CA2142448C - High tensile strength amorphous 1-butene/propylene copolymers - Google Patents
High tensile strength amorphous 1-butene/propylene copolymers Download PDFInfo
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- CA2142448C CA2142448C CA002142448A CA2142448A CA2142448C CA 2142448 C CA2142448 C CA 2142448C CA 002142448 A CA002142448 A CA 002142448A CA 2142448 A CA2142448 A CA 2142448A CA 2142448 C CA2142448 C CA 2142448C
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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
- C08F210/08—Butenes
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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
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Abstract
A process for the production of propylene/1-butene copolymers comprising:
reacting propylene and 1-butene monomers in the presence of a catalyst system comprising: (a) a solid supported catalyst component is prepared by the method comprising:
(i) co-comminuting magnesium halide support base and aluminum trihalide in a molar ratio from about 8:0.5 to about 8:3 in the absence of added electron donor; and (ii) then co-comminuting the product of step (i) in the absence of added electron donor with sufficient titanium tetrahalide to provide a molar ratio of magnesium halide to titanium tetrahalide from about 8:0.1 to about 8:10; (b) a trialkylaluminum co-catalyst, having from 1 to 9 carbon atoms in each alkyl group in an amount such that the AI/Ti ratio is between about 50:1 and about 500:1; (c) an alkoxy silane component of the formula R n Si(OR')4-n where n = 1-3, R = aryl or alkyl and R' = C1-3 alkyl in a sufficient quantity such that the molar ratio of organoaluminum co-catalyst to alkoxy silane is in the range from about20:1 to about 45 :1. Said copolymer being characterized by a propylene content of 25 to 50 wt %, a 1-butene content of 50 to 75 wt % and a tensile strength of at least 300 psig.
reacting propylene and 1-butene monomers in the presence of a catalyst system comprising: (a) a solid supported catalyst component is prepared by the method comprising:
(i) co-comminuting magnesium halide support base and aluminum trihalide in a molar ratio from about 8:0.5 to about 8:3 in the absence of added electron donor; and (ii) then co-comminuting the product of step (i) in the absence of added electron donor with sufficient titanium tetrahalide to provide a molar ratio of magnesium halide to titanium tetrahalide from about 8:0.1 to about 8:10; (b) a trialkylaluminum co-catalyst, having from 1 to 9 carbon atoms in each alkyl group in an amount such that the AI/Ti ratio is between about 50:1 and about 500:1; (c) an alkoxy silane component of the formula R n Si(OR')4-n where n = 1-3, R = aryl or alkyl and R' = C1-3 alkyl in a sufficient quantity such that the molar ratio of organoaluminum co-catalyst to alkoxy silane is in the range from about20:1 to about 45 :1. Said copolymer being characterized by a propylene content of 25 to 50 wt %, a 1-butene content of 50 to 75 wt % and a tensile strength of at least 300 psig.
Description
HIGH TENSILE STRENGTH
TECHNICAL FIELD
This invention relates to substantially improved amorphous propylene/1-butene copolymers that exhibit high tensile strength and storage modulus. The copolymers have properties which make them applicable for use in a variety of applications including adhesives, sealants, coatings and similar materials.
_Z-BACRGROUND OF THE INVENTION
Amorphous polyalphaolefins are presently used in a wide variety of applications including adhesives, sealants and coatings. Additionally, these materials may be blended with other materials to achieve a wide range of desired physical properties. Amorphous polyalphaolefin polymers and processes for making such polymers are disclosed in U.S. Pat. Nos. 4,859,757, 4,847,340 and 4,736,002 There has, however, arisen a need for improved materials with enhanced physical properties. The present invention provides a substantially amorphous propylene/ 1-butene copolymer that exhibits high tensile strength and storage modulus. The enhanced physical properties of the copolymers of the present invention substantially broadens the range of applications in which amorphous polyalphaolefin polymers may be used.
_3-.
STJHIIMARY OF THE INVENTION
The present invention provides novel propylene/1-butene copolymers and a process for making the copolymers.
The copolymers of the present invention comprise from about 25 to 50 wt$ propylene and 50 to 75 wt$ of 1-butene and have excellent tensile strength and storage modulus properties. The tensile strength is preferably greater than 300 psig. The copolymers are completely soluble in boiling heptane and do not exhibit any trace of heat of fusion. The copolyiaers are produced with a catalyst system comprising a solid supported catalyst component, an organoaluminum co-catalyst and an alkoxy silane component.
The alkoxy silane is added to the reactor in a quantity such that the molar ratio of the concentration of the organoaluminum co-catalyst to the alkoxy silane component is 20:45, or more preferably 35:45.
In one preferred embodiment there is provided a process for the production of an amorphous propylene/1-butene copolymers comprising:
reacting propylene and 1-butene mon omers in the presence of a catalyst system comprising:
(a) a solid supported catalyst component prepared by the method comprising: (i) co-comminuting ma gn esium halide support base and aluminum trihalide in a molar ratio from about 8:0.5 to about 8:3 in the absence of added electron donor; and (ii) then co-comminuting the produ c t of step (i) in the absence of added electron donor wi t h sufficient titanium tetrahalide to provide a molar ratio of magriesium halide to titanium tetrahalide from about 80.1 to about 8:1.0 - 3a -(b) a trialkylaluminum co-catalyst, having from 1 to 9 carbon atoms in each alkyl group in an amount such that the Al/Ti ratio is between about 50:1 and about 500:1.
(c) an alkoxy silane component in a sufficient quantity such that the molar ratio of organoaluminum co-catalyst to alkoxy silane is in the range from about 20:1 to about 45:1;
said amorphous copolymer being characterized by a propylene content of 25 to 50 wt% and a 1-butene content of 75 to 50 wt%.
DETAILED DESCRIPTION
The present invention provides substantially amorphous propylene/1-butene copolymers comprising from 25 to 50 wt%
propylene and from about 50 to 75 wt% of 1-butene. The propylene and 1-butene monomers are polymerized at a temperature between about 130 F and about 150 F and a reactor pressure sufficient to maintain the monomers in the liquid phase. The molecular weight of the copolymers may be controlled by the addition of an appropriate amount of a chain terminating agent, for example from about 1.0 to about 2.0 mol% hydrogen based on the monomer feed to the process. The polymerization reaction takes place in the presence of a catalyst system comprising:
(a) a solid catalyst component as described in U.S.
Patent No. 4,736,002 modified to exclude the use of added electron donors during the preparation of the catalyst component.
(b) a trialkylaluminum co-catalyst component having from 1 to 9 carbon atoms in each alkyl group in a sufficient quantity to provide an Al/Ti ratio in the range from about 50:1 to about 500:1 and (c) an alkoxy silane external component of structure RnSi (OR' ) 4_n where n = 1-3, R = aryl or alkyl and R' = C1_3 alkyl in a sufficient quantity such that the molar ratio of organoaluminum co-catalyst to alkoxy silane is in the range WO 94/05711 PC,'T/US93/08222 from about 20:1 to about 45:1.
The alkoxy silane is described as an external component since it is added to the reactor independently of the solid catalyst component and the organoaluminum co-!5 catalyst. Although the polymerization can be carried out in a batch reactor, it is preferred to utilize a continuous process. Usually, pressures in the range of 250 psig and 350 psig are suitable for maintaining the monomers in liquid phase.
The addition of an electron donor such as an alkoxy silane would normally be expected to promote the formation of crystalline polymer. However, it was discovered that within a certain ratio of organoaluminum co-catalyst to an external alkoxy silane, substantially amorphous copolymers of propylene and 1-butene with exceptional tensile properties anci storage modulus could be produced.
The polymerization is carried out in a stirred reactor at average residence times between 1 hour and 3 hours.
Sufficient catalyst quantities are fed to the reactor to result in a polymer content in the reactor slurry of from 10 wt% to about 50 wt%. The reactor effluent is withdrawn from the reactor, and unreacted monomer is flashed from the recovered product polymer.
The solid supported catalyst component has a molar ratio of magniesium chloride to aluminum chloride of about 8:0.5 - 3.0 and preferably about 8:1.0 - 1.5. The molar ratio of magnesium chloride to titanium tetrachloride is between about 8:0.1 - 8:1.0 and preferably about 8: 0. 4 -8:0.6.
The solid catalyst component may be prepared by t.he general methods described in U.S. Patent No. 4,347,158, except that these methods must be modified to exclude the use of electron donor compounds in the preparation of the catalyst. Briefly, the modified method involves co-comminuting magnesium chloride and aluminum trichloride in the absence of an electron donor and then co-comminuting the catalyst support so formed with titanium tetrachloride, also in the absence of an electron donor.
More specifically, the solid supported catalyst component is prepared by the method comprising: (i) co-comminuting magnesium halide support base and aluminum trihalide in a molar ratio from about8:0.5 to about 8:3 in the absence of added electron donor; and (ii) then co-comminuting the product of step (i) in the absence of added electron donor with sufficient titanium tetrahalide to provide a molar ratio of magnesium halide to titanium tetrahalide from about 8:0.4 to about 8:1.
The solid catalyst component is used in conjunction with a trialkylaluminum co-catalyst, having from 1 to 9 w~~~~~48 WO 94/05711 PC'T/US93/08222 carbon atoms in each alkyl group. The preferred organoaluminum co-catalyst is triethylaluminum. The molar ratio of trialky7laluminum co-catalyst to titanium-containing catalyst component, i.e., Al/Ti ratio, should range between about 50:1 and about 500:1, preferably between about 120:1 and about 170:1.
The alkoxy silane component is introduced as a dilute solution in he:ptane., The molar ratio of alkyl aluminum co-catalyst to alkoxy silane, e.g., the Al/Si ratio, should 1.0 range between 20 an<i 45, preferably between about 35:1 and about 45:1. Alkoxy silanes suitable for use in connection with the pre:sent invention include cyclohexyl methyl dimethoxy sileine (CMDMS) and phenyl triethoxy silane (PES).
Cyclohexyl methyl dimethoxy silane and phenyl triethoxy 3.5 silane are avziilable from Huels America, Inc. Piscataway, N.J. 08855-0456. Other alkoxy silanes anticipated to be suitable for -use in, the practice of the present invention include dimethyl diethoxy silane, dodecyl triethoxy silane, methyl pheny7. diet:hoxy silane, dimethyl diisopropenoxy 20 silane, methyl octyl dimethoxy silane and methyl triethoxy silane.
Due to the high activity of the catalyst system employed in the present invention, the process is highly efficient anci typ:ically results in polymer production :25 ranging from about 3000 to 6000 lbs. polymer/lb. titanium 2i42t~~~~
WO 94/05711 PC'T/US93/08222 catalyst/hour. The propene/1-butene copolymers of the present invention have no determinable heat of fusion, as determined by Differential Scanning Calorimetry techniques (DSC), an indication of the amorphous nature of the polymer and the lack of crystallinity in the polymer structure.
The propene/1-butene copolymers of the present invention have excellent properties making them useful in a variety of applications, such as blending components for adhesives, caulking and sealing compounds and others.
Important product properties include melt viscosity, ring and ball softening point, tensile strength and elastic or storage modulus.
The melt viscosity at 375 F is determined by ASTM test method D-3236 using a Brookfield RVT Viscometer and a #27 spindle. For hot melt adhesives the desired viscosity range is between about 1000 and 12,000 cps at 375 F.
The ring and ball softening point determination is carried out using ASTM E-28 test method. One variable affecting the softening point is butene-1 content of the polymer. A decrease in the butene-1 content causes an increase in the ring and ball softening point.
The tensile strength determination is carried out using ASTM D-638 test method. Typically, the tensile strength values of the copolymers of this invention range from about 300 to about 900 psig (2.1 and 6.2 Mpa, _9-respectively). Copolymers having such high tensile strength are produced when the Al/Si ratio is maintained with the range of from about 20:1 to about 45:1.
The storage or elastic modulus is determined by ASTM
D-4440 test method using a BoelinM Reology CSM rheometer.
The storage modulus is a measure of the elasticity of a material. The storage modulus values of the copolymers of this invention range from about 8.0 to about 14.0 Mpa.
Another indication of the amorphous nature of the copolymers of the present invention is the lack of crystalline polymer as evidenced by the fact.that the copolymers contain no heptane insoluble material. Heptane insolubles were determined by Soxhlet extraction of a sample of the copolymer with boiling heptane for six hours.
The invention will be further described with respect to the following examples; however, the scope of the invention is not to be limited thereby.
Polymerization of propylene and 1-butene was performed in a 200 gallon jacketed continuous pilot plant reactor.
The temperature of the reactor was controlled by circulating cooling water in the reactor jacket. The solid supported titanium tetracizloride catalyst component was prepared in accordance with the foregoing description and had a titanium content of from about 2.3 to about 2.7 wt %.
21424 4 zs Slurries containing twenty five wt% of the solid catalyst component were prepared in degassed petrolatum. Five wt %
alkyl aluminum co-catalyst solutions were prepared in normal heptane as were 0.5 wt % alkoxy silane component solutions.
The alkyl aluminum co-catalyst solution and catalyst slurry were introduced into the reactor continuously, as were hydrogen, propylene and butene-1 monomers and the alkoxy silane solution.
Copolymers recovered were tested as described above.
The pertinent operating conditions and test results are set forth in Table 1 below.
ERAMPLE NO. 1 2 3 Reactor Temp., F 140 140 140 Reactor Pres., psig 250 250 240 Triethylaluminum, mol/hr 0.27 0.27 0.27 CMDMS mol/hr 0.0077 0.0062 0.0062 Propylene, lbs/hr 24 23 22 Butene-1, lbs/hr 106 107 108 Hydrogen, lbs/hr 1.8 1.6 1.7 Al/Ti, mol ratio 130 145 170 Al/Si, mol ratio 35 42 42 Catalyst Activity, 4800 5900 6300 lbs/lbs cat./hr*
49d14%~4 4-f TABLE 1 (Continued) EXAMPLE NO. 1 2 3 Butene-1 content, wtt 62 62 63 Melt Viscosity, cps 6550 10350 12050 Ring and Ball Softening Poirit, F 200 202 200 Heat of fusion, J/g 0 0 0 Tensile Strenclth, psig 650 875 875 ~ Elongation Ej Brea:k 300 >669 615 Storage Modulus, Mpa 11 11.4 12.9 Glass Transition, C -39 -39 -38 Heptane Insoliibles 0 0 0 * Based upon solid catalyst component consumption.
The forecfoing examples illustrate the production of an 1.5 amorphous propylene/1-butene copolymer possessing exceptional tensile and storage modulus properties.
The following example illustrates the use of phenyl triethoxy silane (PES) as an external component. Propylene and 1-butene monomers were polymerized using the same catalyst system and under the operating conditions as Examples 1-3 texcept that phenyl triethoxy silane (PES) was substituted for cyclohexyl methyl dimethoxy silane (CMDMS).
Pertinent operating conditions and test results are 2 5 set forth in 'Table 2 below.
WO 94/05711 2~ 42 4 Uh PCT/US93/08222 EXAMPLE NO. 4 Reactor Temp., F 140 Reactor Pres., psig 200 Triethylaluminum mol/hr 0.29 PES mol/hr 0.0076 Propylene, lbs/hr 24 Butene-1, lbs/hr 106 Hydrogen, lbs/hr 1.0 Al/Ti, mol ratio 150 Al/Si, mol ratio 38 Catalyst Activity, 5200 lbs/lbs cat./hr Butene-1 content, wt% 63 Melt Viscosity, cps 8300 Ring and Ball Softening Point, F 193 Heat of fusion, J/g 0 Tensile Strength, psig 670 % Elongation @ Break 300 Storage Modulus, Mpa 12 Glass Transition, C -35 Heptane Insolubles 0 As indicated above, the copolymer produced evidenced the desired high tensile strength, elongation at break and storage modulus properties.
In order to demonstrate the significance of the Al/Si ratio, copolymers were also prepared without the alkoxy silane and at Al/Si ratios of 50 and 100 under the same operating conditions and using the same catalyst system as in Examples 1-3, except that the Al/Si ratio was varied.
Table 3 summarizes the pertinent operating conditions and the results of physical testing.
EXAMPLE 'N(. 5 6 7 7L0 Reactor Temp., F 135 140 140 Reactor Pres., psig 124 185 170 Triethylalumir.ium mol/hr 0.21 0.21 0.21 CMDMS mol/hr 0 0.0020 0.0040 Propylene, lbs/hr 26 25 25 Butene-1, lbs/hr 106 105 105 Hydrogen, lbs/hr 0.90 0.90 1.7 Al/Ti, mol ratio 150 165 150 Al/Si, mol ratio - 100 50 Catalyst, Activity, 7900 9600 8300 lbs/lbs cat./hr Butene-1 content, wt% 68 69 68 Melt Viscosity, cps 8000 5250 10500 Ring andl Ball Softening Poizzt, F 190 177 176 Heat of fusion, J/g 0 0 0 214'~4 P, TABLE 3 (Continued) E%AMPLE NO. 5 6 7 Tensile Strength, psig 46 65 92 % Elongation @ Break 107 270 120 Storage Modulus, Mpa N.D. 2.7 3.3 Glass Transition, C -20 -33 -33 Heptane Insolubles 0 0 0 As indicated above, the use of the alkoxy silane in an amount resulting in a Al/Si ratio outside of the desired range of 20:1 to 45:1 resulted in the production of copolymers that did not exhibit the high tensile strength and storage modulus observed in Examples 1-4.
The following examples further illustrate the significance of the Al/Si ratio in the practice of the present invention. Polymerization of propylene and 1-butene was carried out under the same operating conditions as Examples 1-3 except that the alkoxy silane was added at a rate such that the Al/Si ratio was 20:1 and 30:1.
EXAMPLE NO. 8 9 Reactor Temp., F 140 140 Reactor Pres., psig 310 315 Triethylaluminum mol/hr 0.27 0.27 CMDMS mol/hr 0.013 0.0087 Propylene, lbs/hr 25 24 4, WO 94/05711 PC'T/US93/08222 TABLE 4 (Continued) Butene-1, lbs/hr 105 106 Hydrogen, lbs/hr 2.2 1.9 Al/Ti, mol rati.o 130 202 Al/Si, mol ratio 20 30 Catalyst Activity, 3500 3600 lbs/lbs cat./hr Butene-1 content, wt% 50 52 Melt Viscosity, cps 6650 5900 Ring and Ball Softening Point, F 240 225 Heat of fusion, J/g 0 0 Tensile Strength, psig 700 550 % Elongation @ Break >660 470 Storage Modulus, Mpa N.D. N.D.
Glass Transition, C -34 N.D.
Heptane I:nsolubles N.D. N.D.
As indicated above, when the alkoxy silane was added at a rate such that the molar ratio of triethylaluminum to alkoxy silane was 20:1 and 30:1, the resulting copolymer exhibited the desired high tensile strength and elongation at break.
WO 94/05711 2 1 ~ 2 4 PC.'T/US93/08222 While particular embodiments of the present invention have been illustrated and described, it will be apparent to those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention.
TECHNICAL FIELD
This invention relates to substantially improved amorphous propylene/1-butene copolymers that exhibit high tensile strength and storage modulus. The copolymers have properties which make them applicable for use in a variety of applications including adhesives, sealants, coatings and similar materials.
_Z-BACRGROUND OF THE INVENTION
Amorphous polyalphaolefins are presently used in a wide variety of applications including adhesives, sealants and coatings. Additionally, these materials may be blended with other materials to achieve a wide range of desired physical properties. Amorphous polyalphaolefin polymers and processes for making such polymers are disclosed in U.S. Pat. Nos. 4,859,757, 4,847,340 and 4,736,002 There has, however, arisen a need for improved materials with enhanced physical properties. The present invention provides a substantially amorphous propylene/ 1-butene copolymer that exhibits high tensile strength and storage modulus. The enhanced physical properties of the copolymers of the present invention substantially broadens the range of applications in which amorphous polyalphaolefin polymers may be used.
_3-.
STJHIIMARY OF THE INVENTION
The present invention provides novel propylene/1-butene copolymers and a process for making the copolymers.
The copolymers of the present invention comprise from about 25 to 50 wt$ propylene and 50 to 75 wt$ of 1-butene and have excellent tensile strength and storage modulus properties. The tensile strength is preferably greater than 300 psig. The copolymers are completely soluble in boiling heptane and do not exhibit any trace of heat of fusion. The copolyiaers are produced with a catalyst system comprising a solid supported catalyst component, an organoaluminum co-catalyst and an alkoxy silane component.
The alkoxy silane is added to the reactor in a quantity such that the molar ratio of the concentration of the organoaluminum co-catalyst to the alkoxy silane component is 20:45, or more preferably 35:45.
In one preferred embodiment there is provided a process for the production of an amorphous propylene/1-butene copolymers comprising:
reacting propylene and 1-butene mon omers in the presence of a catalyst system comprising:
(a) a solid supported catalyst component prepared by the method comprising: (i) co-comminuting ma gn esium halide support base and aluminum trihalide in a molar ratio from about 8:0.5 to about 8:3 in the absence of added electron donor; and (ii) then co-comminuting the produ c t of step (i) in the absence of added electron donor wi t h sufficient titanium tetrahalide to provide a molar ratio of magriesium halide to titanium tetrahalide from about 80.1 to about 8:1.0 - 3a -(b) a trialkylaluminum co-catalyst, having from 1 to 9 carbon atoms in each alkyl group in an amount such that the Al/Ti ratio is between about 50:1 and about 500:1.
(c) an alkoxy silane component in a sufficient quantity such that the molar ratio of organoaluminum co-catalyst to alkoxy silane is in the range from about 20:1 to about 45:1;
said amorphous copolymer being characterized by a propylene content of 25 to 50 wt% and a 1-butene content of 75 to 50 wt%.
DETAILED DESCRIPTION
The present invention provides substantially amorphous propylene/1-butene copolymers comprising from 25 to 50 wt%
propylene and from about 50 to 75 wt% of 1-butene. The propylene and 1-butene monomers are polymerized at a temperature between about 130 F and about 150 F and a reactor pressure sufficient to maintain the monomers in the liquid phase. The molecular weight of the copolymers may be controlled by the addition of an appropriate amount of a chain terminating agent, for example from about 1.0 to about 2.0 mol% hydrogen based on the monomer feed to the process. The polymerization reaction takes place in the presence of a catalyst system comprising:
(a) a solid catalyst component as described in U.S.
Patent No. 4,736,002 modified to exclude the use of added electron donors during the preparation of the catalyst component.
(b) a trialkylaluminum co-catalyst component having from 1 to 9 carbon atoms in each alkyl group in a sufficient quantity to provide an Al/Ti ratio in the range from about 50:1 to about 500:1 and (c) an alkoxy silane external component of structure RnSi (OR' ) 4_n where n = 1-3, R = aryl or alkyl and R' = C1_3 alkyl in a sufficient quantity such that the molar ratio of organoaluminum co-catalyst to alkoxy silane is in the range WO 94/05711 PC,'T/US93/08222 from about 20:1 to about 45:1.
The alkoxy silane is described as an external component since it is added to the reactor independently of the solid catalyst component and the organoaluminum co-!5 catalyst. Although the polymerization can be carried out in a batch reactor, it is preferred to utilize a continuous process. Usually, pressures in the range of 250 psig and 350 psig are suitable for maintaining the monomers in liquid phase.
The addition of an electron donor such as an alkoxy silane would normally be expected to promote the formation of crystalline polymer. However, it was discovered that within a certain ratio of organoaluminum co-catalyst to an external alkoxy silane, substantially amorphous copolymers of propylene and 1-butene with exceptional tensile properties anci storage modulus could be produced.
The polymerization is carried out in a stirred reactor at average residence times between 1 hour and 3 hours.
Sufficient catalyst quantities are fed to the reactor to result in a polymer content in the reactor slurry of from 10 wt% to about 50 wt%. The reactor effluent is withdrawn from the reactor, and unreacted monomer is flashed from the recovered product polymer.
The solid supported catalyst component has a molar ratio of magniesium chloride to aluminum chloride of about 8:0.5 - 3.0 and preferably about 8:1.0 - 1.5. The molar ratio of magnesium chloride to titanium tetrachloride is between about 8:0.1 - 8:1.0 and preferably about 8: 0. 4 -8:0.6.
The solid catalyst component may be prepared by t.he general methods described in U.S. Patent No. 4,347,158, except that these methods must be modified to exclude the use of electron donor compounds in the preparation of the catalyst. Briefly, the modified method involves co-comminuting magnesium chloride and aluminum trichloride in the absence of an electron donor and then co-comminuting the catalyst support so formed with titanium tetrachloride, also in the absence of an electron donor.
More specifically, the solid supported catalyst component is prepared by the method comprising: (i) co-comminuting magnesium halide support base and aluminum trihalide in a molar ratio from about8:0.5 to about 8:3 in the absence of added electron donor; and (ii) then co-comminuting the product of step (i) in the absence of added electron donor with sufficient titanium tetrahalide to provide a molar ratio of magnesium halide to titanium tetrahalide from about 8:0.4 to about 8:1.
The solid catalyst component is used in conjunction with a trialkylaluminum co-catalyst, having from 1 to 9 w~~~~~48 WO 94/05711 PC'T/US93/08222 carbon atoms in each alkyl group. The preferred organoaluminum co-catalyst is triethylaluminum. The molar ratio of trialky7laluminum co-catalyst to titanium-containing catalyst component, i.e., Al/Ti ratio, should range between about 50:1 and about 500:1, preferably between about 120:1 and about 170:1.
The alkoxy silane component is introduced as a dilute solution in he:ptane., The molar ratio of alkyl aluminum co-catalyst to alkoxy silane, e.g., the Al/Si ratio, should 1.0 range between 20 an<i 45, preferably between about 35:1 and about 45:1. Alkoxy silanes suitable for use in connection with the pre:sent invention include cyclohexyl methyl dimethoxy sileine (CMDMS) and phenyl triethoxy silane (PES).
Cyclohexyl methyl dimethoxy silane and phenyl triethoxy 3.5 silane are avziilable from Huels America, Inc. Piscataway, N.J. 08855-0456. Other alkoxy silanes anticipated to be suitable for -use in, the practice of the present invention include dimethyl diethoxy silane, dodecyl triethoxy silane, methyl pheny7. diet:hoxy silane, dimethyl diisopropenoxy 20 silane, methyl octyl dimethoxy silane and methyl triethoxy silane.
Due to the high activity of the catalyst system employed in the present invention, the process is highly efficient anci typ:ically results in polymer production :25 ranging from about 3000 to 6000 lbs. polymer/lb. titanium 2i42t~~~~
WO 94/05711 PC'T/US93/08222 catalyst/hour. The propene/1-butene copolymers of the present invention have no determinable heat of fusion, as determined by Differential Scanning Calorimetry techniques (DSC), an indication of the amorphous nature of the polymer and the lack of crystallinity in the polymer structure.
The propene/1-butene copolymers of the present invention have excellent properties making them useful in a variety of applications, such as blending components for adhesives, caulking and sealing compounds and others.
Important product properties include melt viscosity, ring and ball softening point, tensile strength and elastic or storage modulus.
The melt viscosity at 375 F is determined by ASTM test method D-3236 using a Brookfield RVT Viscometer and a #27 spindle. For hot melt adhesives the desired viscosity range is between about 1000 and 12,000 cps at 375 F.
The ring and ball softening point determination is carried out using ASTM E-28 test method. One variable affecting the softening point is butene-1 content of the polymer. A decrease in the butene-1 content causes an increase in the ring and ball softening point.
The tensile strength determination is carried out using ASTM D-638 test method. Typically, the tensile strength values of the copolymers of this invention range from about 300 to about 900 psig (2.1 and 6.2 Mpa, _9-respectively). Copolymers having such high tensile strength are produced when the Al/Si ratio is maintained with the range of from about 20:1 to about 45:1.
The storage or elastic modulus is determined by ASTM
D-4440 test method using a BoelinM Reology CSM rheometer.
The storage modulus is a measure of the elasticity of a material. The storage modulus values of the copolymers of this invention range from about 8.0 to about 14.0 Mpa.
Another indication of the amorphous nature of the copolymers of the present invention is the lack of crystalline polymer as evidenced by the fact.that the copolymers contain no heptane insoluble material. Heptane insolubles were determined by Soxhlet extraction of a sample of the copolymer with boiling heptane for six hours.
The invention will be further described with respect to the following examples; however, the scope of the invention is not to be limited thereby.
Polymerization of propylene and 1-butene was performed in a 200 gallon jacketed continuous pilot plant reactor.
The temperature of the reactor was controlled by circulating cooling water in the reactor jacket. The solid supported titanium tetracizloride catalyst component was prepared in accordance with the foregoing description and had a titanium content of from about 2.3 to about 2.7 wt %.
21424 4 zs Slurries containing twenty five wt% of the solid catalyst component were prepared in degassed petrolatum. Five wt %
alkyl aluminum co-catalyst solutions were prepared in normal heptane as were 0.5 wt % alkoxy silane component solutions.
The alkyl aluminum co-catalyst solution and catalyst slurry were introduced into the reactor continuously, as were hydrogen, propylene and butene-1 monomers and the alkoxy silane solution.
Copolymers recovered were tested as described above.
The pertinent operating conditions and test results are set forth in Table 1 below.
ERAMPLE NO. 1 2 3 Reactor Temp., F 140 140 140 Reactor Pres., psig 250 250 240 Triethylaluminum, mol/hr 0.27 0.27 0.27 CMDMS mol/hr 0.0077 0.0062 0.0062 Propylene, lbs/hr 24 23 22 Butene-1, lbs/hr 106 107 108 Hydrogen, lbs/hr 1.8 1.6 1.7 Al/Ti, mol ratio 130 145 170 Al/Si, mol ratio 35 42 42 Catalyst Activity, 4800 5900 6300 lbs/lbs cat./hr*
49d14%~4 4-f TABLE 1 (Continued) EXAMPLE NO. 1 2 3 Butene-1 content, wtt 62 62 63 Melt Viscosity, cps 6550 10350 12050 Ring and Ball Softening Poirit, F 200 202 200 Heat of fusion, J/g 0 0 0 Tensile Strenclth, psig 650 875 875 ~ Elongation Ej Brea:k 300 >669 615 Storage Modulus, Mpa 11 11.4 12.9 Glass Transition, C -39 -39 -38 Heptane Insoliibles 0 0 0 * Based upon solid catalyst component consumption.
The forecfoing examples illustrate the production of an 1.5 amorphous propylene/1-butene copolymer possessing exceptional tensile and storage modulus properties.
The following example illustrates the use of phenyl triethoxy silane (PES) as an external component. Propylene and 1-butene monomers were polymerized using the same catalyst system and under the operating conditions as Examples 1-3 texcept that phenyl triethoxy silane (PES) was substituted for cyclohexyl methyl dimethoxy silane (CMDMS).
Pertinent operating conditions and test results are 2 5 set forth in 'Table 2 below.
WO 94/05711 2~ 42 4 Uh PCT/US93/08222 EXAMPLE NO. 4 Reactor Temp., F 140 Reactor Pres., psig 200 Triethylaluminum mol/hr 0.29 PES mol/hr 0.0076 Propylene, lbs/hr 24 Butene-1, lbs/hr 106 Hydrogen, lbs/hr 1.0 Al/Ti, mol ratio 150 Al/Si, mol ratio 38 Catalyst Activity, 5200 lbs/lbs cat./hr Butene-1 content, wt% 63 Melt Viscosity, cps 8300 Ring and Ball Softening Point, F 193 Heat of fusion, J/g 0 Tensile Strength, psig 670 % Elongation @ Break 300 Storage Modulus, Mpa 12 Glass Transition, C -35 Heptane Insolubles 0 As indicated above, the copolymer produced evidenced the desired high tensile strength, elongation at break and storage modulus properties.
In order to demonstrate the significance of the Al/Si ratio, copolymers were also prepared without the alkoxy silane and at Al/Si ratios of 50 and 100 under the same operating conditions and using the same catalyst system as in Examples 1-3, except that the Al/Si ratio was varied.
Table 3 summarizes the pertinent operating conditions and the results of physical testing.
EXAMPLE 'N(. 5 6 7 7L0 Reactor Temp., F 135 140 140 Reactor Pres., psig 124 185 170 Triethylalumir.ium mol/hr 0.21 0.21 0.21 CMDMS mol/hr 0 0.0020 0.0040 Propylene, lbs/hr 26 25 25 Butene-1, lbs/hr 106 105 105 Hydrogen, lbs/hr 0.90 0.90 1.7 Al/Ti, mol ratio 150 165 150 Al/Si, mol ratio - 100 50 Catalyst, Activity, 7900 9600 8300 lbs/lbs cat./hr Butene-1 content, wt% 68 69 68 Melt Viscosity, cps 8000 5250 10500 Ring andl Ball Softening Poizzt, F 190 177 176 Heat of fusion, J/g 0 0 0 214'~4 P, TABLE 3 (Continued) E%AMPLE NO. 5 6 7 Tensile Strength, psig 46 65 92 % Elongation @ Break 107 270 120 Storage Modulus, Mpa N.D. 2.7 3.3 Glass Transition, C -20 -33 -33 Heptane Insolubles 0 0 0 As indicated above, the use of the alkoxy silane in an amount resulting in a Al/Si ratio outside of the desired range of 20:1 to 45:1 resulted in the production of copolymers that did not exhibit the high tensile strength and storage modulus observed in Examples 1-4.
The following examples further illustrate the significance of the Al/Si ratio in the practice of the present invention. Polymerization of propylene and 1-butene was carried out under the same operating conditions as Examples 1-3 except that the alkoxy silane was added at a rate such that the Al/Si ratio was 20:1 and 30:1.
EXAMPLE NO. 8 9 Reactor Temp., F 140 140 Reactor Pres., psig 310 315 Triethylaluminum mol/hr 0.27 0.27 CMDMS mol/hr 0.013 0.0087 Propylene, lbs/hr 25 24 4, WO 94/05711 PC'T/US93/08222 TABLE 4 (Continued) Butene-1, lbs/hr 105 106 Hydrogen, lbs/hr 2.2 1.9 Al/Ti, mol rati.o 130 202 Al/Si, mol ratio 20 30 Catalyst Activity, 3500 3600 lbs/lbs cat./hr Butene-1 content, wt% 50 52 Melt Viscosity, cps 6650 5900 Ring and Ball Softening Point, F 240 225 Heat of fusion, J/g 0 0 Tensile Strength, psig 700 550 % Elongation @ Break >660 470 Storage Modulus, Mpa N.D. N.D.
Glass Transition, C -34 N.D.
Heptane I:nsolubles N.D. N.D.
As indicated above, when the alkoxy silane was added at a rate such that the molar ratio of triethylaluminum to alkoxy silane was 20:1 and 30:1, the resulting copolymer exhibited the desired high tensile strength and elongation at break.
WO 94/05711 2 1 ~ 2 4 PC.'T/US93/08222 While particular embodiments of the present invention have been illustrated and described, it will be apparent to those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention.
Claims (19)
1. A process for the production of an amorphous propylene/1-butene copolymers comprising:
reacting propylene and 1-butene monomers in the presence of a catalyst system comprising:
(a) a solid supported catalyst component prepared by the method comprising: (i) co-comminuting magnesium halide support base and aluminum trihalide in a molar ratio from about 8:0.5 to about 8:3 in the absence of added electron donor; and (ii) then co-comminuting the product of step (i) in the absence of added electron donor with sufficient titanium tetrahalide to provide a molar ratio of magnesium halide to titanium tetrahalide from about 8:0.1 to about 8:1.0 (b) a trialkylaluminum co-catalyst, having from 1 to 9 carbon atoms in each alkyl group in an amount such that the Al/Ti ratio is between about 50:1 and about 500:1.
(c) a dialkoxy or trialkoxy silane component in a sufficient quantity such that the molar ratio of organoaluminum co-catalyst to alkoxy silane is in the range from about 20:1 to about 45:1;
said amorphous copolymer being characterized by a propylene content of 25 to 50 wt% and a 1-butene content of 75 to 50 wt%.
reacting propylene and 1-butene monomers in the presence of a catalyst system comprising:
(a) a solid supported catalyst component prepared by the method comprising: (i) co-comminuting magnesium halide support base and aluminum trihalide in a molar ratio from about 8:0.5 to about 8:3 in the absence of added electron donor; and (ii) then co-comminuting the product of step (i) in the absence of added electron donor with sufficient titanium tetrahalide to provide a molar ratio of magnesium halide to titanium tetrahalide from about 8:0.1 to about 8:1.0 (b) a trialkylaluminum co-catalyst, having from 1 to 9 carbon atoms in each alkyl group in an amount such that the Al/Ti ratio is between about 50:1 and about 500:1.
(c) a dialkoxy or trialkoxy silane component in a sufficient quantity such that the molar ratio of organoaluminum co-catalyst to alkoxy silane is in the range from about 20:1 to about 45:1;
said amorphous copolymer being characterized by a propylene content of 25 to 50 wt% and a 1-butene content of 75 to 50 wt%.
2. The process of Claim 1 wherein the propylene and 1-butene monomers are polymerized at a temperature of from 130°F to 150°F.
3. The process of Claim 1 wherein the propylene and 1-butene monomers are polymerized at a pressure from 250 psig to 350 psig.
4. The process of Claim 1 wherein the dialkoxy or trialkoxy silane is selected from the group of alkoxy silanes of the formula R n Si(OR')4-n where n = 1-2, R = aryl or alkyl and R' = C1-3 alkyl.
5. The process of Claim 1 wherein the dialkoxy or trialkoxy silane is selected from the group consisting of cyclohexyl methyl dimethoxy silane and phenyl triethoxy silane.
6. The process of Claim 1 wherein the dialkoxy or trialkoxy silane is selected from the group consisting of dimethyl diethoxy silane, dodecyl triethoxy silane, methyl phenyl diethoxy silane, dimethyl diisopropenoxy silane, methyl octyl dimethoxy silane and methyl triethoxy silane.
7. The process of Claim 1 wherein the copolymer is characterized by a tensile strength of at least 300 psig.
8. A process for the production of an amorphous propylene/1-butene copolymers comprising:
reacting propylene and 1-butene monomers in the presence of a catalyst system comprising:
(a) a solid supported catalyst component prepared by the method comprising: (i) co-comminuting magnesium halide support base and aluminum trihalide in a molar ratio from about 8:0.5 to about 8:3 in the absence of added electron donor; and (ii) then co-comminuting the product of step (i) in the absence of added electron donor with sufficient titanium tetrahalide to provide a molar ratio of magnesium halide to titanium tetrahalide from about 8:0.1 to about 8:1.SLZERO.
(b) a trialkylaluminum co-catalyst, having from 1 to 9 carbon atoms in each alkyl group in an amount such that the Al/Ti ratio is between about 50:1 and about 500:1.
(c) a dialkoxy or trialkoxy silane component of the formula R n Si(OR')4-n where n = 1-2, R = aryl or alkyl and R' = C1-3 alkyl in a sufficient quantity such that the molar ratio of organoaluminum co-catalyst to alkoxy silane is in the range from about 20:1 to about 45:1;
said amorphous copolymer being characterized by a propylene content of 25 to 50 wt%, a 1-butene content of 75 to 50 wt% and a tensile strength of at least 300 psig.
reacting propylene and 1-butene monomers in the presence of a catalyst system comprising:
(a) a solid supported catalyst component prepared by the method comprising: (i) co-comminuting magnesium halide support base and aluminum trihalide in a molar ratio from about 8:0.5 to about 8:3 in the absence of added electron donor; and (ii) then co-comminuting the product of step (i) in the absence of added electron donor with sufficient titanium tetrahalide to provide a molar ratio of magnesium halide to titanium tetrahalide from about 8:0.1 to about 8:1.SLZERO.
(b) a trialkylaluminum co-catalyst, having from 1 to 9 carbon atoms in each alkyl group in an amount such that the Al/Ti ratio is between about 50:1 and about 500:1.
(c) a dialkoxy or trialkoxy silane component of the formula R n Si(OR')4-n where n = 1-2, R = aryl or alkyl and R' = C1-3 alkyl in a sufficient quantity such that the molar ratio of organoaluminum co-catalyst to alkoxy silane is in the range from about 20:1 to about 45:1;
said amorphous copolymer being characterized by a propylene content of 25 to 50 wt%, a 1-butene content of 75 to 50 wt% and a tensile strength of at least 300 psig.
9. The process of Claim 8 wherein the propylene and 1-butene monomers are polymerized at a temperature of from 130°F to 150°F.
10. The process of Claim 8 wherein the propylene and 1-butene monomers are polymerized at a pressure from 250 psig to 350 psig.
11. The process of Claim 8 wherein the dialkoxy or trialkoxy silane is selected from the group consisting of cyclohexyl methyl dimethoxy silane and phenyl triethoxy silane.
12. The process of Claim 8 wherein the dialkoxy or trialkoxy silane is selected from the group consisting of dimethyl diethoxy silane, dodecyl triethoxy silane, methyl phenyl diethoxy silane, dimethyl diisopropenoxy silane, methyl octyl dimethoxy silane and methyl triethoxy silane.
13. A copolymer comprising:
from 25 to 50 wt% propylene and from 75 to 50 wt% 1-butene characterized by a tensile strength of greater than 300 psig;
said copolymer containing no heptane insolubles and being further characterized by having no detectable heat of fusion.
from 25 to 50 wt% propylene and from 75 to 50 wt% 1-butene characterized by a tensile strength of greater than 300 psig;
said copolymer containing no heptane insolubles and being further characterized by having no detectable heat of fusion.
14. The copolymer of Claim 13 wherein the copolymer is produced by the process comprising:
reacting propylene and 1-butene monomers in the presence of a catalyst system comprising:
(a) a solid supported catalyst component prepared by the method comprising: (i) co-comminuting magnesium halide support base and aluminum trihalide in a molar ratio from about 8:0.5 to about 8:3 in the absence of added electron donor; and (ii) then co-comminuting the product of step (i) in the absence of added electron donor with sufficient titanium tetrahalide to provide a molar ratio of magnesium halide to titanium tetrahalide from about 8:0.1 to about 8:1.0;
(b) a trialkylaluminum co-catalyst, having from 1 to 9 carbon atoms in each alkyl group in an amount such that the Al/Ti ratio is between about 50:1 and about 500:1;
(c) a dialkoxy or trialkoxy silane component in a sufficient quantity such that the molar ratio of organoaluminum co-catalyst to alkoxy silane is in the range from about 20:1 to about 45:1.
reacting propylene and 1-butene monomers in the presence of a catalyst system comprising:
(a) a solid supported catalyst component prepared by the method comprising: (i) co-comminuting magnesium halide support base and aluminum trihalide in a molar ratio from about 8:0.5 to about 8:3 in the absence of added electron donor; and (ii) then co-comminuting the product of step (i) in the absence of added electron donor with sufficient titanium tetrahalide to provide a molar ratio of magnesium halide to titanium tetrahalide from about 8:0.1 to about 8:1.0;
(b) a trialkylaluminum co-catalyst, having from 1 to 9 carbon atoms in each alkyl group in an amount such that the Al/Ti ratio is between about 50:1 and about 500:1;
(c) a dialkoxy or trialkoxy silane component in a sufficient quantity such that the molar ratio of organoaluminum co-catalyst to alkoxy silane is in the range from about 20:1 to about 45:1.
15. The copolymer of Claim 13 wherein the copolymer is produced by polymerizing propylene and 1-butene monomers polymerized at a temperature of from 130°F to 150°F.
16. The copolymer of Claim 13 wherein the copolymer is produced by polymerizing propylene and 1-butene monomers at a pressure from 250 psig to 350 psig.
17. The copolymer of Claim 13 wherein the copolymer is produced with a dialkoxy or trialkoxy silane selected from the group of alkoxy silanes of the formula R n Si(OR')4-n where n = 1-2, R = aryl or alkyl and R' = C1-3 alkyl.
18. The copolymer of Claim 13 wherein the copolymer is produced with a dialkoxy or trialkoxy silane selected from the group consisting of cyclohexyl methyl dimethoxy silane and phenyl triethoxy silane.
19. The copolymer of Claim 13 wherein the copolymer is produced with a dialkoxy or trialkoxy silane selected from the group consisting of dimethyl diethoxy silane, dodecyl triethoxy silane, methyl phenyl diethoxy silane, dimethyl diisopropenoxy silane, methyl octyl diethoxy silane and methyl triethoxy silane.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US941,916 | 1986-12-15 | ||
| US07/941,916 US5302675A (en) | 1992-09-08 | 1992-09-08 | High tensile strength amorphous 1-butene/propylene copolymers |
| PCT/US1993/008222 WO1994005711A1 (en) | 1992-09-08 | 1993-09-08 | High tensile strength amorphous 1-butene/propylene copolymers |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2142448A1 CA2142448A1 (en) | 1994-03-17 |
| CA2142448C true CA2142448C (en) | 2007-10-09 |
Family
ID=26786993
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002142448A Expired - Lifetime CA2142448C (en) | 1992-09-08 | 1993-09-08 | High tensile strength amorphous 1-butene/propylene copolymers |
Country Status (2)
| Country | Link |
|---|---|
| CA (1) | CA2142448C (en) |
| NO (1) | NO303288B1 (en) |
-
1993
- 1993-09-08 CA CA002142448A patent/CA2142448C/en not_active Expired - Lifetime
-
1995
- 1995-03-02 NO NO950826A patent/NO303288B1/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| NO303288B1 (en) | 1998-06-22 |
| NO950826L (en) | 1995-03-02 |
| NO950826D0 (en) | 1995-03-02 |
| CA2142448A1 (en) | 1994-03-17 |
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