JP2000281718A - Polymer, its production and curable composition using it - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a vinyl polymer having different functional groups such as an alkenyl group or the like at the molecular chain ends and a process for producing the polymer, and provide a curable composition using the polymer. SOLUTION: A process for producing a vinyl polymer having functional groups at the molecular chain ends is carried out by adding (I) a compound having a functional group and an internal alkenyl group or (II) a conjugated polyene compound in a living radical polymerization of a radically polymerizable vinyl monomer. A vinyl polymer having functional groups at the molecular chain ends can be produced by the above-described process. A curable composition utilizes the vinyl 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 functional group at a molecular chain terminal, a method for producing the same, and a curable composition containing the polymer.

[0002]

2. Description of the Related Art It is known that a polymer having a functional group at a plurality of molecular chain terminals is crosslinked by itself or in combination with an appropriate curing agent to give a cured product having excellent heat resistance and durability. Have been. Among them, a polymer having an alkenyl group, a hydroxyl group or a crosslinkable silyl group at a terminal is a typical example thereof. The polymer having a terminal alkenyl group is crosslinked and cured by using a hydrosilyl group-containing compound as a curing agent or by utilizing a photoreaction. The polymer having a hydroxyl group at the terminal forms a urethane crosslink by reacting with the polyisocyanate, and is cured. Further, the polymer having a crosslinkable silyl group at the terminal gives a cured product by absorbing moisture in the presence of a suitable condensation catalyst.

The main chain skeleton of such a polymer having an alkenyl group, a hydroxyl group or a crosslinkable silyl group at its terminal includes polyether polymers such as polyethylene oxide, polypropylene oxide and polytetramethylene oxide; polybutadiene, and polybutadiene. Hydrocarbon-based polymers such as isoprene, polychloroprene, polyisobutylene or hydrogenated products thereof; polyethylene-based polymers such as polyethylene terephthalate, polybutylene terephthalate, and polycaprolactone are exemplified. It is used for various purposes.

[0004] Among the polymers obtained by ionic polymerization or polycondensation as exemplified above, vinyl polymers obtained by radical polymerization and having a functional group at a terminal have not yet been practically used. 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 and polyester polymers. ing. Of these, 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 introduce a functional group to the terminal.

If a vinyl polymer having a crosslinkable functional group such as an alkenyl group at the terminal of a molecular chain can be obtained by a simple method, the physical properties of the cured product will be superior to those having a crosslinkable functional group on the side chain. Cured product can be obtained. Therefore, although many researchers have studied the production method, it is not easy to produce them industrially.

JP-A-5-255415 discloses that an alkenyl group-containing disulfide is used as a chain transfer agent.
A method for synthesizing a (meth) acrylic polymer having alkenyl groups at both terminals is disclosed. Further, Japanese Unexamined Patent Publication No.
No. 262808 discloses that a (meth) acrylic polymer having hydroxyl groups at both ends is synthesized using a hydroxyl group-containing disulfide as a chain transfer agent, and alkenyl is added at both ends using the reactivity of the hydroxyl group. A method for synthesizing a (meth) acrylic polymer having a group is disclosed. However, it is not easy to reliably introduce alkenyl groups at both ends by these methods. Further, in order to surely introduce a functional group into the terminal, a large amount of a chain transfer agent must be used, which is a problem in the production process.

[0007]

SUMMARY OF THE INVENTION The present invention provides a vinyl polymer having a functional group at a molecular chain terminal by reliably introducing a functional group at the molecular chain terminal using a compound which is relatively easily available. The purpose is to make it easier to commercialize.

[0008]

It is known that non-activated olefins, such as α-olefins, usually do not polymerize in radical polymerization. The same applies to living radical polymerization, which has been actively studied recently.

As a result of another intensive study, we have found that when an unactivated (low polymerizable) olefin is added to a living radical polymerization system, almost only one olefin is added to its growing end. By utilizing the method, a method for producing a polymer having various functional groups at the terminal has been invented. In the present invention, a functional group can be introduced into a terminal by using an internal olefin compound which is industrially available.

That is, the first invention is to provide a living radical polymerization of a radical polymerizable vinyl monomer by adding a compound (I) having a functional group and an internal alkenyl group during or at the end of the polymerization. A method for producing a vinyl polymer having a functional group at the molecular chain terminal, which comprises introducing the functional group into the molecular chain terminal of the polymer.

The first invention also relates to a vinyl polymer, and more specifically, a vinyl polymer having a functional group at a molecular chain terminal, which can be obtained by the above-mentioned manufacturing method; A vinyl polymer having a crosslinkable silyl group at the molecular chain end, which can be produced by reacting a hydrosilane compound having a crosslinkable silyl group with a vinyl polymer having an alkenyl group at the molecular chain end; and A vinyl polymer having a hydroxyl group or an amino group at the molecular chain end, which can be produced by the above method, by reacting a compound having a functional group capable of reacting with a hydroxyl group or an amino group and a compound having a crosslinkable silyl group. It is also a vinyl polymer having a crosslinkable silyl group at the molecular chain terminal.

Further, the first invention relates to a curable composition containing the above-mentioned vinyl polymer, and specifically, (A) a vinyl polymer having an alkenyl group at a molecular chain terminal which can be produced by the above-mentioned method. And (B) a curable composition containing (B) a compound having at least two hydrosilyl groups; (A) a vinyl polymer having a hydroxyl group or an amino group at a molecular chain terminal, which can be produced by the above method, and ( B) a curable composition containing a compound having at least two functional groups capable of reacting with a hydroxyl group or an amino group; and a vinyl polymer having a crosslinkable silyl group at a molecular chain terminal, which can be produced by the above method. It is also a curable composition containing (A) a vinyl polymer having an epoxy group at the molecular chain end, which can be produced by the above method, and (B) a curing agent for an epoxy resin.

On the other hand, in radical polymerization, it is well known that a conjugated diene compound such as butadiene is usually polymerized, and is industrially practiced. It is also used as a monomer in living radical polymerization. However, there has been no report on the use of this for the introduction of a terminal functional group.

As a result of our intensive studies, we have invented a method for producing a polymer having various functional groups such as alkenyl groups at its terminals by adding a conjugated polyene compound to a living radical polymerization system.

That is, the second present invention provides a method for adding a conjugated polyene compound (II) in a living radical polymerization of a radically polymerizable vinyl monomer to convert a functional group derived from the compound (II) into a polymer. This is a method for producing a vinyl polymer having a functional group at a molecular chain terminal, which is introduced into a molecular chain terminal.

The second invention also relates to a vinyl polymer, specifically, a vinyl polymer having a functional group at a molecular chain terminal, which can be obtained by the above-mentioned method; A vinyl polymer having a crosslinkable silyl group at the molecular chain end, which can be produced by reacting a hydrosilane compound having a crosslinkable silyl group with a vinyl polymer having an alkenyl group at the molecular chain end; and A vinyl polymer having a hydroxyl group or an amino group at the molecular chain end, which can be produced by the above method, by reacting a compound having a functional group capable of reacting with a hydroxyl group or an amino group and a compound having a crosslinkable silyl group. It is also a vinyl polymer having a crosslinkable silyl group at a molecular chain terminal.

Further, the second invention relates to a curable composition containing the above-mentioned vinyl polymer. Specifically, (A) a vinyl polymer having an alkenyl group at a molecular chain terminal which can be produced by the above method. And (B) a curable composition containing (B) a compound having at least two hydrosilyl groups; (A) a vinyl polymer having a hydroxyl group or an amino group at a molecular chain terminal, which can be produced by the above method, and ( B) a curable composition containing a compound having at least two functional groups capable of reacting with a hydroxyl group or an amino group; and a vinyl polymer having a crosslinkable silyl group at a molecular chain terminal, which can be produced by the above method. It is also a curable composition containing (A) a vinyl polymer having an epoxy group at the molecular chain end, which can be produced by the above method, and (B) a curing agent for an epoxy resin.

[0018]

DESCRIPTION OF THE PREFERRED EMBODIMENTS First, the first present invention will be described. According to the first invention, in the living radical polymerization of a radically polymerizable vinyl monomer, the compound (I) having a functional group and an internal alkenyl group is added during or at the end of the polymerization, so that a polymer growing terminal is obtained. The above functional group is introduced into the molecular chain terminal of the polymer by the reaction between the polymer and the internal alkenyl group, whereby a vinyl polymer having a functional group at the molecular chain terminal can be produced. In the first invention,
Since almost one compound (I) can be reacted at one molecular chain terminal, a terminal-functionalized vinyl polymer having a very controlled structure can be obtained. Further, since the vinyl polymer has a functional group bonded to the main chain via a carbon-carbon bond, it is very stable in terms of weather resistance and the like.

The internal alkenyl group contained in the compound (I) is not particularly limited, but the following are exemplified. ^{_{CH 3 -CH = CH-, R 1}} -CH = CH-, CH 3 -
^{C (R 2) = C (} R 3) -, R 1 -C (R 2) = C (R
³ )-,

[0020]

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(Wherein R ¹ , R ² and R ^{3 each} have 1 to 2 carbon atoms)
It is an organic group of 0, preferably a hydrocarbon group, and may combine with each other to form a ring structure. )

R¹, R², R³As a specific example of
Although not limited, the following are exemplified. − (CH₂)_n-CH₃, -CH (CH₃)-(C
H₂)_n-CH₃, -CH (CH₂CH₃)-(C
H₂)_n-CH₃, -CH (CH₂CH₃)₂, -C
(CH₃)₂− (CH₂)_n-CH₃, -C (CH₃)
(CH₂CH₃)-(CH₂)_n-CH₃, -C
₆H₅, -C₆H₅(CH₃), -C₆H₅(CH₃)
₂,-(CH₂)_n-C₆H₅,-(CH₂)_n-C₆
H₅(CH₃),-(CH₂)_n-C₆H₅(CH₃)
₂  (N is an integer of 0 or more, and the total carbon number of each group is 20 or less)

The functional group contained in the compound (I) is not particularly limited, but is preferably a hydroxyl group, an amino group,
Epoxy group, carboxylic acid group, ester group, ether group,
Amide groups, crosslinkable silyl groups, and terminal or internal alkenyl groups. More preferred are a hydroxyl group, an amino group, an epoxy group, a crosslinkable silyl group, and a terminal or internal alkenyl group, and particularly preferred are a terminal or internal alkenyl group.

In the present specification, a terminal alkenyl group means that one carbon atom constituting a carbon-carbon double bond has two carbon atoms.
Hydrogen atoms are bonded, ie, CH ₂ ＣC
Means a group containing Also, an internal alkenyl group is
It means an alkenyl group other than the above terminal alkenyl group.

When the functional group of the compound (I) is a terminal or internal alkenyl group, the compound (I) having a functional group and an internal alkenyl group has two internal alkenyl groups.
Or a compound having both an internal alkenyl group and a terminal alkenyl group.
However, in this case, the two alkenyl groups are not conjugated.

When the functional group of compound (I) is a functional group such as an amino group, a hydroxyl group or a carboxylic acid group, which may affect the polymerization growth terminal or the catalyst, such a functional group is used. Those protected by a general protecting group can be used. Suitable protecting groups include acetyl, silyl, alkoxy and the like. The compound (I) is not particularly limited, but specific examples include the following.

[0027]

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The compound (I) is preferably a cyclic olefin having a functional group. Here, the cyclic olefin is a cyclic hydrocarbon in which a carbon-carbon bond in a part of the ring forms a carbon-carbon double bond. More preferably, it is a cyclic olefin having a terminal alkenyl group or a cyclic olefin having an internal alkenyl group. Particularly preferred are 4-vinylcyclohexene and 1,5-cyclooctadiene.

The "living radical polymerization method" is a radical polymerization which is difficult to control because the polymerization rate is high and a termination reaction due to coupling between radicals is likely to occur. A narrow polymer (Mw / Mn is about 1.1 to 1.5) can be obtained, and the molecular weight can be freely controlled by the charging ratio of the monomer and the initiator.

Therefore, the "living radical polymerization method" can obtain a polymer having a narrow molecular weight distribution and a low viscosity, and can introduce a monomer having a specific functional group into almost any position of the polymer. Since it is possible, it is more preferable in the present invention. In the narrow sense, living polymerization refers to polymerization in which a terminal always has activity and a molecular chain grows, but in general, one in which a terminal is inactivated and one in which a terminal is activated are generally used. Pseudo-living polymerization that grows while in equilibrium is also included. The definition in the present invention is also the latter.

The "living radical polymerization method" has been actively studied by various groups in recent years. Examples thereof include, for example, Journal of American Chemical Society (J. Am. Chem. Soc.), 19
1994, vol. 116, p. 7943, using a cobalt porphyrin complex, Macromolecules, 1994, 2
7, “Atom Transfer Radical Polymerization” using a radical scavenger such as a nitroxide compound as shown in page 7228, an organic halide or the like as an initiator and a transition metal complex as a catalyst
cal Polymerization: ATRP).

Among the "living radical polymerization methods", the "atom transfer radical polymerization method" in which an organic halide or a sulfonyl halide compound or the like is used as an initiator and a vinyl-based monomer is polymerized using a transition metal complex as a catalyst is described above. In addition to the features of the "living radical polymerization method," vinyl-based resins having a specific functional group have halogens at the terminals that are relatively advantageous for the functional group conversion reaction, and have a high degree of freedom in designing initiators and catalysts. It is more preferable as a method for producing a polymer. As this atom transfer radical polymerization method, for example, Ma
tyjaszewski et al., Journal of American Chemical Society (J. Am. Chem. S.
oc. 1995, 117, 5614, Macromolecules 199.
5 years, 28 volumes, 7901 pages, Science
e) 1996, 272, 866, WO 96/30
No. 421, WO 97/18247 or S
awamoto et al., Macromolecules (Macro)
moleculars), 1995, Vol. 28, p. 1721. In the present invention, there is no particular limitation on which method is used, but an atom transfer radical polymerization method is preferable from the viewpoint of easy control.

Of these living radical polymerizations,
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. Such compounds are not limited, but include 2,2,6,6-substituted-1-piperidinyloxy radicals and 2,2,5,5-substituted-1
Preferred are nitroxy free radicals from cyclic hydroxyamines, such as pyrrolidinyloxy radicals. 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 (TE
MPO), 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, 1,1,3,3-tetramethyl-2-isoindolinyloxy radical, N, N-di-t-butylamineoxy radical and the like. Can be Instead of nitroxy free radicals, galvinoxyl
yl) Stable free radicals such as free radicals 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 both 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
As reported in US Pat. No. 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.

[0037]

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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 the functional group at the terminal can be obtained. When this is used in the method of the present invention, a vinyl polymer having functional groups at both ends can be obtained.

The polymerization conditions such as the monomer, solvent and polymerization temperature used in the polymerization using a radical scavenger such as the above-mentioned nitroxide compound are not limited, but may be the same as those used for atom transfer radical polymerization described below. .

Next, a more preferred atom transfer radical polymerization method as the living radical polymerization of the present invention will be described. In this atom transfer radical polymerization, an organic halide, particularly an organic halide having a highly reactive carbon-halogen bond (for example, an ester compound having a halogen at the α-position or a compound having a halogen at the benzyl position), or a halogen compound A sulfonyl halide compound is used as an initiator. Examples of the catalyst include Group 7 and 8 of the periodic table.
A metal complex having a Group 5, 9, 10, or 11 element as a central metal is used. As the metal species, particularly 0 valence and 1 valence
Valent copper, divalent ruthenium, and divalent iron are preferred. If specifically exemplified, cuprous chloride, cuprous bromide, cuprous iodide, cuprous cyanide, cuprous oxide, cuprous acetate,
Cuprous perchlorate and the like. When a copper compound is used, 2,2′-bipyridyl and its derivatives, 1,10-phenanthroline and its derivatives, alkylamines such as tributylamine, tetramethylethylenediamine, pentamethyldiethylenetriamine, hexamethyl A ligand such as a polyamine such as triethylenetetraamine is added. Also, a tristriphenylphosphine complex of divalent ruthenium chloride (RuCl
₂ (PPh ₃ ) ₃ ) is also suitable as a catalyst. When this catalyst is used, an aluminum compound such as trialkoxyaluminum is added to increase the activity. Further, a tristriphenylphosphine complex of divalent iron chloride (FeCl ₂ (PPh ₃ ) ₃ ) is also suitable as a catalyst.

In this polymerization method, an organic halide,
Or a sulfonyl halide compound is used as an initiator
Can be To give a concrete example, C₆H₅-CH₂X, C₆H₅-C (H) (X) C
H₃, C₆H₅-C (X) (CH₃)₂, (However, in the above chemical formula, C₆H₅Is a phenyl group, X is
Chlorine, bromine or iodine) R⁴-C (H) (X) -CO₂R⁵, R⁴-C (C
H₃) (X) -CO₂R⁵, R⁴-C (H) (X) -C
(O) R⁵, R⁴-C (CH₃) (X) -C (O)
R ⁵, Where R⁴, R⁵Is a hydrogen atom or a group having 1 to 20 carbon atoms
An alkyl group, an aryl group, or an aralkyl group, and X is a salt
Element, bromine or iodine) R⁴-C₆H₄-SO₂X, (where R is⁴Is a hydrogen atom or carbon number 1-20
X is an alkyl group, an aryl group, or an aralkyl group of
Chlorine, bromine, or iodine).

When an organic halide or a sulfonyl halide compound having a functional group other than the functional group (starting point) that initiates polymerization is used, a vinyl polymer having a functional group easily introduced into both terminals can be obtained. can get. Examples of such a functional group include an alkenyl group, a hydroxyl group, an epoxy group, an amino group, an amide group, and a silyl group.

The organic halide having an alkenyl group is not particularly limited, and examples thereof include those having a structure represented by the general formula 1. ^{R 11 R 12 C (X)} -R 13 -R 14 -C (R 6) = CH 2 (1) ( wherein, ^{R 6} is hydrogen or a methyl ^{group,, R} 11, R ¹²
Is hydrogen or a monovalent alkyl group having 1 to 20 carbon atoms,
Aryl or aralkyl, or those linked to each other at the other ^{end,,, R 13} is, -C (O) O- (ester group), - C (O) - ( keto group), or o-, m-,
p-phenylene group, R ¹⁴ is a direct bond,
X is chlorine, bromine, or iodine, which is a divalent organic group having a carbon number of 20 or less, and X is chlorine, bromine, or iodine. And carbon-
The halogen bond is activated and the polymerization starts.

The substituent R¹¹, R¹²As a specific example,
Hydrogen, methyl, ethyl, n-propyl, isopropyl
Pill, n-butyl, pentyl, hexyl, etc.
I can do it. R¹¹And R¹²Is annular at the other end
A skeleton may be formed. In such a case, -R¹¹
-R¹²-Is, for example, -CH₂CH₂-, -CH₂CH
₂CH₂-, -CH₂CH₂CH₂CH₂-, -CH₂
CH₂CH₂CH₂CH ₂-, Etc. are exemplified.

As specific examples of the organic halide having an alkenyl group represented by the general formula 1, XCH ₂ C (O) O (CH ₂ ) _n CH ＝ CH ₂ , H ₃ C
C (H) (X) C (O) O (CH ₂ ) _n CH = CH ₂ ,
_{(H 3 C) 2 C (} X) C (O) O (CH 2) n CH = C
H ₂ , CH ₃ CH ₂ C (H) (X) C (O) O (C
H ₂ ) _n CH = CH ₂ ,

[0046]

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

[0048]

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(In each of the above formulas, X is chlorine, bromine,
Or iodine, n represents an integer of 1 to 20, m is an integer of _{0~20) o, m, p-} XCH 2 -C 6 H 4 - (CH 2) n -CH
_{= CH 2, o, m,} p-CH 3 C (H) (X) -C 6 H
_{4 - (CH 2) n -CH} = CH 2, o, m, p-CH 3
_{CH 2 C (H) (X} ) -C 6 H 4 - (CH 2) n -CH
ＣＨCH ₂ , wherein X is chlorine, bromine or iodine, and n is an integer of 0 to 20. o, m, p-XCH ₂ —C ₆ H ₄ — (CH ₂ ) _n —O—
_{(CH 2) m -CH = CH} 2, o, m, p-CH 3 C
_{(H) (X) -C 6} H 4 - (CH 2) n -O- (C
_{H 2) m -CH = CH 2} , o, m, p-CH 3 CH 2 C
_{(H) (X) -C 6} H 4 - (CH 2) n -O- (C
_{H 2) m CH = CH 2} , ( in each formula above, X is chlorine, bromine or iodine, n represents an integer of 1 to 20, m is 0 to 20 integer) o,, m, p- XCH 2 - _{C 6 H 4 -O- (CH 2} ) n -
_{CH = CH 2, o, m} , p-CH 3 C (H) (X) -C
_{6 H 4 -O- (CH 2)} n -CH = CH 2, o, m, p
_{-CH 3 CH 2 C (H)} (X) -C 6 H 4 -O- (CH
_{2) n -CH = CH 2,} ( in each formula above, X is chlorine, bromine or iodine, n represents 0 to 20 _{integer) o, m, p-XCH} 2 -C 6 H 4 -O-, ( CH ₂ ) _n −
_{O- (CH 2) m -CH =} CH 2, o, m, p-CH 3
_{C (H) (X) -C} 6 H 4 -O- (CH 2) n -O-
_{(CH 2) m -CH = CH} 2, o, m, p-CH 3 CH
_{2 C (H) (X)} -C 6 H 4 -O- (CH 2) n -O-
(CH ₂ ) _m —CH ＝ CH ₂ , wherein X is chlorine, bromine, or iodine, n is an integer of 1 to 20, and m is an integer of 0 to 20.

The organic halide having an alkenyl group further includes a compound represented by the general formula 2. H ₂ C = C (R ⁶ ) -R ¹⁴ -C (R ¹¹ ) (X) -R ¹⁵ -R ¹² (2) (wherein, R ⁶ , R ¹¹ , R ¹² , R ¹⁴ and X are as defined above. the ^{same, R 15} represents a direct bond, -C (O) O- (ester group), - C (O) - ( keto group), or, o-, m-,
represents a p-phenylene group)

R ¹⁴ is a direct bond or a group having 1 to 20 carbon atoms.
Is a divalent organic group (which may contain one or more ether bonds), but if it is a direct bond, a vinyl group is bonded to the carbon to which the halogen is bonded, and an allyl halide Is a monster. In this case, since the carbon-halogen bond is activated by the adjacent vinyl group, R ¹⁵
Need not necessarily have a C (O) O group or a phenylene group, and may be a direct bond. When R ¹⁴ is not a direct bond, R ¹⁵ is preferably a C (O) O group, a C (O) group, or a phenylene group in order to activate a carbon-halogen bond.

If the compound of the general formula 2 is specifically exemplified,
If CH₂= CHCH₂X, CH₂= C (CH₃) CH
₂X, CH₂= CHC (H) (X) CH₃, CH₂= C
(CH₃) C (H) (X) CH₃, CH₂= CHC
(X) (CH₃)₂, CH₂= CHC (H) (X) C₂
H₅, CH₂= CHC (H) (X) CH (CH₃)₂,
CH₂= CHC (H) (X) C₆H₅, CH₂= CHC
(H) (X) CH₂C₆H₅, CH₂= CHCH₂C
(H) (X) -CO₂R, CH₂= CH (CH₂)₂C
(H) (X) -CO₂R, CH₂= CH (CH ₂)₃C
(H) (X) -CO₂R, CH₂= CH (CH₂)₈C
(H) (X) -CO₂R, CH₂= CHCH₂C (H)
(X) -C₆H₅, CH₂= CH (CH ₂)₂C (H)
(X) -C₆H₅, CH₂= CH (CH₂)₃C (H)
(X) -C₆H₅(In the above formulas, X represents chlorine, bromine, or iodine.
And R represents an alkyl group having 1 to 20 carbon atoms, an aryl group,
Aralkyl group) and the like.

Specific examples of the sulfonyl halide compound having an alkenyl group include: o-, m-, p-CH ₂ ＣＨCH— (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 formula mentioned above, X is chlorine, bromine or iodine, n represents an integer of 0 to 20) or the like.

In the case of an initiator having an alkenyl group, it is necessary to pay attention to the polymerization conditions and the reaction conditions with the olefin compound to be added since the alkenyl group of the initiator may also react with the polymerization terminal. A specific example is that an olefin compound is added at an early stage of polymerization.

Organic halide having a crosslinkable silyl group
Is not particularly limited, for example, the structure represented by the general formula 3
Are exemplified. R¹¹R¹²C (X) -R¹³-R¹⁴-C (H) (R⁶) CH₂− [Si (R ¹⁶ )_2-b(Y)_bO]_m-Si (R¹⁷)_3-a(Y)_a (3) (where R⁶, R¹¹, R¹², R¹³, R¹⁴, R
¹⁶, R¹⁷, A, b, m, X and Y are the same as described above)

If the compound of the general formula 3 is specifically exemplified,
XCH₂C (O) O (CH₂)_nSi (OCH₃)₃,
CH₃C (H) (X) C (O) O (CH₂)_nSi (O
CH₃)₃, (CH₃)₂C (X) C (O) O (C
H₂)_nSi (OCH₃)₃, XCH₂C (O) O (C
H₂)_nSi (CH₃) (OCH₃)₂, CH₃C
(H) (X) C (O) O (CH₂)_nSi (CH₃)
(OCH₃)₂, (CH₃)₂C (X) C (O) O (C
H₂)_nSi (CH₃) (OCH₃)₂(In each of the above formulas, X is chlorine, bromine, iodine, and n is
An integer from 0 to 20, XCH₂C (O) O (CH₂)_nO (CH₂)_mSi
(OCH₃)₃, H₃CC (H) (X) C (O) O (C
H₂)_nO (CH₂)_mSi (OCH₃)₃, (H
₃C)₂C (X) C (O) O (CH₂)_nO (CH₂)
_mSi (OCH₃)₃, CH₃CH₂C (H) (X) C
(O) O (CH₂)_nO (CH₂)_mSi (OCH₃)
₃, XCH₂C (O) O (CH₂)_nO (CH₂)_mS
i (CH₃) (OCH₃)₂, H₃CC (H) (X) C
(O) O (CH₂)_nO (CH₂)_m-Si (CH₃)
(OCH₃)₂, (H₃C)₂C (X) C (O) O (C
H₂)_nO (CH₂)_m-Si (CH₃) (OCH₃)
₂, CH₃CH₂C (H) (X) C (O) O (CH₂)
_nO (CH₂)_m-Si (CH₃) (OCH₃)₂(In each of the above formulas, X is chlorine, bromine, iodine, and n is
An integer of 1 to 20, m is an integer of 0 to 20)

O, m, p-XCH₂-C₆H₄− (CH
₂)₂Si (OCH₃)₃, O, m, p-CH₃C
(H) (X) -C₆H₄− (CH₂)₂Si (OC
H₃)₃, O, m, p-CH₃CH₂C (H) (X)-
C₆H₄− (CH₂)₂Si (OCH₃)₃, O, m,
p-XCH₂-C₆H₄− (CH₂)₃Si (OC
H₃)₃, O, m, p-CH₃C (H) (X) -C₆H
₄− (CH₂)₃Si (OCH₃)₃, O, m, p-C
H₃CH₂C (H) (X) -C₆H₄− (CH₂)₃S
i (OCH₃)₃, O, m, p-XCH₂-C₆H₄−
(CH₂)₂-O- (CH₂) ₃Si (OCH₃)₃,
o, m, p-CH₃C (H) (X) -C₆H₄− (CH
₂)₂-O- (CH₂)₃Si (OCH₃)₃, O,
m, p-CH₃CH₂C (H) (X) -C₆H₄− (C
H₂)₂-O- (CH₂)₃Si (OCH₃)₃, O,
m, p-XCH₂-C₆H₄-O- (CH₂)₃Si
(OCH₃)₃, O, m, p-CH₃C (H) (X)-
C₆H₄-O- (CH₂)₃Si (OCH₃) ₃, O,
m, p-CH₃CH₂C (H) (X) -C₆H₄-O-
(CH₂)₃-Si (OCH₃)₃, O, m, p-XC
H₂-C₆H₄-O- (CH₂)₂-O- (CH₂)₃
-Si (OCH₃)₃, O, m, p-CH₃C (H)
(X) -C ₆H₄-O- (CH₂)₂-O- (CH₂)
₃Si (OCH₃)₃, O, m, p-CH₃CH₂C
(H) (X) -C₆H₄-O- (CH₂)₂-O- (C
H₂) ₃Si (OCH₃)₃(In the above formulas, X represents chlorine, bromine, or iodine.
Element) and the like.

Organic halide having a crosslinkable silyl group
Further has a structure represented by the general formula 4.
Is exemplified. (R¹⁷)_3-a(Y)_aSi- [OSi (R¹⁶)_2-b(Y)_b]_m-CH ₂ -C (H) (R⁶) -R¹⁴-C (R¹¹) (X) -R^Fifteen-R¹² (4) (where R⁶, R¹¹, R¹², R¹⁴, R^Fifteen, R
¹⁶, R¹⁷, A, b, m, X and Y are the same as described above)

If such compounds are specifically exemplified,
If (CH₃O)₃SiCH₂CH₂C (H) (X) C₆H
₅, (CH₃O)₂(CH₃) SiCH₂CH₂C
(H) (X) C₆H₅, (CH₃O)₃Si (CH₂)
₂C (H) (X) -CO₂R, (CH₃O)₂(C
H₃) Si (CH₂)₂C (H) (X) -CO₂R,
(CH₃O)₃Si (CH₂)₃C (H) (X) -CO
₂R, (CH₃O)₂(CH₃) Si (CH₂)₃C
(H) (X) -CO₂R, (CH₃O)₃Si (C
H₂)₄C (H) (X) -CO₂R, (CH₃O)
₂(CH₃) Si (CH₂)₄C (H) (X) -CO₂
R, (CH₃O)₃Si (CH₂)₉C (H) (X)-
CO₂R, (CH₃O)₂(CH₃) Si (CH₂)₉
C (H) (X) -CO₂R, (CH₃O)₃Si (CH
₂)₃C (H) (X) -C₆H₅, (CH₃O)₂(C
H₃) Si (CH₂)₃C (H) (X) -C ₆H₅,
(CH₃O)₃Si (CH₂)₄C (H) (X) -C₆
H₅, (CH₃O)₂(CH₃) Si (CH₂)₄C
(H) (X) -C₆H₅(In the above formulas, X represents chlorine, bromine, or iodine.
And R represents an alkyl group having 1 to 20 carbon atoms, an aryl group,
Aralkyl group) and the like.

An organic halide having a hydroxyl group,
Alternatively, 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,
An aryl group, an aralkyl group, and n is an integer of 1 to 20)

The organic halide having an amino group or the sulfonyl halide compound is not particularly limited, and examples thereof include the following. H ₂ N- _{(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 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 an epoxy group or the sulfonyl halide compound is not particularly limited, and examples thereof include the following.

[0062]

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(In 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) in order to obtain a vinyl polymer having two or more functional groups in one molecule. Is an organic halide having two or more starting points or a sulfonyl halide compound is used as an initiator. To give a concrete example,

[0064]

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[0065]

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And the like. The radically polymerizable vinyl monomer used in this polymerization is not particularly limited, and various types can be used. Further, since the polymerization system shown here is living polymerization, it is possible to produce a block copolymer by successive addition of a polymerizable monomer. 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, (meth) ) -Tert-butyl acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, n-heptyl (meth) acrylate, (meth) acrylic acid -N-octyl, (meth)
2-ethylhexyl acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, phenyl (meth) acrylate, toluyl (meth) acrylate, benzyl (meth) acrylate, ( 2-methoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, 2- (meth) acrylate
Hydroxyethyl, 2-hydroxypropyl (meth) acrylate, stearyl (meth) acrylate, (meth)
Glycidyl acrylate, 2-aminoethyl (meth) acrylate, γ- (methacryloyloxypropyl) trimethoxysilane, ethylene oxide adduct of (meth) acrylic acid, trifluoromethylmethyl (meth) acrylate, (meth) acryl 2-trifluoromethylethyl acrylate, 2-perfluoroethylethyl (meth) acrylate, 2-perfluoroethyl-2- (meth) acrylate
Perfluorobutylethyl, 2-perfluoroethyl (meth) acrylate, perfluoromethyl (meth) acrylate, diperfluoromethylmethyl (meth) acrylate, 2-perfluoromethyl-2- (meth) acrylate
(Meth) acrylic monomers such as perfluoroethylmethyl, 2-perfluorohexylethyl (meth) acrylate, 2-perfluorodecylethyl (meth) acrylate, 2-perfluorohexadecylethyl (meth) acrylate Styrene monomers such as styrene, vinyltoluene, α-methylstyrene, chlorostyrene, styrenesulfonic acid and salts; fluorine-containing vinyl monomers such as perfluoroethylene, perfluoropropylene, and vinylidene fluoride; vinyltrimethoxysilane, vinyltrimethoxysilane Silicon-containing vinyl monomers such as ethoxysilane; maleic anhydride, maleic acid, monoalkyl and dialkyl esters of maleic acid; fumaric acid, monoalkyl and dialkyl esters of fumaric acid; maleimide, methyl maleate , Maleimide monomers such as ethylmaleimide, propylmaleimide, butylmaleimide, 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 esters such as vinyl acetate, vinyl propionate, vinyl pivalate, vinyl benzoate and vinyl cinnamate; alkenes such as ethylene and propylene; vinyl chloride, vinylidene chloride and chloride Allyl, allyl alcohol and the like can be mentioned, and these may be used alone or a plurality may be copolymerized. Of these, styrene-based monomers and (meth) acrylic monomers are preferred from the viewpoint of the physical properties of the product, and acrylate esters are preferred because of the high reactivity of the functional group introduction reaction and the low glass transition point of the present invention. Based monomers are preferred,
Particularly, butyl acrylate is preferred.

The polymerization can be carried out without solvent or in various solvents. These are not particularly limited, but, for example, hydrocarbon solvents such as benzene and toluene; ether solvents such as diethyl ether and tetrahydrofuran;
Halogenated hydrocarbon solvents such as methylene chloride and chloroform; ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone; methanol, ethanol,
Alcohol solvents such as 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 propylene carbonate And a mixture of two or more of them. The polymerization can be carried out at room temperature to 200 ° C., preferably at 50 to 150 ° C.

During the polymerization and at the end of the polymerization, when the compound (I) having a functional group and an internal alkenyl group is added, almost one compound is added to each terminal via the alkenyl group. The functional group of (I) is introduced into the terminal of the polymer. The term "end point of the polymerization" as used herein means the time when preferably 80% or more of the monomer has reacted, more preferably 90% or more, particularly preferably 95% or more, and particularly preferably 99% or more.

The amount of the compound (I) to be added is not particularly limited. Since the reactivity of the alkenyl group of these compounds is not very high, it is preferable to increase the amount added in order to increase the reaction rate. On the other hand, in order to reduce the cost, the amount added is equal to the growth terminal. It is preferable to be closer, and it is necessary to optimize it according to the situation.

When a compound having two or more alkenyl groups including an internal alkenyl group is used as compound (I) in order to introduce an alkenyl group at the terminal, an excess amount may be added to the polymerization growth terminal. preferable. In the case of an equal amount or a smaller amount than the terminal, both of the two alkenyl groups may react and may couple the polymerization terminal. In the case of a compound in which two alkenyl groups have the same reactivity, the probability of the occurrence of coupling is statistically determined according to the amount added in excess. Therefore, it is preferably at least 1.5 times, more preferably at least 3 times, particularly preferably at least 5 times.

The first aspect of the present invention is a vinyl polymer having a functional group at a molecular chain terminal, which can be obtained by the above production method. The terminal functional group is introduced by adding an alkenyl group to a growing terminal in living radical polymerization of a vinyl polymer. Therefore, the vinyl polymer having a functional group at the end of the molecular chain has almost one functional group per one terminal of the polymer by only direct carbon-carbon bond without intervening a hetero atom in the molecular chain. It is characterized by being connected.

The number of terminal groups contained in one molecule of the polymer is not particularly limited, but when it is used in a curable composition or the like, it is preferable that two or more are contained. The polymer of the present invention has a molecular weight distribution, that is, a ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) measured by gel permeation chromatography of preferably 1.8 or less, It is more preferably 1.6 or less, most preferably 1.3 or less.

The polymer of the present invention has a number average molecular weight of 500 to 500.
The range of 100,000 is preferable, and 3000 to 40,000
Is more preferred. When the molecular weight is 500 or less, it is difficult for the vinyl polymer to exhibit its original properties,
If it is more than 0000, handling becomes difficult.

The polymer produced in the present invention may be used as it is, or may be converted to another functional group by further performing a conversion reaction. Specifically, an alkenyl group can be converted to a crosslinkable silyl group by a hydrosilylation reaction with a hydrosilane compound having a crosslinkable silyl group. As the vinyl polymer having an alkenyl group at the terminal, any of those obtained by the method described above can be suitably used.

The hydrosilane compound is not particularly limited.
However, a typical example is a compound represented by the general formula 5
Things are illustrated. H- [Si (R¹⁹)_2-b(Y)_bO]_m-Si (R²⁰)_3-a(Y)_a (5) (where R¹⁹, R²⁰Has 1 to 20 carbon atoms
Alkyl group, aryl group having 6 to 20 carbon atoms, 7 to 7 carbon atoms
20 aralkyl groups, or (R ′)₃SiO- (R '
Is a monovalent hydrocarbon group having 1 to 20 carbon atoms,
R 'may be the same or different.
A triorganosiloxy group represented by ¹⁹Or R
²⁰When two or more are present, even if they are the same
Well, they can be different. Y is hydroxyl group or hydrolysis
And when Y is two or more, they are the same
May be present or different. a is 0, 1, 2,
Or 3 and b represents 0, 1, or 2. m is
It is an integer of 0 to 19. However, a + mb ≧ 1
And satisfy)

The hydrolyzable group represented by Y is
There is no particular limitation, and conventionally known ones can be used,
Specifically, hydrogen, a halogen atom, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amide group,
Examples thereof include an acid amide group, an aminooxy group, a mercapto group, and an alkenyloxy group, and an alkoxy group is particularly preferable because of its mild hydrolyzability and easy handling. The hydrolyzable group or hydroxyl group is one to one silicon atom.
Bonding is possible in three ranges, and the sum of a + mb, that is, the sum of the hydrolyzable groups is preferably in the range of 1 to 5.
When two or more hydrolyzable groups or hydroxyl groups are bonded to the reactive silicon group, they may be the same or different. The silicon atom constituting the crosslinkable silicon compound is
The number may be one or two or more, but in the case of silicon atoms linked by a siloxane bond, the number may be up to about 20.

Specific examples of R ¹⁹ and R ²⁰ in the general formula 5 include, for example, an alkyl group such as a methyl group and an ethyl group, a cycloalkyl group such as a cyclohexyl group, an aryl group such as a phenyl group, and an aralkyl group such as a benzyl group. Group,
(R ′) ₃ SiO wherein R ′ is a methyl group, a phenyl group, etc.
And a triorganosilyl group represented by-.

Among these hydrosilane compounds, particularly
General formula 6 H-Si (R²⁰)_3-a(Y)_a (6) (where R²⁰, Y and a are the same as above. )
Is hydrosilane compound with bridging group easily available?
Are preferred. Having a crosslinkable group represented by the general formula 5 or 6
HSiCl is a specific example of the hydrosilane compound₃, HSi (CH₃) Cl₂, HSi (CH
₃)₂Cl, HSi (OCH₃)₃, HSi (CH₃)
(OCH₃)₂, HSi (CH₃)₂OCH₃, HSi
(OC₂H₅)₃, HSi (CH₃) (OC
₂H₅)₂, HSi (CH₃)₂OC₂H₅, HSi
(OC₃H₇)₃, HSi (C₂H₅) (OC
H₃)₂, HSi (C₂H₅)₂OCH₃, HSi (C
₆H₅) (OCH₃)₂, HSi (C₆H₅)₂(OC
H₃), HSi (CH₃) (OC (O) CH₃)₂, H
Si (CH₃)₂O- [Si (CH₃)₂O]₂-Si
(CH₃) (OCH₃)₂, HSi (CH₃) [ON
= C (CH₃)₂]₂  (However, in the above chemical formula, C₆H₅Represents a phenyl group
And the like).

When such a hydrosilane compound having a crosslinkable silyl group is added to a vinyl polymer having an alkenyl group at a terminal, a hydrosilylation catalyst is used. Examples of such a hydrosilylation catalyst include a radical initiator such as an organic peroxide and an azo compound, and a transition metal catalyst.

The radical initiator is not particularly limited, and various types can be used. For example,
t-butyl peroxide, 2,5-dimethyl-2,5-
Di (t-butylperoxy) hexane, 2,5-dimethyl-2,5-di (t-butylperoxy) -3-hexyne, dicumyl peroxide, t-butylcumyl peroxide, α, α′-bis (t Dialkyl peroxides such as -butylperoxy) isopropylbenzene, benzoyl peroxide, p-chlorobenzoyl peroxide, m-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, diacyl peroxides such as lauroyl peroxide, t-butyl perbenzoate Peroxy dicarbonate such as diisopropyl percarbonate, di-2-ethylhexyl percarbonate, 1,1-di (t-butylperoxy) cyclohexane, 1,1-di (t -Butyl peroxy)-
And peroxyketals such as 3,3,5-trimethylcyclohexane.

Examples of the transition metal catalyst include a platinum solid, a dispersion of platinum solid in a carrier such as alumina, silica and carbon black, chloroplatinic acid, chloroplatinic acid and alcohol, aldehyde, and the like. Complexes with ketones, platinum-
An olefin complex and a platinum (0) -divinyltetramethyldisiloxane complex are exemplified. Examples of catalysts other than platinum compounds include RhCl (PPh ₃ ) ₃ , RhCl ₃ ,
uCl ₃ , IrCl ₃ , FeCl ₃ , AlCl ₃ , Pd
Cl ₂ · H ₂ O, NiCl ₂ , TiCl _{4 and the} like. These catalysts may be used alone or in combination of two or more. The amount of the catalyst is not particularly limited, but may be 10 ^-1 based on 1 mol of the alkenyl group in the polymer.
It may employed in the range of to 10 ^-8 mol, and it is preferably employed in the range of ¹⁰ -3 ^~10 -6 mol. 1
If the amount is less than ^0-8 mol, curing does not sufficiently proceed. Also, since the hydrosilylation catalyst is expensive, 10 ^-1 mol
It is preferable not to use the above.

The hydroxyl group at the terminal of the molecular chain can be converted to an alkenyl group by a condensation reaction with an allyl chloride or allyl bromide using an alkaline compound. Further, it can be converted to an epoxy group by a similar reaction using epichlorohydrin. Furthermore, the hydroxyl group or amino group at the terminal of the molecular chain can be converted into a crosslinkable silyl group by reaction with a compound having a functional group capable of reacting with the hydroxyl group or amino group and a crosslinkable silyl group. Examples of the functional group that reacts with a hydroxyl group or an amino group include a halogen, a carboxylic acid halide, a carboxylic acid, and an isocyanate group. Isocyanate groups are preferred in that the decomposition of the reactive silyl group hardly occurs.

Such an isoform having a crosslinkable silyl group
There is no particular limitation on the cyanate-based compound, and any known compounds may be used.
Can be used. To show a specific example, (CH₃O)₃Si- (CH₂)_n-NCO, (CH₃
O)₂(CH₃) Si- (CH₂)_n-NCO, (C₂
H₅O)₃Si- (CH₂)_n-NCO, (C₂H
₅O)₂(CH₃) Si- (CH₂)_n-NCO, (i
-C₃H₇O)₃Si- (CH₂)_n-NCO, (i-
C₃H₇O)₂(CH₃) Si- (CH₂)_n-NC
O, (CH₃O)₃Si- (CH₂)_n-NH- (CH
₂)_m-NCO, (CH₃O)₂(CH₃) Si- (C
H₂)_n-NH- (CH₂)_m-NCO, (C₂H
₅O)₃Si- (CH₂)_n-NH- (CH₂)_m-N
CO, (C₂H ₅O)₂(CH₃) Si- (CH₂)_n
-NH- (CH₂)_m-NCO, (i-C₃H₇O)₃
Si- (CH₂)_n-NH- (CH₂)_m-NCO,
(I-C₃H₇O)₂(CH₃) Si- (CH₂)_n−
NH- (CH₂)_m—NCO, (where n and m are integers of 1 to 20) and the like.
You.

A vinyl polymer having a hydroxyl group at a terminal,
The reaction of the isocyanate compound having a crosslinkable silyl group can be performed without a solvent or in various solvents, and the reaction temperature is 0 ° C to 100 ° C, preferably 20 ° C to 50 ° C.
° C. In this case, a tin catalyst or a tertiary amine catalyst exemplified above to promote the reaction between the hydroxyl group and the isocyanate group can be used.

Further, a first aspect of the present invention is a curable composition containing the above-mentioned vinyl polymer having a functional group at a molecular chain terminal and utilizing various crosslinking reactions. The polymer having an alkenyl group at the terminal is (A) a polymer having an alkenyl group,
(B) a compound having at least two hydrosilyl groups,
And a curable composition containing

The vinyl polymer having an alkenyl group at the terminal of the component (A) may be used alone or as a mixture of two or more. The molecular weight of the component (A) is not particularly limited, but is preferably in the range of 500 to 100,000, more preferably 3000 to 40000. When it is less than 500, the intrinsic properties of the vinyl polymer are hardly exhibited, and when it is more than 100,000, the viscosity or the solubility becomes extremely low, and the handling becomes difficult.

The hydrosilyl group-containing compound as the component (B) is not particularly limited, and various compounds can be used. That is, linear polysiloxanes represented by the general formula 7 or ^{_{8 R 15 3 SiO- [Si (}} R 15) 2 O] a - [Si (H) (R 16) O] b - [Si (R 16) ^{_{(R 17) O] C -SiR}} 15 3 (7) HR 15 2 SiO- [Si (R 15) 2 O] a - [Si (H) (R 16) O] b - [Si (R 16) ( R ¹⁷ ) O] _C— SiR ¹⁵ ₂ H (8) (wherein R ¹⁵ and R ¹⁶ are an alkyl group having 1 to 6 carbon atoms or a phenyl group, and R ¹⁷ is an alkyl group having 1 to 10 carbon atoms or carbon) An aralkyl group of the number 7 to 10, a is 0
≦ a ≦ 100, b is 2 ≦ b ≦ 100, C is 0 ≦ C ≦ 10
A cyclic siloxane represented by the general formula 9)

[0088]

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(Wherein R ¹⁵ and R ^{16 each} have 1 to 6 carbon atoms)
Is an alkyl group or a phenyl group, and R ¹⁷ has 1 carbon atom
An alkyl group having 10 to 10 or an aralkyl group having 7 to 10 carbon atoms, d is 0 ≦ d ≦ 8, e is 2 ≦ e ≦ 10, and f is 0 ≦ f ≦
An integer of 8 and 3 ≦ d + e + f ≦ 10) can be used.

These may be used alone or as a mixture of two or more.
May be used. Among these siloxanes,
A phenyl group from the viewpoint of compatibility with
Chain siloxane represented by general formulas 10 and 11,
Cyclic siloxanes represented by general formulas 12 and 13 are preferred. (CH₃)₃SiO- [Si (H) (CH₃) O]_g− [Si (C₆H₅)₂O]_h-Si (CH₃)₃ (10) (CH₃)₃SiO- [Si (H) (CH₃) O]_g− [Si (CH₃) ｛CH ₂ C (H) (R¹⁸) C₆H₅} O]_h-Si (CH₃)₃ (11) (where R¹⁸Is hydrogen or a methyl group, g is 2 ≦ g ≦ 1
00 and h are integers of 0 ≦ h ≦ 100, C₆H₅Is phenyl
Indicates a group)

[0091]

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Wherein R ¹⁸ is hydrogen or a methyl group;
i is 2 ≦ i ≦ 10, j is 0 ≦ j ≦ 8, and 3 ≦ i + j ≦
An integer of 10 and C ₆ H ₅ is a phenyl group) As the curing agent having at least two or more hydrosilyl groups of the component (B), further, a low molecular weight compound having two or more alkenyl groups in the molecule is A compound obtained by subjecting a hydrosilyl group-containing compound represented by any of the general formulas 7 to 13 to an addition reaction so that a part of the hydrosilyl group remains even after the reaction can also be used. Various compounds can be used as the compound having two or more alkenyl groups in the molecule. For example, 1,4-pentadiene, 1,5-hexadiene, 1,6-heptadiene,
1,7-octadiene, 1,8-nonadiene, 1,9-
Hydrocarbon compounds such as decadiene, ether compounds such as O, O'-diallylbisphenol A and 3,3'-diallylbisphenol A, diallyl phthalate, diallyl isophthalate, Ester compounds such as allyl trimellitate and tetraallyl pyromellitate; and carbonate compounds such as diethylene glycol diallyl carbonate.

The above-mentioned alkenyl group-containing compound can be slowly added dropwise to an excess amount of the hydrosilyl group-containing compound represented by the general formulas 7 to 13 in the presence of a hydrosilylation catalyst to obtain the compound. Among these compounds, the following compounds are preferred in consideration of the availability of raw materials, the ease of removal of excess siloxane, and the compatibility of the component (A) with the polymer.

[0094]

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The polymer (A) and the curing agent (B) can be mixed in any ratio, but from the viewpoint of curability, the molar ratio of the alkenyl group to the hydrosilyl group is in the range of 5 to 0.2. It is particularly preferable that the ratio be 2.5 to 0.4. When the molar ratio is 5 or more, only a cured product with insufficient curing and insufficient tackiness is obtained, and when it is less than 0.2, a large amount of active hydrosilyl groups remains in the cured product even after curing. , Cracks and voids are generated, and a uniform and strong cured product cannot be obtained.

The curing reaction between the polymer (A) and the curing agent (B) proceeds by mixing and heating the two components.
To proceed the reaction more quickly, a hydrosilylation catalyst is added. Such hydrosilylation catalysts include:
The various types already described are used.

The vinyl polymer having a crosslinkable silyl group at the terminal of the molecular chain can be used as a curable composition containing the vinyl polymer as a main component. When a vinyl polymer having a crosslinkable silyl group at the terminal is brought into contact with moisture, the vinyl polymer is three-dimensionally cured by a crosslinking reaction and cured. Since the hydrolysis rate varies depending on the temperature, humidity, and type of the hydrolyzable group, an appropriate hydrolyzable group must be selected according to the use conditions.

A condensation catalyst may be added to accelerate the curing reaction. Titanate such as tetrabutyl titanate and tetrapropyl titanate as the condensation catalyst;
Organic tin compounds such as dibutyltin dilaurate, dibutyltin maleate, dibutyltin diacetate, tin octylate, tin naphthenate; lead octylate, butylamine, octylamine, dibutylamine, monoethanolamine, diethanolamine, triethanolamine, diethylenetriamine, Triethylenetetramine, oleylamine,
Octylamine, cyclohexylamine, benzylamine, diethylaminopropylamine, xylylenediamine, triethylenediamine, guanidine, diphenylguanidine, 2,4,6-tris (dimethylaminomethyl) phenol, morpholine, N-methylmorpholine,
1,3-diazabicyclo (5,4,6) undecene-7
Amine compounds such as carboxylic acid salts thereof; low molecular weight polyamide resin obtained from excess polyamine and polybasic acid; reaction product of excess polyamine and epoxy compound; silane coupling agent having amino group, for example, γ -Aminopropyltrimethoxysilane, N- (β
One or more known silanol catalysts such as (-aminoethyl) aminopropylmethyldimethoxysilane may be used as necessary. The amount used is 0.01 to 10% by weight based on the vinyl polymer having a crosslinkable silyl group at the terminal.
It is preferred to use them. When an alkoxy group is used as the hydrolyzable group Y, it is preferable to use a curing catalyst since the curing speed is slow only with this polymer.

If a condensation catalyst is mixed with the vinyl polymer having a crosslinkable silyl group at the terminal, which is a main component, as required, and cured, a uniform cured product can be obtained. The curing condition is not particularly limited, but is generally 0 to 100 ° C, preferably 10 to 50 ° C, for about 1 hour to 1 week. The properties of the cured product depend on the main chain skeleton and molecular weight of the polymer to be used, but can be made widely from rubbery to resinous.

If a condensation catalyst is mixed with the vinyl polymer having a crosslinkable silyl group at the terminal, which is the main component, as required, and cured, a uniform cured product can be obtained. The curing condition is not particularly limited, but is generally 0 to 100 ° C, preferably 10 to 50 ° C, for about 1 hour to 1 week. The properties of the cured product depend on the main chain skeleton and molecular weight of the polymer to be used, but can be made widely from rubbery to resinous.

Further, a vinyl polymer having a hydroxyl group at a molecular chain terminal can be used as a curable composition containing the vinyl polymer as a main component. The curable composition comprises the following two components:
Essential components are (A) a vinyl polymer having a hydroxyl group at a terminal, and (B) a compound having two or more functional groups capable of reacting with a hydroxyl group. However, the polymer may have an amino group instead of a hydroxyl group.

The vinyl polymer having a hydroxyl group at the terminal of the component (A) may be used alone or in combination of two or more. The molecular weight is not particularly limited, but is 500 to 1
It is preferably in the range of 00000. If it is less than 500, the intrinsic characteristics of the vinyl polymer are hardly exhibited, and 1
If it is more than 00000, the viscosity or the solubility becomes extremely low, and handling may be difficult.

The compound having two or more functional groups capable of reacting with a hydroxyl group of the component (B) is not particularly limited. For example, a polyvalent isocyanate compound having two or more isocyanate groups in one molecule, methylol Aminoplast resins such as fluorinated melamine and its alkyl etherified product or low condensation product; polyfunctional carboxylic acid and its halide; and the like.

As the polyvalent isocyanate compound having two or more isocyanate groups in one molecule, conventionally known compounds can be used. For example, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate,
4,4'-diphenylmethane diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, meta-xylylene diisocyanate, 1,5-naphthalene diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate Isocyanate compounds such as triisocyanate such as B-45 made of oil and fat, burette polyisocyanate compound such as Sumidule N (manufactured by Sumitomo Bayer Urethane), Desmodur IL, HL (manufactured by Bayer AG), Coronate EH ( Polyisocyanate compounds having an isocyanurate ring, such as Nippon Polyurethane Industry Co., Ltd., and Sumidur L (manufactured by Sumitomo Bayer Urethane Co., Ltd.) Adduct polyisocyanate compounds, adduct polyisocyanate compounds such as Coronate HL (manufactured by Nippon Polyurethane Co., Ltd.) and the like can be mentioned. Further, a blocked isocyanate may be used. These may be used alone or in combination of two or more.

The mixing ratio of the polymer having a hydroxyl group at a terminal to the compound having two or more isocyanate groups is not particularly limited. NC
(O / OH (molar ratio)) is preferably from 0.5 to 3.0, more preferably from 0.8 to 2.0.

A vinyl polymer having a hydroxyl group at a terminal and 2
If necessary, a known catalyst such as an organotin compound or a tertiary amine may be added in order to accelerate the curing reaction with a compound having two or more isocyanate groups.

Specific examples of the organotin compound include tin octylate, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin mercaptide, dibutyltin thiocarboxylate, dibutyltin dimaleate, and dioctyltin thiocarboxylate. As the tertiary amine catalyst, triethylamine,
N, N-dimethylcyclohexylamine, N, N,
N ′, N′-tetramethylethylenediamine, N, N,
N ′, N′-tetramethylpropane 1,3-diamine,
N, N, N ', N'-tetramethylhexane 1,6-diamine, N, N, N', N ", N" -pentamethyldiethylenetriamine, N, N, N ', N ", N ''
-Pentamethyldipropylenetriamine, tetramethylguanidine, triethylenediamine, N, N'-dimethylpiperazine, N-methylmorpholine, 1,2-dimethylimidazole, dimethylaminoethanol, dimethylaminoethoxyethanol, N, N, N'- Trimethylaminoethylethanolamine, N-methyl-N'-
(2-Hydroxyethyl) piperazine, N- (2-hydroxyethyl) morpholine, bis (2-dimethylaminoethyl) ether, ethylene glycol bis (3-dimethyl) aminopropyl ether and the like are exemplified.

The aminoplast resin used in the curable composition of the present invention is not particularly limited, and may be an addition reaction product of melamine and formaldehyde (a methylol compound), a low-condensation product of melamine and formaldehyde, or an alkyl etherified product thereof. And urea resins. These may be used alone or in combination of two or more. For the purpose of accelerating the curing reaction of the aminoplast resin with the (meth) acrylic polymer having a hydroxyl group at a terminal, a known catalyst such as paratoluenesulfonic acid or benzenesulfonic acid may be added.

In the curable composition of the present invention, 1
The compound having two or more carboxyl groups in the molecule is not particularly limited, for example, oxalic acid, malonic acid,
Polyfunctional carboxylic acids or anhydrides such as succinic acid, glutaric acid, adipic acid, phthalic acid, phthalic anhydride, terephthalic acid, trimellitic acid, pyromellitic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, and,
These halides may be used, and these may be used alone or in combination of two or more.

If the two components (A) and (B) of the present invention and, if necessary, a curing catalyst are mixed and cured, a uniform cured product having excellent deep curability can be obtained. The curing conditions are not particularly limited, but are generally 0 ° C to 100 ° C, preferably 20 ° C to 80 ° C.

The properties of the cured product depend on the main chain skeleton and molecular weight of the polymer of the component (A) and the curing agent of the component (B). it can.

Further, the polymer having an epoxy group at the terminal of the molecular chain can be made into a curable composition containing (A) a polymer having an epoxy group at a terminal and (B) a curing agent for an epoxy resin. (B) Various curing agents can be used.
Examples include aliphatic amines, aromatic amines, acid anhydrides, urea, melamine, and phenolic resins.

The specific uses of the cured product obtained from the composition of the present invention as described above include sealing materials,
Adhesives, adhesives, elastic adhesives, paints, powder coatings, foams, potting materials for electric and electronic devices, films, molding materials,
Artificial marble and the like.

Next, the second present invention will be described. In the second invention, in the living radical polymerization of a radical polymerizable vinyl monomer, the conjugated polyene compound (II)
Is added, a reaction between the polymer growth terminal and the conjugated polyene structure results in a functional group derived from the compound (II) (an alkenyl group after the reaction of the conjugated polyene structure, and a compound (I)
When I) has a functional group other than the conjugated polyene structure, the functional group) is introduced into the molecular chain terminal of the polymer, whereby a vinyl polymer having a functional group at the molecular chain terminal can be produced. In the second aspect of the present invention, almost one compound (II) can be reacted with one molecular chain terminal.
An end-functionalized vinyl polymer with a very controlled structure can be obtained. Further, since the vinyl polymer has a functional group bonded to the main chain via a carbon-carbon bond, it is very stable in terms of weather resistance and the like.

The conjugated polyene structure in the conjugated polyene compound (II) is not particularly limited, but the following are exemplified. _{CH 2 = CH-CH = CH-} , CH 2 = C (CH 3) -
_{CH = CH-, CH 2 = CH} -C (CH 3) = CH-,
_{CH 2 = CH-CH = C} (CH 3) -, R'-C
(R ″) = C (R ¹ ) −C (R ² ) = C (R ³ ) −, C
_{H 2 = CH-CH = CH} -CH = CH-,

[0116]

Embedded image

(Wherein R ′, R ″, R ¹ , R ² and R ³ are a hydrogen atom or an organic group having 1 to 20 carbon atoms, preferably a hydrocarbon group, which may be the same or different, They may combine with each other to form a ring structure.)

R ', R ", R¹, R², R³Examples of
Although not particularly limited, the following are exemplified.
You. − (CH₂)_n-CH₃, -CH (CH₃)-(C
H₂)_n-CH₃, -CH (CH₂CH₃)-(C
H₂)_n-CH₃, -CH (CH₂CH₃)₂, -C
(CH₃)₂− (CH₂)_n-CH₃, -C (CH₃)
(CH₂CH₃)-(CH₂)_n-CH₃, -C
₆H₅, -C₆H₅(CH₃), -C₆H₅(CH₃)
₂,-(CH₂)_n-C₆H₅,-(CH₂)_n-C₆
H₅(CH₃),-(CH₂)_n-C₆H₅(CH₃)
₂  (N is an integer of 0 or more, and the total carbon number of each group is 20 or less)

Among these, the conjugated polyene structure is preferably a conjugated diene structure from the viewpoint of availability. The conjugated polyene compound (II) may be a compound having only a conjugated polyene structure or a compound having a conjugated polyene structure and another functional group. In the case of a compound having only a conjugated polyene structure, the functional group introduced to the molecular chain terminal of the polymer is an alkenyl group. In the case of a compound having a conjugated polyene structure and another functional group,
The functional groups to be introduced are an alkenyl group and the other functional groups described above.

The functional group introduced into the terminal of the molecular chain of the polymer is not particularly limited, but is preferably a hydroxyl group, an amino group, an epoxy group, a carboxylic acid group, an ester group, an ether group, an amide group, a crosslinkable silyl group. And terminal or internal alkenyl groups. More preferably, a hydroxyl group,
An amino group, an epoxy group, a crosslinkable silyl group, and a terminal or internal alkenyl group, particularly preferably a terminal or internal alkenyl group. When the compound (II) has a terminal or internal alkenyl group other than the conjugated polyene structure, the compound and the conjugated polyene structure are not conjugated.

When the functional group of the compound (II) is a functional group such as an amino group, a hydroxyl group or a carboxylic acid group, which may affect the polymerization growth terminal or the catalyst, such a functional group is used. Those protected by a general protecting group can be used. Suitable protecting groups include acetyl, silyl, alkoxy and the like. The conjugated polyene compound (II) is not particularly limited, but specific examples include the following.

[0122]

Embedded image

(R is a hydrogen atom or an organic group having 1 to 20 carbon atoms.) In particular, isoprene, piperylene and butadiene are preferred from the viewpoint of the balance between reactivity and availability.

The living radical polymerization and the polymerization conditions applied to the second present invention and the radical polymerizable vinyl monomer used are the same as those described in the first present invention.

In the above production method, the timing of adding the conjugated polyene compound (II) is preferably the end point of the polymerization in order to obtain a polymer having a controlled structure. Here, the end point of the polymerization is preferably about 80 mol% of all the monomers.
At the time when the above has reacted, more preferably at least 90 mol%,
More preferably, it is at the time when 95 mol% or more, particularly preferably 99 mol% or more has reacted.

The amount of the conjugated polyene compound (II) to be added is not particularly limited. By adding the same number of moles as the number of moles of the molecular chain terminal, almost one (one set) is added to each molecular chain terminal. Functional groups can be introduced.

The vinyl polymer having a functional group at the terminal of the molecular chain obtained by the above method can be obtained by using an atom transfer radical polymerization method as a living radical polymerization method.
Along with the introduced functional group, a halogen group remains at the end of the molecular chain. When such a polymer is treated with an alkaline compound, the remaining terminal halogen groups can be removed by a substitution reaction or an elimination reaction. The alkaline compound is not particularly limited, and examples thereof include inorganic compounds such as sodium hydroxide and potassium hydroxide.

The vinyl polymer obtained by the second production method of the present invention also has the above-mentioned properties,
A curable composition similar to the above can be obtained.

[0129]

EXAMPLES Specific examples of the present invention will be described below, but the present invention is not limited to the following examples.

Example 1 In a 200-mL glass reaction vessel, butyl acrylate (100.0 mL, 8
9.4 g, 697.5 mmol), cuprous bromide (375
mg, 2.62 mmol), diethyl 2,5-dibromoadipate (3.14 g, 8.72 mmol) and acetonitrile (10 mL). Heat and stir at 70 ° C, and add pentamethyldiethylenetriamine (0.18m
L, 151 mg, 0.87 mmol) was added to initiate polymerization.

After 125 minutes, 4-vinylcyclohexene (22.67 mL, 18.86 g, 174.4 mmol)
) Was added and pentamethyldiethylenetriamine was added. At this point, the polymerization rate of butyl acrylate is about 9
It was 0%. Heating and stirring at 70 ° C. was continued for 280 minutes. After treating the mixture with activated alumina, excess 4-vinylcyclohexene (boiling point 126 ° C.) was distilled off by heating under reduced pressure. ¹ H-NMR confirmed that the internal alkenyl group of 4-vinylcyclohexene was consumed, and that the polymer had a terminal alkenyl group.

Example 2 Polymerization was carried out in the same manner as in Example 1, except that 1,5-cyclooctadiene was added instead of 4-vinylcyclohexene. Processing in the same way, ¹ H-NM
By R, it was confirmed that an alkenyl group had been introduced into the polymer.

(Example 3) When methyldichlorosilane was reacted with a poly (butyl acrylate) polymer having an alkenyl group at the terminal synthesized by the same method as in Examples 1 and 2 using a platinum catalyst, hydrosilyl was obtained. Conversion proceeded, and a silyl group was introduced into the polymer terminal.

(Example 4) When water and a tin catalyst were added to a polybutyl acrylate polymer having a crosslinkable silyl group introduced into the terminal synthesized in the same manner as in Example 3, a rubber-like cured product was obtained. Obtained.

Example 5 Polymerization was carried out by atom transfer radical polymerization using butyl acrylate, cuprous bromide, diethyl 2,5-dibromoadipate, acetonitrile, and pentamethyldiethylenetriamine. At the end of the polymerization, isoprene was added. After treating the mixture with activated alumina, volatiles were distilled off by heating under reduced pressure. ¹ H-
NMR confirmed that an alkenyl group had been introduced into the polymer.

Example 6 When a polybutyl acrylate polymer having a terminal alkenyl group introduced and synthesized by the same method as in Example 1 was reacted with methyldichlorosilane using a platinum catalyst, hydrosilylation was effected. Progress proceeded, and a silyl group was introduced into the polymer terminal.

(Example 7) When water and a tin catalyst were added to a polybutyl acrylate polymer having a crosslinkable silyl group introduced into the terminal synthesized in the same manner as in Example 2, a rubber-like cured product was obtained. Obtained.

(Example 8) Introduction of alkenyl group by myrcene [0138] Cuprous bromide (0.375 g, 2.62 mmol) and acetonitrile (5.00 mL) were added to a 100 mL glass reaction vessel under a nitrogen atmosphere. The mixture was heated and stirred for 30 minutes. A solution obtained by dissolving diethyl 2,5-dibromoadipate (1.57 g, 4.36 mmol) in butyl acrylate (50.0 mL, 0.349 mol) was added thereto, and the mixture was stirred at 70 ° C. for 20 minutes. Add pentamethyldiethylenetriamine (91.0 μL, 0.437 m
mol) was added. 170 minutes after the start of polymerization, myr
Cene (3-methylene-7-methyl-1,6-octadiene) (14.8 mL, 87.2 mmol) was added and after 230 minutes pentamethyldiethylenetriamine (91.0 μL, 0.437 mmol) was added. 3
Heating was stopped after 35 minutes. At this time, the consumption rate of butyl acrylate was 90.7% according to GC measurement. After the mixture was diluted with ethyl acetate and treated with activated alumina, the volatiles were evaporated under reduced pressure by heating to obtain a pale yellow polymer.
According to GPC measurement (in terms of polystyrene) of the obtained polymer, the number average molecular weight was 10,700 and the weight average molecular weight was 126.
00, molecular weight distribution was 1.18. ¹ H-NM
R measurement revealed that the diene moiety was selectively reacting, and the alkenyl group introduction rate based on the number average molecular weight was 1.16.

[0139]

According to the present invention, the vinyl polymer having a functional group at the terminal of the molecular chain is stable since the terminal functional group is bonded to the main chain by a carbon-carbon bond, and is introduced at the terminal. Because the structure is well controlled with only one functional group,
It is useful for use in curable compositions and the like. Further, according to the production method of the present invention, a vinyl polymer having a functional group at a molecular chain terminal as described above can be produced easily and economically from easily available raw materials. Further, the vinyl polymer can provide a rubber-like cured product excellent in heat resistance and weather resistance by itself or in combination with an appropriate curing agent.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08L 101/02 C08L 101/02 (72) Inventor Tadashi Fujita 1-2, Yoshida-cho, Hyogo-ku, Kobe-shi, Hyogo Prefecture. 80 Kanebuchi Chemical Industry Co., Ltd. Functional Materials RD Center Kobe Research Center

Claims (51)

[Claims] In the living radical polymerization of a radically polymerizable vinyl monomer, a compound (I) having a functional group and an internal alkenyl group is added during or at the end of the polymerization, so that the functional group is polymerized. A method for producing a vinyl polymer having a functional group at a molecular chain terminal, which is introduced into the molecular chain terminal of the above. 2. The functional group introduced into the molecular chain terminal is a hydroxyl group, an amino group, an epoxy group, a carboxylic acid group, an ester group, an ether group, an amide group, a crosslinkable silyl group, or a terminal or internal alkenyl group. The method according to claim 1. 3. The method according to claim 2, wherein the functional group introduced into the terminal of the molecular chain is a hydroxyl group, an amino group, an epoxy group, a crosslinkable silyl group, or a terminal or internal alkenyl group. 4. The method according to claim 3, wherein the functional group introduced into the terminal of the molecular chain is a terminal or internal alkenyl group. 5. The production method according to claim 1, wherein the compound (I) is a cyclic olefin having a functional group. 6. The method according to claim 5, wherein the compound (I) is a cyclic olefin having a terminal alkenyl group or a cyclic olefin having an internal alkenyl group. 7. The method according to claim 6, wherein the compound (I) is 4-vinylcyclohexene or 1,5-cyclooctadiene. 8. The production method according to claim 1, wherein the living radical polymerization is an atom transfer radical polymerization. 9. The method according to claim 8, wherein a complex of copper, nickel, ruthenium or iron is used as the metal complex catalyst. 10. The method according to claim 9, wherein a copper complex is used as the metal complex catalyst. 11. The initiator according to claim 8, wherein an organic halide having a functional group other than the starting point or a sulfonyl halide compound having a functional group other than the starting point is used.
The production method according to any one of the above. 12. The production method according to claim 8, wherein an initiator having a plurality of starting points is used as the initiator. 13. A vinyl polymer having a functional group at a molecular chain terminal, which can be obtained by the production method according to claim 1. Description: 14. The polymer according to claim 13, wherein the vinyl polymer is a (meth) acrylate polymer. 15. The polymer according to claim 14, wherein the vinyl polymer is an acrylate polymer. 16. The polymer according to claim 15, wherein the vinyl polymer is a butyl acrylate polymer. 17. A number average molecular weight of 500 to 100,000
The polymer according to any one of claims 13 to 16, which is: 18. The method according to claim 13, wherein the value of the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) measured by gel permeation chromatography is less than 1.8. A polymer according to claim 1. 19. A method of reacting a vinyl polymer having an alkenyl group at a molecular chain terminal with a hydrosilane compound having a crosslinkable silyl group, which can be produced by the method according to any one of claims 1 to 12. A vinyl polymer having a crosslinkable silyl group at a molecular chain terminal that can be produced. 20. The method according to claim 1, 2, 3, 8, 9, 10, 1.
By reacting a compound having a functional group capable of reacting with a hydroxyl group or an amino group and a compound having a crosslinkable silyl group with a vinyl polymer having a hydroxyl group or an amino group at a molecular chain terminal, which can be produced by the method according to 1 or 12. A vinyl polymer having a crosslinkable silyl group at a molecular chain terminal that can be produced. 21. (A) a vinyl polymer having an alkenyl group at a molecular chain terminal which can be produced by the method according to any one of claims 1 to 12, and (B) having at least two hydrosilyl groups. A curable composition comprising a compound. (A) Claims 1, 2, 3, 8, 9, 1
A vinyl polymer having a hydroxyl group or an amino group at the molecular chain end, which can be produced by the method described in 0, 11 or 12, and
(B) a curable composition comprising: a compound having at least two functional groups capable of reacting with a hydroxyl group or an amino group. 23. The curable composition according to claim 22, wherein the component (B) is a polyvalent isocyanate. 24. The method of claim 1, 2, 3, 8, 9, 10, 1.
13. A curable composition comprising a vinyl polymer having a crosslinkable silyl group at a molecular chain terminal, which can be produced by the method described in 1 or 12. (A) Claims 1, 2, 3, 8, 9, 1
13. A curable composition comprising: a vinyl polymer having an epoxy group at a molecular chain terminal, which can be produced by the method described in 0, 11, or 12, and (B) a curing agent for an epoxy resin. 26. A conjugated polyene compound (II) in living radical polymerization of a radically polymerizable vinyl monomer.
To introduce a functional group derived from the compound (II) into a molecular chain terminal of the polymer,
A method for producing a vinyl polymer having a functional group at a molecular chain terminal. 27. The functional group introduced into the molecular chain terminal may be a hydroxyl group, an amino group, an epoxy group, a carboxylic acid group, an ester group, an ether group, an amide group, a crosslinkable silyl group, or a terminal or internal alkenyl group. 27. The method according to claim 26. 28. The functional group introduced into a molecular chain terminal may be a hydroxyl group, an amino group, an epoxy group, a crosslinkable silyl group, or
28. The production method according to claim 27, which is a terminal or internal alkenyl group. 29. The method according to claim 28, wherein the functional group introduced into the terminal of the molecular chain is a terminal or internal alkenyl group. 30. The conjugated polyene structure in the conjugated polyene compound (II) is a conjugated diene structure.
10. The production method according to any one of 9. 31. The method according to claim 30, wherein the conjugated polyene compound (II) is isoprene, piperylene or butadiene. 32. The production method according to claim 26, wherein the living radical polymerization is atom transfer radical polymerization. 33. As the metal complex catalyst, copper, nickel,
The method according to claim 32, wherein a ruthenium or iron complex is used. 34. The method according to claim 33, wherein a copper complex is used as the metal complex catalyst. 35. An organic halide having a functional group other than the starting point, or a sulfonyl halide compound having a functional group other than the starting point, as the initiator.
5. The production method according to any one of 4. 36. The production method according to claim 32, wherein an initiator having a plurality of starting points is used as the initiator. 37. The production method according to claim 26, wherein the conjugated polyene compound (II) is added at the end of the polymerization reaction. 38. Terminals remaining by further treating a vinyl-based polymer having a functional group at a molecular chain terminal obtained by the production method according to any one of claims 26 to 37 with an alkaline compound. A vinyl polymer having a functional group at a molecular chain terminal, which can be obtained by removing a halogen group. 39. A vinyl polymer having a functional group at a molecular chain terminal, which can be obtained by the production method according to any one of claims 26 to 38. 40. The polymer according to claim 39, wherein the vinyl polymer is a (meth) acrylate polymer. 41. The polymer according to claim 40, wherein the vinyl polymer is an acrylate polymer. 42. The polymer according to claim 41, wherein the vinyl polymer is a butyl acrylate polymer. 43. A number average molecular weight of 500 to 100,000
43. The polymer according to any one of claims 39 to 42. 44. The method according to any one of claims 39 to 43, wherein the value of the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) measured by gel permeation chromatography is less than 1.8. A polymer according to claim 1. 45. A vinyl polymer having an alkenyl group at a molecular chain terminal, which can be produced by the method according to any one of claims 26 to 38, is reacted with a hydrosilane compound having a crosslinkable silyl group. A vinyl polymer having a crosslinkable silyl group at a molecular chain terminal that can be produced. 46. The method according to claim 29,30,32,33,3.
The vinyl polymer having a hydroxyl group or an amino group at the molecular chain terminal which can be produced by the method described in 4, 35, 36, 37 or 38 has a functional group capable of reacting with a hydroxyl group or an amino group and a crosslinkable silyl group. A vinyl polymer having a crosslinkable silyl group at a molecular chain terminal, which can be produced by reacting a compound. 47. (A) a vinyl polymer having an alkenyl group at a molecular chain terminal, which can be produced by the method according to any one of claims 26 to 38, and (B) at least two hydrosilyl groups. A curable composition comprising a compound. (A) Claims 29, 30, 32, and 3
3, 34, 35, 36, 37 or 38, a vinyl polymer having a hydroxyl group or an amino group at a molecular chain terminal, and (B) a functional group capable of reacting with a hydroxyl group or an amino group. A curable composition comprising a compound having two compounds. 49. The curable composition according to claim 48, wherein the component (B) is a polyvalent isocyanate. 50. The method according to claim 29,30,32,33,3.
A curable composition comprising a vinyl polymer having a crosslinkable silyl group at a molecular chain terminal, which can be produced by the method described in 4, 35, 36, 37 or 38. (A) Claims 29, 30, 32, and 3
3. A vinyl polymer having an epoxy group at a molecular chain terminal, which can be produced by the method described in 3, 34, 35, 36, 37, or 38, and (B) a curing agent for an epoxy resin. Curable composition.