GB1589873A - Process for polymerising olefins - Google Patents
Process for polymerising olefins Download PDFInfo
- Publication number
- GB1589873A GB1589873A GB4461076A GB4461076A GB1589873A GB 1589873 A GB1589873 A GB 1589873A GB 4461076 A GB4461076 A GB 4461076A GB 4461076 A GB4461076 A GB 4461076A GB 1589873 A GB1589873 A GB 1589873A
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- GB
- United Kingdom
- Prior art keywords
- polysulphone
- carbon atoms
- range
- derived
- quaternary ammonium
- 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.)
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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
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
-
- 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
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- Chemical & Material Sciences (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)
Description
(54) A PROCESS FOR POLYMERISING OLEFINS
(71) We, B.P. CHEMICALS LI
MITED, of Britannic House, Moor Lane,
London, EC2Y 9BU, a British Company, do hereby declare the invention for which we pray that a patent may be granted to us, and the method by which it is to be performed to be particularly described in and by the following statement:
The present invention relates to a process for polymerising 1-olefins. More particularly the invention relates to a process for polymerising 1-olefins under particle form process conditions in a liquid diluent wherein the risk of reactor fouling is reduced.
A number of commercial processes for polymerising ethylene or mixtures of ethylene with other 1-olefins comprise contacting the monomeric material with a suspension of an ethylene polymerisation catalyst in a liquid hydrocarbon diluent under conditions such that at least part of the polymer is produced in the form of solid particles. This type of process is known in the art as a particle form process. An example of a process of this type is the
Phillips (registered Trade Mark) particle form process wherein ethylene is contacted with a suspension of a catalyst comprising chromium oxide supported on silica in a liquid hydrocarbon diluent and under conditions such that the polyethylene forms as a suspension of solid particles in the liquid hydrocarbon. The Phillips particle form process is described, for example, in UK
Specifications 853,414, 886,784 and 899,156.
Another example of a particle form process is the supported Ziegler catalysed polymerisation of 1-olefins wherein a particulate supported Ziegler catalyst, for example a titanium tetrachloride/magnesia catalyst, suspended in a liquid hydrocarbon diluent is contacted with the monomeric 1-olefin, e.g.
ethylene, in the presence of a Ziegler catalyst activator and the reaction is carried out under conditions such that the polymer forms as particles suspended in the diluent.
A problem that is frequently encountered in operating particle form processes, e.g.
the particle form polymerisation of ethylene, is that deposits of polymer can build up on the interior surfaces of the polymerisation reactor and any ancillary equipment which contacts the suspension of polymer particles. This type of reactor fouling can lead to poor heat transfer in the reactor, non-uniformity of the product polymer, loss of efficiency of pumping or agitation apparatus in the reactor and a reduction in the productivity of the process.
The majority of modern plants employing the particle form process are designed to operate in a continuous or semi-continuous manner and under these circumstances reactor fouling can lead to expensive plant shut-downs. It is an object of the present invention to provide an improved process for carrying out particle form polymerisation.
According the present invention provides a process for polymerising monomeric material comprising one or more 1-olefins or a 1-olefin and a diene comprising contacting the monomer with a polymerization catalyst suspended in a liquid hydrocarbon diluent under particle form process conditions in the presence of a polysulphone comprising a substantially 1:1 copolymer of sulphur dioxide and 1-olefinically unsaturated monomer wherein the copolymerised units of the 1-olefinically unsaturated monomer comprise 80-100% (by number) of units derived from one or more 1-alkenes having 6 to 24 carbon atoms and 0-20% of units derived from one or more compounds having the formula ACH:CHB wherein A is a group having the formula CXH2xCOOH wherein x is from 0 to 17 and B is hydrogen or carboxyl, with the proviso that when B is carboxyl x is 0, and wherein A and B together can be an anhydride group.
1-olefins suitably employed in the process of the present invention are, for example, ethylene or mixtures of ethylene with other 1-olefins such as propylene, 1-butene, 1pentene, 1-hexene and 4-methyl pentene-1, or with dienes such as 1,3-butadiene and isoprene. The process is particularly useful for the hompolymerization of ethylene or the copolymerization of ethylene with up to 40% by weight of other 1-olefins or dienes.
Particle form processes for polymerising 1-olefins, e.g. the Phillips process, the supported Ziegler catalysed process and the
Union Carbide process (employing n- bonded chromium complexes are well known in the art and for further details regarding these processes reference may be made to the numerous patent publications covering such processes.
The polysulphone employed in the present invention suitably has a weight average molecular weight in the range 10,000 to 1,500,000, preferably in the range 50,000 to 900,000. The units derived from the one of more 1-alkenes are preferably derived from straight chain alkenes having 6-18 carbon atoms, for example 1-hexene, 1-heptene, 1-octene, 1-decene, 1-dodecene. 1hexadecene and l-octadecene. Examples of units derived from the one or more compounds having the formula ACH:CHB are units derived from maleic acid, acrylic acid, 5-hexenoic acid. For further details of polysulphones suitable for use in the present invention reference may be made to UK patent specifications 1,432,265, 1,432,266 and US patent specifications 3.811,848 and 3,917,466.
The quantity of polysulphone employed in the process of the present invention is suitably in the range .005 to 20 mg per litre of hydrocarbon diluent.
In a preferred embodiment according to the present invention the polymerisation process compriscs contacting the monomeric material with a polymerisation catalyst suspended in a liquid hydrocarbon diluent under particle form process conditions in the presence of the polysulphone (as hereinbefore defined) and (A) a quaternary ammonium compound or (B) a polymeric polyamine having the general formula R N [(C H 2 C H 0 H C H N R ').. CH2 C H OH C H N R - R 2 N H ) - (CH2CHOHCHlNR')CH] H~y wherein Rl is an aliphatic hydrocarbyl group of 8 to 24 carbon atoms, R2 is an alkylene group of 2 to 6 carbon atoms, RX is the group -R-- HNR', R is Rl or an N-aliphatic hydrocarbyl alkylene group having the formula R1NHR--; a, b and c are integers of 0-20 and x is 1 or 2; with the proviso that when R is Rl then a is an integer of 2 to 20 and b = c = 0, and when R is R'NlIR2- then a is 0 and b+c is an integer of 2 to 20.
In the process of the present invention it is particularly preferred to use the defined polysulphone together with the polymeric polyamine defined in (B) above.
Quaternary ammonium compounds suitably employed in the present invention are tetrahydrocarbyl ammonium salts, for ex- ample tetra-alkyl ammonium salts or trialkyl monaralkyl ammonium salts; quaternary ammonium compounds containing three hydrocarbyl groups and a fourth hetero group linked to the quaternised nitrogen atom, for example compounds containing the cation R5R6R7N+(CH2CR8Ho)nH wherein R5, R6 and R7 are hydrocarbyl groups, R8 is hydrogen or methyl and n is 1 to 20; or phospholipids, lecithins or betaines. Preferred quaternary ammonium compounds are tetra-alkyl ammonium salts wherein at least one of the alkyl groups contains at least 8 carbon atoms. Particularly preferred are tetra-alkyl ammonium halides or nitrites wherein at least one of the alkyl groups is a hydrocarbon radical derived from tall oil, tallow, soy bean oil, coconut oil or cottonseed oil. Quaternary ammonium compounds of this type are sold by Armour (Chicago, Illinois) under the trade name of Arquard. For further details of suitable quaternary ammonium compounds reference may be made to UK patent 1,432,265, 1,432,266 and US patent 3,811,848.
The polymeric polyamines which can be suitably employed in the process of the present invention are described in US patent 3,917,466, in particular at column 6 line 42 to column 9 line 29.
The polymeric polyamine may be prepared for example by heating an aliphatic primary monoamine or N-aliphatic hydrocarbyl alkylene diamine with epichlorohydrin in the molar proportion of from 1:1 to 1:1.5 at a temperature of 50 to 100"C in the presence in solvent, eg a mixture of xylene and isopropanol, adding a strong base, eg sodium hydroxide and continuing the heating at 50 to 100"C for about 2 hours. The product containing the polymeric polyamine may then be separated by decanting and then flashing off the solvent.
The polymeric polyamine is preferably the product of reacting an aliphatic primary amine containing at least 8 carbon atoms and preferably at least 12 carbon atoms with epichlorohydrin. Examples of such aliphatic primary amines are those derived from tall oil, tallow, soy bean oil, coconut oil and cotton seed oil. The polymeric polyamine derived from the reaction of tallowamine with epichlorohydrin is preferred. A method of preparing such a polyamine is disclosed in US patent specification 3,917,466, column 12, preparation B-1.
When it is desired to use a quaternary ammonium compound or a polymeric polyamine together with the polysulphone in the process of the present invention the weight ratio of polysulphone: polymeric polyamine is preferably in the range from 100:1 to 1:100, most preferably 5:1 to 1:5.
The concentration of polysulphone plus quaternary ammonium compound or polysulphone plus polyamine in the liquid hydrocarbon diluent is preferably in the range .005 to 100 mg per litre, most preferably 0.05 to 10 mg per litre.
WHAT WE CLAIM IS:
1. A process for polymerising monomeric material comprising one or more 1-olefins or a 1-olefin and a diene comprising contacting the monomeric material with a polymerisation catalyst suspended in a liquid hydrocarbon diluent under particle form process conditions in the presence of a polysulphone comprising a substantially 1:1 copolymer of sulphur dioxide and 1-olefinically unsaturated monomer wherein the copolymerised units of the 1-olefinically unsaturated monomer comprise 80-100% (by number) of units derived from one or more 1-alkenes having 6 to 24 carbon atoms and 0-20% of units derived from one or more compounds having the formula ACH:CHB wherein A is a group having the formula CXH2xCOOH wherein x is from 0 to 17 and B is hydrogen or carboxyl, with the proviso that when B is carboxyl x is 0, and wherein A and B together can be an anhydride group.
2. A process as claimed in claim 1 wherein the monomeric material which is polymerised under the particle form process conditions is ethylene or a mixture of ethylene with up to 40% by weight of other 1-olefinic or dienic monomer.
3. A process as claimed in claim 1 or 2 wherein the polysulphone has a weight average molecular weight in the range 50,000 to 900,000.
4. A process as claimed in any preceding claim wherein the copolymerised units derived from the one or more 1-alkenes are derived from straight chain alkenes having 6 to 18 carbon atoms.
5. A process as claimed in claim 4 wherein the 1-alkene is 1-decene.
6. A process as claimed in any preceding claim wherein the units having the formula
ACH:CHB are units derived from maleic acid, acrylic acid or 5-hexenoic acid.
7. A process as claimed in any preceding claim wherein the quantity of polysulphone employed in the particle form polymerisation is in the range 0.005 to 20 mg per litre of liquid hydrocarbon diluent.
8. A process as claimed in any preceding claim wherein in addition to the polysulphone there is present in the polymerisation (A) a quaternary ammonium compound or (B) a polymeric polyamine having the general formula RN [(CH2CHOHCH2NR1)a- (CH2CHOHCH2NRl-R2-NH)b- (CH2CHoHCH2NR3)cH]xH2-x wherein R1 is an aliphatic hydrocarbyl group of 8 to 24 carbon atoms, R2 is an alkylene group of 2 to 6 carbon atoms, R3 is the group -R2
HNR', R is R or an N-aliphatic hydrocarbyl alkylene group having the formula R'NHR-;a,band c are integers of 0-20 and x is 1 or 2; with the proviso that when R is
R1 then a is an integer of 2 to 20 and b = c = 0, and when R is R1NHR2- then a is 0 and b+c is an integer of 2 to 20.
9. A process as claimed in claim 8 wherein the quaternary ammonium compound (A) is a tetra-alkyl ammonium halide or nitrite wherein at least one of alkyl groups is a hydrocarbon radical derived from tall oil, tallow, soy bean oil, coconut oil or cottonseed oil.
10. A process as claimed in claim 8 wherein the polymeric polyamine is the product derived by heating an aliphatic primary monoamine or an N-aliphatic hydrocarbyl alkylene diamine with epichlorohydrin.
11. A process as claimed in claim 10 wherein the aliphatic primary monoamine contains at least 8 carbon atoms.
12. A process as claimed in claim 11 wherein the aliphatic primary monoamine contains at least 12 carbon atoms.
13. A process as claimed in claim 10 wherein the aliphatic primary monoamine is derived from tall oil, tallow, soy bean oil, coconut oil or cottonseed oil.
14. A process as claimed in any one of claims 8-13 wherein the weight ratio of polysulphone to the quaternary ammonium compound (A) Qr to the polymeric polyamine (B) is in the range 5:1 to 1:5.
15. A process as claimed in any one of claims 8-14 wherein the concentration of polysulphone together with the quaternary ammonium compound (A) or the polymeric polyamine (B) in the liquid hydrocarbon diluent is in the range 0.005 to 100 mg per litre.
16. A process as claimed in claim 15 wherein the said concentration of polysulphone together with A or B is in the range 0.05 to 10 mg per litre.
17. A polyolefin prepared by the process claimed in any preceding claim.
**WARNING** end of DESC field may overlap start of CLMS **.
Claims (17)
1. A process for polymerising monomeric material comprising one or more 1-olefins or a 1-olefin and a diene comprising contacting the monomeric material with a polymerisation catalyst suspended in a liquid hydrocarbon diluent under particle form process conditions in the presence of a polysulphone comprising a substantially 1:1 copolymer of sulphur dioxide and 1-olefinically unsaturated monomer wherein the copolymerised units of the 1-olefinically unsaturated monomer comprise 80-100% (by number) of units derived from one or more 1-alkenes having 6 to 24 carbon atoms and 0-20% of units derived from one or more compounds having the formula ACH:CHB wherein A is a group having the formula CXH2xCOOH wherein x is from 0 to 17 and B is hydrogen or carboxyl, with the proviso that when B is carboxyl x is 0, and wherein A and B together can be an anhydride group.
2. A process as claimed in claim 1 wherein the monomeric material which is polymerised under the particle form process conditions is ethylene or a mixture of ethylene with up to 40% by weight of other 1-olefinic or dienic monomer.
3. A process as claimed in claim 1 or 2 wherein the polysulphone has a weight average molecular weight in the range 50,000 to 900,000.
4. A process as claimed in any preceding claim wherein the copolymerised units derived from the one or more 1-alkenes are derived from straight chain alkenes having 6 to 18 carbon atoms.
5. A process as claimed in claim 4 wherein the 1-alkene is 1-decene.
6. A process as claimed in any preceding claim wherein the units having the formula
ACH:CHB are units derived from maleic acid, acrylic acid or 5-hexenoic acid.
7. A process as claimed in any preceding claim wherein the quantity of polysulphone employed in the particle form polymerisation is in the range 0.005 to 20 mg per litre of liquid hydrocarbon diluent.
8. A process as claimed in any preceding claim wherein in addition to the polysulphone there is present in the polymerisation (A) a quaternary ammonium compound or (B) a polymeric polyamine having the general formula RN [(CH2CHOHCH2NR1)a- (CH2CHOHCH2NRl-R2-NH)b- (CH2CHoHCH2NR3)cH]xH2-x wherein R1 is an aliphatic hydrocarbyl group of 8 to 24 carbon atoms, R2 is an alkylene group of 2 to 6 carbon atoms, R3 is the group -R2
HNR', R is R or an N-aliphatic hydrocarbyl alkylene group having the formula R'NHR-;a,band c are integers of 0-20 and x is 1 or 2; with the proviso that when R is
R1 then a is an integer of 2 to 20 and b = c = 0, and when R is R1NHR2- then a is 0 and b+c is an integer of 2 to 20.
9. A process as claimed in claim 8 wherein the quaternary ammonium compound (A) is a tetra-alkyl ammonium halide or nitrite wherein at least one of alkyl groups is a hydrocarbon radical derived from tall oil, tallow, soy bean oil, coconut oil or cottonseed oil.
10. A process as claimed in claim 8 wherein the polymeric polyamine is the product derived by heating an aliphatic primary monoamine or an N-aliphatic hydrocarbyl alkylene diamine with epichlorohydrin.
11. A process as claimed in claim 10 wherein the aliphatic primary monoamine contains at least 8 carbon atoms.
12. A process as claimed in claim 11 wherein the aliphatic primary monoamine contains at least 12 carbon atoms.
13. A process as claimed in claim 10 wherein the aliphatic primary monoamine is derived from tall oil, tallow, soy bean oil, coconut oil or cottonseed oil.
14. A process as claimed in any one of claims 8-13 wherein the weight ratio of polysulphone to the quaternary ammonium compound (A) Qr to the polymeric polyamine (B) is in the range 5:1 to 1:5.
15. A process as claimed in any one of claims 8-14 wherein the concentration of polysulphone together with the quaternary ammonium compound (A) or the polymeric polyamine (B) in the liquid hydrocarbon diluent is in the range 0.005 to 100 mg per litre.
16. A process as claimed in claim 15 wherein the said concentration of polysulphone together with A or B is in the range 0.05 to 10 mg per litre.
17. A polyolefin prepared by the process claimed in any preceding claim.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB4461076A GB1589873A (en) | 1977-10-27 | 1977-10-27 | Process for polymerising olefins |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB4461076A GB1589873A (en) | 1977-10-27 | 1977-10-27 | Process for polymerising olefins |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| GB1589873A true GB1589873A (en) | 1981-05-20 |
Family
ID=10434069
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB4461076A Expired GB1589873A (en) | 1977-10-27 | 1977-10-27 | Process for polymerising olefins |
Country Status (1)
| Country | Link |
|---|---|
| GB (1) | GB1589873A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5037913A (en) * | 1987-02-24 | 1991-08-06 | Albus S.A. | Hydroxylated acrylic copolymer binder for paints |
-
1977
- 1977-10-27 GB GB4461076A patent/GB1589873A/en not_active Expired
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5037913A (en) * | 1987-02-24 | 1991-08-06 | Albus S.A. | Hydroxylated acrylic copolymer binder for paints |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PS | Patent sealed | ||
| PCNP | Patent ceased through non-payment of renewal fee |