EP0217803A1 - Terpolymer production - Google Patents

Terpolymer production

Info

Publication number
EP0217803A1
EP0217803A1 EP85905557A EP85905557A EP0217803A1 EP 0217803 A1 EP0217803 A1 EP 0217803A1 EP 85905557 A EP85905557 A EP 85905557A EP 85905557 A EP85905557 A EP 85905557A EP 0217803 A1 EP0217803 A1 EP 0217803A1
Authority
EP
European Patent Office
Prior art keywords
ethylene
stage
terpolymer
butene
melting point
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP85905557A
Other languages
German (de)
French (fr)
Inventor
Raymond J. Ehrig
John J. Godfrey
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Braskem America Inc
Original Assignee
USS Engineers and Consultants Inc
Aristech Chemical Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by USS Engineers and Consultants Inc, Aristech Chemical Corp filed Critical USS Engineers and Consultants Inc
Publication of EP0217803A1 publication Critical patent/EP0217803A1/en
Withdrawn legal-status Critical Current

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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
    • C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
    • 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
    • C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
    • C08F297/06—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the coordination type
    • C08F297/08—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the coordination type polymerising mono-olefins
    • 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

Definitions

  • Terpolymers comprising 90% or more propylene having a DSC melting point lower than 140-145°C cannot be prepared in hexane slurry at 60°C because the polymer particles swell by absorbing the hexane diluent, become very sticky, and thereby cause agglomeration and reactor fouling.
  • 1-butene as a termonomer along with small amounts of ethylene is not new, its advantage over ethylene of not increasing the solubility of the polymer as much as ethylene has not been fully utilized in the past because a satisfactory method of manufacturing the polymer has not been conceived to take advantage of the unique contributions of 1-butene while also benefiting from the use of ethylene to modify a basically polypropylene product.
  • the reader may also be interested in Shirai et al 3,642,951, Saito et al 4,066,718, Furutachi et al 4,128,606, and particularly Scoggin 3,525,781, which teaches preparing block copolymers continuously by feeding batch prepolymers into a continuous polymerization zone, Baba et al 4,433,110, which provides propylene and 1-butene polymerization in a first stage and propylene and ethylene polymerization in a second stage, and particularly Frese et al 3,959,409, which discloses the production of crystalline propylene/ethylene/butene-1 terpolymers in series-connected reactors, the ethylene being introduced only in the second or subsequent reactors. See also the large number of examples of terpolymer production in Suzuki et al US Patent 4,304,890. The feed of ethylene is increased, compared to propylene, after the first stage in Sennari et al 3,670,053.
  • the two-stage process may be operated conveniently on a commercial scale by using two continuous reactors in series.
  • the following examples demonstrating the process use, for convenience, the process equivalent of two reactors in series, namely a single batch reactor wherein the batch is treated in a first and a second stage. Concentrations of the termonomers are maintained in the first and second stages of the batch reactor at levels equivalent to those in two reactors in series operating continuously and at steady-state conditions.
  • hexane slurry polymerization system where the first reactor is charged with hexane or other solvent for propylene, about one-half percent to about one percent of a titanium tetrachlor ide catalyst supported on magnesium chloride and about 2.5-3.0% of a solution of 10% tr iethylaluminum in hexane. Temperature is preferably maintained at about 35oC and pressure is about 150 psig.
  • the termonomer composition in the reactor to produce a product melting in the range of 130o to 140°C is typically the following as determined by sampling the reactor gas cap and analyzing for the weight ratio of monomers by vapor-phase chromatography: First Stage Second Stage
  • the ethylene component of the termonomer mixture is maintained at a higher level than in the first stage by supplementing the liquid termonomer feed with ethylene typically in 3 psig increments.
  • Product melt flows in the range of 5 to 55 are produced by maintaining levels of hydrogen in the reactor of 0.025 and 0.25 weight percent in stages 1 and 2, respectively, in the gas cap, by vapor-phase chromatography.
  • This process with variations in the content of ethylene and 1-butene of plus or minus five percent and consequent possible variations in content of propylene, will produce a terpolymer having a DSC melting point of about 135 oC, typically about 130o to 140oC, and containing about 3.1 weight percent ethylene and about 4.3 weight percent 1-butene.
  • Our invention includes products recovered from the above process containing from about 3% to about 4% ethylene and about 3% to about 5.6% 1-butene and having a melting point between 130o and 140oC., according to the formula:
  • C 2 and C 4 are the concentrations of ethylene and 1-butene in weight percent.
  • C 2 and C 4 are the concentrations of ethylene and 1-butene in weight percent.
  • the product slurry is in the form of small particles dispersed in the hexane diluent.
  • the size of the terpolymer particles is determined primarily by the size of the original catalyst particles.
  • the terpolymer particles isolated from the reactor slurry have a size ranging from 200 to 2,000 microns diameter,
  • terpolymer product having an ethylene content in the lower part of its range and a 1-butene content in the higher part of its range, in order to minimize the portion of product which is undesirable because it is soluble in hexane.
  • the reactor was loaded with hexane and catalyst components, and 1 psig was maintained in the reactor gas caps for one hour at 35°C by feeding propylene.
  • the catalyst used was a commercial Montedison FTlSS catalyst.
  • the initial reactor charge at 35°C is carried out as indicated in the table of examples.
  • a stirred, jacketed reactor of 300 psig maximum operating pressure was used to make up and feed the termonomer mixtures to the polymerization reactor.
  • 1-butene, propylene, and ethylene were charged in that order to give the liquid-phase feed composition indicated in the table of examples below.
  • the termonomer mixture was then heated to 30°C to raise its pressure above 150 psig so that it could be metered by way of a needle valve to the polymerization reactor, on demand, to maintain 150 psig.
  • the termonomer feed mixture of the compositions indicated in the table of examples was fed to the polymerization reactor, on demand, to maintain the "First Stage" gas cap composition shown above at 150 psig. Demand is manifested immediately when the reaction begins.
  • the second-stage was started by supplementing the termonomer feed with 3 psig incremental additions of ethylene to elevate the ethylene content of the reactor gas cap to 2-4 wt.% ethylene.
  • the more desirable products for our purposes are those of examples 12 and 13, having good or excellent processability with a melting point between 130°C and 140°C, providing good heat sealability.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)

Abstract

Des terpolymères comprenant du propylène et de petites quantités d'éthylène et de butène-1 sont produits par un procédé en deux étapes. Un terpolymère aléatoire à point de fusion relativement élevé est obtenu pendant une première étape et un terpolymère aléatoire à point de fusion relativement bas présentant une teneur en éthylène plus élevée est produit pendant une deuxième étape de manière à être dispersé dans le produit de la première étape. Les deux étapes du traitement peuvent être exécutées dans un seul réacteur à charge discontinue ou dans deux réacteurs continus en série.Terpolymers comprising propylene and small amounts of ethylene and butene-1 are produced by a two-step process. A relatively high melting point random terpolymer is obtained in a first step and a relatively low melting point random terpolymer having a higher ethylene content is produced in a second step so as to be dispersed in the product of the first step . The two stages of the treatment can be carried out in a single batch reactor or in two continuous reactors in series.

Description

TERPOLYMER PRODUCTION
Technical Field
Terpolymers comprising 90% or more propylene having a DSC melting point lower than 140-145°C cannot be prepared in hexane slurry at 60°C because the polymer particles swell by absorbing the hexane diluent, become very sticky, and thereby cause agglomeration and reactor fouling. While the use of 1-butene as a termonomer along with small amounts of ethylene is not new, its advantage over ethylene of not increasing the solubility of the polymer as much as ethylene has not been fully utilized in the past because a satisfactory method of manufacturing the polymer has not been conceived to take advantage of the unique contributions of 1-butene while also benefiting from the use of ethylene to modify a basically polypropylene product.
In the past, numerous combinations of monomers, principally ethylene and propylene, have been introduced into the same or different reactors with or without the presence of a chain terminator such as hydrogen between the stages. See, for example, Davison et al 2,839,515, Edmonds, Jr. 3,970,719, Cox 3,264,184, Short 3,318,976, Kontos 3,378,606, Hassell 3,378,608, Hagemeyer, Jr. et al 3,529,037, Gobran et al 3,649,579, Koga et al 3,974,236, and Shiga et al 4,254,237. Many such processes have as their objective the manufacture of block copolymers and/or dispersions of particles in a matrix in which particles of one structure are evenly distributed within a medium comprising a polymer of another, more or less modified, polymer. Both batch and continuous processes for producing such composite products are found in the-prior art.
The reader may also be interested in Shirai et al 3,642,951, Saito et al 4,066,718, Furutachi et al 4,128,606, and particularly Scoggin 3,525,781, which teaches preparing block copolymers continuously by feeding batch prepolymers into a continuous polymerization zone, Baba et al 4,433,110, which provides propylene and 1-butene polymerization in a first stage and propylene and ethylene polymerization in a second stage, and particularly Frese et al 3,959,409, which discloses the production of crystalline propylene/ethylene/butene-1 terpolymers in series-connected reactors, the ethylene being introduced only in the second or subsequent reactors. See also the large number of examples of terpolymer production in Suzuki et al US Patent 4,304,890. The feed of ethylene is increased, compared to propylene, after the first stage in Sennari et al 3,670,053.
We are not aware of any rationale in the prior art for utilizing 1-butene to facilitate the manufacture of low melting point polymers of propylene and a small amount of ethylene.
Disclosure of Invention
We have invented a two-stage polymerization process which employs three monomers in each stage, under carefully controlled concentration conditions, to produce a polymer having unique desirable properties. The two-stage process may be operated conveniently on a commercial scale by using two continuous reactors in series. The following examples demonstrating the process use, for convenience, the process equivalent of two reactors in series, namely a single batch reactor wherein the batch is treated in a first and a second stage. Concentrations of the termonomers are maintained in the first and second stages of the batch reactor at levels equivalent to those in two reactors in series operating continuously and at steady-state conditions.
In our process, high concentrations of propylene and 1-butene are maintained in the reaction zone throughout, but only low concentrations of the very reactive ethylene are maintained. The major distinguishing difference between stages is that the ethylene concentration is increased in the second stage to promote greater incorporation of ethylene into the terpolymer system, thereby lowering the melting point of the product of the two stages into the desirable low temperature range of 130º to 140 ºC.
Specifically, we propose a hexane slurry polymerization system where the first reactor is charged with hexane or other solvent for propylene, about one-half percent to about one percent of a titanium tetrachlor ide catalyst supported on magnesium chloride and about 2.5-3.0% of a solution of 10% tr iethylaluminum in hexane. Temperature is preferably maintained at about 35ºC and pressure is about 150 psig. The termonomer composition in the reactor to produce a product melting in the range of 130º to 140°C is typically the following as determined by sampling the reactor gas cap and analyzing for the weight ratio of monomers by vapor-phase chromatography: First Stage Second Stage
ethylene 1.2 3.4 propylene 93.9 90.5
1-butene 4.9 6.1
100.0 100.0
In the second stage, the ethylene component of the termonomer mixture is maintained at a higher level than in the first stage by supplementing the liquid termonomer feed with ethylene typically in 3 psig increments. Product melt flows in the range of 5 to 55 are produced by maintaining levels of hydrogen in the reactor of 0.025 and 0.25 weight percent in stages 1 and 2, respectively, in the gas cap, by vapor-phase chromatography.
This process, with variations in the content of ethylene and 1-butene of plus or minus five percent and consequent possible variations in content of propylene, will produce a terpolymer having a DSC melting point of about 135 ºC, typically about 130º to 140ºC, and containing about 3.1 weight percent ethylene and about 4.3 weight percent 1-butene. Our invention includes products recovered from the above process containing from about 3% to about 4% ethylene and about 3% to about 5.6% 1-butene and having a melting point between 130º and 140ºC., according to the formula:
- 5.0689(C2) - 2.1135 (C4) + 161.56 = 130° to 140ºC
where C2 and C4 are the concentrations of ethylene and 1-butene in weight percent. We have found that our terpolymers having a melting point between 130°C and 140ºC have excellent heat sealability. The product slurry is in the form of small particles dispersed in the hexane diluent. The size of the terpolymer particles is determined primarily by the size of the original catalyst particles. The terpolymer particles isolated from the reactor slurry have a size ranging from 200 to 2,000 microns diameter,
Within the above formula, we prefer to make terpolymer product having an ethylene content in the lower part of its range and a 1-butene content in the higher part of its range, in order to minimize the portion of product which is undesirable because it is soluble in hexane. Specifically, we prefer product made by controlling the gas cap concentrations of C2 and C4 at about 3.2 to 3.4% and 6.1 to 6.4%, respectively.
In the following examples, the reactor was loaded with hexane and catalyst components, and 1 psig was maintained in the reactor gas caps for one hour at 35°C by feeding propylene. The catalyst used was a commercial Montedison FTlSS catalyst.
After loading the reactor with hexane and catalyst components, and. optionally carrying out the pre-polymerization step, the initial reactor charge at 35°C is carried out as indicated in the table of examples.
A stirred, jacketed reactor of 300 psig maximum operating pressure was used to make up and feed the termonomer mixtures to the polymerization reactor. 1-butene, propylene, and ethylene were charged in that order to give the liquid-phase feed composition indicated in the table of examples below. The termonomer mixture was then heated to 30°C to raise its pressure above 150 psig so that it could be metered by way of a needle valve to the polymerization reactor, on demand, to maintain 150 psig. The termonomer feed mixture of the compositions indicated in the table of examples was fed to the polymerization reactor, on demand, to maintain the "First Stage" gas cap composition shown above at 150 psig. Demand is manifested immediately when the reaction begins.
The second-stage was started by supplementing the termonomer feed with 3 psig incremental additions of ethylene to elevate the ethylene content of the reactor gas cap to 2-4 wt.% ethylene.
The more desirable products for our purposes are those of examples 12 and 13, having good or excellent processability with a melting point between 130°C and 140°C, providing good heat sealability.

Claims

Claims
1. Method of making a modified polypropylene in hexane slurry, said polypropylene having improved low-temperature thermal properties comprising
(a) maintaining in a first stage under polymerizing conditions a hexane-catalyst slurry in equilibrium with a gas phase composition comprising about 93.9% propylene, about 4.65% to about 5.15% 1-butene, and about 1.14% to about 1.26% ethylene, to form a dispersion in said slurry of terpolymer particles, and
(b) then imposing on said slurry of terpolymer particles, under polymerizing conditions in.a second stage, a concentration of ethylene in the gas phase increased to about 2% to about 4%, thereby forming a substrate terpolymer including about 3% to about 4% ethylene and about 3% to about 5.6% 1-butene.
2. Method of claim 1 wherein the concentrations of monomers in step (a) are maintained in the slurry by maintaining the reaction vessel at a pressure of from about 140 psig to about 160 psig.
3. Method of claim 1 wherein the second stage of the process is conducted in a reaction vessel different from the first stage.
4. Method of claim 1 wherein no 1-butene is fed to the second stage.
5. Method of claim 1 including the step of recovering a polymer product having a melting point of about 130ºC to about 140°C.
6. Method of claim 1 wherein the gas cap concentration of ethylene in the second step is maintained at about 3.23% to about 3.57%.
7. A terpolymer having a melting point of about 130ºC to about 140ºC and made by the process of claim 1.
8. A terpolymer having a melting point of about 130ºC to about 140ºC and made by the process of claim 6.
EP85905557A 1985-04-01 1985-10-15 Terpolymer production Withdrawn EP0217803A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US71859185A 1985-04-01 1985-04-01
US718591 1985-04-01

Publications (1)

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EP0217803A1 true EP0217803A1 (en) 1987-04-15

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EP (1) EP0217803A1 (en)
JP (1) JPS62502405A (en)
WO (1) WO1986005794A1 (en)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
IT1221653B (en) * 1987-11-27 1990-07-12 Ausimonti Spa PROPYLENE CRYSTALLINE COPOLYMERS
FI104824B (en) * 1997-06-24 2000-04-14 Borealis As Process for producing propylene polymers
EP3257877B1 (en) * 2016-06-16 2023-10-04 Borealis AG Nucleated propylene-ethylene-butylene terpolymers and moulded articles made thereof

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2352980C3 (en) * 1973-10-23 1980-03-13 Chemische Werke Huels Ag, 4370 Marl Process for the production of crystalline propene-ethene-butene-1 terpolymers
JPS607645B2 (en) * 1976-04-19 1985-02-26 チッソ株式会社 Method for producing a copolymer polypropylene by pre-polymerization activation of a catalyst for the copolymer
JPS58162620A (en) * 1982-03-23 1983-09-27 Mitsubishi Petrochem Co Ltd Olefin block copolymer

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO8605794A1 *

Also Published As

Publication number Publication date
WO1986005794A1 (en) 1986-10-09
JPS62502405A (en) 1987-09-17

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