JP2001323015A - Method for purifying vinyl-based polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for removing a metal catalyst remaining in a vinyl-based polymer produced by an atom transfer radical polymerization. SOLUTION: The vinyl-based polymer produced by the atom transfer radical polymerization is brought into contact with activated carbon or an inorganic adsorbent to purify the vinyl-based polymer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a method for purifying a vinyl polymer.

[0002]

2. Description of the Related Art Living polymerization involves not only control of molecular weight and molecular weight distribution, but also block copolymer, graft copolymer,
Accurate synthesis of a wide variety of functional polymers such as star polymers and telechelic polymers is possible. In recent years, a polymerization system capable of living polymerization has been found in radical polymerization. Examples thereof include an organic halide or a sulfonyl halide compound as an initiator, groups 8 and 9 of the periodic table,
Atom transfer radical polymerization using a metal complex having a Group 10 or Group 11 element as a central metal as a catalyst is exemplified. (See, eg, Matyjaszewski et al., J. Am. Che.
m. Soc. 1995, 117, 5614, Macro
molecules 1995, 28, 7901, Sc
issue 1996, 272, 866, or Sa
Wamoto et al., Macromolecules 19
95, 28, 1721).

However, since a transition metal complex as a polymerization catalyst remains in a vinyl polymer produced by atom transfer radical polymerization, problems such as coloring of the polymer, influence on physical properties, and environmental safety arise. .

The present inventors have found that a polymer can be purified by bringing a vinyl polymer obtained by atom transfer radical polymerization into contact with an adsorbent such as aluminum silicate (JP-A-11-193307). ).

[0005]

However, the amount of the adsorbent used is relatively large, about the same weight as that of the polymer, and the load on the environment due to disposal and the increase in the purification cost due to the adsorbent may be problems. The present invention solves this problem and provides an economical and efficient method for purifying a vinyl polymer.

[0006]

The present invention provides a method for purifying a vinyl polymer produced by using atom transfer radical polymerization of a vinyl monomer using a transition metal complex as a polymerization catalyst. This is a purification method characterized by removing a metal catalyst remaining in a vinyl polymer by contacting with an activated carbon or an inorganic adsorbent.

[0007] The present invention is also the above purification method, wherein the inorganic adsorbent is a basic adsorbent.

[0008] The present invention is also the above-mentioned purification method, wherein the vinyl polymer is a (meth) acrylic polymer.

The present invention also provides the above-mentioned purification method, wherein the vinyl polymer has at least one reactive functional group in the molecule.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION Atom transfer radical polymerization in the present invention is one of living radical polymerization in which an organic halide or a sulfonyl halide compound is used as an initiator,
This is a method of radically polymerizing a vinyl monomer using a metal complex having a transition metal as a central metal as a catalyst. Specifically, for example, Matyjaszewski et al., Journal of American Chemical Society (JA)
m. Chem. Soc. ) 1995, 117, 56
14 pages, Macromolecules
ules) 1995, 28, 7901, Science 1996, 272, 866.
Page, WO96 / 30421, WO97 / 1824
No. 7, WO98 / 01480, WO98 / 4
No. 0415, or Sawamoto et al., Macromolecules 19
1995, 28, 1721, JP-A-9-208616
And JP-A-8-41117. Atom transfer radical polymerization First, atom transfer radical polymerization will be described in detail.

In the atom transfer radical polymerization, an organic halide, particularly an organic halide having a highly reactive carbon-halogen bond (for example, a carbonyl compound having a halogen at the α-position or a compound having a halogen at the benzyl position), Alternatively, a sulfonyl halide compound or the like is used as an initiator. For 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 ³ —C (H) (X) —CO ₂ R ⁴ , R ³ -C (CH ₃ )
^{_{(X) -CO 2 R 4,}} R 3 -C (H) (X) -C (O)
R ⁴ , R ³ —C (CH ₃ ) (X) —C (O) R ⁴ , wherein R ³ and R ⁴ are a hydrogen atom or an alkyl, aryl, or aralkyl group having 1 to 20 carbon atoms , X is chlorine, bromine, or iodine. R ³ —C ₆ H ₄ —SO ₂ X (In each of the above formulas, R ³ is a hydrogen atom or a carbon atom.
To 20 alkyl groups, aryl groups, or aralkyl groups, and X is chlorine, bromine, or iodine).

By performing atom transfer radical polymerization of a vinyl monomer using an organic halide or a sulfonyl halide compound as an initiator, a vinyl polymer having a terminal structure represented by the general formula (1) can be obtained. —C (R ¹ ) (R ² ) (X) (1) (wherein R ¹ and R ² each represent a group bonded to an ethylenically unsaturated group of a vinyl monomer. X represents chlorine, bromine or iodine. An organic halide or a sulfonyl halide compound having both a functional group that initiates polymerization and a specific functional group that does not initiate polymerization can be used as an initiator for atom transfer radical polymerization. In such a case, a vinyl polymer having a specific functional group at one main chain terminal and a terminal structure represented by the general formula (1) at the other main chain terminal is obtained. Examples of such a specific functional group include an alkenyl group, a crosslinkable silyl group, a hydroxyl group, an epoxy group, an amino group, and an amide group.

The organic halide having an alkenyl group is not limited, and examples thereof include those having a structure represented by the general formula (2). R ⁶ R ⁷ C (X) —R ⁸ —R ⁹ —C (R ⁵ ) ＝ CH ₂ (2) (wherein, R ⁵ is hydrogen or a methyl group, and R ⁶ and R ⁷ are hydrogen or carbon A monovalent alkyl group, an aryl group, or an aralkyl group of the formulas 1 to 20, or ones linked to each other at the other end, R ⁸ represents —C (O) O— (ester group), —C (O) — ( Keto group), or o-, m-, p
A phenylene group, R ⁹ is a direct bond, or has 1 to 2 carbon atoms;
X is a divalent organic group which may contain one or more ether bonds. X is chlorine, bromine, or iodine. Specific examples of the substituents R ⁶ and R ⁷ include hydrogen, methyl, and ethyl. , N-propyl group, isopropyl group, butyl group,
Examples include a pentyl group and a hexyl group. R ⁶ and R ⁷ may be linked at the other end to form a cyclic skeleton.

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

[0015]

Embedded image (In each formula mentioned above, X is 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 (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 , CH ₃ CH ₂ C (H) (X) C (O) O (CH ₂ ) _n O (C
H ₂ ) _m CH = CH ₂ ,

[0016]

Embedded image(In each of the above formulas, X represents chlorine, bromine, or iodine.
Prime, n is an integer of 1 to 20, m is an integer of 0 to 20) o, m, p-XCH_Two-C₆H_Four− (CH_Two)_n-CH = C
H_Two, O, m, p-CH_ThreeC (H) (X) -C₆H_Four− (CH_Two)
_n-CH = CH_Two, O, m, p-CH_ThreeCH_TwoC (H) (X) -C₆H_Four− (C
H_Two)_n-CH = CH_Two(In 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− (C
H_Two)_n-O- (CH_Two)_mCH = CH_Two(In the above formulas, X represents chlorine, bromine, or iodine.
Prime, n is an integer of 1 to 20, m is an integer of 0 to 20) o, m, p-XCH_Two-C₆H_Four-O- (CH_Two)_n-CH
= CH_Two, O, m, p-CH_ThreeC (H) (X) -C₆H_Four-O- (C
H_Two)_n-CH = CH_Two, O, m, p-CH_ThreeCH_TwoC (H) (X) -C₆H_Four-O-
(CH_Two)_n-CH = CH _Two(In 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-O- (CH_Two)_n-O-
(CH_Two)_m-CH = CH_Two, O, m, p-CH_ThreeC (H) (X) -C₆H_Four-O- (C
H_Two)_n-O- (CH_Two)_m-CH = CH_Two, O, m, p-CH_ThreeCH_TwoC (H) (X) -C₆H_Four-O-
(CH_Two)_n-O- (CH _Two)_m-CH = CH_Two(In 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) As an organic halide having an alkenyl group,
The compound represented by the general formula (3) is exemplified. H_TwoC = C (R^Five) -R⁹-C (R⁶) (X) -R^Ten-R⁷ (3) (where R^Five, R⁶, R⁷, R⁹, X is the same as above, R
^TenIs a direct bond, -C (O) O- (ester group), -C
(O)-(keto group) or o-, m-, p-phenyl
Represents a len group) R⁸Is 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^TenAs C (O) O
Group or phenylene group is not necessary
It may be a combination. R⁹Is not a direct bond,
In order to activate the halogen-halogen bond, R^TenAs C
(O) O group, C (O) group and phenylene group are preferred.

Specific examples of the compound of the general formula (3) are: CH ₂ ＣＨCHCH ₂ X, CH ₂ ＣC (CH ₃ ) CH ₂ X, CH 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 = CHC (H) (X) CH (CH 3) 2, CH 2 = CHC (H) (X) C 6 H 5, CH 2 = CHC
_{(H) (X) CH 2} C 6 H 5, CH 2 = CHCH 2 C (H) (X) -CO 2 R, CH 2 = CH (CH 2) 2 C (H) (X) -CO 2 R CH ₂ ＣＨCH (CH ₂ ) ₃ C (H) (X) —CO ₂ R, CH ₂ ＣＨCH (CH ₂ ) ₈ C (H) (X) —CO ₂ R, CH ₂ ＣＨCHCH 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 of the above formulas, X is chlorine, bromine, or iodine, and R is an alkyl group, aryl group, or aralkyl group having 1 to 20 carbon atoms).

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,), and the like.

Organic halogen having crosslinkable silyl group
The compound is not particularly limited. For example, the compound represented by the general formula (4)
One having a structure shown in FIG. R⁶R⁷C (X) -R⁸-R⁹-C (H) (R^Five) CH_Two− [Si (R¹¹)_2-b(Y)_b O]_m-Si (R¹²)_3-a(Y)_a (4) (where R^Five, R⁶, R⁷, R⁸, R⁹, X is the same as above,
R¹¹, R¹²Is an alkyl group having 1 to 20 carbon atoms,
Aryl group, aralkyl group, or (R ′)_ThreeSiO-
(R ′ is a monovalent hydrocarbon group having 1 to 20 carbon atoms,
The three R's may be the same or different
I) represents a triorganosiloxy group represented by¹¹Ma
Or R¹²When two or more exist, they are the same.
Or may be different. Y is a hydroxyl group or water
A decomposable group, and when two or more Y
They may be one or different. a is 0, 1,
2, or 3, and b represents 0, 1, or 2.
m is an integer of 0-19. Where a + mb ≧ 1
To specifically exemplify the compound of the general formula (4), XCH_TwoC (O) O (CH_Two)_nSi (OCH_Three)_Three, CH_Three
C (H) (X) C (O) O (CH_Two)_nSi (OC
H_Three)_Three, (CH_Three)_TwoC (X) C (O) O (CH_Two)_nSi
(OCH_Three)_Three, XCH_TwoC (O) O (CH_Two)_nSi (C
H_Three) (OCH_Three)_Two, CH_ThreeC (H) (X) C (O) O
(CH_Two)_nSi (CH_Three) (OCH_Three)_Two, (CH_Three)_TwoC
(X) C (O) O (CH_Two)_nSi (CH_Three) (OCH_Three)
_Two(In each of the above formulas, X is chlorine, bromine, iodine, and n is
An integer from 0 to 20, 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(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-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(In the above formulas, X represents chlorine, bromine, or iodine.
Element) and the like.

Further examples of the organic halide having a crosslinkable silyl group include those having a structure represented by the general formula (5).

(R ¹² ) _3-a (Y) _a Si— [OSi (R ¹¹ ) _2-b (Y) _b ] _m —CH ₂ —C (H) (R ⁵ ) —R ⁹ —C (R ^{6) (X) -R 10 -R} 7 (5) ( ^{wherein, R 5, R 7, R} 8, R 9, R 10, R 11, R 12, a,
b, m, X, and Y are the same as above. Specific examples of such a compound include (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) -
CO 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₎ 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 the epoxy group or the sulfonyl halide compound is not particularly limited, and examples thereof include the following.

[0023]

Embedded image (In each of the above formulas, X is chlorine, bromine, or iodine, R is 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 polymer having two or more terminal structures in one molecule of the present invention, an organic halide having two or more starting points or halogen Preferably, a sulfonyl halide compound is used as the initiator. To give a concrete example,

[0024]

Embedded image

[0025]

Embedded image And the like.

The transition metal complex used as the polymerization catalyst is not particularly limited, but is preferably 7
It is a metal complex having a Group 8, 8, 9, 10, or 11 element as a central metal. More preferred are complexes of zero-valent copper, monovalent copper, divalent ruthenium, divalent iron or divalent nickel. Among them, a copper complex is preferable. Specific examples of the monovalent copper compound include:
Examples include cuprous chloride, cuprous bromide, cuprous iodide, cuprous cyanide, cuprous oxide, cuprous perchlorate and the like. When a copper compound is used, 2,2'-bipyridyl or a derivative thereof, 1,10-phenanthroline or a derivative thereof, or tetramethylethylenediamine, pentamethyldiethylenetriamine or hexamethyltris (2-aminoethyl) amine is used to increase the catalytic activity. And the like are added as ligands. In addition, a tristriphenylphosphine complex of divalent ruthenium chloride (RuCl
₂ (PPh ₃ ) ₃ ) is also suitable as a catalyst. When a ruthenium compound is used as a catalyst, aluminum alkoxides are added as an activator. Further, bistriphenylphosphine complex of divalent iron (FeCl ₂ (PP
h ₃ ) ₂ ) a divalent nickel bistriphenylphosphine complex (NiCl ₂ (PPh ₃ ) ₂ ) and a divalent nickel bistributylphosphine complex (NiBr ₂ (P
Bu ₃ ) ₂ ) is also suitable as a catalyst.

There are no particular restrictions on the vinyl monomer used in this polymerization. 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- (meth) acrylate -Hexyl, cyclohexyl (meth) acrylate, n-heptyl (meth) acrylate, n-octyl (meth) acrylate, (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 acid, 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 thereof; fluorine-containing vinyl monomers such as perfluoroethylene, perfluoropropylene and vinylidene fluoride; vinyltrimethoxysilane, vinyl Silicon-containing vinyl monomers such as triethoxysilane; maleic anhydride, maleic acid, monoalkyl and dialkyl esters of maleic acid; fumaric acid, monoalkyl and dialkyl esters of fumaric acid; maleimide, methyl ester Maleimide monomers such as imide, 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 esters such as vinyl acetate, vinyl propionate, vinyl pivalate, vinyl benzoate and vinyl cinnamate; alkenes such as ethylene and propylene; conjugated dienes such as butadiene and isoprene Kind;
Examples thereof include vinyl chloride, vinylidene chloride, allyl chloride, allyl alcohol and the like. These may be used alone or a plurality of them may be copolymerized. Among them, styrene-based monomers and (meth) acrylic-acid-based monomers are preferred from the viewpoint of the physical properties of the product. More preferred are acrylate monomers and methacrylate monomers, particularly preferred are acrylate monomers, and still more preferred is butyl acrylate. In the present invention, these preferred monomers may be copolymerized with other monomers, and may be further subjected to block copolymerization,
In that case, these preferred monomers are 40% by weight.
Preferably, it is included. In the above expression format, for example, (meth) acrylic acid means acrylic acid and / or methacrylic acid.

The polymerization reaction can be carried out without a solvent, but can be carried out in various solvents. The type of solvent is not particularly limited, and examples thereof include hydrocarbon solvents such as benzene and toluene; ether solvents such as diethyl ether, tetrahydrofuran, diphenyl ether, anisole, and dimethoxybenzene; halogenated carbon solvents such as methylene chloride, chloroform, and chlorobenzene. Hydrogen solvent; acetone,
Ketone solvents such as 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; ethyl acetate , Butyl acetate and the like; ester solvents such as ethylene carbonate and propylene carbonate; N, N-dimethylformamide;
Amide solvents such as N-dimethylacetamide and the like can be mentioned. These may be used alone or in combination of two or more. In addition, emulsion type or supercritical fluid CO ₂
Polymerization can also be carried out in a system using as a medium.

Although not limited, the polymerization is carried out at a temperature of 0 to 200 ° C.
And preferably at room temperature to 150 ° C.
Range. With respect to the vinyl polymer, the vinyl monomer constituting the main chain of the vinyl polymer of the present invention is not particularly limited, and those already exemplified can be used.

The molecular weight distribution of the vinyl polymer of the present invention, that is, the ratio of the weight average molecular weight to the number average molecular weight measured by gel permeation chromatography is not particularly limited, but is preferably less than 1.8, and is preferably less than 1.8. Is 1.7 or less, more preferably 1.6 or less,
It is more preferably at most 1.5, particularly preferably at most 1.4, most preferably at most 1.3.
In the GPC measurement in the present invention, chloroform is usually used as a mobile phase, the measurement is performed using a polystyrene gel column, and the number average molecular weight and the like can be determined in terms of polystyrene.

The number average molecular weight of the vinyl polymer of the present invention is not particularly limited, but is preferably in the range of 500 to 1,000,000, more preferably 1000 to 100,000. When the molecular weight is too low, the intrinsic properties of the vinyl polymer are hardly exhibited, and when it is too high, handling becomes difficult. Regarding the reactive functional group A vinyl polymer having a reactive functional group in the molecule can produce various functional materials by utilizing the reactivity of the functional group. For example, a vinyl polymer having at least one reactive functional group in one molecular chain is crosslinked by a vinyl polymer alone or in combination with an appropriate curing agent to give a cured product.
Further, a block copolymer, a graft copolymer, and the like can be synthesized by reacting a reactive functional group of a vinyl polymer with another polymer having a functional group capable of reacting with the reactive functional group. .

The reactive functional group is not particularly restricted but includes, for example, an alkenyl group, a hydroxyl group, an amino group and a crosslinkable silyl group.

The alkenyl group in the present invention is not limited, but is preferably one represented by the general formula (6). ^{_{H 2 C = C (R 13}} ) - (6) (. Wherein, R ¹³ represents an organic group having hydrogen or a C 1-20) In the general formula (6), R ¹³ is hydrogen or 1 carbon atoms 20
Is an organic group. The organic group having 1 to 20 carbon atoms is not particularly limited, but is preferably 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. The following groups are exemplified. _{- (CH 2) n -CH 3} , -CH (CH 3) - (CH 2) n -
_{CH 3, -CH (CH 2 CH} 3) - (CH 2) n -CH 3, -
_{CH (CH 2 CH 3) 2} , -C (CH 3) 2 - (CH 2) n -
_{CH 3, -C (CH 3)} (CH 2 CH 3) - (CH 2) n -C
_{H 3, -C 6 H 5,} -C 6 H 5 (CH 3), - C 6 H 5 (C
_{H 3) 2, - (CH} 2) n -C 6 H 5, - (CH 2) n -C 6 H 5
(CH ₃ ),-(CH ₂ ) _n -C ₆ H ₅ (CH ₃ ) ₂ (n is an integer of 0 or more, and the total number of carbon atoms of each group is 20 or less) Of these, R ¹³ is hydrogen Or a methyl group is more preferable.

Further, although not limited, it is preferable that the alkenyl group of the vinyl polymer is not activated by a carbonyl group, an alkenyl group, or an aromatic ring conjugated to the carbon-carbon double bond.

The form of bonding between the alkenyl group and the main chain of the polymer is not particularly limited, but may be bonded via a carbon-carbon bond, an ester bond, an ester bond, a carbonate bond, an amide bond, a urethane bond, or the like. preferable.

The crosslinkable silyl group of the present invention includes a compound represented by the following general formula (7):-[Si (R ¹¹ ) _2-b (Y) _b O] _m -Si (R ¹² ) _3-a (Y) _a ( 7) In the formula, R ¹¹ and R ¹² are each an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and 7 to 20 carbon atoms.
An aralkyl group, or (R ′) ₃ SiO— (R ′ is a monovalent hydrocarbon group having 1 to 20 carbon atoms, and three R ′
May be the same or different), and R ¹¹ or R ¹² is 2
When there are more than one, they may be the same or different. Y represents a hydroxyl group or a hydrolyzable group, and when two or more Ys are present, they may be the same or different. a is 0, 1, 2, or 3
And b represents 0, 1, or 2. m is 0 to 19
Is an integer. However, it is assumed that a + mb ≧ 1 is satisfied. And a group represented by｝.

Examples of the hydrolyzable group include groups generally used such as a hydrogen atom, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amide group, an aminooxy group, a mercapto group and an alkenyloxy group. Can be Among these, an alkoxy group, an amide group, and an aminooxy group are preferred, but an alkoxy group is particularly preferred because of its mild hydrolyzability and easy handling.

A hydrolyzable group or a hydroxyl group can be bonded to one silicon atom in the range of from 1 to 3, and (a + Σ
b) is preferably in the range of 1 to 5. When two or more hydrolyzable groups or hydroxyl groups are bonded to the crosslinkable silyl group, they may be the same or different. The number of silicon atoms forming a crosslinkable silyl group is one or more. In the case of silicon atoms linked by a siloxane bond or the like, the number is preferably 20 or less. In particular, a crosslinkable silyl group represented by the general formula (8) —Si (R ¹² ) _3-a (Y) _a (8) (wherein R ¹⁰ , Y and a are the same as described above) is available. Is preferred because it is easy.

When the cured product obtained by curing the vinyl polymer of the present invention is particularly required to have rubber-like properties, the molecular weight between cross-linking points which has a large effect on rubber elasticity can be increased, so that the reactive functional group can be obtained. Preferably, at least one of the groups is at the end of the molecular chain. More preferably, all the functional groups have at the molecular chain terminal. The adsorbent used in the present invention for adsorbent purification is activated carbon or an inorganic adsorbent.

Activated carbon is mostly carbonaceous carbon and has high adsorptivity. In the production method, for example, wood, lignite, peat, etc. are treated with zinc chloride, phosphoric acid, or the like as an activator and dry-distilled, or charcoal or the like is activated with steam. Usually, it is powdery or granular, and any of them can be used.

Examples of the inorganic adsorbent include those containing aluminum, magnesium, silicon or the like as a main component alone or a combination thereof. For example, silicon dioxide; magnesium oxide; silica gel; silica-alumina; aluminum silicate; activated alumina; clay-based adsorbents such as acid clay and activated clay; Dawsonite compounds; and hydrotalcite compounds.

Zeolites include natural products and synthetic products, and any of them may be used.

Silicon dioxide is known to be crystalline, amorphous, amorphous, glassy, synthetic, natural, and the like. Here, powdery silicon dioxide can be used.
As silicon dioxide, silicic acid made from clay mineral obtained by acid treatment of activated clay, Carplex BS30
4, Carplex BS304F, Carplex # 6
7. Synthetic silicic acids such as Carplex # 80 (both Shionogi Pharmaceutical Co.), but are not limited thereto.

The aluminum silicate is obtained by substituting a part of silicon of silicic acid with aluminum, and pumice, fly ash, kaolin, bentonite, activated clay, diatomaceous earth and the like are known. Among them, synthetic aluminum silicate has a large specific surface area and a high adsorption capacity. Examples of the synthetic aluminum silicate include KYOWARD 700 series (manufactured by Kyowa Chemical),
However, it is not limited to these.

The hydrotalcite compounds are made of hydrous hydroxides and carbonates of aluminum and magnesium. Synthetic products include, but are not limited to, Kyoward 500 series and Kyoward 1000 (both manufactured by Kyowa Chemical).

Among the above adsorbents, activated carbon or basic inorganic adsorbents are particularly preferred. Examples of the basic inorganic adsorbents include zeolite adsorbents and hydrotalcite compounds, which are collectively referred to as a group of hydrous aluminosilicate minerals such as activated alumina and sodium aluminum silicate. Among them, hydrotalcites Compounds are preferred.

The above adsorbents may be used alone or as a mixture of two or more. Purification with an adsorbent can be performed by bringing the vinyl polymer produced by atom transfer radical polymerization into contact with the adsorbent. When it is brought into contact with the adsorbent, it may be used without solvent or may be diluted with a solvent. A general solvent may be used as the diluting solvent. The temperature and pressure of the adsorbent treatment are not particularly limited, but are generally 0 ° C to 200 ° C at normal pressure, preferably room temperature to 1
It is better to carry out at 80 ° C. The amount of the adsorbent used is in the range of 0.1 to 500 parts by weight per 100 parts by weight of the vinyl polymer, but is more preferably 0.1 to 500 parts by weight from the viewpoint of economy and operation.
It is in the range of 5 to 10 parts by weight.

Various embodiments are possible for the solid-liquid contact between the adsorbent and the polymer or the polymer solution. A batch system in which the mixing and solid-liquid separation is carried out by a batch operation, and the adsorbent is filled in a container A fixed bed system in which a polymer solution is passed, a moving bed system in which a liquid is passed through a moving bed of an adsorbent, and a fluidized bed system in which an adsorbent is fluidized and adsorbed can be used. Furthermore, in addition to the mixing and dispersion by stirring, various operations for improving the dispersion efficiency, such as shaking of the container and the use of ultrasonic waves, can be incorporated as necessary.

After the polymer or the polymer solution is brought into contact with the adsorbent, the adsorbent is removed by filtration, centrifugation, sedimentation, or the like, and if necessary, dilution and washing are performed. Obtain a polymer solution.

In general, the purification treatment using an adsorbent may be performed on a vinyl polymer obtained by atom transfer radical polymerization, but it may be performed on a vinyl polymer having a reactive functional group obtained by modifying the polymer. On the other hand, purification treatment may be performed.

[0051]

EXAMPLES Specific examples are shown below, but the purification method is not limited to the following examples. (Production Example 1) Production method of alkenyl-terminated vinyl polymer CuBr (42.0 g, 0.953 mol) was charged into a 10-L separable flask equipped with a reflux tube and a stirrer, and the inside of the reaction vessel was purged with nitrogen. Acetonitrile (55
9 mL) and stirred in an oil bath at 70 ° C. for 45 minutes. To this, butyl acrylate (1.00 kg), 2.5
-Diethyldibromoadipate (175 g, 0.488
mol), pentamethyldiethylenetriamine (4.0
(0 mL, 19.2 mmol) (hereinafter triamine) was added to initiate the reaction. While heating and stirring at 70 ° C, butyl acrylate (4.0
0 kg) was continuously added dropwise over 190 minutes. During the dropping of butyl acrylate, triamine (4.00 mL, 1
9.2 mmol) was added. Subsequently, after heating and stirring at 70 ° C. for 60 minutes, 1,7-octadiene (1.44 L, 9.
75 mol), triamine (20.5 mL, 0.097
4 mol), and the mixture was further heated and stirred at 70 ° C. for 210 minutes.

The volatile components of the reaction mixture were distilled off under reduced pressure, dissolved in hexane, and the solid content was separated by filtration to obtain an alkenyl group-terminated polymer (polymer [1]). The polymer [1] had a number average molecular weight of 14,000 and a molecular weight distribution of 1.34 as measured by GPC (in terms of polystyrene), and the average number of alkenyl groups introduced per molecule of polymer was ¹ HN.
It was 2.5 as determined by MR analysis. (Production Example 2) Br treatment of alkenyl-terminated vinyl polymer
Method The polymer [1] (10 g) obtained in Production Example 1 and potassium benzoate (0.57 g) were charged into a reaction vessel, and N, N-dimethylacetamide (10 mL, referred to as "DMAC").
Was added and the mixture was heated and stirred at 100 ° C. for 4 hours under a nitrogen atmosphere. DMAC was evaporated under reduced pressure while heating, and toluene was added to the resulting mixture. The solid content was separated by filtration, and the filtrate was concentrated to obtain a polymer containing no bromine group (polymer [2]). (Production Example 3) Br treatment of alkenyl-terminated vinyl polymer
Method The polymer [1] (300 g) obtained in Production Example 1 and potassium acetate (6.68 g) were charged into a reaction vessel, and DMAC (30
0 mL), and the mixture was heated and stirred at 100 ° C. for 8 hours under a nitrogen atmosphere. DMAC was evaporated under reduced pressure while heating, and toluene was added to the resulting mixture. The solid content was separated by filtration, and the filtrate was concentrated to obtain a polymer containing no bromine group (polymer [3]).

Polymers [1] to [1] produced in Production Examples 1 to 3
[3] was purified using the adsorbents shown in Table 1. (Example 1) Purification of vinyl polymer by adsorbent Polymer [1] (5.0 g) was dissolved in toluene (15 mL) and activated clay (0.50 g; Galleon Earth V2,
After adding Mizusawa Chemical Co., Ltd.), the mixture was heated and stirred at 100 ° C. for 1 hour. After diluting with toluene and filtering off the adsorbent, the toluene was distilled off to obtain a vinyl polymer. The resulting polymer was mixed with ultra-high-purity nitric acid and ultra-high-purity sulfuric acid and subjected to microwave decomposition. The amount of residual copper in the decomposition product was quantified using an ICP mass spectrometer (HP-4500 manufactured by Yokogawa Analytical Systems Co., Ltd.). The results are shown in Table 2. (Examples 2 to 18) Purification of vinyl polymer using adsorbent The polymer [1] or the polymer [3] was purified by the same operation as in Example 1 to obtain a polymer. The amount of residual copper was quantified in the same manner as in Example 1. The used adsorbents and purification conditions are shown in Table 2. Comparative Example 1 The amount of copper remaining in the polymer [1] was determined in Example 1.
Quantification was performed in the same manner as described above. Table 2 shows the results. (Comparative Example 2) The amount of copper remaining in the polymer [2] was determined in Example 1.
Quantification was performed in the same manner as described above. Table 2 shows the results.

[0054]

[Table 1]

[0055]

[Table 2]

[0056]

According to the present invention, the residual metal catalyst can be removed by purifying a vinyl polymer produced by atom transfer radical polymerization with activated carbon or an inorganic adsorbent. In particular, by using activated carbon or a basic inorganic adsorbent, the amount of residual metal catalyst can be effectively reduced even with a small amount of adsorbent.

 ────────────────────────────────────────────────── ─── Continuing on the front page F-term (reference) 4J015 CA04 4J100 AA02P AA03P AB02P AB03P AB04P AB07P AB08P AC03P AC04P AC24P AC26P AC27P AD03P AG04P AG05P AG08P AJ02P AJ09P AK32P AL03P AL04P AL08PBAP AP03P02P15 BB10P BB11P BC43P BC54P CA01 FA03 FA08 GA22

Claims (12)

[Claims] 1. A method for purifying a vinyl polymer produced by atom transfer radical polymerization of a vinyl monomer using a transition metal complex as a polymerization catalyst, wherein the vinyl polymer is contacted with activated carbon or an inorganic adsorbent. A purification method, wherein the metal catalyst remaining in the vinyl polymer is removed by the reaction. 2. The purification method according to claim 1, wherein the inorganic adsorbent is a basic adsorbent. 3. The method according to claim 1, wherein the inorganic adsorbent is a hydrotalcite compound. 4. The transition metal complex according to claim 8, wherein the central metal of the transition metal complex is the eighth metal of the periodic table.
A group 1, 9, 9, or 11 element.
3. The purification method according to 3. 5. The purification method according to claim 1, wherein the central metal of the transition metal complex is iron, nickel, ruthenium or copper. 6. The method according to claim 1, wherein the central metal of the transition metal complex is copper. 7. The method according to claim 1, wherein the vinyl polymer is a (meth) acrylic polymer. 8. The purification method according to claim 1, wherein the vinyl polymer is an acrylate polymer. 9. The method according to claim 1, wherein the vinyl polymer is a butyl acrylate polymer. 10. The purification method according to claim 1, wherein the vinyl polymer has at least one reactive functional group in a molecule. 11. The purification method according to claim 10, wherein the reactive functional group is an alkenyl group, a hydroxyl group, an amino group or a crosslinkable silyl group. 12. The purification method according to claim 10, wherein the reactive functional group is present at a molecular chain terminal of the vinyl polymer.