CN103951777B - A kind of ethylene propylene diene rubber and preparation method thereof - Google Patents
A kind of ethylene propylene diene rubber and preparation method thereof Download PDFInfo
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Abstract
The invention provides the preparation method of a kind of ethylene propylene diene rubber, including: under the effect of vanadium series catalyst, alkyl aluminum compound and organic chloride, polyfunctionality compound, ethylene and propylene are carried out polyreaction, obtains ethylene propylene diene rubber；Described polyfunctionality compound includes trimethylolpropane trimethacrylate, diethylene glycol double methacrylate, divinylbenzene or N, N ' methylene bisacrylamide base amide.The present invention uses described polyfunctionality compound to be that Third monomer carries out polyreaction with ethylene and propylene, the addition of described Third monomer will not reduce the catalysis activity of vanadium series catalyst, compared with prior art, the preparation method catalytic efficiency of the ethylene propylene diene rubber that the present invention provides is higher.Additionally, described polyfunctionality compound is cheap, therefore the preparation method cost of the ethylene propylene diene rubber that the present invention provides is relatively low；And in the ethylene propylene diene rubber for preparing of the present invention content of double bond suitably, odorlessness.
Description
Technical field
The present invention relates to the preparing technical field of macromolecular material, particularly relate to a kind of ethylene propylene diene rubber and
Its preparation method.
Background technology
Ethylene propylene diene rubber is ethylene, propylene and the terpolymer of non-conjugated diene hydrocarbon, and it has excellent
Oxidative resistance, ozone resistants and corrosion resistance more, simultaneously because ethylene propylene diene rubber belongs to polyolefin man
Race, it also has fabulous cure.Ethylene propylene diene rubber can be widely used in auto industry, building
Industry and Electrical and Electronic industry.
The Third monomer that at present industrialized production ethylene propylene diene rubber uses have ethylidene norbornene (ENB),
The non-conjugated diene hydrocarbon such as dicyclopentadiene (DCPD) and Isosorbide-5-Nitrae-hexadiene (HD).Application No.
201310033554.7 Chinese patent disclose the preparation method of a kind of ethylene propylene diene rubber, detailed process
For: with nitrogen, reactor is sufficiently displaced from, be sequentially added in reactor the most in proportion polymer solvent,
Vanadium series catalyst solution, alkyl aluminum solutions and activator, the liquid of Third monomer cyclopentenes-dicyclopentadiene
Oligomer, is sufficiently stirred in backward reaction vessel adding ethylene, propylene and the gaseous mixture of hydrogen, controls anti-
The pressure answered is 0.2MPa～0.4MPa, reacts stopped reaction after 30min～90min at 20 DEG C～100 DEG C,
By the sodium hydroxide solution that reaction solution weight percent concentration is 20% obtained wash, evaporate rearmounted
It is dried to constant weight in the vacuum tank of 50 DEG C, obtains ethylene propylene diene rubber.
The ethylene propylene diene rubber that prior art prepares has preferable curability and processing characteristics, but
It is that the Third monomer that prior art uses can reduce the work of catalyst during preparing ethylene propylene diene rubber
Property, therefore the preparation method catalytic efficiency of the ethylene propylene diene rubber that prior art provides is relatively low.
Summary of the invention
In view of this, it is an object of the invention to provide a kind of ethylene propylene diene rubber and preparation method thereof, this
The preparation method of the ethylene propylene diene rubber that invention provides has higher catalytic efficiency.
The invention provides the preparation method of a kind of ethylene propylene diene rubber, including:
Under the effect of vanadium series catalyst, alkyl aluminum compound and organic chloride, by polyfunctionality chemical combination
Thing, propylene and ethylene carry out polyreaction, obtain ethylene propylene diene rubber；Described polyfunctionality compound bag
Include trimethylolpropane trimethacrylate, diethylene glycol double methacrylate, divinylbenzene or N, N '-methylene
Base double propenyl amide.
Preferably, described vanadium series catalyst, alkyl aluminum compound, organic chloride and polyfunctionality chemical combination
The mol ratio of thing is 1:(20～100): (2～15): (5～40).
Preferably, described polyfunctionality compound mass fraction in described ethylene propylene diene rubber is
1%～10%.
Preferably, the temperature of described polyreaction is 0 DEG C～70 DEG C.
Preferably, the time of described polyreaction is 0.5 hour～2.5 hours.
Preferably, the pressure of described polyreaction is 0.1MPa～0.8MPa.
Preferably, the one during described vanadium series catalyst is the compound of vanadium and the coordination compound of vanadium.
Preferably, described organic chloride includes ethyl trichloroacetate, monochloro methane, dichloromethane or three
Chloromethanes.
Preferably, described alkyl aluminum compound is Al2(C2H5)3Cl3、Al3(C2H5)3Cl3、Al(C2H5)2Cl
With Al (C2H5)Cl2In one or more.
The invention provides a kind of ethylene propylene diene rubber, the method described in technique scheme prepare.
The invention provides the preparation method of a kind of ethylene propylene diene rubber, in vanadium series catalyst, alkyl calorize
Under the effect of compound and organic chloride, polyfunctionality compound, ethylene and propylene are carried out polyreaction,
Obtain ethylene propylene diene rubber；Described polyfunctionality compound include trimethylolpropane trimethacrylate, two
Ethylene glycol diacrylate, divinylbenzene or N, N '-methylene bisacrylamide base amide.The present invention uses institute
Stating polyfunctionality compound as Third monomer, and propylene dilute with second carries out polyreaction, and the described 3rd is single
The addition of body will not reduce the catalysis activity of vanadium series catalyst, and compared with prior art, the present invention provides
The preparation method catalytic efficiency of ethylene propylene diene rubber is higher.Additionally, the price of described polyfunctionality compound
Cheap, the preparation method cost making the ethylene propylene diene rubber that the present invention provides is relatively low；And prepared by the present invention
In the ethylene propylene diene rubber obtained the content of double bond suitably, odorlessness.
Test result indicate that, the catalytic efficiency of the ethylene propylene diene rubber preparation method that the present invention provides is 2360
Gram polymer/gram vanadium～8060 grams of polymer/gram vanadium；The double bond quality of the ethylene propylene diene rubber prepared contains
Amount is 2.2%～8.6%, odorlessness.
Accompanying drawing explanation
Fig. 1 is the nmr spectrum of the ethylene propylene diene rubber that the embodiment of the present invention 1 obtains；
The gel permeation chromatography of the ethylene propylene diene rubber that Fig. 2 is the embodiment of the present invention 1 and comparative example 1 obtains
Figure.
Detailed description of the invention
The invention provides the preparation method of a kind of ethylene propylene diene rubber, including:
Under the effect of vanadium series catalyst, alkyl aluminum compound and organic chloride, by polyfunctionality chemical combination
Thing, propylene and ethylene carry out polyreaction, obtain ethylene propylene diene rubber；Described polyfunctionality compound bag
Include trimethylolpropane trimethacrylate, diethylene glycol double methacrylate, divinylbenzene or N, N '-methylene
Base double propenyl amide.
The present invention uses described polyfunctionality compound to be that Third monomer carries out with ethylene and propylene being polymerized instead
Should, the addition of described Third monomer will not reduce the catalyst activity of vanadium series catalyst, with prior art phase
Ratio, the preparation method catalytic efficiency of the ethylene propylene diene rubber that the present invention provides is higher.Additionally, described many officials
Energy degree compound cheap, the preparation method cost making the ethylene propylene diene rubber that the present invention provides is relatively low；
And in the ethylene propylene diene rubber for preparing of the present invention content of double bond suitably, odorlessness.
The present invention is under the effect of vanadium series catalyst, alkyl aluminum compound and organic chloride, by multifunctional
Degree compound, propylene and ethylene carry out polyreaction, obtain ethylene propylene diene rubber；Described polyfunctionality
Compound include trimethylolpropane trimethacrylate, diethylene glycol double methacrylate, divinylbenzene or
N, N '-methylene bisacrylamide base amide.The present invention is preferably by vanadium series catalyst, alkyl aluminum compound, many officials
Energy degree compound and organic chloride mixing, add ethylene in the mixture obtained and propylene be polymerized
Reaction, obtains ethylene propylene diene rubber.
In the present invention, described vanadium series catalyst is preferably the one in the compound of vanadium and the coordination compound of vanadium,
More preferably VCl3、VCl4、VOCl3Or VOCl3NMOH, VOCl3In nMOH, 2.5≤n
≤ 3.5, M be carbon atom number be the alkyl of 5～8；Most preferably VOCl3Or VOCl3·3C8H17OH。
The present invention does not has special restriction to the source of described vanadium series catalyst, uses those skilled in the art to know
The vanadium series catalyst of mentioned kind, obtain as bought by market.
In the present invention, described alkyl aluminum compound is preferably Al2(C2H5)3Cl3、Al3(C2H5)3Cl3、
Al(C2H5)2Cl and Al (C2H5)Cl2In one or more, more preferably Al2(C2H5)3Cl3、
Al3(C2H5)3Cl3With Al (C2H5)2One or more in Cl, most preferably Al2(C2H5)3Cl3With
Al3(C2H5)3Cl3In one or both.It is special that the source of described alkyl aluminum compound is not had by the present invention
Limit, use the alkyl aluminum compound of mentioned kind well known to those skilled in the art, as can be by city
Field is bought and is obtained.
In the present invention, described organic chloride preferably includes ethyl trichloroacetate, monochloro methane, dichloro
Methane or chloroform, more preferably include ethyl trichloroacetate or dichloromethane.The present invention is to described organic
Muriatic source does not has special restriction, uses the organic of mentioned kind well known to those skilled in the art
Chloride, obtains as bought by market.
In the present invention, described polyfunctionality compound includes trimethylolpropane trimethacrylate, diethyl
Diol acrylate, divinylbenzene or N, N '-methylene bisacrylamide base amide；Preferably include three hydroxyl first
Base propane triacrylate (TMPTA), diethylene glycol double methacrylate (DEGDM) or divinyl
Base benzene (DVB)；More preferably include trimethylolpropane trimethacrylate or diethylene glycol double methacrylate.
Described polyfunctionality compound and alkyl aluminum compound are preferably formed solution and carry out above-mentioned poly-by the present invention
Close reaction.In the present invention, the mol ratio of described polyfunctionality compound and alkyl aluminum compound is preferably
1:(1～5), more preferably 1:(2～4), most preferably 1:(2.5～3.5).In the present invention, institute
Stating alkyl aluminum compound can be identical with alkyl aluminum compound described in technique scheme, it is also possible to different.
The present invention carries out polyreaction for Third monomer with ethylene and propylene with described polyfunctionality compound,
The addition of described Third monomer will not reduce the catalysis activity of vanadium series catalyst, therefore the three of present invention offer
The preparation method catalytic efficiency of unit's EP rubbers is higher；The most described polyfunctionality compound cheap,
The preparation method cost making the ethylene propylene diene rubber that the present invention provides is relatively low.The present invention is to described polyfunctionality
The source of compound does not has special restriction, uses many officials of mentioned kind well known to those skilled in the art
Energy degree compound, obtains as bought by market.
In the present invention, described vanadium series catalyst, alkyl aluminum compound, organic chloride and polyfunctionality
The mol ratio of compound is preferably 1:(20～100): (2～15): (5～40), more preferably 1:(25～80):
(5～15): (10～35), most preferably 1:(30～80): (5～12): (10～30).In the present invention
In, described polyfunctionality compound mass fraction in described ethylene propylene diene rubber is preferably 1%～10%,
More preferably 2%～9%, most preferably 2.2%～8.6%.In the present invention, the pressure of described polyreaction
It is preferably 0.1MPa～0.8MPa, more preferably 0.3MPa～0.7MPa, most preferably 0.4MPa.At this
In invention, the mass ratio of described ethylene and propylene is preferably 1:(1～5), more preferably 1:(2～4),
Most preferably 1:2.0.In the present invention, the temperature of described polyreaction is preferably 0 DEG C～70 DEG C, more preferably
It is 20 DEG C～50 DEG C, most preferably 20 DEG C～45 DEG C.In the present invention, the time of described polyreaction is preferred
It is 0.5 hour～2.5 hours, more preferably 0.5 hour～2 hours, most preferably 0.5 hour.
In the present invention, the reaction raw materials of described polyreaction the most also includes organic solvent, and the present invention is excellent
Be selected under the effect of vanadium series catalyst, alkyl aluminum compound and organic chloride, by polyfunctionality compound,
Propylene and ethylene carry out polyreaction in organic solvent, obtain ethylene propylene diene rubber.In the present invention,
Described organic solvent preferably carbon number be the alkane of 5～10, more preferably carbon number be the alkane of 6～8
Hydrocarbon, most preferably hexane or heptane.In the present invention, described polyfunctionality compound and organic solvent
Total mass ratio is preferably 1:(150～220), more preferably 1:(160～200), most preferably 1:(185～200).
The present invention is preferably sealing, is carrying out described polyreaction under conditions of protective gas, as can be
Replace with protective gas in the sealed reactor of 2～3 times and carry out described polyreaction.In the present invention,
Described protective gas is preferably noble gas or nitrogen, more preferably argon or nitrogen, most preferably nitrogen
Gas.The present invention preferably carries out described polyreaction under conditions of stirring.The present invention side to described stirring
Method does not has special restriction, uses stirring technique scheme well known to those skilled in the art.
After above-mentioned polyreaction completes, the product obtained preferably is mixed by the present invention with ethanol solution hydrochloride
Wash after conjunction, be dried, obtain ethylene propylene diene rubber；More preferably ethanol solution hydrochloride is joined described instead
Wash after answering in product mixing, be dried, obtain ethylene propylene diene rubber.In the present invention, described hydrochloric acid second
The mass concentration of alcoholic solution is preferably 3%～8%, more preferably 4%～6%, and most preferably 5%.The present invention
The source of described ethanol solution hydrochloride is not had special restriction, uses well known to those skilled in the art joining
The method preparation of solution processed.It is special that the consumption of described ethanol solution hydrochloride is not had by the present invention
Limiting, described ethanol solution hydrochloride can make above-mentioned product be completely dissolved.
The present invention does not has special restriction to the method for described mixing, uses well known to those skilled in the art
Hybrid technology scheme.The present invention does not has special restriction to described washing and dry method, uses
Washing well known to those skilled in the art and dry technology scheme.In the present invention, described washing
Reagent is preferably ethanol.In invention, described being dried is preferably vacuum drying.
The invention provides a kind of ethylene propylene diene rubber, preparation method described in technique scheme prepare.
The ethylene propylene diene rubber that the present invention provides uses polyfunctionality compound described in technique scheme to be the 3rd list
Body, the double bond content of this ethylene propylene diene rubber is higher and odorlessness.
The present invention uses the method for nuclear magnetic resonance, NMR to test the double bond content of the ethylene propylene diene rubber obtained, test
Result is, the double bond mass content of the ethylene propylene diene rubber that the present invention prepares is 2.2%～8.6%；This
Invention uses differential calorimetry (DSC) to test the glass transition temperature of the ethylene propylene diene rubber obtained,
The glass transition temperature of the ethylene propylene diene rubber that test result provides for the present invention is-45.6 DEG C～-58.3 DEG C；
The number-average molecular weight of the ethylene propylene diene rubber that the present invention is obtained by gel permeation chromatography (GPC) test
And molecular weight distribution, the number-average molecular weight of the ethylene propylene diene rubber that test result provides for the present invention is
8.4×104～12.4 × 104, molecular weight distribution is 3.2～5.2.
The present invention calculates the catalytic efficiency of ethylene propylene diene rubber preparation method described in technique scheme, institute
State catalytic efficiency by the quality of ethylene propylene diene rubber that obtains according to method described in technique scheme with made
Vanadium series catalyst in the ratio of quality of vanadium.Result of calculation is, the ethylene-propylene-diene monomer that the present invention provides
The catalytic efficiency of glue preparation method is 2360 grams of polymer/gram vanadium～8060 grams of polymer/gram vanadium.
The invention provides the preparation method of a kind of ethylene propylene diene rubber, in vanadium series catalyst, alkyl calorize
Under the effect of compound and organic chloride, polyfunctionality compound, ethylene and propylene are carried out polyreaction,
Obtain ethylene propylene diene rubber；Described polyfunctionality compound include trimethylolpropane trimethacrylate, two
Ethylene glycol diacrylate, divinylbenzene or N, N '-methylene bisacrylamide base amide.The present invention uses institute
Stating polyfunctionality compound is that Third monomer carries out polyreaction with ethylene, propylene, described Third monomer
Addition will not reduce the catalysis activity of vanadium series catalyst, compared with prior art, the ternary that the present invention provides
The preparation method polymerization efficiency of EP rubbers is higher.Additionally, described polyfunctionality compound is cheap,
The preparation method cost making the ethylene propylene diene rubber that the present invention provides is relatively low；And what the present invention prepared
In ethylene propylene diene rubber, the content of double bond is higher, odorlessness.
In order to further appreciate that the present invention, the ethylene propylene diene rubber present invention provided below in conjunction with embodiment
And preparation method thereof be described in detail, but it is to be understood that these descriptions are intended merely to further illustrate
The features and advantages of the present invention, and they can not be interpreted as limiting the scope of the present invention.
In the examples below, the raw material that the present invention uses during preparing ethylene propylene diene rubber is city
Sell commodity.
Embodiment 1
Reactor nitrogen is replaced 3 times and is kept the sealing of reactor；Under conditions of stirring, successively
The VOCl of 0.1mmol is added in described reactor3, the Al of 2.0mmol2(C2H5)3Cl3, 2.0mmol
Al3(C2H5)3Cl3With the mixed solution of the trimethylolpropane trimethacrylate (TMPTA) of 1.1g,
Mix after the ethyl trichloroacetate (ETCA) of 0.6mmol and the hexane of 300mL, to the mixture obtained
In be passed through the ethylene and the mixed gas of propylene that mass ratio is 1:2, carry out 30min at 0.4MPa, at 20 DEG C
Polyreaction；Use after adding the ethanol solution hydrochloride that mass percent is 5% in the product obtained
Washing with alcohol, by the product vacuum drying after washing, obtains the ethylene propylene diene rubber of 20.5g.
The ethylene propylene diene rubber embodiment of the present invention 1 obtained carries out nuclear magnetic resonance, NMR test, test result such as figure
Shown in 1, Fig. 1 is the nmr spectrum of the ethylene propylene diene rubber that the embodiment of the present invention 1 obtains, by figure
1 is analyzed understanding, and the double bond mass content of the ethylene propylene diene rubber that the embodiment of the present invention 1 obtains is 8.6%；
By the glass transition temperature of the ethylene propylene diene rubber that the DSC test embodiment of the present invention 1 obtains；Pass through
The number-average molecular weight of the ethylene propylene diene rubber that the GPC test embodiment of the present invention 1 obtains and molecular weight distribution, survey
Test result is as shown in table 1 and Fig. 2, and table 1 turns for the vitrification of the ethylene propylene diene rubber that the embodiment of the present invention obtains
The test result of temperature, number-average molecular weight and molecular weight distribution, Fig. 2 is the embodiment of the present invention 1 and compares
The gel permeation chromatography figure of the ethylene propylene diene rubber that example 1 obtains, in Fig. 2, curve 1 is that the embodiment of the present invention 1 obtains
The gel permeation chromatography figure of the ethylene propylene diene rubber arrived.
The ethylene propylene diene rubber system provided according to the method test embodiment of the present invention 1 described in technique scheme
The catalytic efficiency of Preparation Method, the ethylene propylene diene rubber preparation method that test result provides for the embodiment of the present invention 1
Catalytic efficiency be 8060 grams of polymer/gram vanadium.
Embodiment 2
Reactor nitrogen is replaced 2 times and is kept the sealing of reactor；Under conditions of stirring, successively
The VOCl of 0.1mmol is added in described reactor3, the Al (C of 6.0mmol2H5)2Cl2, the three of 0.6mmol
Ethyl chloroacetate, 1.06g TMPTA and 300mL hexane after mix, be passed through in the mixture obtained
Mass ratio is ethylene and the propylene mixed gas of 1:3,0.4MPa, carry out 30min at 30 DEG C polymerization anti-
Should；Washing with alcohol is used after adding the ethanol solution hydrochloride that mass percent is 5% in the product obtained,
By the product vacuum drying after washing, obtain the ethylene propylene diene rubber of 15.6g.
The double bond of the ethylene propylene diene rubber that the embodiment of the present invention 2 obtains is tested according to the method described in embodiment 1
Content, test result is that the double bond mass content of the ethylene propylene diene rubber that the embodiment of the present invention 2 obtains is
6.2%；The glass of the ethylene propylene diene rubber that the embodiment of the present invention 2 obtains is tested according to the method described in embodiment 1
Glass conversion temperature, number-average molecular weight and molecular weight distribution, test result is as shown in table 1.
The ethylene propylene diene rubber preparation side that the embodiment of the present invention 2 provides is tested according to the method described in embodiment 1
The catalytic efficiency of method, urging of the ethylene propylene diene rubber preparation method that test result provides for the embodiment of the present invention 2
Changing efficiency is 6370 grams of polymer/gram vanadium.
Embodiment 3
Reactor argon is replaced 2 times and is kept the sealing of reactor；Under conditions of stirring, successively
The VCl of 0.1mmol is added in described reactor3, the Al (C of 3.0mmol2H5)Cl2, the Al of 3.0mmol
(C2H5)Cl2With the mixed solution of diethylene glycol double methacrylate (DEGDM) of 0.3g, 0.4mmol
Mix after the hexane of monochloro methane and 300mL, be passed through than the ethylene and third for 1:1 in the mixture obtained
Alkene mixed gas, in 0.6MPa, the polyreaction that carries out 60min at 30 DEG C；In the product obtained
Using washing with alcohol after adding the ethanol solution hydrochloride that mass percent is 5%, the product after washing is true
Empty dry, obtain the ethylene propylene diene rubber of 14.6g.
The double bond of the ethylene propylene diene rubber that the embodiment of the present invention 3 obtains is tested according to the method described in embodiment 1
Content, test result is that the double bond mass content of the ethylene propylene diene rubber that the embodiment of the present invention 3 obtains is
2.2%；The glass of the ethylene propylene diene rubber that the embodiment of the present invention 3 obtains is tested according to the method described in embodiment 1
Glass conversion temperature, number-average molecular weight and molecular weight distribution, test result is as shown in table 1.
The ethylene propylene diene rubber preparation side that the embodiment of the present invention 3 provides is tested according to the method described in embodiment 1
The catalytic efficiency of method, urging of the ethylene propylene diene rubber preparation method that test result provides for the embodiment of the present invention 3
Changing efficiency is 5740 grams of polymer/gram vanadium.
Embodiment 4
Reactor nitrogen is replaced 3 times and is kept the sealing of reactor；Under conditions of stirring, successively
The VCl of 0.1mmol is added in described reactor4, the Al of 5.0mmol2(C2H5)3Cl3, the Al of 4.0mmol
(C2H5)Cl2Mix with after the dichloromethane of TMPTA, 0.7mmol of 1.18g and the hexane of 300mL, to
The mixture obtained is passed through mass ratio than for the ethylene of 1:2.5 and propylene mixed gas, 0.8MPa, 30
The polyreaction of 120min is carried out at DEG C；Adding mass percent in the product obtained is the salt of 5%
By washing with alcohol after acid ethanol solution, by the product vacuum drying after washing, obtain the ternary of 16.4g
EP rubbers.
The double bond of the ethylene propylene diene rubber that the embodiment of the present invention 4 obtains is tested according to the method described in embodiment 1
Content, test result is that the double bond mass content of the ethylene propylene diene rubber that the embodiment of the present invention 4 obtains is
8.6%；The glass of the ethylene propylene diene rubber that the embodiment of the present invention 4 obtains is tested according to the method described in embodiment 1
Glass conversion temperature, number-average molecular weight and molecular weight distribution, test result is as shown in table 1.
The ethylene propylene diene rubber preparation side that the embodiment of the present invention 4 provides is tested according to the method described in embodiment 1
The catalytic efficiency of method, urging of the ethylene propylene diene rubber preparation method that test result provides for the embodiment of the present invention 4
Changing efficiency is 6440 grams of polymer/gram vanadium.
Embodiment 5
Reactor nitrogen is replaced 2 times and is kept the sealing of reactor；Under conditions of stirring, successively
The VOCl of 0.1mmol is added in described reactor3·3C8H17The Al of OH, 3.5mmol3(C2H5)3Cl3、
The Al of 7.5mmol3(C2H5)3Cl3Divinylbenzene (DVB), the chloroform of 0.5mmol with 0.35g
Mix with after the hexane of 300mL, in the mixture obtained, be passed through ethylene and propylene that mass ratio is 1:3.5
Mixed gas, in 0.7MPa, the polyreaction that carries out 150min at 30 DEG C；To the product obtained
Middle addition mass percent be 5% ethanol solution hydrochloride after by washing with alcohol, by the product after washing
Vacuum drying, obtains the ethylene propylene diene rubber of 17.4g.
The double bond of the ethylene propylene diene rubber that the embodiment of the present invention 5 obtains is tested according to the method described in embodiment 1
Content, test result is that the double bond mass content of the ethylene propylene diene rubber that the embodiment of the present invention 5 obtains is
3.2%；The glass of the ethylene propylene diene rubber that the embodiment of the present invention 5 obtains is tested according to the method described in embodiment 1
Glass conversion temperature, number-average molecular weight and molecular weight distribution, test result is as shown in table 1.
The ethylene propylene diene rubber preparation side that the embodiment of the present invention 5 provides is tested according to the method described in embodiment 1
The catalytic efficiency of method, urging of the ethylene propylene diene rubber preparation method that test result provides for the embodiment of the present invention 5
Changing efficiency is 6840 grams of polymer/gram vanadium.
Embodiment 6
Preparing ethylene propylene diene rubber according to the method described in embodiment 2, except for the difference that employing 40 DEG C is anti-
Answer the reaction temperature of 30 DEG C in temperature alternative embodiment 2, use N, N '-methylene bisacrylamide base amide simultaneously
Alternate embodiment 2 obtains TMPTA, obtains the ethylene propylene diene rubber of 14.1g.
The double bond of the ethylene propylene diene rubber that the embodiment of the present invention 6 obtains is tested according to the method described in embodiment 1
Content, test result is that the double bond mass content of the ethylene propylene diene rubber that the embodiment of the present invention 6 obtains is
5.4%；The glass of the ethylene propylene diene rubber that the embodiment of the present invention 6 obtains is tested according to the method described in embodiment 1
Glass conversion temperature, number-average molecular weight and molecular weight distribution, test result is as shown in table 1.
The ethylene propylene diene rubber preparation side that the embodiment of the present invention 6 provides is tested according to the method described in embodiment 1
The catalytic efficiency of method, urging of the ethylene propylene diene rubber preparation method that test result provides for the embodiment of the present invention 6
Changing efficiency is 5540 grams of polymer/gram vanadium.
Embodiment 7
Preparing ethylene propylene diene rubber according to the method described in embodiment 2, except for the difference that employing 50 DEG C is anti-
Answer the reaction temperature of 30 DEG C in temperature alternative embodiment 2, obtain the ethylene propylene diene rubber of 10.4g.
The double bond of the ethylene propylene diene rubber that the embodiment of the present invention 7 obtains is tested according to the method described in embodiment 1
Content, test result is that the double bond mass content of the ethylene propylene diene rubber that the embodiment of the present invention 7 obtains is
4.4%；The glass of the ethylene propylene diene rubber that the embodiment of the present invention 7 obtains is tested according to the method described in embodiment 1
Glass conversion temperature, number-average molecular weight and molecular weight distribution, test result is as shown in table 1.
The ethylene propylene diene rubber preparation side that the embodiment of the present invention 7 provides is tested according to the method described in embodiment 1
The catalytic efficiency of method, urging of the ethylene propylene diene rubber preparation method that test result provides for the embodiment of the present invention 7
Changing efficiency is 4090 grams of polymer/gram vanadium.
Embodiment 8
Preparing ethylene propylene diene rubber according to the method described in embodiment 2, except for the difference that employing 60 DEG C is anti-
Answer the reaction temperature of 30 DEG C in temperature alternative embodiment 2, obtain the ethylene propylene diene rubber of 6.4g.
The double bond of the ethylene propylene diene rubber that the embodiment of the present invention 8 obtains is tested according to the method described in embodiment 1
Content, test result is that the double bond mass content of the ethylene propylene diene rubber that the embodiment of the present invention 8 obtains is
3.6%；The glass of the ethylene propylene diene rubber that the embodiment of the present invention 8 obtains is tested according to the method described in embodiment 1
Glass conversion temperature, number-average molecular weight and molecular weight distribution, test result is as shown in table 1.
The ethylene propylene diene rubber preparation side that the embodiment of the present invention 8 provides is tested according to the method described in embodiment 1
The catalytic efficiency of method, urging of the ethylene propylene diene rubber preparation method that test result provides for the embodiment of the present invention 8
Changing efficiency is 2360 grams of polymer/gram vanadium.
Comparative example 1
Reactor nitrogen is replaced 2 times and is kept the sealing of reactor；Under conditions of stirring, successively
The VOCl of 0.1mmol is added in described reactor3, the Al of 4.0mmol2(C2H5)3Cl3, 0.6mmol
Mix after ethyl trichloroacetate, the ethylidene norbornene (ENB) of 2mL and the hexane of 300mL, to obtaining
Mixture in be passed through the ethylene and propylene mixed gas that mass ratio is 1:2, carry out at 0.4MPa, at 20 DEG C
The polyreaction of 30min；Adding mass percent in the product obtained is the ethanol solution hydrochloride of 5%
Afterwards by washing with alcohol, by the product vacuum drying after washing, obtain the ethylene propylene diene rubber of 15.4g.
The double bond of the ethylene propylene diene rubber that comparative example 1 of the present invention obtains is tested according to the method described in embodiment 1
Content, the double bond mass content of the ethylene propylene diene rubber that comparative example 1 of the present invention obtains is 7.4%；According to enforcement
Method described in example 1 tests the number-average molecular weight of the ethylene propylene diene rubber that comparative example 1 of the present invention obtains, test
Result is as in figure 2 it is shown, the gel of Fig. 2 is the embodiment of the present invention 1 and comparative example 1 obtains ethylene propylene diene rubber
Permeation chromatography figure, in Fig. 2, curve 2 is the gel infiltration color of the ethylene propylene diene rubber that comparative example 1 of the present invention obtains
Spectrogram.
The ethylene propylene diene rubber preparation side that comparative example 1 of the present invention provides is tested according to the method described in embodiment 1
The catalytic efficiency of method, urging of the ethylene propylene diene rubber preparation method that test result provides for comparative example 1 of the present invention
Changing efficiency is 6050 grams of polymer/gram vanadium.
Comparative example 2
Preparing ethylene propylene diene rubber according to the method described in comparative example 1, except for the difference that employing 30 DEG C is anti-
Answer temperature to replace the reaction temperature of 20 DEG C in comparative example 1, obtain the ethylene propylene diene rubber of 10.4g.
The double bond of the ethylene propylene diene rubber that comparative example 2 of the present invention obtains is tested according to the method described in embodiment 1
Content, test result is that the double bond mass content of the ethylene propylene diene rubber that comparative example 2 of the present invention obtains is
8.2%.
The ethylene propylene diene rubber preparation side that comparative example 2 of the present invention provides is tested according to the method described in embodiment 1
The catalytic efficiency of method, urging of the ethylene propylene diene rubber preparation method that test result provides for comparative example 2 of the present invention
Changing efficiency is 4090 grams of polymer/gram vanadium.
Comparative example 3
Preparing ethylene propylene diene rubber according to the method described in comparative example 1, except for the difference that employing 40 DEG C is anti-
Answer temperature to replace the reaction temperature of 20 DEG C in comparative example 1, obtain the ethylene propylene diene rubber of 7.8g.
The double bond of the ethylene propylene diene rubber that comparative example 3 of the present invention obtains is tested according to the method described in embodiment 1
Content, test result is that the double bond mass content of the ethylene propylene diene rubber that comparative example 3 of the present invention obtains is
6.4%.
The ethylene propylene diene rubber preparation side that comparative example 3 of the present invention provides is tested according to the method described in embodiment 1
The catalytic efficiency of method, urging of the ethylene propylene diene rubber preparation method that test result provides for comparative example 3 of the present invention
Changing efficiency is 3060 grams of polymer/gram vanadium.
Comparative example 4
Preparing ethylene propylene diene rubber according to the method described in comparative example 1, except for the difference that employing 50 DEG C is anti-
Answer temperature to replace the reaction temperature of 20 DEG C in comparative example 1, obtain the ethylene propylene diene rubber of 4.9g.
The double bond of the ethylene propylene diene rubber that comparative example 4 of the present invention obtains is tested according to the method described in embodiment 1
Content, test result is that the double bond mass content of the ethylene propylene diene rubber that comparative example 4 of the present invention obtains is
4.2%.
The ethylene propylene diene rubber preparation side that comparative example 4 of the present invention provides is tested according to the method described in embodiment 1
The catalytic efficiency of method, urging of the ethylene propylene diene rubber preparation method that test result provides for comparative example 4 of the present invention
Changing efficiency is 1930 grams of polymer/gram vanadium.
Comparative example 5
Preparing ethylene propylene diene rubber according to the method described in comparative example 1, except for the difference that employing 60 DEG C is anti-
Answer temperature to replace the reaction temperature of 20 DEG C in comparative example 1, obtain the ethylene propylene diene rubber of 2.9g.
The double bond of the ethylene propylene diene rubber that comparative example 5 of the present invention obtains is tested according to the method described in embodiment 1
Content, test result is that the double bond mass content of the ethylene propylene diene rubber that comparative example 5 of the present invention obtains is
3.2%.
The ethylene propylene diene rubber preparation side that comparative example 5 of the present invention provides is tested according to the method described in embodiment 1
The catalytic efficiency of method, urging of the ethylene propylene diene rubber preparation method that test result provides for comparative example 5 of the present invention
Changing efficiency is 1140 grams of polymer/gram vanadium.
Comparative example 6
Reactor nitrogen is replaced 2 times and is kept the sealing of reactor；Under conditions of stirring, successively
The VOCl of 0.1mmol is added in described reactor3, the Al of 4.0mmol2(C2H5)3Cl3, 0.6mmol
Mixing after the hexane of ethyl trichloroacetate and 300mL, being passed through volume ratio in the mixture obtained is 1:2's
Ethylene and propylene mixed gas, in 0.4MPa, the polyreaction that carries out 30min at 20 DEG C；Anti-to obtain
Answer and product adds after the ethanol solution hydrochloride that mass percent is 5% by washing with alcohol, will anti-after washing
Answer product vacuum to be dried, obtain the ethylene propylene monomer of 18.1g.
The ethylene propylene monomer preparation side that comparative example 6 of the present invention provides is tested according to the method described in embodiment 1
The catalytic efficiency of method, urging of the ethylene propylene monomer preparation method that test result provides for comparative example 6 of the present invention
Changing efficiency is 7110 grams of polymer/gram vanadium.
The glass transition temperature of ethylene propylene diene rubber that table 1 embodiment of the present invention obtains, number-average molecular weight and
Molecular weight distribution test result
As seen from the above embodiment, the invention provides the preparation method of a kind of ethylene propylene diene rubber, at vanadium
Under the effect of series catalysts, alkyl aluminum compound and organic chloride, by polyfunctionality compound, ethylene
Carry out polyreaction with propylene, obtain ethylene propylene diene rubber；Described polyfunctionality compound includes three hydroxyl first
Base propane triacrylate, diethylene glycol double methacrylate, divinylbenzene or N, N '-methylene bisacrylamide
Base amide.The present invention uses described polyfunctionality compound to be that Third monomer is polymerized with ethylene and propylene
Reaction, the addition of described Third monomer will not reduce the catalysis activity of vanadium series catalyst, with prior art phase
Ratio, the preparation method catalytic efficiency of the ethylene propylene diene rubber that the present invention provides is higher.Additionally, described many officials
Energy degree compound cheap, the preparation method cost of the ethylene propylene diene rubber that the present invention provides is relatively low；
And in the ethylene propylene diene rubber for preparing of the present invention, the content of double bond is moderate, odorlessness.
The explanation of above example is only intended to help to understand method and the core concept thereof of the present invention.Should
Point out, for those skilled in the art, under the premise without departing from the principles of the invention,
The present invention can also be carried out some improvement and modification, these improve and modification also falls into right of the present invention and wants
In the protection domain asked.Multiple amendment to these embodiments is for those skilled in the art
It will be apparent that generic principles defined herein can be without departing from the spirit or scope of the present invention
In the case of realize in other embodiments.Therefore, the present invention be not intended to be limited to shown in this article these
Embodiment, and it is to fit to the widest scope consistent with principles disclosed herein and features of novelty.
Claims (9)
1. a preparation method for ethylene propylene diene rubber, including:
Under the effect of vanadium series catalyst, alkyl aluminum compound and organic chloride, by polyfunctionality compound,
Propylene and ethylene carry out polyreaction, obtain ethylene propylene diene rubber；Described polyfunctionality compound includes three hydroxyls
Propane tri, diethylene glycol double methacrylate, divinylbenzene or N, N '-methylene bisacrylamide
Base amide；The temperature of described polyreaction is 20 DEG C～45 DEG C.
Method the most according to claim 1, it is characterised in that described vanadium series catalyst, alkyl calorize
The mol ratio of compound, organic chloride and polyfunctionality compound is 1:(20～100): (2～15): (5～40).
Method the most according to claim 1, it is characterised in that described polyfunctionality compound is described
Mass content in ethylene propylene diene rubber is 1%～10%.
Method the most according to claim 1, it is characterised in that the time of described polyreaction is 0.5
Hour～2.5 hours.
Method the most according to claim 1, it is characterised in that the pressure of described polyreaction is
0.1MPa～0.8MPa.
Method the most according to claim 1, it is characterised in that described vanadium series catalyst is the chemical combination of vanadium
One in the coordination compound of thing and vanadium.
Method the most according to claim 1, it is characterised in that described organic chloride includes trichlorine vinegar
Acetoacetic ester, monochloro methane, dichloromethane or chloroform.
Method the most according to claim 1, it is characterised in that described alkyl aluminum compound is
Al2(C2H5)3Cl3、Al(C2H5)2Cl and Al (C2H5)Cl2In one or more.
9. an ethylene propylene diene rubber, is prepared by the method described in any one in claim 1～8.
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| US20070112139A1 (en) * | 2005-11-14 | 2007-05-17 | Ellul Maria D | Peroxide-cured thermoplastic vulcanizates and process for making the same |
| 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 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070112139A1 (en) * | 2005-11-14 | 2007-05-17 | Ellul Maria D | Peroxide-cured thermoplastic vulcanizates and process for making the same |
| 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 |
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