i-ii.-jch.- ■ polyn-erisates described in Example 12 made of 59 »4 u-ev / icrtsproseiit Styrole, 30.6 G-ew'iclitsprosent acrylonitrile and 10 Sichtsprosent polybutadiene'mit those described in example 12 a _n gegebeiien Eigenschaiten were üev 60; iclitsteilen a Kisclipol; / Pierisates-out Acrji-lnitril innij vernincht 74 G-ewicbtsprosent styrene and 26 weight percent the Sigenschaften of letzgenannteri .iöchpolyaerisates are given in the above Table XIII.!.

Heraiiccht these two copolymers with the help of one Laboratory extruder with a diameter of 30 mm for one Temperature of 190 C. The properties of the product thus obtained are summarized in Table XVI.

Table XVI

at '+ 23 ⁰ G O ⁰ G 3 ,8th kg cu / cm ' Il -29 ° C 3 0 ti Il 11 3 , 2 Il

0.9 8 16/186 4 BATH

85 ° ö kg / cn 420 - 11 Il ti 32 500 Il Il 820 Il tt 30th 600

Table XVI (continued)

Dimensional stability iSrucbl. '. <St under tension ^ζ ρ elongation at break
Modulus of elasticity under tension Maximalbelantun, ^ under - ' ^: 'i'e_f;runt;Young's modulus below T3ie ;; unr

Light stability and solvent resistance Well

Example 14

Put in the form given in eirjpiel 1, but under VeMeJiUUi ₁ .; From 56.1 percent by weight of styrene, 28.9 percent by weight of acrylonitrile and 15 percent by weight of polybutadiene (Firestone LV 35 A), a first Iirchpolyrneris-jt, which has the following properties:

Notched impact toughness at +23 de ve rity L o u c t o u t under tension / b elongation at break

Modulus of elasticity under tension and axial load under bending Modulus of elasticity under bending

80 parts of this first hearing polyp are included
20 parts by weight of a copolymer made from 74 ^% by weight of styrene and 26% by weight of acrylonitrile intimately mixed. The properties of the latest Micchpolymörisatos correspond to the values given in Table XIII,
i'ian mixes the two aforementioned i-iinchpolyiaericuit using a laboratory extruder with eiiiei ;. jJui.'cli knife of 30 mm at a temperature of 190 ⁰ G, the properties of the product thus obtained are in the ^y i; cJiiolgendon table XVIl compiled,

BATH ORIGINAL

009816/1864

26th 5 ⁰ G k / i C. / Ci;) 76
285 5 , / cm ² 26, Il 20th 000 Il Il 505 Il Il 17th 500 Il

bey lagza Jxi ::; no T abella JiTII γ. la at +23 ⁰ G H Il Q ⁰ C il biindi gke it «Ι _29 ⁰ C For ,! et un ter υπ; :: tension

Elast Ι ?, ι t ^;; tg module, under tension

supply

astuiig imtor bend

under Uie ^^

Conductivity Stability and Solvent Beatandi ^ Leit Well

17th , 7 kg a / cm 11 , 2 Il Il 8th , 9 Il Il 81 ⁰ G 340 'cm ^ 26th , 7 23 500 Il M- 590 Il Il 21 250 Il Il

ή-'J -Jc'V.'ic ¹ ! Uiteile the first liischpOlynieriastes geruäss Example 14 CIIT indicated there properties are mixed with 60 ^u 'ev / maybe share one -iGChpolymerisates avis 74 u-ewichtsprozent uric styrene. 26 percent by weight of acrylonitrile, intimately mixed, are given in the table

From .tor / "two lüiechpolymerisaten above provides one u-itor V"f> rwendung "a La.boratoriuras extruder having a L of 30 urc'j'iiesser ini.n at 190 G, a mixture ago ₀ The iligen- ,:; '; -. "tone of the ao eiii al share product are shown in Table XVITI

Ta.belle XYHI

Basket.Kihlagzäiji text at + 23 ° C

it -29 ⁰ C

^ riioi-ilast unt-., r tension ',' j isruchdohnun / i.

under tension under iJie

5.4 kg / cm / cm 4.7 Il Il 4.5 Il Il 85., 5 ^° C 435 kg / cm 27 29 500 Il It 765 It Il

0 0 9 Ö 1 β / 1 S 6 Λ

Table XVIII (ITortsutsun ,.)

Young's modulus under sieving 27 200 kg / cm

Liability and solution with "Gelbes tändi _f _; ke it '■ good

Example 16

Hari provides a Li .-. Chpolyiaericp.t in the in -.ei-jjjiol 1 anre. levels Way, but under Verwenlm:?; of 71 Gevyichtprotfänt styrene, 25 Gev / icntsp-vc-xi-t acrylonitrile and 4 percent by weight polybuio, -diene (Firestone WF 35 A) as starting material. This I-iijchpolyrnerisat \; eis the fol ^ endon properties:

Notch resistance at +23 ⁰ O H it O ⁰ G

κ H -29 ⁰ G

Dimensional stability
Breaking load under tension
^c / 'o elongation at break

Modulus of elasticity under tension
Young's modulus below

5 ,1 leg era / 4th , 0 Il Il 4th ⁰ G Il Il 90 495 kg / cm ² 10 32 000 Il It 910 It It 31 000 Il It

37 parts by weight of the first ^ i.-ohpolynerirates thus produced are with 63 parts by weight of a Mi .'- jchpolyumrisates from 33.5 Weight percent styrene, 29 percent by weight acrylonitrile and 37.5 percent by weight α-1-ethylstyrene are intimately mixed. The -uigenGchaftsn of the last-mentioned copolymer are given in Table V been.

mixing the beileii said Ji :: hpolymerLoate HiIiO with a laboratory-üxtruders ult 33 ai .Ourchmesser at a '1'eniporf.itur of 190 ⁰ C, Die - ^ i_ünjciial'ten production of the thus obtained tes are nachioinenden Table XIX susiiLii .- 'ün

BAD ORiQlNAL

009816/1864

i ^v o η: ¹ be 3 tan u 1 gh eit
under S.

barking XIX

box +23

O ⁰ G =

-29 ° G

JJIy s ti a it ät amo dul with tr tension Rrxi'mlbelustung under bending Blasfisitätsmodiil under- Bie ^ 'un ^; Li oht st ability and Lb "suiy smi11 e1-

-f1

Well

1 , 9 ti / cm Il 1 , 4 Il Il 95 ⁰ G Il 555 Il 2 14th , 9 It 33 500 Il 1 • 075 Il 32 700 Il

17th

75 C-rJvichtsteile cies according to! Example 16 her ^ est should first. '.. ivjcipolynierisates with dui ^v there an ^ jo-gebe'cier. Ata 2usaii'eiisetEun ^ and phjrsikalifschen L'indicated there are 25 ^f ic; -, 'ic'itsteile.ii an i-Iioolipolyraerisates AUC 33.5 G-ewiclits-' percent styrene ,. 29% by weight of acrylonitrile and 37.5% by weight of a-Hetlivlotyrol im.i _o . irerMiscf.to The characteristics of the latter; ii3c} ipolymerisates have been compiled in Table Y.

From one of the above enaiates iiisclipolymerisateii, η.'ίίΐ -inter ^ "er '.' Eiid-un ^ a laboratory extruder with a diameter of 30 mm at an inner temperature of 190 ⁰ G a iiioc.! Im-, her. 0 ± e ilir'jenscha-rten riar? so obtained sinrl in ü: from eile XX put together to ■. ■

■ Table XX

Kerbociila _t :, closeness at +23 0- ti ir O ⁰ G

3 ,. 5 kg cm / cm 3, O-
C- Il dd 2, 6th It It

ErucJ-last

505

lc π / cm '

00 98 16/186

_ ₂₈ _ 1589418

Table XX (port setting)

fo elongation at break 15 * 1

Elasticity amcaul under tension 32 500 kg / am Maximum bend ctuntc under bend 960 ""

Modulus of elasticity under bending 32 100 ""

Liability and resistance to solvents Well

0 0 9816/1864

Claims (1)

2.99 Ms 1 Gev / * - 5'o of a thermoplastic llischpolynerisata from 20 to 50 percent by weight of an llonomer from the. Acrylonitrile type and 50 Ms 80 .-fo a lioiioraeren of the styrene type, v / o The elasticizing graft polymer 1 of a butadiene polymer and a graft component is thawed, characterized in that the elasticizing graft polymer is thawed by suspension or bulk suspension polymerization of a mixture of 50-80 trew .- $, styrene-type monomers and 20-50 Wt .- ^ monomers of the acrylonitrile type in the presence of 0 _r 5 Ms 30 wt. 5 & butadiene polymer, based on the total mixture of monomers and butadiene polymer is. "'' ■:: ■ ■. 2,! "Standard masses according to claim 1, characterized in that that the elasticizing graft polymer in a two- stage polymerization process has been established, in which initially a mixture of 50 to 80% monomers of the styrene type and 20 to 50 wt. / S Ilonomeren vom. Acrylonitrile type in the presence of 0.5 to 30% by weight of butadiene -polymerized in bulk to a degree of conversion of 10 to 50 and then the mixture of partially converted Monomers ready in an aqueous suspension polymerization .has been polymerized » For . Montecatini feDISON S, p.A « oo.4 »i.» / iM *. ■; · "- ^8AD0B1GINAL right