WO2004063230A1 - 環化ゴムおよびその製造方法 - Google Patents
環化ゴムおよびその製造方法 Download PDFInfo
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- WO2004063230A1 WO2004063230A1 PCT/JP2004/000282 JP2004000282W WO2004063230A1 WO 2004063230 A1 WO2004063230 A1 WO 2004063230A1 JP 2004000282 W JP2004000282 W JP 2004000282W WO 2004063230 A1 WO2004063230 A1 WO 2004063230A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
- C08C19/00—Chemical modification of rubber
- C08C19/10—Isomerisation; Cyclisation
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- the present invention relates to a cyclized rubber and a method for producing the same. More specifically, a cyclized rubber which can be applied to various applications, has a small residue of an acid catalyst used in a cyclization reaction, and has excellent storage stability, and a cyclized rubber which can easily obtain the cyclized rubber And a method for producing the same. Background art
- Cyclic rubbers with a ring structure introduced into conjugated rubbers such as natural rubber and synthetic polyisoprene rubber have excellent chemical resistance, heat resistance and weather resistance, as well as non-polar polymers such as polyolefins and polyesters. It has excellent adhesion to polar polymers such as polyurethane, alkyd resin, and metals such as iron. Therefore, it is used in a wide variety of applications, such as paints, adhesives, electrical and electronic materials, vehicles for printing ink, optical materials, resists, and dry film resists.
- cyclized rubber is produced by heating a conjugated diene polymer solution (for example, 6 to 10% by weight) at a relatively low concentration in the presence of an acid catalyst for several hours to carry out the cyclization reaction.
- a conjugated diene polymer solution for example, 6 to 10% by weight
- an acid catalyst for example, 6 to 10% by weight
- impurities such as an acid catalyst are extracted into an aqueous layer and removed by water washing several times after the treatment (for example, see Japanese Patent Application Laid-Open No. 57-145103).
- the present inventors have conducted intensive studies to solve such problems of the prior art, and as a result, in the conventional production method, the residue of the acid catalyst used in the cyclization reaction was not sufficiently removed.
- the catalyst residue significantly affects gelation during storage of the cyclized rubber, and instead of washing with a large amount of water, instead of neutralizing the acid catalyst with an alkali, filter it with a filter for efficiency.
- the residue of the acid catalyst can be removed efficiently, and the cyclized rubber obtained in this way is less likely to genole during storage than conventional products, and improves adhesion and dispersibility to various polymers
- the present invention has been found to have excellent properties as an adhesive component for a molding material modifier, a powder coating material, a primer, and the like.
- a main object of the present invention is to provide a cyclized rubber having excellent storage stability which can be applied to various uses, and another object is to provide a cyclized rubber having excellent storage stability. To provide a production method which can be obtained in
- the object of the present invention is achieved by the following 1 to 20 inventions.
- a cyclized conjugated polymer or a derivative thereof wherein the content of the residue of the acid catalyst used in the cyclization reaction is 70 ppm or less, and the weight average molecular weight (Mw) is 1,0.
- a cyclized rubber characterized by being 0 to 1, 000, 0000.
- the above cyclized rubber wherein the polar group is at least one group selected from the group consisting of an acid anhydride group, a carboxyl group, a hydroxyl group, an ester group, an epoxy group and an amino group.
- the cyclized rubber having a cyclization ratio of 10% or more.
- the above cyclized rubber having a gel amount of 10% by weight or less.
- the above-mentioned production method further comprising a step of adding a polar group-containing compound to the reaction solution obtained by filtering the residue of the acid catalyst to react with a cyclized conjugated polymer to introduce a polar group.
- the polar group-containing compound is a compound having at least one polar group selected from the group consisting of an acid anhydride group, a carboxyl group, a hydroxyl group, an ester group, an epoxy group and an amino group.
- the above powder particles having an average particle diameter of 1 to 200 m.
- the above powder particles having a cyclized rubber content of 5% by weight or more.
- a modifier for a polymer molding material containing the above-mentioned cyclized rubber as an active ingredient is provided.
- a cyclization having excellent storage stability which is useful for various uses such as a vehicle component for powder coating, a modifier for molding material, an adhesive component such as a primer and a coating, and a surface treatment agent. Rubber is provided.
- a method for producing a cyclized rubber which can easily obtain the cyclized rubber is provided.
- the cyclized rubber of the present invention has a content of acid catalyst residue used in the cyclization reaction (hereinafter sometimes referred to as “acid catalyst residue”) of not more than 70 ppm and a weight average molecular weight (Mw) of not more than 70 ppm.
- acid catalyst residue used in the cyclization reaction
- Mw weight average molecular weight
- the content of the acid catalyst residue is 70 ppm or less, a cyclized rubber having excellent storage stability is obtained, but it is preferably 50 ppm or less, more preferably 30 ppm or less.
- the acid catalyst residue refers to the acid catalyst used in the cyclization reaction and the reaction product of the acid catalyst and the alcohol added after the cyclization reaction.
- the acid catalyst is p-toluenesulfonic acid
- the cyclized rubber obtained is redissolved in toluene at 20% by weight, and extracted three times with the same amount of water. After concentration of the extracted water, it can be measured with an ion chromatograph.
- the acid catalyst is a metal halide
- the obtained cyclized rubber is wet-decomposed with a mixture of sulfuric acid and nitric acid, and the corresponding metal element is measured by a multi-element simultaneous measurement type high frequency inductively coupled plasma emission spectrometer. be able to.
- the weight average molecular weight of the cyclized rubber of the present invention is preferably from 10,000 to 500,000, and preferably from 50,000 to 300,000. More preferred. If the molecular weight is excessively large, the solution viscosity will increase, which may hinder application or spray coating.
- the molecular weight distribution of the cyclized rubber that is, the weight average molecular weight Z number average molecular weight (Mw ZM n) is usually 4 or less.
- the cyclization rate of the cyclized rubber of the present invention is usually 10% or more, preferably 40 to 95%, more preferably 60 to 90%.
- the cyclization ratio is in this range, the property of improving the adhesiveness with a nonpolar polymer or a polar polymer is improved.
- the cyclization ratio refers to the peak area of the proton derived from the double bond before and after the cyclization reaction of the conjugated gen-based polymer measured by proton NMR analysis.
- the gel amount of the cyclized rubber is usually 10% by weight or less, preferably 5% by weight or less, but it is particularly preferable that the cyclized rubber is substantially a gel-free cyclized rubber. If the amount of gel is large, a problem may occur in the coating process when forming the primer layer described later. There is a potential.
- the method for producing a cyclized rubber according to the present invention comprises the steps of cyclizing a conjugated gen-based polymer in a hydrocarbon solvent in the presence of an acid catalyst, and then neutralizing the acid catalyst by adding an alkali to the reaction solution. Is filtered to remove acid catalyst residues.
- the conjugated gen-based polymer used as a raw material of the cyclized rubber may be a conjugated gen monomer-only polymer or a copolymer of a conjugated gen monomer and another monomer. Good. Further, the copolymer may be any of a random copolymer and a block copolymer.
- conjugated diene monomer examples include 1,3-butadiene, isoprene, 2,3-dimethinole-1,3-butadiene, 2-phenylenolene 1,3-butadiene, 1,3-pentadiene, 1,3-pentadiene, and 2-methylenol-1, Examples thereof include 3_pentagen, 1,3_hexadiene, 4,5-jethyl-1,3-octadiene, and 3-butyl-1,3, octadiene.
- Other monomers include, for example, styrene, o-methyl styrene, p-methyl styrene, m-methyl styrene, 2,4-dimethyl styrene, ethynolestyrene, p-tert-butynole styrene, ⁇ - Methinolestyrene, ⁇ -Methinole ⁇ -Methinolestyrene, ⁇ -Chronolestyrene, m-Chronolestyrene, p-Chronolestyrene, p-Bromostyrene, 2-Methyl-1,4-dichlorostyrene, 2,4-Dib Mouth Aromatic monomer such as styrene, vinylnaphthalene, etc .; Linear olefin monomer such as ethylene, propylene, 1-butene; Cyclic olefin monomer such as
- conjugated diene monomers and other monomers may be used alone or in combination of two or more.
- the content of the conjugated gen monomer unit in the conjugated gen-based polymer is appropriately selected within a range not to impair the effects of the present invention, but is usually 40 mol% or more, preferably 60 mol% or more. %, More preferably 80 mol. / 0 or more. If this content is small, it will be difficult to increase the cyclization rate, and the desired effect of improving physical properties tends to be hardly obtained.
- the polymerization method of the conjugated gen-based polymer may be in accordance with a conventional method.For example, using an appropriate catalyst such as a Ziegler-based polymerization catalyst containing titanium as a catalyst component, an alkyllithium polymerization catalyst, or a radical polymerization catalyst, It is carried out by solution polymerization or emulsion polymerization.
- an appropriate catalyst such as a Ziegler-based polymerization catalyst containing titanium as a catalyst component, an alkyllithium polymerization catalyst, or a radical polymerization catalyst.
- conjugated gen-based polymer used as a raw material of the cyclized rubber include natural rubber, polyisoprene rubber, polybutadiene rubber, butadiene-isoprene copolymer, styrene-isoprene copolymer, styrene-butadiene copolymer, Atarilonitrile-isoprene copolymer, acrylonitrile-butadiene copolymer and the like can be mentioned.
- conjugated gen-based polymers can be masticated as needed to reduce the molecular weight before use.
- isoprene-based rubbers containing isoprene as a main component are preferred because they have a large effect of improving the adhesion to non-polar polymers.
- the cis-1,4 bond amount in isoprene units Is preferably 40% or more, more preferably 60% or more. Cyclization of the conjugated diene polymer is carried out by dissolving the conjugated diene polymer in a hydrocarbon solvent and reacting it in the presence of an acid catalyst.
- the acid catalyst may be any one usually used in cyclization reactions, for example, sulfuric acid; fluoromethanesulfonic acid, difluoromethanesulfonic acid, p-toluenesulfonic acid, xylenesulfonic acid, carbon number 2 to I 6 Alkylbenzene sulfonate having an alkyl group of the following, or an organic sulfone oxide such as an anhydride or an alkyl ester thereof; boron trifluoride, boron trichloride, tin tetrachloride, titanium tetrachloride, aluminum chloride, dimethyl chloride Metal halides such as aluminum monochloride, ethylammonium chloride, aluminum bromide, antimony pentachloride, tungsten hexachloride, and iron chloride. These acid catalysts may be used alone or in combination of two or more.
- an organic sulfonic acid compound is preferable, and p-toluenesulfonic acid is more preferable, because the acid catalyst residue can be easily removed in the filtration step.
- the amount of the acid catalyst used is usually 0.05 per 100 parts by weight of the conjugated diene polymer. 110 parts by weight, preferably 0.1-5 parts by weight, more preferably 0.3-2 parts by weight.
- the hydrocarbon solvent used in the reaction is not particularly limited as long as it does not inhibit the cyclization reaction.
- Examples thereof include aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene; n-pentane, n-hexane And aliphatic hydrocarbons such as n-heptane and n-octane; alicyclic hydrocarbons such as cyclopentane and cyclohexane; Among these hydrocarbon solvents, those having a boiling point of 70 ° C. or higher are preferred.
- a solvent used for a polymerization reaction of a conjugated gen-based polymer can be used as it is. In this case, an acid catalyst is added to the polymerization reaction solution after the completion of the polymerization.
- the amount of the hydrocarbon solvent used is such that the solid content concentration of the conjugated polymer is usually 5 to 60% by weight, preferably 20 to 40% by weight.
- the cyclization reaction can be performed under any of pressurized, reduced or atmospheric pressure, but is preferably performed under an atmospheric pressure from the viewpoint of easy operation.
- the reaction is performed in a dry air flow, particularly in an atmosphere of dry nitrogen or dry argon, side reactions due to moisture can be suppressed.
- the reaction temperature and reaction time may be in accordance with a conventional method.
- the reaction temperature is usually 50 to 150 ° C, preferably 80 to 110 ° C, and the reaction time is usually 0.5 to: 10 hours, preferably 2 to 5 hours.
- the conjugated gen-based polymer and the hydrocarbon-based solvent are charged into a reaction vessel, and then heated to a predetermined temperature to completely dissolve the conjugated-gen-based polymer. It is preferable to add an acid catalyst to the mixture and carry out the cyclization reaction with stirring.
- the acid catalyst is treated by adding alcohol to the reaction solution after the cyclization reaction.
- the acid catalyst used in the cyclization reaction can be efficiently removed.
- the alkali used in the alkali treatment may be any as long as it forms an insoluble material by neutralizing with the acid catalyst of the cyclization reaction.
- sodium carbonate, potassium carbonate, sodium hydroxide, Carbonates and hydroxides of alkali metals such as lithium and sodium hydrogen carbonate; ammonium hydroxide and the like; acids used in cyclization reactions It can be appropriately selected according to the catalyst and the like.
- a water-soluble alcohol is preferred, and those capable of being added as an aqueous solution at 25 ° C of 10% by weight or more, particularly 20% by weight or more, are preferred. By adding a highly concentrated aqueous solution, the amount of water present in the system is reduced, resulting in easier filtration.
- the amount of the alkali may be appropriately selected, but is usually 1-2 equivalents, preferably 1.1-1.3 equivalents, to the acid catalyst used. If the amount used is small, the removal of the acid catalyst residue will be insufficient, and if it is too large, the residue of the acid catalyst will remain and may cause problems depending on the application.
- the residue of the acid catalyst used in the cyclization reaction is removed by filtering the reaction solution after the alkali treatment with a filter.
- the alkali residue used for the alkali treatment is insoluble in the solvent, and the alkali residue is not dissolved in the solvent. Can be removed.
- the alkali residue is mainly an excess of alkali that does not contribute to the neutralization reaction of the acid catalyst used in the cyclization reaction.
- the amount of the alkali residue is controlled so as to be preferably 100 ppm or less, more preferably 70 ppm or less, with respect to the target cyclized rubber.
- the material of the filter used for filtration is not particularly limited. Specific examples thereof include plastics such as polysulfone, polyethersulfone, and polytetrafluoroethylene; metals such as stainless steel and iron; paper, cloth, glass, and ceramics. Among them, glass fiber, cloth and metal filters can be preferably used.
- the pore size of the filter may be appropriately selected according to the acid catalyst used in the reaction, and is usually from 0:! To 10, preferably from 0.5 to 3 ⁇ .
- a diatomaceous earth such as radiolite and celite
- a filter aid such as activated carbon
- the solvent is removed by a conventional method, and then dried to obtain the desired cyclized rubber.
- the reaction solution after the removal of the acid catalyst residue can be subjected to a modification reaction with a polar group-containing compound, if necessary.
- the polar group-containing compound used in the modification reaction is not particularly limited as long as it can introduce a polar group into the cyclized conjugated polymer, and examples thereof include an acid anhydride group, a carboxyl group, Examples include an ethylenically unsaturated compound having a polar group such as a hydroxyl group, a thiol group, an ester group, an epoxy group, an amino group, an amide group, a cyano group, a silyl group, and a halogen.
- the polar group is preferably an acid anhydride group, a carboxyl group, a hydroxyl group, an ester group, an epoxy group, or an amino group, and more preferably an acid anhydride group, a carboxyl group, or a hydroxyl group, from the viewpoint of improving the adhesiveness ⁇ ! .
- Examples of the compound having an acid anhydride group or a carboxyl group include, for example, ethylenically unsaturated compounds such as maleic anhydride, itaconic anhydride, aconitic anhydride, norbornene dicarboxylic anhydride, atarylic acid, methacrylic acid, and maleic acid.
- maleic anhydride is awarded for its reactivity and economy.
- Examples of the compound containing a hydroxyl group include hydroxyalkyl esters of unsaturated acids such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate; N-methylol (meth) acrylic acid Amides, N- (2-hydroxyethyl) (meth) acrylamides and other unsaturated acid amides having a hydroxyl group; polyethylene glycol mono (meth) acrylate, polypropylene glycolone (meth) Polyalkylene glycol monoesters of unsaturated acids such as acrylates, poly (ethylene glycol propylene glycol) mono (meth) acrylate; polyhydric alcohol monoesters of unsaturated acids such as glycerol mono (meth) acrylate And the like. Of these, hydroxyalkyl esters of unsaturated acids are preferred, and 2-hydroxyethyl acrylate and 2-hydroxyshethyl methacrylate are particularly preferred.
- Examples of other ethylenically unsaturated compounds containing a polar group include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, glycidyl (meth) acrylate, dimethylaminoethyl ( (Meth) acrylate, dimethylaminopropyl (meth) acrylate, (meth) acrylamide, (meth) acrylonitrile, and the like.
- the method for introducing the polar group-containing compound into the cyclized conjugated polymer is not particularly limited. However, when an ethylenically unsaturated compound is added, a known reaction generally called an ene addition reaction or a graft polymerization reaction must be followed.
- This addition reaction is carried out by reacting the cyclized conjugated polymer and the polar group-containing compound in the presence of a radical generator as required.
- a radical generator include peroxides such as di-tert-butyl peroxide, dicumyl peroxide, benzoy ⁇ peroxide, tert-butyl peroxide benzoate, methyl ethyl ketone peroxide; azobisisoiso Azonitrile such as ptyronitrile; and the like.
- the addition reaction may be performed in a solid state or in a solution state, but is preferably performed in a solution state because the reaction can be easily controlled.
- the solvent to be used for example, those similar to the hydrocarbon solvents in the cyclization reaction described above can be mentioned.
- the amount of the polar group-containing compound used is appropriately selected, but the ratio of the introduced polar group is usually 0.1 to 200 mmol, preferably: 100 mmol per 100 g of the modified cyclized rubber. The range is from about! 100 to about 100 mmol, more preferably from about 5 to about 50 mmol.
- the reaction for introducing a polar group can be carried out under any pressure, reduced pressure or atmospheric pressure.However, it is desirable to carry out the reaction under atmospheric pressure from the viewpoint of simplicity of operation. When the reaction is performed in an atmosphere of dry nitrogen or dry argon, side reactions due to moisture can be suppressed.
- the reaction temperature and the reaction time may be in accordance with a conventional method, and the reaction temperature is usually 30 to 250 ° C, preferably 60 to 200 ° C, and the reaction time is usually 0.5. ⁇ 5 hours, preferably :! ⁇ 3 hours.
- the cyclized rubber of the present invention is roughly classified into one having no polar group in its molecular structure and one having a polar group.
- the presence or absence of the polar group and the content thereof affect the performance of the cyclized rubber as a modifier for a molding material or a vehicle component for a coating material, and is appropriately selected according to the required performance.
- Examples of the cyclized rubber having no polar group include cyclized conjugated polymer obtained by polymerizing or copolymerizing a monomer having no polar group, and cyclized natural rubber.
- Specific examples of the cyclized rubber having a polar group in the molecule include a monomer having a polar group.
- a polar group is introduced into a cyclized conjugated polymer by a modification reaction using a polar group-containing compound, a cyclized rubber having desired properties can be easily obtained.
- Examples of the monomer having a polar group include chloroprene, acrylic acid, methacrylic acid, ethyl acrylate, butyl acrylate, hydroxyshethyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, butyl methacrylate, and acrylonitrile. And acrylamide.
- a modification reaction is performed after the cyclization reaction of the conjugated gen polymer.
- the polar group to be introduced into the cyclized conjugated polymer is not particularly limited as long as it can impart a desired polarity, but from the viewpoint of ease of introduction, acid anhydrides can be used. Groups, carboxyl groups and hydroxyl groups are preferred. Further, the modification reaction is performed by adding a polar group-containing compound to the cyclized conjugated polymer as described above, but other methods may be used.
- the cyclized rubber of the present invention is used, if necessary, by adding a coloring agent such as a pigment and a dye; and a compounding agent such as an antioxidant, a filler, a softener, and a wax.
- a coloring agent such as a pigment and a dye
- a compounding agent such as an antioxidant, a filler, a softener, and a wax.
- the compounding agent can be any commonly used one.
- anti-aging agents examples include 2,6-di-t-butylphenol, 2,2, -methylenebis (4-methinolate t-butylphenol), tetrakis [methylene-3- (3,, 5, di-t) 1-butyl-4, -hydroxyphenyl) propionate]
- a phenolic anti-aging agent such as methane; phenyl_ct 1-naphthylamine, diphenyl ⁇ / 1-p-phenylenediamine, N_l, 3-dimethinolebutyl-N '— Amine antioxidants such as phenyl-p-phenylenediamine; phosphorus antioxidants such as tris (nonylphenyl) phosphite;
- filler examples include calcium carbonate, calcium oxide, magnesium oxide, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, magnesium carbonate, calcium silicate, barium sulfate, myriki, silica, carbon black, Examples include talc, clay, titanium dioxide, zinc oxide, glass fiber, and carbon fiber.
- the amount of compounding agent used can be appropriately selected depending on the purpose of compounding and the type of compounding agent.
- the shape of the cyclized rubber can be appropriately selected depending on the application, but is usually in the form of a pellet or powder.
- the solid cyclized rubber, together with the above-mentioned compounding agents, which are added as necessary, is cooled, and then, using a pulverizer such as a bantam mill, jet mill, disk mill, ball mill, or colloid mill. What is necessary is just to put a powder frame.
- the average particle diameter of the powder particles thus obtained is usually 1 ⁇ ! ⁇ 200im, preferably 3 ⁇ ! 1100 ⁇ , more preferably 5 ⁇ m to 50 ⁇ m.
- the average particle diameter is a particle diameter corresponding to a 50% number-based integrated value in a number-based integral curve with respect to the particle diameter, which is measured by a laser diffraction / scattering method.
- the content of the cyclized rubber in the powder particles is usually 5% by weight or more, preferably 10% by weight, more preferably 20% by weight or more, and particularly preferably 30% by weight or more.
- the cyclized rubber of the present invention obtained in this manner does not generate a gel even during long-term storage, and is useful in many applications utilizing the properties of the cyclized rubber.
- the above-mentioned powder particles can be used as a powder coating by making use of excellent adhesion to a resin or a metal.
- a coloring agent is blended, and if necessary, an antioxidant, a filler, a softening agent, a wax and the like are appropriately blended according to a conventional method.
- benzidine, azo, and isodoline pigments are used for yellow coloring
- azo lake, rhodamine lake, quinacridone, naphthol, and diketopyro pyrrolic pigments are used for magenta coloring.
- cyan coloring phthalocyanine pigments and indanthrene pigments are preferably used.
- black coloring carbon black is usually used. Examples of the carbon black include samanore black, acetylene black, channel / black, furnace black, lamp black, and the like.
- dyes When dyes are used as colorants, yellow-colored azo, nitro-, quinoline-, quinophthalone-, and methine-based dyes, magenta-colored anthraquinone-, azo-, and xanthene-based dyes and cyan-colored Is an anthraquinone, phthalocyanine Dyes and indoor diline dyes are preferably used.
- the amount of the colorant to be used may be appropriately selected depending on the desired hue, density, etc., and is preferably 0.1 to 50 parts by weight, more preferably:! To 20 parts by weight.
- Powder coatings can usually be obtained by mixing a cyclized rubber, a colorant and, if necessary, additives contained therein, and pulverizing and classifying the mixture.
- the mixing method is not particularly limited, and for example, there is a method of melt-mixing using a kneader such as a Banbury mixer, a kneader, a mixer roll, a single-screw or twin-screw extruder.
- a kneader such as a Banbury mixer, a kneader, a mixer roll, a single-screw or twin-screw extruder.
- the above-mentioned method may be used as the pulverizing method.
- classification method examples include methods such as air classification, centrifugal classification, and sieve classification.
- the cyclized rubber of the present invention can improve the adhesiveness of various polymer molding materials composed of a thermoplastic resin, a thermosetting resin, an elastomer, and the like, and can improve the dispersibility of different kinds of polymers constituting the polymer molding material. It is also useful as a modifier for a polymer molding material for improving the dispersibility of a compounding agent such as a filler or a pigment in the polymer in the polymer molding material.
- Examples of the polymer used for the polymer molding material to be modified include the following.
- Hydrocarbon resin such as resin, polycarbonate resin, polybutyrate resin, polyarylate resin, and fluorine resin.
- Thermosetting resins such as phenolic resin, cresol resin, urea resin, melamine resin, alkyd resin, furan resin, unsaturated polyester resin, epoxy resin and urethane resin.
- Vulcanized rubber such as natural rubber, polybutadiene rubber, styrene-butadiene rubber, Atari mouth-tolyl-butadiene rubber, etc .
- Elastomers such as Tylene-based thermoplastic elastomer, polyester-based thermoplastic elastomer, and polyamide-based thermoplastic elastomer.
- linear olefinic resins such as polyethylene, polypropylene, and polypentene-11
- cyclic copolymers such as addition copolymers of ethylene and norbornenes, and hydrogenated ring-opening polymers of norpolenes
- hydrocarbon-based thermoplastic resin When blended with a hydrocarbon-based thermoplastic resin, the effect of the cyclized rubber is greatly improved.
- the above polymers can be used alone or in combination of two or more.
- coloring agents such as pigments and dyes; antioxidants, fillers, softeners, waxes, antistatic agents, stabilizers, lubricants, crosslinking agents, antiblocking agents, coloring agents, and light blocking agents
- a compounding agent such as an ultraviolet absorber can also be appropriately compounded.
- the amount of the polymer molding material modifier is appropriately determined according to the type of the polymer molding material and the required performance. It is selected, but usually 0.1 to 50 parts by weight, preferably 0.5 to 20 parts by weight, more preferably 1 to 10 parts by weight per 10 parts by weight of the polymer in the polymer molding material.
- the cyclized rubber of the present invention is used as an adhesive component such as a vehicle component for a primer or a binder component for a paint in a coating agent such as a primer or a paint for the polymer molding material described above, Adhesion can be improved.
- the cyclized rubber is preferably contained in an amount of 2% by weight or more, preferably 5% by weight or more, more preferably 10% by weight or more, based on the total solid content in a coating agent such as a primer or a paint.
- the cyclized rubber When used as a coating agent, the cyclized rubber may be blended with other adhesive components and various additives as necessary.
- adhesive components include, for example, acrylic resin, urethane resin, polyester resin, epoxy resin, melamine resin, alkyd resin, chlorinated olefin resin, silicone rubber, and the like.
- the ratio when the other adhesive component is blended is appropriately selected according to the type and purpose of blending.
- the weight ratio of the cyclized rubber to the other adhesive component is 100: 0 to 5: 95, preferably 80: 20 to 30: 70, more preferably 70: 30 to 50: 5 It is 0.
- additive examples include the same additives as those for the polymer exemplified in the section of the modifier.
- the coating agent containing the cyclized rubber is usually obtained by dissolving or dispersing the cyclized rubber or a mixture of the cyclized rubber and other components in a solvent.
- the solvent to be used may be appropriately selected, and examples thereof include aliphatic hydrocarbon solvents, alicyclic hydrocarbon solvents, aromatic hydrocarbon solvents, ketone solvents, alcohol solvents, ether solvents, and halogens. Solvents, aqueous solvents and the like.
- the amount of the solvent used is such that the solid content concentration of the coating agent is usually 5 to 95% by weight, preferably 15 to 60% by weight.
- the coating agent containing the cyclized rubber of the present invention can also be used as a surface treatment agent for a dispersed material such as various fillers and pigments.
- Surface treatment of the dispersing material with the coating agent improves the dispersibility of the dispersing material in various polymers.
- the filler and pigment to be subjected to the surface treatment those described above can be used.
- the amount of the cyclized rubber to be used is appropriately selected according to the type of the dispersing material and the type of the polymer in which the cyclized rubber is dispersed, but usually 0.1 to 100 parts by weight per 100 parts by weight of the dispersing material. It is preferably used in a proportion of 5 to 20 parts by weight.
- the cyclized rubber of the present invention can also be used as an adhesive for firmly bonding different materials to each other.
- combinations of different materials include, for example, OPP (extended polypropylene), CPP (crystalline polypropylene), polypropylene / polyethylene terephthalate, polypropylene Z ethylene-vinyl acetate copolymer, and polypropylene z aluminum.
- the shape is not particularly limited, but a film shape or a sheet shape is preferable.
- the bonding method include, for example, a method in which a cyclized rubber preliminarily formed into a film is sandwiched between different kinds of materials and then heated and bonded, or a coating agent containing the cyclized rubber is applied to one surface of the material. After that, a method of bonding with the other material surface can be adopted.
- the evaluation was performed as follows.
- the weight-average molecular weight (Mw) and number-average molecular weight (Mn) are determined by gel, permeation, and chromatographic analysis in terms of standard polystyrene, and the numerical values of the weight-average molecular weight and Mw_Mn are shown.
- the cyclization rate was determined by proton NMR measurement according to the methods described in the following documents (i) and (ii).
- the cyclized rubber modified with maleic anhydride has an acid anhydride group derived from the added maleic anhydride and a carboxyl group obtained by hydrolyzing the acid anhydride group.
- the Fourier transform infrared spectrum of this cyclized rubber was measured, the peak intensity of the acid anhydride group (1760 to 1780 cm- 1 ) was measured, and the content of the acid anhydride group was determined by the calibration curve method. I asked.
- the peak intensity of the carboxyl group (1700 cm- 1 ) was measured, and the content of the carboxyl group was measured by the calibration curve method.
- the hydroxyl value of the cyclized rubber modified with the hydroxyl group-containing compound was measured in accordance with the method described in “Standard Oil and Fat Analysis Test Method (Japan Oil Chemistry Association)” 2, 4, 9, 2-83. From this hydroxyl value, the amount of hydroxyl groups in the modified cyclized rubber was determined. (5) Acid catalyst residue
- the cyclization catalyst is P-toluenesulfonic acid
- a solution of 100 g of the cyclized rubber dissolved in 400 g of toluene is extracted three times with 500 ml of water, so that the total 1500 m1 of extracted water becomes 100 m1.
- the evaporator was concentrated, and the concentrated water was measured using an ion chromatograph (Dionetas).
- calibration curves of sodium p-toluenesulfonic acid and p-toluenesulfonic acid were prepared in advance, and their contents with respect to the total amount of the cyclized rubber were determined.
- the lower limit of measurement by the above method is 1 ppm. After the above measurement, the same extraction and extraction water were again concentrated, and the concentrated extraction water was analyzed. As a result, no acid catalyst residue was detected.
- the Na content is measured using an atomic absorption spectrum (SAS 7500: manufactured by Seiko Instruments Inc.), and the Na content based on the total amount of the cyclized rubber is measured. I asked. The Na content derived from the sodium salt of p-toluenesulfonic acid, which is the acid catalyst residue, was subtracted from the Na content to determine the Na content derived from the alkali residue.
- SAS 7500 manufactured by Seiko Instruments Inc.
- the cyclized rubber was cut into 2 mm squares, placed in an oven at 80 ° C (blowing type), and the molecular weight distribution and gel amount over time were measured.
- Powder particles are measured using a laser diffraction / scattering type particle size distribution analyzer (LMS-300 : manufactured by Seishin Enterprise Co., Ltd.). Is shown as an average particle diameter.
- LMS-300 laser diffraction / scattering type particle size distribution analyzer
- polyisoprene cut into 1 Omm square (cis 1,4 unit 73%, transformer 1,4 unit 22%, 3,4 300 parts of 5% per unit, weight average molecular weight of 174,000) were charged together with 700 parts of toluene (polymer concentration: 30%). After the inside of the reactor was replaced with nitrogen, the mixture was heated to 80 ° C and the polyisoprene was completely dissolved in toluene with stirring, and 2.07 parts of p-toluenesulfonic acid (anhydrous) was added. The cyclization reaction was performed at ° C.
- Example 3 Use polyisoprene with 70% cis-1,4 unit, 24% trans-1,4 unit, 6% 3,4,1 unit, weight average molecular weight 141,000, p-toluenesulfonic acid (anhydride) The acid catalyst was removed and the solvent was removed in the same manner as in Example 1 except that the used amount was changed to 2.69 parts, and the reaction was stopped by adding 25% aqueous sodium carbonate solution containing 1.03 parts of sodium carbonate. When the solid content concentration of the cyclized rubber reached 70 to 75% by weight, 9 parts of maleic anhydride was added, and the mixture was reacted at 180 ° C for 1 hour.
- Example 2 when the solid content concentration of the cyclized rubber reached 70 to 75% by weight, 7.5 parts of maleic anhydride was added and reacted at 180 ° C for 1 hour. Then, unreacted maleic anhydride and toluene were removed and dried under reduced pressure in the same manner as in Example 3 to obtain a modified cyclized rubber D. This modified cyclized rubber D was evaluated, and the results are shown in Table 1.
- polyisoprene cut into 10 mm squares (cis 1,4 units 70%, transformer 1,4 units 24%, 4 300 parts of one unit 6%, weight average molecular weight 141,000) were charged together with 4700 parts of toluene (polymer concentration 6%). After the inside of the reactor was replaced with nitrogen, the mixture was heated to 80 ° C and the polyisoprene was completely dissolved in toluene under stirring. Then, p-toluenesulfonic acid (anhydrous) (10.8 parts) was added. The cyclization reaction was performed at ° C.
- Table 1 shows the following.
- the cyclized rubber produced within the scope of the present invention has a low content of acid catalyst residue and is excellent in storage stability (Examples 1 to 5). .
- the obtained coating film was uniform, and the adhesion of the coating film was 100/100 as measured by a grid test, indicating that the adhesion was excellent.
- a powder coating was obtained and evaluated in the same manner as in Example 6, except that Cyclic Rubber B was used instead of Cyclic Rubber B after accelerated test at 80 ° C for 240 hours.
- the coating film obtained using this powder coating was non-uniform and had poor adhesion.
- a two-component curable urethane metallic paint (trade name RB-212 (trade name, manufactured by Nippon Bee Chemical Co., Ltd.) and a trade name RB-288 (trade name, )) was coated in two coats such that the film thickness of the entire paint was 40 ⁇ . After coating, the coating was dried at 23 ° C for 15 minutes, dried at 80 ° C for 30 minutes by a non-circulating drier, and then left at room temperature for 24 hours.
- the adhesion of the coating film of the obtained coated test piece was measured by a grid test, and was 100,100, indicating that the adhesion was excellent.
- a coated test piece was obtained in the same manner as in Example 7, except that the cyclized rubber C was replaced with the cyclized rubber G after an accelerated test at 80 ° C for 240 hours.
- the above-mentioned flow time is a flow time at 20 ° C. according to the Ford Cup No. 4 method specified in JIS K5400.
- polypropylene J-3054HP: Idemitsu Petrochemical Co., Ltd.
- J-3054HP Idemitsu Petrochemical Co., Ltd.
- the above-mentioned primer was coated on the above-mentioned polypropylene molded body that had been thoroughly washed with water with a spray pressure of 3.5 to 5. OMPa to a film thickness of 10 m. .
- a two-component curable urethane-based metallic paint (trade name: RB-212 (base coating) and trade name: RB-288 (taliya paint) manufactured by Nippon Bee Chemical Co., Ltd.) Two coats were applied so that the film thickness of the film became 40 / xm. After coating, the coating was dried at 23 ° C for 15 minutes, dried at 80 ° C for 30 minutes in a non-circulating dryer, and then left at room temperature for 24 hours.
- Example 5 A primer was prepared in the same manner as in Example 8, except that the cyclized rubber G was used instead of the cyclized rubber C after a 240-hour acceleration test at 80 ° C. If this primer was to be spray-painted, the spray gun was clogged and could not be painted cleanly, and further evaluation was stopped.
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- 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)
- Compositions Of Macromolecular Compounds (AREA)
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Abstract
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Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
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WO2005092940A1 (ja) * | 2004-03-29 | 2005-10-06 | Zeon Corporation | ブロック共重合体およびその製造方法 |
WO2007049739A1 (ja) * | 2005-10-28 | 2007-05-03 | Zeon Corporation | 酸素吸収性樹脂組成物、酸素吸収性フィルム及び酸素吸収性多層体 |
WO2007049740A1 (ja) * | 2005-10-28 | 2007-05-03 | Zeon Corporation | 酸素吸収性バリアー樹脂組成物、これからなるフィルム、多層構造体及び包装容器 |
JP2007119607A (ja) * | 2005-10-28 | 2007-05-17 | Nippon Zeon Co Ltd | 酸素吸収性樹脂組成物、酸素吸収性フィルム並びに酸素吸収性多層体 |
JP2007119606A (ja) * | 2005-10-28 | 2007-05-17 | Nippon Zeon Co Ltd | 酸素吸収性樹脂組成物、酸素吸収性フィルム並びに酸素吸収性多層体 |
US7776961B2 (en) | 2003-12-04 | 2010-08-17 | Zeon Corporation | Oxygen absorber |
JP5082848B2 (ja) * | 2005-05-31 | 2012-11-28 | 日本ゼオン株式会社 | 酸素吸収剤、酸素吸収性フィルム及び包装容器 |
CN104159931A (zh) * | 2012-03-07 | 2014-11-19 | 株式会社普利司通 | 聚合物、含该聚合物的橡胶组合物、通过交联该橡胶组合物获得的交联橡胶组合物以及具有该交联橡胶组合物的轮胎 |
JPWO2021261489A1 (ja) * | 2020-06-24 | 2021-12-30 |
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JPS5770102A (en) * | 1980-10-21 | 1982-04-30 | Japan Synthetic Rubber Co Ltd | Production of high-purity cylized diene polymer |
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JP2004059890A (ja) * | 2002-07-31 | 2004-02-26 | Yamashita Rubber Co Ltd | 接着性ゴム組成物 |
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JPS5996112A (ja) * | 1982-11-26 | 1984-06-02 | Toyo Soda Mfg Co Ltd | 高純度イソプレン重合体環化物の製造方法 |
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JPS60186505A (ja) * | 1984-03-05 | 1985-09-24 | Kuraray Co Ltd | 共役ジエン系重合体環化物の製造方法 |
JPS61126102A (ja) * | 1984-11-22 | 1986-06-13 | Nippon Zeon Co Ltd | 環化ポリイソプレンの製造方法 |
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JP2001207036A (ja) * | 2000-01-28 | 2001-07-31 | Asahi Kasei Corp | 熱可塑性エラストマー組成物 |
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JPS5770102A (en) * | 1980-10-21 | 1982-04-30 | Japan Synthetic Rubber Co Ltd | Production of high-purity cylized diene polymer |
JPS5815504A (ja) * | 1981-07-22 | 1983-01-28 | Japan Synthetic Rubber Co Ltd | ジエン系重合体環化物の製造方法 |
JP2004059890A (ja) * | 2002-07-31 | 2004-02-26 | Yamashita Rubber Co Ltd | 接着性ゴム組成物 |
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US7776961B2 (en) | 2003-12-04 | 2010-08-17 | Zeon Corporation | Oxygen absorber |
US7772326B2 (en) | 2004-03-29 | 2010-08-10 | Zeon Corporation | Block copolymer and method for producing same |
WO2005092940A1 (ja) * | 2004-03-29 | 2005-10-06 | Zeon Corporation | ブロック共重合体およびその製造方法 |
JP5082848B2 (ja) * | 2005-05-31 | 2012-11-28 | 日本ゼオン株式会社 | 酸素吸収剤、酸素吸収性フィルム及び包装容器 |
JP2007119607A (ja) * | 2005-10-28 | 2007-05-17 | Nippon Zeon Co Ltd | 酸素吸収性樹脂組成物、酸素吸収性フィルム並びに酸素吸収性多層体 |
JP2007119606A (ja) * | 2005-10-28 | 2007-05-17 | Nippon Zeon Co Ltd | 酸素吸収性樹脂組成物、酸素吸収性フィルム並びに酸素吸収性多層体 |
WO2007049740A1 (ja) * | 2005-10-28 | 2007-05-03 | Zeon Corporation | 酸素吸収性バリアー樹脂組成物、これからなるフィルム、多層構造体及び包装容器 |
US8053051B2 (en) | 2005-10-28 | 2011-11-08 | Zeon Corporation | Oxygen-absorbing barrier resin composition, film comprising the same, multilayer structure, and packing container |
WO2007049739A1 (ja) * | 2005-10-28 | 2007-05-03 | Zeon Corporation | 酸素吸収性樹脂組成物、酸素吸収性フィルム及び酸素吸収性多層体 |
CN104159931A (zh) * | 2012-03-07 | 2014-11-19 | 株式会社普利司通 | 聚合物、含该聚合物的橡胶组合物、通过交联该橡胶组合物获得的交联橡胶组合物以及具有该交联橡胶组合物的轮胎 |
US9499647B2 (en) | 2012-03-07 | 2016-11-22 | Bridgestone Corporation | Polymer, rubber composition containing polymer, crosslinked rubber composition obtained by crosslinking rubber composition, and tire having crosslinked rubber composition |
JPWO2021261489A1 (ja) * | 2020-06-24 | 2021-12-30 | ||
JP7153412B2 (ja) | 2020-06-24 | 2022-10-14 | 根上工業株式会社 | ゴム粒子及びその製造方法 |
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