EP0894101A1 - Procede de production de matieres de moulage modifiees avec du caoutchouc acrylique et matieres de moulage obtenues a l'aide dudit procede - Google Patents

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

Info

Publication number
EP0894101A1
EP0894101A1 EP97920682A EP97920682A EP0894101A1 EP 0894101 A1 EP0894101 A1 EP 0894101A1 EP 97920682 A EP97920682 A EP 97920682A EP 97920682 A EP97920682 A EP 97920682A EP 0894101 A1 EP0894101 A1 EP 0894101A1
Authority
EP
European Patent Office
Prior art keywords
monomers
mixture
acrylic rubber
alm
polymerization
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
EP97920682A
Other languages
German (de)
English (en)
Inventor
Graham Edmund Mc Kee
Bernhard Rosenau
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 EP0894101A1 publication Critical patent/EP0894101A1/fr
Ceased legal-status Critical Current

Links

Classifications

    • 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
    • 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
    • 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
    • C08F290/044—Polymers of aromatic monomers as defined in group C08F12/00

Definitions

  • the invention relates to a process for the production of a molding compound modified with acrylic rubber by graft polymerization of monomers forming the graft shell in the presence of an acrylic rubber dissolved or swollen in the monomers and containing macromonomers as comonomers.
  • ASA molding compounds modified with acrylic rubber, which have good weather resistance, high impact strength and good flow properties.
  • a disadvantage of this preparation in emulsion is the need to remove auxiliaries when working up the molding materials in order to avoid later disruptions in their processing (discoloration, speck formation, corrosion). In particular, wishes remain regarding the impact strength, tear resistance and the gloss properties of the surfaces of molded parts made from it.
  • DE-B 11 82 811 published over 30 years ago, it is known to polymerize an acrylic ester together with a crosslinking monomer in solution to produce a rubber-modified molding composition, with the monomers to be grafted on after conversion of only 20 to 40% by weight of the monomers Styrene and acrylonitrile are added, the polymerization of which is then carried out in substance (mass) or solution. Due to the non-constant composition during the grafting reaction and due to the fact that rubber units are polymerized into the graft shell, the Vicat softening temperature is reduced and further mechanical properties of the resulting molding composition deteriorate.
  • the object of the invention was to produce 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.
  • This object could be achieved if an acrylic rubber modified by copolymerization with a macromonomer is produced, into which the graft shell and partly the the polymer matrix-forming monomers are dissolved or swollen, and this mixture is polymerized in one or more stages, at least the first stage of the graft polymerization up to a conversion of over 15 and preferably from 20 to 40% by weight of the monomers as thermal or radical-initiated polymerization in bulk (in bulk) or as solution polymerization.
  • the present invention thus relates to a process for producing a molding composition (A) modified with acrylic rubber (A2) by (a) copolymerizing a mixture (A2M) of
  • R 1 is a hydrogen atom or a methyl group and R 2 is an alkyl group with 1 to 32 C atoms
  • (a2) at least one macromonomer (A2m2) with a final copolymerizable C C double bond and an average molecular weight M w of about 1500 to 40,000, which contains units of at least one of the monomers (Alm) in copolymerized form and is fully or partially compatible with the polymers or copolymers of the monomers (Alm), (a3) optionally at least one further copolymerizable olefinically unsaturated monomer (A2m3) in an amount of less than 50% by weight of the amount of alkyl acrylate or methacrylate (A2ml), to form an acrylic rubber (A2) with a glass transition temperature below 0 ° C,
  • Alm whose polymers or copolymers have a glass transition temperature of at least + 20 ° C., to a mixture (AM), and
  • the method according to the invention is described as a 3-stage method for reasons of clarity, the method is also used if only the 3rd stage is carried out, i.e. the special acrylic rubber (A2) dissolved or swollen in monomers (Alm) is polymerized as indicated.
  • A2 the special acrylic rubber
  • Alm dissolved or swollen in monomers
  • Acrylic esters with a linear or at most single-branched alkyl alcohol with 4 to 12 carbon atoms are very suitable. Esters of n-butanol and 2-ethylhexyl alcohol are preferred.
  • the glass transition temperature T g of the resulting acrylic rubber (A2) can be set for a given macromonomer content, the glass transition temperature T g being below 0 ° C., in particular below -10 ° C. and should preferably be below -20 ° C.
  • This setting of the glass transition temperature is based on the fact that the glass transition temperature of alkyl acrylate and methacrylate polymers initially decreases with increasing length of the side chains, passes through a minimum for C 7 -alkyl acrylate or Cio-alkyl methacrylate and then again increases.
  • the content of alkyl acrylate or methacrylate (A2ml) in the mixture (A2M) is approximately 50 to 99.9 and preferably 80 to more than 90% by weight, based on the total amount of monomers (including macromonomers) in the mixture (A2M).
  • R 3 represents a hydrogen atom or a methyl group.
  • the macromonomer can be polymerized into the resulting acrylic ester copolymer via this double bond.
  • Suitable macromonomers which are also commercially available, have an average molecular weight M w of 1500 to 40,000, preferably from 2000 to 20,000 g / mol. Since the macromonomers are mostly produced by anionic polymerization and in particular using lithium hydrocarbons as initiators, the initiator concentration largely determines the resulting molecular weight of the macromonomers, which have a very narrow molecular weight distribution (M w / Mn mostly ⁇ 1.1). The molecular weight can be determined, for example, by vapor phase osmosis. The preparation of macromonomers is described in the literature.
  • Macromonomers are preferred which are wholly or partly compatible with the polymers or copolymers to be prepared from the monomers (Alm) and which contain at least some of the monomer units of the monomers (Alm) copolymerized in the macromonomer chain.
  • macromonomers whose chains are at least partially formed from units of such monomers (Alm) are particularly suitable for the production of ASA molding compositions in which predominantly styrene, ⁇ -methylstyrene and acrylonitrile are used as monomers (Alm).
  • the amount of macromonomers (A2m2) in mixture (A2M) is generally about 1 to 50, in particular 2 to 25,% by weight, based on the total amount of monomers (including macromonomers) in the mixture (A2M).
  • further copolymerizable olefinically unsaturated monomers (A2m3) in an amount of generally less than 50% by weight of the amount of alkyl acrylate and / or alkyl methacrylate (A2ml) in the mixture (A2M) can also be used.
  • 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 dihydrodicyclopentadienyl acrylate or methacrylate.
  • Monomers with non-conjugated double bonds and in particular allyl methacrylate and dihydrodicyclopentadienyl acrylate or methacrylate are preferred.
  • the content of the mixture (A2M) in these crosslinking monomers or in the grafting of the monomers (Alm) supports 0 to 20, in particular 0.3 to 15 and particularly preferably 0.3 to 12% by weight, based on the Total amount of monomers (including macromonomers) in the mixture (A2M).
  • Examples of other comonomers (A2m3) for the production of acrylic rubber (A2), which can be present in particular in amounts of 1 to 20% by weight, based on the total amount of monomers (including macromonomers) in the mixture (A2M), are styrene and acrylonitrile , Acrylic acid, methacrylic acid, maleic anhydride, maleimide, glycidyl methacrylate, acrylamide, methacrylamide and derivatives of these amides such as N-methylol methacrylamide, N-methylol acrylamide and ethers and esters of these N-methylol compounds such as their methyl or n-butyl ether or their Acetates.
  • Comonomers which bring about a linkage of acrylic rubber (A2) (graft base) and graft shell from the monomers (Alm) by chemical crosslinking reactions are advantageous. Also by using comonomers with peroxide or diazo groups in the production of the acrylic rubber (A2), such as tert-butyl-3-isopropenylcumyl peroxide or tert-butyl peroxi- crotonate, which radicals in the polymerization of the mixture (AM) by thermal decomposition and thus form graft branches, the graft yield during the polymerization of the mixture (AM) can be increased and the bond between acrylic rubber (A2) and the graft shell from the monomers (Alm) can thus be promoted.
  • comonomers with peroxide or diazo groups such as tert-butyl-3-isopropenylcumyl peroxide or tert-butyl peroxi- crotonate, which radicals in the polymerization of the mixture (
  • the copolymerization of the monomers (A2ml) with (A2m2) and optionally (A2m3) can be carried out in a known manner and is preferably initiated with radical initiators and in particular as solution polymerization or emulsion polymerization.
  • Suitable monomers (Alm), which later also form the graft shell (AI), are styrene, ⁇ -methylstyrene, nuclear-cyclized styrenes, acrylonitrile, methacrylonitrile, alkyl acrylates and alkyl methacrylates such as methyl methacrylate.
  • Monomers and monomer mixtures which give a polymer with a glass transition temperature of above + 20 ° C. and preferably above + 50 ° C. are preferably used. It is particularly preferred to use a mixture of more than 50 and in particular 60 to 80% by weight of styrene and less than 50 and in particular 20 to 40% by weight of acrylonitrile as monomers (Alm).
  • the amount of monomers (Alm) in the mixture (AM) depends in particular on the desired content of acrylic rubber (A2) in the resulting molding composition (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.
  • the polymerization of the monomers (Alm) in the presence of the acrylic rubber (A2) (mixture AM) dissolved or swollen in the monomers (Alm) takes place in one or more stages, the proportions of the different monomers (Alm) also changing in the stages can be.
  • the graft polymerization is preferably carried out as a thermally or free-radically initiated polymerization at a temperature of from room temperature to 200 ° C. and in particular from 50 to 160 ° C.
  • the single-stage or multi-stage polymerization must take place at least in its initial phase and up to a conversion of more than 15, preferably more than 20 to 40,% by weight of the monomers as bulk polymerization (bulk polymerization) or as solution polymerization. After this initial phase, the polymerization can then be continued and ended with another known polymerization method, advantageously as a suspension. ion 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 compound (A) must have sufficient strength in spite of 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 acrylic rubbers occur in grafted form as particles with a diameter between 0.1 and 20 and preferably between 0.1 and 10 ⁇ m.
  • the molding compositions (A) produced according to the invention have improved impact strength, notched impact strength, notched impact strength and good flow behavior. Moldings made from it also have the advantage that their surface gloss is greatly reduced and the surfaces are often matt.
  • the polyvinyl alcohol used (Moviol® 30-92 from Hoechst AG) had a degree of hydrolysis of 92 mol% and a viscosity of the 4% aqueous solution at 20 ° C. of 30 mPa.s (DIN 53015).
  • the impact strength values in kJ / m 2 were determined in accordance with DIN 53 453-K, edition 5/75.
  • the values for the core impact strength in kJ / m 2 were determined in accordance with DIN 53 753-L-30, edition 4/81. The flow behavior and thus the processability was assessed on the basis of the melt flow rate in g / 10 min, which was measured according to ISO 1133 at 200 ° C. and a load of 21.6 kg.
  • the glass transition temperature was determined using the DSC method (K.H. Illers, Macromolecular Chemistry 127 (1969) 1) and in accordance with ASTM 3416.
  • the average molecular weight of the commercial macromonomers used was given by the manufacturer.
  • SAN macromonomer AN-6 was purchased from Toman. It has a chain of a copolymer of 75% styrene and 25% acrylonitrile irr - a terminal methacrylate group and, according to the figure, has a molecular weight M w of 6000.
  • the rest of feeds 1 and 2 were metered in over 4 hours.
  • the mixture was then polymerized to a conversion of 93%, with 145 mg of AIBN being metered in after 9 and 15 hours of polymerization.
  • the mixture was cooled and stabilized with 0.12% (based on the amount of n-butyl acrylate) of octadecyl 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate as an antioxidant.
  • the acrylic rubber (A2) has a glass transition temperature of below -25 ° C.
  • Example 2 The procedure was as in Example 1, but the SAN macromonomer in feed 1 was omitted and replaced by a corresponding amount of n-butyl acrylate (A2ml).
  • Notched impact strength (kJ / m 2 ) 2.2 3.1 2.5 1.7

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Graft Or Block Polymers (AREA)

Abstract

L'invention concerne des matières de moulage modifiées avec du caoutchouc et présentant une meilleure résistance aux chocs et un bon comportement au fluage, obtenues par polymérisation par greffage spéciale de monomères formant des coques de greffage dures tels que le styrène et le nitrile acrylique, en présence d'un copolymérisat ester acrylique-macromonomère élastomère dissous ou macéré dans ces monomères. La polymérisation par greffage 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.
EP97920682A 1996-04-15 1997-04-14 Procede de production de matieres de moulage modifiees avec du caoutchouc acrylique et matieres de moulage obtenues a l'aide dudit procede Ceased EP0894101A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19614845 1996-04-15
DE19614845A DE19614845A1 (de) 1996-04-15 1996-04-15 Verfahren zur Herstellung von mit Acrylkautschuk modifizierten Formmassen und so erhältliche Formmassen
PCT/EP1997/001869 WO1997039038A1 (fr) 1996-04-15 1997-04-14 Procede de production de matieres de moulage modifiees avec du caoutchouc acrylique et matieres de moulage obtenues a l'aide dudit procede

Publications (1)

Publication Number Publication Date
EP0894101A1 true EP0894101A1 (fr) 1999-02-03

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
EP97920682A Ceased EP0894101A1 (fr) 1996-04-15 1997-04-14 Procede de production de matieres de moulage modifiees avec du caoutchouc acrylique et matieres de moulage obtenues a l'aide dudit procede

Country Status (5)

Country Link
US (1) US6111024A (fr)
EP (1) EP0894101A1 (fr)
KR (1) KR20000005460A (fr)
DE (1) DE19614845A1 (fr)
WO (1) WO1997039038A1 (fr)

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KR101188349B1 (ko) 2008-12-17 2012-10-05 제일모직주식회사 투명성 및 내스크래치성이 향상된 폴리카보네이트계 수지 조성물
US8735490B2 (en) 2009-12-30 2014-05-27 Cheil Industries Inc. Thermoplastic resin composition having improved impact strength and melt flow properties
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KR101469263B1 (ko) 2011-12-22 2014-12-05 제일모직주식회사 열가소성 수지 조성물 및 그 성형품
EP2881408B1 (fr) 2013-12-04 2017-09-20 Lotte Advanced Materials Co., Ltd. Copolymère à base de styrène et composition de résine thermoplastique le comprenant
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US9856371B2 (en) 2014-06-27 2018-01-02 Lotte Advanced Materials Co., Ltd. Thermoplastic resin composition and low-gloss molded article made therefrom
US9850333B2 (en) 2014-06-27 2017-12-26 Lotte Advanced Materials Co., Ltd. Copolymers and thermoplastic resin composition including the same
US9790362B2 (en) 2014-06-27 2017-10-17 Lotte Advanced Materials Co., Ltd. Thermoplastic resin composition and molded article made using the same
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Also Published As

Publication number Publication date
US6111024A (en) 2000-08-29
KR20000005460A (ko) 2000-01-25
WO1997039038A1 (fr) 1997-10-23
DE19614845A1 (de) 1997-10-16

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