WO1989003847A1 - Catalysts for the preparation of amorphous copolymers of propylene and olefins - Google Patents
Catalysts for the preparation of amorphous copolymers of propylene and olefins Download PDFInfo
- Publication number
- WO1989003847A1 WO1989003847A1 PCT/US1988/003637 US8803637W WO8903847A1 WO 1989003847 A1 WO1989003847 A1 WO 1989003847A1 US 8803637 W US8803637 W US 8803637W WO 8903847 A1 WO8903847 A1 WO 8903847A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- catalyst
- weight percent
- aluminum
- ticl
- supported
- Prior art date
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- 239000003054 catalyst Substances 0.000 title claims abstract description 90
- 229920005606 polypropylene copolymer Polymers 0.000 title description 5
- 238000002360 preparation method Methods 0.000 title description 3
- 150000001336 alkenes Chemical class 0.000 title description 2
- 238000000034 method Methods 0.000 claims abstract description 33
- 229920001577 copolymer Polymers 0.000 claims abstract description 30
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000000203 mixture Substances 0.000 claims abstract description 22
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 claims abstract description 22
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims abstract description 17
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims abstract description 17
- 229910010062 TiCl3 Inorganic materials 0.000 claims abstract description 15
- 230000001070 adhesive effect Effects 0.000 claims abstract description 13
- 229910003074 TiCl4 Inorganic materials 0.000 claims abstract description 10
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims abstract description 10
- 239000000853 adhesive Substances 0.000 claims abstract 2
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 claims description 18
- 239000002904 solvent Substances 0.000 claims description 9
- 230000003068 static effect Effects 0.000 claims description 9
- 241000411998 Gliricidia Species 0.000 claims description 8
- 235000009664 Gliricidia sepium Nutrition 0.000 claims description 8
- 239000004820 Pressure-sensitive adhesive Substances 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 8
- -1 polypropylene Polymers 0.000 claims description 8
- 239000000523 sample Substances 0.000 claims description 7
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 6
- 239000004743 Polypropylene Substances 0.000 claims description 6
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 claims description 6
- 150000002170 ethers Chemical class 0.000 claims description 6
- MTZQAGJQAFMTAQ-UHFFFAOYSA-N ethyl benzoate Chemical compound CCOC(=O)C1=CC=CC=C1 MTZQAGJQAFMTAQ-UHFFFAOYSA-N 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- QPJVMBTYPHYUOC-UHFFFAOYSA-N methyl benzoate Chemical compound COC(=O)C1=CC=CC=C1 QPJVMBTYPHYUOC-UHFFFAOYSA-N 0.000 claims description 6
- 150000002895 organic esters Chemical class 0.000 claims description 6
- 229920001155 polypropylene Polymers 0.000 claims description 6
- 239000000155 melt Substances 0.000 claims description 5
- 239000012943 hotmelt Substances 0.000 claims description 3
- 229910001502 inorganic halide Inorganic materials 0.000 claims description 3
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 3
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 claims description 3
- 229940095102 methyl benzoate Drugs 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- SQBBHCOIQXKPHL-UHFFFAOYSA-N tributylalumane Chemical compound CCCC[Al](CCCC)CCCC SQBBHCOIQXKPHL-UHFFFAOYSA-N 0.000 claims description 3
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 claims description 3
- 229920000089 Cyclic olefin copolymer Polymers 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 241000721701 Lynx Species 0.000 description 12
- 239000000047 product Substances 0.000 description 12
- 239000000178 monomer Substances 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 8
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- 230000003247 decreasing effect Effects 0.000 description 5
- 239000003085 diluting agent Substances 0.000 description 5
- 239000000758 substrate Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- 239000011707 mineral Substances 0.000 description 3
- 229920000098 polyolefin Polymers 0.000 description 3
- 235000015096 spirit Nutrition 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 1
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1-dodecene Chemical compound CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 241001296096 Probles Species 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000000306 component Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 150000001924 cycloalkanes Chemical class 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- CCCMONHAUSKTEQ-UHFFFAOYSA-N octadec-1-ene Chemical compound CCCCCCCCCCCCCCCCC=C CCCMONHAUSKTEQ-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- 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
- C08F2410/00—Features related to the catalyst preparation, the catalyst use or to the deactivation of the catalyst
- C08F2410/04—Dual catalyst, i.e. use of two different catalysts, where none of the catalysts is a metallocene
Definitions
- This invention relates to a novel titanium-based catalyst mixture for the synthesis of pressuresensitive adhesives that are amorphous copolymers of propylene and 1-olefins in a high temperature solution process.
- Amorphous polyolefins particularly propylene/hexene copolymers, are generally useful as pressure-sensitive adhesives.
- Pressure-sensitive adhesives for medical tape applications require a balance of high viscosity, good strength and good tack.
- U.S. Patent 3,954,697 discloses single component, hot-melt, pressure-sensitive adhesives that are propylene copolymers containing 40 to 60 mole percent hexene and having a 130°C to 148°C softening point. While the copolymers of this patent are useful, they are limited in their utility to substrates with a higher melting point than the copolymer. Application of amorphous propylene-hexene copolymers disclosed in this patent to substrates such as polyethylene is difficult without melting the substrate which results in undesirable holes and puckers in the substrate. The amorphous propylene/hexene copolymers disclosed in the prior art are made by use of single catalysts with an aluminum-alkyl cocatalyst. It has been discovered that a mixture of certain catalysts hereinafter described provide amorphous propylene-hexene copolymers with an unexpected balance of properties ideally suited for use as pressure-sensitive adhesives for medical tape applications.
- the present invention is directed to a catalyst mixture comprising:
- the present invention is also directed to a process for preparing an amorphous propylene/higher 1-olefin copolymer comprising contacting propylene and a higher 1-olefin with the above-described catalyst mixture for a sufficient reaction period and under conditions such that the desired copolymer is formed.
- the present invention is further directed to a copolymer that is prepared from the process of the invention.
- the copolymer of the present invention is a hot-melt, pressure-sensitive adhesive comprising an amorphous propylene/hexene copolymer.
- copolymer containing about40 to about 75 weight percent 1-hexene, said copolymer having a melt viscosity of about 5,000 to about 50,000 centipoises (cp) at 190°C, a softening point of about 90°C to about 125°C, a probe tack of at least about 500 grams, a quick stick of at least 1.5 pounds per inch, and a static shear of at least about 10 hours.
- cp centipoises
- the weight percent of supported catalyst (a) is about 15 to about 45 (based on the weight of (a) plus (b)), more preferably about 25; that the weight percent of preactivated catalyst (b) is about 85 to about 55 (based on the weight of (a) plus (b)), more preferably about 75; and that the molar ratio of aluminum-alkyl:Ti-chloride is about 1:1 to about 1.5:1, more preferably about 1.25:1.
- the supported catalyst useful in the present invention preferably comprises TiCl 4 supported on MgCl 2 .
- the amount of TiCl 4 on the support is preferably about 1 to about 15 weight percent; more preferably about 1 to about 10 weight percent; and most preferably about 10 weight percent.
- the supported catalyst can optionally contain up to about 25 weight percent organic esters and ethers.
- organic esters and ethers are typically present in commercial supported catalyst preparations and can include, for example, anisole, ethyl benzoate, methyl benzoate, and the like.
- a commercially available supported catalyst suitable for use in the present invention is Lynx 705, available from Catalyst Resources, Inc., Houston, Texas.
- the preactivated catalyst useful in the present invention is preactivated TiCl 3 .
- the TiCl 3 used to prepare the preactivated TiCl 3 can be any of the commonly available forms of TiCl 3 such as aluminum reduced and activated TiCl 3 (AA-TiCl 3 ), hydrogen reduced and activated TiCl 3 , or chemically reduced TiCl 3 . In the case of AA-TiCl 3 , the TiCl 3 is complexed with AlCl 3 .
- the TiCl 3 can be preactivated by any suitable means known in the catalyst art.
- preactivate TiCl 3 by prepolymerizing propylene to about the 10 to 50 percent polypropylene level to obtain a preactivated catalyst comprising about 10 to 50 weight percent polypropylene and about 90 to 50 weight percent TiCl 3 .
- a preferred weight ratio of TiCl 3 to polypropylene is about 50 to 50.
- the preactivated catalyst prepared from chemically reduced TiCl 3 may also contain traces of other inorganic substances such as A1Cl 3 .
- a commercially available preactivated catalyst for use in the present invention is Lynx 900 (prepared from chemically reduced TiCl 3 ), available from Catalyst Resources, Inc., Houston, Texas.
- the aluminum-alkyl cocatalyst useful in the present invention complexes with the Ti-chloride (i.e., both TiCl 3 and TiCl 4 ).
- alkyl refers to C 2 to C 6 alkyls.
- Preferred aluminum-alkyls are triethyl aluminum, tributyl aluminum, and triisobutyl aluminum.
- the most preferred catalyst is triethyl aluminum.
- Higher 1-olefins suitable for use in the present invention include, for example, heptene-1, octene-1, nonene-1, decene-1, dodecene-1, octadecene-1, and the like.
- the process of the present invention can be characterized as a high temperature solution polymerization process.
- Preferred conditions for the process of the present invention include a temperature at about 140°C to about 200°C, and a pressure of about 400 to about 2000 pounds per square inch gauge (psig); more preferred is a temperature of from about 150°C to about 180°C and a pressure of about 1000 to about 1500 psig.
- the process preferably takes place under an inert atmosphere, such as nitrogen or argon, for a time sufficient to form the desired product, for example, about 1/2 to about 10 hours, with about 2 to about 4 hours being preferred.
- the process generally is preferably carried out with agitation, e.g., stirring.
- a solvent or diluent is used for the process of the present invention, particularly as a diluent for the catalyst mixture.
- Organic solvents which can be used for the addition of catalyst mixtures and diluent include, for example, aliphatic alkanes or cycloalkanes such as propane, pentane, hexane, heptane, cyclohexane, and the like, or hydrogenated aromatic compounds such as decahydronaphthalene, or aromatic hydrocarbons such as benzene, toluene, xylene, and the like.
- the nature of the solvent is subject to considerable variation but should be a liquid form at the reaction conditions and essentially inert to the reactants and reaction products.
- a petroleum fraction of suitable boiling range such as mineral spirits (a sulfuric acid washed paraffinic hydrocarbon boiling at 180°C to 220°C) is a particularly good and preferred solvent or diluent.
- the process of the present invention can be performed either continuously or batchwise; preferred is continuously.
- a continuous process generally the catalyst mixture in solvent and monomer mixture are fed into a suitable reactor and polymerization is allowed to occur under polymerization conditions.
- the catalyst mixture is charged into the reactor first. After polymerization it is typically desired to remove unreacted monomer, deactivate the catalyst and further purify the copolymer, for example, by passing through an alumina bed and/or filtration and subsequent solvent removal.
- the propylene/hexene-1 copolymer produced by the process of the present invention has a unique balance of adhesive properties.
- the copolymer contains about 40 to 75 weight percent hexene-1, preferably 55 to 65 weight percent hexene-1. Hexene content can be determined by either C 13 nuclear magnetic resonance or by Fourier transfer infrared spectroscopy.
- the copolymer has a melt viscosity of about 5,000 to about 50,000 cp at 190°C, preferably about 15,000 to about 25,000 cp at 190°C.
- the softening point of the copolymer of the present invention is between about 90°C and about 125°C, preferably between about 95°C and about
- the softening point can be determined using the Ring and Ball method described in ASTM
- the copolymer of the present invention has a probe tack of at least about 500 grams, preferably between about 500 grams and about 650 grams. Probe tack can be measured on a Polyken Probe Tack tester at a dwell time of 2 seconds and a carrier speed of
- the copolymer of the present invention has a quick stick of at least about 1.5 pounds per inch, preferably about 1.7.
- Quick stick can be determined by Pressure-Sensitive Tape Council (PSTC) Procedure
- the copolymer of the present invention has a
- Peel adhesion can be determined using Procedure PSTC-1.
- the copolymer of the present invention has a static shear of at least about 10 hours, preferably about 15 hours.
- Static shear can be determined using Procedure PSTC-7 with 1 kilogram (kg) weight. The time taken for coated tape to completely separate from the test panel is reported as the static shear value.
- the following examples are to illustrate the invention but should not be interpreted as a limitation thereon. All percentages are by weight unless specified otherwise. For the following examples, the following general conditions were used: A 6.7-gallon stirred loop reactor was fed continuously with the monomer mixture and a catalyst slurry using mineral spirits as diluent.
- the polymerization was controlled at a pressure of 1,000 psi and a temperature of 150°C to 180°C depending on the amorphous propylene/hexene (APH) viscosity target.
- APH amorphous propylene/hexene
- the APH product containing unreacted monomers, catalyst, and some solvent was transferred continuously to a letdown tank where the monomers were flashed overhead.
- the product was then subjected to a steam/air catalyst deactivation process in the solvent stripper and finally pumped through an alumina bed.
- the finished product was characterized by viscosity, ring and ball softening point (RBSP), weight percent hexene by infrared, and adhesive property determination.
- RBSP ring and ball softening point
- Table I shows how the changes in catalyst, catalyst mole ratio, and reaction conditions affect the polymer yield, monomer conversions, and the viscosity, RBSP, and hexene content of the APH product.
- Table II shows the effect of catalyst and catalyst mole ratio on the adhesive properties of the APH products.
- Example 1 through 8 the triethyl aluminum (AlEt 3 )/Lynx 900 catalyst was evaluated for production of pressure-sensitive APH.
- the catalyst mole ratio, temperature, and propylene and hexene feeds were varied in an effort to produce a 20,000 cp viscosity APH with a good balance of adhesive properties.
- This catalyst at a AlEt 3 /Ti-halide mole ratio of 0.5/1 gave the best results considering polymer yield and APH adhesive properties. Raising the catalyst mole ratio from 0.5/1 to 1/1 increases the polymer yield somewhat but also increases the APH visocity considerably at a reactor temperature of 162°C.
- APH was produced in a batch polymerization process using a 2-liter stainless steel stirred autoclave.
- the catalyst (0.7 gram) AlEt./Lynx 705 at a AlEt 3 /TiCl, mole ratio of 4/1 was charged to a preheated autoclave containing 100 mL mineral spirits, 800 mL hexene, and 500 psi C 3 H 6 .
- the polymerization was conducted at 140°C, a pressure of 400 psi and a reaction time of 180 minutes.
- the discharged polymer was recovered by vacuum stripping at 230°C for 3 hours.
- the final product (200 grams) contained 51% hexene, and had a viscosity of 8.125 cp and a RBSP of 98°C. Its adhesive properties showed good probe tack (780 grams), good 180° peel adhesion (3.0 pounds per inch), fair quick stick (1.3 pounds per inch) and very poor static shear adhesion (1.1 hours).
- Example 10 through 18 a mixed catalyst consisting of Lynx 900 and Lynx 705 was evaluated for the production of pressure-sensitive APH.
- the catalyst composition, catalyst mole ratio, temperature, and propylene and hexene feeds were varied in an effort to optimize the balance of adhesive properties of APH. Best results were obtained with a catalyst consisting of 75% Lynx 900 and 25% Lynx 705 cocatalyzed with AlEt 3 at a AlEt 3 to Ti-halide mole ratio of 1/1 to 1.25/1.
- APH containing 59% to 60% hexane and having the desired viscosity of about 20,000 cp and a RBSP of 118°C to 119°C showed a very good balance of adhesive properties. See Examples 12 and 15.
- the APH products combined good probe tack (659 to 693 grams), good quick stick (1.5 to 1.7 pounds per inch), and good 180° peel adhesion (2.5 to 2.8 pounds per inch) with good static shear adhesion 19 to 22 hours). They also proved to be nonirritants to the human skin. This combination of properties makes them particularly well-suited for medical tape application. Examples 19 and 20 (Comparative)
- Example 19 the AlEt 3 /AA-TiCl 3 catalyst was evaluated for the production of pressure-sensitive APH.
- This catalyst system was taught for APH synthesis in U.S. Patent 3,954,697.
- Table II APH varying from 59% to 64% in hexene content exhibits adhesive properties very much inferior to APH produced with the catalyst of this invention.
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
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Abstract
Disclosed is a catalyst mixture comprising TiCl3, TiCl4, and an aluminum-alkyl cocatalyst. The catalyst mixture is particularly advantageous for the synthesis of pressure-sensitive amorphous adhesives that are copolymeres of propylene and 1-olefin, such as 1-hexene, in a high temperature solution process.
Description
CATALYSTS FOR THE PREPARATION OF AMORPHOUS COPOLYMERS OF PROPYLENE AND OLEFINS
Field of Invention
This invention relates to a novel titanium-based catalyst mixture for the synthesis of pressuresensitive adhesives that are amorphous copolymers of propylene and 1-olefins in a high temperature solution process.
Background of the Invention
Commerical catalysts based on TiCl3 or TiCl4 produce either amorphous polyolefins with good strength and poor tack or produce amorphous polyolefins with good tack and poor strength.
Amorphous polyolefins, particularly propylene/hexene copolymers, are generally useful as pressure-sensitive adhesives. Pressure-sensitive adhesives for medical tape applications require a balance of high viscosity, good strength and good tack.
U.S. Patent 3,954,697 discloses single component, hot-melt, pressure-sensitive adhesives that are propylene copolymers containing 40 to 60 mole percent hexene and having a 130°C to 148°C softening point. While the copolymers of this patent are useful, they are limited in their utility to substrates with a higher melting point than the copolymer. Application of amorphous propylene-hexene copolymers disclosed in this patent to substrates such as polyethylene is difficult without melting the substrate which results in undesirable holes and puckers in the substrate.
The amorphous propylene/hexene copolymers disclosed in the prior art are made by use of single catalysts with an aluminum-alkyl cocatalyst. It has been discovered that a mixture of certain catalysts hereinafter described provide amorphous propylene-hexene copolymers with an unexpected balance of properties ideally suited for use as pressure-sensitive adhesives for medical tape applications.
Summary of the Invention
The present invention is directed to a catalyst mixture comprising:
(a) About 5 to about 50 weight percent (based on the weight of (a) plus (b)) of a supported catalyst comprising TiCl, supported on an inorganic halide salt,
(b) About 95 to about 50 weight percent (based on the weight of (a) plus (b)) of a preactivated catalyst comprising preactivated TiCl3, and
(c) An aluminum-alkyl cocatalyst at a molar ratio of aluminum-alkyl:Ti-chloride at about 0.25:1 to about 2:1.
The present invention is also directed to a process for preparing an amorphous propylene/higher 1-olefin copolymer comprising contacting propylene and a higher 1-olefin with the above-described catalyst mixture for a sufficient reaction period and under conditions such that the desired copolymer is formed.
The present invention is further directed to a copolymer that is prepared from the process of the invention. The copolymer of the present invention is a hot-melt, pressure-sensitive adhesive comprising an amorphous propylene/hexene copolymer. containing about40 to about 75 weight percent 1-hexene, said copolymer having a melt viscosity of about 5,000 to about 50,000 centipoises (cp) at 190°C, a softening point of about 90°C to about 125°C, a probe tack of at least about 500 grams, a quick stick of at least 1.5 pounds per inch, and a static shear of at least about 10 hours.
Detailed Description of the Invention The teachings of U.S. Patent 3,954,697 link copolymer composition with its softening point. It is taught that as the weight percent polymerized hexene in the copolymer increases, the softening point decreases. Thus, as in most prior art copolymer systems, the softening point varies with comonomer concentration in the copolymer in a regular manner from the value of the softening point of the homopolymer of one monomer to the value of the homopolymer of the second monomer. In this case the softening point of the amorphous propylene-hexene copolymer ranges from the value for polyhexene (80°C) to the value for polypropylene (151ºC).
However, it has been surprisingly discovered in the present invention that at a given hexene incorporation level in the copolymer it is possible to vary the softening point by making an appropriate choice of catalyst mixture and cocatalyst.
In the catalyst mixture of the present invention it is preferred that the weight percent of supported catalyst (a) is about 15 to about 45 (based on the weight of (a) plus (b)), more preferably about 25;
that the weight percent of preactivated catalyst (b) is about 85 to about 55 (based on the weight of (a) plus (b)), more preferably about 75; and that the molar ratio of aluminum-alkyl:Ti-chloride is about 1:1 to about 1.5:1, more preferably about 1.25:1. The supported catalyst useful in the present invention preferably comprises TiCl4 supported on MgCl2. The amount of TiCl4 on the support is preferably about 1 to about 15 weight percent; more preferably about 1 to about 10 weight percent; and most preferably about 10 weight percent. The supported catalyst can optionally contain up to about 25 weight percent organic esters and ethers. Such organic esters and ethers are typically present in commercial supported catalyst preparations and can include, for example, anisole, ethyl benzoate, methyl benzoate, and the like. A commercially available supported catalyst suitable for use in the present invention is Lynx 705, available from Catalyst Resources, Inc., Houston, Texas.
The preactivated catalyst useful in the present invention is preactivated TiCl3. The TiCl3 used to prepare the preactivated TiCl3 can be any of the commonly available forms of TiCl3 such as aluminum reduced and activated TiCl3 (AA-TiCl3), hydrogen reduced and activated TiCl3, or chemically reduced TiCl3. In the case of AA-TiCl3, the TiCl3 is complexed with AlCl3. The TiCl3 can be preactivated by any suitable means known in the catalyst art. It is preferred to preactivate TiCl3 by prepolymerizing propylene to about the 10 to 50 percent polypropylene level to obtain a preactivated catalyst comprising about 10 to 50 weight percent polypropylene and about 90 to 50 weight percent TiCl3. A preferred weight ratio of TiCl3 to polypropylene is about 50 to 50. The
preactivated catalyst prepared from chemically reduced TiCl3 may also contain traces of other inorganic substances such as A1Cl3. A commercially available preactivated catalyst for use in the present invention is Lynx 900 (prepared from chemically reduced TiCl3), available from Catalyst Resources, Inc., Houston, Texas.
The aluminum-alkyl cocatalyst useful in the present invention complexes with the Ti-chloride (i.e., both TiCl3 and TiCl4). As used herein "alkyl" refers to C2 to C6 alkyls. Preferred aluminum-alkyls are triethyl aluminum, tributyl aluminum, and triisobutyl aluminum. The most preferred catalyst is triethyl aluminum. Although the preferred .process of the present invention produces a copolymer of propylene/hexene-1, the process is not so limited and is applicable for production of copolymers of propylene and other higher 1-olefins. Higher 1-olefins suitable for use in the present invention include, for example, heptene-1, octene-1, nonene-1, decene-1, dodecene-1, octadecene-1, and the like.
The process of the present invention can be characterized as a high temperature solution polymerization process.
Preferred conditions for the process of the present invention include a temperature at about 140°C to about 200°C, and a pressure of about 400 to about 2000 pounds per square inch gauge (psig); more preferred is a temperature of from about 150°C to about 180°C and a pressure of about 1000 to about 1500 psig. The process preferably takes place under an inert atmosphere, such as nitrogen or argon, for a time sufficient to form the desired product, for example, about 1/2 to about 10 hours, with about 2 to
about 4 hours being preferred. The process generally is preferably carried out with agitation, e.g., stirring.
It is also preferred that a solvent or diluent is used for the process of the present invention, particularly as a diluent for the catalyst mixture. Organic solvents which can be used for the addition of catalyst mixtures and diluent include, for example, aliphatic alkanes or cycloalkanes such as propane, pentane, hexane, heptane, cyclohexane, and the like, or hydrogenated aromatic compounds such as decahydronaphthalene, or aromatic hydrocarbons such as benzene, toluene, xylene, and the like. The nature of the solvent is subject to considerable variation but should be a liquid form at the reaction conditions and essentially inert to the reactants and reaction products. A petroleum fraction of suitable boiling range such as mineral spirits (a sulfuric acid washed paraffinic hydrocarbon boiling at 180°C to 220°C) is a particularly good and preferred solvent or diluent.
The process of the present invention can be performed either continuously or batchwise; preferred is continuously. In a continuous process, generally the catalyst mixture in solvent and monomer mixture are fed into a suitable reactor and polymerization is allowed to occur under polymerization conditions. Preferably, the catalyst mixture is charged into the reactor first. After polymerization it is typically desired to remove unreacted monomer, deactivate the catalyst and further purify the copolymer, for example, by passing through an alumina bed and/or filtration and subsequent solvent removal.
The propylene/hexene-1 copolymer produced by the process of the present invention has a unique balance of adhesive properties. The copolymer contains about
40 to 75 weight percent hexene-1, preferably 55 to 65 weight percent hexene-1. Hexene content can be determined by either C13 nuclear magnetic resonance or by Fourier transfer infrared spectroscopy. The copolymer has a melt viscosity of about 5,000 to about 50,000 cp at 190°C, preferably about 15,000 to about 25,000 cp at 190°C.
The melt viscosity of the polymer can be determined by using a Brookfield Thermosel Viscometer according to the methodology described in American
Society for Testing and Materials (ASTM) Method
D-1824-66.
The softening point of the copolymer of the present invention is between about 90°C and about 125°C, preferably between about 95°C and about
120°C. The softening point can be determined using the Ring and Ball method described in ASTM
Method E-28.
The copolymer of the present invention has a probe tack of at least about 500 grams, preferably between about 500 grams and about 650 grams. Probe tack can be measured on a Polyken Probe Tack tester at a dwell time of 2 seconds and a carrier speed of
2 centimeters (cm)/second (sec). The copolymer of the present invention has a quick stick of at least about 1.5 pounds per inch, preferably about 1.7. Quick stick can be determined by Pressure-Sensitive Tape Council (PSTC) Procedure
PSTC-5. The copolymer of the present invention has a
180° peel adhesion of at least about 2.5 pounds per inch; preferably about 3.0. Peel adhesion can be determined using Procedure PSTC-1.
The copolymer of the present invention has a static shear of at least about 10 hours, preferably about 15 hours. Static shear can be determined using
Procedure PSTC-7 with 1 kilogram (kg) weight. The time taken for coated tape to completely separate from the test panel is reported as the static shear value. The following examples are to illustrate the invention but should not be interpreted as a limitation thereon. All percentages are by weight unless specified otherwise. For the following examples, the following general conditions were used: A 6.7-gallon stirred loop reactor was fed continuously with the monomer mixture and a catalyst slurry using mineral spirits as diluent. The polymerization was controlled at a pressure of 1,000 psi and a temperature of 150°C to 180°C depending on the amorphous propylene/hexene (APH) viscosity target. The APH product containing unreacted monomers, catalyst, and some solvent was transferred continuously to a letdown tank where the monomers were flashed overhead. The product was then subjected to a steam/air catalyst deactivation process in the solvent stripper and finally pumped through an alumina bed. The finished product was characterized by viscosity, ring and ball softening point (RBSP), weight percent hexene by infrared, and adhesive property determination.
In general the following reaction conditions . were maintained.
Reactor Temp, °C 162
Reactor Glycol Jacket Temp, °C 154 Reactor Pressure, psig 1000
Stirrer Speed, 750
Revolutions per Minute (RPM) Propylene Charge, 3.07 pound (1b)/hour (hr) Hexene Charge, 1b/hr 6.17
Catalyst Charge, grams (g)/hr 1.2 Residence Time, hr 3.3
Polymer Produced, 1b/hr 7.5
Table I shows how the changes in catalyst, catalyst mole ratio, and reaction conditions affect the polymer yield, monomer conversions, and the viscosity, RBSP, and hexene content of the APH product. Table II shows the effect of catalyst and catalyst mole ratio on the adhesive properties of the APH products.
Examples 1 through 8 (Comparative)
In Examples 1 through 8 the triethyl aluminum (AlEt3)/Lynx 900 catalyst was evaluated for production of pressure-sensitive APH. The catalyst mole ratio, temperature, and propylene and hexene feeds were varied in an effort to produce a 20,000 cp viscosity APH with a good balance of adhesive properties. This catalyst at a AlEt3/Ti-halide mole ratio of 0.5/1 gave the best results considering polymer yield and APH adhesive properties. Raising the catalyst mole ratio from 0.5/1 to 1/1 increases the polymer yield somewhat but also increases the APH visocity considerably at a reactor temperature of 162°C. Increasing the reactor temperature from 162°C to 171°C decreased the viscosity from 42,000 cp to the desired 20,000 cp but had a very detrimental effect on polymer yield, decreasing it from 5,758 to 1,400 pounds APH per pound of catalyst. APH produced with AlEt3/ Lynx 900 catalyst at a mole ratio of
1/1 had also very poor quick stick, 0.7 to 0.8 pounds per inch. Decreasing the AlEt3/Ti-halide mole ratio from 0.5/1 to 0.25/1 decreased the APH yield from about 4,000 to 2,000 pounds per pound and decreased he viscosity from 20,000 cp to 8,500 cp. To bring the viscosity up into specification range
the reactor temperature had to be lowered from 161°C to 156°C and the propylene feed had to be raised from 3.1 to 3.4 pounds per hour. These changes resulted in APH having a viscosity of 15,500 cp and a hexene content of 59%. The adhesive properties of this product are inferior to those of the best APH produced with the AlEt3/Lynx 900 catalyst at a mole ratio of 0.5/1, especially in probe tack and static shear. Compare Example 4 with Example 8 in Tables I and II.
To meet the specifications of pressure-sensitive adhesives for medical tape applications, products should exhibit a viscosity of about 20,000 cp, a proble tack of 650 to 700 grams, a quick stick of 1.5 to 2.0 pounds per inch, a 180° peel adhesion of 2.5 to 3.0 pounds per inch, and a static shear adhesion of 15 to 20 hours. In an effort to produce such a product propylene and hexene was copolymerized using the AlEt3/Lynx 900 catalyst system. The effect of catalyst mole ratio, reactor temperature, and product composition on the polymer yield and APH adhesive properties was studied. The best APH product for the medical tape application contained 62% hexene and was produced at 163°C using the AlEt3/Lynx 900 catalyst at a AlEt3/TiCl3 mole ratio of 0.5/1 See
Example 4.
Example 9 (Comparative)
APH was produced in a batch polymerization process using a 2-liter stainless steel stirred autoclave. The catalyst (0.7 gram) AlEt./Lynx 705 at a AlEt3/TiCl, mole ratio of 4/1 was charged to a preheated autoclave containing 100 mL mineral spirits, 800 mL hexene, and 500 psi C3H6. The polymerization was conducted at 140°C, a pressure of 400 psi and a reaction time of 180 minutes. The
discharged polymer was recovered by vacuum stripping at 230°C for 3 hours. The final product (200 grams) contained 51% hexene, and had a viscosity of 8.125 cp and a RBSP of 98°C. Its adhesive properties showed good probe tack (780 grams), good 180° peel adhesion (3.0 pounds per inch), fair quick stick (1.3 pounds per inch) and very poor static shear adhesion (1.1 hours).
Examples 10 through 18
In Examples 10 through 18 a mixed catalyst consisting of Lynx 900 and Lynx 705 was evaluated for the production of pressure-sensitive APH. The catalyst composition, catalyst mole ratio, temperature, and propylene and hexene feeds were varied in an effort to optimize the balance of adhesive properties of APH. Best results were obtained with a catalyst consisting of 75% Lynx 900 and 25% Lynx 705 cocatalyzed with AlEt3 at a AlEt 3 to Ti-halide mole ratio of 1/1 to 1.25/1. APH containing 59% to 60% hexane and having the desired viscosity of about 20,000 cp and a RBSP of 118°C to 119°C showed a very good balance of adhesive properties. See Examples 12 and 15. The APH products combined good probe tack (659 to 693 grams), good quick stick (1.5 to 1.7 pounds per inch), and good 180° peel adhesion (2.5 to 2.8 pounds per inch) with good static shear adhesion 19 to 22 hours). They also proved to be nonirritants to the human skin. This combination of properties makes them particularly well-suited for medical tape application.
Examples 19 and 20 (Comparative)
In Examples 19 and 20 the AlEt3/AA-TiCl3 catalyst was evaluated for the production of pressure-sensitive APH. This catalyst system was taught for APH synthesis in U.S. Patent 3,954,697. As can be seen in Table II APH varying from 59% to 64% in hexene content exhibits adhesive properties very much inferior to APH produced with the catalyst of this invention.
Claims
1. A catalyst mixture comprising:
(a) about 5 to about 50 weight percent
(based on the weight of (a) plus (b)) of a supported catalyst comprising
TiCl4, supported on an inorganic halide salt.
(b) about 95 to about 50 weight percent (based on the weight of (a) plus (b)) of a preactivated catalyst comprising preactivated TiCl3, and
(c) an aluminum-alkyl cocatalyst at a molar ratio of aluminum-alkyl: Ti-chloride of about 0.25:1 to about 2:1.
2. The catalyst of Claim 1 wherein said supported catalyst comprises about 1 to about 15 weight percent TiCl4 supported on MgCl2.
3. The catalyst of Claim 1 wherein said preactivated catalyst comprises TiCl3 plus about 10 to 50 weight percent polypropylene.
4. The catalyst of Claim 1 wherein said aluminum-alkyl cocatalyst is selected from the group consisting of triethyl aluminum, tributyl aluminum, and triisobutyl aluminum.
5. The catalyst of Claim 1 wherein said aluminum-alkyl cocatalyst is triethyl aluminum.
6. The catalyst of Claim 1 wherein the amount of supported catalyst is about 15 to about 45 weight percent, the amount of preactivated catalyst is about 85 weight percent to about 55 weight percent, and the molar ratio of aluminum-alkyl:Ti-chloride is about 1:1 to about 1.5:1.
7. The catalyst of Claim 1 wherein the amount of supported catalyst is about 25 weight percent, the amount of preactivated catalyst is about 75 weight percent and the molar ratio of aluminum-alkyl:Ti-chloride is about 1.25:1.
8. The catalyst of Claim 1 wherein the supported catalyst additionally contains up to about 25 weight percent organic esters and ethers.
9. The catalyst of Claim 8 wherein said organic esters and ethers are selected from the group consisting of anisole, ethyl benzoate and methyl benzoate.
10. A process for preparing an amorphous propylene higher 1-olefin copolymer comprising contacting propylene and a higher 1-olefin with a catalyst mixture comprising:
(a) about 5 to about 50 weight percent
(based on the weight of (a) plus (b))
of a supported catalyst comprising TiCl4 supported on an inorganic halide salt),
(b) about 95 to about 50 weight percent
(based on the weight of (a) plus (b)) of a preactivated catalyst comprising preactivated TiCl3, and
(c) an aluminum-alkyl cocatalyst at a molar ratio of aluminum-alkyl: Ti-chloride of about 0.25:1 to about 2:1;
said process occurring for a sufficient reaction period and under conditions such that the desired copolymer is formed.
11. The process of Claim 10 wherein said higher 1-olefin is 1-hexene.
12. The process of Claim 10 carried out in an inert atmosphere at a temperature of about 140°C to about 200°C, a pressure of about 400 to about 2000 psig, in the presence of a suitable solvent and for a reaction period of about 1/2 to about 10 hours.
13. The process of Claim 10 carried out in an inert atmosphere at a temperature of about 150°C to about 180°C, a pressure of about 1000 to about 1500 psig in the presence of a suitable solvent, and for a reaction period of about 2 to about 4 hours.
14. The process of Claim 10 wherein said supported catalyst comprises about 1 to about 15 weight percent TiCl4 supported on MgCl2.
15. The process of Claim 10 wherein said preactivated catalyst comprises TiCl4 plus about 50 weight percent polypropylene.
16. The process of Claim 10 wherein said aluminum-alkyl cocatalyst is selected from the group consisting of triethyl aluminum, tributyl aluminum, and triisobutyl aluminum.
17. The process of Claim 10 wherein said aluminum-alkyl cocatalyst is triethyl aluminum.
18. The process of Claim 10 wherein, in the catalyst mixture, the amount of supported catalyst is about 15 to about 45 weight percent, the amount of preactivated catalyst is about 85 to about 55 weight percent, and the molar ratio of aluminum-alkyl:Ti-chloride is about 1:1 to about 1.5:1.
19. The process of Claim 10 wherein, in the catalyst mixture, the amount of supported catalyst is about 25 weight percent, the amount of preactivated catalyst is about 75 weight percent, and the molar ratio of aluminum-alkyl:Ti-chloride is about
1.25:1.
20. The process of Claim 10 wherein the supported catalyst of said catalyst mixture additionally contains up to about 25 weight percent organic esters and ethers.
21. The process of Claim 20 wherein said organic esters and ethers are selected from the group consisting of anisole, ethyl benzoate, and methyl benzoate.
22. A hot-melt, pressure-sensitive adhesive comprising an amorphous propylene-hexene copolymer containing about 40 to about 75 weight percent 1-hexene, having a melt viscosity of about 5,000 to about 50,000 cp at 190°C, a softening point of about 90°C to about 125°C, a probe tack of at least about 500 grams, a quick stick of at least about 1.5 pounds per inch, a 180° peel adhesion of at least about 2.5 pounds per inch, and a static shear adhesion of at least about 10 hours.
23. The adhesive of Claim 22 containing about 55 to about 65 weight percent 1-hexene and wherein the melt viscosity is about 15,000 to about 25,000 cp at 190°C, and the softening point is about 95ºC to about 120°C.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
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KR1019890701189A KR890701649A (en) | 1987-10-28 | 1988-10-19 | Catalyst for the preparation of amorphous copolymers of propylene and olefins |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US11368387A | 1987-10-28 | 1987-10-28 | |
US113,683 | 1987-10-28 |
Publications (1)
Publication Number | Publication Date |
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WO1989003847A1 true WO1989003847A1 (en) | 1989-05-05 |
Family
ID=22350887
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US1988/003637 WO1989003847A1 (en) | 1987-10-28 | 1988-10-19 | Catalysts for the preparation of amorphous copolymers of propylene and olefins |
Country Status (3)
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KR (1) | KR890701649A (en) |
CA (1) | CA1328447C (en) |
WO (1) | WO1989003847A1 (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6084041A (en) * | 1995-10-10 | 2000-07-04 | Borealis A/S | Process for making propylene homo or copolymers |
US6562914B1 (en) | 1995-10-10 | 2003-05-13 | Borealis A/S | Process for making propylene homo or copolymers |
WO2011006776A1 (en) | 2009-07-14 | 2011-01-20 | Basell Poliolefine Italia S.R.L. | Process for the preparation of polymer of 1-butene |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB951579A (en) * | 1962-08-08 | 1964-03-04 | Deputy Minister Of The Ministe | Process for preparing polymers of propylene with regulated molecular weight and isotacticity |
US3954697A (en) * | 1975-03-31 | 1976-05-04 | Eastman Kodak Company | Poly(higher-1-olefin-co-propylene) copolymers as hot-melt, pressure-sensitive adhesives |
-
1988
- 1988-10-13 CA CA000579979A patent/CA1328447C/en not_active Expired - Lifetime
- 1988-10-19 WO PCT/US1988/003637 patent/WO1989003847A1/en unknown
- 1988-10-19 KR KR1019890701189A patent/KR890701649A/en not_active IP Right Cessation
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB951579A (en) * | 1962-08-08 | 1964-03-04 | Deputy Minister Of The Ministe | Process for preparing polymers of propylene with regulated molecular weight and isotacticity |
US3954697A (en) * | 1975-03-31 | 1976-05-04 | Eastman Kodak Company | Poly(higher-1-olefin-co-propylene) copolymers as hot-melt, pressure-sensitive adhesives |
US4072812A (en) * | 1975-03-31 | 1978-02-07 | Eastman Kodak Company | Poly(higher-1-olefin/propylene) copolymers as hot-melt pressure-sensitive adhesives |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6084041A (en) * | 1995-10-10 | 2000-07-04 | Borealis A/S | Process for making propylene homo or copolymers |
US6562914B1 (en) | 1995-10-10 | 2003-05-13 | Borealis A/S | Process for making propylene homo or copolymers |
WO2011006776A1 (en) | 2009-07-14 | 2011-01-20 | Basell Poliolefine Italia S.R.L. | Process for the preparation of polymer of 1-butene |
US8598285B2 (en) | 2009-07-14 | 2013-12-03 | Basell Poliolefine Italia, s.r.l. | Process for the preparation of polymer of 1-butene |
Also Published As
Publication number | Publication date |
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CA1328447C (en) | 1994-04-12 |
KR890701649A (en) | 1989-12-21 |
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