Terminally unsaturated polyolefin and method for producing the same

1. A terminally unsaturated polyolefin, which is selected from the group consisting of:

a propylene homopolymer;

a propylene-based copolymer consisting of propylene, ethylene and one or more α-olefins each having 4 to 10 carbon atoms, such that the propylene-based copolymer comprises 10 mol % or less of said ethylene and the one or more α-olefins each having 4 to 10 carbon atoms;

a butene-1 homopolymer; and

a butene-1-based copolymer consisting of butene-1, ethylene, propylene and one or more α-olefins each having 5 to 10 carbon atoms, such that the butene-1-based copolymer comprises 10 mol % or less of said ethylene, said propylene and the α-olefins each having 5 to 10 carbon atoms

wherein the terminally unsaturated polyolefin satisfies the following (1) to (4):

(1) a mesopentad fraction [mmmm] of propylene chain unit or butene-1 chain unit is 20 to 80 mol %;

(2) a number of terminal vinylidene groups per molecule is 1.3 to 2.5;

(3) a weight-average molecular weight Mw is 500 to 100,000; and

(4) a molecular weight distribution Mw/Mn is 1.1 to 2.6.

2. The polyolefin according to claim 1 , which is a propylene homopolymer.

3. A method for producing the terminally unsaturated polyolefin according to claim 1 , the method comprising decomposing a raw material polyolefin in the presence of an inert gas,

wherein:

the raw material polyolefin is selected from the group consisting of:

a propylene homopolymer;

a propylene-based copolymer consisting of ethylene and one or more α-olefins each having 4 to 10 carbon atoms, such that the propylene-based copolymer comprises 10 mol % or less of said ethylene and the α-olefins each having 4 to 10 carbon atoms;

a butene-1 homopolymer; and

a butene-1-based copolymer consisting of butene-1, ethylene, propylene and one or more α-olefins each having 5 to 10 carbon atoms, such that the butene-1-based copolymer comprises 10 mol % or less of said ethylene, said propylene and the α-olefins each having 5 to 10 carbon atoms; and

the raw material polyolefin satisfies the following (5) and (6);

(5) a tacticity [mmmm] of propylene chain unit or butene-1 chain unit is 20 to 80 mol %; and

(6) a weight average molecular weight Mw is 4000 to 1,000,000.

4. The method according to claim 3 , wherein the decomposition is a heat decomposition reaction in which the raw material polyolefin is heat treated at a temperature of 300 to 400° C. for 30 minutes to 10 hours.

5. The method according to claim 3 , wherein the decomposition is a radical decomposition reaction in which an organic peroxide is added in an amount of 0.05 to 2 mass % relative to the raw material polyolefin at 160 to 300° C.

6. The method according to claim 5 , wherein a one minute half life temperature of the organic peroxide is 140 to 270° C.

7. A terminally unsaturated polyolefin obtained by decomposing a raw material polyolefin selected from the group consisting of:

a propylene homopolymer;

a propylene-based copolymer consisting of propylene, ethylene and one or more α-olefins each having 4 to 10 carbon atoms, such that the propylene-based copolymer comprises 10 mol % or less of said ethylene and the α-olefins each having 4 to 10 carbon atoms;

a butene-1 homopolymer; and

a butene-1-based copolymer consisting of butene-1, ethylene, propylene and one or more α-olefins each having 5 to 10 carbon atoms, such that the butene-1-based copolymer comprises 10 mol % or less of said ethylene, said propylene and the α-olefins each having 5 to 10 carbon atoms,

wherein the terminally unsaturated polyolefin satisfies the following (7) to (10):

(7) a number of terminal vinylidene groups per molecule (fv) is 1.3 to 2.5;

(8) fv≧−2 (Mp/Mm)+2 wherein Mp is the number average molecular weight of the terminally unsaturated polyolefin, Mm is the number average molecular weight of the raw material polyolefin, and Mp/Mm is 0.05 to 0.8;

(9) a weight average molecular weight Mw is 500 to 100,000; and

(10) a molecular weight distribution Mw/Mn is 1.1 to 2.6.

8. The terminally unsaturated polyolefin according to claim 7 , which is a terminally unsaturated polyolefin obtained by decomposing a propylene homopolymer or a propylene-based copolymer, wherein a propylene chain unit of the propylene homopolymer or the propylene-based copolymer comprises an atactic structure, a syndiotactic structure or an isotactic structure.

9. The terminally unsaturated polyolefin according to claim 7 , wherein the raw material polyolefin is a propylene homopolymer.

10. A method for producing the terminally unsaturated polyolefin according to claim 7 , the method comprising decomposing a raw material polyolefin in the presence of an inert gas,

wherein:

the raw material polyolefin is selected from the group consisting of:

a propylene homopolymer;

a propylene-based copolymer consisting of propylene, ethylene and one or more α-olefins each having 4 to 10 carbon atoms, such that the propylene-based copolymer comprises 10 mol % or less of said ethylene and the α-olefins each having 4 to 10 carbon atoms;

a butene-1 homopolymer; and

a butene-1-based copolymer consisting of butene-1, ethylene, propylene and one or more α-olefins each having 5 to 10 carbon atoms, such that the butene-1-based copolymer comprises 10 mol % or less of said ethylene, said propylene and the α-olefins each having 5 to 10 carbon atoms; and

the raw material polyolefin has a weight-average molecular weight of 4000 to 1,000,000.

11. A functional polyolefin, comprising the terminally unsaturated polyolefin according to claim 1 , wherein 5 mol % or more of the terminal vinylidene groups of the terminally unsaturated polyolefin comprise a functional group.

12. The functional polyolefin according to claim 11 , wherein the functional group is one or more selected from the group consisting of a hydroxyl group, an epoxy group, an isocyanate group, an alkoxysilicon group, an alkylsilicon group, a carboxyl group, an amino group and an acid anhydride structure.

13. A cross-linked body obtained by wet curing the functional polyolefin according to claim 11 comprising at least an alkoxysilicon group as the functional group.

14. A reaction product obtained by reacting the terminally unsaturated polyolefin according to claim 1 with an organohydrogen polysiloxane having two or more SiH groups per molecule.

15. A method for producing a graft copolymer or a thermoplastic resin composition comprising the graft copolymer, the method comprising graft polymerizing, in the presence of 0.001 to 10 parts by mass of a radical polymerization initiator at 40 to 230° C.:

100 parts by mass of a combination of 20 to 100 mass % of the terminally unsaturated polyolefin according to claim 1 and 0 to 80 mass % of another polyolefin other than the terminally unsaturated polyolefin; and

0.2 to 300 parts by mass of one or more monomers selected from the group consisting of the following [I] to [IV]:

[I] acrylic acid and acrylic acid's derivatives comprising an acrylic group;

[II] methacrylic acid and methacrylic acid's derivatives comprising a methacrylic group;

[III] vinylesters and vinylesters' derivatives comprising a vinyl group and an ester structure, or vinylalkoxysilane; and

[IV] styrene and styrene's derivatives comprising a styryl group, or

0.2 to 300 parts by mass of a mixture of one or more monomers selected from the group consisting of the following Group A:

[V] maleic anhydride and substituted maleic anhydride;

[VI] maleic acid and its esters;

[VII] maleimide and substituted maleimide, and

one or more monomers selected from the group consisting of the following Group B:

[I] acrylic acid and acrylic acid's derivatives comprising an acrylic group;

[II] methacrylic acid and methacrylic acid's derivatives comprising a methacrylic group;

[III] vinylesters and vinylesters' derivatives comprising a vinyl group and an ester structure, or vinylalkoxysilane;

[IV] styrene and styrene's derivatives comprising a styryl group; and

[VIII] α-olefin.

16. The method according to claim 15 , wherein the graft polymerization occurs in the presence of a chain transfer agent.

17. A method for producing a graft copolymer or a thermoplastic resin comprising the graft copolymer, the method comprising contacting a mixture, comprising the terminally unsaturated polyolefin according to claim 1 and a monomer (a) which is substantially not radically homopolymerizable, with a monomer (b) which is copolymerizable with the monomer (a).

18. A product comprising the functional polyolefin according to claim 11 , said product selected from the group consisting of an adhesive, a compatibilizer, a dispersant, and a coating agent.

19. A product comprising the functional polyolefin according to claim 11 , said product selected from the group consisting of a reactive hot melt adhesive, a sealing agent, and a potting agent.

20. A functional polyolefin, comprising the terminally unsaturated polyolefin according to claim 7 , wherein 5 mol % or more of the terminal vinylidene groups of the terminally unsaturated polyolefin comprise a functional group.

21. The functional polyolefin according to claim 20 , wherein the functional group is one or more selected from the group consisting of a hydroxyl group, an epoxy group, an isocyanate group, an alkoxysilicon group, an alkylsilicon group, a carboxyl group, an amino group and an acid anhydride structure.

22. A cross-linked body obtained by wet curing the functional polyolefin according to claim 20 comprising at least an alkoxysilicon group as the functional group.

23. A reaction product obtained by reacting the terminally unsaturated polyolefin according to claim 7 with an organohydrogen polysiloxane having two or more SiH groups per molecule.

24. A method for producing a graft copolymer or a thermoplastic resin composition comprising the graft copolymer, the method comprising graft polymerizing, in the presence of 0.001 to 10 parts by mass of a radical polymerization initiator at 40 to 230° C.:

100 parts by mass of a combination of 20 to 100 mass % of the terminally unsaturated polyolefin according to claim 7 and 0 to 80 mass % of another polyolefin other than the terminally unsaturated polyolefin; and

0.2 to 300 parts by mass of one or more monomers selected from the group consisting of the following [I] to [IV]:

[I] acrylic acid and acrylic acid's derivatives comprising an acrylic group;

[II] methacrylic acid and methacrylic acid's derivatives comprising a methacrylic group;

[III] vinylesters and vinylesters' derivatives comprising a vinyl group and an ester structure, or vinylalkoxysilane; and

[IV] styrene and styrene's derivatives comprising a styryl group, or

0.2 to 300 parts by mass of a mixture of one or more monomers selected from the group consisting of the following Group A:

[V] maleic anhydride and substituted maleic anhydride;

[VI] maleic acid and its esters;

[VII] maleimide and substituted maleimide, and

one or more monomers selected from the group consisting of the following Group B:

[I] acrylic acid and methacrylic acid's derivatives comprising a methacrylic group;

[II] methacrylic acid and methacrylic acid's derivatives comprising a methacrylic group;

[III] vinylesters and vinylesters' derivatives comprising a vinyl group and an ester structure, or vinylalkoxysilane;

[IV] styrene and styrene's derivatives comprising a styryl group; and

[VIII] α-olefin.

25. The method according to claim 24 wherein the graft polymerization occurs in the presence of a chain transfer agent.

26. A method for producing a graft copolymer or a thermoplastic resin comprising the graft copolymer, the method comprising contacting a mixture, comprising the terminally unsaturated polyolefin according to claim 7 and a monomer (a) which is substantially not radically homopolymerizable, with a monomer (b) which is copolymerizable with the monomer (a).