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WO2003004543A1 - Procede de preparation de copolymere, copolymere obtenu au moyen de ce procede et produit durci et film de revetement associes - Google Patents

Procede de preparation de copolymere, copolymere obtenu au moyen de ce procede et produit durci et film de revetement associes Download PDF

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Publication number
WO2003004543A1
WO2003004543A1 PCT/JP2002/005138 JP0205138W WO03004543A1 WO 2003004543 A1 WO2003004543 A1 WO 2003004543A1 JP 0205138 W JP0205138 W JP 0205138W WO 03004543 A1 WO03004543 A1 WO 03004543A1
Authority
WO
WIPO (PCT)
Prior art keywords
monomer
copolymer
acrylate
group
macromonomer
Prior art date
Application number
PCT/JP2002/005138
Other languages
English (en)
Japanese (ja)
Inventor
Michihiro Kaai
Yasuhiko Mori
Original Assignee
Toagosei Co., Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Toagosei Co., Ltd. filed Critical Toagosei Co., Ltd.
Priority to JP2003510709A priority Critical patent/JP4001108B2/ja
Publication of WO2003004543A1 publication Critical patent/WO2003004543A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/04—Polymers provided for in subclasses C08C or C08F

Definitions

  • the macromonomer in the above-mentioned Mac-mouth monomer composition has a structure represented by the following formula (1). (M)schreib
  • the second butyl monomer having an atariloyl group broadens the molecular weight distribution of the copolymer obtained by using the macromonomer composition, that is, increases the degree of dispersion (weight average molecular weight, number average molecular weight) and increases the gel It is used to promote the production of Specific examples of the second butyl monomer include methyl acrylate, ethyl acrylate, pentyl acrylate, butyl acrylate, isoptyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, radiuryl acrylate, Examples include acrylic acid esters such as decyl acrylate, hexyl acrylate, orisoporinole acrylate, benzyl acrylate, 2-hydroxyl acrylate, 2-hydroxypropyl acrylate, and acrylic acid.
  • polyfunctional monomer examples include dialkylaminoalkyl methacrylate, polyalkylene glycol dimethacrylate, alkyl diol dimethacrylate, polyalkylene glycol diacrylate, and alkyl diol dialkyl. Acrylates and the like.
  • the polymerization time is preferably from 0.05 to 2 hours, more preferably from 0.1 to 1 hour. If the polymerization time is too short, the yield of the macromonomer may be low. If the polymerization time is too long, coloring of the macromonomer composition may become intense.
  • the macromonomer composition in the present invention can be produced by polymerizing the macromonomer composition by a known method within the range of the above conditions. Continuous polymerization method, batch weight Synthetic method, polymerization method using a tubular reactor, and the like are included. Among the continuous polymerization methods, a continuous polymerization method using a continuous stirred tank reactor is a preferable method. According to this method, the macromonomer can be obtained efficiently, and the reaction proceeds smoothly when the obtained macromonomer composition is copolymerized with the copolymerization monomer, and the macromonomer and This is because the reaction rate of the vinyl monomer for copolymerization tends to increase.
  • a known radical polymerization initiator can be used.
  • the radical polymerization initiator include peroxides and azo compounds.
  • peroxides include hydrogen peroxide, alkyl hydroperoxides such as t-butyl hydroperoxide, dialkyl peroxides such as g-butinoreperoxide, and t-butyl peroxide.
  • esters such as zeros, percarbonates, persulfuric acid, peracids, and ketone peroxides.
  • the azo compound include azobisisobutyronitrile and 11-butyl azocyanocyclohexene.
  • a known chain transfer agent can be used if necessary.
  • the macromonomer in the macromonomer composition thus obtained has a structure represented by the following formula (1). (M) n
  • M means a monomer unit
  • n is a natural number representing the degree of polymerization
  • X is one COOR, one CONR2, one OR, one OCOR, one OCOOR, one NC 0 ⁇ R, It is a halogen atom, a CN or a phenyl group or an aryl group which may have a substituent.
  • the first bubble monomer includes a vinyl monomer having hydrogen at the a-position.
  • the bubble monomer having hydrogen at the a-position include acrylates such as ethyl acrylate, butyl acrylate, cyclohexyl acrylate, and acrylic acid.
  • a vinyl monomer having a hydrogen atom at the a-position is 30% by mass or more, and other vinyl monomers used for copolymerization are 70% by mass.
  • the vinyl monomer mixture contained below is preferably used.
  • the polymerization time is usually 0.1 to 30 hours, preferably 0.3 to 20 hours, more preferably 0.5 to 15 hours, and particularly preferably 1 to 10 hours.
  • the concentration of the monomer or the like is large, the mixture of the macromonomer composition and the copolymerizing monomer has a high viscosity because the molecular weight distribution of the macromonomer composition is large, and the mixture is applied.
  • the resulting coating film may have poor smoothness.
  • the macromonomer composition used in the present invention has a small molecular weight distribution of the macromonomer composition.
  • the mixture of the macromonomer composition and the first monomer has a low viscosity, a coating film obtained by applying this mixture tends to have good smoothness. Further, since such a coating film becomes a polymer or gel having a large molecular weight distribution by the polymerization reaction, excellent coating film performance can be exhibited.
  • the coating material is applied to an object to be coated and cured, so that volume shrinkage is small, and strength and solvent resistance can be improved.
  • the average molecular weight of the macromonomer composition of Production Example 1 was measured by gel permeation chromatography using a tetrahydrofuran solvent (hereinafter, referred to as GPC).
  • GPC tetrahydrofuran solvent
  • Mn number average molecular weight
  • Mw weight average molecular weight
  • the concentration of the terminal ethylenically unsaturated bond contained in the macromonomer was measured by 1 H-NMR, and was found to be 0.88.
  • Table 1 shows the types and amounts of the macromonomer production monomer, the amount of the solvent, the amount of the polymerization initiator, and the reaction temperature.
  • a macromonomer composition was produced in the same manner as in Production Example 1 except that the composition was changed as described above. Furthermore, the average molecular weight and macromonomer content of the produced macromonomer composition were analyzed.
  • Table 2 shows the results. In the following description, cyclohexyl acrylate is referred to as CHA, acrylic acid as AA, 1,6-hexanediol diacrylate as HDDA, and methylethyl ketone as MEK. table 1
  • Example 11 in the THF dissolution test of the film, the shape was broken and no gel remained. However, in the xylene dissolution test, the shape of the film was maintained, and the remaining gel was sufficiently confirmed.
  • the copolymer may be modified to be used as a raw material for an adhesive, a filler, or the like.
  • the first butyl monomer may be an acrylate or acrylic acid.
  • the molecular weight distribution of the obtained copolymer can be broadened, or gel can be more easily generated.
  • Vinyl monomers other than the first vinyl monomer used in the copolymerization may include a polyfunctional monomer. In this case, the molecular weight distribution of the obtained copolymer can be broadened, or gel can be more easily generated.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Paints Or Removers (AREA)

Abstract

L'invention concerne un procédé de préparation d'un copolymère dans lequel une composition de macromonomère et un monomère vinylique comprenant un atome d'hydrogène en position α sont mis à réagir à une température comprise entre 20 et 150 °C, en présence d'un solvant ou dans une condition exempte de solvant, la composition de macromonomère comprenant un macromonomère obtenu par polymérisation d'un monomère vinylique doté d'un groupe acryloyle à une concentration en monomère élevée, de manière que la somme du monomère et du polymère soit comprise dans le mélange de réaction de polymérisation à au moins 50 % en masse et à une température de polymérisation élevée compris entre 180 et 350°C. L'invention concerne également un copolymère obtenu au moyen du procédé, un produit durci et un film de revêtement préparé à partir du copolymère. Celui-ci présente une large distribution de poids moléculaire ou est capable de former un gel et est, par conséquent, conçu pour être utilisé comme agent de revêtement pouvant être durci par polymérisation radiale.
PCT/JP2002/005138 2001-07-03 2002-05-28 Procede de preparation de copolymere, copolymere obtenu au moyen de ce procede et produit durci et film de revetement associes WO2003004543A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2003510709A JP4001108B2 (ja) 2001-07-03 2002-05-28 硬化物及び塗膜の製造方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2001-201680 2001-07-03
JP2001201680 2001-07-03

Publications (1)

Publication Number Publication Date
WO2003004543A1 true WO2003004543A1 (fr) 2003-01-16

Family

ID=19038599

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2002/005138 WO2003004543A1 (fr) 2001-07-03 2002-05-28 Procede de preparation de copolymere, copolymere obtenu au moyen de ce procede et produit durci et film de revetement associes

Country Status (3)

Country Link
JP (1) JP4001108B2 (fr)
TW (1) TW593371B (fr)
WO (1) WO2003004543A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008132916A1 (fr) * 2007-04-24 2008-11-06 Soken Chemical & Engineering Co., Ltd. Composition adhésive comprenant un polymère acrylique à extrémité réactive et utilisation de cette composition

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5310813A (en) * 1990-08-24 1994-05-10 Toagosei Chemical Industry Co., Ltd. Thermosetting coating resin and process for producing the same
EP0687690A1 (fr) * 1994-06-13 1995-12-20 Rohm And Haas Company Procédé de polymérization à haute température et produits ainsi obtenus
US5618898A (en) * 1992-02-10 1997-04-08 Toagosei Chemical Industry Co., Ltd. Weather-resistant solvent-based coating obtained by polymerization with thioether bond converted to sulfone bond
WO1998047927A1 (fr) * 1997-04-23 1998-10-29 E.I. Du Pont De Nemours And Company Procede de synthese pour macromonomeres
WO1999007755A2 (fr) * 1997-08-05 1999-02-18 Sc Johnson Commercial Markets, Inc. Procede de preparation de macromeres
JPH11228645A (ja) * 1998-02-12 1999-08-24 Mitsubishi Rayon Co Ltd アクリル系シラップ組成物
WO2000005272A1 (fr) * 1998-07-24 2000-02-03 Rohm And Haas Company Composition aqueuse
WO2001004163A1 (fr) * 1999-07-12 2001-01-18 Toagosei Co., Ltd. Processus de production d'une resine de dispersion aqueuse

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5310813A (en) * 1990-08-24 1994-05-10 Toagosei Chemical Industry Co., Ltd. Thermosetting coating resin and process for producing the same
US5618898A (en) * 1992-02-10 1997-04-08 Toagosei Chemical Industry Co., Ltd. Weather-resistant solvent-based coating obtained by polymerization with thioether bond converted to sulfone bond
EP0687690A1 (fr) * 1994-06-13 1995-12-20 Rohm And Haas Company Procédé de polymérization à haute température et produits ainsi obtenus
WO1998047927A1 (fr) * 1997-04-23 1998-10-29 E.I. Du Pont De Nemours And Company Procede de synthese pour macromonomeres
WO1999007755A2 (fr) * 1997-08-05 1999-02-18 Sc Johnson Commercial Markets, Inc. Procede de preparation de macromeres
JPH11228645A (ja) * 1998-02-12 1999-08-24 Mitsubishi Rayon Co Ltd アクリル系シラップ組成物
WO2000005272A1 (fr) * 1998-07-24 2000-02-03 Rohm And Haas Company Composition aqueuse
WO2001004163A1 (fr) * 1999-07-12 2001-01-18 Toagosei Co., Ltd. Processus de production d'une resine de dispersion aqueuse

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008132916A1 (fr) * 2007-04-24 2008-11-06 Soken Chemical & Engineering Co., Ltd. Composition adhésive comprenant un polymère acrylique à extrémité réactive et utilisation de cette composition
US8124706B2 (en) 2007-04-24 2012-02-28 Soken Chemical & Engineering Co., Ltd. Adhesive composition comprising end-reactive acrylic polymer and uses thereof

Also Published As

Publication number Publication date
JPWO2003004543A1 (ja) 2004-10-28
TW593371B (en) 2004-06-21
JP4001108B2 (ja) 2007-10-31

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