CA1046196A - Process for the preparation of ethylene-propylene-butadiene terpolymers with high yield - Google Patents
Process for the preparation of ethylene-propylene-butadiene terpolymers with high yieldInfo
- Publication number
- CA1046196A CA1046196A CA231,789A CA231789A CA1046196A CA 1046196 A CA1046196 A CA 1046196A CA 231789 A CA231789 A CA 231789A CA 1046196 A CA1046196 A CA 1046196A
- Authority
- CA
- Canada
- Prior art keywords
- process according
- compounds
- vanadium
- molar ratio
- varies
- 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.)
- Expired
Links
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
- C08F210/02—Ethene
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
This invention relates to the preparation of ethylene-propylene-butadiene terpolymers and more particularly to the catalyst system as used in the polymerization reaction, this system consisting of a mixture comprising:
a) one or more vanadium compounds soluble in the polymerization solvent medium b) one or more halogenated organic-aluminium com-pounds c) one or more Lewis or Bronsted compounds d) one or more compounds amongst organic compounds containing the group CX3, thionyl chloride and hexachlorocyclopentadiene.
By using said catalyst system amorphous or sub-stantially amorphous terpolymers are obtained in a very high yield, which renders any purification step superfluous.
This invention relates to the preparation of ethylene-propylene-butadiene terpolymers and more particularly to the catalyst system as used in the polymerization reaction, this system consisting of a mixture comprising:
a) one or more vanadium compounds soluble in the polymerization solvent medium b) one or more halogenated organic-aluminium com-pounds c) one or more Lewis or Bronsted compounds d) one or more compounds amongst organic compounds containing the group CX3, thionyl chloride and hexachlorocyclopentadiene.
By using said catalyst system amorphous or sub-stantially amorphous terpolymers are obtained in a very high yield, which renders any purification step superfluous.
Description
The present invention relates to a process for the polymerization of ethylene, propylene and 1,3-butadiene to amorphous or substantially amorphous terpolymers, which may be vulcanized with high yields of cross-linking by means of conventional recipes hased on sulphur, characterized in that the polymerization yields~ referred to the used cata-lyst, are high so as to make superfluous a phase of purifi-cation or of washing.
Ethylene-propylene-butadiene terpolymers are described in the previous art. However, only exceptionally it is possibIe to obtain said polymers having a statistical distri-bution, either intermolecularly or intramolecularly of the monomeric unities, the only one able to ensure homogeneous vulcanization with sulphur.
The di~ferent polymerization behaviour of the mono-olefins as to the conjugated olefins, already widely pointed out in the literature, justifies the objective difficulty of obtaining unsaturated gums of practical interest beginning from ethylene, propylene and butadiene. Furthermore the polymerization yields are not satisfactory and anyhow always noticeably lower than the ones which may be obtained by re-placing the butadiene with non conju~ated diolefins.
The Applicant has now surprisingly found that it is possible to obtain terpolymers ethylene-propylene-butadiene, amorphous or substantially amorphous and homogeneously vulca-nizable by means of conventional recipes for unsaturated rubbers by means of a process characterized in that mixtures ethylene, propylene and butadiene are let to react, in the conditions hereinafter specified, in presence of aromatic solvents and of a catalyst prepared beginning from :
Ethylene-propylene-butadiene terpolymers are described in the previous art. However, only exceptionally it is possibIe to obtain said polymers having a statistical distri-bution, either intermolecularly or intramolecularly of the monomeric unities, the only one able to ensure homogeneous vulcanization with sulphur.
The di~ferent polymerization behaviour of the mono-olefins as to the conjugated olefins, already widely pointed out in the literature, justifies the objective difficulty of obtaining unsaturated gums of practical interest beginning from ethylene, propylene and butadiene. Furthermore the polymerization yields are not satisfactory and anyhow always noticeably lower than the ones which may be obtained by re-placing the butadiene with non conju~ated diolefins.
The Applicant has now surprisingly found that it is possible to obtain terpolymers ethylene-propylene-butadiene, amorphous or substantially amorphous and homogeneously vulca-nizable by means of conventional recipes for unsaturated rubbers by means of a process characterized in that mixtures ethylene, propylene and butadiene are let to react, in the conditions hereinafter specified, in presence of aromatic solvents and of a catalyst prepared beginning from :
2.
~046196 a) one or more compounds of vanadium soluble in said solvents ;
b) one or more compounds of aluminium having the gene-ral formula RlR2AlX, wherein Rl and R2 ~ the same or different, may be hydrogen, alkyl, cycloalkyl~ alkyl-aryl or aryl with 1-18 carbon atoms and X = chlorine or bromine;
c) one or more and compounds according to Lewis or accord-ing to Br~nsted;
d) one or more compounds chosen in the group formed by ~
1. organic compounds containing the group CX3 with ~ ;
X = halogen~ -2. thionyl-chloride,
~046196 a) one or more compounds of vanadium soluble in said solvents ;
b) one or more compounds of aluminium having the gene-ral formula RlR2AlX, wherein Rl and R2 ~ the same or different, may be hydrogen, alkyl, cycloalkyl~ alkyl-aryl or aryl with 1-18 carbon atoms and X = chlorine or bromine;
c) one or more and compounds according to Lewis or accord-ing to Br~nsted;
d) one or more compounds chosen in the group formed by ~
1. organic compounds containing the group CX3 with ~ ;
X = halogen~ -2. thionyl-chloride,
3. hexachlorocyclopentadiene.
The vanadium compounds mentioned in point a) comprise tetravalent and pentavalent, and complex trivalent vanadium halides~ the alcoholates~ the chelates and generally the complex compounds either of vanadium or of vanadyl.
For complexes we mean all the compounds characterized by bonds among the vanadium and unidentate and bidentate organic binders~ where the term "bond" is defined as an ion or a molecule bound to the metal or considered bound to the metal and the terms "unidentate and bidentate" mean a molecule which has one or~ respectively, two positions with which may form covalent bonds or coordination bonds with the metal.
Characteristic examples of compounds of the vanadium which may be used are formed by vanadium tetrachloride (pre-ferably stabilized in SiC14 solution)~ vanadyl-trichloride~
vanadium trichloride complexed with three molecules of tetra-hydrofurane, vanadium triacetylacetonate, vanadyl diacetyla-cetonate, vanadyl triisopropylate~ vanadium tetra(dimethyl-amide)~ and so on.
The components b) of the catalyst system are the alu-.
104~196 minium dihydrocarbylhalides~ among which the preferred ones, for cost and availability reasons, are the diethyl-monochloride and the diisobutylmonochloride of aluminium.
Similar results are obtained by making use of the corresponding bromides. Also the hydrides of aluminium hydrocarbyl-halides may be advantageously used.
The components c) of the catalyst object of the present invent on are all the acid compounds according Lewis and according Bronsted~ and comprise either the pluri-halogenated compounds of the metals of the III and IV Group of the periodic system~ or the compounds able to free H~
ions~ i.e the organic acids~ the inorganic acids and the water. A condition to be respected is that they are suffi-ciently soluble in the reaction hydrocarbon means or that are solubilized by reaction with other catalytlc compounds.
Examples of said compounds are the boron trichloride, the aluminium trichloride~ the aluminium monoethylchloride, the aluminium mono-isobutyldichloride~ the aluminium tri-bromide, the tin tetrachloride, the acetic acid~ the benzoic acid~ the water and so on.
The components d) of the catalytic system are~ as already specified, those organic compounds which present in their molecular one or more groups CX3 being X the halogen.
In particular, the esters of the trichloroacetic acid and the free acid trichloroacetic besides the thionyl chloride and the hexachlorocyclopentadiene are active.
A certain activity but a minor one, is shown by the trichlorotoluene~ the para-chlorotrichlorotoluene~ the chloride of the trichloroacetic acidg the carbon tetrachloride.
The molar ratio between the components b) and a) is normal-ly high as the vanadium compound is used in a very little amount. Said ratio is higher than 10 : 1 and normally comprised
The vanadium compounds mentioned in point a) comprise tetravalent and pentavalent, and complex trivalent vanadium halides~ the alcoholates~ the chelates and generally the complex compounds either of vanadium or of vanadyl.
For complexes we mean all the compounds characterized by bonds among the vanadium and unidentate and bidentate organic binders~ where the term "bond" is defined as an ion or a molecule bound to the metal or considered bound to the metal and the terms "unidentate and bidentate" mean a molecule which has one or~ respectively, two positions with which may form covalent bonds or coordination bonds with the metal.
Characteristic examples of compounds of the vanadium which may be used are formed by vanadium tetrachloride (pre-ferably stabilized in SiC14 solution)~ vanadyl-trichloride~
vanadium trichloride complexed with three molecules of tetra-hydrofurane, vanadium triacetylacetonate, vanadyl diacetyla-cetonate, vanadyl triisopropylate~ vanadium tetra(dimethyl-amide)~ and so on.
The components b) of the catalyst system are the alu-.
104~196 minium dihydrocarbylhalides~ among which the preferred ones, for cost and availability reasons, are the diethyl-monochloride and the diisobutylmonochloride of aluminium.
Similar results are obtained by making use of the corresponding bromides. Also the hydrides of aluminium hydrocarbyl-halides may be advantageously used.
The components c) of the catalyst object of the present invent on are all the acid compounds according Lewis and according Bronsted~ and comprise either the pluri-halogenated compounds of the metals of the III and IV Group of the periodic system~ or the compounds able to free H~
ions~ i.e the organic acids~ the inorganic acids and the water. A condition to be respected is that they are suffi-ciently soluble in the reaction hydrocarbon means or that are solubilized by reaction with other catalytlc compounds.
Examples of said compounds are the boron trichloride, the aluminium trichloride~ the aluminium monoethylchloride, the aluminium mono-isobutyldichloride~ the aluminium tri-bromide, the tin tetrachloride, the acetic acid~ the benzoic acid~ the water and so on.
The components d) of the catalytic system are~ as already specified, those organic compounds which present in their molecular one or more groups CX3 being X the halogen.
In particular, the esters of the trichloroacetic acid and the free acid trichloroacetic besides the thionyl chloride and the hexachlorocyclopentadiene are active.
A certain activity but a minor one, is shown by the trichlorotoluene~ the para-chlorotrichlorotoluene~ the chloride of the trichloroacetic acidg the carbon tetrachloride.
The molar ratio between the components b) and a) is normal-ly high as the vanadium compound is used in a very little amount. Said ratio is higher than 10 : 1 and normally comprised
4.
104~i196 between 50 : 1 to 100 : 1. HoweYer, when the concentration of the vanadium ls lower than 5 0 10 5 mole/liter~ the ratio Al/V is preferably comprised between 100 : 1 and 500 : 1~ While the optimum amount nf the used vanadium com-pound varies between 1 . 10-4 and 1 10 5 mole/liter~ the amount of the compound of aluminium varies between 1 and 8. 10-3 mole/liter. --The molar ratio between the components c) and b) is critical. This ratio, in the case in which c) is an inorganic or organo-metallic plurihalogenated compound~ may be expressed with the global ratio between the gram atoms of halogen and the ones of aluminium contained in the reactants b~ and c).
This ratio X/Al must be comprised between l and 1.25 or~ preferably, between 1.05 and 1.15.
~5 In the case in which c) ii a protonic acid or the water~
the ratio between b) and c) i~ chosen in the range between 10 : 1 and 1 : 1 or~ preferably~ between 4 : 1 and 2 : 1.
The molar ratio between the components d) and b) of the catalyst may vary widely, also in relation to the parti-cular Gompound d) and to the modalities of reaction. It is generally lower than l and is preferably chosen in the range comprised between 1 : 4 and 1 : 1.
All the above-mentioned reactions are effected in pre-sence of a hydrocarbon which~ according to a characteristic of the present invention, is of aromatic type. Howe~er, also mixtures of aromatic hydrocarbons with aliphatic~ cyclo-aliphatic hydrocarbons or halogenated hydrocarbons and mixtu-res with the above-mentioned ones may be used.
Therefore~ even if solvents as the benzene and the toluene are preferred~ it is possible to use the chlorobenzene or mixtures benzene/cyclohexane; toluene/n-heptane, chloro-benzene/tetrachloroethylene and so on.
104~;~96 The polymerization temperature is chosen in a wide range. Generally operation is made at temperatures higher than the room temperature in order to avoid the use of expensive refrigerator-cycles. Therefore the more suit-able range i~ comprised between 20 and 800C~ even if it iB
not excluded the possibility of operation at lower or higher temperatures~ for example between 0 and 120C.
The polymerizations are effected under moderate pressures of ethylene (2 - 20 kg/cm2). The pressure of propylene varies from 1 to 20 atmospheres and over~ in function of the temperature and of the quantity of used solvent.
For the regulation of the molecular weights is added, if necessary~ hydrogen to the system even if a sufficient regulation is obtained~ while the temperature of polymeri-zation is let to vary.
EXAMPLE
In a steel autoclave with enameled inner walls~ having the capacity of 5 liters~ equipped with mechanical stirrer ~0 and with jacket for the thermoregulation with circulating liquid, equipped with valves~ one of which with dipping pipe, for the introduction of the reagents~ has been introduced a solution obtained by - anhydrous toluene cc 670 - butadiene g 12.5 ( 2 5)2 cc 1.5 - Al(C2H5)C12 g o.l65 By means of a little cylinder g 750 of propylene have been introduced. At this point the autoclave has been thermosta tated at 50C. -The internal pressure has rised to 13.5 kg/cm .
Ethylene has been added up to the total pressure of 18 5 kg/cm at 50C.
:., `: :
1046196 ~:
By means o~ a pump it has been introduced in 20l a solution containing 33.5 mg of vanadium-triacetylacetonate ,,,~ ~
and 0.42 cc (3.5 mM) of methyl-trichloroacetate in 50 cc of ~ -toluene, ' ,' Afte~ o~her 30 minutes it has been introduced slowly (in about 40~) a second solution of toluene (50 cc) contain- ' ' ing 0.66 cc of CCl3COOCH3.
In the course of the test it has been fed the ethy~
lene consumed little by little by keeping the total pressure at 18.5 kg/~m . The polymerization is finished after 130 ~' minutes from the beginning.
The polymer has been coagulated wi,th methanol and dried under vacuum at 50C: g 135 (28~500 g per gram of metal vanadium) have been weighed.
The infs~ared analysis revealed the presence of l.2% by weight of butadienic unities l~4 trans- and the 33 ~0 of pro-pylenic unities. The examination with X rays shows absence of crystallinity. The intrinsic viscosity / ~ 7 measured in toluene at 30C is of l.5 dl/g.
The polymer has been subjected to vulcanization for 60 minutes at 150C in admixture with the following compounds , ' (parts for 100 parts of polymer): ' - stearic acid - zinc oxide 5 - carbon black HAF So - mercaptobenzothiazole 0.75 - tetramethylthiuramemonosulfide 1.5 - sulphur 2 The v1llca,nized product, subjected to traction~ has given 1,he following results : tensile stress 250 kg/cm ultimate elongation 500 %, 200 % modulus 6l kg/cm ; 300 %
modu,lus l25 kg/cm , "tension set" l5 %.
~` ' : ' ,' ~ ' . ~ ' ' ' ,' ~ ' ln the autoclave described in Example 1 has been charged a solution prepared with :
- anhydrous toluene cc 700 ( 2 5)2 cc ~.5 - AlBr3 g 0.21 - butadiene g 18 Then propylene has been added (g 780) and, after having thermostatated at 50C~ethylene up to reach the total pressu-re of 19 kg/cm2.
In the course of 20 minutes has been introduced a solution of toluene (50 cc) wherein had been dissolved 33.5 mg of vanadium triacetylacetonate and 0.80 g (7 mM) of thionyl chloride. Starting from the 30t minute from the beginning~ has been introduced gradually further SOC12 (o.83 g) in toluene solution (50 cc) in a time of about 20 whereas the internal pressure of the autoclave was kept at 19 kg/cm2 (50G) by introduction of further ethylene.
The reaction product was discharged after one hour and coagulated with methanol : g 102 of gummy polymer were obtain-ed. This gummy polymer is formed by 1.4 % of butadiene unities 1.4 trans (Infrared examination) and by 36 % of propylenic unities: Mooney viscosity ML 100 ( 1 + 4) = 78; the crystalli-nity X rays was absent.
The polymer, vulcanized as described in Example 1~ has given the following results :
- tensile stress 235 kg/cm - ultimate elongation 480 %
- 300 % modulus 118 kg/cm 3 - "tension set" 14 %
In the autoclave described in the Example 1 has been 104~
effected a test at the temperature of the melting ice~ used for the thermostatation The ~ollowing reagents have been introduced :
- anhydrous toluene cc 720 ( 2 5)2 cc 1.5 - Al(C2H5)C12 g 0.15 - butadiene g 18 - CCl 3-COOH g 0.48 - propylene g 810 After having reached the equilibrium temperature~ which inside the autoclave is of 7C~ ethylene has been added in such a way that the pressure of 4 kg/cm2 has brought firmly to 6 kg/cm .
The polymerization has begun by addition of vanadium ~5 triacetylacetonate (mg 17.5) dissolved in toluene (cc 50)~
introduced in 20~ by means of a pump.
During the test~ which lasted 45 minutes~ has been -fed further ethylene by keeping the pressure at 6 kg/cm (at 7C).
G 52 were obtained of coagulated polymer containing 1.5 ~ of butadienic unities 1.4 trans- (weight of propylenic unities : 32 ~ (by weight) - [~ toluene 30C: 2.3. The `
polymer results amorphous at the rays X examination.
In the autoclave described in Example 1~ has been intro-duced a solution containing :
- toluene cc 720 ( 2 5)2 cc 2.2 - - Al(C2H5)C12 g 0.18 - butadiene g 18 Also 770 g of propylene have been introduced by means .
104~ 6 of a little cylinder. The autoclave has been thermostatated at 50C. The observed internal pressure was of 13.5 kg/cm and has been elevated at 18.5 kg/cm by addition of ethylene (whose partial pressure at 50C was therefore of 5 kg/cm ).
In the course of 10 minutes we introduced in the auto-clave a solution prepared with - toluene cc ~0 - V¦acac)3; acac = acetyl-acetonate mg 17.5 - CCl -COOCH cc 0.6 By keeping the autoclave under stirring~ starting from the 20th minute from the beginning of the polymerization has been introduced gradually (in about 20' a toluenic solution ~100 cc) containing dissolved 1.2 cc of methyl trichloro-acetate.
The autoclave has been opened after one hour of poly-merization. The polymer has been isolated in the usual way :
g 155~ equal to 60~000 g for gram of metal vanadium have been obtained. The product has resulted amorphous at the rays X examination and contains 1.8 % of butadienic unities and 33 % of propylenic unities (by weight)~ The / ~ 7 in toluene at 30 was of 1.5 dl/g~
10 .
104~i196 between 50 : 1 to 100 : 1. HoweYer, when the concentration of the vanadium ls lower than 5 0 10 5 mole/liter~ the ratio Al/V is preferably comprised between 100 : 1 and 500 : 1~ While the optimum amount nf the used vanadium com-pound varies between 1 . 10-4 and 1 10 5 mole/liter~ the amount of the compound of aluminium varies between 1 and 8. 10-3 mole/liter. --The molar ratio between the components c) and b) is critical. This ratio, in the case in which c) is an inorganic or organo-metallic plurihalogenated compound~ may be expressed with the global ratio between the gram atoms of halogen and the ones of aluminium contained in the reactants b~ and c).
This ratio X/Al must be comprised between l and 1.25 or~ preferably, between 1.05 and 1.15.
~5 In the case in which c) ii a protonic acid or the water~
the ratio between b) and c) i~ chosen in the range between 10 : 1 and 1 : 1 or~ preferably~ between 4 : 1 and 2 : 1.
The molar ratio between the components d) and b) of the catalyst may vary widely, also in relation to the parti-cular Gompound d) and to the modalities of reaction. It is generally lower than l and is preferably chosen in the range comprised between 1 : 4 and 1 : 1.
All the above-mentioned reactions are effected in pre-sence of a hydrocarbon which~ according to a characteristic of the present invention, is of aromatic type. Howe~er, also mixtures of aromatic hydrocarbons with aliphatic~ cyclo-aliphatic hydrocarbons or halogenated hydrocarbons and mixtu-res with the above-mentioned ones may be used.
Therefore~ even if solvents as the benzene and the toluene are preferred~ it is possible to use the chlorobenzene or mixtures benzene/cyclohexane; toluene/n-heptane, chloro-benzene/tetrachloroethylene and so on.
104~;~96 The polymerization temperature is chosen in a wide range. Generally operation is made at temperatures higher than the room temperature in order to avoid the use of expensive refrigerator-cycles. Therefore the more suit-able range i~ comprised between 20 and 800C~ even if it iB
not excluded the possibility of operation at lower or higher temperatures~ for example between 0 and 120C.
The polymerizations are effected under moderate pressures of ethylene (2 - 20 kg/cm2). The pressure of propylene varies from 1 to 20 atmospheres and over~ in function of the temperature and of the quantity of used solvent.
For the regulation of the molecular weights is added, if necessary~ hydrogen to the system even if a sufficient regulation is obtained~ while the temperature of polymeri-zation is let to vary.
EXAMPLE
In a steel autoclave with enameled inner walls~ having the capacity of 5 liters~ equipped with mechanical stirrer ~0 and with jacket for the thermoregulation with circulating liquid, equipped with valves~ one of which with dipping pipe, for the introduction of the reagents~ has been introduced a solution obtained by - anhydrous toluene cc 670 - butadiene g 12.5 ( 2 5)2 cc 1.5 - Al(C2H5)C12 g o.l65 By means of a little cylinder g 750 of propylene have been introduced. At this point the autoclave has been thermosta tated at 50C. -The internal pressure has rised to 13.5 kg/cm .
Ethylene has been added up to the total pressure of 18 5 kg/cm at 50C.
:., `: :
1046196 ~:
By means o~ a pump it has been introduced in 20l a solution containing 33.5 mg of vanadium-triacetylacetonate ,,,~ ~
and 0.42 cc (3.5 mM) of methyl-trichloroacetate in 50 cc of ~ -toluene, ' ,' Afte~ o~her 30 minutes it has been introduced slowly (in about 40~) a second solution of toluene (50 cc) contain- ' ' ing 0.66 cc of CCl3COOCH3.
In the course of the test it has been fed the ethy~
lene consumed little by little by keeping the total pressure at 18.5 kg/~m . The polymerization is finished after 130 ~' minutes from the beginning.
The polymer has been coagulated wi,th methanol and dried under vacuum at 50C: g 135 (28~500 g per gram of metal vanadium) have been weighed.
The infs~ared analysis revealed the presence of l.2% by weight of butadienic unities l~4 trans- and the 33 ~0 of pro-pylenic unities. The examination with X rays shows absence of crystallinity. The intrinsic viscosity / ~ 7 measured in toluene at 30C is of l.5 dl/g.
The polymer has been subjected to vulcanization for 60 minutes at 150C in admixture with the following compounds , ' (parts for 100 parts of polymer): ' - stearic acid - zinc oxide 5 - carbon black HAF So - mercaptobenzothiazole 0.75 - tetramethylthiuramemonosulfide 1.5 - sulphur 2 The v1llca,nized product, subjected to traction~ has given 1,he following results : tensile stress 250 kg/cm ultimate elongation 500 %, 200 % modulus 6l kg/cm ; 300 %
modu,lus l25 kg/cm , "tension set" l5 %.
~` ' : ' ,' ~ ' . ~ ' ' ' ,' ~ ' ln the autoclave described in Example 1 has been charged a solution prepared with :
- anhydrous toluene cc 700 ( 2 5)2 cc ~.5 - AlBr3 g 0.21 - butadiene g 18 Then propylene has been added (g 780) and, after having thermostatated at 50C~ethylene up to reach the total pressu-re of 19 kg/cm2.
In the course of 20 minutes has been introduced a solution of toluene (50 cc) wherein had been dissolved 33.5 mg of vanadium triacetylacetonate and 0.80 g (7 mM) of thionyl chloride. Starting from the 30t minute from the beginning~ has been introduced gradually further SOC12 (o.83 g) in toluene solution (50 cc) in a time of about 20 whereas the internal pressure of the autoclave was kept at 19 kg/cm2 (50G) by introduction of further ethylene.
The reaction product was discharged after one hour and coagulated with methanol : g 102 of gummy polymer were obtain-ed. This gummy polymer is formed by 1.4 % of butadiene unities 1.4 trans (Infrared examination) and by 36 % of propylenic unities: Mooney viscosity ML 100 ( 1 + 4) = 78; the crystalli-nity X rays was absent.
The polymer, vulcanized as described in Example 1~ has given the following results :
- tensile stress 235 kg/cm - ultimate elongation 480 %
- 300 % modulus 118 kg/cm 3 - "tension set" 14 %
In the autoclave described in the Example 1 has been 104~
effected a test at the temperature of the melting ice~ used for the thermostatation The ~ollowing reagents have been introduced :
- anhydrous toluene cc 720 ( 2 5)2 cc 1.5 - Al(C2H5)C12 g 0.15 - butadiene g 18 - CCl 3-COOH g 0.48 - propylene g 810 After having reached the equilibrium temperature~ which inside the autoclave is of 7C~ ethylene has been added in such a way that the pressure of 4 kg/cm2 has brought firmly to 6 kg/cm .
The polymerization has begun by addition of vanadium ~5 triacetylacetonate (mg 17.5) dissolved in toluene (cc 50)~
introduced in 20~ by means of a pump.
During the test~ which lasted 45 minutes~ has been -fed further ethylene by keeping the pressure at 6 kg/cm (at 7C).
G 52 were obtained of coagulated polymer containing 1.5 ~ of butadienic unities 1.4 trans- (weight of propylenic unities : 32 ~ (by weight) - [~ toluene 30C: 2.3. The `
polymer results amorphous at the rays X examination.
In the autoclave described in Example 1~ has been intro-duced a solution containing :
- toluene cc 720 ( 2 5)2 cc 2.2 - - Al(C2H5)C12 g 0.18 - butadiene g 18 Also 770 g of propylene have been introduced by means .
104~ 6 of a little cylinder. The autoclave has been thermostatated at 50C. The observed internal pressure was of 13.5 kg/cm and has been elevated at 18.5 kg/cm by addition of ethylene (whose partial pressure at 50C was therefore of 5 kg/cm ).
In the course of 10 minutes we introduced in the auto-clave a solution prepared with - toluene cc ~0 - V¦acac)3; acac = acetyl-acetonate mg 17.5 - CCl -COOCH cc 0.6 By keeping the autoclave under stirring~ starting from the 20th minute from the beginning of the polymerization has been introduced gradually (in about 20' a toluenic solution ~100 cc) containing dissolved 1.2 cc of methyl trichloro-acetate.
The autoclave has been opened after one hour of poly-merization. The polymer has been isolated in the usual way :
g 155~ equal to 60~000 g for gram of metal vanadium have been obtained. The product has resulted amorphous at the rays X examination and contains 1.8 % of butadienic unities and 33 % of propylenic unities (by weight)~ The / ~ 7 in toluene at 30 was of 1.5 dl/g~
10 .
Claims (11)
1. A process for the preparation of ethylene-propylene-butadiene terpolymers, characterized in that the polymerization reaction is carried out in an aromatic solvent and in presence of a catalytic system formed by:
a) one or more vanadium compounds soluble in the above-mentioned aromatic solvent and selected from the group consisting of tetra- and pentavalent vanadium and complex trivalent vanadium halides, vanadium alcoholates, vanadium and vanadyl chelates;
b) one or more aluminium compounds having the formula R1R2AlX wherein R1 and R2 are the same or different and represent alkyl, cycloalkyl, alkylaryl and aryl radicals containing from 1 to 18 carbon atoms or hydrogen and X is chlorine or bromine;
c) one or more compounds soluble or which may be solubilized in the reaction medium and selected from the group consisting of plurihalogenated compounds of elements of Group III or IV of the Periodical Table and acid compounds able to free protons;
d) one or more organic compounds containing in their molecule a CX3 group with X halogen, thionyl chlorine or hexa-chloro-cyclopentadiene.
a) one or more vanadium compounds soluble in the above-mentioned aromatic solvent and selected from the group consisting of tetra- and pentavalent vanadium and complex trivalent vanadium halides, vanadium alcoholates, vanadium and vanadyl chelates;
b) one or more aluminium compounds having the formula R1R2AlX wherein R1 and R2 are the same or different and represent alkyl, cycloalkyl, alkylaryl and aryl radicals containing from 1 to 18 carbon atoms or hydrogen and X is chlorine or bromine;
c) one or more compounds soluble or which may be solubilized in the reaction medium and selected from the group consisting of plurihalogenated compounds of elements of Group III or IV of the Periodical Table and acid compounds able to free protons;
d) one or more organic compounds containing in their molecule a CX3 group with X halogen, thionyl chlorine or hexa-chloro-cyclopentadiene.
2. Process according to claim 1, characterized in that the amount of component a) varies from to/0-4 to 10-5 mole/liter.
3. Process according to claim 1, characterized in that the amount of component b) varies from 1 to 8.10-3 mole/liter.
4. Process according to claim 1, characterized in that the molar ratio X/Al between the components b) and c) when c) is a plurihalogenated compound, varies from 1.00 to 1.25, the molar ratio X/Al representing the global ratio between the gram atoms of halogen and aluminium contained in components b) and c).
5. Process according to claim 1, characterized in that the molar ratio X/Al between components b) and c) when c) is a protonic acid, varies from 10 : 1 to 1 : 1,the molar ratio X/Al representing the global ratio between the gram atoms of halogen and aluminium contained in components b) and c).
6. Process according to claim 5, characterized in that said molar ratio varies from 4 : 1 to 2 : 1.
7. Process according to claim 1, characterized in that the molar ratio between components d) and b) is comprised between 1 : 4 and 1 : 1.
8. Process according to claim 1, characterized in that the aromatic solvent is in admixture with an aliphatic, cyclo-aliphatic or halogenated hydrocarbon.
9. Process according to claim 1, characterized in that the reaction is effected at a temperature comprised between 0 and 120°C.
10. Process according to claim 9, characterized in that said temperature is comprised between 20° and 80°C.
11. Process according to claim 1, characterized in that the reaction is effected at a pressure of propylene varying from 1 to 20 atmospheres.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IT25935/74A IT1017871B (en) | 1974-08-02 | 1974-08-02 | PROCEDURE FOR THE PREPARATION IN HIGH YIELD OF ETHYL NOR PROPYLENE BUTADIENE TERPOLYMERS |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1046196A true CA1046196A (en) | 1979-01-09 |
Family
ID=11218184
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA231,789A Expired CA1046196A (en) | 1974-08-02 | 1975-07-18 | Process for the preparation of ethylene-propylene-butadiene terpolymers with high yield |
Country Status (17)
| Country | Link |
|---|---|
| JP (1) | JPS5137985A (en) |
| AU (1) | AU8309875A (en) |
| BE (1) | BE832054A (en) |
| CA (1) | CA1046196A (en) |
| CH (1) | CH606149A5 (en) |
| DD (1) | DD119250A5 (en) |
| DE (1) | DE2534496C2 (en) |
| DK (1) | DK351675A (en) |
| FR (1) | FR2280657A1 (en) |
| GB (3) | GB1519477A (en) |
| IL (1) | IL47733A0 (en) |
| IT (1) | IT1017871B (en) |
| LU (1) | LU73124A1 (en) |
| NL (1) | NL7509171A (en) |
| NO (1) | NO752705L (en) |
| SE (1) | SE7508742L (en) |
| ZA (1) | ZA754583B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS52156195A (en) * | 1976-06-22 | 1977-12-26 | Mitsubishi Chem Ind Ltd | Production of solid catalyst and olefin polymers |
| JPS52156795A (en) * | 1976-06-23 | 1977-12-27 | Mitsubishi Chem Ind Ltd | Production of solid catalyst and olefin polymers |
| IT1197320B (en) * | 1986-10-02 | 1988-11-30 | Ausimont Spa | CATALYSTS FOR THE PREPARATION OF ELASTOMERIC, SATURATED AND UNSATURED OLEFINIC COPOLYMERS, AND VOPOLYMERS WITH THEM OBTAINED |
| US5219961A (en) * | 1987-07-30 | 1993-06-15 | Ausimont S.P.A. | Catalysts for preparing saturated elastomeric olefinic copolymers and terpolymers |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR1370358A (en) * | 1962-09-28 | 1964-08-21 | Hoechst Ag | Process for the preparation of copolymers of alpha-olefins and diolefins using mixed organometallic modified catalysts |
| FR1471472A (en) * | 1965-03-25 | 1967-03-03 | Huels Chemische Werke Ag | Process for preparing high molecular weight copolymers from 1-olefins alone or as a mixture with polyolefins |
| FR1477275A (en) * | 1965-05-08 | 1967-04-14 | Huels Chemische Werke Ag | Process for preparing high molecular weight amorphous copolymers, from 1-olefins alone or in mixture with poly-olefins |
| SE358644B (en) * | 1968-12-31 | 1973-08-06 | Montedison Spa | |
| US3682870A (en) * | 1969-01-15 | 1972-08-08 | Goodrich Co B F | Process for the preparation of linear,high molecular weight,sulphur vulcanizable copolymer of ethylene,propylene and 1,3-butadiene and catalyst systems used therein |
| US3756995A (en) * | 1970-04-10 | 1973-09-04 | Japan Synthetic Rubber Co Ltd | Svanadium compound trialkyl aluminum haloorganic acid catalytic proces |
-
1974
- 1974-08-02 IT IT25935/74A patent/IT1017871B/en active
-
1975
- 1975-07-16 ZA ZA00754583A patent/ZA754583B/en unknown
- 1975-07-16 AU AU83098/75A patent/AU8309875A/en not_active Expired
- 1975-07-17 GB GB3275/78A patent/GB1519477A/en not_active Expired
- 1975-07-17 GB GB3274/78A patent/GB1519476A/en not_active Expired
- 1975-07-17 GB GB30116/75A patent/GB1519472A/en not_active Expired
- 1975-07-18 IL IL47733A patent/IL47733A0/en unknown
- 1975-07-18 CA CA231,789A patent/CA1046196A/en not_active Expired
- 1975-07-29 FR FR7523698A patent/FR2280657A1/en active Granted
- 1975-07-31 CH CH1007675A patent/CH606149A5/xx not_active IP Right Cessation
- 1975-07-31 LU LU73124A patent/LU73124A1/xx unknown
- 1975-07-31 NL NL7509171A patent/NL7509171A/en not_active Application Discontinuation
- 1975-07-31 DD DD187602A patent/DD119250A5/xx unknown
- 1975-08-01 DE DE2534496A patent/DE2534496C2/en not_active Expired
- 1975-08-01 NO NO752705A patent/NO752705L/no unknown
- 1975-08-01 SE SE7508742A patent/SE7508742L/en unknown
- 1975-08-01 DK DK351675A patent/DK351675A/en unknown
- 1975-08-01 BE BE158881A patent/BE832054A/en unknown
- 1975-08-01 JP JP50093240A patent/JPS5137985A/ja active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| IT1017871B (en) | 1977-08-10 |
| GB1519477A (en) | 1978-07-26 |
| SE7508742L (en) | 1976-02-03 |
| DD119250A5 (en) | 1976-04-12 |
| LU73124A1 (en) | 1976-03-02 |
| FR2280657A1 (en) | 1976-02-27 |
| IL47733A0 (en) | 1975-10-15 |
| JPS5137985A (en) | 1976-03-30 |
| AU8309875A (en) | 1977-01-20 |
| CH606149A5 (en) | 1978-10-31 |
| DE2534496A1 (en) | 1976-02-12 |
| FR2280657B1 (en) | 1979-07-13 |
| DE2534496C2 (en) | 1982-01-21 |
| NO752705L (en) | 1976-02-03 |
| ZA754583B (en) | 1976-07-28 |
| BE832054A (en) | 1976-02-02 |
| GB1519472A (en) | 1978-07-26 |
| NL7509171A (en) | 1976-02-04 |
| GB1519476A (en) | 1978-07-26 |
| DK351675A (en) | 1976-02-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA1263104A (en) | Polymerization catalyst, production and use | |
| US4011383A (en) | Tetra(neophyl) zirconium and its use in process for the polymerization of olefins | |
| EP0516743B1 (en) | Transition metal catalyst composition for olefin polymerization | |
| US4001195A (en) | Copolymerization of olefins | |
| EP0997481B1 (en) | Improved process for preparation of butyl rubber using activated alkylaluminium halides | |
| US4017525A (en) | Tetra(neophyl) zirconium | |
| US5064796A (en) | Support adjuvant for improved vanadium polymerization catalyst | |
| US3707520A (en) | Polymers of cyclopentene obtained by polymerizing to a predetermined conversion and adding mono or diolefin thereto | |
| US4239874A (en) | Cyclopentene copolymerization process | |
| HUT59421A (en) | Process for producing ethylene/propylene/ethylidene-norbornene resin | |
| US3457244A (en) | Process for preparing a polymer | |
| US4458027A (en) | Olefin polymerization catalysts | |
| CA1046196A (en) | Process for the preparation of ethylene-propylene-butadiene terpolymers with high yield | |
| EP0550075A1 (en) | Use of methylene-bridged derivatives of cyclopentadienyl dicarbollide complexes of titanium, zirconium and hafnium as polymerization catalysts | |
| US4181790A (en) | Copolymerization of ethylene employing an organic chlorine compound-activated Ziegler-Natta catalyst | |
| US3933769A (en) | Sulfur vulcanizable interpolymers | |
| EP0209104B1 (en) | Intermetallic compound | |
| KR100330059B1 (en) | Elastomer Ethylene-Propylene Copolymer Production Catalyst | |
| US4361686A (en) | Preparation of copolymers of ethylene with at least one other 1-monoolefin and an optional unconjugated diene | |
| EP0435627B1 (en) | Supported olefin polymerization catalyst | |
| US3674754A (en) | Vulcanizable ethylene/propylene copolymers and process for their preparation | |
| US3480599A (en) | Unsaturated interpolymers of linear aliphatic heptadienes and/or heptatrienes and alpha-olefins | |
| US3991262A (en) | Sulfur vulcanizable interpolymers | |
| Dall'Asta et al. | Polymerization of cyclobutene rings. VII. Polymerization of bicyclo [4, 2, 0] octa‐7‐ene and bicyclo [3, 2, 0] hepta‐2, 6‐diene with Ziegler‐Natta catalysts and with group VIII metal halides | |
| EP0375199B1 (en) | Supported vanadium catalyst for production of polyolefins of controlled molecular weight distribution |