CN106589246B - A kind of modified EPT rubber and preparation method thereof - Google Patents
A kind of modified EPT rubber and preparation method thereof Download PDFInfo
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- CN106589246B CN106589246B CN201510684670.4A CN201510684670A CN106589246B CN 106589246 B CN106589246 B CN 106589246B CN 201510684670 A CN201510684670 A CN 201510684670A CN 106589246 B CN106589246 B CN 106589246B
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- 0 O=C(C1*2C3C=CC1C3)OC2=O Chemical compound O=C(C1*2C3C=CC1C3)OC2=O 0.000 description 5
- RUKVGXGTVPPWDD-UHFFFAOYSA-N Cc(cc1C)cc(C)c1N(CC1)CN1c1c(C)cc(C)cc1C Chemical compound Cc(cc1C)cc(C)c1N(CC1)CN1c1c(C)cc(C)cc1C RUKVGXGTVPPWDD-UHFFFAOYSA-N 0.000 description 1
Abstract
The invention discloses a kind of modified EPT rubber and preparation method thereof.The modified EPT rubber is made ethylene propylene diene rubber graft modification by the carbic anhydride of structure shown in formula (1), on the basis of the weight of the modified EPT rubber, the grafting rate of the modified EPT rubber is 0.4-3.5 weight %.The preparation method of the modified EPT rubber includes：Under the conditions of the ring opening cross-metathesis reaction of alkene, in the presence of the catalyst of the structure shown in formula (2), ethylene propylene diene rubber is contacted in organic solvent with carbic anhydride.The preparation method of modified EPT rubber provided by the invention has the advantages that grafting rate height, rapid reaction, step are simply easily implemented, and, modified EPT rubber provided by the invention is compared with unmodified ethylene propylene diene rubber, degree of unsaturation is 0.44-0.68mol/kg, and curingprocess rate improves.
Description
Technical field
The present invention relates to a kind of modified EPT rubber and preparation method thereof.
Background technique
Ethylene propylene diene rubber (EPDM) has the physical and chemical performances such as excellent high resiliency, viscoplasticity, electrical insulating property, in work
The application of engineering plastics toughening and ozone-resistant aging etc. is very prominent.But since ethylene propylene diene rubber belongs to nonpolar rubber
Glue, oil resistant, chemical-resistant reagent, tack and mutual viscosity are poor, it is difficult to be blended with polar polymer, therefore its application range by
To certain limitation.Therefore, ethylene propylene diene rubber is modified to enhance the compatibility of itself and polar polymer and seem especially
It is important.
In the prior art mainly by the way that ethylene propylene diene rubber and maleic anhydride (MAH) are carried out graft reaction, in rubber
Highly polar group is introduced in strand, there is graft highly polar and reactive, so that the graft of preparation is as one
The coupling agent or dispersing agent of the multi-functional macromolecule interfacial compatilizer of kind and filler filled polymer, before having a wide range of applications
Scape.
The graft reaction of rubber and MAH mainly based on radical reaction, can in melt, lotion and solution state into
Row, including the methods of fusion-grafting, irradiation grafting, solution graft copolymerization.Using different initiation systems, the free radical mode of generation is not
Together, grafting rate and grafting efficiency are also different.
The grafting rate that melt grafting is grafted MAH is not high, and remove after the completion of grafting residual monomer and when initiator compared with
For difficulty, products obtained therefrom smell is dense, and Color whiteness is low.The grafting rate and grafting efficiency of irradiation grafting method grafting MAH generally all compares
Melt grafting is high.But irradiation grafting be easy to cause the crosslinking of rubber, and side reaction is not easily controlled, and equipment cost is higher.This
Outside, when reaction temperature exceeds a certain range, polymer molecular chain will appear degradation or crosslinking side reaction.
CN101402711B discloses a kind of method using high-energy ray radiation grafting maleic anhydride with ethylene propylene terpolymer,
It is using ethylene propylene diene rubber as raw material, and using maleic anhydride as grafted monomers, plasticizer, reinforcing agent and vulcanization retarder is added through molten
Melt blending, carries out shooting high the graft that ethylene propylene diene rubber and maleic anhydride is made in beta radiation before melting extrusion, which produces
The grafting rate of object is 1.2-3.6%.
CN102643391B discloses one kind method for preparing grafting maleic anhydride with ethylene propylene terpolymer.This method is by ternary
EP rubbers, initiator, maleic anhydride, styrene monomer, hexamethylphosphoric acid triamide composition pass through melt grafting produce
Grafting maleic anhydride with ethylene propylene terpolymer.The grafting rate of this method is 0.59-1.42%.
Solution grafting is grafted MAH compared with other grafting methods, and reaction condition temperature is low, by-product is few, the grafting of MAH
Rate and utilization rate are all higher.But the reaction time of existing solution grafting is too long, production efficiency is low, and existing grafting method
The pendant double bonds of modified EP rubbers just disappear after being grafted MAH, so that the vulcanization of EP rubbers is more difficult.
Summary of the invention
The purpose of the present invention is overcoming the drawbacks described above of the prior art, a kind of modified EPT rubber and its preparation are provided
Method.
The present invention provides a kind of modified EPT rubber, wherein the modified EPT rubber passes through knot shown in formula (1)
Ethylene propylene diene rubber graft modification is made in the carbic anhydride of structure, using the weight of the modified EPT rubber as base
Standard, the grafting rate of the modified EPT rubber are 0.4-3.5 weight %,
The present invention also provides a kind of preparation method of above-mentioned modified EPT rubber, this method includes：In alkene
Under the conditions of ring opening cross-metathesis reaction, in the presence of the catalyst of the structure shown in formula (2), by ethylene propylene diene rubber and formula (1)
The carbic anhydride of shown structure is contacted in organic solvent,
In formula (2), R1For hydrogen, the alkenyl of C2-C20, the alkynyl of C2-C20, the alkyl of C1-C20, C6-C20 aryl,
The carboxylate of C2-C20, the alkoxy of C1-C20, the alkenyloxy of C2-C20, the chain oxy-acetylene of C2-C20, C6-C20 virtue
Oxygroup, the alkylthio group of C1-C20, the alkyl sulphonyl of C1-C20 or C1-C20 Alkylsulfinyl,
X1And X2Anion ligand is each independently,
L1And L2It is each independently neutral ligand, and optionally L1And L2It can be interconnected to form in two coordinations
Property ligand.
The present invention is by using the ruthenium carbene catalyst catalysis ethylene propylene diene rubber of structure shown in formula (2) and formula (1) institute
Show that the ring opening cross-metathesis reaction of the alkene of the carbic anhydride of structure makes the modified EPT rubber being prepared
Degree of unsaturation is 0.44-0.68mol/kg, also, also has grafting rate high by the modified EPT rubber that this method obtains
Advantage, specifically, the grafting rate of modified EPT rubber provided by the invention are 0.4-3.5 weight %.Furthermore the present invention mentions
The modified EPT method for preparing rubber of confession has the characteristics that rapid reaction and step are simply easily implemented.
Compared with unmodified ethylene propylene diene rubber, curingprocess rate has centainly modified EPT rubber provided by the invention
Raising, the possible reason is the present invention opens the carbic anhydride of structure shown in formula (1) and ethylene propylene diene rubber by alkene
After ring cross-metathesis, the double bond content of the side chain of EP rubbers can be increased, be conducive to sulfidation, so that vulcanization speed
Degree improves.
In addition, the present invention can be obtained by specific catalyst adding manner has higher degree of unsaturation and higher grafting
The modified EPT rubber of rate.Preferably, the catalyst divides in 2-6 addition reaction system, and adjacent addition twice
Time interval be 3-15 minute, arbitrarily twice addition catalyst amount difference account for the total additional amount of catalyst 5 weight % hereinafter, with
The degree of unsaturation and grafting rate that catalyst is conducive to improve modified EPT rubber is added in such mode.
Other features and advantages of the present invention will the following detailed description will be given in the detailed implementation section.
Detailed description of the invention
The drawings are intended to provide a further understanding of the invention, and constitutes part of specification, with following tool
Body embodiment is used to explain the present invention together, but is not construed as limiting the invention.In the accompanying drawings：
Fig. 1 is the infrared spectrogram for the modified EPT rubber that embodiment according to the present invention 1 obtains, wherein a is indicated
The infrared spectroscopy of unmodified ethylene propylene diene rubber, b indicate the infrared spectroscopy of modified EPT rubber.
Specific embodiment
Detailed description of the preferred embodiments below.It should be understood that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
The present invention provides a kind of modified EPT rubber, wherein the modified EPT rubber passes through knot shown in formula (1)
Ethylene propylene diene rubber graft modification is made in the carbic anhydride of structure, using the weight of the modified EPT rubber as base
Standard, the grafting rate of the modified EPT rubber are 0.4-3.5 weight %, preferably 2-3.5 weight %,
Improvements of the invention essentially consist in the modified EPT rubber of offer compared to unmodified EPDM
Rubber, the double bond content in side chain increase, and on the basis of the weight of the modified EPT rubber, the modified ternary second
The grafting rate of third rubber is 0.4-3.5 weight %, and the degree of unsaturation of the modified EPT rubber is 0.44-0.68mol/
kg。
According to the present invention, the weight average molecular weight of the modified EPT rubber is 100,000-40 ten thousand.
According to the present invention, the degree of unsaturation of the modified EPT rubber is 0.44-0.68mol/kg, preferably
0.53-0.68mol/kg。
In the present invention, the degree of unsaturation of the modified EPT rubber passes through iodometric determination.
In accordance with the present invention it is preferred that the preparation method of the modified EPT rubber includes：In the open loop crossover of alkene
Under metathesis reaction conditions, in the presence of the catalyst of the structure shown in formula (2), by structure shown in ethylene propylene diene rubber and formula (1)
Carbic anhydride contacted in organic solvent,
In formula (2), R1For hydrogen, the alkenyl of C2-C20, the alkynyl of C2-C20, the alkyl of C1-C20, C6-C20 aryl,
The carboxylate of C2-C20, the alkoxy of C1-C20, the alkenyloxy of C2-C20, the chain oxy-acetylene of C2-C20, C6-C20 virtue
Oxygroup, the alkylthio group of C1-C20, the alkyl sulphonyl of C1-C20 or C1-C20 Alkylsulfinyl,
X1And X2Anion ligand is each independently,
L1And L2It is each independently neutral ligand, and optionally L1And L2It can be interconnected to form in two coordinations
Property ligand.
In formula (2), R1The preferably aryl of C6-C20, more preferably phenyl.
In formula (2), X1And X2It can be common various anion ligands, such as respectively can be halide ion, preferably
For chloride ion；
In formula (2), L1And L2It respectively can be common various neutral ligands, specific example may include but unlimited
In：Phosphine, amine, thioether, Cabbeen or substituted or unsubstituted imidazolidine.Preferably, L1And L2For phosphine, Cabbeen or substitution or
Unsubstituted imidazolidine.It is highly preferred that L1For substituted or unsubstituted imidazolidine, L2For phosphine.
Phosphine can all be replaced for the hydrogen partial in various phosphine molecules or by organic group the compound to be formed, preferably
For trialkyl phosphine, the organic group is identical or different, selected from alkyl group (alkyl group of such as C1-C10) and can respectively replace
Or unsubstituted naphthenic base (the substituted or unsubstituted naphthenic base of such as C6-C12), preferably it each is selected from substituted or unsubstituted ring
Alkyl, more preferably cyclohexyl.Specifically, the example of the phosphine can include but is not limited to：Trimethyl-phosphine, triethyl phosphine, three
One of normal-butyl phosphine, three sec-butyl phosphines, tripropyl phosphine, three amyl phosphines, three hexyl phosphines, tri octyl phosphine and tricyclohexyl phosphine or
It is a variety of.
Substituted or unsubstituted imidazolidine can be the imidazolidine of structure shown in formula (3),
In formula (3), R2And R3It is each independently the aryl of substituted or unsubstituted C6-C20；R2And R3Each independently
PreferablyR4、R5、R6、R7And R8It is identical or different, it respectively can the alkyl selected from hydrogen or C1-C5；R2With
R3More preferablyR2And R3Further preferablyThe specific example of the alkyl of C1-C5 can
To include but is not limited to：Methyl, ethyl, n-propyl, isopropyl, normal-butyl, sec-butyl, isobutyl group, tert-butyl and n-pentyl.
In the preferred embodiment of the present invention, in formula (2), R1For phenyl, L1For substituted or unsubstituted imidazoles
Alkane, L2For phosphine, X1And X2For chloride ion.In a kind of preferred embodiment of the invention, in formula (2), R1For phenyl, L1ForL2For trialkyl phosphine, X1And X2For chloride ion.
Modified EPT rubber according to the present invention, it is optimal in order to make the catalyst that there is better catalytic effect
Selection of land, the catalyst are the catalyst of structure shown in formula (5),
In above-mentioned formula (5), PCy3Indicate that tricyclohexyl phosphine, Ph indicate phenyl.
Catalyst shown in above-mentioned formula (5) can be commercially available.
According to the present invention, the alkenyl of C2-C20 can be straight chain or branch, and specific example can include but is not limited to：
Vinyl, acrylic, cyclobutenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decene base, undecenyl, ten
Two carbene bases.
According to the present invention, the alkynyl of C2-C20 can be straight chain or branch, and specific example can include but is not limited to：
Acetenyl, propinyl, butynyl, pentynyl, hexin base, heptynyl, octynyl, n-heptylacetylene base, decynyl.
According to the present invention, the alkyl of C1-C20 can be linear chain or branched chain, and specific example can include but is not limited to：
Methyl, ethyl, propyl, butyl, amyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, octadecyl.
According to the present invention, the specific example of the aryl of C6-C20 can include but is not limited to：Phenyl, aminomethyl phenyl, naphthalene.
According to the present invention, the carboxylate of C2-C20 refers to containing in strandGroup, tool
Body example can include but is not limited to：Methyl propionate base, ethyl acetate base, propyl formate base.
According to the present invention, the specific example of the alkoxy of C1-C20 can include but is not limited to：Methoxyl group, ethyoxyl, third
Oxygroup, isopropoxy, butoxy, sec-butoxy, tert-butoxy, amoxy, hexyloxy, oxygroup in heptan, octyloxy, nonyl epoxide, the last of the ten Heavenly stems
Oxygroup, octadecane epoxide.
According to the present invention, the specific example of the alkenyloxy of C2-C20 can include but is not limited to：1- allyloxy, 2- alkene
Butoxy, 1- alkene pentyloxy.
According to the present invention, the specific example of the chain oxy-acetylene of C2-C20 can include but is not limited to：1- propynyloxy base, 2- alkynes
Butoxy, 1- alkynes amoxy.
According to the present invention, the specific example of the aryloxy group of C6-C20 can include but is not limited to：Phenoxy group, naphthalene oxygroup.
According to the present invention, the alkylthio group of C1-C20 is the C1-C20 for the linear chain or branched chain being bonded by a sulphur atom
Alkyl, specific example include but is not limited to：Methyl mercapto (CH3- S-), ethylmercapto group, rosickyite base, butylthio, penta sulfenyl, 1- methyl-prop
Sulfenyl, 2- methyl-prop sulfenyl and 1,1- dimethylethylthio.
According to the present invention, the specific example of the alkyl sulphonyl of C1-C20 can include but is not limited to：Methyl sulphonyl, second
Base sulfonyl, sulfonyl propyl base, butyl sulfonyl, nonyl sulfonyl.
According to the present invention, the specific example of the Alkylsulfinyl of C1-C20 can include but is not limited to：Methyl thionyl
Base, ethylsulfinyl-1 base.
According to the present invention, the addition manner of the catalyst is not particularly limited, can be by catalyst to be added at one time
Mode or the mode that is added several times be added to ethylene propylene diene rubber and contacted with the carbic anhydride of structure shown in formula (1)
Reaction system in, it is contemplated that catalyst, which is added at one time, to be easy so that side reaction occurs for carbic anhydride in reaction system,
It is preferred that the mode being added several times is added.It is highly preferred that the catalyst divides in 2-6 addition reaction system, and it is adjacent twice
Addition time interval be 3-15 minute, arbitrarily the difference of the amount of addition catalyst accounts for 5 weight % of the total additional amount of catalyst twice
Hereinafter, degree of unsaturation and grafting rate that catalyst is conducive to improve modified EPT rubber are added in this way.Into one
It walks preferably, in order to make catalyst play better catalytic effect, by the catalyst as a solution (i.e. by the catalysis
Agent is dissolved in the organic solvent) divide in 2-6 addition reaction system, and adjacent addition time interval twice is 3-15 points
Clock, the difference that the amount of catalyst is arbitrarily added twice account for the 5 weight % or less of the total additional amount of catalyst.
According to the present invention, the ring opening cross-metathesis reaction of the alkene preferably carries out under an inert atmosphere.The inertia
Atmosphere refers to the gas that cannot participate in reaction, such as：One of group 0 element gas or more in nitrogen and the periodic table of elements
Kind, group 0 element gas such as argon gas in the periodic table of elements.
According to the present invention, there is no particular limitation for the condition of the ring opening cross-metathesis reaction of the alkene, can be with ability
The conventional selection in domain, for example, the condition of the ring opening cross-metathesis reaction of the alkene includes：Reaction temperature is 0-150 DEG C, instead
It is 0.1-5 hours between seasonable；Under preferable case, the condition of the ring opening cross-metathesis reaction of the alkene includes：Reaction temperature
It is 20-100 DEG C, the reaction time is 0.1-3 hours.
According to the present invention, the dosage of the ethylene propylene diene rubber, carbic anhydride and the catalyst can be wider
It changes in range, as long as may be implemented to be swift in response and obtain having target saturation degree and the high modified EPT rubber of grafting rate
The purpose of glue, generally, relative to the ethylene propylene diene rubber of 100 parts by weight, the dosage of the carbic anhydride is
0.05-40 parts by weight, preferably 0.5-20 parts by weight；The dosage of the catalyst is 0.05-10 parts by weight, preferably 0.2-5
Parts by weight.
According to the present invention, the ethylene propylene diene rubber can be various ethylene propylene diene rubbers commonly used in the art, such as
On the basis of the total weight of the ethylene propylene diene rubber, the content of ethylene unit unit is 50-70 in the ethylene propylene diene rubber
Weight %, Third monomer content be 4-6 weight %；The weight average molecular weight of the ethylene propylene diene rubber is 100,000-40 ten thousand；It is described
Third monomer can be various Third monomers commonly used in the art, such as can be Isosorbide-5-Nitrae-hexadiene, dicyclopentadiene
(DCPD) and one of 5- ethylidene -2- norbornene or a variety of, preferably 5- ethylidene -2- norbornene (ENB).
When the Third monomer in the ethylene propylene diene rubber is ENB, the modified EPT rubber contains structure list
First A, structural unit B, structural unit C and structural unit D, wherein the structural unit A is the list with structure shown in formula (1 ')
Member, the structural unit B are the unit with structure shown in formula (2 '), and the structural unit C is with structure shown in formula (3 ')
Unit, the structural unit D be the unit with structure shown in formula (4 ')；
According to the present invention, it can be existing various for preparing organic solvent used in the method for modified EPT rubber
Can be as the organic substance of reaction media, under preferable case, the organic solvent is toluene, dimethylbenzene, chlorobenzene, C6-C12
One of cycloalkane, the linear paraffin of C5-C10, tetrahydrofuran, acetone and Isosorbide-5-Nitrae-dioxane are a variety of, further preferably
For toluene, dimethylbenzene, chlorobenzene, pentamethylene, hexamethylene, methyl cyclopentane, cycloheptane, pentane, n-hexane, normal octane, tetrahydro
One of furans, acetone and 1,4- dioxane are a variety of；Most preferably toluene and/or dimethylbenzene.These solvents are ok
It is used alone, can also be used in mixed way.The dosage of the organic solvent can be the conventional selection of this field, no longer superfluous herein
It states.
According to the present invention, the preparation method of the modified EPT rubber further includes purification step.The purification step
It can be the conventional purification step in this field, for example, the reaction solution obtained after reaction is filtered with nickel screen, and into filtrate
Acetone is added and forms precipitating, is then filtered, washed and dried resulting sediment.
According to the present invention, the carbic anhydride of structure shown in the formula (1) can be commercially available, can also be by existing
There is the method for technology to be prepared.For example, the carbic anhydride of structure shown in the formula (1) is prepared by the following method：In Di
Under the conditions of Er Si-Alder reaction, the cyclopentadiene of structure shown in formula (4) is connect in organic solvent with maleic anhydride
Touching,
According to the present invention, the cyclopentadiene of structure shown in the formula (4) and the dosage of maleic anhydride can be wider
In the range of change, as long as the carbic anhydride of structure shown in formula (4) can be generated.Generally, knot shown in the formula (4)
The cyclopentadiene of structure and the molar ratio of maleic anhydride can be 1：0.4-1.2, preferably 1：0.6-1.
According to the present invention, the Diels-Alder reaction condition can be the conventional selection of this field, such as can wrap
It includes：The temperature of reaction is 80-250 DEG C, preferably 100-230 DEG C；The time of reaction is 0.1-50 hours, and preferably 0.5-10 is small
When.
According to the present invention, preparing the organic solvent in carbic anhydride is that existing various can be used as reaction media
Organic substance, under preferable case, the organic solvent is selected from one of ether, tetrahydrofuran and toluene or a variety of.It is described
The dosage of organic solvent is referred to the prior art and is reasonably selected, and details are not described herein.
The preparation method of the carbic anhydride of structure shown in the formula (1) further includes purification step, and the purification step can
To carry out referring to the prior art, details are not described herein.
In addition, the present invention also provides the preparation method of above-mentioned modified EPT rubber, this method includes in alkene
Under the conditions of ring opening cross-metathesis reaction, in the presence of the catalyst of the structure shown in formula (2), by ethylene propylene diene rubber and formula (1)
The carbic anhydride of shown structure is contacted in organic solvent,
In formula (2), R1For hydrogen, the alkenyl of C2-C20, the alkynyl of C2-C20, the alkyl of C1-C20, C6-C20 aryl,
The carboxylate of C2-C20, the alkoxy of C1-C20, the alkenyloxy of C2-C20, the chain oxy-acetylene of C2-C20, C6-C20 virtue
Oxygroup, the alkylthio group of C1-C20, the alkyl sulphonyl of C1-C20 or C1-C20 Alkylsulfinyl,
X1And X2Anion ligand is each independently,
L1And L2It is each independently neutral ligand, and optionally L1And L2It can be interconnected to form in two coordinations
Property ligand.
In formula (2), R1The preferably aryl of C6-C20, more preferably phenyl.
In formula (2), X1And X2It can be common various anion ligands, such as respectively can be halide ion, preferably
For chloride ion；
In formula (2), L1And L2It respectively can be common various neutral ligands, specific example may include but unlimited
In：Phosphine, amine, thioether, Cabbeen or substituted or unsubstituted imidazolidine.Preferably, L1And L2For phosphine, Cabbeen or substitution or
Unsubstituted imidazolidine.It is highly preferred that L1For substituted or unsubstituted imidazolidine, L2For phosphine.
Phosphine can all be replaced for the hydrogen partial in various phosphine molecules or by organic group the compound to be formed, preferably
For trialkyl phosphine, the organic group is identical or different, selected from alkyl group (alkyl group of such as C1-C10) and can respectively replace
Or unsubstituted naphthenic base (the substituted or unsubstituted naphthenic base of such as C6-C12), preferably it each is selected from substituted or unsubstituted ring
Alkyl, more preferably cyclohexyl.The example of the phosphine is consistent with above description, and details are not described herein.
Substituted or unsubstituted imidazolidine can be the imidazolidine of structure shown in formula (3),
In formula (3), R2And R3It is each independently the aryl of substituted or unsubstituted C6-C20；R2And R3Each independently
PreferablyR4、R5、R6、R7And R8It is identical or different, it respectively can the alkyl selected from hydrogen or C1-C5；R2With
R3More preferablyR2And R3Further preferablyThe specific example of the alkyl of C1-C5 with
Above description is consistent, and details are not described herein.
In the preferred embodiment of the present invention, in formula (2), R1For phenyl, L1For substituted or unsubstituted imidazoles
Alkane, L2For phosphine, X1And X2For chloride ion.In a kind of preferred embodiment of the invention, in formula (2), R1For phenyl, L1ForL2For trialkyl phosphine, X1And X2For chloride ion.
According to the method for the present invention, in order to make the catalyst have better catalytic effect, most preferably, the catalysis
Agent is the catalyst of structure shown in formula (5),
In above-mentioned formula (5), PCy3Indicate that tricyclohexyl phosphine, Ph indicate phenyl.
Catalyst shown in above-mentioned formula (5) can be commercially available.
According to the method for the present invention, the alkenyl of C2-C20, the alkynyl of C2-C20, the alkyl of C1-C20, C6-C20 aryl,
The carboxylate of C2-C20, the alkoxy of C1-C20, the alkenyloxy of C2-C20, the chain oxy-acetylene of C2-C20, C6-C20 virtue
Oxygroup, the alkylthio group of C1-C20, the alkyl sulphonyl of C1-C20, C1-C20 Alkylsulfinyl specific example with retouch above
It states unanimously, details are not described herein.
According to the method for the present invention, the addition manner of the catalyst is consistent with above description, and details are not described herein.
According to the present invention, the ring opening cross-metathesis reaction of the alkene preferably carries out under an inert atmosphere.The inertia
Atmosphere is consistent with above description, and details are not described herein.
According to the present invention, there is no particular limitation for the condition of the ring opening cross-metathesis reaction of the alkene, can be with ability
The conventional selection in domain, for example, the condition of the ring opening cross-metathesis reaction of the alkene includes：Reaction temperature is 0-150 DEG C, instead
It is 0.1-5 hours between seasonable；Under preferable case, the condition of the ring opening cross-metathesis reaction of the alkene includes：Reaction temperature
It is 20-100 DEG C, the reaction time is 0.1-3 hours.
According to the present invention, the dosage of the ethylene propylene diene rubber, carbic anhydride and the catalyst can be wider
It is changed in range, as long as the purpose for being swift in response and obtaining the high modified EPT rubber of grafting rate may be implemented, one
As, relative to the ethylene propylene diene rubber of 100 parts by weight, the dosage of the carbic anhydride is 0.05-40 parts by weight, excellent
It is selected as 0.5-20 parts by weight；The dosage of the catalyst is 0.05-10 parts by weight, preferably 0.2-5 parts by weight.
According to the present invention, the type selection, the definition of the organic solvent of the ethylene propylene diene rubber, type and dosage choosing
Select consistent with above description, details are not described herein.
When the Third monomer is ENB, the modified EPT rubber contains structural unit A, structural unit B, knot
Structure unit C and structural unit D, the structural unit A, structural unit B, structural unit C and structural unit D specific structure with it is upper
Text description is consistent, and details are not described herein.
According to the present invention, the preparation method of the modified EPT rubber further includes purification step.The purification step
Consistent with above description, details are not described herein.
According to the present invention, the carbic anhydride of structure shown in the formula (1) can be commercially available, can also be by existing
There is the method for technology to be prepared.For example, the carbic anhydride of structure shown in the formula (1) is prepared by the following method：In Di
Under the conditions of Er Si-Alder reaction, the cyclopentadiene of structure shown in formula (4) is connect in organic solvent with maleic anhydride
Touching,
According to the present invention, the dosage selection of the cyclopentadiene and maleic anhydride of structure shown in the formula (4), Di
Er Si-Alder reaction condition and the selection of the type and dosage of the organic solvent are consistent with above description, no longer superfluous herein
It states.
The preparation method of the carbic anhydride of structure shown in the formula (1) further includes purification step, and the purification step can
To carry out referring to the prior art, details are not described herein.
In following preparation example and embodiment, the performance measurement being related to is as follows：
(1) by after purification grafting samples and ethylene propylene diene rubber be pressed into 160 DEG C of lower dies the film of thickness about 0.1mm, use
BRUKER company's T ENSOR-27 type Fourier infrared spectrograph is characterized；
(2) grafting rate (PG) is measured in accordance with the following methods：
1g graft is accurately weighed, 50mL xylene solvent (being purchased from Shanghai Yue Feng Chemical Co., Ltd.) is added, is heated to
Graft all after dissolution, is cooled to room temperature, and adding 10mL concentration is the KOH- ethanol solution of 0.03mol/L (through oxalic acid-second
Alcoholic solution calibration), it is titrated after stirring 10min with oxalic acid-ethanol solution, using phenolphthalein as indicator, when indicator is aobvious red
Stop titration.Grafting rate is calculated as follows：
In formula, PG is mass fraction, that is, grafting rate of carbic anhydride in graft, %；M is the quality of graft, g；C1
For the concentration of KOH- ethanol solution, mol/L；V1For the volume of KOH- ethanol solution, mL；C2For oxalic acid-ethanol solution concentration,
mol/L；V2For oxalic acid-ethanol solution volume, mL.
(3) fusing point of carbic anhydride is molten using the WRS-1C of Shanghai Shen Guang instrument and meter Co., Ltd production in preparation example
Point instrument measurement, the calculation formula of yield are as follows：
In formula, Y：Yield, %；mIt is real：The actual production of carbic anhydride, g；mReason：Reaction is participated in maleic anhydride
Measure the theoretical yield of the carbic anhydride calculated, g；
(4) for the degree of unsaturation of modified EPT rubber by iodometric determination, specific method is as follows：Accurately weigh 2g
Modified EPT rubber sample is placed in 250mL ground conical flask, and 50mLCCl is added4Dissolve sample, with pipette plus
Enter 20mL Iodide Bromide (IBr) solution, open in dark place 1h after fulling shake, and the potassium iodide that 10 weight % of 10mL concentration is then added is molten
Liquid shakes up, and when being titrated to solution in yellow with 0.1N sodium thiosulfate standard solution, 5mL starch indicator is added, continues to titrate
Disappear to blue is terminal.Blank test is done simultaneously.Degree of unsaturation is calculated as follows：
In formula, V0：Blank test consumes the volume of sodium thiosulfate standard solution, mL；V：Sample consumption sodium thiosulfate
The volume of standard solution, mL；C：The concentration of sodium thiosulfate standard solution, mol/L；m：Sample mass, g.Degree of unsaturation in formula
Unit be mol/kg.
(5) weight average molecular weight of modified EPT rubber is measured by gel permeation chromatography (GPC) method, and instrument is
Waters 1515Isocratic HPLC gel permeation chrommatograph.
Preparation example 1
Preparation method of the preparation example for the carbic anhydride of structure shown in formula (1).
15.7 grams of maleic anhydride (0.16mol) is added in the reaction flask of 100mL, toluene 40mL sets reaction flask
Stirring is cooled to 5 DEG C in thermostated cooling bath, and 14 grams of cyclopentadiene (0.2mol) is added dropwise by constant pressure funnel, controls reaction flask
In temperature be no more than 15 DEG C, reaction is warming up to 120 DEG C after being added dropwise and continues stirring 1 hour, it is cooling that white crystals are precipitated,
Carbic anhydride crude product is filtered out, then again with toluene is recrystallized, and filtration drying obtains 19.0 grams of carbic anhydride, nadik
The fusing point (mp) of acid anhydrides is 165.8 DEG C -167 DEG C, yield 72.3%.
Embodiment 1
The present embodiment is for illustrating modified EPT rubber provided by the invention and preparation method thereof.
By 8 grams of ethylene propylene diene rubbers (3280, be purchased from Yanshan Petrochemical company, ethylene unit unit in ethylene propylene diene rubber
Content is 55 weight %, the content of Third monomer is 5 weight %, and weight average molecular weight is 300,000, and the Third monomer is the Asia 5- second
Base -2- norbornene (ENB)), carbic anhydride made from 1 gram of preparation example 1 is in N2Under protection, it is dissolved in 90mL xylene solution
Reaction system is formed to being completely dissolved；Weighing the catalyst of structure shown in 0.05 gram of formula (5) simultaneously, (being commercially available from lark prestige science and technology has
Limit company, same as below), it is dissolved in 10mL xylene solution, obtains catalyst solution C1.
Obtained reaction system is heated to 70 DEG C, 2mL catalyst solution C1 is first added into reaction system, reacts 5min
Afterwards, remaining 8mL catalyst solution C1 is uniformly divided into 4 parts, is added in reaction system in such a way that portion is added in every 5min, to
After reaction system 5min is added in last portion catalyst solution C1, stop reaction, the reaction time is 30min in total.End of reaction
Reaction solution is filtered with nickel screen while hot afterwards, and acetone is added into filtrate and removes impurity, and is precipitated.Sediment is isolated,
Sediment is cleaned up to filtrate clarification with acetone, is put the precipitate in 60 DEG C of vacuum drying ovens after drying 14h, is obtained modified ternary
EP rubbers A1.Infrared spectrum measurement is carried out to modified EPT rubber, (a indicates unmodified EPDM to the result is shown in Figure 1
The infrared spectrogram of rubber, b indicate the infrared spectrogram of modified EPT rubber), infrared spectrogram is the result shows that nadik
Acid anhydrides has been grafted on ethylene propylene diene rubber.Furthermore analysis measurement is carried out to other performances of modified EPT rubber, tied
Fruit is shown in Table 1.
Embodiment 2
Modified EPT rubber is prepared using method same as Example 1, the difference is that reaction system is heated
To 70 DEG C, then the catalyst solution C1 of 10mL is added at one time in reaction system, reacts 30min.Obtain modified ternary
EP rubbers A2.Infrared spectrum measurement is carried out to modified EPT rubber, the results showed that carbic anhydride has been grafted to three
On first EP rubbers.In addition, carrying out analysis measurement to other performances of modified EPT rubber respectively, 1 the results are shown in Table.
Embodiment 3
Modified EPT rubber is prepared using method same as Example 2, the difference is that reaction system is heated
To 70 DEG C, then 10mL catalyst solution C1 is added in two portions in reaction system, the time of addition is respectively by reactant
After carrying out 15min with reaction when i.e. reaction starts when system is heated to 70 DEG C, each additional amount is 5mL, and stopping is anti-after reacting 30min
It answers.Obtain modified EPT rubber A3.Infrared spectrum measurement is carried out to modified EPT rubber, the results showed that nadic acid
Acid anhydride has been grafted on ethylene propylene diene rubber.Furthermore analysis measurement is carried out to other performances of modified EPT rubber, as a result
It is shown in Table 1.
Comparative example 1
Modified EPT rubber is prepared using method same as Example 1, the difference is that using identical weight
Maleic anhydride replaces carbic anhydride.Obtain the modified EPT rubber D1 of reference.To the modified EPT rubber of reference
Carry out infrared spectrum measurement, the results showed that maleic anhydride is non-grafted on ethylene propylene diene rubber.And to reference modified EPT
Rubber D1 carries out analysis measurement, the results are shown in Table 1.
Comparative example 2
By ethylene propylene diene rubber (3280, be purchased from Yanshan Petrochemical company, the content of ethylene unit unit in ethylene propylene diene rubber
Content for 55 weight %, Third monomer is 5 weight %, and weight average molecular weight is 300,000, and the Third monomer is ENB) do not change
The ethylene propylene diene rubber of property carries out analysis measurement as reference EP rubbers D2, and to reference ethylene propylene diene rubber D2, as a result sees
Table 1.
Embodiment 4
The present embodiment is for illustrating modified EPT rubber provided by the invention and preparation method thereof.
Modified EPT rubber is prepared using method same as Example 1, the difference is that the reaction time is 1 small
When, i.e., after reaction system 35min is added in last a catalyst solution, stop reaction.Obtain modified EPT rubber A4.
Infrared spectrum measurement is carried out to modified EPT rubber, the results showed that carbic anhydride has been grafted to ethylene propylene diene rubber
On.Furthermore analysis measurement is carried out to other performances of modified EPT rubber respectively, the results are shown in Table 1.
Embodiment 5
Modified EPT rubber is prepared using method same as Example 1, the difference is that reaction system is heated
To 40 DEG C, modified EPT rubber A5 is obtained.Infrared spectrum measurement is carried out to modified EPT rubber, the results showed that Na Di
Gram acid anhydrides has been grafted on ethylene propylene diene rubber.Furthermore analysis survey is carried out to other performances of modified EPT rubber respectively
It is fixed, it the results are shown in Table 1.
Embodiment 6
Modified EPT rubber is prepared using method same as Example 1, the difference is that the Na Di of 0.8g is added
Gram acid anhydrides, obtains modified EPT rubber A6.Infrared spectrum measurement is carried out to modified EPT rubber, the results showed that Na Di
Gram acid anhydrides has been grafted on ethylene propylene diene rubber.Furthermore analysis survey is carried out to other performances of modified EPT rubber respectively
It is fixed, it the results are shown in Table 1.
Embodiment 7
Modified EPT rubber is prepared using method same as Example 1, the difference is that weighing 0.08g formula (5)
The catalyst of shown structure is dissolved in 10mL xylene solution, is divided into 5 parts, every part of adding manner and embodiment 1
It is identical, obtain modified EPT rubber A7.Infrared spectrum measurement is carried out to modified EPT rubber, as a result, it has been found that nadik
Acid anhydrides has been grafted on ethylene propylene diene rubber.Furthermore analysis survey is carried out to other performances of modified EPT rubber respectively
It is fixed, it the results are shown in Table 1.
Embodiment 8
The present embodiment is for illustrating modified EPT rubber provided by the invention and preparation method thereof.
By 8 grams of ethylene propylene diene rubbers (3280, be purchased from Yanshan Petrochemical company, ethylene unit unit in ethylene propylene diene rubber
Content is 55 weight %, the content of Third monomer is 5 weight %, and weight average molecular weight is 300,000, and the Third monomer is ENB),
Carbic anhydride made from 0.04 gram of preparation example 1 is in N2Under protection, it is dissolved in 90mL xylene solution to being completely dissolved being formed instead
Answer system；The catalyst for weighing structure shown in 0.4 gram of formula (5) simultaneously, is dissolved in 10mL xylene solution, is catalyzed
Agent solution C8.
Reaction system is heated to 100 DEG C, 2mL catalyst solution C8 is first added into reaction system, after reacting 5min, is remained
Remaining 8mL catalyst solution C8 is uniformly divided into 4 parts, is added in reaction system in such a way that portion is added in every 5min, to last
After reaction system 5min is added in a catalyst solution C8, stop reaction, the reaction time is 30min in total.After completion of the reaction will
Reaction solution is filtered with nickel screen while hot, and acetone is added into filtrate and removes impurity, and is precipitated.Sediment is isolated, with third
Ketone cleans sediment until filtrate clarification, puts the precipitate in 60 DEG C of vacuum drying ovens after drying 14h, obtain modified EPT
Rubber A8.Infrared spectrum measurement is carried out to modified EPT rubber, the results showed that carbic anhydride has been grafted to ternary second
On third rubber.In addition, carrying out analysis measurement to other performances of modified EPT rubber respectively, 1 the results are shown in Table.
Embodiment 9
The present embodiment is for illustrating modified EPT rubber provided by the invention and preparation method thereof.
By 8 grams of ethylene propylene diene rubbers, (ESPRENE 305 is purchased from SUMITOMO CHEMICAL, ethylene unit unit in ethylene propylene diene rubber
Content be 65 weight %, the content of Third monomer is 7 weight %, weight average molecular weight is 120,000, and the Third monomer is bicyclic
Pentadiene (DCPD)), carbic anhydride made from 1.6 grams of preparation examples 1 is in N2Under protection, it is dissolved in 90mL xylene solution to complete
Fully dissolved forms reaction system；The catalyst for weighing structure shown in 0.016 gram of formula (5) simultaneously, is dissolved in 90mL dimethylbenzene
In solution, catalyst solution C9 is obtained.
Reaction system is heated to 20 DEG C, 2mL catalyst solution C9 is added into reaction system, it is remaining after reacting 15min
8mL catalyst solution be uniformly divided into 4 parts, by every 15min be added it is a in a manner of be added in reaction system, to last a
After reaction system 105min is added in catalyst solution, stop reaction, the reaction time is 3h in total.Reaction solution is taken advantage of after completion of the reaction
Heat is filtered with nickel screen, and acetone is added into filtrate and removes impurity, and is precipitated.Sediment is isolated, it is heavy to be cleaned with acetone
Starch puts the precipitate in 60 DEG C of vacuum drying ovens after drying 14h until filtrate clarification, obtains modified EPT rubber A9.
Infrared spectrum measurement is carried out to modified EPT rubber, the results showed that carbic anhydride has been grafted to ethylene propylene diene rubber
On.Furthermore analysis measurement is carried out to other performances of modified EPT rubber respectively, the results are shown in Table 1.
Comparative example 3
By ethylene propylene diene rubber, (ESPRENE 305 is purchased from SUMITOMO CHEMICAL, ethylene unit unit in ethylene propylene diene rubber
Content is 65 weight %, the content of Third monomer is 7 weight %, and weight average molecular weight is 120,000, and the Third monomer is DCPD) i.e.
Unmodified ethylene propylene diene rubber carries out analysis measurement as reference EP rubbers D3, and to reference ethylene propylene diene rubber D3, knot
Fruit is shown in Table 1.
Embodiment 10
Modified EPT rubber is prepared using method same as Example 1, the difference is that using shown in formula (6)
The catalyst (being commercially available from lark prestige Science and Technology Ltd.) of structure replaces the catalyst of structure shown in formula (5), obtains modified ternary
EP rubbers A10.Infrared spectrum measurement is carried out to modified EPT rubber, the results showed that carbic anhydride has been grafted to three
On first EP rubbers.Furthermore analysis measurement is carried out to other performances of modified EPT rubber respectively, the results are shown in Table 1.
In above-mentioned formula (6), PCy3Indicate that tricyclohexyl phosphine, Ph indicate phenyl.
Embodiment 11
Modified EPT rubber is prepared using method same as Example 1, the difference is that using shown in formula (7)
The catalyst (being commercially available from lark prestige Science and Technology Ltd.) of structure replaces the catalyst of structure shown in formula (5), obtains modified ternary
EP rubbers A11.Infrared spectrum measurement is carried out to modified EPT rubber, the results showed that carbic anhydride has been grafted to three
On first EP rubbers, analysis measurement furthermore is carried out to other performances of modified EPT rubber respectively, the results are shown in Table 1.
In above-mentioned formula (7), L isPCy3Indicate tricyclohexyl phosphine.
Table 1
Test case 1
The modified EPT rubber A1-A11 prepared in 1-11 of the embodiment of the present invention is vulcanized by the following method
Performance measurement.
Modified EPT rubber A1 prepared by the embodiment of the present invention of 100 parts by weight is placed on two roll rubber mixing mill,
At 35 ± 5 DEG C of temperature, the activated zinc oxide of 5 parts by weight, the stearic acid of 1 parts by weight, the carbon black of 80 parts by weight is successively added
The ASTM103# of (N550, Shanghai Cabot Chemical Co., Ltd.), 50 parts by weight is oily (Ningbo co evolution work Co., Ltd), 1 weight
The Vulcanization accelerator TMTD (the single-minded rubber Science and Technology Ltd. in Shanghai) of part is measured, (Shijiazhuang is sharp to open up chemical science and technology to the Sulfur of 1.5 parts by weight
Co., Ltd), it is uniformly mixed and is kneaded, the time of mixing is 21 minutes, obtains blend.Again by blend in temperature
160 DEG C, vulcanize 15 minutes on the hydraulic flat vulcanizer of pressure 15MPa, the ethylene propylene diene rubber film after being vulcanized.
According to the testing to the ethylene propylene diene rubber film after vulcanization of the method in GB/T16584-1996, sulphur is recorded
Change speed parameter sulfurizing time TC90, test result is shown in Table 2.
Modified EPT rubber A2-A11 is carried out to the measurement of curability according to the method described above, test result is shown in Table 2.
Contrast test example 1
Ethylene propylene diene rubber film is prepared using method identical with test case 1, the difference is that using commercially available ternary
EP rubbers (3280, it is purchased from Yanshan Petrochemical company, the content of ethylene unit unit is 55 weight %, the in ethylene propylene diene rubber
The content of three monomers is 5 weight %, and weight average molecular weight is 300,000, and the Third monomer is by ENB) replace modified EPT rubber
Glue.Test result is shown in Table 2.
Contrast test example 2
Ethylene propylene diene rubber film is prepared using method identical with test case 1, the difference is that using commercially available ternary
EP rubbers (ESPRENE 305 is purchased from SUMITOMO CHEMICAL, in ethylene propylene diene rubber the content of ethylene unit unit be 65 weight %,
The content of Third monomer is 7 weight %, and weight average molecular weight is 120,000, and the Third monomer is by DCPD) replace modified EPT
Rubber.Test result is shown in Table 2.
Table 2
From table 1 it follows that carbic anhydride can be grafted by the ring opening cross-metathesis reaction by using alkene
Onto ethylene propylene diene rubber, and grafting rate is relatively high, rapid reaction.
By embodiment 1 and embodiment 9 respectively compared with comparative example 2 and comparative example 3 (unmodified ethylene propylene diene rubber), this
The degree of unsaturation for inventing obtained modified EPT rubber is 0.44-0.68mol/kg, with unmodified ethylene propylene diene rubber
Degree of unsaturation have certain raising, this may be because the present invention is by the carbic anhydride of structure shown in formula (1) and ternary second
Third rubber can increase the pendant double bonds of ethylene propylene diene rubber after alkene ring opening cross-metathesis reaction.By 1 He of embodiment
Embodiment 2 is compared, it can be seen that using the grafting for the modified EPT rubber that the method that catalyst is added dropwise by several times obtains
Rate is higher, this may be due to being added at one time catalyst after, catalyst concn is larger in system, and carbic anhydride is easily opened
Ring metathesis polymerization side reaction eventually leads to degree of unsaturation and grafting so that the carbic anhydride quantity for participating in graft reaction is reduced
Rate decline.In addition, passing through embodiment 2 to embodiment 11, it can be seen that reaction can be efficiently controlled by adjusting reaction condition
Degree, so as to obtain the modified EPT rubber with expected grafting rate.
It can be seen that modified EPT rubber provided by the invention and unmodified ethylene-propylene-diene monomer from the data of table 2
Glue is compared, and curingprocess rate improves.
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above
Detail within the scope of the technical concept of the present invention can be with various simple variants of the technical solution of the present invention are made, this
A little simple variants all belong to the scope of protection of the present invention.
It is further to note that specific technical features described in the above specific embodiments, in not lance
In the case where shield, it can be combined in any appropriate way.In order to avoid unnecessary repetition, the present invention to it is various can
No further explanation will be given for the combination of energy.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should also be regarded as the disclosure of the present invention.
Claims (23)
1. a kind of modified EPT rubber, which is characterized in that the modified EPT rubber is received by structure shown in formula (1)
Ethylene propylene diene rubber graft modification is made in Dick acid anhydrides, described on the basis of the weight of the modified EPT rubber
The grafting rate of modified EPT rubber is 0.4-3.5 weight %,
2. modified EPT rubber according to claim 1, wherein the degree of unsaturation of the modified EPT rubber
For 0.44-0.68mol/kg.
3. modified EPT rubber according to claim 1 or 2, wherein the preparation of the modified EPT rubber
Method includes：Under the conditions of the ring opening cross-metathesis reaction of alkene, in the presence of the catalyst of the structure shown in formula (2), by three
First EP rubbers is contacted in organic solvent with the carbic anhydride of structure shown in formula (1),
In formula (2), R1For hydrogen, the alkenyl of C2-C20, the alkynyl of C2-C20, the alkyl of C1-C20, the aryl of C6-C20, C2-C20
Carboxylate, the alkoxy of C1-C20, the alkenyloxy of C2-C20, the chain oxy-acetylene of C2-C20, C6-C20 aryloxy group,
The alkylthio group of C1-C20, the alkyl sulphonyl of C1-C20 or C1-C20 Alkylsulfinyl,
X1And X2Anion ligand is each independently,
L1And L2It is each independently neutral ligand, and optionally L1And L2The neutral ligand of two coordinations can be interconnected to form
Body.
4. modified EPT rubber according to claim 3, wherein R1For the aryl of C6-C20；
X1And X2It is each independently halide ion；
L1And L2It is each independently phosphine, amine, thioether, Cabbeen or substituted or unsubstituted imidazolidine.
5. modified EPT rubber according to claim 4, wherein R1For phenyl；X1And X2For chloride ion；L1And L2Respectively
From independently being phosphine, Cabbeen or substituted or unsubstituted imidazolidine.
6. modified EPT rubber according to claim 4, wherein R1For phenyl, L1For substituted or unsubstituted imidazoles
Alkane, L2For phosphine, X1And X2For chloride ion.
7. modified EPT rubber according to claim 6, wherein the phosphine is trialkyl phosphine, and the imidazolidine is
The imidazolidine of structure shown in formula (3),
In formula (3), R2And R3It is each independently the aryl of substituted or unsubstituted C6-C20.
8. modified EPT rubber according to claim 7, wherein R2And R3It is each independently
R4、R5、R6、R7And R8It is each independently selected from hydrogen or the alkyl of C1-C5.
9. modified EPT rubber according to claim 8, wherein R2And R3For
10. modified EPT rubber according to claim 3, wherein the EPDM relative to 100 parts by weight
Rubber, the dosage of the carbic anhydride are 0.05-40 parts by weight, and the dosage of the catalyst is 0.05-10 parts by weight.
11. modified EPT rubber according to claim 3, wherein ethylene unit list in the ethylene propylene diene rubber
The content of member is 50-70 weight %, the content of Third monomer is 4-6 weight %；The weight average molecular weight of the ethylene propylene diene rubber
It is 100,000-40 ten thousand, the Third monomer is one of Isosorbide-5-Nitrae-hexadiene, dicyclopentadiene and 5- ethylidene-2- norbornene
Or it is a variety of.
12. a kind of preparation method of modified EPT rubber, this method include：In the ring opening cross-metathesis reaction item of alkene
Under part, in the presence of the catalyst of the structure shown in formula (2), by the carbic anhydride of structure shown in ethylene propylene diene rubber and formula (1)
It is contacted in organic solvent,
In formula (2), R1For hydrogen, the alkenyl of C2-C20, the alkynyl of C2-C20, the alkyl of C1-C20, the aryl of C6-C20, C2-C20
Carboxylate, the alkoxy of C1-C20, the alkenyloxy of C2-C20, the chain oxy-acetylene of C2-C20, C6-C20 aryloxy group,
The alkylthio group of C1-C20, the alkyl sulphonyl of C1-C20 or C1-C20 Alkylsulfinyl,
X1And X2Anion ligand is each independently,
L1And L2It is each independently neutral ligand, and optionally L1And L2The neutral ligand of two coordinations can be interconnected to form
Body.
13. according to the method for claim 12, wherein R1For the aryl of C6-C20；
X1And X2It is each independently halide ion；
L1And L2It is each independently phosphine, amine, thioether, Cabbeen or substituted or unsubstituted imidazolidine.
14. according to the method for claim 13, wherein R1For phenyl；
X1And X2It is each independently chloride ion；
L1And L2It is each independently phosphine, Cabbeen or substituted or unsubstituted imidazolidine.
15. according to the method for claim 14, wherein R1For phenyl, L1For substituted or unsubstituted imidazolidine, L2For phosphine,
X1And X2For chloride ion.
16. according to the method for claim 15, wherein the phosphine is trialkyl phosphine, and the imidazolidine is knot shown in formula (3)
The imidazolidine of structure,
In formula (3), R2And R3It is each independently the aryl of substituted or unsubstituted C6-C20.
17. according to the method for claim 16, wherein R2And R3It is each independentlyR4、R5、R6、R7
And R8It is each independently selected from hydrogen or the alkyl of C1-C5.
18. according to the method for claim 17, wherein R2And R3For
19. according to the method for claim 12, wherein the ring opening cross-metathesis reaction of the alkene is under an inert atmosphere
It carries out, the condition of the ring opening cross-metathesis reaction of the alkene includes：Reaction temperature is 0-150 DEG C, reaction time 0.1-5
Hour.
20. according to the method for claim 12, wherein described to receive relative to the ethylene propylene diene rubber of 100 parts by weight
The dosage of Dick acid anhydrides is 0.05-40 parts by weight, and the dosage of the catalyst is 0.05-10 parts by weight.
21. method described in 2 or 20 according to claim 1, wherein the catalyst is in a manner of being added at one time or divides more
The mode of secondary addition is added in reaction system.
22. according to the method for claim 21, wherein the catalyst divides in 2-6 addition reaction system, and adjacent two
The time interval of secondary addition is 3-15 minutes, and the difference that the amount of catalyst is arbitrarily added twice accounts for 5 weights of the total additional amount of catalyst
Measure % or less.
23. according to the method for claim 12, wherein the organic solvent is toluene, dimethylbenzene, chlorobenzene, C6-C12
One of cycloalkane, the linear paraffin of C5-C10, tetrahydrofuran, acetone and 1,4- dioxane are a variety of.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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| EP2835381A1 (en) * | 2013-08-09 | 2015-02-11 | Lanxess Elastomers B.V. | Functionalized olefinic copolymers |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| EP2835381A1 (en) * | 2013-08-09 | 2015-02-11 | Lanxess Elastomers B.V. | Functionalized olefinic copolymers |
Non-Patent Citations (1)
| Title |
|---|
| Cross metathesis functionalization of polyolefins;Robert T.Mathers;《Chemical Communications》;20041231(第4期);422-423 * |
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