JP2001323014A - 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 purified by using a centrifugal separator.

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, polymerization systems capable of living polymerization have been found in radical polymerization. As an example, atom transfer radical polymerization using an organic halide or a sulfonyl halide compound as an initiator and a metal complex having a central metal of Group 8, 9, 10, or 11 of the periodic table as a catalyst is known. No. (For example, Matyjasz
ewski et al. Am. Chem. Soc. 199
5,117,5614, Macromolecules
1995, 28, 7901, Science 199
6,272,866, or Sawamoto et al., M.
acromolecules 1995, 28, 172
1).

[0004]

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

[0005] As a method for removing the transition metal complex, alumina column chromatography, purification using an ion exchange resin and purification by reprecipitation have been carried out. However, none of these methods give a sufficiently pure polymer. Moreover, it is hard to say that the method is efficient. The present invention solves this problem and provides an economical and efficient method for purifying a vinyl polymer.

[0006]

SUMMARY OF THE INVENTION The present invention relates to a method for purifying a vinyl polymer produced by utilizing atom transfer radical polymerization of a vinyl monomer using a transition metal complex as a polymerization catalyst. A method for purifying a vinyl polymer, comprising separating and removing a metal catalyst remaining in the polymer based on a difference in density. To separate and remove due to the difference in density,
This refers to separating and removing the target component by utilizing the fact that the density of each component in the mixture is different.

[0007] A centrifugal separator is preferably used as the device used in the present invention for separating and removing according to the difference in density. Also,
The centrifugal separator used in the present invention is preferably a centrifuge. Further, the centrifugal sedimenter used in the present invention is preferably of a separator type.

In the present invention, it is preferable that the central metal of the transition metal complex which is the catalyst for atom transfer radical polymerization is an element belonging to Group 8, 9, 10, or 11 of the periodic table. Further, in the present invention, the vinyl polymer is preferably a (meth) acrylic polymer.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, 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 includes a centrifugal separator and the like. The metal catalyst remaining in the vinyl polymer is removed using an apparatus that separates the catalysts based on the difference in density. The 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, and a vinyl complex is radically polymerized using a metal complex having a transition metal as a central metal as a catalyst. Is the way. Specifically, 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, vol. 272, p. 866, WO 96/30
No. 421, WO97 / 18247, WO98
/ 01480, WO98 / 40415, or Sawamoto et al., Macromolecules (M
acromolecules) 1995, volume 28, 1
721 page, JP-A-9-208616, JP-A-8-208
41117 and the like.

The atom transfer radical polymerization in the present invention includes so-called reverse atom transfer radical polymerization. Reverse atom transfer radical polymerization refers to a state of high oxidation when a general atom transfer radical polymerization catalyst generates radicals (for example, Cu when Cu (I) is used as a catalyst).
(II)), a general radical initiator such as a peroxide is allowed to act on the compound, and as a result, an equilibrium state similar to the atom transfer radical polymerization is produced (Macromo).
recules 1999, 32, 2872).

[0011]Atom transfer radical polymerization  First, the atom transfer radical polymerization will be described in detail. This
In atom transfer radical polymerization of organic halides, especially
Organic halogens with highly reactive carbon-halogen bonds
(For example, a carbonyl compound having a halogen at the α-position)
Or a compound having a halogen at the benzyl position)
Is when a sulfonyl halide compound or the like is used as an initiator.
It is. To give a concrete example, C₆ H_Five -CH_Two X, C₆ H_Five -C (H) (X) CH
_Three , C₆ H_Five -C (X) (CH_Three )_Two (However, in each of the above chemical formulas, C₆ H_Five Is a phenyl group, X
Is chlorine, bromine or iodine) R^Three -C (H) (X) -CO_Two R^Four , R^Three -C (CH
_Three ) (X) -CO_Two R^Four , R^Three -C (H) (X) -C
(O) R^Four , R^Three -C (CH_Three ) (X) -C (O) R
^Four , (In each formula, R^Three , R^Four Is a hydrogen atom or carbon number, respectively
1 to 20 alkyl groups, aryl groups, or aralkyl
Group, X is chlorine, bromine or iodine) R^Three -C₆ H_Four -SO_Two X (where R^Three Is a hydrogen atom or an alkyl having 1 to 20 carbon atoms
X, chlorine, odor,
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) In the formula, R ¹ and R ² each represent a group bonded to the ethylenically unsaturated group of the vinyl monomer. X represents chlorine, bromine or iodine.

As an initiator of the atom transfer radical polymerization, an organic halide or a sulfonyl halide compound having a specific functional group which does not start polymerization together with a functional group which starts polymerization can also be used. 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), R ⁵ is hydrogen or methyl, R ^6, R ⁷ are each hydrogen or a 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, wherein R ⁸ is -C (O) O- (ester group), -C (O)-( Keto group), or o-, m
-, P-phenylene group and R ⁹ may be a direct bond or a divalent organic group having 1 to 20 carbon atoms and may contain one or more ether bonds, and X represents chlorine, bromine or iodine, respectively. . Specific examples of the substituents R ⁶ and R ⁷ include hydrogen, methyl, ethyl, n-propyl, isopropyl, butyl, pentyl, and hexyl. 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 C
H = CH ₂ ,

[0015]

Embedded image

In each of the above formulas, X is chlorine, bromine, or
Or i, and n represents an integer of 0 to 20. XCH_Two C (O) O (CH_Two )_n O (CH_Two )_m CH =
CH_Two , H_Three CC (H) (X) C (O) O (CH_Two )_n O (CH
_Two )_m CH = CH_Two , (H_Three C)_Two C (X) C (O) O (CH_Two )_n O (CH
_Two )_m CH = CH_Two , CH_Three CH_Two C (H) (X) C (O) O (CH_Two )_n O
(CH_Two )_m CH = CH _Two ,

[0017]

Embedded image

In each of the above formulas, X represents chlorine, bromine,
Or iodine, n is an integer of 1 to 20, m is an integer of 0 to 20
Respectively. o, m, p-XCH_Two -C₆ H_Four − (CH_Two )_n -CH
= CH_Two , O, m, p-CH_Three C (H) (X) -C₆ H_Four − (CH
_Two )_n -CH = CH_Two , O, m, p-CH_Three CH_Two C (H) (X) -C₆ H_Four −
(CH_Two )_n -CH = CH_Two In each of the above formulas, X is chlorine, bromine, or iodine;
n represents the integer of 0-20, respectively. o, m, p-XCH_Two -C₆ H_Four − (CH_Two )_n -O-
(CH_Two )_m -CH = CH_Two , O, m, p-CH_Three C (H) (X) -C₆ H_Four − (CH
_Two )_n -O- (CH_Two ) _m -CH = CH_Two , O, m, p-CH_Three CH_Two C (H) (X) -C₆ H_Four −
(CH_Two )_n -O- (CH_Two )_m CH = CH_Two In each of the above formulas, X is chlorine, bromine, or iodine;
n represents an integer of 1 to 20; m represents an integer of 0 to 20;
You. o, m, p-XCH_Two -C₆ H_Four -O- (CH_Two )_n −
CH = CH_Two , O, m, p-CH_Three C (H) (X) -C₆ H_Four -O-
(CH_Two )_n -CH = CH _Two , O, m, p-CH_Three CH_Two C (H) (X) -C₆ H_Four −
O- (CH_Two )_n -CH = CH_Two In each of the above formulas, X is chlorine, bromine, or iodine;
n represents the integer of 0-20, respectively. o, m, p-XCH_Two -C₆ H_Four -O- (CH_Two )_n −
O- (CH_Two )_m -CH = CH_Two , O, m, p-CH_Three C (H) (X) -C₆ H_Four -O-
(CH_Two )_n -O- (CH _Two )_m -CH = CH_Two , O, m, p-CH_Three CH_Two C (H) (X) -C₆ H_Four −
O- (CH_Two )_n -O- (CH_Two )_m -CH = CH_Two In each of the above formulas, X is chlorine, bromine, or iodine;
n represents an integer of 1 to 20; m represents an integer of 0 to 20;
You.

The organic halide having an alkenyl group further includes a compound represented by the general formula (3). H ₂ C = C (R ⁵ ) -R ⁹ -C (R ⁶ ) (X) -R ¹⁰ -R ⁷ (3) In the formula, R ⁵ , R ⁶ , R ⁷ , R ⁹ and X are as defined above. the same. R ¹⁰ represents a direct bond, —C (O) O— (ester group), —C (O) — (keto group), or o—, m—,
represents a p-phenylene group. R ⁹ is a direct bond or a divalent organic group having 1 to 20 carbon atoms (which may contain one or more ether bonds).
A vinyl group is bonded to the carbon to which the halogen is bonded, and the compound is a halogenated allylic compound. In this case, the carbon by the adjacent vinyl group - because halogen bond is activated need not necessarily a C (O) O group or a phenylene group such as R ^10, or may be a direct bond. R ⁹
Is not a direct bond, R ¹⁰ is a C (O) O group, a C (O) group,
Phenylene groups are preferred.

The compound of the general formula (3) is specifically exemplified.
Then CH_Two = CHCH_Two X, CH_Two = C (CH_Three ) CH_Two X, CH_Two = CHC (H) (X) CH_Three , CH_Two = C (CH
_Three ) C (H) (X) CH _Three , CH_Two = CHC (X) (CH_Three )_Two , CH_Two = CHC
(H) (X) C_Two H_Five , CH_Two = CHC (H) (X) CH (CH_Three )_Two , CH_Two = CHC (H) (X) C₆ H_Five , CH_Two = CHC
(H) (X) CH_Two C₆H_Five , CH_Two = CHCH_Two C (H) (X) -CO_Two R, CH_Two = CH (CH_Two )_Two C (H) (X) -CO_Two R, CH_Two = CH (CH_Two )_Three C (H) (X) -CO_Two R, CH_Two = CH (CH_Two )₈ C (H) (X) -CO_Two R, CH_Two = CHCH_Two C (H) (X) -C₆ H_Five , CH_Two = CH (CH_Two )_Two C (H) (X) -C₆ H_Five , CH_Two = CH (CH_Two )_Three C (H) (X) -C₆ H_Five (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 the above formulas, X is chlorine, bromine, or iodine, and n is an integer of 0 to 20).

The organic halide having a crosslinkable silyl group is not particularly limited, and examples thereof include those having a structure represented by the general formula (4). ^{R 6 R 7 C (X)} -R 8 -R 9 -C (H) (R 5) CH 2 - [Si (R 11) 2-b (Y) b O] m -Si (R 12) 3- _a (Y) _a (4) wherein R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and X are the same as above. R ¹¹ and R ¹² each represent an alkyl group having 1 to 20 carbon atoms, an aryl group, an aralkyl group, or (R ′)
_A triorganosiloxy group represented by 3SiO- (R 'is a monovalent hydrocarbon group having 1 to 20 carbon atoms, and three R's may be the same or different). As shown, when two or more R ¹¹ or R ¹² are present, 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
Represents 0, 1, 2, or 3, and b represents 0, 1, or 2. m is an integer of 0-19. Where a + m
It is assumed that b ≧ 1 is satisfied.

The compound of the general formula (4) is specifically exemplified.
Then, XCH_Two C (O) O (CH_Two )_n Si (OCH_Three )_Three ,
CH_Three C (H) (X) C (O) O (CH_Two )_n Si (O
CH_Three )_Three , (CH_Three )_Two C (X) C (O) O (CH
_Two )_n Si (OCH_Three )_Three , XCH_Two C (O) O (CH
_Two )_n Si (CH_Three ) (OCH_Three )_Two , CH_Three C (H)
(X) C (O) O (CH_Two )_n Si (CH_Three ) (OCH
_Three )_Two , (CH_Three )_Two C (X) C (O) O (CH_Two )_n 
Si (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_Two C (O) O (CH_Two )_n O (CH_Two )_m Si
(OCH_Three )_Three , H_Three CC (H) (X) C (O) O (C
H_Two )_n O (CH_Two )_m Si (OCH_Three ) _Three , (H_Three 
C)_Two C (X) C (O) O (CH_Two )_n O (CH_Two )_m 
Si (OCH_Three ) _Three , CH_Three CH_Two C (H) (X) C
(O) O (CH_Two )_n O (CH_Two )_m Si (OCH_Three )
_Three , XCH_Two C (O) O (CH_Two )_n O (CH_Two )_m S
i (CH_Three ) (OCH_Three )_Two, H_Three CC (H) (X) C
(O) O (CH_Two )_n O (CH_Two )_m -Si (CH_Three )
(OCH_Three )_Two , (H_Three C)_Two C (X) C (O) O (C
H_Two )_n O (CH_Two )_m -Si (CH_Three ) (OCH_Three )
_Two , CH_Three CH_Two C (H) (X) C (O) O (CH_Two )
_n O (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 -C₆ H_Four − (CH
_Two )_Two Si (OCH_Three )_Three , O, m, p-CH_Three C
(H) (X) -C₆ H_Four − (CH_Two )_Two Si (OCH
_Three ) _Three , O, m, p-CH_Three CH_Two C (H) (X) -C
₆ H_Four − (CH_Two )_Two Si (OCH_Three )_Three , O, m, p
-XCH_Two -C₆ H_Four − (CH_Two )_Three Si (OCH_Three )
_Three , O, m, p-CH_Three C (H) (X) -C₆ H_Four −
(CH_Two )_Three Si (OCH_Three ) _Three , O, m, p-CH_Three 
CH_Two C (H) (X) -C₆ H_Four − (CH_Two )_Three Si
(OCH_Three )_Three , O, m, p-XCH_Two -C₆ H_Four −
(CH_Two )_Two -O- (CH_Two )_Three Si (OCH_Three )_Three ,
o, m, p-CH_Three C (H) (X) -C₆ H_Four − (CH
_Two )_Two -O- (CH_Two ) _Three Si (OCH_Three )_Three , O,
m, p-CH_Three CH_Two C (H) (X) -C₆ H_Four − (C
H_Two )_Two -O- (CH_Two )_Three Si (OCH_Three )_Three , O,
m, p-XCH_Two -C₆ H_Four -O- (CH_Two )_Three Si
(OCH_Three )_Three , O, m, p-CH_Three C (H) (X)-
C₆ H_Four -O- (CH_Two )_Three Si (OCH _Three )_Three , O,
m, p-CH_Three CH_Two C (H) (X) -C₆ H_Four -O-
(CH_Two )_Three -Si (OCH_Three )_Three , O, m, p-XC
H_Two -C₆ H_Four -O- (CH_Two )_Two -O- (CH_Two )_Three 
-Si (OCH_Three )_Three , O, m, p-CH_Three C (H)
(X) -C₆ H_Four -O- (CH_Two )_Two -O- (CH _Two )
_Three Si (OCH_Three )_Three , O, m, p-CH_Three CH_Two C
(H) (X) -C₆ H_Four -O- (CH_Two )_Two -O- (C
H_Two )_Three Si (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 6, R} 7, 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, (C
_{H 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 Si (CH
_{2) 4 C (H) (} X) -CO 2 R, (CH 3 O) 2 (C
_{H 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 (C
_{H 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 (CH ₃ ) Si (CH ₂ ) ₄ C
_{(H) (X) -C 6} H 5, ( in each formula above, X is chlorine, bromine or iodine,, R is an alkyl group having 1 to 20 carbon atoms, an aryl group, an 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) formula, X is chlorine, bromine or iodine, R represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, an aryl group , An aralkyl group, and n represents 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) n} -OC (O) C (H) (R)
(X) In the formula, X represents chlorine, bromine, or iodine, R represents a hydrogen atom or an alkyl group, an aryl group, an aralkyl group having 1 to 20 carbon atoms, and n represents an integer of 1 to 20.

An organic halide having the above epoxy group,
Alternatively, the sulfonyl halide compound is not particularly limited, and examples thereof include the following.

[0029]

Embedded image

In each of the above formulas, X represents chlorine, bromine or iodine, R represents a hydrogen atom or an alkyl, aryl, or aralkyl group having 1 to 20 carbon atoms, and n represents an integer of 1 to 20, respectively.

In order to obtain a polymer having two or more terminal structures in one molecule according to the present invention, it is preferable to use an organic halide having two or more starting points or a sulfonyl halide compound as an initiator. . To give a concrete example,

[0032]

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[0033]

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And the like.

In the present invention, the catalyst for the atom transfer radical polymerization is preferably one that is insoluble in an organic solvent, that is, a heterogeneous catalyst. The transition metal complex used as the polymerization catalyst is not particularly limited, but is preferably a metal complex having a central metal of Group 8, 9, 10, or 11 of the periodic table. More preferably,
Examples thereof include complexes of zero-valent copper, monovalent copper, divalent ruthenium, divalent iron, and divalent nickel. Among them, a copper complex is preferable. Specific examples of monovalent copper compounds include cuprous chloride, cuprous bromide, cuprous iodide, cuprous cyanide, cuprous oxide, cuprous perchlorate, and the like. is there. 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 enhance the catalytic activity. And the like are added as ligands. In addition, a tristriphenylphosphine complex of divalent ruthenium chloride (Ru
Cl 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, a bis (triphenylphosphine) complex of divalent iron (FeCl ₂ (PPh ₃ ) ₂ ) and a bis (triphenylphosphine) complex of divalent nickel (NiCl ₂ (PPh 3
₃ ) ₂ ) and divalent nickel bistributylphosphine complex (NiBr ₂ (PBu ₃ ) ₂ ) are also suitable as catalysts.

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 acid 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 may be carried out at 0-200 ° C.
And preferably at room temperature to 150 ° C.
Range.

[0040]About vinyl polymer  Vinyl Monomer Constituting Main Chain of Vinyl Polymer of the Present Invention
The marker is not particularly limited, and those already exemplified may be used.
Can be.

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. If the molecular weight is too low, the intrinsic properties of the vinyl polymer are hardly exhibited, and if it is too high, handling becomes difficult.

[0043]For removal of transition metal complex using centrifugal sedimentation machine
about  The present invention provides a vinyl-based monomer using a transition metal complex as a polymerization catalyst.
Produced using the above atom transfer radical polymerization of
In the method for purifying vinyl polymers, mainly centrifugation
Metal catalyst remaining in the vinyl polymer using a separation device
It provides a purification method for removal.

The centrifugation is a separation operation using centrifugal force instead of gravity. Since centrifugal force can be artificially increased unlike gravity, it takes much less time than in a gravitational field. Separation can be performed. Among the centrifugal separators, a centrifugal sedimenter separates using a specific gravity difference of a stock solution, and a centrifugal filter separates using a screen and a filter cloth. Regarding the specific gravity relationship between a solid and a liquid in a solid-liquid suspension, if the specific gravity of the solid exceeds the specific gravity of the liquid, a centrifugal sediment is more preferable, and the specific gravity of the solid is equal to or smaller than the specific gravity of the liquid. If less than that, a centrifugal filter is more preferable.

In the present invention, any of a centrifugal settler and a centrifugal filter can be used. However, when the specific gravity difference between the transition metal complex to be removed and the vinyl polymer to be purified is large and the specific gravity of the transition metal complex is sufficiently large,
The use of a centrifuge is preferred.

Each of the centrifuges has a bowl without a hole, but can be divided into several types according to the method of discharging solids. In the centrifuge, the solids settle on the bowl wall, and the clarified liquid is discharged over a weir provided on the side opposite to the liquid inlet. Examples of the centrifugal sedimentation machine include a cylindrical type, a skimming type, a separation plate type, and a screw decanter type. Since the skimming type generally rotates at a low speed, it has a relatively good sedimentation property, and it is necessary that the separated solid can be taken out with a skimming tube or scraped off with a knife. The decanter type has a mechanism for continuously discharging settled solid particles to the outside, and is generally used when the density difference is large and the solid particle concentration is relatively high. For the cylindrical type, a vertical axis, a high-speed rotating cylindrical bowl is hung from the upper part, the supply of undiluted solution from the lower part, the solids accumulate in the bowl, the separated liquid is discharged from the upper part,
It is a mechanism that is separated by a casing and each is taken out. It is necessary that the solid specific gravity is larger than the liquid specific gravity and the solid content is small, and the solid content is usually 1% or less as a practical range. . The separation plate type is a so-called Laval type, in which a number of umbrella-shaped separation plates are superimposed on a rotating body, and sedimentation separation is performed in a small gap between the separation plates. The centrifugal sedimentation area is larger than that of a cylindrical type and the structure is complicated, so the number of revolutions is 4000 to 10000 r.
pm.

The centrifuge used in the present invention is not limited, but is preferably a separator centrifuge. A general separator-type centrifugal settling machine will be described below, but the present invention is not limited to this. The acceleration generated by the separator centrifuge is about 15000 G at maximum, and the solid is discharged as a thick slurry. This type of bowl is 50 ~
It is composed of 150 conical thin separators.
A spacer having a thickness of 2 mm is provided between the separation plates, and the stock solution passes through the gap. The solids settle on the separating plate and move towards the edge of the plate and settle on the bowl wall. The clarified liquid collects in the center of the bowl and overflows from the bottom or top weir. A feature of the separation plate type is that a large number of umbrella-shaped separation plates are inserted into the rotating body to perform so-called thin layer separation to increase the separation efficiency. The undiluted solution is supplied into the bowl from a supply port provided above the central axis of the rotating body, and the undiluted solution is rotated at a constant speed by a distributor and supplied to the inside of the separator. The umbrella-shaped separation plates are stacked at a small interval, and each separation plate has several holes, each of which is set at the same position to form one conduction tube. The undiluted liquid flows from the lower part of the bowl to the upper part through this conduit, during which the heavy liquid and solid are near the inside of the separation plate, and the light liquid is near the outside of the separation plate. And are discharged to the casing from discharge ports provided in the heads, respectively. Separating plate type centrifugal sedimentation machines are classified into three types: disk type, nozzle type, and self-cleaning type. The separation plate type centrifugal sedimenter used in the present invention is preferably a self-cleaning type, but is not limited thereto. The self-cleaning type centrifugal sedimenter automatically discharges separated solids. In general, in many cases, operating water is supplied from the outside to move a bowl in an axial direction to discharge accumulated solids. The discharge of solids can be performed in an operating state or can be performed with the liquid supply stopped.

It is possible to use the polymer or the polymer solution as it is in the purification operation using a centrifugal sedimentation machine, but if the viscosity of the polymer is high, the polymer or the polymer solution is difficult to settle. Is preferred. The solvent to be diluted is not particularly limited, but a highly polar solvent that dissolves the transition metal catalyst is unsuitable, preferably has a relative dielectric constant at 25 ° C. of 7 or less, more preferably 5 or less, More preferably, it is 3 or less. The polymer or the polymer solution is diluted with a solvent, and the transition metal complex catalyst is removed with a centrifugal sedimenter to obtain the desired clear polymer solution.

[0049]

EXAMPLES Specific examples are shown below, but the purification method of the present invention is not limited to the following examples.

(Production Example 1) 1 equipped with a reflux tube and a stirrer
In a 0 L separable flask, CuBr (50.4 g,
0.35 mol), and the inside of the reaction vessel was purged with nitrogen. Acetonitrile (670 mL) was added, and the mixture was stirred in an oil bath at 70 ° C. for 30 minutes. To this, butyl acrylate (1.20 kg), diethyl 2,5-dibromoadipate (105 g, 0.29 mol), pentamethyldiethylenetriamine (2.44 mL, 11.7 mmol)
(Hereinafter triamine) was added to initiate the reaction. With heating and stirring at 70 ° C., butyl acrylate (4.80 kg) was continuously added dropwise. During the dropping of butyl acrylate, triamine (9.8 mL, 47 mmol
l) was added. After heating and stirring at 70 ° C,
Octadiene (1.73 L), triamine (18.3)
(88 mL), and the mixture was further heated and stirred at 70 ° C. for 4 hours to obtain a reaction mixture containing a polymer (polymerization reaction mixture [1]). The polymer is GPC
The number average molecular weight was 257 as measured (in terms of polystyrene).
The molecular weight distribution was 1.30, and the average number of alkenyl groups introduced per polymer was determined by ¹ H NMR.
It was 2.6 as determined by analysis.

Example 1 The reaction mixture (1) obtained in Production Example 1 was diluted with toluene so that the polymer concentration became 38% by weight. The diluted mixture was poured into a centrifugal sedimentation tube, and the solid content was sedimented using a centrifuge. Maximum turning radius 1
7 cm, the number of rotations was 2000 rpm, and the rotation time was 1 minute. The supernatant was concentrated to obtain a polymer. The polymer was mixed with ultra-high-purity nitric acid and ultra-high-purity sulfuric acid and subjected to microwave decomposition. The amount of copper remaining in the decomposition product was measured using an ICP mass spectrometer (HP-4500 manufactured by Yokogawa Analytical Systems Co., Ltd.), and the amount of copper remaining in the polymer was quantified. Table 1 shows the results.

Examples 2 to 7 The same operation as in Example 1 was carried out except that the number of revolutions was changed, and the amount of residual copper was determined for the obtained polymer. Table 1 also shows the results of the number of rotations and the amount of residual copper.

Example 8 The volatile component of the reaction mixture (1) obtained in Production Example 1 was distilled off under reduced pressure, concentrated, and then diluted with toluene to a polymer concentration of 38% by weight. The diluted mixture was poured into a centrifugal sedimentation tube, and the solid content was sedimented using a centrifuge. Maximum turning radius 17cm, number of rotation 2
000 rpm and a rotation time of 1 minute. The supernatant was concentrated to obtain a polymer. The amount of residual copper was determined for the obtained polymer in the same manner as in Example 1. Table 1 shows the results.

Examples 9 to 14 The same operation as in Example 8 was carried out except that the number of revolutions was changed, and the amount of residual copper in the obtained polymer was determined. Table 1 also shows the results of the number of rotations and the amount of residual copper.

(Production Example 2) 1 equipped with a reflux tube and a stirrer
In a 0 L separable flask, CuBr (50.4 g,
0.35 mol), and the inside of the reaction vessel was purged with nitrogen. Acetonitrile (670 mL) was added, and the mixture was stirred in an oil bath at 70 ° C. for 30 minutes. To this, butyl acrylate (1.20 kg), diethyl 2,5-dibromoadipate (105 g, 0.29 mol), pentamethyldiethylenetriamine (2.44 mL, 11.7 mmol)
(Hereinafter triamine) was added to initiate the reaction. With heating and stirring at 70 ° C., butyl acrylate (4.80 kg) was continuously added dropwise. During the dropping of butyl acrylate, triamine (9.8 mL, 47 mmol
l) was added. After heating and stirring at 70 ° C,
Octadiene (1.73 L), triamine (18.3)
The mixture was further heated and stirred at 70 ° C. for 4 hours to obtain a reaction mixture containing a polymer (polymerization reaction mixture [2]). The polymer is GPC
The number average molecular weight was 266 as measured (in terms of polystyrene).
The molecular weight distribution was 1.27, and the average number of alkenyl groups introduced per molecule of polymer was determined by ¹ H NMR.
As a result of analysis, it was 2.7.

(Example 15) The polymerization reaction mixture (2) obtained in Production Example 2 was diluted with a three-fold amount by weight of toluene, and a centrifugal sedimentation plate (LAPX202, manufactured by Alfa Laval Co., Ltd.) was prepared. To remove solids. Rotation speed 10
000 rpm (maximum G value: 8200 G). The liquid phase was concentrated to obtain a polymer. When the amount of residual copper was determined in the same manner as in Example 1, it was 260 ppm. Since the copper content in the polymer before purification was 3600 ppm, the present invention succeeded in removing 93% of the copper complex remaining in the polymer. This value is the same as in the case of purification using a series of centrifuges.

(Example 16) The polymerization reaction mixture (2) obtained in Production Example 2 was diluted with twice the weight of toluene, and a centrifugal filter (manufactured by Sanyo Chemical Machinery Co., Ltd., filter paper; Advantech Co., Ltd.) ) Qualitative filter paper No. 131, Celite used for precoat; Radiolite # 700 manufactured by Showa Chemical Co., Ltd.)
The solid was separated and removed using. Rotation speed 5000rpm
And The liquid phase was concentrated to obtain a polymer. When the amount of residual copper was determined in the same manner as in Example 1, it was 240 ppm.

[0058]

[Table 1]

[0059]

According to the present invention, a residual metal catalyst can be removed by purifying a vinyl polymer produced by atom transfer radical polymerization using a centrifugal separator. In particular, by using a centrifugal sedimenter, the amount of residual metal catalyst can be effectively reduced even in a short processing time.

 ────────────────────────────────────────────────── ─── Continued on the front page (72) Inventor Yoshiki Nakagawa 1-2-80 Yoshida-cho, Hyogo-ku, Kobe-shi, Hyogo Kanebuchi Chemical Industry Co., Ltd. Functional Materials RD Center Kobe Research Laboratory F-term (reference) 4J015 CA04 4J100 AA02P AA03P AB02P AB03P AC03P AC04P AC24P AC26P AC27P AD03P AG02P AG04P AG08P AJ09P AK32P AL03P AL04P AL05P AL08P AL09P AL10P AL34P AL36P AM02P AM15P AM43P AS02P AS03P BA04P BA08P BA08P BA08P BA08P BA08B BAP

Claims (15)

[Claims] When purifying a vinyl polymer produced by using atom transfer radical polymerization of a vinyl monomer using a transition metal complex as a polymerization catalyst, the metal catalyst remaining in the vinyl polymer is reduced in density. A method for purifying a vinyl polymer, wherein the vinyl polymer is separated and removed by a difference. 2. The purification method according to claim 1, wherein the separation and removal based on the difference in density are performed using a centrifugal separator. 3. The purification method according to claim 2, wherein the vinyl polymer is diluted with a solvent. 4. The purification method according to claim 3, wherein the value of the relative dielectric constant of the solvent used for dilution at 25 ° C. is 7 or less. 5. The method according to claim 2, wherein the centrifugal separator is a centrifuge. 6. The purification method according to claim 5, wherein the centrifugal sedimenter is of a separator type. 7. The purification method according to claim 2, wherein the catalyst for atom transfer radical polymerization is a heterogeneous catalyst. 8. 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.
The purification method according to claim 7, which is a Group 5, 9, 10, or 11 element. 9. The purification method according to claim 8, wherein the central metal of the transition metal complex is iron, nickel, ruthenium or copper. 10. The purification method according to claim 9, wherein the central metal of the transition metal complex is copper. 11. The method according to claim 2, wherein a polyamine compound is used as a catalyst ligand for atom transfer radical polymerization. 12. The purification method according to claim 11, wherein a triamine compound is used as the polyamine compound. 13. The purification method according to claim 2, wherein the vinyl polymer is a (meth) acrylic polymer. 14. The purification method according to claim 13, wherein the vinyl polymer is an acrylate polymer. 15. The purification method according to claim 14, wherein the vinyl polymer is a butyl acrylate polymer.