IPC분류정보
| 국가/구분 |
United States(US) Patent
등록
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| 국제특허분류(IPC7판) |
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| 출원번호 |
US-0139786
(2002-05-05)
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발명자
/ 주소 |
- Stevens, James C.
- Vanderlende, Daniel D.
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| 출원인 / 주소 |
- Dow Global Technologies Inc.
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| 대리인 / 주소 |
Whyte Hirschboeck Dudek SC
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| 인용정보 |
피인용 횟수 :
117 인용 특허 :
125 |
초록
▼
Unique copolymers comprising propylene, ethylene and/or one or more unsaturated comonomers are characterized as having: at least one, preferably more than one, of the following properties: (i) 13C NMR peaks corresponding to a regio-error at about 14.6 and about 15.7 ppm, the peaks of about equal int
Unique copolymers comprising propylene, ethylene and/or one or more unsaturated comonomers are characterized as having: at least one, preferably more than one, of the following properties: (i) 13C NMR peaks corresponding to a regio-error at about 14.6 and about 15.7 ppm, the peaks of about equal intensity, (ii) a B-value greater than about 1.4 when the comonomer content of the copolymer is at least about 3 wt %, (iii) a skewness index, Six, greater than about ?1.20, (iv) a DSC curve with a Tme that remains essentially the same and a Tmax that decreases as the amount of comonomer in the copolymer is increased, and (v) an X-ray diffraction pattern that reports more gamma-form crystals than a comparable copolymer prepared with a Ziegler-Natta catalyst. These polypropylene polymers are made using a nonmetallocene, metal-centered, heteroaryl ligand catalyst. These polymers can be blended with other polymers, and are useful in the manufacture of films, sheets, foams, fibers and molded articles.
대표청구항
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1. A propylene/ethylene copolymer comprising at least about 60 weight percent of units derived from propylene and at least about 0.1 weight percent of units derived from ethylene, the copolymer characterized as having 13C NMR peaks corresponding to a regio-error at about 14.6 and about 15.7 ppm, the
1. A propylene/ethylene copolymer comprising at least about 60 weight percent of units derived from propylene and at least about 0.1 weight percent of units derived from ethylene, the copolymer characterized as having 13C NMR peaks corresponding to a regio-error at about 14.6 and about 15.7 ppm, the peaks of about equal intensity.2. The copolymer of claim 1 further characterized as having a skewness index, Six, greater than about ?1.20.3. The copolymer of claim 1 further characterized as having a DSC curve with a Tme that remains essentially the same and a Tmax that decreases as the amount of ethylene in the copolymer is increased.4. The copolymer of claim 1 further characterized as having an X-ray diffraction pattern exhibiting more gamma-form crystals than a propylene/ethylene copolymer comparable in weight average molecular weight except that it is prepared with a Ziegler-Natta catalyst.5. The copolymer of claim 1 further characterized as having a B-value greater than about 1.3 when the ethylene content of the copolymer is at least about 3 weight percent.6. The copolymer of claim 2 further characterized as having a DSC curve with a Tme that remains essentially the same and a Tmax that decreases as the amount of ethylene in the copolymer is increased.7. The copolymer of claim 2 further characterized as having an X-ray diffraction pattern exhibiting more gamma-form crystals than a propylene/ethylene copolymer comparable in weight average molecular weight except that it is prepared with a Ziegler-Natta catalyst.8. The copolymer of claim 2 further characterized as having a B-value greater than about 1.3 when the ethylene content of the copolymer is at least about 3 weight percent.9. The copolymer of claim 6 further characterized as having an X-ray diffraction pattern exhibiting more gamma-form crystals than a propylene/ethylene copolymer comparable in weight average molecular weight except that it is prepared with a Ziegler-Natta catalyst.10. The copolymer of claim 6 further characterized as having a B-value greater than about 1.3 when the ethylene content of the copolymer is at least about 3 weight percent.11. The copolymer of claim 9 further characterized as having a B-value greater than about 1.3 when the ethylene content of the copolymer is at least about 3 weight percent.12. A process for making the copolymer of claim 1, the process comprising contacting under polymerization conditions propylene and ethylene with a nonmetallocene, metal-centered, heteroaryl ligand catalyst in combination with at least one activator.13. The process of claim 12 which the metal component of the catalyst is at least one of hafnium and zirconium.14. The process of claim 13 in which the catalyst comprises a ligand of the general formula: wherein R1 is characterized by the general formula: where Q1 and Q5 are substituents on the ring other than atom E, with E selected from the group consisting of carbon and nitrogen, and with at least one of Q1 or Q5 having at least 2 atoms; q is 1, 2, 3, 4 or 5; Q″ is selected from the group consisting of hydrogen, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl, substituted heteroalkyl, heterocycloalkyl, substituted hetercycloalkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxyl, aryloxyl, silyl, boryl, phosphino, amino, thio, seleno, halide, nitro, and combinations thereof; T is a bridging group selected from the group consisting of ?CR2R3? and ?SiR2R3? with R2 and R3 independently selected from the group consisting of hydrogen, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl, substituted heteroalkyl, heterocycloalkyl, substituted hetercycloalkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxyl, aryloxyl, silyl, boryl, phosphino, amino, thio, seleno, halide, nitro, and combinations thereof; and J″ is selected from the group consisting of heteroaryl and substituted heteroaryl. 15. The process of claim 14 conducted under solution polymerization conditions.16. The process of claim 14 conducted under slurry polymerization conditions.17. The process of claim 14 conducted under gas phase polymerization conditions.18. The process of claim 14 in which the unsaturated comonomer is at least one of a C4-20 α-olefin, a C4-20 diolefin, a C8-40 vinyl aromatic compound, and a halogen-substituted C8-40 vinyl aromatic compound.19. The process of claim 18 in which the unsaturated comonomer is a C4-12 α-olefin.20. The process of claim 18 in which the unsaturated comonomer is styrene.21. The process of claim 14 in which the comonomer is ethylene.22. A solution phase process for making the copolymer of claim 1, the process comprising contacting propylene and at least one of ethylene and an unsaturated comonomer under solution phase polymerization conditions with a nonmetallocene, metal-centered, heteroaryl ligand catalyst.23. The process of claim 22 in which the catalyst comprises a ligand of the general formula: wherein R1 is characterized by the general formula: where Q1 and Q5 are substituents on the ring other than atom E, with E selected from the group consisting of carbon and nitrogen, and with at least one of Q1 or Q5 having at least 2 atoms; q is 1, 2, 3, 4 or 5; Q″ is selected from the group consisting of hydrogen, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl, substituted heteroalkyl, heterocycloalkyl, substituted hetercycloalkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxyl, aryloxyl, silyl, boryl, phosphino, amino, thio, seleno, halide, nitro, and combinations thereof; T is a bridging group selected from the group consisting of ?CR2R3? and ?SiR2R3? with R2 and R3 independently selected from the group consisting of hydrogen, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl, substituted heteroalkyl, heterocycloalkyl, substituted hetercycloalkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxyl, aryloxyl, silyl, boryl, phosphino, amino, thio, seleno, halide, nitro, and combinations thereof; and J″ is selected from the group consisting of heteroaryl and substituted heteroaryl. 24. The process of claim 23 in which the metal component of the catalyst is at least one of hafnium and zirconium.25. A fabricated article made from the copolymer of claim 1.26. The fabricated article of claim 25 in the form of a film.27. The fabricated article of claim 25 in the form of a molded article.28. The fabricated article of claim 25 in the form of a foam.29. The fabricated article of claim 25 in the form of a sheet.
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