JPH11116606A - Polymer and use - Google Patents

Abstract

PROBLEM TO BE SOLVED: To readily obtain a polymer having a controlled structure and an extended chain or a star structure, by polymerizing a vinyl-based monomer in a living radical polymerization and, at the end point of polymerization, adding a compound containing plural polymerizable C=C bonds. SOLUTION: In a living radical polymerization, preferably, in an atom transfer polymerization, a vinyl-based monomer is polymerized preferably at 0-200 deg.C and, at the end point of polymerization, a compound (e.g. divinylbenzene) containing two or more polymerizable C=C bonds such as formula I (R<1> is Ph, etc.; R<2> is a bi- or poly functional organic group; (n) is >=2), formula II (R<4> is H, etc. ; R<5> is a di- or poly-substituted benzene, etc.), formula III (R<6> is H, etc.; R<7> is a bi- or polyfunctional organic group), etc., is added so that a coupling reaction is caused to give the objective polymer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a vinyl polymer having a chain-extended or star-shaped structure, a method for producing the same, and a composition using the polymer.

[0002]

2. Description of the Related Art A star polymer is a polymer in which a linear arm extends radially from a central portion, and is known to have various properties different from a linear polymer. ing. As a method for synthesizing a star polymer, there are roughly two methods. One is to grow a polymer to be an arm from a central compound or polymer, and the other is to first create a polymer to be an arm and connect them to form a star. Examples of a method for connecting the arms include a method of reacting with a compound having a plurality of functional groups that react with a terminal functional group, and a method of adding a compound having a plurality of polymerizable groups after polymerization of the arm.

[0003] Polymers constituting such a star-shaped polymer include both homopolymers and copolymers, and various types thereof include polystyrene, poly (meth) acrylate, polydiene, polyether, polyester, polysiloxane and the like. There is something. In order to obtain a controlled star-shaped structure, no matter which method is used, anion polymerization, living cationic polymerization or degeneracy is often used because polymerization must be controlled.

[0004]

Among the above-mentioned polymers obtained by ionic polymerization or polycondensation, those of the vinyl type obtained by radical polymerization and having a star-shaped structure are still almost in practical use. Not converted. Above all, a method of constructing a chain extension or a star-shaped structure by bonding polymerization-growth terminals has not been successful. Among vinyl polymers, (meth) acrylic polymers have properties such as high weather resistance and transparency that cannot be obtained with the above-mentioned polyether polymers, hydrocarbon polymers, or polyester polymers. Those having an alkenyl group or a crosslinkable silyl group in a side chain are used for highly weather-resistant paints and the like. On the other hand, it is not easy to control the polymerization of the acrylic polymer due to its side reaction, and it is very difficult to extend the chain or build a star structure after the polymerization.

Accordingly, in the present invention, a method for producing a polymer having a chain-extended or star-shaped structure composed of a radical polymerizable vinyl monomer, and a polymer comprising the same,
It is another object of the present invention to provide a composition using the polymer.

[0006]

The above-mentioned chain-extended polymer or star-shaped polymer is used for living radical polymerization,
Preferably, at the end point of the atom transfer radical polymerization,
It is produced by adding a coupling agent represented by a chemical formula selected from 2 or 3.

[0007]

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(Wherein R ¹ is Ph, CN, CO ₂ R ³
(R ³ is a monovalent organic group), and
R ² is a divalent or higher valent organic group, and n is an integer of 2 or more. )

[0009]

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(In the above formula, R ⁴ is a group selected from H, Me, an organic group having 1 to 20 carbon atoms, and R ⁵ is a di- or more substituted benzene group or a naphthalene group, and n is It is an integer of 2 or more.)

[0011]

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(In the above formula, R ⁶ is a group selected from H, Me, CN, and an organic group having 1 to 20 carbon atoms.
⁷ is a divalent or higher organic group, and n is an integer of 2 or more. In this production method, when a compound having a functional group other than the functional group that initiates polymerization is used as an initiator, a chain-extended polymer or a star polymer having a functional group at a terminal is produced.

[0013] The present invention is also a polymer obtainable by the method of the present invention. This polymer is not limited to those produced by the method of the present invention. The polymer of the present invention also has a feature that the molecular weight distribution is narrow. Furthermore, a curable composition can be obtained by combining the polymer having a hydroxyl group at the terminal of the present invention with a compound having two or more functional groups capable of reacting with a hydroxyl group in one molecule.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention provides a method for polymerizing a vinyl monomer in living radical polymerization,
By adding a compound having two or more polymerizable carbon-carbon double bonds, a chain-extended polymer or
This is a method for producing a star polymer. The compound having two or more polymerizable carbon-carbon double bonds is not particularly limited, but is preferably a compound represented by a chemical formula selected from general formulas 1, 2, and 3.

[0015]

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(Wherein R ¹ is Ph, CN, CO ₂ R ³
(R ³ is a monovalent organic group), and
R ² is a divalent or higher valent organic group, and n is an integer of 2 or more. )

[0017]

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(In the above formula, R ⁴ is a group selected from H, Me, and an organic group having 1 to 20 carbon atoms, and R ⁵ is a di- or more substituted benzene group or a naphthalene group, and n is It is an integer of 2 or more.)

[0019]

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(In the above formula, R ⁶ is a group selected from H, Me, CN and an organic group having 1 to 20 carbon atoms.
⁷ is a divalent or higher organic group, and n is an integer of 2 or more. These compounds will be described later in detail. First, living radical polymerization will be described below. Living radical polymerization is radical polymerization in which the activity of the polymerization terminal is maintained without loss. In a narrow sense, living polymerization refers to polymerization in which the terminal always has activity, but generally includes pseudo-living polymerization in which the terminal is inactivated and the activated one is in an equilibrium state. . The definition in the present invention is also the latter. Living radical polymerization has been actively studied in recent years by various groups.
Examples thereof include a cobalt porphyrin complex (JA)
m. Chem. Soc. 1994, 116, 7943)
Using radical scavengers such as and nitroxide compounds (Macromolecules, 1994, 27,
7228), atom transfer radical polymerization using an organic halide or the like as an initiator and a transition metal complex as a catalyst (Atom T
transfer Radical Polymeriz
ation). Atom transfer radical polymerization is carried out using an organic halide or a sulfonyl halide compound as an initiator and a metal complex having a transition metal as a central metal as a catalyst. Specifically, Matyjasz
ewski et al. Am. Chem. Soc. 1
995, 117, 5614, Macromolecul
es 1995, 28, 7901, Science 1
996, 272, 866; or Sawamoto et al., Macromolecules 1995, 2;
8,1721, International Patent Publications WO96 / 30421 and WO97 / 18247. According to these methods, the polymerization rate is generally very high, and the polymerization proceeds in a living manner and the molecular weight distribution is narrow (that is, Mw / Mn), although the polymerization is a radical polymerization in which a termination reaction such as coupling between radicals is likely to occur. The polymer has a value of about 1.1 to 1.5), and the molecular weight can be freely controlled by the charge ratio of the monomer and the initiator.

In the present invention, there is no particular restriction on which method is used, but atom transfer radical polymerization is preferred from the viewpoint of easy control. First, a method using a radical scavenger such as a nitroxide compound will be described. In this polymerization, a stable nitroxy free radical (= NO) is generally used as a radical capping agent. Examples of such compounds include, but are not limited to, 2,2,6,6-substituted-1-piperidinyloxy radical and 2,2,5,5-substituted-1-pyrrolidinyloxy radical. Nitroxy free radicals from cyclic hydroxyamines are preferred. As the substituent, an alkyl group having 4 or less carbon atoms such as a methyl group and an ethyl group is suitable.
Specific nitroxy free radical compounds include, but are not limited to, 2,2,6,6-tetramethyl-1-
Piperidinyloxy radical (TEMPO), 2,2
6,6-tetraethyl-1-piperidinyloxy radical, 2,2,6,6-tetramethyl-4-oxo-1-
Piperidinyloxy radical, 2,2,5,5-tetramethyl-1-pyrrolidinyloxy radical, 1,1,1
3,3-tetramethyl-2-isoindolinyloxy radical, N, N-di-t-butylamineoxy radical and the like. Instead of the nitroxy free radical, a stable free radical such as galvinoxyl free radical may be used.

The above radical capping agent is used in combination with a radical generator. It is considered that the reaction product of the radical capping agent and the radical generator serves as a polymerization initiator, and the polymerization of the addition-polymerizable monomer proceeds. The combination ratio of the two is not particularly limited, but 0.1 to 10 mol of the radical initiator is appropriate for 1 mol of the radical capping agent.

As the radical generator, various compounds can be used, but a peroxide capable of generating a radical under polymerization temperature conditions is preferable. Examples of the peroxide include, but are not limited to, diacyl peroxides such as benzoyl peroxide and lauroyl peroxide; dialkyl peroxides such as dicumyl peroxide and di-t-butyl peroxide; diisopropyl peroxydicarbonate; Peroxycarbonates such as (4-t-butylcyclohexyl) peroxydicarbonate, t-butyl peroxyoctoate, t-
There are alkyl peresters such as butyl peroxybenzoate. Particularly, benzoyl peroxide is preferred. Further, a radical generator such as a radical-generating azo compound such as azobisisobutyronitrile may be used instead of the peroxide.

Macromolecules 199
5, 28, 2993, instead of using a radical capping agent and a radical generator together,
An alkoxyamine compound as shown below may be used as an initiator.

[0025]

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When an alkoxyamine compound is used as an initiator, if it has a functional group such as a hydroxyl group as shown in the above figure, a polymer having a functional group at the terminal can be obtained. When this is used in the method of the present invention, a star polymer having a functional group at a terminal can be obtained. Polymerization conditions such as a monomer, a solvent, and a polymerization temperature used in the polymerization using the radical scavenger such as the nitroxide compound are not limited, and may be the same as those used for atom transfer radical polymerization described below.

Next, the living radical polymerization of the present invention
A more preferable atom transfer radical polymerization will be described.
You. In this atom transfer radical polymerization, organic halogenation
Products, especially those having highly reactive carbon-halogen bonds.
Organic halides (for example, S
Ter compounds and compounds with a halogen at the benzyl position
Product) or a sulfonyl halide compound as an initiator
It is preferable to use them. The above living radical polymerization
Transition metal complexes used as catalysts
However, preferred are 7, 8, 9, 10, 11
Group III transition metal complexes are more preferably zero-valent.
Copper, monovalent copper, divalent ruthenium, divalent iron or divalent
And a complex of nickel. Among them, copper complex
preferable. Specific examples of the monovalent copper compound include:
Cuprous chloride, cuprous bromide, cuprous iodide, cuprous cyanide
Copper, cuprous oxide, cuprous perchlorate and the like. Copper compound
When used, 2,2'-bipyri is used to enhance the catalytic activity.
Jill and its derivatives, 1,10-phenanthroline and
Its derivatives, tetramethylethylenediamine, pentame
Tildiethylenetriamine, hexamethyltris (2-
Addition of ligands such as polyamines such as aminoethyl) amine
Is done. Also, trivalent trivalent ruthenium chloride
Nylphosphine complex (RuCl_Two(PPh_Three)_Three) Also catalyst
It is suitable as. Using ruthenium compounds as catalysts
Aluminum alkoxides as the activator
Is added. Furthermore, bis (triphenylphos) of divalent iron
Fin complex (FeCl_Two(PPh_Three) _Two) Divalent nickel
Bistriphenylphosphine complex (NiCl_Two(P
Ph_Three)_Two) And divalent nickel bistributyl
Sphine complex (NiBr_Two(PBu_Three)_Two) Is also a catalyst
It is suitable.

In the atom transfer radical polymerization, an organic halide (for example, an ester compound having a halogen at the α-position or a compound having a halogen at the benzyl position), a sulfonyl halide compound, or the like is used as an initiator without limitation. . As a specific example, C ₆ H ₅ —CH
_{2 X, C 6 H 5 -C} (H) (X) CH 3, C 6 H 5 -C (X)
(CH ₃ ) ₂ , where C ₆ H ₅ is a phenyl group, X is chlorine, bromine, or iodine. R ⁸ —C (H) (X) —CO ₂ R ⁹ , R ⁸ — C (CH ₃ )
^{_{(X) -CO 2 R 9,}} R 8 -C (H) (X) -C (O)
R ⁹ , R ⁸ —C (CH ₃ ) (X) —C (O) R ⁹ , wherein,
R ⁸ and R ⁹ are the same or different and are a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms, X is chlorine, bromine, or ^{_{iodine) R 8 -C 6 H 4 -SO}} 2 X, ( in each formula above, R ⁸ a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, 6 carbon atoms
An aryl group having 20 or an aralkyl group having 7 to 20 carbon atoms, and X is chlorine, bromine, or iodine).

In atom transfer radical polymerization, an initiator having two or more initiation sites is often used. In the present invention, a monofunctional initiator is preferred. As an initiator of the atom transfer radical polymerization, an organic halide or a sulfonyl halide compound having a functional group other than the functional group that initiates the polymerization can also be used. In such a case, a vinyl polymer having a functional group at the terminal of the main chain is produced, and by coupling the polymer with the method of the present invention,
A polymer having a functional group at the terminal is obtained. Examples of such a functional group include an alkenyl group, a crosslinkable silyl group, a hydroxyl group, an epoxy group, an amino group, and an amide group.

An organic halide having an alkenyl group;
Not limited to, for example, having a structure represented by general formula 4.
Are exemplified. R¹¹R¹²C (X) -R¹³-R¹⁴-C (R^Ten) = CH_Two(4) (where R^TenIs hydrogen or a methyl group, R¹¹, R¹²Is water
An alkyl or a monovalent alkyl group having 1 to 20 carbon atoms,
Or aralkyl, or each other at the other end
Concatenated, R¹³Is -C (O) O- (ester
Group), -C (O)-(keto group), or o-, m-, p
-Phenylene group, R¹⁴Is a direct bond or has 1 to 2 carbon atoms
0 divalent organic group containing one or more ether bonds
X may be chlorine, bromine, or iodine.¹¹, R¹²Specific examples of hydrogen, methyl group,
Ethyl group, n-propyl group, isopropyl group, butyl
Group, pentyl group, hexyl group and the like. R ¹¹And R
¹²May be linked at the other end to form a cyclic skeleton
No.

Specific examples of the organic halide having an alkenyl group represented by the general formula 4 include XCH ₂ C
(O) O (CH ₂ ) _n CH = CH ₂ , H ₃ CC (H) (X)
C (O) O (CH ₂ ) _n CH = CH ₂ , (H ₃ C) ₂ C
(X) C (O) O (CH ₂ ) _n CH = CH ₂ , CH ₃ CH ₂
C (H) (X) C (O) O (CH ₂ ) _n CH = CH ₂ ,

[0032]

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(In each of the above formulas, X represents chlorine, bromine,
Or iodine, n represents an integer of _{0~20) XCH 2 C (O)} O (CH 2) n O (CH 2) m CH = C
H ₂ , H ₃ CC (H) (X) C (O) O (CH ₂ ) _n O (C
H ₂ ) _m CH = CH ₂ , (H ₃ C) ₂ C (X) C (O) O
(CH ₂ ) _n O (CH ₂ ) _m CH = CH ₂ , CH ₃ CH ₂ C
(H) (X) C (O) O (CH ₂ ) _n O (CH ₂ ) _m CH =
CH ₂ ,

[0034]

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(In each of the above formulas, X represents chlorine, bromine,
Or iodine, n is an integer of 1 to 20, m is an integer of 0 to 20
Number) o, m, p-XCH_Two-C₆H_Four− (CH_Two)_n-CH = C
H_Two, O, m, p-CH_ThreeC (H) (X) -C₆H_Four− (C
H_Two)_n-CH = CH_Two, O, m, p-CH_ThreeCH_TwoC
(H) (X) -C₆H_Four− (CH_Two)_n-CH = CH_Two,
(In each of the above formulas, X represents chlorine, bromine, or iodine.
Prime, n is an integer of 0 to 20) o, m, p-XCH_Two-C₆H_Four− (CH_Two)_n-O- (C
H_Two)_m-CH = CH_Two, O, m, p-CH_ThreeC (H)
(X) -C₆H_Four− (CH_Two)_n-O- (CH_Two)_m-CH =
CH_Two, O, m, p-CH_ThreeCH_TwoC (H) (X) -C₆H
_Four− (CH_Two)_n-O- (CH_Two)_mCH = CH_Two,(above
In each formula, X is chlorine, bromine, or iodine, and n is 1
O, m, p-XCH_Two-C₆H_Four-O- (CH_Two)_n-CH
= CH_Two, O, m, p-CH_ThreeC (H) (X) -C₆H_Four−
O- (CH_Two)_n-CH = CH_Two, O, m, p-CH _ThreeCH
_TwoC (H) (X) -C₆H_Four-O- (CH_Two)_n-CH = C
H_Two, (In each of the above formulas, X is chlorine, bromine, or
Iodine, n is an integer of 0 to 20) o, m, p-XCH_Two-C₆H_Four-O- (CH_Two)_n-O-
(CH_Two)_m-CH = CH_Two, O, m, p-CH_ThreeC (H)
(X) -C₆H_Four-O- (CH_Two)_n-O- (CH_Two) _m-C
H = CH_Two, O, m, p-CH_ThreeCH_TwoC (H) (X)-
C₆H_Four-O- (CH _Two)_n-O- (CH_Two)_m-CH = CH
_Two, (In each of the above formulas, X is chlorine, bromine, or
Urine, n is an integer of 1 to 20, m is an integer of 0 to 20) As an organic halide having an alkenyl group,
The compound represented by the general formula 5 is exemplified. H_TwoC = C (R^Ten) -R¹⁴-C (R¹¹) (X) -R^Fifteen-R¹² (5) (where R^Ten, R¹¹, R¹², R¹⁴, X is the same as above, R
^FifteenIs a direct bond, -C (O) O- (ester group), -C
(O)-(keto group) or o-, m-, p-phenyl
Represents a len group) R¹⁴Is a direct bond or a divalent organic group having 1 to 20 carbon atoms
(Which may contain one or more ether bonds)
Is a direct bond, the carbon to which the halogen is bonded
With a vinyl group bonded to the halogenated allylic compound
is there. In this case, the carbon-halogen is linked by an adjacent vinyl group.
Is activated, so that R^FifteenAs C (O) O
Group or phenylene group is not necessary
It may be a combination. R¹⁴Is not a direct bond,
In order to activate the halogen-halogen bond, R^FifteenAs C
(O) O group, C (O) group and phenylene group are preferred.

If the compound of formula 5 is specifically exemplified,
_{CH 2 = CHCH 2 X, CH} 2 = C (CH 3) CH 2 X, C
H ₂ ＣＨCHC (H) (X) CH ₃ , CH ₂ ＣC (CH ₃ ) C
(H) (X) CH ₃ , CH ₂ ＣＨCHC (X) (CH ₃ ) ₂ ,
CH ₂ ＣＨCHC (H) (X) C ₂ H ₅ , CH ₂ ＣＨCHC
(H) (X) CH (CH ₃ ) ₂ , CH ₂ ＣＨCHC (H)
(X) C ₆ H ₅ , CH ₂ ＣＨCHC (H) (X) CH ₂ C
_{6 H 5, CH 2 = CHCH} 2 C (H) (X) -CO 2 R, C
H ₂ ＣＨCH (CH ₂ ) ₂ C (H) (X) —CO ₂ R, CH _{2
= CH (CH 2) 3 C} (H) (X) -CO 2 R, CH 2 = C
_{H (CH 2) 8 C (} H) (X) -CO 2 R, CH 2 = CHC
_{H 2 C (H) (X} ) -C 6 H 5, CH 2 = CH (CH 2) 2 C
_{(H) (X) -C 6} H 5, CH 2 = CH (CH 2) 3 C
_{(H) (X) -C 6} H 5, ( in each formula above, X is chlorine, bromine or iodine, R represents an alkyl group having 1 to 20 carbon atoms, an aryl group, an aralkyl group,) and the like, etc. it can.

Specific examples of the sulfonyl halide compound having an alkenyl group include o-, m-, p-C
_{H 2 = CH- (CH 2)} n -C 6 H 4 -SO 2 X, o-, m
_{-, p-CH 2 = CH-} (CH 2) n -O-C 6 H 4 -SO 2
X, (in each of the above formulas, X is chlorine, bromine, or iodine, and n is an integer of 0 to 20).

Organic halogen having a crosslinkable silyl group
The compound is not particularly limited.
One having a structure is exemplified. R¹¹R¹²C (X) -R¹³-R¹⁴-C (H) (R^Ten) CH_Two− [Si (R¹⁶)_2-b(Y)_bO]_m-Si (R¹⁷)_3-a(Y)_a(6) (where R^Ten, R¹¹, R¹², R¹³, R¹⁴, X is as above
J, R¹⁶, R¹⁷Is an alkyl having 1 to 20 carbon atoms
Group, aryl group, aralkyl group, or (R ′) _ThreeSi
O- (R 'is a monovalent hydrocarbon group having 1 to 20 carbon atoms;
And the three R's may be the same or different
A) a triorganosiloxy group represented by¹⁶
Or R¹⁷When there are two or more
May be different. Y is a hydroxyl group or
Represents a water-decomposable group, and when two or more Y are present,
They may be the same or different. a is 0,
1, 2, or 3, and b represents 0, 1, or 2.
You. m is an integer of 0-19. However, a + mb ≧ 1
Is satisfied.) The compound of the general formula 6 is
Specifically, XCH_TwoC (O) O (CH_Two)
_nSi (OCH_Three)_Three, CH_ThreeC (H) (X) C (O) O
(CH_Two)_nSi (OCH_Three)_Three, (CH_Three)_TwoC (X) C
(O) O (CH_Two)_nSi (OCH_Three)_Three, XCH_TwoC
(O) O (CH_Two)_nSi (CH_Three) (OCH_Three)_Two, CH _Three
C (H) (X) C (O) O (CH_Two)_nSi (CH_Three)
(OCH_Three)_Two, (CH_Three)_TwoC (X) C (O) O (C
H_Two)_nSi (CH_Three) (OCH_Three)_Two, (Each of the above equations
X is chlorine, bromine, iodine, and n is an integer of 0 to 20.
Number,) XCH_TwoC (O) O (CH_Two)_nO (CH_Two)_mSi (OC
H_Three)_Three, H_ThreeCC (H) (X) C (O) O (CH_Two)_nO
(CH_Two)_mSi (OCH_Three)_Three, (H_ThreeC)_TwoC (X) C
(O) O (CH_Two)_nO (CH_Two)_mSi (OCH_Three)_Three, C
H_ThreeCH_TwoC (H) (X) C (O) O (CH_Two)_nO (CH
_Two)_mSi (OCH_Three)_Three, XCH_TwoC (O) O (CH_Two)_n
O (CH_Two)_mSi (CH_Three) (OCH_Three)_Two, H_ThreeCC
(H) (X) C (O) O (CH_Two)_nO (CH_Two)_m-Si
(CH_Three) (OCH_Three)_Two, (H_ThreeC)_TwoC (X) C (O)
O (CH_Two)_nO (CH_Two)_m-Si (CH_Three) (OCH_Three)
_Two, CH_ThreeCH _TwoC (H) (X) C (O) O (CH_Two)_nO
(CH_Two)_m-Si (CH_Three) (OCH_Three)_Two, (Each of the above
In the formula, X is chlorine, bromine, iodine, and n is 1-20.
An integer, m is an integer of 0 to 20) o, m, p-XCH_Two-C₆H_Four− (CH_Two)_TwoSi (OC
H_Three)_Three, O, m, p-CH_ThreeC (H) (X) -C₆H_Four−
(CH_Two)_TwoSi (OCH_Three)_Three, O, m, p-CH_ThreeCH_Two
C (H) (X) -C₆H_Four− (CH_Two)_TwoSi (OC
H_Three)_Three, O, m, p-XCH_Two-C₆H_Four− (CH_Two)_ThreeS
i (OCH_Three)_Three, O, m, p-CH_ThreeC (H) (X)-
C₆H_Four− (CH_Two)_ThreeSi (OCH_Three)_Three, O, m, p-C
H_ThreeCH_TwoC (H) (X) -C₆H_Four− (CH_Two)_ThreeSi (O
CH_Three)_Three, O, m, p-XCH_Two-C₆H_Four− (CH_Two)_Two
-O- (CH_Two)_ThreeSi (OCH_Three)_Three, O, m, p-CH
_ThreeC (H) (X) -C₆H_Four− (CH_Two)_Two-O- (CH_Two)
_ThreeSi (OCH_Three)_Three, O, m, p-CH_ThreeCH_TwoC (H)
(X) -C₆H_Four− (CH_Two)_Two-O- (CH_Two)_ThreeSi (O
CH_Three)_Three, O, m, p-XCH_Two-C₆H_Four-O- (C
H_Two)_ThreeSi (OCH_Three)_Three, O, m, p-CH_ThreeC (H)
(X) -C₆H_Four-O- (CH_Two)_ThreeSi (OCH_Three)_Three,
o, m, p-CH_ThreeCH_TwoC (H) (X) -C₆H_Four-O-
(CH_Two)_Three-Si (OCH_Three)_Three, O, m, p-XCH_Two
-C₆H_Four-O- (CH_Two)_Two-O- (CH_Two)_Three-Si (O
CH_Three)_Three, O, m, p-CH_ThreeC (H) (X) -C₆H_Four
-O- (CH_Two)_Two-O- (CH_Two)_ThreeSi (OCH_Three)_Three,
o, m, p-CH_ThreeCH_TwoC (H) (X) -C₆H_Four-O-
(CH_Two)_Two-O- (CH_Two)_ThreeSi (OCH_Three)_Three,(the above
In each formula, X is chlorine, bromine, or iodine), etc.
No.

As the organic halide having a crosslinkable silyl group, those having a structure represented by the general formula 7 are further exemplified. ^{_{(R 17) 3-a (}} Y) a Si- [OSi (R 16) 2-b (Y) b] m -CH 2 -C (H) (R 10) -R 14 -C (R 11) ( ^{X) -R 15 -R 12 (7} ) ( ^{wherein, R 10, R 11, R} 12, R 14, R 15, R 16, R 17,
a, b, m, X, and Y are the same as described above. If such a compound is specifically exemplified, (CH ₃
O) ₃ SiCH ₂ CH ₂ C (H) (X) C ₆ H ₅ , (CH
_{3 O) 2 (CH 3)} SiCH 2 CH 2 C (H) (X) C
_{6 H 5, (CH 3 O} ) 3 Si (CH 2) 2 C (H) (X) -C
O ₂ R, (CH ₃ O) ₂ (CH ₃ ) Si (CH ₂ ) ₂ C (H)
(X) —CO ₂ R, (CH ₃ O) ₃ Si (CH ₂ ) ₃ C
_{(H) (X) -CO 2} R, (CH 3 O) 2 (CH 3) Si
_{(CH 2) 3 C (H} ) (X) -CO 2 R, (CH 3 O) 3 S
_{i (CH 2) 4 C (} H) (X) -CO 2 R, (CH 3 O) 2
_{(CH 3) Si (CH 2} ) 4 C (H) (X) -CO 2 R,
_{(CH 3 O) 3 Si (} CH 2) 9 C (H) (X) -CO
_{2 R, (CH 3 O)} 2 (CH 3) Si (CH 2) 9 C (H)
(X) —CO ₂ R, (CH ₃ O) ₃ Si (CH ₂ ) ₃ C
_{(H) (X) -C 6} H 5, (CH 3 O) 2 (CH 3) Si
_{(CH 2) 3 C (H} ) (X) -C 6 H 5, (CH 3 O) 3 Si
_{(CH 2) 4 C (H} ) (X) -C 6 H 5, (CH 3 O) 2 (C
_{H 3) Si (CH 2)} 4 C (H) (X) -C 6 H 5, ( in each formula above, X is chlorine, bromine or iodine, R represents an alkyl group having 1 to 20 carbon atoms, aryl Group, aralkyl group) and the like.

The organic halide having a hydroxyl group or the sulfonyl halide compound is not particularly limited, and examples thereof include the following. HO- (CH ₂₎ in _{n -OC (O) C (H} ) (R) (X) ( the formulas above, X is chlorine, bromine or iodine, R represents a hydrogen atom or an alkyl having 1 to 20 carbon atoms, Group,
(Aryl group, aralkyl group, n is an integer of 1 to 20) The organic halide having the amino group or the sulfonyl halide compound is not particularly limited, and examples thereof include the following. H ₂ N— (CH ₂ ) _n —OC (O) C (H) (R) (X) (In each of the above formulas, X is chlorine, bromine, or iodine, and R is a hydrogen atom or a carbon atom having 1 to 20 carbon atoms. An alkyl group of
(Aryl group, aralkyl group, n is an integer of 1 to 20) The organic halide having the epoxy group or the sulfonyl halide compound is not particularly limited, and examples thereof include the following.

[0041]

Embedded image

(In each of the above formulas, X represents chlorine, bromine,
Or iodine and R are a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, an aryl group, an aralkyl group, and n is an integer of 1 to 20.) The vinyl monomer used in the present invention is not particularly limited. Can be used. For example, (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate,
N-butyl (meth) acrylate, isobutyl (meth) acrylate, -tert-butyl (meth) acrylate,
N-pentyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, n-heptyl (meth) acrylate, n-octyl (meth) acrylate, (meth) 2-ethylhexyl acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, (meth)
Phenyl acrylate, toluyl (meth) acrylate,
Benzyl (meth) acrylate, (meth) acrylic acid-2
-Methoxyethyl, 3-methoxybutyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate,
2-hydroxypropyl (meth) acrylate, stearyl (meth) acrylate, glycidyl (meth) acrylate, 2-aminoethyl (meth) acrylate, γ- (methacryloyloxypropyl) trimethoxysilane,
Ethylene oxide adduct of (meth) acrylic acid, trifluoromethylmethyl (meth) acrylate, 2-trifluoromethylethyl (meth) acrylate, 2-perfluoroethylethyl (meth) acrylate, (meth) acrylic acid 2-perfluoroethyl-2-perfluorobutylethyl, 2-perfluoroethyl (meth) acrylate,
Perfluoromethyl (meth) acrylate, diperfluoromethylmethyl (meth) acrylate, 2-perfluoromethyl-2-perfluoroethylmethyl (meth) acrylate, 2-perfluorohexylethyl (meth) acrylate, (Meth) acrylic acid-based monomers such as 2-perfluorodecylethyl (meth) acrylate and 2-perfluorohexadecylethyl (meth) acrylate; styrene,
Styrene-based monomers such as vinyltoluene, α-methylstyrene, chlorostyrene, styrenesulfonic acid and salts thereof; fluorine-containing vinyl monomers such as perfluoroethylene, perfluoropropylene, and vinylidene fluoride;
Silicon-containing vinyl monomers such as vinyltrimethoxysilane and vinyltriethoxysilane; maleic anhydride, maleic acid, monoalkyl and dialkyl esters of maleic acid; fumaric acid, monoalkyl and dialkyl esters of fumaric acid; maleimide, methyl Maleimide monomers such as maleimide, ethylmaleimide, propylmaleimide, butylmaleimide, hexylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, phenylmaleimide, and cyclohexylmaleimide; vinyl monomers containing a nitrile group such as acrylonitrile and methacrylonitrile; acrylamide; Vinyl monomers containing an amide group such as methacrylamide; vinyl acetate, vinyl propionate, vinyl pivalate, vinyl benzoate Le, vinyl esters such as vinyl cinnamate, ethylene, alkenes such as propylene, butadiene, conjugated dienes such as isoprene, vinyl chloride, vinylidene chloride, allyl chloride, allyl alcohol and the like. These may be used alone or a plurality of them may be copolymerized. In the case of copolymerization, random copolymerization or block copolymerization may be used, but block copolymerization is preferred. Among them, a meta (acryl) monomer, an acrylonitrile monomer, an aromatic vinyl monomer, a fluorine-containing vinyl monomer, and a silicon-containing vinyl monomer are preferred from the viewpoint of the physical properties of the product. More preferred are acrylate monomers and methacrylate monomers, and even more preferred is butyl acrylate. In the present invention, these preferable monomers may be copolymerized with other monomers. In such a case, it is preferable that these preferable monomers are contained in a weight ratio of 40%. In the above expression format, for example, (meth) acrylic acid means acrylic acid and / or methacrylic acid.

The living radical polymerization of the present invention can be carried out without a solvent or in various solvents. Examples of the solvent include hydrocarbon solvents such as benzene and toluene;
Ether solvents such as diethyl ether, tetrahydrofuran, diphenyl ether, anisole and dimethoxybenzene; halogenated hydrocarbon solvents such as methylene chloride, chloroform and chlorobenzene; ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone;
Alcohol solvents such as methanol, ethanol, propanol, isopropanol, n-butyl alcohol and tert-butyl alcohol; nitrile solvents such as acetonitrile, propionitrile and benzonitrile; ester solvents such as ethyl acetate and butyl acetate; ethylene carbonate And carbonate-based solvents such as propylene carbonate. These can be used alone or in combination of two or more. The polymerization can also be carried out in an emulsion system or a system using a supercritical fluid CO ₂ as a medium.

The polymerization of the present invention is not particularly limited, but can be carried out in the range of 0 ° C. to 200 ° C., preferably room temperature to 150 ° C. When a compound having two or more polymerizable carbon-carbon double bonds is added at the end of such a living radical polymerization, a coupling reaction occurs and a polymer having a chain-extended or star-shaped structure is generated. Is generated. The end point of the polymerization is defined as the time when preferably 80% or more of the monomer has reacted, more preferably 90%.
The time when the above has reacted is particularly preferably the time when 95% or more has reacted, and most preferably the time when 99% or more has reacted.

The compound having two or more polymerizable carbon-carbon double bonds is not limited.
It is selected from the compounds shown in 2 and 3.

[0046]

Embedded image

(Wherein R ¹ is Ph, CN, CO ₂ R ³
(R ³ is a monovalent organic group), and
R ² is a divalent or higher valent organic group, and n is an integer of 2 or more. )

[0048]

Embedded image

(In the above formula, R ⁴ is a group selected from H, Me, and an organic group having 1 to 20 carbon atoms, and R ⁵ is a di- or more substituted benzene group or a naphthalene group, and n is It is an integer of 2 or more.)

[0050]

Embedded image

(Where R is⁶Is H, Me, CN, carbon
A group selected from organic groups represented by Formulas 1 to 20, and
⁷Is a divalent or higher valent organic group, and n is an integer of 2 or more.
You. In each of the above formulas, R^Three, R^FourAnd R⁶Represented by
The organic group is not particularly limited, but the following are examples.
Is shown. − (CH_Two)_n-CH_Three, -CH (CH_Three)-
(CH_Two)_n-CH_Three, -CH (CH_TwoCH_Three)-(CH_Two)
_n-CH_Three, -CH (CH_TwoCH_Three)_Two, -C (CH_Three)_Two−
(CH_Two)_n-CH_Three, -C (CH_Three) (CH_TwoCH_Three)-
(CH_Two)_n-CH_Three, -C₆H_Five, -C₆H_Five(CH_Three),-
C₆H_Five(CH_Three)_Two,-(CH_Two)_n-C₆H_Five,-(C
H_Two)_n-C₆H_Five(CH_Three),-(CH_Two)_n-C₆H_Five(C
H_Three)_Two(N is an integer of 0 or more, and the total carbon number of each group is 20
Below) In each of the above formulas, R^TwoAnd R⁷Is a divalent or higher organic group
Yes, but not limited, examples include:
You. − (CH_Two)_n-(N represents an integer of 1 to 20
You. ); -CH (CH_Three)-, -CH (CH_TwoCH_Three)
-, -C (CH_Three)_Two-, -C (CH_Three) (CH_TwoCH_Three)
-, -C (CH_TwoCH_Three)_Two-, -CH_TwoCH (CH_Three)
-;-( CH_Two)_n-O-CH_Two-(N is an integer of 1 to 19
Represents a number. ); -CH (CH_Three) -O-CH_Two-, -CH
(CH _TwoCH_Three) -O-CH_Two-, -C (CH_Three)_Two-O-
CH_Two-, -C (CH_Three) (CH_TwoCH_Three) -O-CH_Two−,
-C (CH_TwoCH_Three)_Two-O-CH_Two-,-(CH_Two)_Two-O
C (O)-;-(CH_Two)_n-OC (O)-(CH_Two)_m−
(M and n are the same or different and each represents an integer of 0 to 19)
You. However, 0 ≦ m + n ≦ 19 is satisfied. ) ;-( CH
_Two)_n-C (O) O- (CH_Two)_m-(M and n are the same or
Is different and represents an integer of 0 to 19. Where 0 ≦ m +
It satisfies n ≦ 19. ); -CH_Two-C (O) O- (C
H_Two)_Two-O-CH_Two-, -CH (CH_Three) -C (O) O-
(CH_Two)_Two-O-CH_Two-, And the like.

Further, R ² and R ⁷ may contain a benzene ring. Specific examples of this case include o-, m-,
_{p-C 6 H 4 -,} o-, m-, p-C 6 H 4 -CH 2 -, o
_{-, m-, p-C 6} H 4 -O-CH 2 -, o-, m-, p
_{-C 6 H 4 -O-CH (} CH 3) -, o-, m-, p-C 6
_{H 4 -O-C (CH 3} ) 2 -; o-, m-, p-C 6 H 4 -
_{(CH 2) n - (.} N represents an integer of 0 to 14); o
_{-, m-, p-C 6} H 4 -O- (CH 2) n- (n is 0
Represents an integer of ~ 14. ); O-, m-, p- CH 2 -C 6
_{H 4 -, o-, m-,} p-CH 2 -C 6 H 4 -CH 2 -, o
_{-, m-, p-CH 2} -C 6 H 4 -O-CH 2 -, o-, m
_{-, p-CH 2 -C 6} H 4 -O-CH (CH 3) -; o-,
_{m-, p-CH 2 -C 6} H 4 -O-C (CH 3) 2 -; o
_{-, m-, p-CH 2} -C 6 H 4 - (CH 2) n - (n is
Represents an integer of 0 to 13. ); O-, m-, p- CH 2 -
_{C 6 H 4 -O- (CH 2} ) n - (. N is an integer of 0~13); o-, m-, p -C (O) -C 6 H 4 -C (O)
_{O- (CH 2) n - (} n represents an integer of 0 to 12.), And the like.

If the above compounds are specifically exemplified, there is no particular limitation, but 1,3-divinylbenzene,
4-divinylbenzene, 1,2-diisopropenylbenzene, 1,3-diisopropenylbenzene, 1,4-diisopropenylbenzene, 1,3-divinylnaphthalene, 1,8-divinylnaphthalene, 2,4- Polyvinyl such as divinyl biphenyl, 1,2-divinyl-3,4-dimethylbenzene, 1,3-divinyl-4,5,8-tributylnaphthalene, 2,2'-divinyl-4-ethyl-4'-propylbiphenyl Examples include aromatic compounds, poly (meth) acrylates such as ethylene glycol dimethacrylate, and ethylene glycol diacrylate. Of these, polyvinyl aromatic compounds are preferred, and divinylbenzene is more preferred.

The amount of the compound having two or more polymerizable alkenyl groups is not particularly limited, but the number of olefins is preferably equal to or greater than the number of growing terminals of the polymer serving as an arm. If the amount is small, a large amount of uncoupled polymer may remain. More preferably, the amount of the compound having two or more polymerizable alkenyl groups is not particularly limited, but the number of the olefins is preferably 20 times or less the number of the growing ends of the polymer serving as the arm, more preferably. Is 10 times or less, particularly preferably 5 times or less. The reaction conditions after the addition of the coupling agent are not particularly limited, and may be the same as the polymerization conditions of the polymer serving as the arm.

Further, the present invention is a polymer obtainable by the method of the present invention. This polymer is not limited to those produced by the method of the present invention. The polymer of the present invention may be, but is not limited to, a molecular weight distribution, ie, gel permeation chromatography (GP).
It also has the feature that the ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) measured in C) is narrow. The value of the molecular weight distribution is preferably 3 or less, more preferably 2 or less, more preferably 1.8 or less, particularly preferably 1.6 or less, and particularly preferably 1.4 or less. And most preferably 1.3 or less. In the GPC measurement in the present invention, although not particularly limited, usually, chloroform is used as a mobile phase, and the measurement is performed using a polystyrene gel column. The number average molecular weight and the like can be determined in terms of polystyrene. It is known that the molecular weight of star polymers measured by GPC generally falls below the true molecular weight.

The polymer having a hydroxyl group at the terminal obtained by the present invention contains two or more functional groups capable of reacting with a hydroxyl group in one molecule.
A curable composition is obtained by combining with a compound having at least one compound. The composition of the present invention containing a polymer having a hydroxyl group at the terminal (hereinafter, referred to as polymer (I)) may be a known low molecular weight compound having a hydroxyl group or a conventionally known polymer in addition to the polymer (I). (Acrylic polyols, polyether polyols, polyester polyols, polycarbonate polyols, polybutadiene polyols, polyolefin polyols, etc.).

The number of functional groups capable of reacting with a hydroxyl group is 2 per molecule.
The compound (a) having two or more isomers is not particularly limited. For example, the compound (b) having two or more isocyanate groups in one molecule (b) an aminoplast such as a methylolated melamine and its alkyl etherified product or low condensed product Compound (d) having two or more carboxyl groups in one molecule such as resin (c), polyfunctional carboxylic acid and its halide, and the like.

The compound (b) having two or more isocyanate groups in one molecule is a so-called polyfunctional isocyanate compound. As the polyfunctional isocyanate compound (b), any of conventionally known compounds can be used. For example, tolylene diisocyanate, 4,4
Isocyanate compounds such as 4'-diphenylmethane diisocyanate, hexamethyl diisocyanate, xylylene diisocyanate, meta-xylylene diisocyanate, 1,5-naphthalene diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated toluylene diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate; Bullet polyisocyanate compounds such as Sumidur N (manufactured by Sumitomo Bayer Urethane Co.); Desmodur IL, HL (Bayer A.
G. FIG. Polyisocyanate compounds having an isocyanurate ring such as Coronate EH (manufactured by Nippon Polyurethane Industry Co., Ltd.); adduct polyisocyanate compounds such as Sumidur L (manufactured by Sumitomo Bayer Urethane Co., Ltd.); Coronate HL (Japan) Adduct polyisocyanate compounds such as those manufactured by Polyurethane Co., Ltd.). These can be used alone or in combination of two or more. Further, a blocked isocyanate may be used.

In order to make use of the better weather resistance of the composition comprising the polymer (I) and the polyfunctional isocyanate compound (b), the polyfunctional isocyanate compound (b)
As, for example, hexamethylene diisocyanate,
It is preferable to use an isocyanate compound having no aromatic ring, such as hydrogenated diphenylmethane diisocyanate and Sumidur N (manufactured by Sumitomo Bayer Urethane Co., Ltd.).

The mixing ratio of the polymer (I) and the polyfunctional isocyanate compound (b) having two or more isocyanate groups in one molecule is not particularly limited,
For example, the ratio of the isocyanate group of this compound (b) to the hydroxyl group of the polymer (I) (NCO / O
H (molar ratio)) is preferably 0.5 to 1.5, and more preferably 0.8 to 1.2. However, when this composition is used for applications requiring excellent weather resistance, the composition may be used in a molar ratio of NCO / OH up to about 3.0.

In order to promote the urethanization reaction between the polymer (I), which is a component in the polymer (I) -containing composition, and the polyfunctional isocyanate compound (b), an organic compound may be used, if necessary. Known catalysts such as tin compounds and tertiary amines can be used freely. The aminoplast resin (c) used in the polymer (I) -containing composition is not particularly limited, and examples thereof include a reaction product (a methylol compound) of a triazine ring-containing compound represented by the following general formula and formaldehyde, Examples include a low-condensation product of a triazine ring-containing compound and formaldehyde, a derivative thereof, and a urea resin.

[0062]

Embedded image

(In the formula, X represents an amino group, a phenyl group, a cyclohexyl group, a methyl group or a vinyl group.) The triazine ring-containing compound represented by the above general formula is not particularly limited. Benzoguanamine, cyclohexanecarboguanamine, methylguanamine, vinylguanamine and the like can be mentioned. These may be used alone or in combination of two or more.

The reaction product of the triazine ring-containing compound and formaldehyde or a derivative thereof is not particularly limited, and examples thereof include hexamethoxymethylmelamine and tetramethoxymethylbenzoguanamine. Also,
The low-condensation product of the triazine ring-containing compound and formaldehyde or a derivative thereof is not particularly limited, but, for example, the triazine-containing compound is -NH-
CH ₂ —O—CH ₂ —NH— bond and / or —NH—
Examples thereof include a low-condensation product in which several compounds are bonded via a CH ₂ —NH— bond and an alkyl etherified formaldehyde resin (Cymel (manufactured by Mitsui Cyanamid Co., Ltd.)). These aminoplast resins (c) may be used alone or in combination of two or more.

The aminoplast resin (c) exemplified above.
The ratio between the triazine ring-containing compound and formaldehyde used when synthesizing is different depending on the intended use, but the molar ratio of the triazine ring-containing compound to formaldehyde (triazine ring-containing compound / formaldehyde) is 1 to 3. It is preferably in the range of 6. Next, the polymer (I) and the aminoplast resin (c) in the polymer (I) -containing composition containing, as essential components, the polymer (I) and the aminoplast resin (c) as the compound (a) Is preferably 95: 5 to 50:50, more preferably 80:20 to 60:40.

In the composition containing the polymer (I) and the aminoplast resin (c) as essential components, known compositions such as paratoluenesulfonic acid and benzenesulfonic acid are used to promote the reaction. It is free to use this catalyst. Compound (d) having two or more carboxyl groups in one molecule, which is used in the polymer (I) -containing composition
As is not particularly limited, for example, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, phthalic acid, phthalic anhydride, terephthalic acid, trimellitic acid, trimellitic anhydride, pyromellitic acid, Pyromellitic anhydride, maleic acid, maleic anhydride, fumaric acid,
Examples thereof include polyfunctional carboxylic acids such as itaconic acid, diphenic acid and naphthalenedicarboxylic acid or anhydrides thereof, halides thereof, and polymers having a plurality of carboxyl groups. Only one compound (d) may be used, or two or more compounds may be used in combination. Compound (d)
And the molar ratio of hydroxyl groups in the polymer (I) (compound (d)
/ Hydroxyl group in the polymer (I)) is preferably 1 to 3, and more preferably 1 to 2.

The polymer produced in the present invention is used in, but not limited to, lubricating oil compositions. In the case of a polymer having a functional group at the terminal, its hydroxyl group,
An elastomer can be obtained by using a functional group such as a crosslinkable silyl group or an alkenyl group as it is, or converting it into another functional group such as a crosslinkable silyl group to cause a crosslinking reaction. Specific examples of this use include sealing materials, adhesives, adhesives, elastic adhesives, paints, powder coatings, foams, potting materials for electric and electronic devices, films, gaskets, various molding materials, artificial marble, etc. is there.

[0068]

EXAMPLES Specific examples of the present invention will be described below, but the present invention is not limited to the following examples. Example 1 A 30 mL glass reaction vessel was charged with butyl acrylate (1
0.0 mL, 8.94 g, 69.75 mmol), cuprous bromide (250 mg, 1.74 mmol), pentamethyldiethylenetriamine (0.364 mL, 302 m
g, 1.74 mmol) and toluene (1 mL), and after cooling, degassed under reduced pressure and then replaced with nitrogen gas.
After stirring well, methyl 2-bromopropionate (0.
195 mL, 291 mg, 1.74 mmol) were added, and the mixture was heated and stirred at 70 ° C. After 30 minutes, divinylbenzene (3.49 mmol) was added, and heating and stirring were continued at 70 ° C. The mixture was diluted with ethyl acetate, and the resulting insoluble solid was filtered. After that, the filtrate was washed twice with diluted hydrochloric acid and once with brine.
Washed twice. The organic layer was dried over Na ₂ SO ₄ and volatiles were distilled off under reduced pressure to obtain a star-shaped poly (butyl acrylate). At the time of adding divinylbenzene, the conversion of butyl acrylate was 99% or more, the number average molecular weight of the produced polymer was 4,900, and the molecular weight distribution was 1.26 by GPC measurement (in terms of polystyrene). The finally obtained main product has a number average molecular weight of 52100 and a molecular weight distribution of 1.24.
Met. Example 2 In a 30 mL glass reaction vessel, butyl acrylate (1
0.0 mL, 8.94 g, 69.75 mmol), cuprous bromide (250 mg, 1.74 mmol), pentamethyldiethylenetriamine (0.364 mL, 302 m
g, 1.74 mmol) and toluene (1 mL), and after cooling, degassed under reduced pressure and then replaced with nitrogen gas.
After stirring well, methyl 2-bromopropionate (0.
195 mL, 291 mg, 1.74 mmol) were added, and the mixture was heated and stirred at 70 ° C. After 30 minutes, divinylbenzene (0.87 mmol) was added, and heating and stirring were continued at 70 ° C. The mixture was diluted with ethyl acetate, and the resulting insoluble solid was filtered. After that, the filtrate was washed twice with diluted hydrochloric acid and once with brine.
Washed twice. The organic layer was dried over Na ₂ SO ₄ and volatiles were distilled off under reduced pressure to obtain a star-shaped poly (butyl acrylate). At the time when divinylbenzene was added, the conversion of butyl acrylate was 99% or more, the number average molecular weight of the produced polymer was 4,800 by GPC measurement (polystyrene conversion), and the molecular weight distribution was 1.22. The finally obtained main product had a number average molecular weight of 33,300 and a molecular weight distribution of 1.19. Example 3 A 30 mL glass reaction vessel was charged with butyl acrylate (1
0.0 mL, 8.94 g, 69.75 mmol), cuprous bromide (250 mg, 1.74 mmol), pentamethyldiethylenetriamine (0.364 mL, 302 m
g, 1.74 mmol) and toluene (1 mL), and after cooling, degassed under reduced pressure and then replaced with nitrogen gas.
After stirring well, 2-hydroxyethyl bromopropionate (344 mg, 1.74 mmol) was added and 70
The mixture was heated and stirred at ℃. After 35 minutes, divinylbenzene (0.
87 mmol) of an n-hexane solution was added, and heating and stirring were continued at 70 ° C., and the reaction was stopped after 8 hours. The mixture was diluted with ethyl acetate and the catalyst was removed through a column of activated alumina to obtain a hydroxyl-terminated star-shaped poly (butyl acrylate) (yield 5.20 g). The conversion of butyl acrylate is 99% or more. The number average molecular weight of the finally obtained star polymer, which is the main product, is 36,000 by GPC measurement (in terms of polystyrene), and the molecular weight distribution is 1.5.
It was 8. Example 4 Star-shaped poly (butyl acrylate) having a hydroxyl group at the terminal obtained in Example 3 (0.5 g) and a trifunctional isocyanate compound represented by the following formula (B-45, manufactured by YAS YAS) (0.13)
5g) were mixed well. The mixing ratio was such that the molar ratio of the hydroxyl group of the (meth) acrylic polymer to the isocyanate group of the isocyanate compound was 1/1.

The above mixture was defoamed under reduced pressure, poured into a mold, and cured by heating at 80 ° C. for 15 hours. A rubber-like cured product was obtained. The obtained cured product was immersed in toluene for 24 hours, and the gel fraction was calculated from the weight change before and after. The result was 96%, and it was confirmed that a hydroxyl group was quantitatively introduced into the terminal. Example 5 In a 100 mL glass reaction vessel, methyl 2-bromopropionate (0.195 mL, 291 mg, 1.74 mm)
ol) as the initiator, cuprous bromide (250 mg, 1.74 m
mol), pentamethyldiethylenetriamine as a catalyst, butyl acrylate (10.0 mL, 8.94 g,
69.75 mmol) was polymerized at 70 ° C. Polymerization rate 9
At 8%, divinylbenzene (0.87 mmol)
Was added and the polymerization was continued. FIG. 1 shows a time-dependent change in GPC analysis of a sample from the polymerization system. Before the addition of divinylbenzene, the linear polymer had a number average molecular weight of 6000 and a molecular weight distribution of 1.38, and the final star polymer had a number average molecular weight of 34000 and a molecular weight distribution of 1.57. It can be seen that almost all linear polymers are star polymers, and that the star polymers produced are monodisperse and have a very narrow molecular weight distribution.

[0070]

FIG.

[0071]

According to the present invention, a polymer having a chain-extended or star-shaped structure whose structure is easily controlled can be obtained from various radically polymerizable monomers. A similar polymer having a terminal can also be obtained. Further, the polymer of the present invention has a feature that the molecular weight distribution is narrow. A curable composition can be obtained from a polymer having a hydroxyl group at the terminal and a compound having two or more functional groups capable of reacting with the hydroxyl group in one molecule.

[Brief description of the drawings]

FIG. 1 shows the time course of GPC analysis of the polymer of Example 5.

Claims (14)

[Claims] 1. A chain-extended polymer by polymerizing a vinyl monomer in living radical polymerization and adding a compound having two or more polymerizable carbon-carbon double bonds at a polymerization end point, A method for producing a star polymer. 2. The compound according to claim 1, wherein the compound having two or more polymerizable carbon-carbon double bonds is a compound represented by a chemical formula selected from the general formulas 1, 2, and 3. Method. Embedded image (In the above formula, R ¹ is a group selected from Ph, CN, and CO ₂ R ³ (R ³ is a monovalent organic group), and R ² is a divalent or higher organic group, and n is It is an integer of 2 or more.) (In the above formula, R ⁴ is a group selected from H, Me, and an organic group having 1 to 20 carbon atoms, and R ⁵ is a disubstituted or more benzene group or a naphthalene group, and n is 2 or more. It is an integer.) (Wherein R ⁶ is H, Me, CN, having 1 to 20 carbon atoms)
And R ⁷ is a divalent or higher valent organic group, and n is an integer of 2 or more. ) 3. The method according to claim 1, wherein the polymerizable olefin monomer is a (meth) acrylic monomer, an acrylonitrile monomer, an aromatic vinyl monomer, a fluorine-containing vinyl monomer and a silicon-containing vinyl monomer. Production method. 4. The method according to claim 1, wherein the living radical polymerization is an atom transfer radical polymerization. 5. The method according to claim 4, wherein the metal complex used as a catalyst for the atom transfer radical polymerization is copper, nickel, ruthenium or iron. 6. The method according to claim 4, wherein the initiator of the atom transfer radical polymerization is a compound having another functional group in addition to the functional group that initiates the polymerization. 7. The method according to claim 6, wherein the functional group of the initiator having a functional group is a hydroxyl group. 8. The method according to claim 6, wherein the functional group of the initiator having a functional group is a crosslinkable silyl group. 9. The method according to claim 1, wherein the compound having two or more polymerizable carbon-carbon double bonds to be added is divinylbenzene or diisopropenylbenzene. 10. The polymer produced by living radical polymerization before adding a compound having two or more polymerizable carbon-carbon double bonds is a block copolymer. 10. The method according to any one of claims 9 to 9. 11. The method according to claim 1, wherein the molecular weight of the produced polymer is at least twice as large as before the addition of the coupling agent.
The method according to any one of claims 10 to 10. 12. The method according to claim 1, wherein the molecular weight distribution of the produced polymer is 2 or less. 13. A chain-extended polymer or a star-shaped polymer obtainable by the method according to any one of claims 1 to 12. 14. The polymer according to claim 13, wherein a polymer having a hydroxyl group at a terminal and a functional group capable of reacting with the hydroxyl group are one.
A composition comprising, as an essential component, a compound having two or more compounds in a molecule.