Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F8/00—Chemical modification by after-treatment
  • C08F8/04—Reduction, e.g. hydrogenation
• • 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
  • C08F16/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
  • C08F16/02—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an alcohol radical
  • C08F16/04—Acyclic compounds
  • C08F16/08—Allyl alcohol
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F2/00—Processes of polymerisation
  • C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
• • 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
  • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
  • C08F210/14—Monomers containing five or more carbon atoms
• • 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
  • C08F216/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
  • C08F216/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an alcohol radical
  • C08F216/04—Acyclic compounds
  • C08F216/08—Allyl alcohol
• • 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
  • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
  • C08F212/02—Monomers containing only one unsaturated aliphatic radical
  • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
  • C08F212/06—Hydrocarbons
  • C08F212/08—Styrene
• • 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
  • C08F2800/00—Copolymer characterised by the proportions of the comonomers expressed
  • C08F2800/10—Copolymer characterised by the proportions of the comonomers expressed as molar percentages
• • 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
  • C08F2800/00—Copolymer characterised by the proportions of the comonomers expressed
  • C08F2800/20—Copolymer characterised by the proportions of the comonomers expressed as weight or mass percentages

Definitions

• Olefin polymers having polar groups in the structure having compatibility with various polar resins, excellent adhesiveness and colorability, are being widely used industrially. Although there have been various reports on production methods of olefin polymers having polar groups, most of the methods include introduction of polar-group-containing monomers through graft polymerization.
• Japanese Patent Application Laid- Open No.2005-113038 discloses a higher ⁇ -olefin polymer containing a polar group in which the polar group has been introduced by allowing a higher ⁇ -olefin polymer to react with a decomposition agent and a polar compound.
• EP Patent No. 1674483 discloses a higher ⁇ -olefin polymer containing a polar group in which the polar group has been introduced by allowing a higher ⁇ -olefin polymer to react with a decomposition agent and a polar compound.
• graft polymerization there is concern about degradation of the produced polymer due to oxidization and dispersibility of the polar group.
• such a method cannot be considered to be satisfactory in securing product quality.
• the present inventors have found that by allowing an allyl alcohol to react with an radically polymerizable aliphatic olefin compound, an unsaturated carboxylic acid or unsaturated carboxylic acid ester in the presence of a radical polymerization initiator, or by hydrogenating a copolymer of an allyl alcohol and an radical polymerizable aromatic monomer, a polymer having a polar group can be efficiently produced, whereby completing the present invention .
• R represents an aliphatic hydrocarbon group having 2 to 20 carbon atoms, which may be branched or include a cyclic structure
• a copolymer of an allyl alcohol and an olefin compound or a copolymer of an allyl alcohol, an olefin compound and an unsaturated carboxylic acid or unsaturated carboxylic acid ester can be efficiently produced.
• the allyl alcohol copolymer obtained by the present invention having a polar group, is excellent in compatibility with various resins and adhesion. Also, since the copolymer has a hydrophobic group, it is excellent in electric insulating property, low water absorption, thermal stability and surface activity effect. Thanks to these properties, the copolymer is useful as a resin improver, components in coating agent, ink, adhesive agent and primer, high- performance wax, compatibilizer, surfactant, additive for grease, urethane material and polyester material.
• the bonding mode of the copolymer of the monomer unit represented by formula (1), the monomer unit represented by formula (2) and a monomer unit derived from unsaturated carboxylic acid or unsaturated carboxylic acid ester may be random or block, depending on polymerization conditions. In consideration for enhancement in compatibility with various resins, random mode is preferred.
• the composition of each monomer unit can be controlled by changing blending ratios between the allyl alcohol corresponding to the monomer unit represented by formula (1) , the olefin compound corresponding to the monomer unit represented by formula (2) and the unsaturated carboxylic acid or unsaturated carboxylic acid ester at the time of conducting polymerization and polymerization conditions.
• the concentration of the monomer unit represented by formula (1) be from 3 to 50 mol% based on the total monomer units, more preferably 4 to 40 mol%, most preferably 10 to 30 mol%. If the concentration of the monomer unit represented by formula (1) is less than 3 mol%, adhesiveness markedly decreases, and if it exceeds 50 mol%, compatibility with resins having low polarity decreases .
• olefin compound corresponding to the monomer unit represented by formula (2) used in copolymerization method in the present invention examples include straight chain terminal olefins such as 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene and 1-tricosens, terminal olefins having a branched terminal such as 3- methyl-1-butene, 4-methyl-l-pentene, 3-methyl-l-pentene, 4 , 4-dimethyl-l-pentene, 3-methyl-l-heptene, 3-methyl-l- nonene and 3-methyl-l-undecene
• straight chain terminal olefins such as 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-de
• Example of such solvents include hydrocarbon solvents such as toluene, benzene and t-butylbenzene, ketone solvents such as acetone, and halogen solvents such as dichloromethane, chloroform, and chlorobenzene .
• hydrocarbon solvents such as toluene, benzene and t-butylbenzene
• ketone solvents such as acetone
• halogen solvents such as dichloromethane, chloroform, and chlorobenzene .
• This copolymerization reaction may be conducted by using a radical polymerization initiator. Any radical polymerization initiator may be used as long as it can generate radicals by heat, ultraviolet ray, electron beam, radiation or the like. Preferred are those having a half-life of 1 hour or more at the reaction temperature.
• ketone peroxides such as methylethyl ketone peroxide, methylisobutylketone peroxide and cyclohexanone peroxide
• diacyl peroxides such as benzoyl peroxide, decanoyl peroxide and lauroyl peroxide
• dialkyl peroxides such as dicumyl peroxide, t-butylcumyl peroxide and di-t-butyl peroxide
• peroxyketals such as 1, 1-di (t-hexylperoxy) -3, 3, 5- trimethylcyclohexane, 1, 1-bis (t-hexylperoxy) cyclohexane,
• alkylperoxy esters such as t-butylperoxypivalate, t- butylperoxy-2-ethylhexanoate, t-butylperoxyisobutyrate, di-t-butylperoxyhexahydroterephthalate, di-t- butylperoxyazelate, t-butylperoxy-3, 5, 5- trimethylhexanoate, t-hexylperoxy-2-ethylhexanoate,
• the use amount of the polymerization initiator varies depending on the reaction temperature and composition ratio of monomers and cannot be flatly defined. Generally, it is preferred that the amount be 0.1 to 15 parts by mass based on 100 parts by mass of the total amount of radically polymerizable monomers, particularly preferably 1 to 10 parts by mass. If the amount of the radical polymerization initiator to be added is less than 0.1 parts by mass, polymerization reaction does not readily proceed and if it exceeds 15 parts by mass, the molecular weight of the obtained copolymer becomes too low and such an excessive amount of the initiator is not preferred in consideration for the cost.
• Method B Hydrogenation of a copolymer of an allyl alcohol and a radically polymerizable aromatic monomer
• a copolymer of an allyl alcohol and a radically polymerizable aromatic monomer is obtained.
• the aromatic ring of the copolymer is hydrogenated (hydrogenation) .
• a copolymer (allyl alcohol/styrene copolymer) obtained according to the method described in US Patent No. 5444141 or those commercially available may be used.
• catalysts containing Rh, Ru or Pd as the catalyst component are particularly preferred are catalysts of Rh-carbon, Ru-carbon, Ru- alumina, Pd-carbon, and Pd-alumina.
• Rh-carbon Rh-carbon
• Ru-carbon Rh-carbon
• Ru- alumina rut-alumina
• Pd-carbon platinum-carbon
• Pd-alumina alumina
• the reaction may be carried out under normal pressure or increased pressure. In order for the reaction to proceed efficiently, increased pressure is preferred. Generally the reaction is carried out under a gauge pressure of 0 to 30 MPaG, preferably 1 to 20 MPaG, more preferably 2 to 15 MPaG.
• the allyl alcohol copolymer as the reaction product is isolated by known procedures and treatment (such as filtration, eluting out with solvent, washing with water, separation, distilling-off of solvent and reprecipitation) .
• Example 2 is a x H-NMR Spectrum of the copolymer obtained in
• Example 10 is a 1 H-NMR Spectrum of the copolymer obtained in

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• Chemical & Material Sciences (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• General Chemical & Material Sciences (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

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• 2008
  • 2008-06-11 JP JP2008152788A patent/JP5475967B2/ja not_active Expired - Fee Related
  • 2008-12-17 TW TW097149173A patent/TW200938554A/zh unknown
  • 2008-12-22 WO PCT/JP2008/073899 patent/WO2009082022A1/en not_active Ceased
  • 2008-12-22 US US12/810,444 patent/US20100286354A1/en not_active Abandoned
  • 2008-12-22 CN CN200880122886XA patent/CN101910217A/zh active Pending
  • 2008-12-22 EP EP08865006A patent/EP2229412A1/en not_active Withdrawn
  • 2008-12-22 KR KR1020107010634A patent/KR20100097657A/ko not_active Withdrawn

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