EP2493936A1 - Homopolymères et copolymères des (méth)acrylates (d'ester) d'acide hydroxyisobutyrique - Google Patents

Homopolymères et copolymères des (méth)acrylates (d'ester) d'acide hydroxyisobutyrique

Info

Publication number
EP2493936A1
EP2493936A1 EP10771366A EP10771366A EP2493936A1 EP 2493936 A1 EP2493936 A1 EP 2493936A1 EP 10771366 A EP10771366 A EP 10771366A EP 10771366 A EP10771366 A EP 10771366A EP 2493936 A1 EP2493936 A1 EP 2493936A1
Authority
EP
European Patent Office
Prior art keywords
meth
weight
acid
acrylate
hydroxyisobutyric acid
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.)
Withdrawn
Application number
EP10771366A
Other languages
German (de)
English (en)
Inventor
Rüdiger CARLOFF
Roger Recktenwald
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.)
Roehm GmbH Darmstadt
Original Assignee
Evonik Roehm GmbH
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 Evonik Roehm GmbH filed Critical Evonik Roehm GmbH
Publication of EP2493936A1 publication Critical patent/EP2493936A1/fr
Withdrawn legal-status Critical Current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
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/14—Esterification
    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
    • 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
    • C08F8/50—Partial depolymerisation
    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen

Definitions

  • the invention relates to novel poly (meth) acrylates for the preparation of molding compositions.
  • the invention relates to novel poly (meth) acrylates for the preparation of molding compositions.
  • ester group If the ester group is an alkyl group, the heat resistance is the higher the short-chain the alkyl group.
  • the glass transition temperature of polymethylmethacrylate (differential scanning calorimetry, DSC for short) is 112 ° C to 118 ° C, depending on Polymerization temperature.
  • the glass transition temperature of poly-n-butyl methacrylate is only about 25 ° C to 30 ° C.
  • the property of the poly (meth) acrylate can be selectively changed.
  • Ester group tend to have a lower thermal stability than polymethyl methacrylate (PMMA).
  • PMMA polymethyl methacrylate
  • cyclohexene is split off in cyclohexyl methacrylate at temperatures above 270 ° C. and even a short residence time in the processing machine.
  • the cleaved ester group remains either in the polymer and thus in the product or is removed with simultaneous degassing during processing and collected as condensate. In both cases, unwanted foreign substances are generated which entail a separate assessment of the toxicology of the product.
  • the cleaved ester groups are usually not reusable in the process.
  • EP 0 113 105 is a mixture of PMMA and a
  • Formulation step a demonstrable embrittlement of the molding compound under prolonged weathering.
  • JP 11 222 460 are tricyclic, unsaturated compounds with a weakly acid-modified Implemented polymethacrylate. These groups may be after processing of the polymer where the acid groups would interfere with the application of high energy radiation
  • JP 2000 347 410 These are five types of alcohols which are esterified with methacrylic acid prior to polymerization: monocyclic, heterocyclic, higher cyclic, e.g. di- or tricyclic groups, ethers which have a Cl bridge to the ester group and compounds which are esterified via a tertiary alcohol.
  • the latter group includes only pure alkyl or
  • halogen-substituted alkyl groups These methacrylates can be copolymerized with other methacrylates. For all compounds are after the polymerization
  • JP 11 024 274. This may include but not limited to the following, type of
  • R 4 is used only as Cl, C2 or C3 radical.
  • Substances are formed by cleavage.
  • (Meth) acrylate-based which is characterized by two aspects: First, the method obtains a molding composition which is at least 1% by weight, preferably at least 2% by weight and more preferably at least 4% by weight
  • the methacrylic repeat units are thermally recovered from a prepolymer by a polymer-analogous reaction.
  • the polymer-analogous reaction is preferably the removal of one
  • the process of the invention is that this low molecular weight substance is methacrylic acid or an ester of methacrylic acid.
  • polymer-analogous cleavage takes place thermally. More specifically, the invention
  • extruder or polymerization can also be the removal of the residual monomers and / or the remaining liberated low molecular weight compounds.
  • Cleavage products can be used again for the monomer synthesis or for polymer production.
  • At least 80% by weight, preferably at least 90% by weight and particularly preferably at least 95% by weight, of the methacrylic acid released therefrom and / or liberated esters of methacrylic acid are removed from the molding composition by means of reduced pressure together with residual monomers.
  • prepolymer in this context means the polymer which is present before acid groups are formed by a polymer-analogous cleavage of low molecular weight substances.
  • a particular aspect of the present invention is that the prepolymer repeats units of the - hydroxyisobutyric acid (meth) acrylate and / or a
  • Alkyl ester of hydroxyisobutyric (meth) acrylate contains.
  • an elimination reaction results in the formation of a chain-linked acid group and, depending on the repeat unit
  • Methacrylic acid or an alkyl ester of methacrylic acid released there are two different methods:
  • the prepolymer is passed through
  • R 5 is hydrogen or a
  • Methyl group and R is an alkyl, cycloalkyl, ether, oligoether, silyl or functional alkyl group with hydroxyl, amine, silyl, acid, ester ⁇ or epoxy groups.
  • R 6 is a simple one
  • Alkyl group such as tert-butyl, n-butyl, iso-propyl, propyl, ethyl or methyl. Most preferably, it is a methyl group and thus in total
  • the radical R 6 is one or more additionally esterified ⁇ -hydroxyisobutyric acid groups.
  • the (meth) acrylic acid may be esterified with one to four further molecules of the hydroxyisobutyric acid.
  • the last esterified molecule can alternatively also be a
  • Alkyl esters of ⁇ -hydroxyisobutyric acid act.
  • n is a number between 0 and 10, preferably between 0 and 4 and especially
  • R 7 corresponds to R 6, with the proviso that further ⁇ -hydroxyisobutyric acid recurring units are excluded.
  • esters esters esterified methacrylates are used. This affects both the optional
  • R can represent the same groups or di- or oligomers as carried out in the first method.
  • Both the monomer synthesis in the first preparation process of the prepolymer and the polymer-analogous reaction of the second preparation process can be carried out via different reactions.
  • transesterification also occurs, for example. of MMA or tert-butyl methacrylate or the reaction with an acid halide such as (meth) acryloyl chloride or the reaction with (meth) acrylic anhydride in question.
  • transesterification catalysts can be added in the case of transesterification. Surprisingly, it was found that these remaining catalysts in the product in the
  • Transesterification catalysts also other prepolymers according to the invention, which were obtained after the first preparation process or by an esterification reaction, can be added.
  • transesterification catalysts for example, LiOH, LiOCH3, LiNH2, CaO, Ca (OH) 2, NaOH, NaOCH3, basic
  • Isopropyl titanate, isobutyl titanate, titanium hydroxide, Titanium dioxide, dioctyltin oxide, dibutyltin oxide, sulfuric acid are used.
  • the first preparation process for the prepolymers is preferred over the second.
  • the molding composition is preferred to at least 1% by weight
  • Poly (meth) acrylate molding compositions from the components known in the art. By choosing different repeating units, material properties such as e.g. Polarity,
  • Water absorption, optics or haptics can be adjusted.
  • the methacrylate-based molding compositions of the invention are composed of at least 40% by weight, preferably at least 60% by weight and more preferably from at least 80% by weight
  • the molding compositions may contain a number of comonomers.
  • the molding compositions may also be composed of other non (meth) acrylic acid-based but copolymerizable with these
  • Monomers are built up. Examples of these are styrene, methylstyrene, norbornene, cyclohexylmaleimide, itaconic acid or maleic anhydride.
  • the molding compositions may contain small amounts of acrylates.
  • Acrylate repeating units have opposite Methacrylate repeating units have a higher ceiling temperature, and thus show, in particular at
  • Molding compounds of this kind may contain up to 20% by weight, preferably up to 10% by weight.
  • Acrylate repeating units can also be completely or partially realized, for example, by using the process according to the invention in the form of acrylic acid repeating units.
  • the molding compositions according to the invention can preferably be prepared by means of bulk polymerization.
  • the molding compositions are particularly preferably produced by a continuous bulk polymerization. This can be carried out in one or more extruders or kneaders.
  • the initiation of the polymerization is generally carried out by adding radical polymerization initiators.
  • the free-radical polymerization initiators are lipophilic so that they are in the mixture of
  • Useful compounds include, besides the classic azo initiators, such as
  • Peroxy compounds such as. B. tert. -Amylperoxyneodecanoate, tert. Amyl peroxypivalate, tert. Butyl peroxypivalate, tert-amyl peroxy-2-ethylhexanoate, tert. Butyl peroxy-2-ethylhexanoate, tert. -Amylperoxy-3,5,5-trimethylhexanoate, ethyl-3,3-di- (tert -amylperoxy) butyrate,
  • Decanoyl peroxide lauryl peroxide, benzoyl peroxide, tert-Butylperneodecanoat and any mixtures of the above Links.
  • AIBN is most preferred.
  • the initiation can alternatively also be carried out using known photoinitiators by irradiation with UV rays or the like.
  • the common, commercially available compounds such.
  • Benzoin isopropyl ether benzoin isobutyl ether, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-isopropylthioxanthone,
  • Dibenzosuberone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bisacylphosphine oxide and others are used, said photoinitiators being used alone or in combination of two or more or in combination with one of the above polymerization initiators.
  • the amount of initiators can vary widely
  • Range of 0.01 to 5% by weight based on the weight of the total composition is given. Particular preference is given to amounts in the range from 0.01 to 2% by weight, in particular amounts in the range from 0.01 to 0.5% by weight, in each case based on the weight of the total composition.
  • Called chain transfer agents in particular of the known mercaptans, such as
  • Molecular weight regulator in general in amounts of from 0.01 to 5% by weight, based on the monomer mixture, preferably in amounts of from 0.01 to 2% by weight and more preferably in
  • Molecular weight regulators n-dodecylmercaptan, octylmercaptan, mercaptoethanol or methyl-3-mercaptopropionate used.
  • Impact modifier which is an elastomeric phase of crosslinked Polymerisatteilchen included.
  • the impact modifier can be prepared in per se known manner by bead polymerization or by
  • Emulsion polymerization can be obtained.
  • preferred embodiments are:
  • Impact modifiers provide crosslinked particles having a mean particle size in the range of 50 to
  • Such particles can, for example, by the
  • free radical polymerization of mixtures are obtained which are generally at least 40% by weight, preferably 50% by weight to 70% by weight of methyl methacrylate, 20% by weight to 80% by weight, preferably 25% by weight to 35% by weight of butyl acrylate and 0.1% by weight to 2% by weight, preferably 0.5% to 1% by weight of a crosslinking monomer, e.g. B. a polyfunctional (meth) acrylate, such as. B.
  • vinyl compounds can be copolymerized.
  • preferred comonomers include C1-C4 alkyl (meth) acrylates, such as ethyl acrylate or
  • Butyl methacrylate preferably methyl acrylate, or other vinylic polymerizable monomers such. Styrene.
  • the mixtures for producing the aforementioned particles may preferably comprise from 0% by weight to 10% by weight, preferably from 0.5% by weight to 5% by weight, of comonomers.
  • Particularly preferred toughening modifiers are polymerizate particles which have a two-layer, particularly preferably a three-layer core-shell structure.
  • Such core-shell polymers are described inter alia in EP 0 113 924, EP 0 522 351, EP 0 465 049 and EP 0 683 028.
  • the core as well as the shells can be in addition to those mentioned
  • Monomers in each case contain further monomers. These have been previously set forth, with particularly preferred comonomers having a crosslinking effect.
  • the particle size of the impact modifier is usually in the range of 50 to 1000 nm, preferably 100 to 500 nm and more preferably from 150 to 450 nm, without this being a restriction.
  • the molding compositions according to the invention are processed into shaped bodies. For this purpose, conventional methods of the art such as injection molding, extrusion, pressing, sintering, as well as other shaping methods are suitable.
  • the design of the molded body has no limits. Corresponding to their high heat resistance, the focus of the application naturally lies with moldings, the high
  • Light conductor applications light guide plates or optical lenses in lighting technology, as well as moldings in the temperature-sensitive areas of motor vehicles such as headlight lenses, taillights or fog lights
  • Another aspect of the present invention are the moldings obtainable from the molding compositions prepared according to the invention.
  • this relates to molded articles which are obtained from molding compositions which are composed of at least 40% by weight of repeating units of (meth) acrylic acid.
  • the same shaped articles can be distinguished by having a transparency in the range of> 89% to 92%, preferably of> 90.5% to 92%. Important for these applications are the
  • the molding compositions according to the invention are also used in the production of optically demanding moldings. Especially with very long flow paths and / or complicated molding geometries high processing temperatures are necessary.
  • the invention also provides moldings obtainable from molding compositions, as obtainable by the process described above.
  • Moldings made of this material can be exposed in the long term to significantly higher temperatures than moldings made of other highly transparent thermoplastics such.
  • Invention characterized in that it has a transparency in the range of> 89% to 92%, preferably> 90.5% to 92%.
  • molding compositions obtained by the process described above in coextrusion, e.g. as a coextrusion layer, coating or as a component in a polymer blend.
  • oligomeric a-HIBSM-MA is m> 1.
  • Methyl methacrylate 42% by weight
  • a-HIBSM-MA solution 7.5% by weight (consisting of 80% by weight of a-HIBSM-MA and 10% by weight of a dimeric ⁇ -HIBSM-MA and 10% by weight of oligomeric ⁇ -HIBSM-MA) b.) Solvent (50% by weight)
  • the initiator used was 0.9% by weight of tert-butylperneodecanoate and, as chain transfer agent, 0.24% by weight of methyl-3-mercaptopropionate, in each case based on the liquid
  • reaction mixture was 6 hours with the initiator at 80 ° C.
  • composition of the gaseous and solid fission products was investigated by GC and GC-MS.
  • the mass decrease after 15 minutes was 12% by weight.
  • the glass transition temperature determined by the DSC according to DIN ISO 11357-2 of the copolymer is at 114 ° C. before the
  • Methyl methacrylate 49.5% by weight
  • the initiator used was 0.9% by weight of tert-butylperneodecanoate and, as chain transfer agent, 0.24% by weight of methyl-3-mercaptopropionate, in each case based on the liquid
  • reaction mixture was 6 hours with the initiator at 80 ° C.
  • the glass transition temperature determined by DSC as in example 1 was 114 ° C.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne de nouveaux poly(méth)acrylates pour la production de matières moulables. L'invention concerne en particulier de nouveaux méthacrylates présentant des groupes ester qui, lors de la séparation, ne libèrent, le cas échéant, que très peu de constituants qui ne sont pas à nouveau copolymérisables. Grâce à la copolymérisation de tels monomères lors de la production des nouveaux poly(méth)acrylates pour matières moulables, la stabilité dimensionnelle à chaud de ces dernières n'est modifiée que de manière minimale ou est même améliorée.
EP10771366A 2009-10-30 2010-09-07 Homopolymères et copolymères des (méth)acrylates (d'ester) d'acide hydroxyisobutyrique Withdrawn EP2493936A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102009046197A DE102009046197A1 (de) 2009-10-30 2009-10-30 Homopolymere und Copolymere der Hydroxyisobuttersäure(ester)(meth)acrylate
PCT/EP2010/063067 WO2011051032A1 (fr) 2009-10-30 2010-09-07 Homopolymères et copolymères des (méth)acrylates (d'ester) d'acide hydroxyisobutyrique

Publications (1)

Publication Number Publication Date
EP2493936A1 true EP2493936A1 (fr) 2012-09-05

Family

ID=43304724

Family Applications (1)

Application Number Title Priority Date Filing Date
EP10771366A Withdrawn EP2493936A1 (fr) 2009-10-30 2010-09-07 Homopolymères et copolymères des (méth)acrylates (d'ester) d'acide hydroxyisobutyrique

Country Status (8)

Country Link
US (1) US8669338B2 (fr)
EP (1) EP2493936A1 (fr)
JP (1) JP5591342B2 (fr)
CN (1) CN102574942A (fr)
BR (1) BR112012009219A2 (fr)
DE (1) DE102009046197A1 (fr)
TW (1) TW201134867A (fr)
WO (1) WO2011051032A1 (fr)

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KR20150099558A (ko) 2012-12-19 2015-08-31 쓰리엠 이노베이티브 프로퍼티즈 컴파니 분해성 단량체 및 중합체로부터 제조된 감압 접착제
EP3369787B1 (fr) * 2017-03-03 2019-05-08 Evonik Röhm GmbH Compositions de résine (méth)acrylique durcissable ayant une viscosité améliorée
EP3450422A1 (fr) 2017-08-29 2019-03-06 Evonik Röhm GmbH Procédé de fabrication des matières à mouler optiques
JP7067229B2 (ja) * 2018-04-17 2022-05-16 信越化学工業株式会社 反応性ケイ素含有基を有するポリマーおよびその製造方法
EP4083175A4 (fr) * 2019-12-24 2023-09-13 Mitsubishi Gas Chemical Company, Inc. COMPOSÉ ESTER D'ACIDE a-HYDROXYISOBUTYRIQUE ET COMPOSITION DE PARFUM
TW202200642A (zh) * 2020-06-26 2022-01-01 德商羅姆有限公司 具有提升熱穩定性的光學級別模制組成物
WO2022250166A1 (fr) 2021-05-28 2022-12-01 三菱瓦斯化学株式会社 ESTER D'ACIDE ISOBUTYRIQUE COMPRENANT UN GROUPE ALCÉNOYLOXY EN POSITION α, COMPOSITION DE PARFUM ET UTILISATION EN TANT QUE PARFUM

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Also Published As

Publication number Publication date
TW201134867A (en) 2011-10-16
BR112012009219A2 (pt) 2016-08-23
US8669338B2 (en) 2014-03-11
CN102574942A (zh) 2012-07-11
JP5591342B2 (ja) 2014-09-17
US20120172563A1 (en) 2012-07-05
DE102009046197A1 (de) 2011-05-05
JP2013509461A (ja) 2013-03-14
WO2011051032A1 (fr) 2011-05-05

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