CN103804607A - Preparation method of ethylene-propylene-polybutadiene copolymer - Google Patents

Preparation method of ethylene-propylene-polybutadiene copolymer Download PDF

Info

Publication number
CN103804607A
CN103804607A CN201410048843.9A CN201410048843A CN103804607A CN 103804607 A CN103804607 A CN 103804607A CN 201410048843 A CN201410048843 A CN 201410048843A CN 103804607 A CN103804607 A CN 103804607A
Authority
CN
China
Prior art keywords
propylene
ethylene
polybutadiene copolymer
present
catalyzer
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.)
Pending
Application number
CN201410048843.9A
Other languages
Chinese (zh)
Inventor
代全权
姚伟
张学全
白晨曦
那丽华
张春雨
毕吉福
于琦周
张贺新
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.)
Changchun Institute of Applied Chemistry of CAS
Original Assignee
Changchun Institute of Applied Chemistry of CAS
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 Changchun Institute of Applied Chemistry of CAS filed Critical Changchun Institute of Applied Chemistry of CAS
Priority to CN201410048843.9A priority Critical patent/CN103804607A/en
Publication of CN103804607A publication Critical patent/CN103804607A/en
Pending legal-status Critical Current

Links

Images

Abstract

The invention provides a preparation method of an ethylene-propylene-polybutadiene copolymer. The preparation method comprises the following steps: a. under the action of a first catalytic system, carrying out first polymerization reaction on butadiene to obtain a polybutadiene reaction system; and b. under the action of a second catalytic system, carrying out second polymerization reaction on ethylene and propylene in the polybutadiene reaction system to obtain the ethylene-propylene-polybutadiene copolymer. In the preparation method provided by the invention, the first catalytic system does not have influence on the catalytic activity of the second catalytic system; as a catalyst adopted by the preparation method in the preparation of the polybutadiene and a catalyst adopted in the preparation of the ethylene-propylene-polybutadiene copolymer do not influence each other, impurities having influence on the catalytic activity of the catalysts for catalyzing the polymerization of the ethylene, the propylene and the polybutadiene are not introduced into the polybutadiene prepared by the preparation method, so that the catalytic activity of the catalyst adopted by the method provided by the invention in the preparation of the ethylene-propylene-polybutadiene copolymer is high.

Description

A kind of preparation method of ethylene-propylene-polybutadiene copolymer
Technical field
The present invention relates to ethylene-propylene rubber(EPR) technical field, relate in particular to a kind of preparation method of ethylene-propylene-polybutadiene copolymer.
Background technology
Ethylene-propylene rubber(EPR) has multiple good physicochemical property, is very important starting material in rubber item industry.According to the kind of polymerization single polymerization monomer in ethylene-propylene rubber(EPR), ethylene-propylene rubber(EPR) can be divided into ethylene propylene rubber and Ethylene Propylene Terpolymer graft copolymer, ethylene propylene rubber is synthetic by ethene and copolymerization of propylene, in its molecular chain, do not contain two keys, can not carry out sulfidizing to it, therefore the range of application of ethylene propylene rubber is less; Ethylene Propylene Terpolymer graft copolymer carries out monomer-grafted preparing on ethylene propylene rubber, by the different monomer of grafting on ethylene propylene rubber, can obtain the Ethylene Propylene Terpolymer graft copolymer of polarity, dyeability, oil-proofness, thermostability and better mechanical property, than ethylene propylene rubber, Ethylene Propylene Terpolymer graft copolymer has wide Application Areas.
The method of preparing Ethylene Propylene Terpolymer graft copolymer has free radical grafting modification method, chain Transfer Copolymerization method and macromonomer graft polymerization method (grafting through) conventionally, adopt free radical grafting modification method and chain Transfer Copolymerization method can produce homopolymer in the process of preparation Ethylene Propylene Terpolymer graft copolymer, thereby affect the performance of Ethylene Propylene Terpolymer graft copolymer; And adopt in the molecular chain of the Ethylene Propylene Terpolymer graft copolymer that free radical grafting modification method and chain Transfer Copolymerization method prepare side chain lengths irregular, therefore the grafting number of side chain on each molecular chain in uncontrollable Ethylene Propylene Terpolymer graft copolymer, thus the performance of Ethylene Propylene Terpolymer graft copolymer further affected.Adopt macromonomer graft polymerization method can effectively overcome above-mentioned free radical grafting modification method and the chain Transfer Copolymerization legal system shortcoming for Ethylene Propylene Terpolymer graft copolymer, therefore macromonomer graft polymerization method becomes the effective ways of preparation second the third graft copolymer.
Publication number is that the Chinese patent of CN101709105A discloses a kind of method of preparing ethylene-propylene-polybutadiene copolymer, detailed process is, in the reaction vessel of the 0.5L fully replacing with nitrogen, add hexane, the vanadium series catalyst of 0.10mmol, trichlorine triethyl two aluminium of 3.0mmol, the 0.15g1 of 300mL, the polyhutadiene that 2-structural content is 20wt% and the ethyl trichloroacetate of 0.60mmol; At 20 ℃, carry out the polyreaction of 15 minutes to the mixed gas that passes into ethene and propylene in described reactor, in described mixed gas, the mol ratio of ethene and propylene is 1:2; After described polyreaction finishes, in the polymeric reaction product obtaining, add the ethanol solution hydrochloride that 5mL hydrochloric acid mass concentration is 5%, then for polymerisate, after washing with alcohol, vacuum-drying, can obtain ethylene-propylene-polybutadiene copolymer by described.
Although aforesaid method can prepare the good ethylene-propylene-polybutadiene copolymer of processing characteristics, but this method that prior art provides catalytic activity of catalyzer in the time preparing ethylene-propylene-polybutadiene copolymer is lower, need to use a large amount of catalyzer, increase the production cost of ethylene-propylene-polybutadiene copolymer.
Summary of the invention
In view of this, the object of the present invention is to provide a kind of preparation method of ethylene-propylene-polybutadiene copolymer, method provided by the invention catalytic activity of catalyzer in the time preparing ethylene-propylene-polybutadiene copolymer is higher, without adopting a large amount of catalyzer, effectively reduce the production cost of ethylene-propylene-polybutadiene copolymer.
The preparation method who the invention provides a kind of ethylene-propylene-polybutadiene copolymer, comprises the following steps:
A, under the effect of the first catalyst system, divinyl is carried out to the first polyreaction, obtain polyhutadiene reaction system; Described the first catalyst system comprises, the first catalyzer, electron donor and the first aluminum contained compound, described the first catalyzer comprises one or more in Titanium series catalyst, nickel catalyst, chromium-based catalysts, molybdenum series catalyst, Fe-series catalyst and cobalt series catalyst;
Described electron donor comprises one or more in itrogenous organic substance, oxygen-bearing organic matter, sulfurous organic compound, phosphorus-containing matter, alkalimetal hydride, halogen simple substance and fluorine boron compound;
Described the first aluminum contained compound comprises one or more in the derivative of aluminum alkyls and aluminum hydride;
B, under the effect of the second catalyst system, ethene and propylene are carried out to the second polyreaction in described polyhutadiene reaction system, obtain ethylene-propylene-polybutadiene copolymer; Described the second catalyst system comprises the second catalyzer, the second aluminum contained compound and activator, and described the second catalyzer comprises vanadium series catalyst;
Described the second aluminum contained compound comprises one or more in the derivative of aluminum alkyls and aluminum hydride;
Described activator comprises containing oxygen and contains one or more in nitrogen compound, Organohalogen compounds and sulfonyl chloride compound.
Preferably, in described step a, the mol ratio of the first catalyzer, electron donor, the first aluminum contained compound and divinyl is 1:(1～15): (10～100): (20～1200).
Preferably, in described step a, the reaction pressure of the first polyreaction is 1MPa～3MPa.
Preferably, in described step a, the temperature of reaction of the first polyreaction is 0 ℃～70 ℃.
Preferably, in described step a, the reaction times of the first polyreaction is 20min～60min.
Preferably, in described step a, in the polyhutadiene of polyhutadiene reaction system 1, the content of 2-structure is 20wt%～90wt%.
Preferably, in described step a, in the divinyl of polyhutadiene reaction system and described step b, the mol ratio of the second catalyzer is (13～400): l;
In described step b, the mol ratio of activator and the second catalyzer is (5～20): 1;
In described step b, the mol ratio of the second aluminum contained compound and the second catalyzer is (40～66): 1.
Preferably, in described step b, the reaction pressure of the second polyreaction is 2MPa～6MPa.
Preferably, in described step b, the temperature of reaction of the second polyreaction is 0 ℃～70 ℃.
Preferably, in described step b, the reaction times of the second polyreaction is 20min～70min.
The preparation method who the invention provides a kind of ethylene-propylene-polybutadiene copolymer, comprises the following steps: a, under the effect of the first catalyst system, divinyl is carried out to the first polyreaction, and obtain polyhutadiene reaction system; Described the first catalyst system comprises, the first catalyzer, electron donor and the first aluminum contained compound, described the first catalyzer comprises one or more in Titanium series catalyst, nickel catalyst, chromium-based catalysts, molybdenum series catalyst, Fe-series catalyst and cobalt series catalyst; Described electron donor comprises one or more in itrogenous organic substance, oxygen-bearing organic matter, sulfurous organic compound, phosphorus-containing matter, alkalimetal hydride, halogen simple substance and fluorine boron compound; Described the first aluminum contained compound comprises one or more in the derivative of aluminum alkyls and aluminum hydride; B, under the effect of the second catalyst system, ethene and propylene are carried out to the second polyreaction in described polyhutadiene reaction system, obtain ethylene-propylene-polybutadiene copolymer; Described the second catalyst system comprises the second catalyzer, the second aluminum contained compound and activator, and described the second catalyzer comprises vanadium series catalyst, and described the second aluminum contained compound comprises one or more in the derivative of aluminum alkyls and aluminum hydride; Described activator comprises containing oxygen and contains one or more in nitrogen compound, Organohalogen compounds and sulfonyl chloride compound.In the present invention, comprise the first catalyzer, the first catalyst system of electron donor and the first aluminum contained compound is to comprising the second catalyzer, the catalytic activity of the second catalyst system of the second aluminum contained compound and activator does not affect, between the catalyzer adopting while preparing polyhutadiene due to the present invention and the catalyzer that adopts while preparing ethylene-propylene-polybutadiene copolymer, do not influence each other, make the present invention not introduce and affect catalyzed ethylene in the process of preparing polyhutadiene, the impurity of the catalyst activity of propylene and polyhutadiene polymerization, the impurity of catalyst activity while not preparing ethylene-propylene-polybutadiene copolymer containing impact in the polyhutadiene of preparing due to the present invention, therefore method provided by the invention catalytic activity of catalyzer in the time preparing ethylene-propylene-polybutadiene copolymer is higher, the consumption of catalyzer is less, method provided by the invention has reduced the production cost of ethylene-propylene-polybutadiene copolymer effectively.
In addition, both contained the two keys that can be used for sulfuration in ethylene-propylene-polybutadiene copolymer provided by the invention, and had again long chain branched, therefore ethylene-propylene-polybutadiene copolymer provided by the invention has good curability and mechanical property.And do not influence each other between the catalyzer that adopts while preparing polyhutadiene of the present invention and the catalyzer that adopts while preparing ethylene-propylene-polybutadiene copolymer, make the present invention in polyhutadiene reaction system, prepare ethylene-propylene-polybutadiene copolymer by direct in-situ, compared with prior art, the present invention has avoided preparing in the process of polyhutadiene polyhutadiene solution has been separated, the operation of purifying, therefore preparation method's technique of ethylene-propylene-polybutadiene copolymer provided by the invention is simple, be convenient to scale operation ethylene-propylene-polybutadiene copolymer.
Experimental result shows, the catalytic activity of method provided by the invention catalyzer in the time preparing ethylene-propylene-polybutadiene copolymer is 138.7g/mmol～180.8g/mmol, and the catalytic activity of catalyzer is higher.The glass transition temp of ethylene-propylene-polybutadiene copolymer that the present invention prepares is-59.1 ℃～-46.1 ℃, and number-average molecular weight is 2.2 × 10 -4～5.0 × 10 -4, propylene content is 22.5wt%～35.7wt%, double bond content is 1.0%～3.0%, has good curability; The tensile strength of ethylene-propylene-polybutadiene copolymer that the present invention prepares is 15.50MPa～18.51MPa, 300% stress at definite elongation is 8.90MPa～13.23MPa, elongation at break is that 284.27%～415.93%, Shao Er hardness is 63 degree～78 degree, has good mechanical property.
Accompanying drawing explanation
Fig. 1 is the gel permeation chromatography figure of ethylene-propylene-polybutadiene copolymer of obtaining of the embodiment of the present invention 1;
Fig. 2 is the infrared spectrum of ethylene-propylene-polybutadiene copolymer of obtaining of the embodiment of the present invention 1;
Fig. 3 is the hydrogen nuclear magnetic resonance spectrogram of ethylene-propylene-polybutadiene copolymer of obtaining of the embodiment of the present invention 1;
Fig. 4 is the relation curve between number of branches and the molecular weight of ethylene-propylene-polybutadiene copolymer of obtaining of the embodiment of the present invention.
Embodiment
The preparation method who the invention provides a kind of ethylene-propylene-polybutadiene copolymer, comprises the following steps:
A, under the effect of the first catalyst system, divinyl is carried out to the first polyreaction, obtain polyhutadiene reaction system; Described the first catalyst system comprises, the first catalyzer, electron donor and the first aluminum contained compound, described the first catalyzer comprises one or more in Titanium series catalyst, nickel catalyst, chromium-based catalysts, molybdenum series catalyst, Fe-series catalyst and cobalt series catalyst;
Described electron donor comprises one or more in itrogenous organic substance, oxygen-bearing organic matter, sulfurous organic compound, phosphorus-containing matter, alkalimetal hydride, halogen simple substance and fluorine boron compound;
Described the first aluminum contained compound comprises one or more in the derivative of aluminum alkyls and aluminum hydride;
B, under the effect of the second catalyst system, ethene and propylene are carried out to the second polyreaction in described polyhutadiene reaction system, obtain ethylene-propylene-polybutadiene copolymer; Described the second catalyst system comprises the second catalyzer, the second aluminum contained compound and activator, and described the second catalyzer comprises vanadium series catalyst;
Described the second aluminum contained compound comprises one or more in the derivative of aluminum alkyls and aluminum hydride;
Described activator comprises containing oxygen and contains one or more in nitrogen compound, Organohalogen compounds and sulfonyl chloride compound.
In the present invention, comprise the first catalyzer, the first catalyst system of electron donor and the first aluminum contained compound is to comprising the second catalyzer, the catalytic activity of the second catalyst system of the second aluminum contained compound and activator does not affect, between the catalyzer adopting while preparing polyhutadiene due to the present invention and the catalyzer that adopts while preparing ethylene-propylene-polybutadiene copolymer, do not influence each other, make the present invention not introduce and affect catalyzed ethylene in the process of preparing polyhutadiene, the impurity of the catalyst activity of propylene and polyhutadiene polymerization, the impurity of catalyst activity while not preparing ethylene-propylene-polybutadiene copolymer containing impact in the polyhutadiene of preparing due to the present invention, therefore method provided by the invention catalytic activity of catalyzer in the time preparing ethylene-propylene-polybutadiene copolymer is higher, the consumption of catalyzer is less, method provided by the invention has reduced the production cost of ethylene-propylene-polybutadiene copolymer effectively.
In addition, both contained the two keys that can be used for sulfuration in ethylene-propylene-polybutadiene copolymer provided by the invention, and had again long chain branched, therefore ethylene-propylene-polybutadiene copolymer provided by the invention has good curability and mechanical property.And do not influence each other between the catalyzer that adopts while preparing polyhutadiene of the present invention and the catalyzer that adopts while preparing ethylene-propylene-polybutadiene copolymer, make the present invention in polyhutadiene reaction system, prepare ethylene-propylene-polybutadiene copolymer by direct in-situ, compared with prior art, the present invention has avoided preparing in the process of polyhutadiene polyhutadiene solution has been separated, the operation of purifying, therefore preparation method's technique of ethylene-propylene-polybutadiene copolymer provided by the invention is simple, be convenient to scale operation ethylene-propylene-polybutadiene copolymer.
The present invention is under the effect of the first catalyst system, divinyl is carried out to the first polyreaction, obtain polyhutadiene reaction system, described the first catalyst system comprises, the first catalyzer, electron donor and the first aluminum contained compound, described the first catalyzer comprises one or more in Titanium series catalyst, nickel catalyst, chromium-based catalysts, molybdenum series catalyst, Fe-series catalyst and cobalt series catalyst; Described electron donor comprises one or more in itrogenous organic substance, oxygen-bearing organic matter, sulfurous organic compound, phosphorus-containing matter, alkalimetal hydride, halogen simple substance and fluorine boron compound; Described the first aluminum contained compound comprises one or more in the derivative of aluminum alkyls and aluminum hydride; Preferably the first catalyst system is joined in divinyl and carries out the first polyreaction, obtain polyhutadiene reaction system.
In the present invention, the reaction times of described the first polyreaction is preferably 20min～60min, and more preferably 25min～40min, most preferably is 30min.In the present invention, the reaction pressure of described the first polyreaction is preferably 1MPa～3MPa, and more preferably 1.5MPa～2.5MPa, most preferably is 2MPa.In the present invention, the temperature of reaction of described the first polyreaction is preferably 0 ℃～70 ℃, and more preferably 5 ℃～60 ℃, most preferably be 10 ℃～50 ℃, be the most preferably 20 ℃～40 ℃.The present invention preferably carries out the first polyreaction under the protection of nitrogen, more preferably in the process reactor of nitrogen replacement, carries out the first polyreaction.
In the present invention, described the first catalyst system comprises the first catalyzer, electron donor and the first aluminum contained compound, and described the first catalyzer comprises one or more in Titanium series catalyst, nickel catalyst, chromium-based catalysts, molybdenum series catalyst, Fe-series catalyst and cobalt series catalyst; Described electron donor comprises one or more in itrogenous organic substance, oxygen-bearing organic matter, sulfurous organic compound, phosphorus-containing matter, alkalimetal hydride, halogen simple substance and fluorine boron compound; Described the first aluminum contained compound comprises one or more in the derivative of aluminum alkyls and aluminum hydride.
In the present invention, described the first catalyst system comprises the first catalyzer, and described the first catalyzer can be prepared the polyhutadiene with 1,2-structure.In the present invention, described the first catalyzer comprises one or more in Titanium series catalyst, nickel catalyst, chromium-based catalysts, molybdenum series catalyst, Fe-series catalyst and cobalt series catalyst, preferably includes the one in Titanium series catalyst, nickel catalyst, chromium-based catalysts, molybdenum series catalyst, Fe-series catalyst and cobalt series catalyst.In the present invention, described Titanium series catalyst preferably includes Ti (OR) 4, TiCl 4, Ti (acac) 3, TiC1 3with one or more in two luxuriant titaniums, more preferably comprise Ti (OR) 4, TiCl 4, Ti (acac) 3, TiC1 3with the one in two luxuriant titaniums, Ti (OR) 4in R be preferably alkyl, aryl or phenyl, more preferably alkyl, most preferably is methyl.
In the present invention, described nickel catalyst preferably includes isocaprylic acid nickel, nickel naphthenate, Ni (acac) 2, one or more in nickelous oxalate and nickel sulfamic acid, more preferably comprise isocaprylic acid nickel, nickel naphthenate, Ni (acac) 2, one in nickelous oxalate and nickel sulfamic acid.
In the present invention, described chromium-based catalysts preferably includes Cr (Na ph) 3, CrO 3, Cr (acac) 3, Cr (CNC 6h 5) 6, CrCl 2, Cr (EHA) 3and CrCl 2(dmpe) 2in one or more, more preferably comprise Cr (Naph) 3, CrO 3, Cr (acac) 3, Cr (CNC 6h 5) 6, CrCl 2, Cr (EHA) 3and CrCl 2(dmpe) 2in one.
In the present invention, described molybdenum series catalyst preferably includes MoO 3, MoCl 5, MoO 2(OR1) 2, MoCl 3(R2COO) 2, MoCl 3(OR3) 2, one or more in isocaprylic acid molybdenum, molybdenum naphthenate and Methionin complexing molybdenum, more preferably comprise MoO 3, MoCl 5, MoO 2(OR1) 2, MoCl 3(R2COO) 2, MoCl 3(OR3) 2, one in isocaprylic acid molybdenum, molybdenum naphthenate and Methionin complexing molybdenum, MoO 2(OR1) 2in R1 be preferably alkyl, aryl or phenyl, more preferably alkyl, most preferably is methyl; MoCl 3(R2COO) 2in R2 be preferably alkyl, aryl or phenyl, more preferably alkyl, most preferably is methyl; MoCl 3(OR3) 2in R3 be preferably alkyl, aryl or phenyl, more preferably alkyl, most preferably is methyl.
In the present invention, described Fe-series catalyst preferably includes FeCl 3, iron naphthenate, Fe (acac) 3, Fe (CF 3sO 3) 3, ironic citrate, Methionin Complexing Iron, Fe (acac) 2, FeCl 2, isocaprylic acid iron and Fe (phen) 2in one or more; More preferably comprise FeCl 3, iron naphthenate, Fe (acac) 3, Fe (CF 3sO 3) 3, ironic citrate, Methionin Complexing Iron, Fe (acac) 2, FeCl 2, isocaprylic acid iron and Fe (phen) 2in one.
In the present invention, described cobalt series catalyst preferably includes cobalt iso-octoate, cobalt naphthenate, Co (acac) 2, Co (CF 3sO 3) 3, CoCl 2, Co (CF 3sO 3) 2, Co (acac) 3, Methionin complex cobalt, Co (CH 3cOO) 2and C 63h 90coN 14o 14one or more in P; More preferably comprise cobalt iso-octoate, cobalt naphthenate, Co (acac) 2, Co (CF 3sO 3) 3, CoCl 2, Co (CF 3sO 3) 2, Co (acac) 3, Methionin complex cobalt, Co (CH 3cOO) 2and C 63h 90coN 14o 14one in P.
The present invention does not have special restriction to the source of described the first catalyzer, adopts the catalyzer of mentioned kind well known to those skilled in the art, as bought and be obtained by market.
In the present invention, described the first catalyst system comprises electron donor, and described electron donor comprises one or more in itrogenous organic substance, oxygen-bearing organic matter, sulfurous organic compound, phosphorus-containing matter, alkalimetal hydride, halogen simple substance and fluorine boron compound; Preferably include the one in itrogenous organic substance, oxygen-bearing organic matter, sulfurous organic compound, phosphorus-containing matter, alkalimetal hydride, halogen simple substance and fluorine boron compound.In the present invention, described itrogenous organic substance preferably includes ethamine, 1, and one or more in 10-phenanthroline, benzoglyoxaline and 1,10-phen more preferably comprise ethamine, 1, the one in 10-phenanthroline, benzoglyoxaline and 1,10-phen.
In the present invention, described oxygen-bearing organic matter preferably includes isooctyl alcohol, tetrahydrofuran (THF), methyl benzoate, n-butyl phthalate, 2,3-di-isopropyl succsinic acid diethyl ester, 9, one or more in 3-methoxymethyl diphenylene-oxide, dibenzoyl peroxide, ether, positive propyl ether, boron trifluoride diethyl etherate and boron trifluoride methyl ether; More preferably comprise isooctyl alcohol, tetrahydrofuran (THF), methyl benzoate, n-butyl phthalate, 2,3-di-isopropyl succsinic acid diethyl ester, 9, the one in 3-methoxymethyl diphenylene-oxide, dibenzoyl peroxide, ether, positive propyl ether, boron trifluoride diethyl etherate and boron trifluoride methyl ether.
In the present invention, described sulfurous organic compound preferably includes one or both in dimethyl sulfoxide (DMSO) and butyl thiocyanide, more preferably comprises the one in methyl sulfoxide and butyl thiocyanide.
In the present invention, described phosphorus-containing matter preferably includes one or more in triphenylphosphate, tritolyl phosphate, diethyl phosphite, dimethylphosphite, phosphorous acid di-isooctyl, dibutyl phosphite, phosphorous acid dipropyl and diphenyl phosphite, more preferably comprises the one in triphenylphosphate, tritolyl phosphate, diethyl phosphite, dimethylphosphite, phosphorous acid di-isooctyl, dibutyl phosphite, phosphorous acid dipropyl and diphenyl phosphite.
In the present invention, described alkalimetal hydride preferably includes CaH 2, one or more in NaH and KH, more preferably comprise CaH 2, one in NaH and KH, most preferably be CaH 2.
In the present invention, described halogen simple substance preferably includes I 2, Cl 2and Br 2in one or more, more preferably comprise I 2, Cl 2and Br 2in one, most preferably be I 2.
In the present invention, described fluorine boron compound preferably includes one or more in boron trifluoride, boron trifluoride diethyl etherate and boron trifluoride methyl ether, more preferably comprises the one in boron trifluoride, boron trifluoride diethyl etherate and boron trifluoride methyl ether.
The present invention does not have special restriction to the described source of giving electronics, adopts the electron donor of mentioned kind well known to those skilled in the art, as bought and be obtained by market.
In the present invention, described the first catalyst system comprises the first aluminum contained compound, described the first aluminum contained compound comprises one or more in the derivative of aluminum alkyls and aluminum hydride, more preferably comprises the one in the derivative of aluminum alkyls and aluminum hydride, most preferably comprises aluminum alkyls.In the present invention, described aluminum alkyls preferably includes one or more in the compound of the chemical formula shown in (I)～formula (IV) that has formula, more preferably comprises the one in the compound with chemical formula shown in formula (I)～formula (IV):
R4 3Al（I）；R5 2AlX1（II）；R6 3Al 2X2 3（III）；R7AlX3 2（IV）；
R4 in formula (I) is preferably alkyl, and the alkyl that more preferably carbonatoms is 1～5 most preferably is methyl, ethyl or butyl.
R5 in formula (II) is preferably alkyl, and the alkyl that more preferably carbonatoms is 1～5 most preferably is methyl or ethyl, is the most preferably ethyl; X1 in formula (II) is preferably halogen, and more preferably chlorine, iodine or bromine, most preferably be chlorine.
R6 in formula (III) is preferably alkyl, and the alkyl that more preferably carbonatoms is 1～5 most preferably is methyl or ethyl, is the most preferably ethyl; X2 in formula (III) is preferably halogen, and more preferably chlorine, iodine or bromine, most preferably be chlorine.
R7 in formula (IV) is preferably alkyl, and the alkyl that more preferably carbonatoms is 1～5 most preferably is methyl, ethyl or butyl, is the most preferably ethyl or butyl; X3 in formula (IV) is preferably halogen, and more preferably chlorine, iodine or bromine, most preferably be chlorine.
In the present invention, the derivative of described aluminum hydride preferably includes one or more in the compound with chemical formula shown in formula V and formula (VI), more preferably comprises the one in the compound with chemical formula shown in formula V and formula (VI):
HAlX4 2·B（V）；HX5AlNR8 2（VI）；
X4 in formula V is preferably halogen, and more preferably chlorine, iodine or bromine, most preferably be chlorine; B in formula V is for being preferably Lewis base.
R8 in formula (VI) is preferably alkyl, and the alkyl that more preferably carbonatoms is 1～5 most preferably is methyl, ethyl or butyl, is the most preferably methyl or ethyl, and the X5 in formula (VI) is preferably halogen, and more preferably chlorine, iodine or bromine, most preferably be chlorine.
The present invention does not have special restriction to the source of described the first aluminum contained compound, adopts the aluminum contained compound of mentioned kind well known to those skilled in the art, as bought and be obtained by market.
In the present invention, described divinyl is preferably butadiene solution, and the volumetric molar concentration of described butadiene solution is preferably 0.5mol/L～3mol/L, and more preferably 1mol/L～2.5mol/L, most preferably is 1.5mol/L～2mol/L.The present invention does not have special restriction to the solvent in described butadiene solution, adopts the solvent of solubilized divinyl well known to those skilled in the art; In the present invention, the solvent in described butadiene solution is preferably hexane.
In the present invention, the mol ratio of described the first catalyzer, electron donor, the first aluminum contained compound and divinyl is preferably 1:(1～15): (10～100): (20～1200), more preferably 1:(2～10): (15～80): (40～1000), most preferably be 1:(3～8): (20～60): (100～800), are the most preferably 1:(4～6): (30～50): (200～600).
The present invention, under the effect of above-mentioned the first catalyst system, carries out the first polyreaction by divinyl, obtains polyhutadiene reaction system.In the present invention, in the polyhutadiene of described polyhutadiene reaction system 1, the content of 2-structure is preferably 20wt%～90wt%, and more preferably 30wt%～80wt%, most preferably is 40wt%～70wt%, is the most preferably 50wt%～60wt%.
Obtain after polyhutadiene reaction system, the present invention is under the effect of the second catalyst system, ethene and propylene are carried out to the second polyreaction in described polyhutadiene reaction system, obtain ethylene-propylene-polybutadiene copolymer, described the second catalyst system comprises the second catalyzer, the second aluminum contained compound and activator, and described the second catalyzer comprises vanadium series catalyst; Described the second aluminum contained compound comprises one or more in the derivative of aluminum alkyls and aluminum hydride; Described activator comprises containing oxygen and contains one or more in nitrogen compound, Organohalogen compounds and sulfonyl chloride compound.In the present invention, above-mentioned the first catalyst system does not affect the catalytic activity of described the second catalyst system, between the catalyzer adopting while preparing polyhutadiene due to the present invention and the catalyzer that adopts while preparing ethylene-propylene-polybutadiene copolymer, do not influence each other, make the present invention not introduce and affect catalyzed ethylene in the process of preparing polyhutadiene, the impurity of the catalyst activity of propylene and polyhutadiene polymerization, the impurity of catalyst activity while not preparing ethylene-propylene-polybutadiene copolymer containing impact in the polyhutadiene of preparing due to the present invention, therefore method provided by the invention catalytic activity of catalyzer in the time preparing ethylene-propylene-polybutadiene copolymer is higher, the consumption of catalyzer is less, method provided by the invention has reduced the production cost of ethylene-propylene-polybutadiene copolymer effectively.
In addition, between the catalyzer adopting while preparing polyhutadiene due to the present invention and the catalyzer that adopts while preparing ethylene-propylene-polybutadiene copolymer, do not influence each other, make the present invention in above-mentioned polyhutadiene reaction system, prepare ethylene-propylene-polybutadiene copolymer by direct in-situ, compared with prior art, the present invention has avoided preparing in the process of polyhutadiene polyhutadiene solution has been separated, the operation of purifying, therefore preparation method's technique of ethylene-propylene-polybutadiene copolymer provided by the invention is simple, be convenient to scale operation ethylene-propylene-polybutadiene copolymer.
The present invention is under the effect of the second catalyst system, ethene and propylene are carried out to the second polyreaction in described polyhutadiene reaction system, obtain ethylene-propylene-polybutadiene copolymer, described the second catalyst system comprises the second catalyzer, the second aluminum contained compound and activator, and described the second catalyzer comprises vanadium series catalyst; Described the second aluminum contained compound comprises one or more in the derivative of aluminum alkyls and aluminum hydride; Described activator comprises containing oxygen and contains one or more in nitrogen compound, Organohalogen compounds and sulfonyl chloride compound; Preferably the second catalyst system, ethene and propylene are joined successively in described polyhutadiene reaction system and carry out the second polyreaction, obtain ethylene-propylene-polybutadiene copolymer.
In the present invention, the temperature of reaction of described the second polyreaction is preferably 0 ℃～70 ℃, and more preferably 10 ℃～60 ℃, most preferably be 20 ℃～50 ℃, be the most preferably 30 ℃～40 ℃.In the present invention, the reaction pressure of described the second polyreaction is preferably 2MPa～6MPa, and more preferably 3MPa～5MPa, most preferably is 4MPa.In the present invention, the reaction times of described the second polyreaction is preferably 20min～70min, and more preferably 30min～60min, most preferably is 40min～50min, is the most preferably 45min.
Fully carry out in order to make above-mentioned the second polyreaction, the present invention is preferably by described polyhutadiene reaction system and solvent, then under the effect of the second catalyst system, ethene and propylene are carried out to the second polyreaction in described polyhutadiene reaction system, obtain ethylene-propylene-polybutadiene copolymer.The present invention does not have special restriction to described solvent, adopts the solvent adopting while preparing ethylene-propylene-polybutadiene copolymer well known to those skilled in the art.In the present invention, described solvent can with polyhutadiene solution described in technique scheme in solvent phase with, also can be different.In the present invention, described solvent is preferably hexane.The present invention does not have special restriction to the consumption of described solvent, and the consumption of described solvent can make above-mentioned the second catalyst system dissolve.
In the present invention, described the second catalyst system comprises the second catalyzer, the second aluminum contained compound and activator, and described the second catalyzer comprises vanadium series catalyst, and described the second aluminum contained compound comprises one or more in the derivative of aluminum alkyls and aluminum hydride; Described activator comprises containing oxygen and contains one or more in nitrogen compound, Organohalogen compounds and sulfonyl chloride compound.
In the present invention, described the second catalyst system comprises the second catalyzer, and described the second catalyzer comprises vanadium series catalyst.In the present invention, described vanadium series catalyst preferably includes one or more in the covalent compound of vanadium and the coordination compound of vanadium; More preferably comprise the one in the covalent compound of vanadium and the coordination compound of vanadium, most preferably comprise the covalent compound of vanadium.
In the present invention, the covalent compound of described vanadium preferably includes V (acac) 3, VO (OR9) 3, VO (acac) 3, VO (OR10) 2c1, VO (OR11) Cl 2, VC1 4and VOC1 3in one or more, more preferably comprise V (acac) 3, VO (OR9) 3, VO (acac) 3, VO (OR10) 2c1, VO (OR11) Cl 2, VC1 4and VOC1 3in one, VO (OR9) 3in R9 be preferably alkyl, aryl or phenyl, more preferably alkyl, most preferably is methyl; VO (OR10) 2r10 in C1 is preferably alkyl, aryl or phenyl, and more preferably alkyl, most preferably is methyl; VO (OR11) Cl 2in R11 be preferably alkyl, aryl or phenyl, more preferably alkyl, most preferably is methyl.
In the present invention, the part in the coordination compound of described vanadium preferably includes fatty alcohol, amine, phosphoric acid ester, beta-diketon, 8-hydroxy-quinoline or phenol; More preferably comprise fatty alcohol or phosphoric acid ester, most preferably comprise phosphoric acid ester.In the present invention, described fatty alcohol preferably includes the one in Pentyl alcohol, n-Octanol and isooctyl alcohol, more preferably comprises the one in n-Octanol and isooctyl alcohol, most preferably comprises isooctyl alcohol; In the present invention, described amine preferably includes the one in Diisopropylamine, methacetin and beta-diketo mono imine, more preferably comprises the one in methacetin and beta-diketo mono imine, most preferably comprises beta-diketo mono imine; In the present invention, described phosphoric acid ester preferably includes the one in diisooctyl phosphorous acid ester, tributyl phosphate and diethyl phosphite, more preferably comprises the one in tributyl phosphate and diethyl phosphite, most preferably comprises diethyl phosphite.The source of the coordination compound of the present invention to described vanadium does not have special restriction, adopts the coordination compound of the vanadium of mentioned kind well known to those skilled in the art, as bought and be obtained by market.
The present invention does not have special restriction to the source of described vanadium class catalyzer, adopt the vanadium class catalyzer of mentioned kind well known to those skilled in the art, in the present invention, described vanadium class catalyzer both can be bought and be obtained by market, also can adopt the preparation method of vanadium compounds well known to those skilled in the art to prepare.
In the present invention, described the second catalyst system comprises the second aluminum contained compound, and described the second aluminum contained compound comprises one or more in the derivative of aluminum alkyls and aluminum hydride; More preferably comprise the one in the derivative of aluminum alkyls and aluminum hydride; Most preferably comprise aluminum alkyls.In the present invention, the Kind and source of the derivative of described aluminum alkyls and aluminum hydride is consistent with the Kind and source of the derivative of the aluminum alkyls described in technique scheme and aluminum hydride, does not repeat them here.In the present invention, described the second aluminum contained compound can be identical with the first aluminum contained compound described in technique scheme, also can be different.
In the present invention, described the second catalyst system comprises activator, described activator comprises containing oxygen and contains one or more in nitrogen compound, Organohalogen compounds and sulfonyl chloride compound, more preferably comprise containing oxygen and containing the one in nitrogen compound, Organohalogen compounds and sulfonyl chloride compound, most preferably comprise Organohalogen compounds.In the present invention, describedly preferably include 1 containing oxygen and containing nitrogen compound, one or more in 10-o-phenanthroline, beta-diketo mono imine and Methyl disulfide carbonyl oxalamide, more preferably comprise 1, one in 10-o-phenanthroline, beta-diketo mono imine and Methyl disulfide carbonyl oxalamide, most preferably comprises Methyl disulfide carbonyl oxalamide.In the present invention, described Organohalogen compounds preferably include CH 3cl, methyl trichloroacetate, ethyl trichloroacetate, CH 2cl 2and CHCl 3in one or more; More preferably comprise CH 3cl, methyl trichloroacetate, ethyl trichloroacetate, CH 2cl 2and CHCl 3in one.In the present invention, described sulfonyl chloride compound preferably includes one or more in benzene sulfonyl chloride, p-acetaminobenzenesulfonyl chloride and dichloramine-T, more preferably comprise the one in benzene sulfonyl chloride, p-acetaminobenzenesulfonyl chloride and dichloramine-T, most preferably comprise the one in p-acetaminobenzenesulfonyl chloride and dichloramine-T, the most preferably include dichloramine-T.
The present invention does not have special restriction to the source of described activator, adopts the activator of mentioned kind well known to those skilled in the art, as bought and be obtained by market.
In the present invention, the mol ratio of divinyl is preferably l:(13～400 described in described the second catalyzer and technique scheme), more preferably l:(40～140), elect l:(45～60 most as).In the present invention, the mol ratio of described the second catalyzer and activator is preferably 1:(5～20), more preferably 1:(8～15), most preferably be 1:(10～12).In the present invention, the mol ratio of described the second catalyzer and the second aluminum contained compound is preferably 1:(40～66), more preferably 1:(45～55), most preferably be 1:(48～53).
After described the second polyreaction finishes, the present invention preferably mixes the reaction soln obtaining with ethanol solution hydrochloride, obtain reaction product; By described reaction product washing, dry, obtain ethylene-propylene-polybutadiene copolymer; More preferably in the reaction soln obtaining, add ethanol solution hydrochloride, obtain reaction product; By described reaction product washing, dry, obtain ethylene-propylene-polybutadiene copolymer.The present invention does not have special restriction to the consumption of described ethanol solution hydrochloride, and the consumption of described ethanol solution hydrochloride can make the reaction product in described reaction soln separate out.In the present invention, in described ethanol solution hydrochloride, the mass concentration of hydrochloric acid is preferably 3%～7%, and more preferably 4%～6%, most preferably be 5%.
Obtain after reaction product, the present invention preferably, by described reaction product washing, dry, obtains ethylene-propylene-polybutadiene copolymer.The present invention does not have special restriction to the method for described washing, adopts the technical scheme of washing well known to those skilled in the art.In invention, the solution of described washing is preferably ethanol.The present invention does not have special restriction to described dry method, adopts dry technology scheme well known to those skilled in the art.In the present invention, the described dry vacuum-drying that is preferably.In the present invention, described dry temperature is preferably 30 ℃～50 ℃, more preferably 35 ℃～45 ℃, most preferably is 40 ℃.The present invention does not have special restriction to the described dry time, and described reaction product is dried to constant weight.
Prepare after ethylene-propylene-polybutadiene copolymer, the present invention has calculated the catalytic activity of the second catalyst system when aforesaid method is prepared ethylene-propylene-polybutadiene copolymer, and the catalytic activity of described the second catalyzer adopts the quality of ethylene-propylene-polybutadiene copolymer that in the unit time, unit vol catalyzer prepares to characterize.Calculation result is, when method provided by the invention is prepared ethylene-propylene-polybutadiene copolymer, the catalytic activity of catalyzer is 138.7g/mmol～180.8g/mmol, and the catalytic activity of catalyzer is higher.
The present invention has tested the glass transition temp of ethylene-propylene-polybutadiene copolymer that the present invention obtains by differential scanning calorimetry (DSC), test result is that the glass transition temp of ethylene-propylene-polybutadiene copolymer that the present invention obtains is-59.1 ℃～-46.1 ℃.
The present invention has tested the number-average molecular weight of ethylene-propylene-polybutadiene copolymer that the present invention obtains by gel osmoticing chromatogram analysis, test result is that the number-average molecular weight of ethylene-propylene-polybutadiene copolymer that the present invention obtains is 2.2 × 10 -4～5.0 × 10 -4.
Ethylene-propylene-the polybutadiene copolymer obtaining is carried out examination of infrared spectrum and proton nmr spectra test by the present invention, by known to the comprehensive analysis of examination of infrared spectrum result and proton nmr spectra test result, in ethylene-propylene-polybutadiene copolymer provided by the invention, the content of propylene is 22.5wt%～35.7wt%.
The present invention tests the content of two keys in ethylene-propylene-polybutadiene copolymer that the present invention obtains by iodimetry,iodometry.In the present invention, in described iodimetry,iodometry test ethylene-propylene-polybutadiene copolymer, the detailed process of double bond content is:
Take ethylene-propylene-polybutadiene copolymer prepared by 0.2g～0.5g the present invention to dry iodine flask, the quality that records ethylene-propylene-polybutadiene copolymer is G, to the trichloromethane that adds 10mL in described iodine flask, described ethylene-propylene-polybutadiene copolymer is dissolved completely; To the Wijs reagent that adds 25mL in above-mentioned iodine flask, shake iodine flask, mixes the solution in described iodine flask again, and described iodine flask is placed 0.5 hour the dark place of 25 ℃, and the solution in described iodine flask becomes yellow; Then described iodine flask is taken out from dark place, be that 0.1mol/L～0.15mol/L Sulfothiorine standard titration solution carries out titration by volumetric molar concentration, the volumetric molar concentration that records Sulfothiorine standard titration solution is c, until the yellow in above-mentioned iodine flask disappears, the volume of the Sulfothiorine standard titration solution that record consumes is V0; In described iodine flask, add starch indicating liquid, continue titration, and shake described iodine flask, until the blueness in above-mentioned iodine flask disappears.
Separately do blank test, except not adding ethylene-propylene-polybutadiene copolymer prepared by the present invention, other operations are identical, and the volume that records the Sulfothiorine standard titration solution consuming is V.Double bond content in ethylene-propylene-polybutadiene copolymer of preparing according to the formula calculating the present invention shown in formula (I):
Figure BDA0000465318940000141
Test result is, in ethylene-propylene-polybutadiene copolymer that the present invention obtains, the content of two keys is 1.0%～3.0%, and ethylene-propylene-polybutadiene copolymer that the present invention obtains has good curability.
The present invention according to GB/T528-1992 " mensuration of vulcanized rubber and thermoplastics rubber tensile property " standard testing tensile strength, 300% stress at definite elongation, the elongation at break of ethylene-propylene-polybutadiene copolymer of obtaining of the present invention, test result is, the tensile strength of ethylene-propylene-polybutadiene copolymer that the present invention obtains is 15.50MPa～18.51MPa, 300% stress at definite elongation is 8.90MPa～13.23MPa, and elongation at break is 284.27%～415.93%.The present invention according to the standard testing of GB/T531-1992 " vulcanized rubber shore a hardness test method " the Shao Er hardness of ethylene-propylene-polybutadiene copolymer of obtaining, test result is that the Shao Er hardness of ethylene-propylene-polybutadiene copolymer that the present invention obtains is 62 degree～86 degree.Ethylene-propylene-polybutadiene copolymer that the present invention obtains has good mechanical property.
The preparation method who the invention provides a kind of ethylene-propylene-polybutadiene copolymer, comprises the following steps: a, under the effect of the first catalyst system, divinyl is carried out to the first polyreaction, and obtain polyhutadiene reaction system; Described the first catalyst system comprises the first catalyzer, electron donor and the first aluminum contained compound, and described the first catalyzer comprises one or more in Titanium series catalyst, nickel catalyst, chromium-based catalysts, molybdenum series catalyst, Fe-series catalyst and cobalt series catalyst; Described electron donor comprises one or more in itrogenous organic substance, oxygen-bearing organic matter, sulfurous organic compound, phosphorus-containing matter, alkalimetal hydride, halogen simple substance and fluorine boron compound; Described the first aluminum contained compound comprises one or more in the derivative of aluminum alkyls and aluminum hydride; B, under the effect of the second catalyst system, ethene and propylene are carried out to the second polyreaction in described polyhutadiene reaction system, obtain ethylene-propylene-polybutadiene copolymer; Described the second catalyst system comprises the second catalyzer, the second aluminum contained compound and activator, and described the second catalyzer comprises vanadium series catalyst; Described the second aluminum contained compound comprises one or more in the derivative of aluminum alkyls and aluminum hydride; Described activator comprises containing oxygen and contains one or more in nitrogen compound, Organohalogen compounds and sulfonyl chloride compound.In the present invention, comprise the first catalyzer, the first catalyst system of electron donor and the first aluminum contained compound is to comprising the second catalyzer, the catalytic activity of the second catalyst system of the second aluminum contained compound and activator does not affect, between the catalyzer adopting while preparing polyhutadiene due to the present invention and the catalyzer that adopts while preparing ethylene-propylene-polybutadiene copolymer, do not influence each other, make the present invention not introduce and affect catalyzed ethylene in the process of preparing polyhutadiene, the impurity of the catalyst activity of propylene and polyhutadiene polymerization, the impurity of catalyst activity while not preparing ethylene-propylene-polybutadiene copolymer containing impact in the polyhutadiene of preparing due to the present invention, therefore method provided by the invention catalytic activity of catalyzer in the time preparing ethylene-propylene-polybutadiene copolymer is higher, the consumption of catalyzer is less, method provided by the invention has reduced the production cost of ethylene-propylene-polybutadiene copolymer effectively.
In addition, both contained the two keys that can be used for sulfuration in ethylene-propylene-polybutadiene copolymer provided by the invention, and had again long chain branched, therefore ethylene-propylene-polybutadiene copolymer provided by the invention has good curability and mechanical property.And do not influence each other between the catalyzer that adopts while preparing polyhutadiene of the present invention and the catalyzer that adopts while preparing ethylene-propylene-polybutadiene copolymer, make the present invention in polyhutadiene reaction system, prepare ethylene-propylene-polybutadiene copolymer by direct in-situ, compared with prior art, the present invention has avoided preparing in the process of polyhutadiene polyhutadiene solution has been separated, the operation of purifying, therefore preparation method's technique of ethylene-propylene-polybutadiene copolymer provided by the invention is simple, be convenient to scale operation ethylene-propylene-polybutadiene copolymer.
In order further to understand the present invention, below in conjunction with embodiment, the preparation method of ethylene-propylene-polybutadiene copolymer provided by the invention is described in detail, but they can not be interpreted as to limiting the scope of the present invention.
In following examples, raw material used is commercial goods.
Embodiment 1
The cobalt iso-octoate of the divinyl hexane solution that is 1.0mol/L by 20mL volumetric molar concentration, 0.05mmol, the dimethylphosphite of 0.25mmol and 1.00mmol triethyl aluminum add successively in the 0.5L of nitrogen replacement reactor, under 2MPa, the condition of 10 ℃, carry out the first polyreaction of 60min, the polyhutadiene reaction system obtaining;
The polyhutadiene reaction system obtaining is carried out to examination of infrared spectrum and proton nmr spectra test, by known to the comprehensive analysis of examination of infrared spectrum result and proton nmr spectra test result, in the polyhutadiene of the polyhutadiene reaction system that the embodiment of the present invention 1 obtains 1, the content of 2-structure is 59wt%.
In above-mentioned polyhutadiene reaction system, add successively 200ml hexane, 0.15mmol V (acac) 3, 8.00mmol trichlorine triethyl two aluminium and 3.00mmol methyl trichloroacetate, the mixture obtaining is stirred; In described mixture, pass into ethene and propylene mixed gas again, under 3MPa, the condition of 10 ℃, carry out the second polyreaction of 45min; In described ethene and propylene mixed gas, ethene and propylene mol ratio are 1:4.
After above-mentioned the second polyreaction finishes, in the reaction soln obtaining, add the ethanol solution hydrochloride that 5mL hydrochloric acid mass concentration is 5%, obtain reaction product; By described reaction product with after washing with alcohol at 40 ℃ vacuum-drying to constant weight, obtain ethylene-propylene-polybutadiene copolymer.
The catalytic activity of catalyzer when the method providing according to the method test embodiment of the present invention 1 described in technique scheme is prepared ethylene-propylene-polybutadiene copolymer, test result is, when the embodiment of the present invention 1 is prepared ethylene-propylene-polybutadiene copolymer, the catalytic activity of catalyzer is 138.7g/mmol, and the catalytic activity of catalyzer is higher.
Test according to the method described above glass transition temp, number-average molecular weight, propylene content and the double bond content of ethylene-propylene-polybutadiene copolymer that the embodiment of the present invention 1 obtains, test result is as shown in Fig. 1～Fig. 3 and table 1, and Fig. 1 is the gel permeation chromatography figure of ethylene-propylene-polybutadiene copolymer of obtaining of the embodiment of the present invention 1; Fig. 2 is the infrared spectrum of ethylene-propylene-polybutadiene copolymer of obtaining of the embodiment of the present invention 1; Fig. 3 is the hydrogen nuclear magnetic resonance spectrogram of ethylene-propylene-polybutadiene copolymer of obtaining of the embodiment of the present invention 1; Glass transition temp, number-average molecular weight, propylene content and the double bond content test result of ethylene-propylene-polybutadiene copolymer that table 1 obtains for the embodiment of the present invention and comparative example.As shown in Table 1, ethylene-propylene-polybutadiene copolymer that the embodiment of the present invention 1 obtains has good curability.
Tensile strength, 300% stress at definite elongation, elongation at break and the Shao Er hardness of the ethylene-propylene-polybutadiene copolymer obtaining according to the method test embodiment of the present invention 1 described in technique scheme, test result is as shown in table 2, tensile strength, 300% stress at definite elongation, elongation at break and the Shao Er hardness test result of ethylene-propylene-polybutadiene copolymer that table 2 obtains for the embodiment of the present invention.As shown in Table 2, ethylene-propylene-polybutadiene copolymer that the embodiment of the present invention 1 obtains has good mechanical property.
Embodiment 2
Prepare ethylene-propylene-polybutadiene copolymer according to the method described in embodiment 1, different is the cobalt iso-octoate adopting in cobalt naphthenate alternative embodiment 1, adopts the dimethylphosphite in diethyl phosphite alternative embodiment 1.
According to the method described in embodiment 1, test implementation example 2 prepares in the polyhutadiene of polyhutadiene reaction system in ethylene-propylene-polybutadiene copolymer process 1, the content of 2-structure, and test result is, in the polyhutadiene that the embodiment of the present invention 2 obtains 1, the content of 2-structure is 55.4wt%.
The catalytic activity of catalyzer when the method that detects embodiment 2 and provide according to the method described in embodiment 1 is provided after ethylene-propylene-polybutadiene copolymer prepares ethylene-propylene-polybutadiene copolymer, test result is, when the embodiment of the present invention 2 is prepared ethylene-propylene-polybutadiene copolymer, the catalytic activity of catalyzer is 156.5g/mmol, and the catalytic activity of catalyzer is higher.
Glass transition temp, number-average molecular weight, propylene content and the double bond content of the ethylene-propylene-polybutadiene copolymer obtaining according to the method test embodiment of the present invention 2 described in embodiment 1, test result is as shown in table 1, as shown in Table 1, ethylene-propylene-polybutadiene copolymer that the embodiment of the present invention 1 obtains has good curability.
Embodiment 3
Prepare ethylene-propylene-polybutadiene copolymer according to the method described in embodiment 1, different is to adopt Co (acac) 2cobalt iso-octoate in alternative embodiment 1, adopts the dimethylphosphite in triphenylphosphate alternative embodiment 1.
According to the method described in embodiment 1, test implementation example 3 prepares in the polyhutadiene of polyhutadiene reaction system in ethylene-propylene-polybutadiene copolymer process 1, the content of 2-structure, and test result is, in the polyhutadiene that the embodiment of the present invention 3 obtains 1, the content of 2-structure is 53.2wt%.
The catalytic activity of catalyzer when the method that detects embodiment 3 and provide according to the method described in embodiment 1 is provided after ethylene-propylene-polybutadiene copolymer prepares ethylene-propylene-polybutadiene copolymer, test result is, when the embodiment of the present invention 3 is prepared ethylene-propylene-polybutadiene copolymer, the catalytic activity of catalyzer is 145.4g/mmol, and the catalytic activity of catalyzer is higher.
Glass transition temp, number-average molecular weight, propylene content and the double bond content of the ethylene-propylene-polybutadiene copolymer obtaining according to the method test embodiment of the present invention 3 described in embodiment 1, test result is as shown in table 1, as shown in Table 1, ethylene-propylene-polybutadiene copolymer that the embodiment of the present invention 3 obtains has good curability.
Tensile strength, 300% stress at definite elongation, elongation at break and the Shao Er hardness of the ethylene-propylene-polybutadiene copolymer obtaining according to the method test embodiment of the present invention 3 described in embodiment 1, test result is as shown in table 2, as shown in Table 2, ethylene-propylene-polybutadiene copolymer that the embodiment of the present invention 3 obtains has good mechanical property.
Embodiment 4
Prepare ethylene-propylene-polybutadiene copolymer according to the method described in embodiment 1, different is to adopt Co (CF 3sO 3) 3cobalt iso-octoate in alternative embodiment 1, adopts the dimethylphosphite in tritolyl phosphate alternative embodiment 1.
According to the method described in embodiment 1, test implementation example 4 prepares in the polyhutadiene of polyhutadiene reaction system in ethylene-propylene-polybutadiene copolymer process 1, the content of 2-structure, and test result is, in the polyhutadiene that the embodiment of the present invention 4 obtains 1, the content of 2-structure is 23.6wt%.
The catalytic activity of catalyzer when the method that detects embodiment 4 and provide according to the method described in embodiment 1 is provided after ethylene-propylene-polybutadiene copolymer prepares ethylene-propylene-polybutadiene copolymer, test result is, when the embodiment of the present invention 4 is prepared ethylene-propylene-polybutadiene copolymer, the catalytic activity of catalyzer is 168.6g/mmol, and the catalytic activity of catalyzer is higher.
Glass transition temp, number-average molecular weight, propylene content and the double bond content of the ethylene-propylene-polybutadiene copolymer obtaining according to the method test embodiment of the present invention 4 described in embodiment 1, test result is as shown in table 1, as shown in Table 1, ethylene-propylene-polybutadiene copolymer that the embodiment of the present invention 4 obtains has good curability.
Embodiment 5
Prepare ethylene-propylene-polybutadiene copolymer according to the method described in embodiment 1, different is to adopt CoCl 2cobalt iso-octoate in alternative embodiment 1, adopts the dimethylphosphite in ethamine alternative embodiment 1.
According to the method described in embodiment 1, test implementation example 5 prepares in the polyhutadiene of polyhutadiene reaction system in ethylene-propylene-polybutadiene copolymer process 1, the content of 2-structure, and test result is, in the polyhutadiene that the embodiment of the present invention 5 obtains 1, the content of 2-structure is 56.9wt%.
The catalytic activity of catalyzer when the method that detects embodiment 5 and provide according to the method described in embodiment 1 is provided after ethylene-propylene-polybutadiene copolymer prepares ethylene-propylene-polybutadiene copolymer, test result is, when the embodiment of the present invention 5 is prepared ethylene-propylene-polybutadiene copolymer, the catalytic activity of catalyzer is 173.2g/mmol, and the catalytic activity of catalyzer is higher.
Glass transition temp, number-average molecular weight, propylene content and the double bond content of the ethylene-propylene-polybutadiene copolymer obtaining according to the method test embodiment of the present invention 5 described in embodiment 1, test result is as shown in table 1, as shown in Table 1, ethylene-propylene-polybutadiene copolymer that the embodiment of the present invention 5 obtains has good curability.
Embodiment 6
Prepare ethylene-propylene-polybutadiene copolymer according to the method described in embodiment 1, different is to adopt Co (CF 3sO 3) 2cobalt iso-octoate in alternative embodiment 1, adopts the dimethylphosphite in isooctyl alcohol alternative embodiment 1.
According to the method described in embodiment 1, test implementation example 6 prepares in the polyhutadiene of polyhutadiene reaction system in ethylene-propylene-polybutadiene copolymer process 1, the content of 2-structure, and test result is, in the polyhutadiene that the embodiment of the present invention 6 obtains 1, the content of 2-structure is 88.5wt%.
The catalytic activity of catalyzer when the method that detects embodiment 6 and provide according to the method described in embodiment 1 is provided after ethylene-propylene-polybutadiene copolymer prepares ethylene-propylene-polybutadiene copolymer, test result is, when the embodiment of the present invention 6 is prepared ethylene-propylene-polybutadiene copolymer, the catalytic activity of catalyzer is 139.9g/mmol, and the catalytic activity of catalyzer is higher.
Glass transition temp, number-average molecular weight, propylene content and the double bond content of the ethylene-propylene-polybutadiene copolymer obtaining according to the method test embodiment of the present invention 6 described in embodiment 1, test result is as shown in table 1, as shown in Table 1, ethylene-propylene-polybutadiene copolymer that the embodiment of the present invention 6 obtains has good curability.
Embodiment 7
Prepare ethylene-propylene-polybutadiene copolymer according to the method described in embodiment 1, different is to adopt Co (acac) 3cobalt iso-octoate in alternative embodiment 1, adopts the dimethylphosphite in 1,10-phenanthroline alternative embodiment 1.
According to the method described in embodiment 1, test implementation example 7 prepares in the polyhutadiene of polyhutadiene reaction system in ethylene-propylene-polybutadiene copolymer process 1, the content of 2-structure, and test result is, in the polyhutadiene that the embodiment of the present invention 7 obtains 1, the content of 2-structure is 78.4wt%.
The catalytic activity of catalyzer when the method that detects embodiment 7 and provide according to the method described in embodiment 1 is provided after ethylene-propylene-polybutadiene copolymer prepares ethylene-propylene-polybutadiene copolymer, test result is, when the embodiment of the present invention 7 is prepared ethylene-propylene-polybutadiene copolymer, the catalytic activity of catalyzer is 139.2g/mmol, and the catalytic activity of catalyzer is higher.
Glass transition temp, number-average molecular weight, propylene content and the double bond content of the ethylene-propylene-polybutadiene copolymer obtaining according to the method test embodiment of the present invention 7 described in embodiment 1, test result is as shown in table 1, as shown in Table 1, ethylene-propylene-polybutadiene copolymer that the embodiment of the present invention 7 obtains has good curability.
Embodiment 8
Prepare ethylene-propylene-polybutadiene copolymer according to the method described in embodiment 1, different is the cobalt iso-octoate adopting in Methionin complex cobalt alternative embodiment 1, adopts the dimethylphosphite in tetrahydrofuran (THF) alternative embodiment 1.
According to the method described in embodiment 1, test implementation example 8 prepares in the polyhutadiene of polyhutadiene reaction system in ethylene-propylene-polybutadiene copolymer process 1, the content of 2-structure, and test result is, in the polyhutadiene that the embodiment of the present invention 8 obtains 1, the content of 2-structure is 80.3wt%.
The catalytic activity of catalyzer when the method that detects embodiment 8 and provide according to the method described in embodiment 1 is provided after ethylene-propylene-polybutadiene copolymer prepares ethylene-propylene-polybutadiene copolymer, test result is, when the embodiment of the present invention 8 is prepared ethylene-propylene-polybutadiene copolymer, the catalytic activity of catalyzer is 142.8g/mmol, and the catalytic activity of catalyzer is higher.
Glass transition temp, number-average molecular weight, propylene content and the double bond content of the ethylene-propylene-polybutadiene copolymer obtaining according to the method test embodiment of the present invention 8 described in embodiment 1, test result is as shown in table 1, as shown in Table 1, ethylene-propylene-polybutadiene copolymer that the embodiment of the present invention 8 obtains has good curability.
Tensile strength, 300% stress at definite elongation, elongation at break and the Shao Er hardness of the ethylene-propylene-polybutadiene copolymer obtaining according to the method test embodiment of the present invention 8 described in embodiment 1, test result is as shown in table 2, as shown in Table 2, ethylene-propylene-polybutadiene copolymer that the embodiment of the present invention 8 obtains has good mechanical property.
Embodiment 9
Prepare ethylene-propylene-polybutadiene copolymer according to the method described in embodiment 1, different is to adopt Co (CH 3cOO) 2cobalt iso-octoate in alternative embodiment 1, adopts the dimethylphosphite in dimethyl sulfoxide (DMSO) alternative embodiment 1.
According to the method described in embodiment 1, test implementation example 9 prepares in the polyhutadiene of polyhutadiene reaction system in ethylene-propylene-polybutadiene copolymer process 1, the content of 2-structure, and test result is, in the polyhutadiene that the embodiment of the present invention 9 obtains 1, the content of 2-structure is 46.5wt%.
The catalytic activity of catalyzer when the method that detects embodiment 9 and provide according to the method described in embodiment 1 is provided after ethylene-propylene-polybutadiene copolymer prepares ethylene-propylene-polybutadiene copolymer, test result is, when the embodiment of the present invention 9 is prepared ethylene-propylene-polybutadiene copolymer, the catalytic activity of catalyzer is 163.7g/mmol, and the catalytic activity of catalyzer is higher.
Glass transition temp, number-average molecular weight, propylene content and the double bond content of the ethylene-propylene-polybutadiene copolymer obtaining according to the method test embodiment of the present invention 9 described in embodiment 1, test result is as shown in table 1, as shown in Table 1, ethylene-propylene-polybutadiene copolymer that the embodiment of the present invention 9 obtains has good curability.
Embodiment 10
Prepare ethylene-propylene-polybutadiene copolymer according to the method described in embodiment 1, different is to adopt C 63h 90coN 14o 14cobalt iso-octoate in P alternative embodiment 1, adopts the dimethylphosphite in positive propyl ether alternative embodiment 1.
According to the method described in embodiment 1, test implementation example 10 prepares in the polyhutadiene of polyhutadiene reaction system in ethylene-propylene-polybutadiene copolymer process 1, the content of 2-structure, and test result is, in the polyhutadiene that the embodiment of the present invention 10 obtains 1, the content of 2-structure is 90.4wt%.
The catalytic activity of catalyzer when the method that detects embodiment 10 and provide according to the method described in embodiment 1 is provided after ethylene-propylene-polybutadiene copolymer prepares ethylene-propylene-polybutadiene copolymer, test result is, when the embodiment of the present invention 10 is prepared ethylene-propylene-polybutadiene copolymer, the catalytic activity of catalyzer is 174.3g/mmol, and the catalytic activity of catalyzer is higher.
Glass transition temp, number-average molecular weight, propylene content and the double bond content of the ethylene-propylene-polybutadiene copolymer obtaining according to the method test embodiment of the present invention 10 described in embodiment 1, test result is as shown in table 1, as shown in Table 1, ethylene-propylene-polybutadiene copolymer that the embodiment of the present invention 10 obtains has good curability.
Tensile strength, 300% stress at definite elongation, elongation at break and the Shao Er hardness of the ethylene-propylene-polybutadiene copolymer obtaining according to the method test embodiment of the present invention 10 described in embodiment 1, test result is as shown in table 2, as shown in Table 2, ethylene-propylene-polybutadiene copolymer that the embodiment of the present invention 10 obtains has good mechanical property.
Embodiment 11
Ti (the OCH of the divinyl hexane solution that is 0.5mol/L by 20mL volumetric molar concentration, 0.01mmol 3) 4, 0.15mmol methyl benzoate and 1.00mmol trimethyl aluminium add successively in the 0.5L of nitrogen replacement reactor, under 1MPa, the condition of 40 ℃, carry out the first polyreaction of 60min, the polyhutadiene reaction system obtaining;
The polyhutadiene reaction system obtaining is carried out to examination of infrared spectrum and proton nmr spectra test, by known to the comprehensive analysis of examination of infrared spectrum result and proton nmr spectra test result, in the polyhutadiene of the polyhutadiene reaction system that the embodiment of the present invention 11 obtains 1, the content of 2-structure is 70.3wt%.
In above-mentioned polyhutadiene reaction system, add successively 200ml hexane, 0.20mmol VO (OCH 3) 3, 8.00mmol triisobutyl aluminium and 1.00mmol CH 2cl 2, the mixture obtaining is stirred; In described mixture, pass into ethene and propylene mixed gas again, under 2MPa, the condition of 50 ℃, carry out the second polyreaction of 60min; In described ethene and propylene mixed gas, ethene and propylene mol ratio are 1:6.
After above-mentioned the second polyreaction finishes, in the reaction soln obtaining, add the acidic alcohol that 5mL hydrochloric acid mass concentration is 5%, obtain reaction product; By described reaction product with after washing with alcohol at 40 ℃ vacuum-drying to constant weight, obtain ethylene-propylene-polybutadiene copolymer.
The catalytic activity of catalyzer when the method that detects embodiment 11 and provide according to the method described in embodiment 1 is provided after ethylene-propylene-polybutadiene copolymer prepares ethylene-propylene-polybutadiene copolymer, test result is, when the embodiment of the present invention 11 is prepared ethylene-propylene-polybutadiene copolymer, the catalytic activity of catalyzer is 156.7g/mmol, and the catalytic activity of catalyzer is higher.
Glass transition temp, number-average molecular weight, propylene content and the double bond content of the ethylene-propylene-polybutadiene copolymer obtaining according to the method test embodiment of the present invention 11 described in embodiment 1, test result is as shown in table 1, as shown in Table 1, ethylene-propylene-polybutadiene copolymer that the embodiment of the present invention 11 obtains has good curability.
Embodiment 12
Prepare ethylene-propylene-polybutadiene copolymer according to the method described in embodiment 11, different is to adopt TiCl 4ti (OCH in alternative embodiment 11 3) 4, adopt the methyl benzoate in n-butyl phthalate alternative embodiment 11.
According to the method described in embodiment 1, test implementation example 12 prepares in the polyhutadiene of polyhutadiene reaction system in ethylene-propylene-polybutadiene copolymer process 1, the content of 2-structure, and test result is, in the polyhutadiene that the embodiment of the present invention 12 obtains 1, the content of 2-structure is 40.5wt%.
The catalytic activity of catalyzer when the method that detects embodiment 12 and provide according to the method described in embodiment 1 is provided after ethylene-propylene-polybutadiene copolymer prepares ethylene-propylene-polybutadiene copolymer, test result is, when the embodiment of the present invention 12 is prepared ethylene-propylene-polybutadiene copolymer, the catalytic activity of catalyzer is 178.1g/mmol, and the catalytic activity of catalyzer is higher.
Glass transition temp, number-average molecular weight, propylene content and the double bond content of the ethylene-propylene-polybutadiene copolymer obtaining according to the method test embodiment of the present invention 12 described in embodiment 1, test result is as shown in table 1, as shown in Table 1, ethylene-propylene-polybutadiene copolymer that the embodiment of the present invention 12 obtains has good curability.
Embodiment 13
Prepare ethylene-propylene-polybutadiene copolymer according to the method described in embodiment 11, different is to adopt Ti (acac) 3ti (OCH in alternative embodiment 11 3) 4, adopt the methyl benzoate in 2,3-di-isopropyl succsinic acid diethyl ester alternative embodiment 11.
According to the method described in embodiment 1, test implementation example 13 prepares in the polyhutadiene of polyhutadiene reaction system in ethylene-propylene-polybutadiene copolymer process 1, the content of 2-structure, and test result is, in the polyhutadiene that the embodiment of the present invention 13 obtains 1, the content of 2-structure is 55.5wt%.
The catalytic activity of catalyzer when the method that detects embodiment 13 and provide according to the method described in embodiment 1 is provided after ethylene-propylene-polybutadiene copolymer prepares ethylene-propylene-polybutadiene copolymer, test result is, when the embodiment of the present invention 13 is prepared ethylene-propylene-polybutadiene copolymer, the catalytic activity of catalyzer is 147.7g/mmol, and the catalytic activity of catalyzer is higher.
Glass transition temp, number-average molecular weight, propylene content and the double bond content of the ethylene-propylene-polybutadiene copolymer obtaining according to the method test embodiment of the present invention 13 described in embodiment 1, test result is as shown in table 1, as shown in Table 1, ethylene-propylene-polybutadiene copolymer that the embodiment of the present invention 13 obtains has good curability.
Embodiment 14
Prepare ethylene-propylene-polybutadiene copolymer according to the method described in embodiment 11, different is to adopt TiC1 3ti (OCH in alternative embodiment 11 3) 4, adopt the methyl benzoate in 9,3-methoxymethyl diphenylene-oxide alternative embodiment 11.
According to the method described in embodiment 1, test implementation example 14 prepares in the polyhutadiene of polyhutadiene reaction system in ethylene-propylene-polybutadiene copolymer process 1, the content of 2-structure, and test result is, in the polyhutadiene that the embodiment of the present invention 14 obtains 1, the content of 2-structure is 56.7wt%.
The catalytic activity of catalyzer when the method that detects embodiment 14 and provide according to the method described in embodiment 1 is provided after ethylene-propylene-polybutadiene copolymer prepares ethylene-propylene-polybutadiene copolymer, test result is, when the embodiment of the present invention 14 is prepared ethylene-propylene-polybutadiene copolymer, the catalytic activity of catalyzer is 178.2g/mmol, and the catalytic activity of catalyzer is higher.
Glass transition temp, number-average molecular weight, propylene content and the double bond content of the ethylene-propylene-polybutadiene copolymer obtaining according to the method test embodiment of the present invention 14 described in embodiment 1, test result is as shown in table 1, as shown in Table 1, ethylene-propylene-polybutadiene copolymer that the embodiment of the present invention 14 obtains has good curability.
Embodiment 15
Prepare ethylene-propylene-polybutadiene copolymer according to the method described in embodiment 11, that different is the Ti (OCH adopting in two luxuriant titanium alternative embodiments 11 3) 4, adopt the methyl benzoate in dibenzoyl peroxide alternative embodiment 11.
According to the method described in embodiment 1, test implementation example 15 prepares in the polyhutadiene of polyhutadiene reaction system in ethylene-propylene-polybutadiene copolymer process 1, the content of 2-structure, and test result is, in the polyhutadiene that the embodiment of the present invention 15 obtains 1, the content of 2-structure is 58.6wt%.
The catalytic activity of catalyzer when the method that detects embodiment 15 and provide according to the method described in embodiment 1 is provided after ethylene-propylene-polybutadiene copolymer prepares ethylene-propylene-polybutadiene copolymer, test result is, when the embodiment of the present invention 15 is prepared ethylene-propylene-polybutadiene copolymer, the catalytic activity of catalyzer is 168.1g/mmol, and the catalytic activity of catalyzer is higher.
Glass transition temp, number-average molecular weight, propylene content and the double bond content of the ethylene-propylene-polybutadiene copolymer obtaining according to the method test embodiment of the present invention 15 described in embodiment 1, test result is as shown in table 1, as shown in Table 1, ethylene-propylene-polybutadiene copolymer that the embodiment of the present invention 15 obtains has good curability.
Embodiment 16
The Cr (Naph) of the divinyl hexane solution that is 1.5mol/L by 40mL volumetric molar concentration, 0.05mmol 3, 0.05mmol diphenyl phosphite and 0.50mmol methylaluminoxane (MAO) add successively in the 0.5L of nitrogen replacement reactor, under 3MPa, the condition of 50 ℃, carry out the first polyreaction of 30min, the polyhutadiene reaction system obtaining;
The polyhutadiene reaction system obtaining is carried out to examination of infrared spectrum and proton nmr spectra test, by known to the comprehensive analysis of examination of infrared spectrum result and proton nmr spectra test result, in the polyhutadiene of the polyhutadiene reaction system that the embodiment of the present invention 16 obtains 1, the content of 2-structure is 59.3wt%.
In above-mentioned polyhutadiene reaction system, add successively 280ml hexane, 0.15mmol VO (acac) 3, 8.00mmol ethyl aluminum dichloride and 3.00mmol ethyl trichloroacetate, the mixture obtaining is stirred; In described mixture, pass into ethene and propylene mixed gas again, under 6MPa, the condition of 70 ℃, carry out the second polyreaction of 70min; In described ethene and propylene mixed gas, ethene and propylene mol ratio are 1:2.
After above-mentioned the second polyreaction finishes, in the reaction soln obtaining, add the acidic alcohol that 5mL hydrochloric acid mass concentration is 5%, obtain reaction product; By described reaction product with after washing with alcohol at 40 ℃ vacuum-drying to constant weight, obtain ethylene-propylene-polybutadiene copolymer.
The catalytic activity of catalyzer when the method that detects embodiment 16 and provide according to the method described in embodiment 1 is provided after ethylene-propylene-polybutadiene copolymer prepares ethylene-propylene-polybutadiene copolymer, test result is, when the embodiment of the present invention 16 is prepared ethylene-propylene-polybutadiene copolymer, the catalytic activity of catalyzer is 171.7g/mmol, and the catalytic activity of catalyzer is higher.
Glass transition temp, number-average molecular weight, propylene content and the double bond content of the ethylene-propylene-polybutadiene copolymer obtaining according to the method test embodiment of the present invention 16 described in embodiment 1, test result is as shown in table 1, as shown in Table 1, ethylene-propylene-polybutadiene copolymer that the embodiment of the present invention 16 obtains has good curability.
Embodiment 17
Prepare ethylene-propylene-polybutadiene copolymer according to the method described in embodiment 16, different is to adopt CrO 3cr (Naph) in alternative embodiment 16 3, adopt the diphenyl phosphite in phosphorous acid dipropyl alternative embodiment 16.
According to the method described in embodiment 1, test implementation example 17 prepares in the polyhutadiene of polyhutadiene reaction system in ethylene-propylene-polybutadiene copolymer process 1, the content of 2-structure, and test result is, in the polyhutadiene that the embodiment of the present invention 17 obtains 1, the content of 2-structure is 80.6wt%.
The catalytic activity of catalyzer when the method that detects embodiment 17 and provide according to the method described in embodiment 1 is provided after ethylene-propylene-polybutadiene copolymer prepares ethylene-propylene-polybutadiene copolymer, test result is, when the embodiment of the present invention 17 is prepared ethylene-propylene-polybutadiene copolymer, the catalytic activity of catalyzer is 139.3g/mmol, and the catalytic activity of catalyzer is higher.
Glass transition temp, number-average molecular weight, propylene content and the double bond content of the ethylene-propylene-polybutadiene copolymer obtaining according to the method test embodiment of the present invention 17 described in embodiment 1, test result is as shown in table 1, as shown in Table 1, ethylene-propylene-polybutadiene copolymer that the embodiment of the present invention 17 obtains has good curability.
Tensile strength, 300% stress at definite elongation, elongation at break and the Shao Er hardness of the ethylene-propylene-polybutadiene copolymer obtaining according to the method test embodiment of the present invention 17 described in embodiment 1, test result is as shown in table 2, as shown in Table 2, ethylene-propylene-polybutadiene copolymer that the embodiment of the present invention 17 obtains has good mechanical property.
Embodiment 18
Prepare ethylene-propylene-polybutadiene copolymer according to the method described in embodiment 16, different is to adopt Cr (acac) 3cr (Naph) in alternative embodiment 16 3, adopt the diphenyl phosphite in dibutyl phosphite alternative embodiment 16.
According to the method described in embodiment 1, test implementation example 18 prepares in the polyhutadiene of polyhutadiene reaction system in ethylene-propylene-polybutadiene copolymer process 1, the content of 2-structure, and test result is, in the polyhutadiene that the embodiment of the present invention 18 obtains 1, the content of 2-structure is 88.4wt%.
The catalytic activity of catalyzer when the method that detects embodiment 18 and provide according to the method described in embodiment 1 is provided after ethylene-propylene-polybutadiene copolymer prepares ethylene-propylene-polybutadiene copolymer, test result is, when the embodiment of the present invention 18 is prepared ethylene-propylene-polybutadiene copolymer, the catalytic activity of catalyzer is 168.1g/mmol, and the catalytic activity of catalyzer is higher.
Glass transition temp, number-average molecular weight, propylene content and the double bond content of the ethylene-propylene-polybutadiene copolymer obtaining according to the method test embodiment of the present invention 18 described in embodiment 1, test result is as shown in table 1, as shown in Table 1, ethylene-propylene-polybutadiene copolymer that the embodiment of the present invention 18 obtains has good curability.
Embodiment 19
Prepare ethylene-propylene-polybutadiene copolymer according to the method described in embodiment 16, different is to adopt Cr (CNC 6h 5) 6cr (Naph) in alternative embodiment 16 3, adopt the diphenyl phosphite in tritolyl phosphate alternative embodiment 16.
According to the method described in embodiment 1, test implementation example 19 prepares in the polyhutadiene of polyhutadiene reaction system in ethylene-propylene-polybutadiene copolymer process 1, the content of 2-structure, and test result is, in the polyhutadiene that the embodiment of the present invention 19 obtains 1, the content of 2-structure is 83.2wt%.
The catalytic activity of catalyzer when the method that detects embodiment 19 and provide according to the method described in embodiment 1 is provided after ethylene-propylene-polybutadiene copolymer prepares ethylene-propylene-polybutadiene copolymer, test result is, when the embodiment of the present invention 19 is prepared ethylene-propylene-polybutadiene copolymer, the catalytic activity of catalyzer is 158.6g/mmol, and the catalytic activity of catalyzer is higher.
Glass transition temp, number-average molecular weight, propylene content and the double bond content of the ethylene-propylene-polybutadiene copolymer obtaining according to the method test embodiment of the present invention 19 described in embodiment 1, test result is as shown in table 1, as shown in Table 1, ethylene-propylene-polybutadiene copolymer that the embodiment of the present invention 19 obtains has good curability.
Embodiment 20
Prepare ethylene-propylene-polybutadiene copolymer according to the method described in embodiment 16, different is to adopt CrCl 2cr (Naph) in alternative embodiment 16 3, adopt the diphenyl phosphite in tritolyl phosphate alternative embodiment 16.
According to the method described in embodiment 1, test implementation example 20 prepares in the polyhutadiene of polyhutadiene reaction system in ethylene-propylene-polybutadiene copolymer process 1, the content of 2-structure, and test result is, in the polyhutadiene that the embodiment of the present invention 20 obtains 1, the content of 2-structure is 86.2wt%.
The catalytic activity of catalyzer when the method that detects embodiment 20 and provide according to the method described in embodiment 1 is provided after ethylene-propylene-polybutadiene copolymer prepares ethylene-propylene-polybutadiene copolymer, test result is, when the embodiment of the present invention 20 is prepared ethylene-propylene-polybutadiene copolymer, the catalytic activity of catalyzer is 171.2g/mmol, and the catalytic activity of catalyzer is higher.
Glass transition temp, number-average molecular weight, propylene content and the double bond content of the ethylene-propylene-polybutadiene copolymer obtaining according to the method test embodiment of the present invention 20 described in embodiment 1, test result is as shown in table 1, as shown in Table 1, ethylene-propylene-polybutadiene copolymer that the embodiment of the present invention 20 obtains has good curability.
Embodiment 21
Prepare ethylene-propylene-polybutadiene copolymer according to the method described in embodiment 16, different is to adopt Cr (EHA) 3cr (Naph) in alternative embodiment 16 3, adopt the diphenyl phosphite in phosphorous acid di-isooctyl alternative embodiment 16.
According to the method described in embodiment 1, test implementation example 21 prepares in the polyhutadiene of polyhutadiene reaction system in ethylene-propylene-polybutadiene copolymer process 1, the content of 2-structure, and test result is, in the polyhutadiene that the embodiment of the present invention 21 obtains 1, the content of 2-structure is 77.2wt%.
The catalytic activity of catalyzer when the method that detects embodiment 21 and provide according to the method described in embodiment 1 is provided after ethylene-propylene-polybutadiene copolymer prepares ethylene-propylene-polybutadiene copolymer, test result is, when the embodiment of the present invention 21 is prepared ethylene-propylene-polybutadiene copolymer, the catalytic activity of catalyzer is 161.8g/mmol, and the catalytic activity of catalyzer is higher.
Glass transition temp, number-average molecular weight, propylene content and the double bond content of the ethylene-propylene-polybutadiene copolymer obtaining according to the method test embodiment of the present invention 21 described in embodiment 1, test result is as shown in table 1, as shown in Table 1, ethylene-propylene-polybutadiene copolymer that the embodiment of the present invention 21 obtains has good curability.
Embodiment 22
Prepare ethylene-propylene-polybutadiene copolymer according to the method described in embodiment 16, different is to adopt CrCl 2(dmpe) 2cr (Naph) in alternative embodiment 16 3, adopt the diphenyl phosphite in 1,10-phenanthroline alternative embodiment 16.
According to the method described in embodiment 1, test implementation example 22 prepares in the polyhutadiene of polyhutadiene reaction system in ethylene-propylene-polybutadiene copolymer process 1, the content of 2-structure, and test result is, in the polyhutadiene that the embodiment of the present invention 22 obtains 1, the content of 2-structure is 74.5wt%.
The catalytic activity of catalyzer when the method that detects embodiment 22 and provide according to the method described in embodiment 1 is provided after ethylene-propylene-polybutadiene copolymer prepares ethylene-propylene-polybutadiene copolymer, test result is, when the embodiment of the present invention 22 is prepared ethylene-propylene-polybutadiene copolymer, the catalytic activity of catalyzer is 177.2g/mmol, and the catalytic activity of catalyzer is higher.
Glass transition temp, number-average molecular weight, propylene content and the double bond content of the ethylene-propylene-polybutadiene copolymer obtaining according to the method test embodiment of the present invention 22 described in embodiment 1, test result is as shown in table 1, as shown in Table 1, ethylene-propylene-polybutadiene copolymer that the embodiment of the present invention 22 obtains has good curability.
Embodiment 23
The divinyl hexane solution that is 0.1mol/L by 70mL volumetric molar concentration, the FeCl of 0.35mmol 3, 0.35mmol dimethylphosphite and 3.50mmol triethyl aluminum add successively in the 0.5L of nitrogen replacement reactor, under 1MPa, the condition of 20 ℃, carry out the first polyreaction of 60min, the polyhutadiene reaction system obtaining;
The polyhutadiene reaction system obtaining is carried out to examination of infrared spectrum and proton nmr spectra test, by known to the comprehensive analysis of examination of infrared spectrum result and proton nmr spectra test result, in the polyhutadiene of the polyhutadiene reaction system that the embodiment of the present invention 23 obtains 1, the content of 2-structure is 55.4wt%.
To beta-diketo mono imine vanadium (III) title complex, 10.00mmol aluminium diethyl monochloride and the 3.00mmol1 that add successively 230ml hexane, 0.15mmol in above-mentioned polyhutadiene reaction system, 10-o-phenanthroline, stirs the mixture obtaining; In described mixture, pass into ethene and propylene mixed gas again, under 4MPa, the condition of 30 ℃, carry out the second polyreaction of 20min; In described ethene and propylene mixed gas, ethene and propylene mol ratio are 3:4.
After above-mentioned the second polyreaction finishes, in the reaction soln obtaining, add the acidic alcohol that 5mL hydrochloric acid mass concentration is 5%, obtain reaction product; By described reaction product with after washing with alcohol at 40 ℃ vacuum-drying to constant weight, obtain ethylene-propylene-polybutadiene copolymer.
The catalytic activity of catalyzer when the method that detects embodiment 23 and provide according to the method described in embodiment 1 is provided after ethylene-propylene-polybutadiene copolymer prepares ethylene-propylene-polybutadiene copolymer, test result is, when the embodiment of the present invention 23 is prepared ethylene-propylene-polybutadiene copolymer, the catalytic activity of catalyzer is 173.6g/mmol, and the catalytic activity of catalyzer is higher.
Glass transition temp, number-average molecular weight, propylene content and the double bond content of the ethylene-propylene-polybutadiene copolymer obtaining according to the method test embodiment of the present invention 23 described in embodiment 1, test result is as shown in table 1, as shown in Table 1, ethylene-propylene-polybutadiene copolymer that the embodiment of the present invention 23 obtains has good curability.
Embodiment 24
Prepare ethylene-propylene-polybutadiene copolymer according to the method described in embodiment 23, that different is the FeCl adopting in iron naphthenate alternative embodiment 23 3, adopt the dimethylphosphite in diethyl phosphite alternative embodiment 23.
According to the method described in embodiment 1, test implementation example 24 prepares in the polyhutadiene of polyhutadiene reaction system in ethylene-propylene-polybutadiene copolymer process 1, the content of 2-structure, and test result is, in the polyhutadiene that the embodiment of the present invention 24 obtains 1, the content of 2-structure is 53.2wt%.
The catalytic activity of catalyzer when the method that detects embodiment 24 and provide according to the method described in embodiment 1 is provided after ethylene-propylene-polybutadiene copolymer prepares ethylene-propylene-polybutadiene copolymer, test result is, when the embodiment of the present invention 24 is prepared ethylene-propylene-polybutadiene copolymer, the catalytic activity of catalyzer is 166.7g/mmol, and the catalytic activity of catalyzer is higher.
Glass transition temp, number-average molecular weight, propylene content and the double bond content of the ethylene-propylene-polybutadiene copolymer obtaining according to the method test embodiment of the present invention 24 described in embodiment 1, test result is as shown in table 1, as shown in Table 1, ethylene-propylene-polybutadiene copolymer that the embodiment of the present invention 24 obtains has good curability.
Tensile strength, 300% stress at definite elongation, elongation at break and the Shao Er hardness of the ethylene-propylene-polybutadiene copolymer obtaining according to the method test embodiment of the present invention 24 described in embodiment 1, test result is as shown in table 2, as shown in Table 2, ethylene-propylene-polybutadiene copolymer that the embodiment of the present invention 24 obtains has good mechanical property.
Embodiment 25
Prepare ethylene-propylene-polybutadiene copolymer according to the method described in embodiment 23, different is to adopt Fe (acac) 3feCl in alternative embodiment 23 3, adopt the dimethylphosphite in triphenylphosphate alternative embodiment 23.
According to the method described in embodiment 1, test implementation example 25 prepares in the polyhutadiene of polyhutadiene reaction system in ethylene-propylene-polybutadiene copolymer process 1, the content of 2-structure, and test result is, in the polyhutadiene that the embodiment of the present invention 25 obtains 1, the content of 2-structure is 23.6wt%.
The catalytic activity of catalyzer when the method that detects embodiment 25 and provide according to the method described in embodiment 1 is provided after ethylene-propylene-polybutadiene copolymer prepares ethylene-propylene-polybutadiene copolymer, test result is, when the embodiment of the present invention 25 is prepared ethylene-propylene-polybutadiene copolymer, the catalytic activity of catalyzer is 164.5g/mmol, and the catalytic activity of catalyzer is higher.
Glass transition temp, number-average molecular weight, propylene content and the double bond content of the ethylene-propylene-polybutadiene copolymer obtaining according to the method test embodiment of the present invention 25 described in embodiment 1, test result is as shown in table 1, as shown in Table 1, ethylene-propylene-polybutadiene copolymer that the embodiment of the present invention 25 obtains has good curability.
Embodiment 26
Prepare ethylene-propylene-polybutadiene copolymer according to the method described in embodiment 23, different is to adopt Fe (CF 3sO 3) 3feCl in alternative embodiment 23 3, adopt the dimethylphosphite in tritolyl phosphate alternative embodiment 23.
According to the method described in embodiment 1, test implementation example 26 prepares in the polyhutadiene of polyhutadiene reaction system in ethylene-propylene-polybutadiene copolymer process 1, the content of 2-structure, and test result is, in the polyhutadiene that the embodiment of the present invention 26 obtains 1, the content of 2-structure is 56.9wt%.
The catalytic activity of catalyzer when the method that detects embodiment 26 and provide according to the method described in embodiment 1 is provided after ethylene-propylene-polybutadiene copolymer prepares ethylene-propylene-polybutadiene copolymer, test result is, when the embodiment of the present invention 26 is prepared ethylene-propylene-polybutadiene copolymer, the catalytic activity of catalyzer is 168.9g/mmol, and the catalytic activity of catalyzer is higher.
Glass transition temp, number-average molecular weight, propylene content and the double bond content of the ethylene-propylene-polybutadiene copolymer obtaining according to the method test embodiment of the present invention 26 described in embodiment 1, test result is as shown in table 1, as shown in Table 1, ethylene-propylene-polybutadiene copolymer that the embodiment of the present invention 26 obtains has good curability.
Embodiment 27
Prepare ethylene-propylene-polybutadiene copolymer according to the method described in embodiment 23, that different is the FeCl adopting in ironic citrate alternative embodiment 23 3, adopt the dimethylphosphite in benzoglyoxaline alternative embodiment 23.
According to the method described in embodiment 1, test implementation example 27 prepares in the polyhutadiene of polyhutadiene reaction system in ethylene-propylene-polybutadiene copolymer process 1, the content of 2-structure, and test result is, in the polyhutadiene that the embodiment of the present invention 27 obtains 1, the content of 2-structure is 88.5wt%.
The catalytic activity of catalyzer when the method that detects embodiment 27 and provide according to the method described in embodiment 1 is provided after ethylene-propylene-polybutadiene copolymer prepares ethylene-propylene-polybutadiene copolymer, test result is, when the embodiment of the present invention 27 is prepared ethylene-propylene-polybutadiene copolymer, the catalytic activity of catalyzer is 144.8g/mmol, and the catalytic activity of catalyzer is higher.
Glass transition temp, number-average molecular weight, propylene content and the double bond content of the ethylene-propylene-polybutadiene copolymer obtaining according to the method test embodiment of the present invention 27 described in embodiment 1, test result is as shown in table 1, as shown in Table 1, ethylene-propylene-polybutadiene copolymer that the embodiment of the present invention 27 obtains has good curability.
Embodiment 28
Prepare ethylene-propylene-polybutadiene copolymer according to the method described in embodiment 23, that different is the FeCl adopting in Methionin Complexing Iron alternative embodiment 23 3, adopt the dimethylphosphite in 1,10-phen alternative embodiment 23.
According to the method described in embodiment 1, test implementation example 28 prepares in the polyhutadiene of polyhutadiene reaction system in ethylene-propylene-polybutadiene copolymer process 1, the content of 2-structure, and test result is, in the polyhutadiene that the embodiment of the present invention 28 obtains 1, the content of 2-structure is 78.4wt%.
The catalytic activity of catalyzer when the method that detects embodiment 28 and provide according to the method described in embodiment 1 is provided after ethylene-propylene-polybutadiene copolymer prepares ethylene-propylene-polybutadiene copolymer, test result is, when the embodiment of the present invention 28 is prepared ethylene-propylene-polybutadiene copolymer, the catalytic activity of catalyzer is 146.4g/mmol, and the catalytic activity of catalyzer is higher.
Glass transition temp, number-average molecular weight, propylene content and the double bond content of the ethylene-propylene-polybutadiene copolymer obtaining according to the method test embodiment of the present invention 28 described in embodiment 1, test result is as shown in table 1, as shown in Table 1, ethylene-propylene-polybutadiene copolymer that the embodiment of the present invention 28 obtains has good curability.
Embodiment 29
Prepare ethylene-propylene-polybutadiene copolymer according to the method described in embodiment 23, different is to adopt Fe (acac) 2feCl in alternative embodiment 23 3, adopt the dimethylphosphite in 1,10-phenanthroline alternative embodiment 23.
According to the method described in embodiment 1, test implementation example 29 prepares in the polyhutadiene of polyhutadiene reaction system in ethylene-propylene-polybutadiene copolymer process 1, the content of 2-structure, and test result is, in the polyhutadiene that the embodiment of the present invention 29 obtains 1, the content of 2-structure is 80.3wt%.
The catalytic activity of catalyzer when the method that detects embodiment 29 and provide according to the method described in embodiment 1 is provided after ethylene-propylene-polybutadiene copolymer prepares ethylene-propylene-polybutadiene copolymer, test result is, when the embodiment of the present invention 29 is prepared ethylene-propylene-polybutadiene copolymer, the catalytic activity of catalyzer is 156.7g/mmol, and the catalytic activity of catalyzer is higher.
Glass transition temp, number-average molecular weight, propylene content and the double bond content of the ethylene-propylene-polybutadiene copolymer obtaining according to the method test embodiment of the present invention 29 described in embodiment 1, test result is as shown in table 1, as shown in Table 1, ethylene-propylene-polybutadiene copolymer that the embodiment of the present invention 29 obtains has good curability.
Tensile strength, 300% stress at definite elongation, elongation at break and the Shao Er hardness of the ethylene-propylene-polybutadiene copolymer obtaining according to the method test embodiment of the present invention 29 described in embodiment 1, test result is as shown in table 2, as shown in Table 2, ethylene-propylene-polybutadiene copolymer that the embodiment of the present invention 29 obtains has good mechanical property.
Embodiment 30
Prepare ethylene-propylene-polybutadiene copolymer according to the method described in embodiment 23, different is to adopt FeCl 2feCl in alternative embodiment 23 3, adopt the dimethylphosphite in butyl thiocyanide alternative embodiment 23.
According to the method described in embodiment 1, test implementation example 30 prepares in the polyhutadiene of polyhutadiene reaction system in ethylene-propylene-polybutadiene copolymer process 1, the content of 2-structure, and test result is, in the polyhutadiene that the embodiment of the present invention 30 obtains 1, the content of 2-structure is 55.4wt%.
The catalytic activity of catalyzer when the method that detects embodiment 30 and provide according to the method described in embodiment 1 is provided after ethylene-propylene-polybutadiene copolymer prepares ethylene-propylene-polybutadiene copolymer, test result is, when the embodiment of the present invention 30 is prepared ethylene-propylene-polybutadiene copolymer, the catalytic activity of catalyzer is 175.2g/mmol, and the catalytic activity of catalyzer is higher.
Glass transition temp, number-average molecular weight, propylene content and the double bond content of the ethylene-propylene-polybutadiene copolymer obtaining according to the method test embodiment of the present invention 30 described in embodiment 1, test result is as shown in table 1, as shown in Table 1, ethylene-propylene-polybutadiene copolymer that the embodiment of the present invention 30 obtains has good curability.
Embodiment 31
Prepare ethylene-propylene-polybutadiene copolymer according to the method described in embodiment 23, that different is the FeCl adopting in isocaprylic acid iron alternative embodiment 23 3, adopt the dimethylphosphite in dimethyl sulfoxide (DMSO) alternative embodiment 23.
According to the method described in embodiment 1, test implementation example 31 prepares in the polyhutadiene of polyhutadiene reaction system in ethylene-propylene-polybutadiene copolymer process 1, the content of 2-structure, and test result is, in the polyhutadiene that the embodiment of the present invention 31 obtains 1, the content of 2-structure is 53.2wt%.
The catalytic activity of catalyzer when the method that detects embodiment 31 and provide according to the method described in embodiment 1 is provided after ethylene-propylene-polybutadiene copolymer prepares ethylene-propylene-polybutadiene copolymer, test result is, when the embodiment of the present invention 31 is prepared ethylene-propylene-polybutadiene copolymer, the catalytic activity of catalyzer is 171.8g/mmol, and the catalytic activity of catalyzer is higher.
Glass transition temp, number-average molecular weight, propylene content and the double bond content of the ethylene-propylene-polybutadiene copolymer obtaining according to the method test embodiment of the present invention 31 described in embodiment 1, test result is as shown in table 1, as shown in Table 1, ethylene-propylene-polybutadiene copolymer that the embodiment of the present invention 31 obtains has good curability.
Tensile strength, 300% stress at definite elongation, elongation at break and the Shao Er hardness of the ethylene-propylene-polybutadiene copolymer obtaining according to the method test embodiment of the present invention 31 described in embodiment 1, test result is as shown in table 2, as shown in Table 2, ethylene-propylene-polybutadiene copolymer that the embodiment of the present invention 31 obtains has good mechanical property.
Embodiment 32
Prepare ethylene-propylene-polybutadiene copolymer according to the method described in embodiment 23, different is to adopt Fe (phen) 2feCl in alternative embodiment 23 3, adopt the dimethylphosphite in positive propyl ether alternative embodiment 23.
According to the method described in embodiment 1, test implementation example 32 prepares in the polyhutadiene of polyhutadiene reaction system in ethylene-propylene-polybutadiene copolymer process 1, the content of 2-structure, and test result is, in the polyhutadiene that the embodiment of the present invention 32 obtains 1, the content of 2-structure is 23.6wt%.
The catalytic activity of catalyzer when the method that detects embodiment 32 and provide according to the method described in embodiment 1 is provided after ethylene-propylene-polybutadiene copolymer prepares ethylene-propylene-polybutadiene copolymer, test result is, when the embodiment of the present invention 32 is prepared ethylene-propylene-polybutadiene copolymer, the catalytic activity of catalyzer is 180.1g/mmol, and the catalytic activity of catalyzer is higher.
Glass transition temp, number-average molecular weight, propylene content and the double bond content of the ethylene-propylene-polybutadiene copolymer obtaining according to the method test embodiment of the present invention 32 described in embodiment 1, test result is as shown in table 1, as shown in Table 1, ethylene-propylene-polybutadiene copolymer that the embodiment of the present invention 32 obtains has good curability.
Embodiment 33
The divinyl hexane solution that is 0.1mol/L by 20mL volumetric molar concentration, the MoCl of 0.05mmol 5, 0.05mmol triphenylphosphine and 0.50mmol HClAlN (CH 3) 2add successively in the 0.5L of nitrogen replacement reactor, under 3MPa, the condition of 70 ℃, carry out the first polyreaction of 20min, the polyhutadiene reaction system obtaining;
The polyhutadiene reaction system obtaining is carried out to examination of infrared spectrum and proton nmr spectra test, by known to the comprehensive analysis of examination of infrared spectrum result and proton nmr spectra test result, in the polyhutadiene of the polyhutadiene reaction system that the embodiment of the present invention 33 obtains 1, the content of 2-structure is 56.9wt%.
In above-mentioned polyhutadiene reaction system, add successively 200ml hexane, 0.15mmol VC1 4, 8.00mmol HClAlN (CH 3) 2with 3.00mmol benzene sulfonyl chloride, the mixture obtaining is stirred; In described mixture, pass into ethene and propylene mixed gas again, under 5MPa, the condition of 20 ℃, carry out the second polyreaction of 20min; In described ethene and propylene mixed gas, ethene and propylene mol ratio are 4:5.
After above-mentioned the second polyreaction finishes, in the reaction soln obtaining, add the acidic alcohol that 5mL hydrochloric acid mass concentration is 5%, obtain reaction product; By described reaction product with after washing with alcohol at 40 ℃ vacuum-drying to constant weight, obtain ethylene-propylene-polybutadiene copolymer.
The catalytic activity of catalyzer when the method that detects embodiment 33 and provide according to the method described in embodiment 1 is provided after ethylene-propylene-polybutadiene copolymer prepares ethylene-propylene-polybutadiene copolymer, test result is, when the embodiment of the present invention 33 is prepared ethylene-propylene-polybutadiene copolymer, the catalytic activity of catalyzer is 178.7g/mmol, and the catalytic activity of catalyzer is higher.
Glass transition temp, number-average molecular weight, propylene content and the double bond content of the ethylene-propylene-polybutadiene copolymer obtaining according to the method test embodiment of the present invention 33 described in embodiment 1, test result is as shown in table 1, as shown in Table 1, ethylene-propylene-polybutadiene copolymer that the embodiment of the present invention 33 obtains has good curability.
Embodiment 34
Prepare ethylene-propylene-polybutadiene copolymer according to the method described in embodiment 33, different is to adopt MoO 2(OCH 3) 2moCl in alternative embodiment 33 5, adopt the dimethylphosphite in diethyl phosphite alternative embodiment 33.
According to the method described in embodiment 1, test implementation example 34 prepares in the polyhutadiene of polyhutadiene reaction system in ethylene-propylene-polybutadiene copolymer process 1, the content of 2-structure, and test result is, in the polyhutadiene that the embodiment of the present invention 34 obtains 1, the content of 2-structure is 88.5wt%.
The catalytic activity of catalyzer when the method that detects embodiment 34 and provide according to the method described in embodiment 1 is provided after ethylene-propylene-polybutadiene copolymer prepares ethylene-propylene-polybutadiene copolymer, test result is, when the embodiment of the present invention 34 is prepared ethylene-propylene-polybutadiene copolymer, the catalytic activity of catalyzer is 146.7g/mmol, and the catalytic activity of catalyzer is higher.
Glass transition temp, number-average molecular weight, propylene content and the double bond content of the ethylene-propylene-polybutadiene copolymer obtaining according to the method test embodiment of the present invention 34 described in embodiment 1, test result is as shown in table 1, as shown in Table 1, ethylene-propylene-polybutadiene copolymer that the embodiment of the present invention 34 obtains has good curability.
Tensile strength, 300% stress at definite elongation, elongation at break and the Shao Er hardness of the ethylene-propylene-polybutadiene copolymer obtaining according to the method test embodiment of the present invention 34 described in embodiment 1, test result is as shown in table 2, as shown in Table 2, ethylene-propylene-polybutadiene copolymer that the embodiment of the present invention 34 obtains has good mechanical property.
Embodiment 35
Prepare ethylene-propylene-polybutadiene copolymer according to the method described in embodiment 33, different is to adopt MoCl 3(C 2h 5cOO) 2moCl in alternative embodiment 33 5, adopt the dimethylphosphite in triphenylphosphate alternative embodiment 33.
According to the method described in embodiment 1, test implementation example 35 prepares in the polyhutadiene of polyhutadiene reaction system in ethylene-propylene-polybutadiene copolymer process 1, the content of 2-structure, and test result is, in the polyhutadiene that the embodiment of the present invention 35 obtains 1, the content of 2-structure is 78.4wt%.
The catalytic activity of catalyzer when the method that detects embodiment 35 and provide according to the method described in embodiment 1 is provided after ethylene-propylene-polybutadiene copolymer prepares ethylene-propylene-polybutadiene copolymer, test result is, when the embodiment of the present invention 35 is prepared ethylene-propylene-polybutadiene copolymer, the catalytic activity of catalyzer is 151.2g/mmol, and the catalytic activity of catalyzer is higher.
Glass transition temp, number-average molecular weight, propylene content and the double bond content of the ethylene-propylene-polybutadiene copolymer obtaining according to the method test embodiment of the present invention 35 described in embodiment 1, test result is as shown in table 1, as shown in Table 1, ethylene-propylene-polybutadiene copolymer that the embodiment of the present invention 35 obtains has good curability.
Embodiment 36
Prepare ethylene-propylene-polybutadiene copolymer according to the method described in embodiment 33, different is to adopt MoCl 3(OCH 3) 2moCl in alternative embodiment 33 5, adopt the dimethylphosphite in tritolyl phosphate alternative embodiment 33.
According to the method described in embodiment 1, test implementation example 36 prepares in the polyhutadiene of polyhutadiene reaction system in ethylene-propylene-polybutadiene copolymer process 1, the content of 2-structure, and test result is, in the polyhutadiene that the embodiment of the present invention 36 obtains 1, the content of 2-structure is 80.3wt%.
The catalytic activity of catalyzer when the method that detects embodiment 36 and provide according to the method described in embodiment 1 is provided after ethylene-propylene-polybutadiene copolymer prepares ethylene-propylene-polybutadiene copolymer, test result is, when the embodiment of the present invention 36 is prepared ethylene-propylene-polybutadiene copolymer, the catalytic activity of catalyzer is 161.4g/mmol, and the catalytic activity of catalyzer is higher.
Glass transition temp, number-average molecular weight, propylene content and the double bond content of the ethylene-propylene-polybutadiene copolymer obtaining according to the method test embodiment of the present invention 36 described in embodiment 1, test result is as shown in table 1, as shown in Table 1, ethylene-propylene-polybutadiene copolymer that the embodiment of the present invention 36 obtains has good curability.
Embodiment 37
Prepare ethylene-propylene-polybutadiene copolymer according to the method described in embodiment 33, that different is the MoCl adopting in isocaprylic acid molybdenum alternative embodiment 33 5, adopt the dimethylphosphite in ethamine alternative embodiment 33.
According to the method described in embodiment 1, test implementation example 37 prepares in the polyhutadiene of polyhutadiene reaction system in ethylene-propylene-polybutadiene copolymer process 1, the content of 2-structure, and test result is, in the polyhutadiene that the embodiment of the present invention 37 obtains 1, the content of 2-structure is 55.4wt%.
The catalytic activity of catalyzer when the method that detects embodiment 37 and provide according to the method described in embodiment 1 is provided after ethylene-propylene-polybutadiene copolymer prepares ethylene-propylene-polybutadiene copolymer, test result is, when the embodiment of the present invention 37 is prepared ethylene-propylene-polybutadiene copolymer, the catalytic activity of catalyzer is 172.7g/mmol, and the catalytic activity of catalyzer is higher.
Glass transition temp, number-average molecular weight, propylene content and the double bond content of the ethylene-propylene-polybutadiene copolymer obtaining according to the method test embodiment of the present invention 37 described in embodiment 1, test result is as shown in table 1, as shown in Table 1, ethylene-propylene-polybutadiene copolymer that the embodiment of the present invention 37 obtains has good curability.
Tensile strength, 300% stress at definite elongation, elongation at break and the Shao Er hardness of the ethylene-propylene-polybutadiene copolymer obtaining according to the method test embodiment of the present invention 37 described in embodiment 1, test result is as shown in table 2, as shown in Table 2, ethylene-propylene-polybutadiene copolymer that the embodiment of the present invention 37 obtains has good mechanical property.
Embodiment 38
Prepare ethylene-propylene-polybutadiene copolymer according to the method described in embodiment 33, that different is the MoCl adopting in molybdenum naphthenate alternative embodiment 33 5, adopt the dimethylphosphite in 1,10-phenanthroline alternative embodiment 33.
According to the method described in embodiment 1, test implementation example 38 prepares in the polyhutadiene of polyhutadiene reaction system in ethylene-propylene-polybutadiene copolymer process 1, the content of 2-structure, and test result is, in the polyhutadiene that the embodiment of the present invention 38 obtains 1, the content of 2-structure is 88.4wt%.
The catalytic activity of catalyzer when the method that detects embodiment 38 and provide according to the method described in embodiment 1 is provided after ethylene-propylene-polybutadiene copolymer prepares ethylene-propylene-polybutadiene copolymer, test result is, when the embodiment of the present invention 38 is prepared ethylene-propylene-polybutadiene copolymer, the catalytic activity of catalyzer is 144.9g/mmol, and the catalytic activity of catalyzer is higher.
Glass transition temp, number-average molecular weight, propylene content and the double bond content of the ethylene-propylene-polybutadiene copolymer obtaining according to the method test embodiment of the present invention 38 described in embodiment 1, test result is as shown in table 1, as shown in Table 1, ethylene-propylene-polybutadiene copolymer that the embodiment of the present invention 38 obtains has good curability.
Embodiment 39
Prepare ethylene-propylene-polybutadiene copolymer according to the method described in embodiment 33, that different is the MoCl adopting in Methionin complexing molybdenum alternative embodiment 33 5, adopt CaH 2dimethylphosphite in alternative embodiment 33.
According to the method described in embodiment 1, test implementation example 39 prepares in the polyhutadiene of polyhutadiene reaction system in ethylene-propylene-polybutadiene copolymer process 1, the content of 2-structure, and test result is, in the polyhutadiene that the embodiment of the present invention 39 obtains 1, the content of 2-structure is 83.2wt%.
The catalytic activity of catalyzer when the method that detects embodiment 39 and provide according to the method described in embodiment 1 is provided after ethylene-propylene-polybutadiene copolymer prepares ethylene-propylene-polybutadiene copolymer, test result is, when the embodiment of the present invention 39 is prepared ethylene-propylene-polybutadiene copolymer, the catalytic activity of catalyzer is 180.7g/mmol, and the catalytic activity of catalyzer is higher.
Glass transition temp, number-average molecular weight, propylene content and the double bond content of the ethylene-propylene-polybutadiene copolymer obtaining according to the method test embodiment of the present invention 39 described in embodiment 1, test result is as shown in table 1, as shown in Table 1, ethylene-propylene-polybutadiene copolymer that the embodiment of the present invention 39 obtains has good curability.
Embodiment 40
Prepare ethylene-propylene-polybutadiene copolymer according to the method described in embodiment 33, different is to adopt MoO 3moCl in alternative embodiment 33 5, adopt I 2dimethylphosphite in alternative embodiment 33.
According to the method described in embodiment 1, test implementation example 40 prepares in the polyhutadiene of polyhutadiene reaction system in ethylene-propylene-polybutadiene copolymer process 1, the content of 2-structure, and test result is, in the polyhutadiene that the embodiment of the present invention 40 obtains 1, the content of 2-structure is 86.2wt%.
The catalytic activity of catalyzer when the method that detects embodiment 40 and provide according to the method described in embodiment 1 is provided after ethylene-propylene-polybutadiene copolymer prepares ethylene-propylene-polybutadiene copolymer, test result is, when the embodiment of the present invention 40 is prepared ethylene-propylene-polybutadiene copolymer, the catalytic activity of catalyzer is 180.8g/mmol, and the catalytic activity of catalyzer is higher.
Glass transition temp, number-average molecular weight, propylene content and the double bond content of the ethylene-propylene-polybutadiene copolymer obtaining according to the method test embodiment of the present invention 40 described in embodiment 1, test result is as shown in table 1, as shown in Table 1, ethylene-propylene-polybutadiene copolymer that the embodiment of the present invention 40 obtains has good curability.
Embodiment 41
The isocaprylic acid nickel of the divinyl hexane solution that is 0.1mol/L by 20mL volumetric molar concentration, 0.05mmol, the boron trifluoride of 0.05mmol and 0.50mmol triisobutyl aluminium add successively in the 0.5L of nitrogen replacement reactor, under 3MPa, the condition of 0 ℃, carry out the first polyreaction of 60min, the polyhutadiene reaction system obtaining;
The polyhutadiene reaction system obtaining is carried out to examination of infrared spectrum and proton nmr spectra test, by known to the comprehensive analysis of examination of infrared spectrum result and proton nmr spectra test result, in the polyhutadiene of the polyhutadiene reaction system that the embodiment of the present invention 41 obtains 1, the content of 2-structure is 77.2wt%.
In above-mentioned polyhutadiene reaction system, add successively 200ml hexane, 0.15mmol VOC1 3, 8.00mmol trichlorine triethyl two aluminium and 1.5mmol CHCl 3, the mixture obtaining is stirred; In described mixture, pass into ethene and propylene mixed gas again, under 6MPa, the condition of 0 ℃, carry out the second polyreaction of 45min; In described ethene and propylene mixed gas, ethene and propylene mol ratio are 1:3.
After above-mentioned the second polyreaction finishes, in the reaction soln obtaining, add the acidic alcohol that 5mL hydrochloric acid mass concentration is 5%, obtain reaction product; By described reaction product with after washing with alcohol at 40 ℃ vacuum-drying to constant weight, obtain ethylene-propylene-polybutadiene copolymer.
The catalytic activity of catalyzer when the method that detects embodiment 41 and provide according to the method described in embodiment 1 is provided after ethylene-propylene-polybutadiene copolymer prepares ethylene-propylene-polybutadiene copolymer, test result is, when the embodiment of the present invention 41 is prepared ethylene-propylene-polybutadiene copolymer, the catalytic activity of catalyzer is 178.5g/mmol, and the catalytic activity of catalyzer is higher.
Glass transition temp, number-average molecular weight, propylene content and the double bond content of the ethylene-propylene-polybutadiene copolymer obtaining according to the method test embodiment of the present invention 41 described in embodiment 1, test result is as shown in table 1, as shown in Table 1, ethylene-propylene-polybutadiene copolymer that the embodiment of the present invention 41 obtains has good curability.
Tensile strength, 300% stress at definite elongation, elongation at break and the Shao Er hardness of the ethylene-propylene-polybutadiene copolymer obtaining according to the method test embodiment of the present invention 41 described in embodiment 1, test result is as shown in table 2, as shown in Table 2, ethylene-propylene-polybutadiene copolymer that the embodiment of the present invention 41 obtains has good mechanical property.
Embodiment 42
Prepare ethylene-propylene-polybutadiene copolymer according to the method described in embodiment 41, different is the isocaprylic acid nickel adopting in nickel naphthenate alternative embodiment 41, adopts the boron trifluoride in boron trifluoride diethyl etherate alternative embodiment 41.
According to the method described in embodiment 1, test implementation example 42 prepares in the polyhutadiene of polyhutadiene reaction system in ethylene-propylene-polybutadiene copolymer process 1, the content of 2-structure, and test result is, in the polyhutadiene that the embodiment of the present invention 42 obtains 1, the content of 2-structure is 74.5wt%.
The catalytic activity of catalyzer when the method that detects embodiment 42 and provide according to the method described in embodiment 1 is provided after ethylene-propylene-polybutadiene copolymer prepares ethylene-propylene-polybutadiene copolymer, test result is, when the embodiment of the present invention 42 is prepared ethylene-propylene-polybutadiene copolymer, the catalytic activity of catalyzer is 172.5g/mmol, and the catalytic activity of catalyzer is higher.
Glass transition temp, number-average molecular weight, propylene content and the double bond content of the ethylene-propylene-polybutadiene copolymer obtaining according to the method test embodiment of the present invention 42 described in embodiment 1, test result is as shown in table 1, as shown in Table 1, ethylene-propylene-polybutadiene copolymer that the embodiment of the present invention 42 obtains has good curability.
Embodiment 43
Prepare ethylene-propylene-polybutadiene copolymer according to the method described in embodiment 41, different is to adopt Ni (acac) 2isocaprylic acid nickel in alternative embodiment 41, adopts the boron trifluoride in boron trifluoride methyl ether alternative embodiment 41.
According to the method described in embodiment 1, test implementation example 43 prepares in the polyhutadiene of polyhutadiene reaction system in ethylene-propylene-polybutadiene copolymer process 1, the content of 2-structure, and test result is, in the polyhutadiene that the embodiment of the present invention 43 obtains 1, the content of 2-structure is 55.4wt%.
The catalytic activity of catalyzer when the method that detects embodiment 43 and provide according to the method described in embodiment 1 is provided after ethylene-propylene-polybutadiene copolymer prepares ethylene-propylene-polybutadiene copolymer, test result is, when the embodiment of the present invention 43 is prepared ethylene-propylene-polybutadiene copolymer, the catalytic activity of catalyzer is 168.2g/mmol, and the catalytic activity of catalyzer is higher.
Glass transition temp, number-average molecular weight, propylene content and the double bond content of the ethylene-propylene-polybutadiene copolymer obtaining according to the method test embodiment of the present invention 43 described in embodiment 1, test result is as shown in table 1, as shown in Table 1, ethylene-propylene-polybutadiene copolymer that the embodiment of the present invention 43 obtains has good curability.
Comparative example 1
In the reaction vessel of the 0.5L fully replacing with nitrogen, add the hexane of 300mL, the VOC1 of 0.10mmol 3, trichlorine triethyl two aluminium of 3.0mmol, 0.15g1, the polyhutadiene that 2-structural content is 20wt% and the ethyl trichloroacetate of 0.60mmol; At 20 ℃, make the pressure of described reactor reach 4MPa to the mixed gas that passes into ethene and propylene in described reactor, carry out the polyreaction of 15 minutes, in described mixed gas, the mol ratio of ethene and propylene is 1:2; After described polyreaction finishes, in the polymeric reaction product obtaining, add the ethanol solution hydrochloride that 5mL hydrochloric acid mass concentration is 5%, then for polymerisate, after washing with alcohol, vacuum-drying, can obtain ethylene-propylene-polybutadiene copolymer by described.
The catalytic activity of catalyzer when the method that detects comparative example 1 and provide according to the method described in embodiment 1 is provided after ethylene-propylene-polybutadiene copolymer prepares ethylene-propylene-polybutadiene copolymer, test result is, when comparative example 1 of the present invention is prepared ethylene-propylene-polybutadiene copolymer, the catalytic activity of catalyzer is 108.07g/mmol, and the catalytic activity of catalyzer is lower.
Glass transition temp, number-average molecular weight, propylene content and the double bond content of the ethylene-propylene-polybutadiene copolymer obtaining according to the method test comparative example 1 of the present invention described in embodiment 1, test result is as shown in table 1.
Adopt multi-angle laser light scattering system and gel chromatograph combined system (MALLS-GPC/SEC) to test the relation between number of branches and the molecular weight of ethylene-propylene-polybutadiene copolymer that the embodiment of the present invention obtains, as shown in Figure 4, Fig. 4 is the relation curve between number of branches and the molecular weight of ethylene-propylene-polybutadiene copolymer of obtaining of the embodiment of the present invention to test result.Find out as shown in Figure 4, the number of branches of ethylene-propylene-polybutadiene copolymer provided by the invention increases along with the increase of molecular weight, and ethylene-propylene-polybutadiene copolymer provided by the invention has long chain branched, makes it have good mechanical property.
Glass transition temp, number-average molecular weight, propylene content and the double bond content test result of ethylene-propylene-polybutadiene copolymer that table 1 embodiment of the present invention and comparative example obtain
Figure BDA0000465318940000421
Figure BDA0000465318940000431
Tensile strength, 300% stress at definite elongation, elongation at break and the Shao Er hardness test result of ethylene-propylene-polybutadiene copolymer that table 2 embodiment of the present invention obtains
Figure BDA0000465318940000432
Figure BDA0000465318940000441
The preparation method who the invention provides a kind of ethylene-propylene-polybutadiene copolymer, comprises the following steps: a, under the effect of the first catalyst system, divinyl is carried out to the first polyreaction, and obtain polyhutadiene reaction system; Described the first catalyst system comprises, the first catalyzer, electron donor and the first aluminum contained compound, described the first catalyzer comprises one or more in Titanium series catalyst, nickel catalyst, chromium-based catalysts, molybdenum series catalyst, Fe-series catalyst and cobalt series catalyst; Described electron donor comprises one or more in itrogenous organic substance, oxygen-bearing organic matter, sulfurous organic compound, phosphorus-containing matter, alkalimetal hydride, halogen simple substance and fluorine boron compound; Described the first aluminum contained compound comprises one or more in the derivative of aluminum alkyls and aluminum hydride; B, under the effect of the second catalyst system, ethene and propylene are carried out to the second polyreaction in described polyhutadiene reaction system, obtain ethylene-propylene-polybutadiene copolymer; Described the second catalyst system comprises the second catalyzer, the second aluminum contained compound and activator, and described the second catalyzer comprises vanadium series catalyst, and described the second aluminum contained compound comprises one or more in the derivative of aluminum alkyls and aluminum hydride; Described activator comprises containing oxygen and contains one or more in nitrogen compound, Organohalogen compounds and sulfonyl chloride compound.In the present invention, comprise the first catalyzer, the first catalyst system of electron donor and the first aluminum contained compound is to comprising the second catalyzer, the catalytic activity of the second catalyst system of the second aluminum contained compound and activator does not affect, between the catalyzer adopting while preparing polyhutadiene due to the present invention and the catalyzer that adopts while preparing ethylene-propylene-polybutadiene copolymer, do not influence each other, make the present invention not introduce and affect catalyzed ethylene in the process of preparing polyhutadiene, the impurity of the catalyst activity of propylene and polyhutadiene polymerization, the impurity of catalyst activity while not preparing ethylene-propylene-polybutadiene copolymer containing impact in the polyhutadiene of preparing due to the present invention, therefore method provided by the invention catalytic activity of catalyzer in the time preparing ethylene-propylene-polybutadiene copolymer is higher, the consumption of catalyzer is less, method provided by the invention has reduced the production cost of ethylene-propylene-polybutadiene copolymer effectively.
In addition, both contained the two keys that can be used for sulfuration in ethylene-propylene-polybutadiene copolymer provided by the invention, and had again long chain branched, therefore ethylene-propylene-polybutadiene copolymer provided by the invention has good curability and mechanical property.And do not influence each other between the catalyzer that adopts while preparing polyhutadiene of the present invention and the catalyzer that adopts while preparing ethylene-propylene-polybutadiene copolymer, make the present invention in polyhutadiene reaction system, prepare ethylene-propylene-polybutadiene copolymer by direct in-situ, compared with prior art, the present invention has avoided preparing in the process of polyhutadiene polyhutadiene solution has been separated, the operation of purifying, therefore preparation method's technique of ethylene-propylene-polybutadiene copolymer provided by the invention is simple, be convenient to scale operation ethylene-propylene-polybutadiene copolymer.
The explanation of above embodiment is just for helping to understand method of the present invention and core concept thereof.It should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention, can also carry out some improvement and modification to the present invention, these improvement and modification also fall in the protection domain of the claims in the present invention.

Claims (10)

1. a preparation method for ethylene-propylene-polybutadiene copolymer, comprises the following steps:
A, under the effect of the first catalyst system, divinyl is carried out to the first polyreaction, obtain polyhutadiene reaction system; Described the first catalyst system comprises, the first catalyzer, electron donor and the first aluminum contained compound, described the first catalyzer comprises one or more in Titanium series catalyst, nickel catalyst, chromium-based catalysts, molybdenum series catalyst, Fe-series catalyst and cobalt series catalyst;
Described electron donor comprises one or more in itrogenous organic substance, oxygen-bearing organic matter, sulfurous organic compound, phosphorus-containing matter, alkalimetal hydride, halogen simple substance and fluorine boron compound;
Described the first aluminum contained compound comprises one or more in the derivative of aluminum alkyls and aluminum hydride;
B, under the effect of the second catalyst system, ethene and propylene are carried out to the second polyreaction in described polyhutadiene reaction system, obtain ethylene-propylene-polybutadiene copolymer; Described the second catalyst system comprises the second catalyzer, the second aluminum contained compound and activator, and described the second catalyzer comprises vanadium series catalyst;
Described the second aluminum contained compound comprises one or more in the derivative of aluminum alkyls and aluminum hydride;
Described activator comprises containing oxygen and contains one or more in nitrogen compound, Organohalogen compounds and sulfonyl chloride compound.
2. method according to claim 1, is characterized in that, in described step a, the mol ratio of the first catalyzer, electron donor, the first aluminum contained compound and divinyl is 1:(1～15): (10～100): (20～1200).
3. method according to claim 1, is characterized in that, in described step a, the reaction pressure of the first polyreaction is 1MPa～3MPa.
4. method according to claim 1, is characterized in that, in described step a, the temperature of reaction of the first polyreaction is 0 ℃～70 ℃.
5. method according to claim 1, is characterized in that, in described step a, the reaction times of the first polyreaction is 20min～60min.
6. want the method described in 1 according to right, it is characterized in that, in described step a, in the polyhutadiene of polyhutadiene reaction system 1, the content of 2-structure is 20wt%～90wt%.
7. method according to claim 1, is characterized in that, in described step a, in the divinyl of polyhutadiene reaction system and described step b, the mol ratio of the second catalyzer is (13～400): l;
In described step b, the mol ratio of activator and the second catalyzer is (5～20): 1;
In described step b, the mol ratio of the second aluminum contained compound and the second catalyzer is (40～66): 1.
8. method according to claim 1, is characterized in that, in described step b, the reaction pressure of the second polyreaction is 2MPa～6MPa.
9. method according to claim 1, is characterized in that, in described step b, the temperature of reaction of the second polyreaction is 0 ℃～70 ℃.
10. method according to claim 1, is characterized in that, in described step b, the reaction times of the second polyreaction is 20min～70min.
CN201410048843.9A 2014-02-12 2014-02-12 Preparation method of ethylene-propylene-polybutadiene copolymer Pending CN103804607A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201410048843.9A CN103804607A (en) 2014-02-12 2014-02-12 Preparation method of ethylene-propylene-polybutadiene copolymer

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201410048843.9A CN103804607A (en) 2014-02-12 2014-02-12 Preparation method of ethylene-propylene-polybutadiene copolymer

Publications (1)

Publication Number Publication Date
CN103804607A true CN103804607A (en) 2014-05-21

Family

ID=50702035

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201410048843.9A Pending CN103804607A (en) 2014-02-12 2014-02-12 Preparation method of ethylene-propylene-polybutadiene copolymer

Country Status (1)

Country Link
CN (1) CN103804607A (en)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104391076A (en) * 2014-11-03 2015-03-04 乌鲁木齐市华泰隆化学助剂有限公司 Detection method of content of bis (3,5,5-trimethyl hexanoyl) peroxide in initiator Tx-36
CN104530272A (en) * 2014-12-23 2015-04-22 中国科学院长春应用化学研究所 Catalyst for polydiene synthesis and preparation method thereof
CN113277954A (en) * 2021-06-17 2021-08-20 英德市匠心新材料股份有限公司 Amino acid metal chelate micro-nano powder and preparation method thereof
CN114763390A (en) * 2021-01-11 2022-07-19 中国石油化工股份有限公司 Method for improving activity and stability of main catalyst for molybdenum-series high-vinyl butadiene polymerization reaction
CN114874554A (en) * 2021-02-05 2022-08-09 中国石油化工股份有限公司 Ethylene propylene diene monomer/polypropylene thermoplastic elastomer composition, thermoplastic elastomer material and application
WO2024054387A1 (en) * 2022-09-08 2024-03-14 Entegris, Inc. Bis (arene) metal complexes and related methods

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1557847A (en) * 2002-12-27 2004-12-29 中国科学院长春应用化学研究所 Process for preparing high vinyl polybutadiene rubber
CN1639250A (en) * 2002-03-12 2005-07-13 巴塞尔聚烯烃意大利有限公司 Polyolefin compositions having high fluidity
JP2007063391A (en) * 2005-08-31 2007-03-15 Ube Ind Ltd Manufacturing process of modified butadiene rubber
CN101709105A (en) * 2009-12-02 2010-05-19 中国科学院长春应用化学研究所 Ethylene-propylene-diene methylene using liquid-state oligomers of diolefin as third monomer and method for preparing same
CN102863590A (en) * 2012-10-17 2013-01-09 中国科学院长春应用化学研究所 Preparation method of EPDM (Ethylene-Propylene-Diene Monomer) rubber

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1639250A (en) * 2002-03-12 2005-07-13 巴塞尔聚烯烃意大利有限公司 Polyolefin compositions having high fluidity
CN1557847A (en) * 2002-12-27 2004-12-29 中国科学院长春应用化学研究所 Process for preparing high vinyl polybutadiene rubber
JP2007063391A (en) * 2005-08-31 2007-03-15 Ube Ind Ltd Manufacturing process of modified butadiene rubber
CN101709105A (en) * 2009-12-02 2010-05-19 中国科学院长春应用化学研究所 Ethylene-propylene-diene methylene using liquid-state oligomers of diolefin as third monomer and method for preparing same
CN102863590A (en) * 2012-10-17 2013-01-09 中国科学院长春应用化学研究所 Preparation method of EPDM (Ethylene-Propylene-Diene Monomer) rubber

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
姚伟等: "原位聚合法制备具有长链支化的新型三元乙丙橡胶", 《2013年全国高分子学术论文报告会》 *

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104391076A (en) * 2014-11-03 2015-03-04 乌鲁木齐市华泰隆化学助剂有限公司 Detection method of content of bis (3,5,5-trimethyl hexanoyl) peroxide in initiator Tx-36
CN104530272A (en) * 2014-12-23 2015-04-22 中国科学院长春应用化学研究所 Catalyst for polydiene synthesis and preparation method thereof
CN104530272B (en) * 2014-12-23 2017-04-19 中国科学院长春应用化学研究所 Catalyst for polydiene synthesis and preparation method thereof
CN114763390A (en) * 2021-01-11 2022-07-19 中国石油化工股份有限公司 Method for improving activity and stability of main catalyst for molybdenum-series high-vinyl butadiene polymerization reaction
CN114874554A (en) * 2021-02-05 2022-08-09 中国石油化工股份有限公司 Ethylene propylene diene monomer/polypropylene thermoplastic elastomer composition, thermoplastic elastomer material and application
CN114874554B (en) * 2021-02-05 2023-11-10 中国石油化工股份有限公司 Ethylene propylene diene monomer/polypropylene thermoplastic elastomer composition, thermoplastic elastomer material and application
CN113277954A (en) * 2021-06-17 2021-08-20 英德市匠心新材料股份有限公司 Amino acid metal chelate micro-nano powder and preparation method thereof
CN113277954B (en) * 2021-06-17 2023-04-28 英德市匠心新材料股份有限公司 Amino acid metal chelate micro-nano powder and preparation method thereof
WO2024054387A1 (en) * 2022-09-08 2024-03-14 Entegris, Inc. Bis (arene) metal complexes and related methods

Similar Documents

Publication Publication Date Title
CN103804607A (en) Preparation method of ethylene-propylene-polybutadiene copolymer
Wang et al. Bis (imino) pyridines incorporating doubly fused eight-membered rings as conformationally flexible supports for cobalt ethylene polymerization catalysts
Abu-Surrah et al. New bis (imino) pyridine-iron (II)-and cobalt (II)-based catalysts: synthesis, characterization and activity towards polymerization of ethylene
Pellecchia et al. Isotactic‐specific polymerization of propene with an iron‐based catalyst: polymer end groups and regiochemistry of propagation
Gao et al. Chromium complexes supported by phenanthrene-imine derivative ligands: synthesis, characterization and catalysis on isoprene cis-1, 4 polymerization
Xiao et al. Accelerating ethylene polymerization using secondary metal ions in tetrahydrofuran
CN109879992B (en) Application of para-phenyl-containing alpha-diimine nickel (II) complex in catalyzing 3-heptene chain walking polymerization
Rosar et al. Palladium complexes with simple iminopyridines as catalysts for polyketone synthesis
Zhang et al. A Trinuclear Pd− Diimine Catalyst for “Core-First” Synthesis of Three-Arm Star Polyethylenes via Ethylene “Living” Polymerization
Rosar et al. Palladium‐Catalyzed Ethylene/Methyl Acrylate Co‐Oligomerization: The Effect of a New Nonsymmetrical α‐Diimine with the 1, 4‐Diazabutadiene Skeleton
CN110305169A (en) A kind of substitution bipyridyl trivalent iron complex and the preparation method and application thereof
Perry et al. Organometallic mediated radical polymerization of vinyl acetate using bis (imino) pyridine vanadium trichloride complexes
CN109762027A (en) para-aryl-containing substituted α -diimine nickel complex and preparation method and application thereof
CN103819618A (en) Preparation method of ethylene-propylene-polyisoprene copolymer
CN103842392B (en) Group of the lanthanides diimine pyridine complex, include the catalyst system and catalyzing of this diimine pyridine complex and the method for the (co) polymerization for conjugated diene
Talzi et al. Ethylene polymerization in the presence of iron (II) 2, 6-bis (imine) pyridine complex: structures of key intermediates
US20170362352A1 (en) Metal-phosphinesulfonate acetonitrile complex for insertion copolymerization of functional olefins
CN105985473A (en) Catalyst precursor and preparation method thereof, catalyst and application thereof and ethylene homopolymerization method
Michiue et al. Tantalum complexes incorporating tris (pyrazolyl) borate ligands: syntheses, structures, and ethylene polymerization behavior
Valdebenito et al. Acetamidine complexes as catalysts for ethylene polymerization
EP2104687B1 (en) Single component, phosphine-free, initiators for ethylene homopolymerization and copolymerization with functionalized co-monomers
WO2016156243A1 (en) Polymerization of michael-type monomers
Vaultier et al. New insights on Ni-based catalysts for stereospecific polymerization of butadiene
CN109879997A (en) A kind of preparation method of trans- 3,4- poly- (1- aryl -1,3- butadiene)
RU2487898C1 (en) Method of producing norbornene oligomers with terminal double bond

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
RJ01 Rejection of invention patent application after publication

Application publication date: 20140521

RJ01 Rejection of invention patent application after publication