EP0894100A1 - Procede de production de matieres de moulage modifiees a l'aide de caoutchouc acrylique et matieres de moulage obtenues a l'aide dudit procede - Google Patents

Procede de production de matieres de moulage modifiees a l'aide de caoutchouc acrylique et matieres de moulage obtenues a l'aide dudit procede

Info

Publication number
EP0894100A1
EP0894100A1 EP97918135A EP97918135A EP0894100A1 EP 0894100 A1 EP0894100 A1 EP 0894100A1 EP 97918135 A EP97918135 A EP 97918135A EP 97918135 A EP97918135 A EP 97918135A EP 0894100 A1 EP0894100 A1 EP 0894100A1
Authority
EP
European Patent Office
Prior art keywords
monomers
mixture
acrylic rubber
chemically reactive
monomer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
EP97918135A
Other languages
German (de)
English (en)
Inventor
Graham Edmund Mc Kee
Bernhard Rosenau
Walter Heckmann
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Publication of EP0894100A1 publication Critical patent/EP0894100A1/fr
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
    • C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/04—Polymers provided for in subclasses C08C or C08F
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
    • C08F8/32—Introducing nitrogen atoms or nitrogen-containing groups by reaction with amines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/003—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S525/00—Synthetic resins or natural rubbers -- part of the class 520 series
    • Y10S525/902—Core-shell

Definitions

  • the invention relates to a process for the production of molding compositions modified with acrylic rubber by polymerizing monomers forming the graft shell in the presence of an acrylic rubber dissolved or swollen in the monomers and containing monomers with chemically reactive groups.
  • ASA molding compounds modified with acrylic rubber and in particular styrene-acrylonitrile copolymers (ASA molding compounds) modified with acrylic rubber, which have high impact strength and good flow properties and a reduced surface gloss of the molded parts produced therefrom .
  • ASA molding compositions in emulsion is widely described in the patent literature (cf., for example, DE-A 19 11 882, DE-A 28 26 925, DE-A 31 29 378, DE-A 31 29 472, DE- A 31 49 046, DE-A 31 49 358, DE-A 32 06 136, DE-A 32 27 555).
  • a disadvantage of this production is the need to remove auxiliary substances when working up the molding compositions, in order to avoid later disruptions in their processing (discoloration, speck formation, corrosion). In particular, however, wishes regarding the impact strength, tear strength and gloss properties of molded parts made therefrom remain open.
  • the invention was based on the object of producing molding compositions modified with acrylic rubber which can be processed to give molded parts with improved impact strength, good flow properties and reduced surface gloss.
  • the graft polymerization can then be carried out in one or more stages, the polymerization at least in the first stage and up to a conversion of more than 15 and preferably 20 to 40% by weight of the monomers as bulk or thermally initiated polymerization (bulk polymerization ) (preferably) or as solution polymerization.
  • the present invention thus relates to a process for producing a molding composition (A) modified with acrylic rubber
  • R 1 is a hydrogen atom or a methyl group and R 2 is an alkyl group having 1 to 32 C atoms
  • A2m2 copolymerizable olefinically unsaturated monomer which contains a chemically reactive group (A2m2x)
  • A2m3 optionally at least one further copolymerizable olefinically unsaturated monomer (A2m3)
  • Amounts of the monomers (A2m2) and (A2m3) are smaller than the amount of the monomer (A2ml) to an acrylic rubber (A2) with a glass transition temperature of below 0 ° C, (b) dissolving or swelling of the polymerized acrylic rubber (A2), optionally with the addition of an inert solvent, in one or more, forming a hard graft shell (Al), the olefinically unsaturated monomers (Alm), the polymers or copolymers of which have a glass transition temperature of at least + 20 ° C.
  • Distillates by the selection of acrylates, methacrylates or mixtures thereof, at a given content can be adjusted to certain monomers (A2m2) and (A2m3) the glass transition temperature T g of the resulting acrylic rubber (A2), wherein the glass transition temperature T g below 0 ° C, in particular below -10 ° C and preferably below -20 ° C.
  • This setting of the glass transition temperature is based on the fact that the glass transition temperature of acrylate and methacrylate polymers initially decreases with increasing length of the side chains, goes through a minimum with C 7 -alkyl acrylate or C ⁇ o-alkyl methacrylate and then again it rises.
  • the content of alkyl methacrylate or acrylate in the mixture (A2M) is at least 50, preferably at least 80,% by weight, based on the total amount of monomers in the mixture (A2M).
  • the mixture (A2M) also contains at least one copolymerizable olefinically unsaturated monomer (A2m2) which contains a chemically reactive group (A2m2x).
  • A2m2x a chemically reactive group
  • Examples of such chemically reactive groups are epoxy, amino, amide, hydroxyl, carboxylic acid anhydride and carboxyl groups.
  • Monomers of this type are known and are commercially available.
  • Examples of comonomers (A2m2) are e.g.
  • unsaturated glycidyl esters and glycidyl ethers such as glycidyl (meth) acrylate, aminoalkyl (meth) acrylic esters and amides, such as N-2-aminoethyl methacrylamide or aminohydroxypropyl methacrylate, 2-hydroxyethyl (meth) acrylate, (meth) acrylamide, N-hydroxymethyl (meth ) acrylamides, their esters and ethers such as N-methoxymethyl- (meth) acrylamide, maleic anhydride, acrylic acid, methacrylic acid or crotonic acid.
  • glycidyl (meth) acrylate aminoalkyl (meth) acrylic esters and amides, such as N-2-aminoethyl methacrylamide or aminohydroxypropyl methacrylate, 2-hydroxyethyl (meth) acrylate, (meth) acrylamide, N-hydroxymethyl (meth ) acrylamides
  • the mixture (A2M) generally contains the monomers (A2m2) in an amount of 1 to 25 and in particular 3 to 15% by weight, based on the total amount of monomers in the mixture (A2M) used to prepare the acrylic rubber.
  • Small amounts of other copolymerizable olefinically unsaturated monomers can also be used to produce the acrylic rubber (A2), the sum of the amounts of the monomers (A2m2) and (A2m3) generally being less than the amount of alkyl acrylate and / or alkyl methacrylate ( A2ml).
  • Such further comonomers (A2m3) are, in particular, monomers with at least two olefinically unsaturated double bonds, such as allyl methacrylate or acrylate, 1,4-butanediol dimethacrylate or acrylate, divinylbenzene, triallyl cyanurate and dihydrodicyclopentadienylate or acrylate.
  • monomers with non-conjugated double bonds and in particular allyl meth- acrylate or acrylate and dihydrodicyclopentadienyl methacrylate or acrylate.
  • the content of the mixture (A2M) in these crosslinking monomers or in the grafting of the monomers (bn) is 0 to 20, in particular 0.3 to 15 and preferably 0.3 to 12% by weight, based on the total amount of monomers in the mixture (A2M).
  • Increased grafting of the acrylic rubber (A2) can also be achieved by additional use of a comonomer with a group which forms free radicals by thermal decomposition, e.g. Comonomers with peroxy or azo groups.
  • a comonomer with a group which forms free radicals by thermal decomposition e.g. Comonomers with peroxy or azo groups.
  • Such comonomers are tert-butyl-3-isopropenylcumyl peroxide, tert-butyl peroxycrotonate and tert-butyl monoperoxymaleate.
  • the preferred amount is 0.3 to 5% by weight of the monomers in the mixture (A2M).
  • the copolymerization of the monomers (A2ml) with (A2m2) and optionally (A2m3) can be carried out in a known manner, in particular as polymerization in solution or in emulsion, and is preferably started with radical initiators.
  • the chemically reactive groups (A2m2x) of the monomers (A2m2) should be largely preserved.
  • the acrylic rubber (A2) After the finished polymerization and any necessary removal of residual monomers or isolation of the acrylic rubber (A2), according to the invention, this is dissolved or at least well swollen in the monomers (Alm) which later form the graft shell and, if appropriate, polymer matrix, optionally with addition required amounts of a suitable inert solvent or solvent mixture and with stirring and / or heating the mixture.
  • the amount of solvent added is not more than 50% by weight of the sum of the amounts of monomers (Alm) and acrylic rubber (A2).
  • Suitable monomers (Alm) which later essentially form the harder graft shell are styrene, ⁇ -methylstyrene, alkylated styrenes with preferably C 1 -C 4 -alkyl radicals, acrylonitrile, methacrylonitrile, acrylamide or methacrylamide, N- Phenylmaleimide, alkyl acrylates and methacrylates with 1 to 4 carbon atoms in the alkyl radicals, such as in particular methyl methacrylate.
  • Monomers and monomer mixtures are used which give a polymer or copolymer with a glass transition temperature of above + 20 ° C. and preferably above + 50 ° C.
  • the monomer (Alm) a mixture of an alkenylbenzene monomer such as styrene and acrylonitrile, in which the alkenylbenzene monomers are preferably present in an amount of 50 to 80% by weight and the acrylonitrile in an amount of 20 to 50% by weight of the mixture amount is present.
  • the amount of monomers (Alm) in the mixture (AM) depends in particular on the desired content of acrylic rubber (A2) in the resulting molding compositions (A). In general, the amount by weight of the monomers (Alm) in the mixture (AM) is 2/3 times to about 100 times and in particular 3 to 20 times the amount of acrylic rubber (A2) present.
  • these monomers (Alm) are in a subordinate amount, in particular in an amount of 1 to 25% by weight of the amount of the monomers ( Alm) in the mixture (AM), a monomer (Almf) and / or polymer (AIPf) compatible or partially compatible with the monomers (Alm), each of which contains at least one chemically reactive group which is compatible with the the comonomer (A2m2) can react in the chemically reactive groups (A2m2x) introduced into the acrylic rubber (A2) or, with the aid of an added polyfunctional crosslinker (AMV), enables coupling with the chemically reactive groups (A2m2x) of the acrylic rubber (A2)
  • a crosslinking agent (AMV) with at least two identical chemically reactive groups which are associated with the chemically reactive groups in the acrylic rubber (A2) and the chemically reactive groups in the monomers (Almf) and / or poly
  • a suitable crosslinker is, for example, a diamine or polyamine with at least two primary or secondary amino groups, such as alkylenediamines and preferably ethylenediamine.
  • the acrylic rubber (A2) contains, for example, epoxy groups, it is suitable to add monomers (Almf) and / or polymers (AIPf) which, for example, amino groups (preferably primary or secondary amino groups), hydroxyl groups, amide groups, carboxyl groups Contain groups or carboxylic anhydride groups, such as ß-hydroxyethyl (meth) acrylate, its copolymers, aminoalkyl (meth) acrylamides, their copolymers, maleic anhydride and their copolymers, (meth) acrylic acid and its copolymers.
  • Amino groups it is suitable to add such monomers (Almf) and / or polymers (AIPf) to the mixture (AM), which e.g. Contain epoxy, carboxylic acid anhydride or carboxyl groups, such as glycidyl (meth) acrylate, glycidyl (meth) acrylate copolymers, maleic anhydride and maleic anhydride copolymers etc.
  • AIPf monomers
  • AIPf polymers
  • the amount of chemically reactive monomers (Almf) and / or chemically reactive polymers (AIPf) to be added depends inter alia on according to the proportion of the chemically reactive groups in them and the amount of acrylic rubber (A2) and the calculated amount of the epoxy, amino, carboxylic anhydride or carboxyl groups bound in it. Depending on the type and reactivity of these groups in acrylic rubber (A2) and in the monomers (Almf) or
  • Polymer (AIPf) should have the molar concentration of the chemically reactive groups in the added monomer (Almf) and / or polymer (AIPf) at least the calculated molar concentration of the epoxy, amino, hydroxyl, amide, carboxylic anhydride or car- correspond to boxyl groups in acrylic rubber (A2) or significantly exceed them.
  • the polymerization of the monomers (Alm) in the presence of the acrylic rubber (A2) dissolved or swollen in the monomers (Alm) and any added solvent and optionally of the polymer (AIPf) (mixture AM) is preferably carried out as a thermally or free-radically initiated polymerization in a Temperature from room temperature up to 200 ° C and in particular from 50 to 160 ° C.
  • the polymerization can take place in one or more stages.
  • the polymerization, at least in the first stage and up to a conversion of more than 15, preferably more than 20 to 40,% by weight of the monomers, is carried out as bulk or thermally initiated polymerization in bulk (mass polymerization) or as solution polymerization. If desired, the polymerization can then be continued and ended with a different polymerization method after this first stage, advantageously as suspension polymerization in the presence of known initiators and stabilizers for suspension polymerization.
  • the upper limit of the content of acrylic rubber (A2) results from the fact that the molding composition (A) must have sufficient strength despite the embedded domains of the rubber.
  • the lower limit is essentially determined by the fact that sufficient energy is absorbed by the molding compound in the event of deformation.
  • the molding compositions (A) produced according to the invention have improved impact strength, notched impact strength and good flow behavior. Moldings made from it also have the great advantage that their surfaces are mostly matt or almost matt. They can also be used advantageously as matting agents for other compatible or partially compatible polymer molding compositions.
  • the polyvinyl alcohol used (Moviol® 30-92 from Hoechst AG) had a degree of hydrolysis of 92 mol% and a viscosity of the 4% strength aqueous solution at 20 ° C. of 30 mPa.s.
  • the impact strength values in kJ / m 2 were determined in accordance with DIN 53 453-K, edition 5/75.
  • the values for the notched impact strength in kJ / m 2 were determined in accordance with DIN 53 4534-K, edition 5/75. The impact strength and notched impact strength were measured on small standard bars which were injection molded at a temperature of the plastic melt of 240 ° C. and a mold temperature of 60 ° C.
  • the gloss was assessed on 2 mm thick round disks which were injection molded at a temperature of the plastic melt of 220 ° C. and a mold temperature of 60 ° C.
  • the glass transition temperature was determined using the DSC method (K.H. Illers, Makromolekulare Chemie 127 (1969) page 1).
  • the polymerization mixture was cooled and stabilized with 19 g of octadecyl 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate as an antioxidant.
  • the turnover was 92%.
  • Example 1 The procedure was as in Example 1, but an acrylic rubber according to the invention, consisting of 97.7% n-butyl acrylate and 2.3% allyl methacrylate, was used. Properties of the molding composition not produced according to the invention are shown in Table 1.
  • EXAMPLE 3 (According to the Invention) The procedure was as in Example 1, but 7.8% of the stated monomer mixture of styrene (Alml) and acrylonitrile (Alm2) was obtained from a copolymer of 73.5% styrene and 24.5% acrylate tril and 2% maleic anhydride (polymer AIPf) replaced. Properties of the molding composition produced according to the invention are given in Table 1.
  • Example 6 (According to the Invention) (a) Production of Acrylic Rubber (A2) 20 1685 g of toluene were introduced into a flask, heated to 75 ° C. under nitrogen and then 5% of the following feeds 1 and 2 were initially introduced with stirring.
  • A2 Acrylic Rubber
  • Feed 1 Feed 2 25 750 g n-butyl acrylate 818 mg azobisisobutyronitrile (A2 ml) (AIBN) 17.6 g allyl methacrylate 40 ml toluene

Abstract

Pour produire des matières de moulage présentant une bonne résistance aux intempéries, une meilleure résistance aux chocs et de bonnes caractéristiques de fluage, on produit un copolymérisat d'ester acrylique élastomère, contenant des comonomères incorporés par polymérisation avec des groupes chimiquement réactifs. Ce copolymérisat est dissous ou macéré dans des monomères formant des coques de greffage dures, tels que du styrène et du nitrile acrylique. Le mélange monomère-copolymérisat qui en résulte est soumis à une polymérisation par greffage, après adjonction de monomères et/ou de polymères comportant des groupes chimiquement réactifs et éventuellement après adjonction d'un réticulant chimiquement réactif, qui se poursuit, jusqu'à ce que plus de 15 % en poids des monomères soient convertis, sous forme de polymérisation initiée par voie thermique ou radicalaire dans la substance ou la solution. Ces matières de moulage s'utilisent comme agents de matité pour des mélanges polymères.
EP97918135A 1996-04-15 1997-04-14 Procede de production de matieres de moulage modifiees a l'aide de caoutchouc acrylique et matieres de moulage obtenues a l'aide dudit procede Ceased EP0894100A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19614846 1996-04-15
DE19614846A DE19614846A1 (de) 1996-04-15 1996-04-15 Verfahren zur Herstellung von mit Acrylkautschuk modifizierten Formmassen und so erhältliche Formmassen
PCT/EP1997/001870 WO1997039039A1 (fr) 1996-04-15 1997-04-14 Procede de production de matieres de moulage modifiees a l'aide de caoutchouc acrylique et matieres de moulage obtenues a l'aide dudit procede

Publications (1)

Publication Number Publication Date
EP0894100A1 true EP0894100A1 (fr) 1999-02-03

Family

ID=7791323

Family Applications (1)

Application Number Title Priority Date Filing Date
EP97918135A Ceased EP0894100A1 (fr) 1996-04-15 1997-04-14 Procede de production de matieres de moulage modifiees a l'aide de caoutchouc acrylique et matieres de moulage obtenues a l'aide dudit procede

Country Status (5)

Country Link
US (1) US6051656A (fr)
EP (1) EP0894100A1 (fr)
KR (1) KR20000005462A (fr)
DE (1) DE19614846A1 (fr)
WO (1) WO1997039039A1 (fr)

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6395828B1 (en) * 2001-09-26 2002-05-28 Bayer Corporation Low gloss ASA resin
WO2008141093A1 (fr) * 2007-05-09 2008-11-20 Buckman Laboratories International, Inc. Émulsions de collage à base d'asa pour le papier et le carton
JP4898621B2 (ja) * 2007-10-05 2012-03-21 三菱重工業株式会社 風力発電装置
KR100998875B1 (ko) 2008-10-29 2010-12-08 제일모직주식회사 저광 특성이 우수한 내후성 열가소성 수지 및 그 제조 방법
KR101286503B1 (ko) 2009-12-31 2013-07-16 제일모직주식회사 저광 특성이 우수한 내후성 열가소성 수지 조성물 및 그 제조 방법
EP2341090B1 (fr) 2009-12-31 2012-09-12 Cheil Industries Inc. Résine thermoplastique résistante aux intempéries et dotée d'une excellente caractéristique de faible brillance et son procédé de préparation
KR20120076301A (ko) 2010-12-29 2012-07-09 제일모직주식회사 내열성과 내후성이 우수한 저광 열가소성 수지 조성물
KR101469263B1 (ko) 2011-12-22 2014-12-05 제일모직주식회사 열가소성 수지 조성물 및 그 성형품

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DE1911882B2 (de) * 1969-03-08 1975-04-17 Basf Ag, 6700 Ludwigshafen Schlagfeste thermoplastische Massen
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Also Published As

Publication number Publication date
KR20000005462A (ko) 2000-01-25
DE19614846A1 (de) 1997-10-16
US6051656A (en) 2000-04-18
WO1997039039A1 (fr) 1997-10-23

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