WO2007043662A1 - Polymère d’isobutylène et son procédé de production - Google Patents

Polymère d’isobutylène et son procédé de production Download PDF

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WO2007043662A1
WO2007043662A1 PCT/JP2006/320489 JP2006320489W WO2007043662A1 WO 2007043662 A1 WO2007043662 A1 WO 2007043662A1 JP 2006320489 W JP2006320489 W JP 2006320489W WO 2007043662 A1 WO2007043662 A1 WO 2007043662A1
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Prior art keywords
isobutylene
polymer
monomer
polymerization
lewis acid
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PCT/JP2006/320489
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English (en)
Japanese (ja)
Inventor
Ryuji Fukuda
Takanori Hatano
Tomoyuki Yoshimi
Keizo Hayashi
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Kaneka Corporation
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Priority claimed from JP2005298696A external-priority patent/JP2009007383A/ja
Priority claimed from JP2005347480A external-priority patent/JP2009007385A/ja
Priority claimed from JP2006040817A external-priority patent/JP2009007386A/ja
Application filed by Kaneka Corporation filed Critical Kaneka Corporation
Publication of WO2007043662A1 publication Critical patent/WO2007043662A1/fr

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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
    • C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
    • C08F297/02—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type
    • 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
    • C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer

Definitions

  • the present invention relates to an isobutylene polymer and a method for producing the same.
  • An isobutylene polymer can be usually obtained by cationic polymerization of an isobutylene monomer together with other monomers as desired.
  • Non-patent Document 1 a polymer block mainly composed of isobutylene and a polymer block composed mainly of an aromatic vinyl monomer and having an isobutylene block copolymer which is composed mainly of an isobutylene homopolymer are also produced.
  • Patent Document 1 US Patent No. 4946899 Specification
  • Patent Document 2 Japanese Patent Publication No. 7-59601
  • Non-Patent Document 1 J. P. Kennedy and B. Ivan, Designed Polymers by Carbo reactive Molecular Engineering: Theory and Practice, Carl Hanser Verlag, Kunststoff, 1992
  • An object of the present invention is to provide an isobutylene-based polymer that is less colored and has a stable color tone, and a method that can produce such an isobutylene-based polymer in view of the above-described problems of the prior art. It is what. Means for solving the problem
  • the first present invention is an isobutylene polymer obtained by polymerizing a monomer component containing isoprene in the presence of a polymerization initiator and a Lewis acid catalyst,
  • the isobutylene polymer is characterized in that the amount of metal residue derived from the Lewis acid catalyst in the isopylene polymer is 90 ppm or less.
  • a preferred embodiment relates to the isobutylene polymer in which the polymerization initiator has a structure represented by the following general formula (1).
  • X represents a halogen atom, an alkoxy group having 1 to 6 carbon atoms or an acyloxy group.
  • R 1 and R 2 are the same or different, and are a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms.
  • R 3 represents a monovalent or polyvalent aromatic hydrocarbon group or a monovalent or polyvalent aliphatic or alicyclic hydrocarbon group, n represents a natural number of 1 to 6.
  • the polymerization initiator represented by the general formula (1) is represented by the formula C
  • the above-mentioned isobutylene polymer is at least one selected from the group consisting of
  • the present invention relates to the above-mentioned isobutylene polymer in which the Lewis acid catalyst is tetrachloride-titanium.
  • a preferred embodiment includes a polymer block (a) having the isobutylene-based polymer strength isobutylene monomer as a main component and a polymer block (b) having a monomer other than isopylene as a main component. It is related with the said isobutylene type polymer which is a block copolymer to do.
  • a preferred embodiment relates to the isobutylene polymer which is a monomeric aromatic vinyl monomer other than the above isoprene.
  • the aromatic vinyl monomer is styrene, p-methyl.
  • the present invention relates to the above isobutylene polymer, which is at least one selected from the group consisting of rustyrene, monomethylstyrene, and indene force.
  • the isobutylene polymer is
  • the present invention relates to the above-mentioned isobutylene polymer, which is at least one block copolymer selected from the group consisting of:
  • the second invention is a step (I) of polymerizing a monomer component containing isobutylene in the presence of a Lewis acid catalyst;
  • the obtained polymer-containing solution is washed with a basic aqueous solution having a pHIO or higher (III);
  • the polymer-containing solution obtained after the step (III) is further used.
  • the present invention relates to the above production method comprising the step (IV) of filtering with a filter capable of collecting 99% or more of particles having a diameter of 5 / zm or more when the differential pressure before and after the filter is 0.2 MPa.
  • Another aspect of the second aspect of the present invention is a step (I) of polymerizing a monomer component containing isobutylene in the presence of a Lewis acid catalyst;
  • the obtained polymer-containing solution was subjected to a pressure difference of 0.2 MPa before and after the filter.
  • Filter with a filter capable of collecting 99% or more of particles with a diameter of 5 ⁇ m or more (IV);
  • the present invention relates to the above-mentioned production method, wherein the above-mentioned isobutylene polymer strength is mainly composed of isobutylene.
  • the isobutylene polymer is composed of a polymer block (a) containing an isobutylene monomer as a main component and a polymer block containing an aromatic butyl monomer as a main component ( b) It relates to the above production method which is a polymer which also has strength.
  • the polymerization reaction is carried out with at least one selected from the group consisting of primary and secondary monohalogenated hydrocarbons having 3 to 8 carbon atoms, aliphatic, alicyclic and aromatic. And at least one selected from the group consisting of group hydrocarbons.
  • a preferred embodiment relates to the above production method, wherein the Lewis acid catalyst is a halogenated metal.
  • a preferred embodiment relates to the above production method, wherein the halogenated metal is tetrasalt titanium.
  • a preferred embodiment relates to the above production method, wherein the basic aqueous solution is a sodium hydroxide aqueous solution.
  • the isobutylene polymer of the present invention is obtained by polymerizing a monomer component containing isobutylene in the presence of a polymerization initiator and a Lewis acid catalyst.
  • the polymer is characterized in that the amount of metal residue derived from the Lewis acid catalyst is 90 ppm or less.
  • the isobutylene-based polymer may be a homopolymer composed only of isoprene, or may be a copolymer obtained by polymerizing isopylene and other monomers. Especially, what has isobutylene as a main component is preferable.
  • the “main component” means a monomer component that occupies 60% by weight or more of all monomers constituting the polymer (or polymer block). Of all monomers constituting the polymer, isobutylene More preferred is a polymer containing 80% by weight or more of ethylene.
  • the isobutylene-based polymer also includes a polymer block ( a ) containing an isobutylene monomer as a main component and a polymer block (b) containing a monomer other than isobutylene as a main component.
  • An isobutylene block copolymer is preferred.
  • the monomer other than isobutylene as the main component in the block (b) is not particularly limited as long as it is a monomer capable of cationic polymerization, but an aliphatic or alicyclic olefin-based monomer.
  • the aliphatic or alicyclic olefin-based monomer is not particularly limited, and examples thereof include ethylene, propylene, 1-butene, 2-methyl 1-butene, 3-methyl 1-butene, and pentene. Hexene, cyclohexene, 4-methyl-1-pentene, vinylcyclohexene, otaten, norbornene and the like.
  • the aromatic bulle monomer is not particularly limited.
  • the above-mentioned gen-based monomer is not particularly limited, and examples thereof include butadiene, isoprene, cyclopentane, cyclohexagen, dicyclopentagen, divininolebenzene, and ethylidene norbornene.
  • the butyl ether monomer is not particularly limited.
  • the silanic compound is not particularly limited, and examples thereof include vinyltrichlorosilane, vinylmethyldichlorosilane, vinyldimethylchlorosilane, vinyldimethylmethoxysilane, vinyltrimethylsilane, dibutydichlorosilane, dibutydimethoxysilane, Examples include dibutyldimethylsilane, 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, trivinylmethylsilane, ⁇ -methacryloyloxypropyltrimethoxysilane, and ⁇ -methacryloyloxypropylmethyldimethoxysilane.
  • monomers other than the above-mentioned isobutylene, which is the main component of the polymer block (b), are preferably aromatic vinyl monomers from the balance of physical properties and polymerization characteristics. That is, a block copolymer in which the content of the aromatic vinyl monomer in the polymer block (b) is 60% by weight or more is preferred, and a block copolymer having 80% by weight or more is more preferred. Yes.
  • At least one monomer selected from the group consisting of styrene, ⁇ -methylstyrene, p-methylstyrene, and indene is preferable to use as the aromatic bur monomer. From the viewpoint of cost, it is particularly preferable to use styrene, hymethylstyrene, ⁇ -methylstyrene or a mixture thereof.
  • the polymer block (a) containing isobutylene as a main component may or may not contain a monomer other than isobutylene as a monomer component. However, among all the monomers constituting the polymer block (a), 60% by weight or more, preferably 80% by weight or more is isobutylene.
  • a monomer other than isoprene included in the polymer block (a) cationic polymerization is possible.
  • the monomer is not particularly limited as long as it is a simple monomer, such as aliphatic or cycloaliphatic olefins, aromatic burins, gens, butyl ethers, silanes, burcarbazole, ⁇ -vinene, and acenaphthylene. A monomer is mentioned. These may be used alone or in combination of two or more.
  • the ratio of the polymer block (a) mainly composed of isobutylene and the polymer block (b) mainly composed of an aromatic vinyl monomer in the entire isobutylene polymer is not particularly limited. However, from the viewpoint of various physical properties, the ratio of the polymer block ( a ) based on the isobutylene monomer out of all the monomers in the isobutylene polymer S 40 to 95% by weight, aromatic vinyl type It is preferable that the ratio of the polymer block (b) based on the monomer is 5 to 60% by weight.
  • the ratio of the polymer block (a) based on the isobutylene monomer is preferably from 50 to 50% by weight. It is particularly preferred that the proportion of the polymer block (b) containing 85% by weight of the aromatic bulbure monomer as a main component is 15 to 50% by weight.
  • the number average molecular weight of the isobutylene-based polymer is not particularly limited, but the surface strength such as fluidity, processing 'property, physical properties', etc. is a power of 30000-500000 S, preferably 50000-400000 It is especially preferred. If the number average molecular weight of the isobutylene polymer is lower than 30000, the mechanical properties tend not to be fully expressed, whereas if it exceeds 500,000, it is disadvantageous in terms of fluidity and workability. .
  • the above number average molecular weight is measured using a gel permeation chromatography (GPC) system manufactured by Waters (columns: Shodex K 804, K 802.5 (polystyrene gel) manufactured by Showa Denko KK, mobile phase: black mouth form). This is the measured value.
  • GPC gel permeation chromatography
  • the block copolymer is particularly preferred as a block copolymer (polymer block mainly composed of an aromatic vinyl monomer) from the viewpoint of balance of physical properties.
  • Polymer block mainly composed of a monomer) Polymer block composed mainly of an aromatic vinyl monomer
  • Triblock copolymer (a polymer block composed mainly of an isobutylene monomer) (Polymer block containing aromatic vinyl monomer as the main component) (Polymer block containing isobutylene monomer as the main component) Powerful triblock copolymer (Mainly aromatic vinyl monomer) Polymer block as component) (Polymer block mainly composed of isobutylene monomer) Powerful diblock copolymer, and (Aromatic bulle system)
  • the isobutylene polymer of the present invention is obtained by superposing predetermined monomer components in the presence of a polymerization initiator.
  • the polymerization initiator is not particularly limited, but the general formula (1)
  • X represents a halogen atom, an alkoxy group having 1 to 6 carbon atoms or an acyloxy group.
  • R 1 and R 2 are the same or different, and are a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms.
  • R 3 represents a monovalent or polyvalent aromatic hydrocarbon group or a monovalent or polyvalent aliphatic or alicyclic hydrocarbon group, and n represents a natural number of 1 to 6. It is preferable to use the compound as an initiator.
  • Polymerization initiator is the starting point for cationic polymerization
  • Examples of the compound of the general formula (1) used in the present invention include the following compounds.
  • Tris (1-Chlorone 1-methinoreethinore) benzene is Tris (cyclomouth isopropyl) Also called benzene, tris (2-chloro-2-benzene) benzene or tritamilk chloride.
  • the isobutylene polymer of the present invention is obtained by polymerizing a monomer component containing isobutylene in the presence of a Lewis acid catalyst.
  • the Lewis acid is not particularly limited as long as it can be used for cation polymerization.
  • Metal halides such as A1C1 and AlBr; Organometallic halides such as Et A1C1 and EtAlCl
  • a halogenated metal such as a compound can be preferably used (Et represents an ethyl group).
  • Et represents an ethyl group.
  • TiCl titanium tetrachloride
  • A1C1 and Et A1C1 being particularly preferred.
  • the amount is not particularly limited, but can be set in consideration of the polymerization characteristics or polymerization concentration of the monomer used. Usually, 0.1 to L00 molar equivalent can be used with respect to the polymerization initiator, and preferably in the range of 1 to 50 molar equivalent.
  • an electron donor component can be further present if necessary.
  • This electron donor component is considered to have an effect of stabilizing the growing carbon cation during cationic polymerization, and a polymer having a structure with a narrow molecular weight distribution controlled by the addition of the electron donor. Can be generated.
  • the electron donor component that can be used is not particularly limited, and examples thereof include pyridines, amines, amides, sulfoxides, esters, and metal compounds having an oxygen atom bonded to a metal atom.
  • the number of donors defined as one parameter representing the strength as an electron donor (electron donor) of various compounds is 15-60, t-butylpyridine, 2-t-butylpyridine, 2, 4, 6 trimethylpyridine, 2,6 dimethylpyridine, 2-methylpyridine, pyridine, jetylamine, trimethylamine, triethylamine, tributylamine, N, N-dimethyla -Phosphorus, N, N-dimethylformamide, N, N dimethylacetamide, N, N jetylacetamide, dimethylsulfoxide, diethyl ether, methyl acetate, ethyl acetate, trimethyl phosphate, hexamethyl phosphate triamide, titanium (III) Titanium alkoxides such as methoxide, titanium (IV) methoxide, titanium (IV) isopropoxide, titan (IV) butoxide; power capable of using aluminum alkoxide such as aluminum triethoxide and
  • 2,6 g t-butylpyridine 2 , 6 Dimethyl pyridine, 2 Methyl pyridine, Pyridine, Diethylamine, Trimethylamine, Triethylamine, N, N Dimethylformamide, N, N-Dimethylacetamide, Dimethyl sulfoxide, Titanium (IV) isopropoxide, Titanium ( IV) Butoxide and the like.
  • the number of donors for the various substances mentioned above is shown in “Donor and Acceptor”, by Dardman, Otsuki, Okada, and Academic Publishing Center (1983).
  • 2-methylpyridine, N, N-dimethylacetamide which has a remarkable effect of addition, and titanium (IV) isopropoxide that makes the reaction system uniform are particularly preferable.
  • the electron donor component is used in a molar amount of 0.01 to LO times with respect to the polymerization initiator. Of these, it is preferably used in the range of 0.2 to 4 moles.
  • the polymerization of the isobutylene polymer can be carried out in a solvent, if necessary. Any conventionally known solvent can be used as long as it does not essentially inhibit cationic polymerization. Specifically, methyl chloride, dichloromethane, n-propyl chloride, n-butyl chloride, chloride can be used.
  • Halogenated hydrocarbons such as benzene; alkylbenzenes such as benzene, toluene, xylene, ethylbenzene, propylbenzene, and butylbenzene; linear chains such as ethane, propane, butane, pentane, hexane, heptane, octane, nonane, and decane Aliphatic hydrocarbons; branched aliphatic hydrocarbons such as 2-methylpropane, 2-methylbutane, 2, 3, 3 trimethylpentane, 2, 2, 5 trimethylhexane; cyclohexane, methylcyclohexane, Alicyclic hydrocarbons such as ethylcyclohexane; paraffin oil obtained by hydrorefining petroleum fractions, etc. It can be mentioned.
  • These solvents are used for the polymerization characteristics and formation of the monomers constituting the isobutylene polymer. Considering the balance of the solubility of the polymer, it can be used alone or in combination of two or more. Among them, at least one selected from the group consisting of primary and secondary monohalogenated hydrocarbons having 3 to 8 carbon atoms, and group power consisting of aliphatic, alicyclic and aromatic hydrocarbons are selected. Polymerization in a mixed solvent containing at least one kind is preferable from the viewpoint of improving workability in the water washing step after polymerization and ease of waste water treatment after water washing.
  • the primary monohalogenated hydrocarbons having 3 to 8 carbon atoms and the secondary monohalogenated hydrocarbons having 3 to 8 carbon atoms are not particularly limited, and examples thereof include 1-chloropropane, 1-chloro-2- Methylpropane, 1-chlorobutane, 1-black mouth 2-methylbutane, 1-black mouth one 3-methyl butane, 1-black mouth 2,2 dimethylbutane, 1-black mouth 3,3 dimethylbutane, 1 — 1,3 Dimethylbutane, 1-Black mouthpentane, 1-Black mouthpiece 2-Methylpentane, 1-Black mouthpiece 3-Methinorepentane, 1-Black mouthpiece 4-Methinorepentane, 1-Black mouth hexane 1 chloro-2-methino hexane, 1 chloro 3-methino hexane, 1 chloro 4-methino hexane, 1 chloro 5-methino hexane, 1-heptane, 1 chlorooctane
  • a monohalogenated solvent having 3 carbon atoms a monohalogenated solvent having 4 carbon atoms, a combination of a monohalogenated solvent having 3 carbon atoms and a monohalogenated solvent having 4 carbon atoms, or a monohalogen having 4 to 8 carbon atoms. It may be a combination of at least one of the solvating solvents.
  • a monohalogenated solvent having 3 carbon atoms a monohalogenated solvent having 4 carbon atoms
  • a combination of a monohalogenated solvent having 3 carbon atoms and a monohalogenated solvent having 4 carbon atoms a monohalogen having 4 to 8 carbon atoms.
  • It may be a combination of at least one of the solvating solvents.
  • 1-chloropropane and Z or 1-chlorobutane especially 1-chlorobutane. preferable.
  • the aliphatic or alicyclic hydrocarbon and the aromatic hydrocarbon as the non-halogen solvent are not particularly limited.
  • butane, pentane, neopentane, hexane, heptane, octane, cyclohexane examples include methylcyclohexane, ethylcyclohexane, benzene, toluene, xylene, ethylbenzene and the like. These can be used alone or in combination of two or more.
  • Solubility of isobutylene polymer From the balance of cost, dielectric constant, etc., at least one selected from the group consisting of hexane, cyclohexane, methylcyclohexane, ethylcyclohexane, toluene and xylene is preferred hexane, methylcyclohexane and ethylcyclo Particularly preferred is at least one selected from the group having hexane power.
  • the content of the monohalogen hydrocarbon solvent in the mixed solvent is not particularly limited, and may be set so as to obtain a desired dielectric constant or solubility of the isobutylene polymer. However, it is generally 10 to 98% by weight, preferably 20 to 95% by weight. This is because when the content of the monohalogen hydrocarbon solvent is less than 10%, the reaction rate may become extremely slow, or the polymer may precipitate during the polymerization, and a preferred isobutylene polymer can be obtained. This is because there is not. On the other hand, if it exceeds 98% by weight, it may be difficult to control the reaction with a high polymerization rate.
  • the amount of the solvent used is determined in consideration of the viscosity of the resulting polymer solution and the ease of heat removal. It is preferable that the concentration of the polymer be 1 to 50% by weight. More preferably, the content is 5 to 35% by weight.
  • the isobutylene polymer in the present invention is characterized in that the amount of metal residue derived from the Lewis acid catalyst is 90 ppm or less.
  • the above metal residue is preferably 80 ppm or less, more preferably 60 ppm or less, and even more preferably 40 ppm or less.
  • the amount of metal residue exceeds 90 ppm, the coloring of the polymer, particularly yellowing, becomes remarkable.
  • the yellowness Y. I.
  • the amount of metal residue is a value measured by a calibration curve method using an ICP emission spectrophotometer (Seiko Instruments Inc., SPS-1700R type).
  • the method for producing the isobutylene polymer of the present invention is not particularly limited except that the polymerization of the monomer component containing isobutylene in the presence of a polymerization initiator and a Lewis acid catalyst is performed.
  • a polymerization initiator and a Lewis acid catalyst for example, the above-mentioned solvent, the compound represented by the general formula (1), and, if necessary, an electron donor component are charged into a reaction vessel, and then isobutylene is the main component.
  • a method of polymerizing by adding a Lewis acid and further adding a Lewis acid are charged into a reaction vessel, and then isobutylene is the main component.
  • a method of polymerizing by adding a Lewis acid and further adding a Lewis acid for example, the block copolymer, after the polymerization of the monomer component added to the reaction vessel is substantially completed, the block copolymer may be added by adding another monomer component. it can . Furthermore, if necessary, after the polymerization is substantially completed, another mono
  • the reaction solution is added to a large amount of water to deactivate the Lewis acid catalyst. After removal, the resulting mixture is also subjected to a post-treatment such as removing water, followed by a washing operation.
  • a post-treatment such as removing water, followed by a washing operation.
  • the method for reducing the amount of metal residue derived from the Lewis acid catalyst of the isobutylene polymer there is a method of increasing the number of water washing operations. Also, use a basic aqueous solution with a high pH value when washed with water.
  • the Lewis acid catalyst may be easily removed by lowering the solution concentration during purification. Specifically, the solution concentration at the time of polymerization may be lowered, or a diluting solvent may be added to lower the polymer concentration of the polymerization solution after the polymerization is completed.
  • a method of reducing the amount of metal residue by adding an additive such as a surfactant or an antifoaming agent may be employed.
  • a method of adding a metal alkoxide to a polymerization solution, filtering the precipitated polymerization catalyst residue and fractionating, as described in JP-A-2001-131222, can be mentioned. These methods may be performed alone, or a plurality of methods may be combined.
  • a particularly preferred temperature range is from -80 ° C to 1-30 ° C.
  • the isobutylene polymer of the present invention has a reinforcing agent, a filler, an antioxidant, an ultraviolet absorber, a light stabilizer, a pigment and the like within a range not impairing the physical properties according to the required characteristics according to each application.
  • Surfactants, reaction retarders, flame retardants, fillers, reinforcing agents and the like may be appropriately blended.
  • the antioxidant is not particularly limited, and examples thereof include hindered phenols and hindered amines.
  • the isobutylene-based polymer obtained by the above method is generally adopted for thermoplastic resin.
  • it can be melt-molded by extrusion molding, injection molding, press molding, blow molding or the like.
  • the second aspect of the present invention relates to a method for producing an isobutylene polymer. Specifically, a step (I) of polymerizing a monomer component containing isobutylene in the presence of a Lewis acid catalyst; water is brought into contact with the isobutylene polymer-containing solution obtained in the step (I); The step of deactivating the Lewis acid catalyst ( ⁇ );
  • the obtained polymer-containing solution is washed with a basic aqueous solution having a pHIO or higher (III);
  • the obtained polymer-containing solution is filtered with a filter that can collect 99% or more of particles having a diameter of 5 ⁇ m or more when the differential pressure before and after the filter is 0.2 MPa.
  • Degree (IV) the obtained polymer-containing solution is filtered with a filter that can collect 99% or more of particles having a diameter of 5 ⁇ m or more when the differential pressure before and after the filter is 0.2 MPa.
  • the present invention relates to a process for producing an isobutylene polymer characterized by containing (hereinafter, this process is referred to as Process [B]).
  • the production method [A] is a production method including the above steps (iii) to (III). Details will be described below.
  • Step (I) is a step of polymerizing a monomer component containing isobutylene in the presence of a Lewis acid catalyst.
  • the polymerization method is not particularly limited as long as it is carried out in the presence of a Lewis acid catalyst.
  • a Lewis acid catalyst for example, the above-mentioned solvent, the compound represented by the following general formula (1), and, if necessary, an electron donor component are charged into a reaction vessel, and then a monomer component mainly composed of isobutylene is added. And a method in which a Lewis acid is added to perform polymerization.
  • block copolymers For example, after the polymerization of the monomer component added to the reaction vessel is substantially completed, block copolymerization can be performed by adding another monomer component. Furthermore, if necessary, after the polymerization is substantially completed, another monomer component may be added to continue the polymerization.
  • the monomer component is not particularly limited as long as it contains isobutylene, but those having isobutylene as a main component are preferred.
  • the monomer other than isoprene included in the monomer component is not particularly limited as long as it is a monomer that can be cationically polymerized.
  • aliphatic or alicyclic olefins aromatic bulls.
  • monomers such as gens, butyl ethers, silanes, burcarbazole, ⁇ -vinene, and acenaphthylene. These may be used alone or in combination of two or more.
  • the isobutylene polymer obtained in the present invention contains a polymer block (a) containing isobutylene as a main component and a polymer block (b) containing a monomer other than isobutylene as a main component.
  • An isobutylene block copolymer is included.
  • the monomer other than isobutylene which is the main component of the block (b) is not particularly limited as long as it is a monomer capable of cationic polymerization, but aliphatic or alicyclic olefin-based monomers, Examples thereof include monomers such as aromatic vinyl monomers, gen monomers, butyl ether monomers, silane compounds, burcarbazole, 13 vinylene, and acenaphthylene. These can be used alone or in combination of two or more.
  • the monomer other than the above isobutylene, which is the main component of the polymer block (b), is preferably an aromatic vinyl monomer from the balance of physical properties and polymerization characteristics.
  • the Lewis acid catalyst used in the present invention is not particularly limited as long as it can be used for cationic polymerization, and examples thereof include metal halides such as TiCl, BC1, BF, A1C1, and SnCl.
  • TiCl tetrasalt ⁇ titanium
  • the polymerization solvent used in the step (I) is not particularly limited, and a solvent having a halogenated hydrocarbon power, a non-halogen solvent, or a mixture thereof can be used.
  • a solvent having a halogenated hydrocarbon power, a non-halogen solvent, or a mixture thereof can be used.
  • the group power of primary and secondary monohalogenated hydrocarbons with 3 to 8 carbon atoms is also selected.
  • the surface area of solubility of isobutylene polymers are also preferred.
  • the primary and Z or secondary monohalogenated hydrocarbons having 3 to 8 carbon atoms are not particularly limited, and examples thereof include 1-chlorobutane and black benzene. Among these, 1 chlorobutane is preferred because of the solubility of the isobutylene block copolymer, the ease of detoxification by decomposition, and the balance force such as cost.
  • the aliphatic and Z or aromatic hydrocarbons are not particularly limited.
  • One or more selected from the group consisting of methylcyclohexane, ethylcyclohexane and toluene power are particularly preferred.
  • step (I) although it is not essential, it is preferable to carry out the polymerization in the presence of a polymerization initiator.
  • the polymerization initiator is not particularly limited, but a compound represented by the general formula (1) is preferable.
  • X represents a halogen atom, an alkoxy group having 1 to 6 carbon atoms or an acyloxy group.
  • R 1 and R 2 are the same or different, and are a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms.
  • R 3 represents a monovalent or polyvalent aromatic hydrocarbon group or a monovalent or polyvalent aliphatic or alicyclic hydrocarbon group, n represents a natural number of 1 to 6.
  • Specific examples of the compound of the general formula (1) include (1 chloro 1-methylethyl) benzen [CHC (CH) Cl], 1, 4 bis (1-chloro-1-methylethyl) benzene [1, Four-
  • Tinoleetinole 5 (tert Butinole) benzene [1, 3— (C (CH) C1) — 5— (C (CH)
  • Isopropyl) benzene, bis (2-chloro-2-propynole) benzene! / ⁇ is also called dicumino chloride, and tris (1-chloro-1-1-methylethyl) benzene is tris (cyclochloroisopropyl) benzene, tris ( 2—Black 1 2-Propyl) Benzene! / ⁇ ⁇ is also known as Tricuminolecide Ride].
  • an electron donor component can be further present if necessary.
  • examples of such compounds include pyridines, amines, amides, sulfoxides, esters, or metal compounds having an oxygen atom bonded to a metal atom.
  • the respective components are mixed under cooling, for example, at a temperature of 100 ° C or higher and lower than 0 ° C.
  • a particularly preferred temperature range is -80 ° C to -30 ° C to balance energy costs and polymerization stability.
  • the number average molecular weight of the resulting isobutylene block copolymer is not particularly limited! /, Force From the viewpoint of fluidity, processability, physical properties, etc., the power is preferably 30,000 to 500,000 S, preferably 500 00 Especially preferred power to be ⁇ 400000!
  • step (ii) will be described in detail.
  • the isobutylene polymer-containing solution (also referred to as “polymer solution” or “polymer-containing solution” in this specification) is mainly composed of isobutylene using a Lewis acid catalyst. This is a solution obtained after polymerization of monomer components.
  • the Lewis acid catalyst is deactivated by bringing water into contact with such a polymer-containing solution.
  • a container equipped with a stirrer is preferably used as the apparatus used for deactivation of the Lewis acid catalyst.
  • Arbitrary blades such as screw blades, propeller blades, anchor blades, blade blades, pitched paddle blades, turbine blades, large-size blades, and the like, are not particularly limited in the shape of the stirring blades of the stirrer.
  • the vessel used for deactivation should be a reaction vessel equipped with a generally used stirrer and jacket, which is not particularly limited in shape and shape as long as it has a function of controlling the internal temperature. Can do.
  • a baffle or similar effect can be used to increase the efficiency of stirring. There is no problem even if the thermometer with protective tube is in the container.
  • the temperature at which the catalyst is deactivated is not particularly limited, but a range of 4 to 100 ° C is preferable from the viewpoint of production cost and safety which is preferable in operation. ° C is particularly preferred.
  • step (III) will be described.
  • step (III) after the above step (II), the obtained polymer-containing solution is washed by adding a basic aqueous solution of pHIO or more, thereby sufficiently inactivating the Lewis acid and further removing it. Do. Usually, after the Lewis acid catalyst is deactivated, the polymer solution is sufficiently washed with water, and then a basic aqueous solution is added to the polymer solution.
  • the temperature at the time of washing is not particularly limited, but the range of 4 to 100 ° C is preferably 20 to 80 ° C from the viewpoint of manufacturing cost and safety which is preferable in operation. Particularly preferred.
  • the amount of the aqueous solution used for cleaning is not particularly limited, but the ratio of (aqueous solution: polymer solution) is in the range of 1Z5 to LOZl (volZvol) from the viewpoint of production cost. It is particularly preferable that the production power of the manufacturing cost is in the range of 1Z5 to 5Z1 (volZvol).
  • the pH value of the basic aqueous solution used should be 10 or more in order to remove the catalyst sufficiently. In terms of productivity and safety, the pH value is particularly preferably 10 to 13.
  • the basic aqueous solution to be used is not particularly limited, but it is preferable to use sodium hydroxide (caustic soda) in terms of cost and ease of handling.
  • the primary and secondary carbons having 3 to 8 carbon atoms similar to the polymerization solvent may be used.
  • Mixed solvent or halogenation containing at least one selected from the group consisting of monohalogenated hydrocarbons and at least one selected from the group consisting of aliphatic, alicyclic and aromatic hydrocarbons A single solvent of hydrocarbon, aliphatic hydrocarbon or aromatic hydrocarbon can also be added to the polymer-containing solution after completion of polymerization.
  • the amount of the solvent to be added is not particularly limited, but it is preferable that the ratio of (water: polymer solution) is in the range of 1Z10 to 10Z1 (volZvol) from the viewpoint of production cost. A range of ⁇ 2Z1 (volZvol) is particularly preferred.
  • the catalyst is deactivated with water, and then the polymer solution is dissolved.
  • a basic aqueous solution of pHIO or higher to the solution, the catalyst residue can be enlarged, and the catalyst residue can be sufficiently removed by filtration or the like.
  • the step (IV) described below may be further performed after the step (III). This can further enhance the effect of removing the catalyst residue.
  • Production method [B] is a production method comprising the steps (1), (ii) and (IV). Of these, steps (I) and (ii) are as already described in the section of production method [A].
  • step (IV) water is brought into contact with the polymer solution in step (II) to deactivate the Lewis acid catalyst, and the resulting polymer solution is subjected to a pressure difference of 0.2 before and after the filter.
  • a filter capable of collecting 99% or more of particles having a diameter of 1 m or more is used.
  • the material of the filter is not particularly limited as long as it is a material that does not dissolve in the polymer-containing solution under normal use, such as polypropylene, nylon, and cotton.
  • the filter 1 may be used in multiple stages in order to sufficiently remove the catalyst even with one stage.
  • the group of primary and secondary monohalogenated hydrocarbons having 3 to 8 carbon atoms which is the same as the polymerization solvent, if necessary.
  • Mixed solvent containing at least one selected from the group consisting of aliphatic, alicyclic and aromatic hydrocarbons, or halogenated hydrocarbon, aliphatic hydrocarbon or A single aromatic hydrocarbon solvent may be added to the polymer solution.
  • the amount of the solvent to be added is not particularly limited, but the ratio of (water: polymer solution) is not limited.
  • the range of 1Z10 to 2Zl (vol / vol) is particularly preferable from the viewpoint of production cost, which is preferably in the range of the force SlZlO to 10Zl (volZvol).
  • the isobutylene-based polymer with few metal residues derived from the catalyst of the present invention has little coloration and a stable color tone. Therefore, it can be suitably used for applications requiring transparency and hygiene, and molded products colored with dyes and pigments, particularly molded products colored with light colors. Further, according to the production method of the present invention, an isobutylene polymer with little coloring can be produced.
  • the molecular weight of the isobutylene polymer shown in this example was measured by the following method. Waters GPC system (column: Shodex K-804 (polystyrene gel), Showa Denko KK, mobile phase: black mouth form). The number average molecular weight is expressed in terms of polystyrene.
  • the test piece was a 2 mm thick press sheet, and the yellowness (Y. L) of this test piece was measured using a spectroscopic color difference meter (Spectroo Color Meter SE2000 manufactured by Nippon Denshoku Industries Co., Ltd.). It was.
  • the appearance of the isobutylene polymer was visually observed to determine whether yellowness was observed. A colorless one was marked with ⁇ , a slightly yellow colored one was marked with ⁇ , and a yellow colored one was marked with X.
  • the obtained polymer solution was a highly transparent solution.
  • the solvent was distilled off from the obtained polymer solution, and further dried for 24 hours in a vacuum dryer at 80 ° C. to obtain an isobutylene block copolymer solid.
  • the number average molecular weight was 78,000 and the molecular weight distribution was 1.43.
  • the obtained isobutylene block copolymer was melt-kneaded at 180 ° C by a Laboplast mill (manufactured by Toyo Seiki Seisakusho).
  • the obtained kneaded material was press-molded at 170 ° C. using a compression molding machine (manufactured by Shinfuji Metal Industry Co., Ltd.) to obtain a 2 mm thick sheet.
  • appearance observation and yellowness measurement were performed.
  • the amount of residual Ti was measured by a calibration curve method using an ICP emission spectroscopic analyzer (manufactured by Seiko Instruments Inc., SPS-1700R type). The results are shown in Table 1.
  • Isobutylene type block copolymer was obtained in the same manner as in Example 2 except that 2.46 mL of tetrachloride-titanium was used. As a result of measuring the molecular weight of the obtained isobutylene block copolymer, the number average molecular weight was 74,000 and the molecular weight distribution was 1.45. The obtained polymer was evaluated in the same manner as in Example 1. The results are shown in Table 1.
  • Example 1 By comparing Example 1 and Comparative Example 1, it is possible to reduce the amount of metal residue by mixing and stirring the polymer solution after completion of polymerization with pure water supplemented with an emulsifier. As a result, it can be seen that coloring can be reduced. In addition, it can be seen that the amount of metal residue can be reduced by performing polymerization at a low concentration of the resin or by diluting the resin with a solvent after polymerization (Examples 3 and 4). Comparison of Comparative Examples 2-4).
  • the isobutylene block copolymer having a metal residue derived from the Lewis acid catalyst of the present invention of 90 ppm or less is stable in color, particularly in color with low yellowness. is doing.
  • the molecular weight distribution was 5,000 and the molecular weight distribution was 1.24.
  • 1 L of distilled water was charged into a 3 L separable flask equipped with a stirring blade, a condenser and a baffle, and the pH was adjusted to 10 by adding NaOH and heated to 60 ° C. Thereafter, 1 L of the polymer solution after the catalyst deactivation obtained by the method of Production Example 1 was added and maintained at 60 ° C. with stirring (first washing with water). After 1 hour from the start of stirring, stirring was stopped and the polymer solution phase and the aqueous phase were separated. After discharging the aqueous phase, the same operation was further performed with distilled water (second washing with water) to obtain a polymer solution. Further, the obtained polymer solution was vacuum dried at 60 ° C. for 24 hours to obtain a polymer.
  • the obtained polymer was heated to 180 ° C for 10 minutes with a press machine to form a sheet having a thickness of 2 mm, and the YI value was measured with a color difference meter.
  • the YI value was 15.1. (Table 2).
  • a polymer was obtained in the same manner as in Example 4 except that the aqueous NaOH solution used for the first washing was replaced with one having a pH of 12.
  • the Y.I. value of the obtained polymer was measured, the Y.I. value was 14.6 (Table 2).
  • Example 2 After the first washing, distilled water was used without adjusting the pH (without adding NaOH). The procedure was the same as in Example 4, followed by washing with water to obtain a polymer. The YI value of the obtained polymer was measured and found to be 21.7 (Table 2).
  • the polymer solution after catalyst deactivation obtained in Production Example 1 was formed into a sheet without being washed with water.
  • the Y.I. value of the obtained polymer was measured, the Y.I. value was 21.7 (Table 2).
  • the polymers obtained in Examples 4 and 5 are coagulants having excellent transparency with very little coloration. According to the method of the present invention, the coloration of the coagulants is improved. I found that it was possible.
  • the obtained polymer solution was poured into a large amount of water to deactivate the catalyst, thereby stopping the reaction. Thereafter, the polymer solution phase and the aqueous phase were separated with a separatory funnel to obtain a polymer solution after deactivation of the catalyst.
  • a 3 L separable flask equipped with a stirring blade, a condenser and a baffle was charged with 1 L of distilled water and heated to 60 ° C. Then, 1 L of the polymer solution after deactivation of the catalyst was added, and the mixture was not stirred. Force S was maintained at 60 ° C (first washing with water). Stirring was stopped 1 hour after the start of stirring, and the polymer solution phase and the aqueous phase were separated. After draining the aqueous phase, the remaining polymer solution phase is placed in distilled water. Further, the same water washing operation was carried out (2nd water washing) to obtain a water washing polymer solution.
  • the total amount of the washing polymer solution obtained in Production Example 1 was DC- ⁇ ⁇ ⁇ ⁇ ⁇ -001-500 manufactured by Central Filter Industry Co., Ltd. (99% or more of particles having a diameter larger than that when the differential pressure before and after the filter was 0.2 MPa) It filtered using the filter which can be collected.
  • the amount of Ti in the polymer solution after filtration (the amount of metal residue derived from the Lewis acid catalyst) was analyzed, it was 38 ppm based on the solid content of the polymer.
  • the obtained water-washed polymer solution was vacuum-dried at 60 ° C for 24 hours to obtain a polymer.
  • a sheet having a thickness of 2 mm was produced from the obtained polymer with a press.
  • the sheet was produced as follows.
  • the polymer of about 10g placed Fellow plate, 7 minutes preheating at 180 ° C, 10kg / cm 2 - 1 minute at G, yet 50KgZcm 2 - after pressurizing 2 minutes at G, 50kgZcm 2 - 3 minutes cooling at G did.
  • the YI value was 14.0 as shown in Table 3.
  • NXA0.5-5-20 a filter that can collect 99% or more of particles with a diameter of 0.5 ⁇ m or more when the differential pressure before and after the filter is 0.2 MPa
  • a filter that can collect 99% or more of particles with a diameter of 0.5 ⁇ m or more when the differential pressure before and after the filter is 0.2 MPa
  • the amount of Ti in the polymer solution after filtration was analyzed, it was 19 ppm with respect to the solid content of the polymer.
  • Filtration was carried out in the same manner as in Example 8 except that a filter capable of collecting 99% or more of particles having a diameter of 5 ⁇ m or more when the differential pressure before and after the filter was 0.2 MPa.
  • the amount of Ti in the polymer solution after filtration (the amount of metal residue derived from the Lewis acid catalyst) was analyzed, it was 80 ppm based on the solid content of the polymer.
  • the YI value of the obtained polymer was measured in the same manner as in Example 8. The value was 21.9 (Table 3).
  • the amount of Ti contained (the amount of metal residue derived from the Lewis acid catalyst) was analyzed and found to be 240 ppm based on the solid content of the polymer.
  • Filtration was carried out in the same manner as in Example 8 except that a filter capable of collecting 99% or more of particles having a diameter of 10 ⁇ m or more when the differential pressure before and after the filter was 0.2 MPa.
  • the amount of Ti in the polymer solution after filtration (the amount of metal residue derived from the Lewis acid catalyst) was analyzed, it was 120 ppm based on the solid content of the polymer.
  • the isobutylene-based polymer obtained by the above method is generally employed for thermoplastic resin.
  • it can be melt-molded by extrusion molding, injection molding, press molding, blow molding or the like.
  • the isobutylene polymer of the present invention can be used in various applications similar to conventional isobutylene polymers.
  • elastomer materials modifiers such as resin, rubber, asphalt, adhesive base polymer, resin modifiers, knocking materials, sealing materials, sealing materials such as gaskets and plugs, CD dampers, etc.

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
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  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Graft Or Block Polymers (AREA)

Abstract

La présente invention concerne un copolymère séquencé d’isobutylène qui est légèrement coloré et a une tonalité de couleur stable. La présente invention concerne plus spécifiquement un polymère d'isobutylène obtenu par la polymérisation d’un composant monomère contenant un groupe isobutylène en présence d'un initiateur de polymérisation et d'un catalyseur acide de Lewis. Ce polymère d'isobutylène est caractérisé en ce que la quantité résiduelle de métal dérivé du catalyseur acide de Lewis dans le polymère d'isobutylène n'excède pas 90 ppm. La présente invention concerne en outre un procédé de production d’un tel polymère d'isobutylène.
PCT/JP2006/320489 2005-10-13 2006-10-13 Polymère d’isobutylène et son procédé de production WO2007043662A1 (fr)

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
JP2005-298696 2005-10-13
JP2005298696A JP2009007383A (ja) 2005-10-13 2005-10-13 イソブチレン系ブロック共重合体
JP2005-347480 2005-12-01
JP2005347480A JP2009007385A (ja) 2005-12-01 2005-12-01 イソブチレン系重合体の製造方法
JP2006040817A JP2009007386A (ja) 2006-02-17 2006-02-17 イソブチレン系重合体の製造方法
JP2006-040817 2006-02-17

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5322583A (en) * 1976-08-12 1978-03-02 Nippon Petrochemicals Co Ltd Purification of buten polymer
JPH06287256A (ja) * 1993-03-30 1994-10-11 Nippon Zeon Co Ltd ブロック共重合体の取得法
JP2001131222A (ja) * 1999-11-05 2001-05-15 Kanegafuchi Chem Ind Co Ltd イソブチレン系ブロック共重合体の製造方法
JP2002179728A (ja) * 2000-12-15 2002-06-26 Kanegafuchi Chem Ind Co Ltd イソブチレン系ブロック共重合体の製造方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5322583A (en) * 1976-08-12 1978-03-02 Nippon Petrochemicals Co Ltd Purification of buten polymer
JPH06287256A (ja) * 1993-03-30 1994-10-11 Nippon Zeon Co Ltd ブロック共重合体の取得法
JP2001131222A (ja) * 1999-11-05 2001-05-15 Kanegafuchi Chem Ind Co Ltd イソブチレン系ブロック共重合体の製造方法
JP2002179728A (ja) * 2000-12-15 2002-06-26 Kanegafuchi Chem Ind Co Ltd イソブチレン系ブロック共重合体の製造方法

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