ABA type block copolymers

• US 5,314,962 A
• Filed: 06/29/1993
• Issued: 05/24/1994
• Est. Priority Date: 04/07/1987
• 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: Otsu, Takayuki, Himori, Shunichi, Kiriyama, Takashi
• Primary Examiner(s): BERMAN, SUSAN W
• Application Number:
  US08/083,326
• Time in Patent Office: 329 Days
• Field of Search: 522/57, 522/116, 522/176, 522/182, 522/188, 525/92, 525/94, 525/280, 525/294, 525/299
• US Class Current: 525/280
• 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

Abstract

An acrylate is polymerized by the photo-decomposition of ##STR1## to make a polymeric intermediate containing dithiocarbamate groups at both its ends, and a hard polymer-forming monomer is polymerized by the photo-decomposition of this dithiocarbamate group-containing polymeric intermediate to form blocks of a polymer of said hard polymer-forming monomer on both sides of said polymeric intermediate, thereby forming an ABA type block copolymer.

Claims

1. An ABA block copolymer represented by the following formula I:

##STR15## wherein;

two R¹ s, which may be different or identical, stand for a hydrocarbyl group having 1 to 3 carbon atoms,

two R² s, which may be different or identical, stand for a hydrogen atom or a hydrocarbyl group having 1 to 3 carbon atoms,

M¹ stands for an acrylic ester residue represented by the following formula (a);

##STR16## wherein;

R³ is a hydrocarbyl group having 1 to 18 carbon atoms, which may or may not be replaced with an alkoxy or hydroxy group, wherein M¹ contains less than 5% by weight with respect to said acrylic ester residue of at least one monomer selected from the group consisting of acrylic acid, methacrylic acid, aromatic vinyl derivatives and vinyl acetate,

M² stands for at least one residue selected from a methacrylic acid or ester residue represented by the following formula (b);

##STR17## wherein R⁴ is a hydrocarbyl group having 1 to 4 carbon atoms or a hydrogen atom;

an aromatic vinyl residue represented by the following formula (c);

##STR18## wherein R⁵ is a hydrogen atom or a methyl group, and

R⁶ is a phenyl or alkylphenyl group;

or a maleimido residue represented by the following formula (d);

##STR19## wherein R⁷ is a hydrocarbyl group having 1 to 12 carbon atoms, or a phenyl or alkylphenyl group, and n and m each stand for a natural number of 20 to 5000, the copolymer having two glass transition temperatures such that a first glass transition temperature is equivalent to a homopolymer of the monomer M¹ and a second glass transition temperature is equivalent to a homopolymer of the monomer M², the first glass transition temperature being substantially lower than the second glass transition temperature.

2. A block copolymer as recited in claim 1, wherein M² is a methacrylic acid or ester residue of said formula (b) wherein R⁴ denotes a hydrocarbyl group having 1 to 4 carbon atoms or a hydrogen atom.

3. A block copolymer as recited in claim 1, wherein M² is an aromatic vinyl residue of said formula (c) wherein R⁵ denotes a hydrogen atom or a methyl group, and R⁶ denotes a phenyl or alkylphenyl group.

4. A block copolymer as recited in claim 1, wherein M² is a maleimido residue of said formula (d) wherein R⁷ denotes a hydrocarbyl group having 1 to 12 carbon atoms, a phenyl group or an alkylphenyl group.

5. A block copolymer as recited in claim 1, wherein M² is a methacrylic ester residue of said formula (b) wherein R⁴ is a hydrocarbyl group having 1 to 18 carbon atoms.

6. A block copolymer as recited in claim 1, wherein M² is an aromatic vinyl residue of said formula (c) wherein R⁵ denotes a hydrogen atom, and R⁶ denotes a phenyl group.

7. A block copolymer as recited in claim 1, wherein M² is a maleimido residue of said formula (d) wherein R⁷ denotes a hydrocarbyl group having 1 to 12 carbon atoms.

8. A block copolymer as recited in claim 1, wherein --(M²)_m -- comprises at least one essential monomeric residue selected from those of said formulae (b), (c) and (d) and an optional monomeric residue in an amount of below 5% by weight with respect to said essential monomeric residue.

9. A block copolymer as recited in claim 1, wherein M¹ is a butyl acrylate residue, and M² is a methyl methacrylate residue.

10. A block copolymer as recited in claim 1, wherein M¹ is a butyl acrylate residue, and M² is a styrene residue.

11. A block copolymer as recited in claim 1, wherein M¹ is a 2-ethylhexyl acrylate residue, and M² is a methyl methacrylate residue.

12. A block copolymer as recited in claim 1, wherein M¹ is a 2-ethylhexyl acrylate residue, and M² is a styrene residue.

13. A block copolymer as recited in claim 1, which is in the form of an elastomer, sealant, packing, adhesive material, vibration-proof material, sound absorbing material, soling material or hose.

14. An ABA block copolymer represented by the following formula (I):

##STR20## wherein;

two R¹ S, which may be different or identical, are a hydrocarbyl group having 1 to 3 carbon atoms,

two R² S, which may be different or identical, are a hydrogen atom or a hydrocarbyl group having 1 to 3 carbon atoms,

M¹ is an acrylic ester residue represented by the following formula (a);

##STR21## wherein R³ is a hydrocarbyl group having 1 to 18 carbon atoms, which may or may not be replaced with an alkoxy or hydroxy group, wherein M¹ contains less than 5% by weight with respect to said acrylic ester residue of at least one monomer selected from the group consisting of acrylic acid, methacrylic acid, aromatic vinyl derivatives and vinyl acetate,

M² comprises a maleimido residue having the following formula (d) ##STR22## wherein R⁷ is a hydrocarbyl group having 1 to 12 carbon atoms, or a phenyl or alkylphenyl group, and optionally, a residue selected from a methacrylic acid or ester residue having formula (b) ##STR23## wherein R⁴ is a hydrocarbyl group having 1 to 4 carbon atoms or a hydrogen atom;

an aromatic vinyl residue represented by the formula (c);

##STR24## wherein R⁵ is a hydrogen atom or a methyl group, and R⁶ is a phenyl or alkylphenyl group, and n and m are each a natural number of 20 to 5000, the copolymer having two glass transition temperatures such that a first glass transition temperature is equivalent to a homopolymer of the monomer M¹ and a second glass transition temperature is equivalent to a homopolymer of the monomer M², the first glass transition temperature being substantially lower than the second glass transition temperature.

15. The block copolymer of claim 14, wherein R⁷ is a hydrocarbyl group having 1-12 carbon atoms.

16. The block copolymer of claim 14, wherein M¹ is a butyl acrylate residue and --(M²)_m -- consists of an N-phenylmaleimido residue and a methylmethacrylate residue.

17. An ABA type block copolymer represented by the structure (I) ##STR25## wherein two R¹ s which may be different or identical, are a hydrocarbyl group having 1 to 3 carbon atoms,

two R² s which may be different or identical, are a hydrocarbyl group having 1 to 3 carbon atoms,

(M¹)_n is a polymer block derived from acrylic esters of the formula (a):

##STR26## wherein R³ is a hydrocarbyl group having 1 to 18 carbon atoms, which may or may not be replaced with an alkoxy or hydroxy group, and optionally including at least one monomer selected from methacrylic acid, acrylic acid, aromatic vinyl derivatives and vinyl acetate;

(M²)_m is a polymerized block of methyl methacrylate, the number of monomeric units making up each of blocks (M²)_m and (M¹)_n being 20 to 5000.