DE1241107B - Thermoplastic molding compounds from mixtures of copolymers and graft polymers - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY GERMAN W> <W ΓΛΤΕΝΤΛΜΤ

VW

EDITORIAL

Int. Cl

C08f

A λΛ *> Αλ

German class 39 b -22 / (16

Number 1 241 107

File number F37972IVc / 39b

Registration day 5 October 1962

Exhibition day May 24, 1967

It is known to use thermoplastic molding compositions high impact strength by using hard and brittle polymers such as polystyrene or Stsrol-Atrslnitril-Mischpolsmensate, with fur soft, more or less rubber-like polystyrene, such as butadiene-styrene or butadiene-acrylate / lipolizate, combined

They are known to the international community open / in I I / idling! hcsscicr Confidentiality of components the li.iiie hai / aiiigc component for example styrene and Auslnilril in the sense of a Graft polsivu! Isation in Ciegenwart of the already polymerized ktiiitschukaiiiuen component polymerized will AK let / leie linden especially butadicnhomo- and -copolynKiisalc with styrene and / or Acrylonitrile use Jc according to the applied Amount ratios / inherent in these graft polymers resin-like, llicimoplastiM.hcii to kaulsihuk-like elastic (haiakler. You can therefore .yourself as thermopl: istisv.lu * loimm.'isscn seiweiulcl weiden ao or about / tu llcisiclluiu · sokhei mil Un hetpcare themselves tlu.imopl.isliM.hen polymers, / B SIs 1 Oil At rs In it 11I-M isc Ii polymers. mixed svcuien

In the biitisclien PatenisthrtU Ij59 OHO it has already been suggested that its plastic table-elastic molding compounds from 6S bis. 85% of a hard-like copolymer of x-styrene and acrylonitrile and a graft polymer, obtained by polymerizing styrene and acrylonitrile in a ratio of 65 35 to 75 25 to a pol butadiene The masses of the present invention differ from C in this case, the Bntische patent does not reject the use of polybutadicnlaticcs with a particle size below 10Q.ir i; x

In the known processes for the production of these graft polymers, in order to achieve favorable mechanical properties, it is essential to use a block polymer as the graft base, which is obtained by polymerisation in a very concentrated emulsion (which is the result of a very concentrated emulsion). indcrnf.ills are I orrnniasscii with sthlctliten mci.hanisi.hen Dilen, nisbesoiulcre nictlii'jci Si.hl.ii: - and Kerbs, hlag / .ihij; -kcit ei had Πιο I Icrstcllnn «; eiiKs such kon / entricrlen Util. ulRiipolMiieri ·. lll.itev with high IciLlicngrüe and reprodii / icibauii I ickness of the data made graft pole> mcris, it is technically flour simple So is, as mentioned, cmc high monomcrcon / entration selected from thermoplastic form polymerisation
from. Copolymers and graft polymers

Applicant

r-Bayer Aktiengesellschaft,

Leverkusen

Named as the inventor
Dr Karl-1! Rubbed. Meager,
Dr Karl-Heinz Ott, Lcveikuscn,
Dr Karl Dinges, Odcnlbal,
Dr Harry Rohr, Cologne

El h cm nicely water-monomer distribution of z. B less than 1.0 cifoidcihch Aiiliculcm must be marked with. His little Mcnpcn to Iiilj-'iciniillcln Heide measures hUiien you / u that cistcns clic Polymeiisalionsgescliwiiuligkcil is ielatively small and (.Ul ^ / svcns the or I iiuilsions- . Latcx.slabilit.'it while the polynieiization is enough and the inclination / ur Ko.igulalbiUlung is gioß Both phenomena are technically unpleasant and uneconomical

Such concentrated coarse butadiene polymer latices result in useful graft polymers if more than about 50 parts of styrene and acrylonitrile are used grafted onto 100 parts of butadiene polymer

There are also methods known at those poor properties of mixtures of graft polymers and resins due to the addition of one rubbery, ungrafted Polsmcrisats as Diet components are improved by one such addition go andciciscils benefits again, the molded parts are made from Pfiopf polymer composite niches, like ζ B gloss and low cold plastic flow, serlorcn

The use of 111 diluted emulsion manufactured and nut Divin> lben7ol vcinet / tem Polybutadiene also produces Pfiopfpolymciisatc again, which are unsatisfactory in terms of their mechanical properties are

The subject of the invention are thermoplastic molding compounds the end

A 96.85 to dl (weight percent of a mixed polymer from styiol and acyl nitrile or their Alkyl derivatives in the ratio 50.50 to 90.10 and

709 587/595

a .-- »τ * ηιτηκ t

Ii 3,15 to 39 (<cwiehlspio / cnt of a Pfiopfpolyniens.ils from

ii) 5 to 50 I rush a mixture: uis Siyiol to! Aciylintiil in the proportion 50.50 to ¹ X) 10 aiii

b) 100 parts of a polybutadiene latex

characterized in that the graft polymer using a Pol) butadiene latex with a Particle size less than 100 ηψ hcigcblclll is

The Buladienpolymciisat used as a graft base should contain at least 80% butadiene, preferably a Buladicnhomopolymcribatlatcx used

The thermoplastic polymer mixture consisting of components (A) and (B) must be composed in this way be that the total mixture 3 to 30 percent by weight of the rubber-like graft base contains 96.85 to can be calculated from this 61.0 percent by weight for the proportion of the styrene-acrylonite mixed polymer (A) and 3.15 to 39.0 percent by weight for the proportion of the graft polymer component (B) in the miseh polymer mixture

The compounding-varnish molding compounds have a high impact and chopping / ahig wedge on Dci especially voileil lies in ti «. 1 Vetwinihmijsinophchkcit of polybutadiene! .Hit i's mil Utiiiu nutileiei Icilclicngioßc «ils l'fiopl ^ iinull.i ^ i, wililn icihniseh außeioidenllieli cinl.ii.li liei / usullen isi Dci den known vcifiihien isl the use of such a Lalcx not possible

Thermoplastic 1 standard masses with good impact and Keib / aliitäten can ii.ilIi the British Patent Schrill 859 080 eihalien graze, however only if one uses polyhutadiene latices as Plroplurundl.ige polyhutadiene latices with giolien fciMicn, Ciemali devotes the present Rounding can be thcimoplasiischc Γοπιι-masses With very good whipping and kicking characteristics also with the easy) accessible polybutadicnlaticcs with a little 1 hurry hen heigestelll pastures In addition, crfoidciln.h, the components in use the quantities / ti \ given above, which differ from the quantities of the abovementioned briiischen Clearly distinguish the patent specification

Experimentally recognizable! you do this when you have quantities ends in thermoplastic copolymer and graft polymer, like the British one Patent specification, but the prepolymer made of a polybutadiene latex with a small particle size Manufactures Such verisiche are as experiments 6 and 7 of Table 1 have been and are duichgeluhit here again / iisamniengesielli

¹ Vn Polylnilailien in the Pllopl polymerisat
mixture

Parts of graft polymer

Parts SAN-I lar / ..
° / o polybutadiene in the mixture

·) Α-MelIiyktyrol-At. 1 ylnilnl-Ilai /

VtIMIiIi 6 I Viisiuh? V <- 'liiUl ilur voiliC

60

29.2 ι 31

70.8 y 6 p

17,5 '17, p

Ναι Ii hi K isilicui I "ill nt 8V) OSO

M) to M)

15 to M 65 to 68 *) 1 to 30

The attempt (> and 7 / eij'cn clearly gciingeie Keibschlai - '/.' Lliii.'kcilsw'iile than those at Pioduklcn gcm'.lss measured by the enclosed lind

Lim further Voileil results from the fact that the graft polymers at relatively low Proportions of grafted styrene and acrylonite cmc very good compatibility with styrene-acrylonite copolymers It therefore has the same properties in the mixture in order to achieve the same less graft polymer is required for graft polymers with higher proportions of grafted styrene and acrylonitrile So you have the Ability to use a larger proportion of the total in the styrene-acrylonite-polyimnate present in the mixture for itself in a precisely controlled manner (K-wide, molecular weight distribution) to produce what not without further ado with the plucked portion possible isl

The preparation of the Niitadiiiipolymeiisatlatcx serving as the graft base takes place in a known manner duiih Pol) meiization of the monomer (s) in waHrigci 1 niulsion As a comonomer in the Polyineiisalion of butadiene up to 20% others with HuI.hIich misthpolymeiisicibare Monomcic, like wcitore Louiujiieiie Oioleliuc (/. B copies) mlei Vinyliiutiioincre, voi / ui'swiise Styiol iiud / odei Aciyliinnl, or tloien AlkyldiMivate, such as A-MiMliylslyiol or Methaciylniliil, miiveiwi'iulii wuikn Hevot / unl wild butadiene .illcin \ ciwendel

At the lleislelhing diesel Bulailicnpolynieiisatlatices are used when using nichi than 100 parts, preferably 50 parts of water to 100 parts of monomers, and emulsifier amounts of 1 to 10 parts, preferably 3 to 7 parts per 100 parts of monomers, stable LalicCs with medium Particle size !! under 100 m; j. hold egg

The usual sodium, potassium and ammonium salts of long-chain carboxylic acids with 30 to 20 C-atoms, / B stearic acid, oleic acid, dine oil sauce, of shark / acidic, / B disproportionated abielinsauic, of alkyl sulphonates and millals, can be used as emulsifiers, Reaction periods of about 5 to 20 moles of alkyleno \ yd with I Mo! Fatty alcohols with 10 to 20 carbon atoms or alk) phenols, cation-active compounds such as 7. H SaI / von Steanlamin et al. Preferably those emulsifiers are used which, as free acids, have no emulsifying properties

Customary inorganic or organic per compounds or azo compounds, such as, for example, potassium or ammonium pci sulfate, can be used as polymerization catalysts. Ri I. Duly I Ii viii <> pi io \\ d, CuinolhydiopiMoxyd, Λ / o-iliisobiilU 1 s.'uiu mli il. serve, which in ilen lihlichcivuisc in Aiiwuidunn koin-

/ mien quantities, <lh about Ο,'ί to V / ,,, with ais polymnxntionxkatalysaloren can anorgai'f total monomers, one ingosei / t graze Ls is niche odci organic per-compounds or azojch rn ^ ueh, redo \ s \ stemc from the compounds mentioned, such as potassium or amine compounds and reducing agents, such as formmonium persulphate, tcrt butylhydropcrox> d, cumolildclnclsilfov \ lat tnathanolaniin, etc., use hydroperoxide, azo-diisobitic acid regonitrile, as "in" Kcgiiliuung of molecular Kst also possible Rcdoxsystunc from said ücn / gcwichts the usual langkelligen Mcicaplanc as PervciWindungen and Rcduklionsmillcln as Γοπτι-z B n-Odei teit Dodecylnieicaplan / ugcsct / l, aldchydsulloxylat, inter alia Tiialhanolamm / uurwcnden the Polvmeiisaiionslempeiatuicn can For example, salts 20 to K) OC IuMi ₁ I) ¹ U), voizugswcisc weiden tempe- io of the oithophosphoisatircle pyioplioxphoixaiie laluicn / wipe 40, can be used as p1-regulators and «0 C applied. The poly- can be added. The polymcrisalion can be added at nu-nsation at pll widths between 2 and 12 pl! widths between about 2 and Il diii«. grazing, preferably carried out at pH 7 to wild Il, voi / UGT as a PLL for example, the Uegiil.iloicn Polymcrisationstcmpcratur may be about 20 to Sal / c of Oithophosphorsaiirc odci pyrophosphoric 15 100 ⁰ C, preferably 40 to 90'C, be
Acid added. The styrene can be partially or completely replaced by A-Me-The polymerization can be replaced before full ethylstyrene is reached. A replacement of the constant acrylonitrile conversion can be terminated of the monomer; 20 mcrization component (A) with the graft polydei (lel) 'ehiill (in toluene insoluble portion) is merizatomponcnlc (U) can according to .111 sn.li known (limn i'kiIVi as 70 "/ ,, expired cilolgen, iiulun man a mixture bulges The Drlo-Iliiilo ilei so eiliallenen Polymeiisale is Laliccs / in j'eniciiixanion Ko.ij'ulalioii mil I lektiojtiiWlcuiK lOOO.dii Moomy l'laxlizil.l () uo | lci alse (wa70. lylen od lind g <ri bnicnliill. 1111Γ NuIiI iiwi'tsi l / io MonoiiKie, voi .illein butadiene, 33 (kMioil Ί cinpeialiii uliil / l I> ic AiI di s im / iiwrndcnwoiden diiicli nuilcikulations means, thanks to the KoiU 1 vcii Of course, the (liiieh Aiishl.iseii nut Slicksloll odci duah Wassei- dcmisch existing Lmulgiei milliln l! ei both danipfdcstillaiion enilLint in the acidic as well as in the alkaline (all emiilgieicnd lintel of the usual conditions described) and acting (alkyl sulfate) agents die I! omopohnicrix.uion b / \\. MischpoK- 3 0 are mainly ElckirolWe, vi «· /, JJ N'ain'ani ί | Ίι, i> iiivvn VlOv RvIa-, Vflv \\ iM \ -3) tiivi öhre B'.Vli ·« chionJ, Cakiumchtnnd oJer Λfr ^ rnrr . 1 urri ^ u! ^p . 1 f, jncc- \ e> Ji KiMgiii.ii applies in the case of emulsifiers, which in the acidic debicl no longer have the ileixlJliini. / B acid, acetic acid, / in Ko; ij'U-pfiopfcndon Mononii-ion (Sl \ ml and Acnlnitiil) 35 lalion Is lsi also possible, clinch cooling of the / neck 111.i / ii / · im I ak \ tlis, ils Pliopli'iiiiull.i ^ e serve- Cicmisches on ΓοιηροιηΙιποη unlci 0 'C KiufMiliition den Ι'οΚιΙκ'Κ lins (z Il l \> l \ hiil.ulicn) voipeiiomiuen lieibei / uluhien (»Aiisfiieten«)

I ¹ S wiul in piin / ipicll tlei same white vei- Dax after the division clinch I iltialion odei

proceed as in the case of the cleaning, washing and drying activities (described below)

position dei llai / komponenic (A) The avif / upfropfen 40 powder-shaped to koinige polymcnsalgcniisch can

The Monomcicn Siuol and Acrylonitril can act on rolling, kneading or similar

once or during the Polvmci ation facilities at temperatures from 140 to 180'C

are added. The graft polymer latex is compacted and converted into a granulate in the usual way

the Allcrungsschul / miitcl, as 7 B substituted ways are processed, with voi or during

Phenols, added to this process pigments, dyes and

The production of the thermoplastic compo medium can be added

Component (A) is also made from styrene and acyl nitrile

as usual by polishing the monomers in thermoplastic masses to the usual processes

Wadiigei I niulsion Here the usual water-mixed objects can graze

quantities, 1 tmiliMlmcn, regulator, P (> lymeiisationskataly- so the granulate can be treated with Spiil / Gußmasclnncn / u

saloien, pl I-Rcgulalmon and other additives% formed parts are processed with the help of

Wendel Weiden For example, the Mono Schiieckensprit / machines can Piolile, Plallcn

meien- b / w lOKmciixalkonzentiation 20 to 50 "/ ,,, and Kohic made graze the plates let themselves

d. h, to! 00 (howisicile monomers are 400 largely due to vacuum

up to 100 volatile water used 55 different methods /.u housings, containers,

As an example, public emulsifiers are deformed shells.

baft called Naliitim, potassium, ammonium salts The specified parts in the following examples

lnngkellmei lillxaiiion only 10 to 20 carbon atoms, are always parts by weight
Alkylsullalo only contain 10 to 20 <'- atoms, alkylsulfonates

with IO to? <) <-Ahum n. Alk \ laciylsiill.ilc · mil 10 to Co Example I

C alonies. ll.ii / s.'iiuon (/ H Dcnvale dei Abietin- I I loistelliiiij ', dei AusfiinfspiinlnkU

siiiiio) Itoofziu'l wild such lmulj> iloien, the A P0lybuiadn.nl.1lex In cm tliiuMoslos lUihr-

iiiiU'tli.ilh pll 7 diiiih ΙΙιΜιιημ dc 1 lieien seeds line gel.ill wild a solution of 200 lcilwi sal / lieicin

I miill'.iloifigciiscliallin Miliiiui Wassei, 5'leilen des Naliiiims.ilzes tlei dispiopoilio-

AIx Keglee can zm Uej'iilicnmg dex Molecular 65 inert Abietinsamc and 0.1% K.iliuinpeisuiral

weight and tl.imil / 111 I nislcllung of the desired given The LuIt wnd you rulers of Slie-kstoiT

K-Who (it e.g. displaces long-chain mercaptans, like After adding 0.4 parts of dodecyl-

Dodccyl mercaptan. 100 parts of 1,3-butadicn are imprinted with mercaptan.

Then the tempera is raised to 50 to 55 "C" The soon ciiisct / cndo polymerization is after about Finished 20 hours. Small amounts of unreacted butadiene are dutched out of the latex removed under reduced pressure The polymer · The concentration of the ciliary latex is 33%. the in ι U It ro parts liongioße 60 ιημ.

11 Plioplpolymeiis.it Dei above uhaltcne PoIybtilitdicnl.ilcx wnd nut sal / lieicm Wassci .uil such a l'nlyiiic-iis.'ilkoii / cnlialion veidiinnl, d.tlt dci ITt 11 | il pul ν π in isiii li ic n et no Polyniu isalkon / enliation von M) "/ ,, Ik'siI / I In dem / in Vnduiiminj · des 1 atex vcivvdiilcUn W.isseis weiden: iitf It) OI tile des PoIybtilatlicns 0 5 parts of potassium sulphate and 100 parts of the diluted monomers 5 parts of the sodium salt of the disproportionate ab.etinsauie praised. The pH value is adjusted to 9 to 10 with sodium hydroxide solution heated to 65 ^° C. Then in the course of about 0.5 to 4 hours in the various experiments (Table 1), polybutadiene 5.3, 11, 25, 43, 67 and 100 parts of a mixture of 70% styrene are added to 100 parts and 10% acrylonitrile. When the addition is complete, the mixture is stirred for 2 hours at 65 ° C. to complete the polymerization.

C The / um mixing with dun Plioplpolyinuisat Serving styrene-acrylic liquid misalignment components becomes clinch polymization of a mixture made of 70% styrene and 30% aerosol (100 parts) using ISOTulen water, 3 parts N'atriumsal / dci dispiopoilionieilen Abietmsauie and 0.3 parts of potassium pebble egg reverberate as a regulator part Dodecylmeicapl. in einj'osu / t Mn 0,4 lead wttd a K-Wctt nail) I ι k en l sehet, Collulosechemie, Π (I9 "i2), S 60, from SS ulialuu

2 I leiskllimv <l> ι I onnmassui

The Plroplpolymerisallatex (II) wnd with dun Siviol- »5 Acrylnitiil-Mischpolymeiisatlakx (C ') in the desired Ratio mixed and n.iJi / usal / unes anti-aging agent (z ß 2,2'-Vlcthj len-bis-4-meihyl-b-cyi.lohexylphenol) by pouring into the same volume 1% acetic acid coagulates The granular coagulate is filtered off, washed and at 70 to 80'C under The powder is then dried under reduced pressure on a roller at 160 ° C. Fell compacted, which after the l-rk.illui / u a Granulate / grind wnd from dun (n.uuilat willow As in the fuel / gulJveilahien Notinkluistabe manufactured, at which the values in Table I are averaged will.

Table I.

1*) 2 3 attempt 5 6 ·) I ⁷ >> 4th Graft polymer 0 S. Il 41 ί 67 100 Parts of styrene | Acrylonitrile) e 100 parts polybutadiene 25th In dci Miscliuit} · 17.5 IK.4 19.5 25.0 29.2 35 Share Pliopfpolyniciisal 21.9 Parts of Slyiol-Aetylnilril-Mischpolymeiisat 82.5 81.6 «0.5 75.0 70.8 65 (K-Werl55) J 7.5 17.5 17.5 78.1 17.5 17.5 17.5 Share polybutadiene 17.5 Kcrbsehl.ig / aliigkcit (DIN 53 453), kgcm / cm ² 2.5 6.3 9.4 8, X 4.4 3.8 at -I 20'C - - 12.5 5.6 - at -20'C 820 813 813 8 "S 718 756 781 Giciv / bicges tension (DlN 53 452), kg / cm ² 9JO 895 890 731 810 840 905 Ball indentation hardness (Dl N-Ciitw 53 456), kg / cm ² . XS5

*) The comparisons 1, 6 and 7 lie outside the claimed limits

Comparative test i

Instead of the polybuuulia latcx described in Example 1 With an average particle size of 60μ, a polybutadiene latex is used as the graft base with a minor particle size of 200 μm used. Such a latex is obtained if, for example, according to US Pat. No. 2,820,773 vci by using the emulsion polynomialization des Huladiens only 70 parts Wassei and 3 parts Einulgiitoi, in proportions of 1 part ugegcbcn, used The graft polymerization is as in Example I. bc-icliileben, duidifcfuliit, being 25 parts of styrene and Auylnilnl (70:30) to 100 parts polybutadiene aufpolvnifiuicit weutoi! Im lilxi |> cn witcl also, like im lloispii'l I besi.liin.ben, weiti-i veilalnen

The lMCchnis theses Veisuths is (from table II evident.

Table 11

attempt 4th «*) J Graft polymer Parts of Styi oil + acrylonitrile per 100 parts 25th Polybutadiene 25th In the mix 21.9 Share Pfioplpolymcrisat 21.9 Parts Siyrol-Acrylnuril-Mischpoly- 78.1 meiisat (K-Weil 54) 78.1 Parts of polybutadiene in the graft poly J 7.5 mcns.it 17.5 KerbschLij '/ silnpkcit, kgcm / c m- 12.5 bci ί 20 ¹ C 6.1 8.8 at 20 ¹ C -

*) VcTiUch 8 is not in the bcunspruchU.il Cjruucn

H ο ι s ρ ι c I 2

. / \ Example ilonstite the combination of one . (as in example 1 prepared graft poly ^ / its only the styrene-acrylonitrile mixed polymer Powdering ingredients must be used during manufacture f Graft polymer is different from the im

10

Example 1 Icncn Vcifsihicnswpise "Him" nf- / upfiopfoiulc Stviol mill Ai'iylnltilt (/ O; M)) with a tmigcica / eitraum instead of ilbci.

The other conditions are as in example 1 described.

The results of this series of tests are given in Table III again

/ Tabel Ill 9 attempt 11 / ίο ι I. 25th 25th Graft polymer 25th Parts styrene · + ■ acrylonitrile per 100 parts polybutadiene 34.4 21.9 In the mix * / ty I. 28.2 Parts of graft polymer. 65.6 78.1 Parts of styrene acrylic mixed polymer 27.5 71.8 17.5 (K value 54). . ... 22.5 Parts of polybutadiene (as a graft polymer) 23.8 18.8, Kcrbschlaii /. 'Lhigkcit (DIN 53 453), kgcm / cm ^a 18.8 22.5 14.4 at ι 20'C. 494 18.8 719 at -20 ^J C. 575 Grcn / flexural stress (I) IN 53 452), kg / cm ² . ... 465 755 Ball indentation hardness (DIN-Untw 53 456) (60 seconds 570 Value), kg / cm ²

B e ι s ρ ι e 1 3 ₃ o The procedure is as described in Example 1,

This example shows the use of a styrene with the difference that the K value of the styrene-acrylonitrile mixed polymer with a higher K value. Acrylnitnl copolymer 72 is.

Table IV

attempt
12th Graft Polymcnsal Parts of styrene-acrylonitrile per 100 parts of polybutadiene. . . 25th In the mix Parts of graft polymer 21.9 Parts of steel-acrylonitrile copolymer 78.1 Parts of polybutadiene (as a graft polymer) 17.5 Notched impact strength (DIN 53 453), kgcm / cm ² at t20 "C · · · ■ · 21.2 at -20 ⁰ C 16.3 Limit stress (DIN 53 452), kg / cm ² 850 Ball indentation hardness (DIN draft 53456) (60 Sckundcn-Wcrt) kg / cm ² 830

Claims (1)

Claim Thermoplastic molding compounds A. 96.85 to 61 percent by weight of a copolymer from styrene and acrylonitrile or their alkyl derivatives in the ratio 50 · 50 b-s 90 10, B. 3.15 to V) (icwichtspro / xnt of a Pfropfpolyniensals of a) S Ims 50 files of a mixture of styrene iuul Auylmliil im VciltilUnis 50.50 bis 90. IO ιιιιΓ b) 100 parts of a polybutadiene latex,
characterized in that the graft polymer has been produced using a polybutadiene latex with a particle size below 100 μm. Considered Diuck.schriflcir
German Auslcgeschrifl Ni. I 177 314;
British patent Ni. 859 080.