Hydrophilic group-containing AB-type block copolymer

• US 5,190,989 A
• Filed: 11/30/1990
• Issued: 03/02/1993
• Est. Priority Date: 06/23/1987
• Status: Expired due to Fees

• Current Assignee: Mitsubishi Petrochemical Co., Ltd. (Mitsubishi Chemical Group Corp.)
• Original Assignee: Mitsubishi Petrochemical Co., Ltd. (Mitsubishi Chemical Group Corp.)
• Inventors: Himori, Shunichi
• Primary Examiner(s): McCamish, Marion E.
• Assistant Examiner(s): BERMAN, SUSAN W
• Application Number:
  US07/620,389
• Time in Patent Office: 823 Days
• Field of Search: 522/57, 522/176, 522/182, 525/267, 525/301
• US Class Current: 522/57
• CPC Class Codes: C08F 293/00 Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule on to polymers modified by introduction of unsaturated end groups C08F290/02
• CPC Class Codes: C08L 2666/24 Graft or block copolymers according to groups C08L51/00, C08L53/00 or C08L55/02; Derivatives thereof
• CPC Class Codes: C08L 57/00 Compositions of unspecified polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds

Abstract

An AB-type block copolymer represented by formula (I): ##STR1## wherein R¹ represents a hydrocarbon group having 1 to 10 carbon atoms; R² represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms; R³ represents a benzyl group, ##STR2## wherein R⁴ represents an alkyl group having 1 to 10 carbon atoms, or an alkyl group having 1 to 18 carbon atoms; M represents a group represented by the formula (M²)_m --(M¹)_n or (M¹)_m --(M²)_n, each of m and n being a natural number of 20 to 5000; is prepared by a process of first polymerizing either a monomer for forming the M¹ block or a monomer for forming the M² block in the presence of a sulfur-containing compound having formula (XIII): ##STR3## wherein R¹, R² and R³ are as defined above so as to synthesize a polymer initiator having a dithiocarbamate group as indicated in formula (XIII) at the polymer terminal end, and then polymerizing the other monomer in the presence of the polymer initiator obtained in the first step; wherein the polymerization reactions in the first step and in the second step are carried out upon exposure of the monomers to ultraviolet radiation.

Claims

1. An AB-type block copolymer represented by formula (I):

##STR42## wherein R¹ represents a hydrocarbon group having 1 to 10 carbon atoms;

R² represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms;

R³ represents a benzyl group, ##STR43## wherein R⁴ represents an alkyl group having 1 to 10 carbon atoms, or an alkyl group having 1 to 18 carbon atoms;

M represents a group represented by the formula (M²)_m -(M¹)_n or (M¹)_m -(M²)_n, each of m and n being a natural number of 20 to 5,000;

M¹ represents a (meth)acrylate residue represented by the formula;

##STR44## wherein R⁵ represents a hydrogen atom or a methyl group, and R⁶ represents a hydrocarbon group having 1 to 18 carbon atoms, or an aromatic vinyl residue represented by the formula;

##STR45## wherein R⁷ represents a hydrogen atom or a methyl group, R⁸ represents a phenyl group, a halogenated phenyl group or an alkylphenyl group or a fatty acid vinyl ester residue represented by the formula;

##STR46## wherein R⁹ represents a hydrocarbon group having 1 to 18 carbon atoms, M² represents a hydrophilic group-containing vinyl residue represented by any one of the formulae (II) to (XII);

##STR47## wherein R¹⁰, R¹¹ each represent a hydrogen atom, a methyl or a hydroxyl group, and Z represents a hydrogen atom, an alkali metal atom, ammonium or an organic amine;

##STR48## wherein R¹⁰ and Z have the same meanings as in the formula (II), and R¹² represents an alkylene group having 1 to 10 carbon atoms;

##STR49## wherein R¹⁰, R¹¹ and Z have the same meanings as in the formula (II), and R¹² has the same meaning as in the formula (III);

##STR50## wherein R¹⁰ and R¹¹ have the same meanings as in the formula (II), R¹³ and R¹⁴ each represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or a sulfonated alkyl group represented by the formula --R¹² SO₃ Z, wherein R¹² and Z have the same meanings as in the formula (III);

##STR51## wherein R¹⁰, R¹¹ and R¹² have the same meanings as in the formula (IV), and R¹³ and R¹⁴ have the same meanings as in the formula (V);

##STR52## wherein R¹⁰, R¹¹, R¹², R¹³ and R¹⁴ have the same meanings as in the formula (VI), and R¹⁵ represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or a sulfonated alkyl group represented by the formula --R¹² SO₃ Z, wherein R¹² and Z have the same meanings as in the formula (III);

##STR53## wherein R¹⁶ represents a hydroxylated alkyl group having 1 to 18 carbon atoms and having at least one hydroxyl group, and R¹⁰ and R¹¹ have the same meanings as in the formula (II);

##STR54## wherein R¹⁰ and R¹¹ have the same meanings as in the formula (II), and R¹⁷ represents a polyethylene glycol group or a polypropylene glycol group represented by the formula;

##STR55## wherein l represents a natural number of 1 to 10 and X represents an alkyl group having 1 to 10 carbon atoms or Z, --PO₃ H₂, --PO₃ HZ or --PO₃ Z₂, wherein Z has the same meaning as in the formula (II) ##STR56## wherein R¹⁰ and Z have the same meanings as in formula (II);

##STR57## wherein R¹⁰ has the same meaning as in formula (II);

or ##STR58## wherein R¹⁰, R¹¹ and Z have the same meanings as in formula (II); and

M² further represents a vinylpyrrolidone residue or an ammonium salt of the formula (V), (VI) or (VII), prepared by a process, comprising;

a first step of polymerizing either a monomer for forming the M¹ block or a monomer for forming the M² block in the presence of a sulfur-containing compound having formula (XIII);

##STR59## wherein R¹, R² and R³ are as defined above so as to synthesize a polymer initiator having a dithiocarbamate group as indicated in formula (XIII) at the polymer terminal end; and

a second step of polymerizing the other monomer in the presence of the polymer initiator obtained in the first step;

wherein the polymerization reactions in the first step and in the second step are carried out upon exposure to ultraviolet radiation.

2. The block copolymer according to claim 1, wherein the residue M¹ is formed from a (meth)acrylate monomer selected from the group consisting of methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, hexyl (meth)acrylate, isooctyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isononyl (meth)acrylate, decyl (meth)acrylate and stearyl (meth)acrylate.

3. The block copolymer according to claim 1, wherein the residue M² is represented by the formula (II) and formed from a hydrophilic group-containing vinyl monomer selected from the group consisting of (meth)acrylic acid, crotonic acid, sodium (meth)acrylate, potassium crotonate, ammonium (meth)acrylate, ##STR60##

4. A polymer composition comprising a polymeric material and the block copolymer according to claim 1.

5. The polymer composition according to claim 4, wherein the amount of the block copolymer added is 0.01 to 30 parts by weight based on 100 parts by weight of the polymeric material.

6. A process for producing the block copolymer according to claim 1, comprising the steps of:

a first step of polymerizing either a monomer for forming the M¹ block or a monomer for forming the M² block in the presence of a sulfur-containing compound having formula (XIII);

##STR61## wherein R¹ represents a hydrocarbon group having 1 to 10 carbon atoms;

R² represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms;

R³ represents a benzyl group, ##STR62## wherein R⁴ represents an alkyl group having 1 to 18 carbon atoms or an alkyl group having 1 to 18 carbon atoms;

so as to synthesize a polymer initiator having a dithiocarbamate group as indicated in formula (XIII) at the polymer terminal end; and

a second step of polymerizing the other monomer in the presence of the polymer initiator obtained in the first step;

wherein the polymerization reactions in the first step and in the second step are carried out upon exposure to ultraviolet rays.