CA2600362A1 - Process for production of propylene copolymers - Google Patents
Process for production of propylene copolymers Download PDFInfo
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- CA2600362A1 CA2600362A1 CA002600362A CA2600362A CA2600362A1 CA 2600362 A1 CA2600362 A1 CA 2600362A1 CA 002600362 A CA002600362 A CA 002600362A CA 2600362 A CA2600362 A CA 2600362A CA 2600362 A1 CA2600362 A1 CA 2600362A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/04—Monomers containing three or four carbon atoms
- C08F210/06—Propene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/04—Monomers containing three or four carbon atoms
- C08F110/06—Propene
Abstract
The properties and the amounts of polymers produced in the second stage of a polymerization process in the presence of propylene and ethylene or other alpha olefin are controlled by the addition of an external electron donor to the second stage polymerization. The dosage of external donor to the second stage polymerization is based on a percentage of the dosage of external donor to a first stage polymerization of propylene in the process. The external donor added to the second stage is either the same as or different from the external donor added to the first stage.
Description
PROCESS FOR PRODUCTION OF PROPYLENE COPOLYMERS
FIELD OF THE INVENTION
[0001] The present invention relates to the field of processes for the production of polypropylene. More specifically, the present invention relates to processes for producing copolymers of propylene.
BACKGROUND OF THE INVENTION
FIELD OF THE INVENTION
[0001] The present invention relates to the field of processes for the production of polypropylene. More specifically, the present invention relates to processes for producing copolymers of propylene.
BACKGROUND OF THE INVENTION
[0002] Polypropylene in general is produced in a process using multiple gas and/or liquid phase reactors. For a polypropylene impact copolymer, a propylene hoinopolymer is normally produced in a first stage polymerization, followed by ethylene-propylene or other alpha olefin-propylene copolymer in a second stage polymerization. The overall properties of the impact copolymer are a function of the homopolymer produced in the first stage and the copolymer produced in the second stage. Further, the qualities of the homopolymer and copolymer are a function of the polymerization conditions in the first and second stage respectively. As a result, manufacturers are constantly looking for new ways to manipulate polymerization conditions to produce improved impact copolymers. In addition, producing more polymers for a given amounts of catalyst and co-catalyst employed for the polymerization would be beneficial.
[0003] It would be desirable to provide a new method for manipulating the properties as well as the amounts of polynlers produced in the second stage polymerization.
SUMMARY OF THE INVENTION
SUMMARY OF THE INVENTION
[0004] The present invention is a process for producing propylene copolymers.
The process comprises polymerizing propylene in the presence of a Ziegler-Natta catalyst in a first stage comprising at least one gas phase or liquid phase reactor, wherein a first amount of an external donor is added to the first stage. The polymerization product from the first stage is passed to a second stage comprising at least one gas phase or liquid phase reactor, wherein propylene, and ethylene or other alpha-olefin, are polymerized in the presence of the first stage polymerization product. A second amount of an external donor is added to the second stage.
Optionally, an antistatic inhibitor is also added to the second stage.
BRIEF DESCRIPTION OF THE DRAWINGS
Figure 1: Illustrates SEM photos of the cross-sectional area of propylene/ethylene copolymer powders.
DETAILED DESCRIPTION OF THE INVENTION
The process comprises polymerizing propylene in the presence of a Ziegler-Natta catalyst in a first stage comprising at least one gas phase or liquid phase reactor, wherein a first amount of an external donor is added to the first stage. The polymerization product from the first stage is passed to a second stage comprising at least one gas phase or liquid phase reactor, wherein propylene, and ethylene or other alpha-olefin, are polymerized in the presence of the first stage polymerization product. A second amount of an external donor is added to the second stage.
Optionally, an antistatic inhibitor is also added to the second stage.
BRIEF DESCRIPTION OF THE DRAWINGS
Figure 1: Illustrates SEM photos of the cross-sectional area of propylene/ethylene copolymer powders.
DETAILED DESCRIPTION OF THE INVENTION
[0005] Polypropylene copolymers in general are produced in multiple reactors.
For an impact copolymer, a homopolymer is produced in the first stage polymerization, followed by ethylene-propylene or other alpha olefin-propylene copolymer in the second stage polymerization. Other alpha olefins that may be used in lieu of ethylene in the second stage include C4 and higher alpha olefins, preferably C4, C6 or C8 alpha olefins. In particular, the first stage in which the propylene homopolymer is fomied comprises at least one gas phase or liquid phase polymerization reactor. The polymerization product from this first stage is then passed to a second stage comprising at least one gas phase or liquid phase polymerization reactor wherein the copolymer is formed in the presence of the polymerization product from the first stage. The second stage copolymerization is generally accomplished without the addition of additional catalyst. The term liquid phase reactor as used herein is intended to encoinpass both the slurry process and liquid propylene process as described by Ser van der Veii in "Polypropylene and Other Polyolefins", 1990, Elsevier Science Publishing Company, Inc., pp. 119-125. Both the slurry process and the liquid propylene process are described as operating with a suspension of growing polymer particles in a liquid. In the case of the slurry process, the liquid is an inert solvent. In the case of the liquid propylene process it is liquid monomer.
[0006] In most polymerizations using Ziegler-Natta (ZN) type catalysts, the first stage propylene polymerization includes the addition of a co-catalyst comprising a metal alkyl, such as triethylaluminum, and an external electron donor to enhance and/or modify the activity and iso-specificity of the catalyst and thus modify the properties of the propylene homopolyiner produced in the first stage.
For an impact copolymer, a homopolymer is produced in the first stage polymerization, followed by ethylene-propylene or other alpha olefin-propylene copolymer in the second stage polymerization. Other alpha olefins that may be used in lieu of ethylene in the second stage include C4 and higher alpha olefins, preferably C4, C6 or C8 alpha olefins. In particular, the first stage in which the propylene homopolymer is fomied comprises at least one gas phase or liquid phase polymerization reactor. The polymerization product from this first stage is then passed to a second stage comprising at least one gas phase or liquid phase polymerization reactor wherein the copolymer is formed in the presence of the polymerization product from the first stage. The second stage copolymerization is generally accomplished without the addition of additional catalyst. The term liquid phase reactor as used herein is intended to encoinpass both the slurry process and liquid propylene process as described by Ser van der Veii in "Polypropylene and Other Polyolefins", 1990, Elsevier Science Publishing Company, Inc., pp. 119-125. Both the slurry process and the liquid propylene process are described as operating with a suspension of growing polymer particles in a liquid. In the case of the slurry process, the liquid is an inert solvent. In the case of the liquid propylene process it is liquid monomer.
[0006] In most polymerizations using Ziegler-Natta (ZN) type catalysts, the first stage propylene polymerization includes the addition of a co-catalyst comprising a metal alkyl, such as triethylaluminum, and an external electron donor to enhance and/or modify the activity and iso-specificity of the catalyst and thus modify the properties of the propylene homopolyiner produced in the first stage.
[0007] According to the current invention additional external donor is added to the second stage copolymerization, preferably in an amount from about 10 percent to about 200 percent of the ainount of external donor added to the first stage on a molar basis. The external donor added to the second stage may be the same as or different from the externial donor added to the first stage. Exemplary external donors that are useful in the present invention include the non-limiting examples, cyclohexylmethyldimethoxysilane, dicyclopentyldimethoxysilane, diisopropyldimethoxysilane, di-t-butyldimethoxysilane, cyclohexylisopropyldimethoxysilane, n-butylmethyldimethoxysilane, tetraethoxysilane, 3,3,3-trifluoropropylmethyldimethoxysilane and mono and di-alkylaminotriallcoxysilanes. A preferred class of external donors is mono and di-allcylaminotrialkoxysilanes, particularly diethylaminotriethoxysilane. The external donor may be added to the second stage polymerization in any manner as long as one can wet the polymer powders with the external donor. Exemplary methods for injecting the external donor include;
through a monomer feed stream to the polymerization, by spraying into the incoming powder, and/or any reactor port.
through a monomer feed stream to the polymerization, by spraying into the incoming powder, and/or any reactor port.
[0008] According to a preferred enZbodiment of the current invention, the first stage comprises at least one liquid phase loop reactor and the second stage comprises at least one gas phase reactor. Where the second stage copolymerization is a gas phase polymerization, the activity of the catalyst and the composition of the copolymer produced depend on the polymerization conditions and the gas phase ratio, respectively.
[0009] It has been found that addition of additional external donor to the copolymerization increases the amounts of bi-polymer formed and modifies the characteristics of copolymer. Bi-polymer comprises the polymers that are produced in the gas phase reactor at a given gas phase ratio. In the case of the mixture of ethylene and propylene, the bi-polymer is a combination of polyethylene or polyetliylene-like polymer and ethylene/propylene copolymer.
The addition of external donor to the copolymerization of ethylene and propylene increases the amount of bi-polymer formed, increases the molecular weight of ethylene/propylene (EP) copolymer and promotes ethylene incorporation in the copolymer.
Characterization [0010] Several samples of propylene impact copolymers were produced according to the current invention. These materials were tested according to the following methods. The amounts of xylene soluble (XS) and xylene insoluble (XIS) were determined by a method based on ASTM 5492. Molecular weights were determined by high temperature size exclusion chromatography (HSEC) at 140 C. The 75 MHz 13C-NMR spectra were recorded to determine the ethylene content and sequence distributions in each fraction.
The addition of external donor to the copolymerization of ethylene and propylene increases the amount of bi-polymer formed, increases the molecular weight of ethylene/propylene (EP) copolymer and promotes ethylene incorporation in the copolymer.
Characterization [0010] Several samples of propylene impact copolymers were produced according to the current invention. These materials were tested according to the following methods. The amounts of xylene soluble (XS) and xylene insoluble (XIS) were determined by a method based on ASTM 5492. Molecular weights were determined by high temperature size exclusion chromatography (HSEC) at 140 C. The 75 MHz 13C-NMR spectra were recorded to determine the ethylene content and sequence distributions in each fraction.
[0011] For thermal characteristics, DSC (Differential Scanning Calorimetry) was recorded, where polymer was melted at 230 C for 5 minutes and cooled to 0 C at a rate of C/min while recording the recrystallization exotherm. Then, the sample was heated to 190 C
at a rate of 10 C/min to record the melting endotherms.
Donor injection to second-stage gas phase reactor durin2 copolymerization [0012] Several impact copolymers were produced by first polymerizing propylene in a first stage liquid phase polymerization under standard conditions. For the copolymerization of propylene and ethylene in the second stage gas phase polymerization, external donor was injected in amounts about 10 or 20 % of the amount added in the first stage.
The external donor was injected to the second stage gas phase reactor through the monomer feed stream of ethylene.
The donor used in this case was diethylaminotriethoxysilane. To assess the effect of additional antistatic inhibitor, small amounts of Atmer 163, ethoxylated amine, available from CIBA were also injected with the external donor in one sample. While not wishing to be bound by any theory, the inventors believe that the antistatic agent inhibits catalyst activity and thereby modifies the properties of the copolymers produced in the second stage polymerization. The polymers produced with and without additional external donor and Atmer 163 are given in Table I.
Table I
Impact copolymers produced with and without additional external donor and antistatic inhibitor Parameter Unit 2400528B C D E
Dottor to Gas ttone 10 % 20 r'o 20 %
phase reactor dietlrylamino dietltylatrtino diethylatnino trietltoxysilane triethoxysilane triethoxysilane and Atmer163 H2/CZ [ratio] 0.033 0.028 0.034 0.035 Xylene Sols Wt % 19 18.9 20 17.3 XIS XS XIS XS XIS XS XIS XS
C2 % wt 3.0 38.7 3.3 403 3.5 40.9 3.0 39.7 MWD 5.58 4.67 5.11 4.6 5.48 4.26 4.9 4.45 Mn 1000 28.2 52.9 30.7 54.5 28.8 79.4 30.5 73.8 Mw 1000 157 247 157 251 158 338 150 328 Mz 1000 578 895 480 834 643 922 481 951 Mz+1 1000 1404 1958 1353 1794 1923 1783 1051 1886 MFR g/10' 43.4 44 37.6 43.5 Tc - Major C 114 113.5 114.1 114.3 Tc-minor C 93.2 92.6 93.1 NA
Tm-PE C 116 115.2 116.7 NA
Tm-PP C 162.6 162.2 162.5 162.9 % Cryst-DSC % 46 47.5 47 52.3 % Cryst-XRD % 50.1 52.6 50.7 54.8 Flex modulus kpsi 169.1 170.1 167.5 174.3 Izod itlb/in 1.4 .12 1.49 .06 1.46 .1 1.46 .13 TYS4 psi 3455 10 3399 30 3384 8 3521 11 IIMP [-29C] ftlbs 12.8 19.8 20.6 15.3 Rockwell 79.6 .4 81 .3 78.8 .6 83.6 .4 DTUL@66 psi C 86.6 88.3 87.4 86.7 a tensile yield stress; instrumented impact [0013] The results may be summarized as follows.
at a rate of 10 C/min to record the melting endotherms.
Donor injection to second-stage gas phase reactor durin2 copolymerization [0012] Several impact copolymers were produced by first polymerizing propylene in a first stage liquid phase polymerization under standard conditions. For the copolymerization of propylene and ethylene in the second stage gas phase polymerization, external donor was injected in amounts about 10 or 20 % of the amount added in the first stage.
The external donor was injected to the second stage gas phase reactor through the monomer feed stream of ethylene.
The donor used in this case was diethylaminotriethoxysilane. To assess the effect of additional antistatic inhibitor, small amounts of Atmer 163, ethoxylated amine, available from CIBA were also injected with the external donor in one sample. While not wishing to be bound by any theory, the inventors believe that the antistatic agent inhibits catalyst activity and thereby modifies the properties of the copolymers produced in the second stage polymerization. The polymers produced with and without additional external donor and Atmer 163 are given in Table I.
Table I
Impact copolymers produced with and without additional external donor and antistatic inhibitor Parameter Unit 2400528B C D E
Dottor to Gas ttone 10 % 20 r'o 20 %
phase reactor dietlrylamino dietltylatrtino diethylatnino trietltoxysilane triethoxysilane triethoxysilane and Atmer163 H2/CZ [ratio] 0.033 0.028 0.034 0.035 Xylene Sols Wt % 19 18.9 20 17.3 XIS XS XIS XS XIS XS XIS XS
C2 % wt 3.0 38.7 3.3 403 3.5 40.9 3.0 39.7 MWD 5.58 4.67 5.11 4.6 5.48 4.26 4.9 4.45 Mn 1000 28.2 52.9 30.7 54.5 28.8 79.4 30.5 73.8 Mw 1000 157 247 157 251 158 338 150 328 Mz 1000 578 895 480 834 643 922 481 951 Mz+1 1000 1404 1958 1353 1794 1923 1783 1051 1886 MFR g/10' 43.4 44 37.6 43.5 Tc - Major C 114 113.5 114.1 114.3 Tc-minor C 93.2 92.6 93.1 NA
Tm-PE C 116 115.2 116.7 NA
Tm-PP C 162.6 162.2 162.5 162.9 % Cryst-DSC % 46 47.5 47 52.3 % Cryst-XRD % 50.1 52.6 50.7 54.8 Flex modulus kpsi 169.1 170.1 167.5 174.3 Izod itlb/in 1.4 .12 1.49 .06 1.46 .1 1.46 .13 TYS4 psi 3455 10 3399 30 3384 8 3521 11 IIMP [-29C] ftlbs 12.8 19.8 20.6 15.3 Rockwell 79.6 .4 81 .3 78.8 .6 83.6 .4 DTUL@66 psi C 86.6 88.3 87.4 86.7 a tensile yield stress; instrumented impact [0013] The results may be summarized as follows.
[0014] The addition of external donor increased the ethylene (C2) incorporation in ethylene/propylene (EP) copolymer, which is measured as xylene solubles (XS).
[0015] The addition of external donor increased the amounts of bi-polymer, especially in the xylene insoluble (XIS) portion of the polymer. The presence of additional antistatic inhibitor decreased the formation of EP copolymer, i.e. decreased XS.
[0016] The molecular weight (Mw) of XS increased with increasing the amounts of additional external donor. Despite increased hydrogen/ethylene (H2/Ca) ratio, the additional external donor increased the molecular weight (Mw) of EP copolymer (247 vs.
338 Mw/1000), resulting in decrease in MFR.
338 Mw/1000), resulting in decrease in MFR.
[0017] The addition of 20 % external donor to gas phase reactor decreased melt flow rate (MFR) without antistatic inhibitor, but increased MFR with antistatic inhibitor.
[0018] The thermal characteristics of the polymers are comparable to each other, where the overall crystallinity depends on the amounts of xylene solubles.
[0019] Most of the mechanical properties except for the low temperature instrumented impact (IIMP) were comparable. It appears that the instruinented impact depends on the amounts and molecular weight (Mw) of the biopolyiner.
[0020] Since the donor addition to the gas phase reactor promotes the ethylene incorporation, the donor injection into the gas phase reactor is expected to be beneficial to the production of impact copolymer materials that require relatively high Mw EP
copolymer. The SEM photos of the cross-sectional area of the copolymer powders are shown in Figure 1.
copolymer. The SEM photos of the cross-sectional area of the copolymer powders are shown in Figure 1.
[0021] The invention has thus been described in general terms, with reference to specific examples. The full scope of the invention will be apparent to those of ordinary skill in the art based on the appended claims.
Claims (14)
1. A process for producing a propylene copolymer, the process comprising:
in a first stage comprising at least one polymerization reactor, polymerizing propylene in the presence of a Ziegler-Natta catalyst, wherein a first amount of an external donor is added to the first stage, passing a polymerization product from the first stage to a second stage comprising at least one polymerization reactor, and polymerizing propylene and ethylene or other alpha olefin, in the presence of the polymerization product, wherein a second amount of an external donor is added to the second stage.
in a first stage comprising at least one polymerization reactor, polymerizing propylene in the presence of a Ziegler-Natta catalyst, wherein a first amount of an external donor is added to the first stage, passing a polymerization product from the first stage to a second stage comprising at least one polymerization reactor, and polymerizing propylene and ethylene or other alpha olefin, in the presence of the polymerization product, wherein a second amount of an external donor is added to the second stage.
2. The process according to claim 1, wherein the second amount of external donor is from about 10 percent to about 200 percent of the first amount.
3. The process according to claim 1, further comprising:
adding an antistatic inhibitor to the second stage.
adding an antistatic inhibitor to the second stage.
4. The process according to claim 1, wherein the second stage comprises at least one gas phase reactor.
5. The process according to claim 4, wherein the first stage comprises at least one liquid phase reactor.
6. The process according to claim 1, wherein the external donor is selected from the group consisting of cyclohexylmethyldimethoxysilane, dicyclopentyldimethoxysilane, diisopropyldimethoxysilane, di-t-butyldimethoxysilane, cyclohexylisopropyldimethoxysilane, n-butylmethyldimethoxysilane, tetraethoxysilane, 3,3,3-trifluoropropylmethyldimethoxysilane, and mono and di-alkylaminotrialkoxysilanes.
7. The process according to claim 6, wherein the external donor is diethylaininotriethoxysilane.
8. The process according to claim 6, wherein the external donor is cyclohexylmethyldimethoxysilane.
9. The process according to claim 1, wherein the external donor added to the first stage is the same as the external donor added to the second stage.
10. The process according to claim 1, wherein the external donor added to the first stage is different from the external donor added to the second stage.
11. A process for producing a propylene copolymer, the process comprising:
in a first stage comprising at least one liquid phase reactor, polymerizing propylene in the presence of a Ziegler-Natta catalyst, wherein a first amount of an external donor is added to the first stage, passing a polymerization product from the first stage to a second stage comprising at least one gas phase reactor, and polymerizing propylene and ethylene or another alpha olefin, in the presence of the polymerization product, wherein a second amount of the external donor and an antistatic inhibitor are added to the second stage, the second amount of the external donor being from about 10 percent to about percent of the first amount.
in a first stage comprising at least one liquid phase reactor, polymerizing propylene in the presence of a Ziegler-Natta catalyst, wherein a first amount of an external donor is added to the first stage, passing a polymerization product from the first stage to a second stage comprising at least one gas phase reactor, and polymerizing propylene and ethylene or another alpha olefin, in the presence of the polymerization product, wherein a second amount of the external donor and an antistatic inhibitor are added to the second stage, the second amount of the external donor being from about 10 percent to about percent of the first amount.
12. The process according to claim 11, wherein the external donor is selected from the group consisting of cyclohexylmethyldimethoxysilane, dicyclopentyldimethoxysilane, diisopropyldimethoxysilane, di-t-butyldimethoxysilane, cyclohexylisopropyldimethoxysilane, n-butylmethyldimethoxysilane, tetraethoxysilane, 3,3,3-trifluoropropylmethyldimethoxysilane, and mono and di-alkylaminotrialkoxysilanes.
13. The process according to claim 12, wherein the external donor is diethylaminotriethoxysilane.
14. The process according to claim 12, wherein the external donor is cyclohexylmethyl dimethoxysilane.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
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US11/090,523 US8026311B2 (en) | 2005-03-25 | 2005-03-25 | Process for production of propylene copolymers |
US11/090,523 | 2005-03-25 | ||
PCT/US2006/010130 WO2006104756A1 (en) | 2005-03-25 | 2006-03-21 | Process for the production of propylene copolymers |
Publications (2)
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CA2600362A1 true CA2600362A1 (en) | 2006-10-05 |
CA2600362C CA2600362C (en) | 2013-11-12 |
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CA2600362A Expired - Fee Related CA2600362C (en) | 2005-03-25 | 2006-03-21 | Process for production of propylene copolymers |
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US (1) | US8026311B2 (en) |
CA (1) | CA2600362C (en) |
MX (1) | MX2007011777A (en) |
TW (1) | TW200704651A (en) |
WO (1) | WO2006104756A1 (en) |
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EP2171137A4 (en) * | 2007-07-23 | 2012-10-03 | Fina Technology | Resin composition for improved slit film |
US20100125124A1 (en) * | 2008-11-17 | 2010-05-20 | Fina Technology, Inc. | Methods of catalyst activation |
EP2226337A1 (en) * | 2009-03-02 | 2010-09-08 | Borealis AG | Process for the production of polypropylene random copolymers for injection moulding applications |
US20110034651A1 (en) * | 2009-08-06 | 2011-02-10 | Basf Catalysts Llc | Mixed donor system for high melt flow and high activity |
MX362519B (en) * | 2010-12-20 | 2019-01-21 | Braskem America Inc | Propylene-based compositions of enhanced appearance and excellent mold flowability. |
US8685879B2 (en) | 2011-04-29 | 2014-04-01 | Basf Corporation | Emulsion process for improved large spherical polypropylene catalysts |
US10465025B2 (en) | 2014-01-15 | 2019-11-05 | Exxonmobil Chemical Patents Inc. | Low comonomer propylene-based impact copolymers |
US10308740B2 (en) | 2014-02-07 | 2019-06-04 | Eastman Chemical Company | Amorphous propylene-ethylene copolymers |
US11267916B2 (en) | 2014-02-07 | 2022-03-08 | Eastman Chemical Company | Adhesive composition comprising amorphous propylene-ethylene copolymer and polyolefins |
US10647795B2 (en) | 2014-02-07 | 2020-05-12 | Eastman Chemical Company | Adhesive composition comprising amorphous propylene-ethylene copolymer and polyolefins |
US10723824B2 (en) | 2014-02-07 | 2020-07-28 | Eastman Chemical Company | Adhesives comprising amorphous propylene-ethylene copolymers |
US10696765B2 (en) | 2014-02-07 | 2020-06-30 | Eastman Chemical Company | Adhesive composition comprising amorphous propylene-ethylene copolymer and propylene polymer |
US9399686B2 (en) | 2014-02-07 | 2016-07-26 | Eastman Chemical Company | Amorphous propylene-ethylene copolymers |
CN103819595B (en) * | 2014-03-07 | 2016-08-17 | 中石化上海工程有限公司 | Polypropylene manufacturing process |
CN111295399B (en) * | 2017-11-06 | 2022-09-06 | 埃克森美孚化学专利公司 | Propylene-based impact copolymers and process and apparatus for producing |
CN108192005B (en) * | 2017-12-29 | 2021-03-26 | 黄河三角洲京博化工研究院有限公司 | Polyolefin and preparation method thereof |
WO2021080813A1 (en) | 2019-10-22 | 2021-04-29 | Exxonmobil Chemical Patents Inc. | Thermoplastic vulcanizate compositions and processes for the production thereof |
WO2021080803A1 (en) | 2019-10-22 | 2021-04-29 | Exxonmobil Chemical Patents Inc. | Impact copolymer compositions |
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-
2005
- 2005-03-25 US US11/090,523 patent/US8026311B2/en active Active
-
2006
- 2006-03-21 WO PCT/US2006/010130 patent/WO2006104756A1/en active Application Filing
- 2006-03-21 CA CA2600362A patent/CA2600362C/en not_active Expired - Fee Related
- 2006-03-21 MX MX2007011777A patent/MX2007011777A/en active IP Right Grant
- 2006-03-23 TW TW095110115A patent/TW200704651A/en unknown
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