WO2015170735A1 - Élastomère à résistance élevée - Google Patents

Élastomère à résistance élevée Download PDF

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WO2015170735A1
WO2015170735A1 PCT/JP2015/063274 JP2015063274W WO2015170735A1 WO 2015170735 A1 WO2015170735 A1 WO 2015170735A1 JP 2015063274 W JP2015063274 W JP 2015063274W WO 2015170735 A1 WO2015170735 A1 WO 2015170735A1
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monomer
meth
elastomer
monomer component
acrylate
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PCT/JP2015/063274
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English (en)
Japanese (ja)
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河合　道弘
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東亞合成株式会社
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Priority to JP2016517937A priority Critical patent/JP6380528B2/ja
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    • 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
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • 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
    • C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds

Definitions

  • the present invention relates to a high-strength elastomer. More specifically, the present invention relates to a high-strength elastomer having a (semi) interpenetrating network structure.
  • Elastomer materials are used in a wide range of fields including sealing materials and packing materials because they give good moldability and oil resistance.
  • acrylic elastomers mainly composed of acrylic acid esters are also used in seals for automobile parts, gaskets, adhesive product materials, and housings for home appliances because of their excellent transparency, heat resistance, and weather resistance.
  • higher strength elastomer materials are required to improve reliability and durability.
  • Various studies have been made.
  • Patent Document 1 discloses a thermoplastic elastomer obtained by dynamically heat-treating a mixture containing a specific thermoplastic resin and acrylic rubber as an acrylic elastomer in the presence of a crosslinking agent.
  • Patent Document 2 discloses a block copolymer containing a methacrylic ester polymer block and an acrylate polymer block, and a composition containing an acrylic polymer rubber which is an acrylic elastomer. ing.
  • these are composed of a mixture containing an acrylic elastomer and other components, it is difficult to ensure sufficient transparency due to compatibility problems and the like, and in some cases, bleeding problems may occur.
  • JP 2006-124538 A International Publication No. 2002/081561 International Publication No. 2003/093337 JP 2010-1111821 A JP 2012-1596 A
  • Non-Patent Document 1 since the hydrogels or organogels described in Patent Documents 3 to 5 contain a medium such as water or an organic solvent, there has been a problem that properties such as strength are not stabilized due to different contents of the medium. Further, there has been a concern that the performance may change over time due to volatilization or bleeding of the medium. Further, the elastomer described in Non-Patent Document 1 does not contain a medium and exhibits good strength. However, when a tensile stress or the like is applied, a large hysteresis loss occurs. For this reason, when used in applications where stress loading and release are repeated, durability as a material has been a problem.
  • the present invention has been made in view of such circumstances, and is an elastomer that exhibits extremely high strength regardless of mixing with other polymers, fillers, etc., and when tensile stress or the like is applied. Is intended to provide an acrylic elastomer that does not cause hysteresis loss.
  • the second monomer component is added to the first network structure.
  • An elastomer having a (semi) interpenetrating network obtained through a second step of introducing, polymerizing, or polymerizing and crosslinking The first monomer component comprises an anionic vinyl monomer 0.1-30 mol% and a nonionic vinyl monomer 70-99.9 mol%,
  • the polymer obtained from the second monomer component has a glass transition temperature (Tg) of ⁇ 80 to 20 ° C.
  • Tg glass transition temperature
  • substantially no solvent is used,
  • the first invention uses 0.01 to 2 mol% of a crosslinkable monomer based on the total amount of the monomer components excluding the crosslinkable monomer. It is an elastomer as described in above.
  • the third invention is the first invention or the second invention, wherein in the second monomer component, 0 to 2 mol% of the crosslinkable monomer is used with respect to the total amount of the monomer components excluding the crosslinkable monomer.
  • a fourth invention is the elastomer according to any one of the first to third inventions, wherein the second monomer component contains 90 mol% or more of a compound represented by the following general formula (1). is there. [Wherein, R 1 represents a hydrogen atom or a methyl group, and R 2 represents an alkyl group having 1 to 8 carbon atoms or an alkoxyalkyl group having 2 to 8 carbon atoms. ]
  • the acrylic elastomer of the present invention exhibits very high strength. In addition, it is a material excellent in durability without causing hysteresis loss due to stress such as tension. Furthermore, since it is not necessary to mix other polymers, fillers, and the like, problems due to compatibility with these components, bleeding, and the like can be avoided. In addition, since it does not contain a medium such as water or an organic solvent, it becomes possible to exhibit stable performance over time.
  • FIG. 6 is a graph showing the results of a repeated tensile test performed on the elastomer obtained in Example 3. It is the graph which showed the result of the repeated tension test done about the elastomer obtained in Example 14.
  • FIG. 6 is a graph showing the results of a repeated tensile test performed on the elastomer obtained in Comparative Example 4.
  • 10 is a graph showing the results of a repeated tensile test performed on the elastomer obtained in Comparative Example 5.
  • 10 is a graph showing the results of a repeated tensile test performed on the elastomer obtained in Comparative Example 6.
  • (meth) acryl means acryl and / or methacryl
  • (meth) acrylate means acrylate and / or methacrylate
  • the “(meth) acryloyl group” means an acryloyl group and / or a methacryloyl group.
  • the elastomer of the present invention includes a step of forming a first network structure by crosslinking and polymerizing the first polymer (hereinafter referred to as “first step”), and a second monomer in the first network structure.
  • first step a step of forming a first network structure by crosslinking and polymerizing the first polymer
  • second step a step of forming a first network structure by crosslinking and polymerizing the first polymer
  • second monomer in the first network structure A (semi) interpenetrating network structure is obtained by introducing a body component, polymerizing, or polymerizing and cross-linking (hereinafter referred to as “second process”).
  • the interpenetrating network structure means a structure in which the network structure in the first polymer obtained in the first step and the network structure in the second polymer obtained in the second step are intertwined with each other as a whole. To do.
  • the semi-interpenetrating network structure means a structure in which the network structure in the first polymer obtained in the first step and the linear polymer obtained in the second step are intertwined with each other as a whole. .
  • a polymer having a semi-interpenetrating network structure can be obtained.
  • “interpenetrating network structure” and / or “semi-interpenetrating network structure” is described as “(semi) interpenetrating network structure”.
  • interpenetrating network structure and “semi-interpenetrating network structure” are concepts applied not only to the first step and the second step, but also to the polymer obtained through the steps after the third step. .
  • the present invention will be described in detail along each step.
  • a polymer having a first network structure is produced by polymerizing and crosslinking the first monomer component.
  • the first monomer component is composed of 0.1 to 30 mol% of an anionic vinyl monomer and 70 to 99.9 mol% of a nonionic vinyl monomer.
  • the first monomer component needs to be composed of an anionic vinyl monomer and a nonionic vinyl monomer.
  • a cationic vinyl monomer is contained in the first monomer component, hysteresis loss may occur when the obtained elastomer is subjected to tensile stress or the like.
  • anionic vinyl monomers include (meth) acrylic acid, crotonic acid, maleic acid, maleic anhydride, itaconic acid and other carboxyl group-containing monomers and salts thereof; 2-acrylamido-2-methylpropanesulfonic acid Sulfonic acid group-containing monomers such as vinyl sulfonic acid, styrene sulfonic acid and 3-allyloxy-2-hydroxypropane sulfonic acid, and salts thereof, and one or more of these can be used. .
  • the types of salts include alkali metal salts such as lithium, sodium and potassium; alkaline earth metal salts such as calcium salts and barium salts; other metal salts such as magnesium salts and aluminum salts; ammonium salts and organic amine salts Is mentioned.
  • the anionic vinyl monomer is used in an amount of 0.1 to 30 mol% with respect to the total amount of the first monomer component.
  • the first monomer component contains an anionic vinyl monomer of 0.1 mol% or more
  • the second monomer component tends to be easily introduced in the second step described later, and as a result The strength of the resulting elastomer is improved.
  • the amount of the anionic vinyl monomer is too large, the polymer obtained in the first step becomes hard, and the polymer finally obtained may not be suitable for use as an elastomer.
  • the amount of the anionic vinyl monomer used is in the range of 0.1 to 30 mol%, preferably in the range of 1 to 20 mol%, with respect to the total amount of the first monomer component. A range of 3 to 10 mol% is more preferable.
  • a nonionic vinyl monomer is used in addition to the anionic monomer.
  • a nonionic vinyl-based monomer a nonionic (meth) acrylic monomer can be preferably used, and a (meth) acrylic acid alkyl ester compound, a (meth) acrylic acid alkoxyalkyl ester compound, Amide group-containing (meth) acrylic monomers, amino group-containing (meth) acrylic monomers, hydroxyl group-containing (meth) acrylic monomers, terminal alkoxypolyalkylene glycol mono (meth) acrylates, etc. are used. .
  • vinyl monomers such as vinyl acetate, N-vinylformamide, N-vinylacetamide, N-vinylpyrrolidone and styrene may be used.
  • the amount of the nonionic vinyl monomer used is in the range of 70 to 99.9 mol%, preferably in the range of 80 to 99 mol%, and in the range of 90 to 97 mol% with respect to the total amount of the first monomer component. Is more preferable.
  • (meth) acrylic acid alkyl ester compound examples include methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, n-propyl (meth) acrylate, and (meth) acrylic acid n.
  • a (meth) acrylic acid ester compound having an alkyl group having 1 to 12 carbon atoms is preferable, and a (meth) acrylic acid ester compound having an alkyl group having 1 to 8 carbon atoms is more preferable.
  • An acrylic acid ester compound having an alkyl group having 1 to 8 carbon atoms is more preferable.
  • (meth) acrylic acid alkoxyalkyl ester compound examples include methoxymethyl (meth) acrylate, ethoxymethyl (meth) acrylate, methoxyethyl (meth) acrylate and ethoxyethyl (meth) acrylate. These can be used alone or in combination of two or more.
  • amide group-containing (meth) acrylic monomer examples include (meth) acrylamide, tert-butyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, Examples thereof include N-isopropyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, and (meth) acryloylmorpholine, and one or more of these can be used.
  • amino group-containing (meth) acrylic monomers include N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) Examples thereof include acrylate and N, N-dimethylaminopropyl (meth) acrylamide, and one or more of these can be used.
  • hydroxyl group-containing (meth) acrylic monomer examples include 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate and polyethylene glycol mono ( (Meth) acrylate etc. are mentioned, These 1 type (s) or 2 or more types can be used.
  • terminal alkoxy polyalkylene glycol mono (meth) acrylate examples include methoxypolyethylene glycol mono (meth) acrylate, methoxypolypropylene glycol mono (meth) acrylate, ethoxypolyethylene glycol mono (meth) acrylate and ethoxypolypropylene glycol mono (meth) An acrylate etc. are mentioned, These 1 type (s) or 2 or more types can be used.
  • nonionic polyfunctional vinyl monomer having two or more radically polymerizable unsaturated groups as a crosslinkable monomer and / or A nonionic vinyl monomer having a crosslinkable functional group
  • nonionic polyfunctional vinyl monomers include polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, and 1,6-hexanediol.
  • Examples include di- or tri (meth) acrylates of polyols; bisamides such as methylene bis (meth) acrylamide and ethylene bis (meth) acrylamide, divinylbenzene, and allyl (meth) acrylate. It can be used or two or more.
  • (Meth) acrylate is preferred.
  • nonionic vinyl monomer having a crosslinkable functional group examples include trimethoxysilylpropyl (meth) acrylate, triethoxysilylpropyl (meth) acrylate, methyldimethoxysilylpropyl (meth) acrylate, etc.
  • Hydrolyzable silyl group-containing (meth) acrylic acid ester compounds N-methylol (meth) acrylamide; N-alkoxymethyl (meth) acrylamide such as N-methoxymethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide
  • N-methylol (meth) acrylamide N-alkoxymethyl (meth) acrylamide
  • N-methoxymethyl (meth) acrylamide N-butoxymethyl (meth) acrylamide
  • the amount of the crosslinkable monomer used may vary depending on the type of nonionic vinyl monomer used, the intended use of the elastomer to be obtained, etc., but the first monomer excluding the crosslinkable monomer
  • the content is preferably 0.01 to 2 mol%, more preferably 0.02 to 1.5 mol%, still more preferably 0.05 to 1 mol%, based on the total amount of the components. If the amount of the crosslinkable monomer used is 0.01 mol% or more, it is possible to obtain a high strength elastomer. On the other hand, if the amount of the crosslinkable monomer is too large, it may be difficult to introduce the second monomer component into the first network structure in the second step to be described later. The formation of the network structure may be insufficient, and the strength of the elastomer may not reach a satisfactory level. If the amount of the crosslinkable monomer used is 2 mol% or less, a sufficiently high strength elastomer can be obtained.
  • the polymerization of the first monomer component can be performed by a known radical polymerization method, and for example, a solution polymerization method, a suspension polymerization method, a dispersion polymerization method, a bulk polymerization, or the like can be used.
  • polymerization the solvent selected from water, various organic solvents, etc. can be used according to a superposition
  • organic solvents examples include cyclic ethers such as tetrahydrofuran and dioxane, aromatic hydrocarbon compounds such as benzene, toluene and xylene, esters such as ethyl acetate and butyl acetate, ketones such as acetone, methyl ethyl ketone and cyclohexanone, and methyl orthoformate.
  • cyclic ethers such as tetrahydrofuran and dioxane
  • aromatic hydrocarbon compounds such as benzene, toluene and xylene
  • esters such as ethyl acetate and butyl acetate
  • ketones such as acetone, methyl ethyl ketone and cyclohexanone
  • methyl orthoformate examples include alcohols such as methyl orthoacetate, methanol, ethanol, and isopropanol, and one or more of these can be used.
  • the polymerization may be in any form such as thermal polymerization, photopolymerization, or a combination thereof. Among these, the photopolymerization method is preferable because the polymerization reaction easily proceeds quickly.
  • the first monomer component contains the nonionic polyfunctional vinyl-based monomer
  • cross-linking of the polymer proceeds in parallel by polymerizing the first monomer component.
  • a structure is formed.
  • the nonionic vinyl monomer having the crosslinkable functional group is used as the crosslinkable monomer
  • the first reaction can be performed by performing a crosslinking reaction with the crosslinkable functional group as necessary during or after the polymerization.
  • a network structure can be formed.
  • polymerization initiators such as azo compounds, organic peroxides, and inorganic peroxides can be used, but are not particularly limited. You may use the redox type polymerization initiator which consists of a well-known oxidizing agent and a reducing agent.
  • Examples of the azo compound include 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (N-butyl-2-methylpropionamide), 2- (tert-butylazo) -2. -Cyanopropane, 2,2'-azobis (2,4,4-trimethylpentane), 2,2'-azobis (2-methylpropane), etc., and one or more of these are used be able to.
  • organic peroxide examples include 2,2-bis (4,4-di-t-butylperoxycyclohexyl) propane (manufactured by NOF Corporation, trade name “Pertetra A”), 1,1-di (t- Hexylperoxy) cyclohexane (same as “Perhexa HC”), 1,1-di (t-butylperoxy) cyclohexane (same as “PerhexaC”), n-butyl-4,4-di (t-butylperoxy) Valerate ("Perhexa V”), 2,2-di (t-butylperoxy) butane ("Perhexa 22"), t-butyl hydroperoxide ("Perbutyl H"), 1,1,3, 3-tetramethylbutyl hydroperoxide (same as “Perocta H”), t-butylcumyl peroxide (same as “Perbutyl C”), di-tt
  • Examples of the inorganic peroxide include potassium persulfate, sodium persulfate, and ammonium persulfate.
  • Redox polymerization initiators include sodium sulfite, sodium thiosulfate, sodium formaldehyde sulfoxylate, ascorbic acid, ferrous sulfate and the like as reducing agents, potassium peroxodisulfate, hydrogen peroxide, tert-butyl hydroper What used an oxide etc. as an oxidizing agent can be used.
  • the preferred amount of the polymerization initiator used is 0.001 to 1 part by weight, more preferably 0.01 to 1 part by weight, when the total amount of the first monomer is 100 parts by weight.
  • the polymerization temperature is preferably 20 to 150 ° C., more preferably 40 to 100 ° C., although it depends on conditions such as the type and concentration of the monomer used.
  • the polymerization time is preferably 0.5 to 20 hours, and more preferably 1 to 10 hours.
  • a general photopolymerization initiator can be used.
  • Specific examples include 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxycyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopro Pan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, diethoxyacetophenone, oligo ⁇ 2-hydroxy-2-methyl-1- [4- (1-Methylvinyl) phenyl] propanone ⁇ and 2-hydroxy-1- ⁇ 4- [4- (2-hydroxy-2-methylpropionyl) benzyl] phenyl Acetophenone compounds such as -2-
  • Phosphine oxide compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether and benzoin isobutyl ether; titanocene compounds; 1- [4- (4-benzoylphenylsulfanyl) phenyl] -2- Acetophenone / benzophenone hybrid photoinitiators such as methyl-2- (4-methylphenylsulfinyl) propan-1-one; 2- (O-benzoyloxime) -1- [4- (phenylthio)]-1,2- And oxime ester photopolymerization initiators such as octanedione; and camphorquinone.
  • benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether and benzoin isobutyl ether
  • titanocene compounds 1- [4- (4-benz
  • the photopolymerization initiator that can be used in combination with a photosensitizer such as benzophenone is preferably used in an amount of 0.001 to 1 part by weight when the total amount of the first monomer is 100 parts by weight. More preferably 0.005 to 0.1 parts by weight
  • examples of active energy rays to be irradiated include electron beams, ultraviolet rays, visible rays, and X-rays, but ultraviolet rays are preferable because inexpensive devices can be used.
  • the ultraviolet irradiation device is not particularly limited, and examples thereof include a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a black light lamp, a UV electrodeless lamp, and an LED.
  • the irradiation intensity is appropriately adjusted, but 0.01 to 100 mW / cm 2 is appropriate.
  • a more preferable range of the irradiation intensity is 0.01 to 30 mW / cm 2 , and a more preferable range is 0.01 to 5 mW / cm 2 .
  • the irradiation intensity may be constant during the polymerization reaction, or may be changed stepwise or continuously. Depending on the state of the polymerization reaction, irradiation may be temporarily stopped during the reaction.
  • substantially no solvent is used in the second step following the first step. For this reason, when the solvent was not used in the first step, the obtained polymer having the first network structure was cut or pulverized into an appropriate shape as needed without particularly adding a solvent or the like. It is used for the second step later.
  • a solvent used in the first step, the polymer having the first network structure is subjected to the second step after the solvent has been distilled off by a treatment such as heating under reduced pressure. It is preferable to carry out the first step without using a solvent in that the step of distilling off the solvent can be omitted.
  • ⁇ Second step> the second monomer component is added to the polymer obtained in the first step, and the second monomer component is introduced into the first network structure, followed by polymerization or polymerization and crosslinking.
  • a polymer (elastomer) having a (semi) interpenetrating network structure is produced.
  • substantially no solvent is used.
  • the fact that a solvent is not substantially used means that a solvent such as an organic solvent is not intentionally used, and the organic solvent or the like contained as an impurity in a raw material component such as a monomer. It is allowed to mix.
  • an anionic group contained in the polymer having the first network structure may be dissociated in the solvent.
  • the second step proceeds with the first network structure relatively expanded due to electrostatic repulsion or the like, and a polymer having a (semi) interpenetrating network structure is obtained.
  • the elastomer obtained in the state in which the first network structure spreads is irreversibly cut by the bond of the first polymer when a tensile stress is applied.
  • the reason why the hysteresis loss does not occur in the present invention is not necessarily clear, but when no solvent is used in the second step, the first network structure of the resulting elastomer is not in a fully extended state in the bond.
  • the second monomer component various vinyl unsaturated compounds having radical polymerizability can be used. From the viewpoint of obtaining a polymer suitable for an elastomer having elasticity and flexibility, the following The compound represented by the general formula (1) is preferable. [Wherein, R 1 represents a hydrogen atom or a methyl group, and R 2 represents an alkyl group having 1 to 8 carbon atoms or an alkoxyalkyl group having 2 to 8 carbon atoms. ]
  • Specific compounds represented by the general formula (1) include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and (meth) acrylic.
  • the proportion of the compound represented by the general formula (1) in the total amount of the second monomer component is preferably 50 mol% or more, more preferably 80 mol% or more, and 95 mol% or more. Is more preferable.
  • the second monomer component in addition to the compound represented by the general formula (1), other monomers copolymerizable therewith can be used.
  • the copolymerizable monomer include ⁇ , ⁇ -ethylenically unsaturated carboxylic acid monomers such as (meth) acrylic acid, itaconic acid, maleic acid, and fumaric acid; n-nonyl (meth) acrylate, (Meth) acrylic acid alkyl ester compounds having an alkyl group having 9 or more carbon atoms such as (meth) acrylic acid isononyl, (meth) acrylic acid decyl, (meth) acrylic acid dodecyl; styrene, ⁇ -methylstyrene, vinyltoluene, etc.
  • Vinyl aromatic monomers such as cyclohexyl (meth) acrylate, methyl cyclohexyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, cyclododecyl (meth) acrylate, isobornyl (meth) acrylate, etc.
  • Aliphatic cyclic vinyl monomer 2-hydroxyethyl (meth) acrylate, 3-hydride (meth) acrylate Hydroxyl-containing monomers such as xylpropyl, 4-hydroxybutyl (meth) acrylate, polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate and polyethylene-polypropylene glycol mono (meth) acrylate; acrylamide, (meth) acrylonitrile, Examples thereof include vinyl acetate, and one or more of these can be used.
  • the second monomer component may contain a crosslinkable monomer.
  • the crosslinkable monomer the same monomers as those described in the first step can be used.
  • an elastomer having an interpenetrating network structure can be obtained, and when no crosslinkable monomer is used, a semi-interpenetrating structure is obtained.
  • An elastomer having a network structure is obtained. In any form, the effects of the present invention are achieved.
  • the amount of the crosslinkable monomer used in the second monomer component may vary depending on the type of monomer used and the intended use of the elastomer to be obtained.
  • the content is preferably 0 to 2 mol%, more preferably 0.001 to 1.0 mol%, still more preferably 0.005 to 0.5 mol%, more preferably 0.00 to 0.5 mol% based on the total amount of the monomer components. Most preferred is 01 to 0.1 mol%. If the amount of the crosslinkable monomer used is 2 mol% or less, a flexible elastomer can be obtained.
  • the glass transition temperature of the polymer obtained from the second monomer is in the range of ⁇ 80 to 20 ° C., preferably in the range of ⁇ 70 to 10 ° C., more preferably ⁇ It is in the range of 60 to 0 ° C.
  • Tg exceeds 20 ° C., the resulting polymer becomes too hard and may not be suitable for use as an elastomer.
  • Tg does not fall below ⁇ 80 ° C. due to restrictions on the raw material monomers.
  • the value of Tg is obtained from the result of DSC measurement of a polymer obtained from the second monomer.
  • the DSC measurement is performed under a nitrogen atmosphere under a temperature increase rate of 10 ° C./min.
  • Tg is determined based on the type and amount of monomer components excluding the crosslinkable monomer.
  • each of the homopolymers described in “POLYMER HANDBOOK 4th edition” published by John Wiley & Sons, Inc.
  • equation (1) based on Tg. 1 / Tg ⁇ W (a) / Tg (a) ⁇ + ⁇ W (b) / Tg (b) ⁇ + ⁇ W (c) / Tg (c) ⁇ + ...
  • Tg Tg of polymer W (a): Weight fraction of structural unit composed of monomer (a) in polymer W (b): Weight fraction of structural unit composed of monomer (b) in polymer W (c): Heavy Weight fraction of structural unit consisting of monomer (c) in coalescence
  • Tg Glass transition temperature of homopolymer of monomer (a)
  • Glass transition temperature of Tg (c) Glass transition temperature of homopolymer of monomer (c)
  • the polymer obtained in the first step and the second monomer component are blended and polymerized after the second monomer component is introduced into the first network structure, Alternatively, polymerization and crosslinking are performed.
  • the method of polymerizing the second monomer component, or polymerizing and crosslinking can be performed by the same method as in the first step.
  • solvents such as water or various organic solvents, are not used in a 2nd process. In this case, it is easy to introduce the second monomer component into the first network structure by using the polymer obtained by the first step after cutting or grinding the polymer itself into an appropriate size. This is preferable.
  • the second monomer component is absorbed in the polymer obtained in the first step and is sufficiently introduced into the first network structure before polymerization or the like. For this reason, after mix
  • the polymer obtained in the first step is sufficiently absorbed, so that it is preferably left for 1 minute or more, more preferably 1 hour or more after standing or stirring. It is preferred to initiate a two-step polymerization.
  • the mass ratio of the first monomer component and the second monomer component needs to be in the range of 1 / 0.1 to 1/30.
  • a preferable range of the mass ratio is 1/1 to 1/10, and a more preferable range is 1/2 to 1/8. If the ratio of the amount of the second monomer component used relative to the first monomer component is less than 0.1, the flexibility of the elastomer may be inferior. If the ratio exceeds 30, the amount of the first network structure is relatively small, so that a sufficient (semi) interpenetrating network structure is not formed, and a satisfactory elastomer strength may not be obtained. .
  • the elastomer of the present invention is obtained through the method described in the first step and the second step, but if necessary, a plasticizer, oil, an anti-aging agent, an inorganic filler, a pigment, an antioxidant, an ultraviolet absorber and the like These known additives may be blended and used. Also, other elastomers can be added and mixed.
  • Example 1 (First step) As the first monomer component, ethyl acrylate (hereinafter referred to as “EA”), acrylic acid (hereinafter referred to as “AA”) and 1,4-butanediol diacrylate (hereinafter referred to as “1,4BDA”) Were mixed at a molar ratio of 90/10 / 0.05. Next, 2,2-dimethoxy-1,2-diphenylethane-1-one (trade name “Irgacure 651” manufactured by BASF Corp.) as a photopolymerization initiator is in a ratio of 0.02 mol% with respect to the total amount of EA and AA. The first monomer solution was prepared by adding and mixing the above.
  • EA ethyl acrylate
  • AA acrylic acid
  • 1,4BDA 1,4-butanediol diacrylate
  • the first monomer solution is poured between two 1 mm thick glass plates sealed with 0.5 mm thick silicone rubber, and irradiated with ultraviolet rays at an illuminance of 0.9 mW / cm 2 using a black light. Started. After 30 minutes, it was confirmed that the polymerization was completed by IR, and a polymer A1 having a first network structure was obtained.
  • EA and Irgacure 651 were mixed at a molar ratio of 100 / 0.02 to prepare a second monomer solution.
  • the polymer A1 was cut into a size of 30 mm ⁇ 80 mm ⁇ 0.5 mm and immersed in a sufficient amount of the second monomer solution.
  • the second monomer component was sufficiently swollen in the polymer A1 by leaving it in this state for 4 hours at room temperature.
  • the polymer A1 sufficiently swollen by the second monomer component was taken out, the monomer liquid adhering to the periphery of the polymer was gently wiped off, and then the weight difference of the polymer A1 before and after swelling was measured.
  • the swelling ratio of the second monomer solution was calculated, a value of 5.3 times was obtained as the swelling ratio.
  • the polymer A1 swollen with the second monomer solution is sandwiched between a polyethylene terephthalate release film having a thickness of 50 ⁇ m and a glass plate having a thickness of 1 mm, and UV light is applied at an illuminance of 0.9 mW / cm 2 using a black light. Irradiation was started. After 30 minutes, it was confirmed that the polymerization was completed by IR, and an elastomer A1 having a semi-interpenetrating network structure was obtained.
  • the obtained elastomer A1 was punched with a No. 6 dumbbell to prepare a test piece, which was subjected to a tensile test.
  • tensile test the tensile strength at break, tensile elongation at break and tensile product calculated from these products and 50% modulus were measured in accordance with JIS-K6251, and the results are shown in Table 3. It was.
  • Examples 2-14 It has a (semi) interpenetrating network structure in the same manner as in Example 1 except that the types and amounts of monomers used in the first monomer solution and the second monomer solution are changed as shown in Table 1.
  • Elastomers A2 to A14 were obtained.
  • the elastomers A2 to A7 and A14 obtained in Examples 2 to 7 and 14 are elastomers having a semi-interpenetrating network structure, and the elastomers A8 to A13 obtained in Examples 8 to 13 are elastomers having an interpenetrating network structure. It is.
  • Table 3 shows the results of tensile tests performed on these.
  • Comparative Examples 1 and 2 Elastomers C1 and C2 were obtained by performing the same operation as in the first step of Example 1, except that the monomer charge (molar ratio) in the first monomer component was changed as shown in Table 2. .
  • the elastomers C1 and C2 are the same as the elastomers A1 and A3 obtained in Examples 1 and 3 and the charged composition of the monomer as the whole elastomer is an elastomer obtained only from the first step, ) It does not have an interpenetrating network structure.
  • Table 3 shows the results of tensile tests performed on the elastomers C1 and C2.
  • Comparative Example 3 An elastomer C3 having a semi-interpenetrating network structure was obtained in the same manner as in Example 1 except that the monomer charge ratio was changed as shown in Table 2. Table 3 shows the results of the tensile test performed on the elastomer C3.
  • Comparative Example 4 As the first monomer component, EA, an ionic monomer having a structure represented by the formula (2) (hereinafter referred to as “monomer A”) and 1,4BDA were used as shown in Table 2. Obtained an elastomer C4 having a semi-interpenetrating network structure in the same manner as in Example 1. Table 3 shows the results of the tensile test performed on the elastomer C4.
  • Comparative Example 5 A polymer C5 was obtained by performing the same operation as in the first step of Example 1, except that the monomer charge (molar ratio) in the first monomer component was changed as shown in Table 2.
  • a second monomer solution was prepared.
  • the polymer C5 is cut into a size of 30 mm ⁇ 80 mm ⁇ 0.5 mm, immersed in a sufficient amount of the second monomer solution, and ammonia water is added to adjust the pH of the second monomer solution to 8.5. It was adjusted.
  • ammonia water is added to adjust the pH of the second monomer solution to 8.5. It was adjusted.
  • Elastomer C5 having a network structure was obtained. Table 3 shows the results of the tensile test performed on the elastomer C5.
  • Comparative Example 6 Elastomer C6 having a semi-interpenetrating network structure was obtained in the same manner as in Comparative Example 5, except that the monomer charge (molar ratio) in the first monomer component was changed as shown in Table 3. Table 3 shows the results of the tensile test performed on the elastomer C6.
  • EA ethyl acrylate BA: butyl acrylate AA: acrylic acid
  • ATBS 2-acrylamido-2-methylpropanesulfonic acid
  • 1,4BDA 1,4-butanediol
  • Examples 1 to 14 are all elastomers belonging to the present invention. Among them, Examples 1 to 7 and 14 are elastomers having a semi-interpenetrating network structure, and Examples 8 to 13 are elastomers having an interpenetrating network structure. All of the elastomers obtained in each example exhibited sufficiently high tensile strength at break. Moreover, as shown in FIGS. 1 and 2, the elastomer of the present invention showed almost no hysteresis loss in the repeated tensile test, and the results showed excellent durability.
  • Comparative Examples 1 and 2 are elastomers having no (semi) interpenetrating network structure. Although these have the same monomer composition as the elastomers obtained in Examples 1 and 3 as a composition of the whole elastomer, their tensile breaking strengths are as low as 0.70 and 1.5 Mpa. It was. Comparative Examples 3 to 6 are elastomers having a semi-interpenetrating network structure. However, Comparative Example 3 was not suitable for use as an elastomer because the amount of anionic vinyl monomer used was larger than that of the present invention, so its breaking strength and breaking elongation were low. In Comparative Example 4, a cationic monomer is included in the first monomer component.
  • Comparative Examples 5 and 6 are experimental examples in which an elastomer having substantially the same composition as in Examples 3 and 14 was obtained, respectively, but the second step was performed in the presence of a solvent. In Comparative Examples 5 and 6, the tensile strength at break of the obtained elastomer was relatively low, and a large hysteresis loss was observed in both repeated tensile tests.
  • the elastomer of the present invention exhibits excellent strength and hardly causes hysteresis loss due to tensile stress. For this reason, application is expected not only for sealing materials and packing materials, but also for fields that require high strength and high durability, such as automotive tire materials, building materials, and medical materials.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Graft Or Block Polymers (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Polymerisation Methods In General (AREA)

Abstract

La présente invention concerne un élastomère ayant une structure de réseau (semi-)interpénétrant, qui est obtenu par : formation d'une première structure de réseau par polymérisation et réticulation d'un premier composant monomère ; et introduction séquentielle d'un deuxième composant monomère dans la première structure de réseau et ensuite polymérisation ou polymérisation et réticulation du deuxième composant monomère. Le premier composant monomère contient de 0,1 à 30 % en moles d'un monomère vinylique anionique ; la température de transition vitreuse (Tg) d'un polymère obtenu à partir du deuxième composant monomère est de -80 °C à 20 °C ; un solvant n'est pas sensiblement utilisé dans la deuxième étape ; et le rapport en masse du premier composant monomère au deuxième composant monomère est de 1/0,1 à 1/100.
PCT/JP2015/063274 2014-05-08 2015-05-08 Élastomère à résistance élevée WO2015170735A1 (fr)

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