Polyolefin polymer containing vinyl groups at both ends and composition thereof
The present invention is a polyolefin polymer containing vinyl groups at both ends thereof, and a composition and a molded product containing the polymer, wherein the polymer contains a constitutional unit derived from at least one selected from the group consisting of ethylene (a), an α-olefin (b) having 3 to 20 carbon atoms, and a cyclic olefin (c), and (1) a ratio of terminal vinylation is 70% or more relative to all of both ends of molecular chains, and (2) an intrinsic viscosity [η] is in the range of 0.01 to 10 dl/g as measured in a decalin solution at 135° C. The polymer of the present invention may be molded by a LIM molding, an injection molding, a transfer molding, a compression molding, and the like, and is excellent in acid resistance, gas permeation resistance, hydrolysis resistance, and dynamic fatigue resistance. From the polymer, a thermoplastic resin composition and a crosslinkable resin composition, and a crosslinked composition having excellent mechanical characteristics are obtained.
1. A polyolefin polymer containing vinyl groups at both ends thereof, containing a constitutional unit derived from at least one selected from the group consisting of an α-olefin having 3 to 20 carbon atoms (b), and a cyclic olefin (c) represented by the following general formula[III];
obtained by metathesis reaction; and having
(1) a ratio of terminal vinylation of 70% or more relative to all of both ends of molecular chains, and
(2) an intrinsic viscosity [η] in the range of 0.01 to 10 dl/g as measured in a decahydronaphthalene solution at 135° C.,
the α-olefin (b) being a propylene (e) and at least one kind of an α-olefin (f) having 4 to 20 carbon atoms,
the constitutional unit derived from the propylene (e) satisfying any one of the following conditions i) to iii)
i) a mesotriad fraction (mm) obtained from 13 C-NMR is 50% or more;
ii) a racemotriad fraction (rr) obtained from 13 C-NMR is 50% or more;
iii) a mesotriad fraction obtained from 13 C-NMR is less than 50% and a racemotriad fraction obtained from 13 C-NMR is less than 50%:
wherein each of R 100 and R 101 may be the same or different and represents a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms; and f represents an integer of 1≦f≦18.
2. The polyolefin polymer containing vinyl groups at both ends thereof according to claim 1 , wherein a constitutional unit derived from polyene (d) represented by the following general formula [IV] is further contained:
wherein each of R 1 and R 2 may be the same or different and represents a hydrogen atom, and an alkyl group having 1 to 8 carbon atoms or an aryl group, and at least one of R 1 and R 2 is a hydrogen atom.
3. The polyolefin polymer containing vinyl groups at both ends thereof according to claim 1 , wherein constitutional units derived from the α-olefin (b), the cyclic olefin (c), and ethylene (a) are contained, and a ratio of the number of moles a of the constitutional unit derived from the ethylene (a) to the total number of moles b of the constitutional unit derived from the α-olefin (b) and moles c of the constitutional unit derived from the cyclic olefin (c), namely a/(b+c), is in the range of 99/1 to 50/50.
4. The polyolefin polymer containing vinyl groups at both ends thereof according to claim 2 , wherein constitutional units derived from the α-olefin (b), the cyclic olefin (c), the polyene (d) and ethylene (a) are contained, and a ratio of the number of moles a of the constitutional unit derived from the ethylene (a) to the total number of moles b of the constitutional unit derived from the α-olefin (b), moles c of the constitutional unit derived from the cyclic olefin (c), and moles d of the constitutional unit derived from the polyene (d), namely a/(b+c+d), is in the range of 99/1 to 50/50.
5. The polyolefin polymer containing vinyl groups at both ends thereof according to claim 1 , wherein constitutional units derived from the α-olefin (b), the cyclic olefin (c) and ethylene (a) are contained,
constitutional units derived from propylene (e) and an α-olefin (f) having 4 to 20 carbon atoms are contained as the constitutional unit derived from the α-olefin (b), and
a ratio of the number of moles e of the constitutional unit derived from the propylene (e) to the total number of moles a of the constitutional unit derived from the ethylene (a), moles f of the constitutional unit derived from the α-olefin (f) having 4 to 20 carbon atoms, and moles c of the constitutional unit derived from the cyclic olefin (c), namely e/(a+f+c), is in the range of 99/1 to 50/50.
6. The polyolefin polymer containing vinyl groups at both ends thereof according to claim 2 , wherein constitutional units derived from the α-olefin (b), the cyclic olefin (c), the polyene (d) and ethylene (a) are contained,
constitutional units derived from propylene (e) and an α-olefin (f) having 4 to 20 carbon atoms are contained as the constitutional unit derived from the α-olefin (b), and
a ratio of the number of moles e of the constitutional unit derived from the propylene (e) to the total number of moles a of the constitutional unit derived from the ethylene (a), moles f of the constitutional unit derived from the α-olefin (f) having 4 to 20 carbon atoms, moles c of the constitutional unit derived from the cyclic olefin (c), and moles d of the constitutional unit derived from the polyene (d), namely e/(a+f+c+d), is in the range of 99/1 to 50/50.
7. The polyolefin polymer containing vinyl groups at both ends thereof according to claim 1 , wherein constitutional units derived from the α-olefin (b), the constitutional units derived from the cyclic olefin (c), and ethylene (a) are contained,
constitutional units derived from propylene (e) and an α-olefin (f) having 4 to 20 carbon atoms are contained as the constitutional unit derived from the α-olefin (b), and
a ratio of the number of moles f of the constitutional unit derived from the α-olefin (0 having 4 to 20 carbon atoms to the total number of moles a of the constitutional unit derived from the ethylene (a), moles e of the constitutional unit derived from the propylene (e), and moles c of the constitutional unit derived from the cyclic olefin (c), namely f/(a+e+c), is in the range of 99/1 to 50/50.
8. The polyolefin polymer containing vinyl groups at both ends thereof according to claim 2 , wherein constitutional units derived from the α-olefin (b), the cyclic olefin (c), the polyene (d) and ethylene (a) are contained,
constitutional units derived from propylene (e) and an α-olefin (1) having 4 to 20 carbon atoms are contained as the constitutional unit derived from the o-olefin (b), and
a ratio of the number of moles f of the constitutional unit derived from the α-olefin (f) having 4 to 20 carbon atoms to the total number of moles a of the constitutional unit derived from the ethylene (a), moles e of the constitutional unit derived from the propylene (e), moles c of the constitutional unit derived from the cyclic olefin (c), and moles d of the constitutional unit derived from the polyene (d), namely f/(a+e+c+d), is in the range of 99/1 to 50/50.
9. A thermoplastic resin composition containing the polyolefin polymer containing vinyl groups at both ends thereof according to claim 1 and at least one kind of other thermoplastic resins (A).
10. A crosslinkable resin composition comprising the polyolefin polymer containing vinyl groups at both ends thereof according to claim 1 , and at least one kind selected from the group consisting of sulfur (B-1), a compound (B-2) having at least two hydrosilyl groups in the molecule thereof, and an organic peroxide (B-3).
11. A crosslinked composition obtained by crosslinking at least part of the composition according to claim 10 .
12. A molded article comprising the polyolefin polymer containing vinyl groups at both ends thereof according to claim 1 .
13. A multilayered laminate having at least one layer comprising:
the polyolefin polymer containing vinyl groups at both ends thereof according to claim 1 .