CN106589245B - 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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Abstract
The invention discloses a kind of modified EPT rubber and preparation method thereof.This method includes that in the presence of the ionized catalyst of the structure shown in formula (2), ethylene propylene diene rubber is contacted in organic solvent with the carbic anhydride of structure shown in formula (1) under the conditions of the ring opening cross-metathesis reaction of alkene.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 the grafting rate of the modified EPT rubber is 0.4-4 weight %；And compared with unmodified ethylene propylene diene rubber, degree of unsaturation 0.44-0.71mol/kg, curingprocess rate improves modified EPT rubber provided by the invention.
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 obtained 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 preparation side of modified EPT rubber is provided
Method and the modified EPT rubber being prepared by this method.
The present invention provides a kind of preparation method of modified EPT rubber, this method include alkene open loop crossover it is multiple
It, will be shown in ethylene propylene diene rubber and formula (1) in the presence of the ionized catalyst of the structure shown in formula (2) under the conditions of decomposition reaction
The carbic anhydride of 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；
Y is anion.
The present invention also provides a kind of modified EPT rubber prepared by the above method.
The present invention is by using shown in the ionized catalyst catalysis ethylene propylene diene rubber of structure shown in formula (2) and formula (1)
The ring opening cross-metathesis reaction of the alkene of the carbic anhydride of structure makes the unsaturation of the modified EPT rubber of preparation
Degree is 0.44-0.71mol/kg, and the modified EPT rubber also has the advantages that grafting rate is high, specifically, is changed with described
Property ethylene propylene diene rubber weight on the basis of, the grafting rate of modified EPT rubber provided by the invention is 0.4-4 weight %.
Furthermore modified EPT method for preparing rubber provided by the invention has the characteristics that rapid reaction and step are simply easily implemented.
By modified EPT rubber provided by the invention compared with unmodified ethylene propylene diene rubber, curingprocess rate has one
Fixed raising, the possible reason is the carbic anhydride of structure shown in formula (1) and ethylene propylene diene rubber are passed through alkene by the present invention
After ring opening cross-metathesis reaction, the double bond content of the side chain of ethylene propylene diene rubber can be increased, be conducive to sulfidation, so that changing
The curingprocess rate of EP rubbers after property is improved.
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 grafting rate and degree of unsaturation 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 preparation method of modified EPT rubber, this method include alkene open loop crossover it is multiple
It, will be shown in ethylene propylene diene rubber and formula (1) in the presence of the ionized catalyst of the structure shown in formula (2) under the conditions of decomposition reaction
The carbic anhydride of 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；
Y is anion, preferably halide ion, more preferably iodide ion, most preferably I5 -；
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) or 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, Y is iodide ion.In a kind of preferred embodiment of the invention, in formula (2), R1
For phenyl, L1ForL2For trialkyl phosphine, X1And X2For chloride ion, Y I5 -。
According to the present invention, in order to make the ionized catalyst have better catalytic effect, the ionized catalyst
For the ionized catalyst of structure shown in formula (5),
In above-mentioned formula (5), PCy3Indicate that tricyclohexyl phosphine, Ph indicate phenyl.
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 and 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 and decyl, undecyl, dodecyl, octadecane
Base.
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 method for the present invention, the addition manner of the ionized catalyst is not particularly limited, can be by catalyst
The nadik of structure shown in ethylene propylene diene rubber and formula (1) is added in the way of being added in a manner of being added at one time or several times
In the reaction system that acid anhydrides is contacted.In view of catalyst is added at one time the carbic anhydride being easy to cause in reaction system
Side reaction occurs, the mode being preferably added several times is added.It is highly preferred that the catalyst divides in 2-6 addition reaction system,
And adjacent addition time interval twice is 3-15 minutes, the difference that the amount of catalyst is arbitrarily added twice accounts for the total additional amount of catalyst
5 weight % hereinafter, in this way be added catalyst be conducive to improve modified EPT rubber degree of unsaturation and connect
Branch rate.It is further preferred that in order to make catalyst play better catalytic effect, the catalyst is (excellent as a solution
The catalyst is dissolved in the organic solvent by choosing) divide in 2-6 addition reaction system, and between the adjacent addition time twice
It is divided into 3-15 minutes, the difference that the amount of catalyst is arbitrarily added twice accounts for the 5 weight % or less of the total additional amount of catalyst.
According to the method for the present invention, the ionized catalyst of structure shown in formula (2) can be common using organic synthesis field
Method synthesis.Such as：It can be by lewis acid and formula (6) compound represented haptoreaction, to obtain knot shown in formula (2)
The compound of structure,
In formula (6), R1、L1、L2、X1And X2Definition with it is described previously identical, this will not be detailed here.
Lewis acid and the catalytic condition of formula (6) compound represented are not particularly limited.Generally, described to connect
The temperature of touching can be 20-100 DEG C, and the molar ratio of lewis acid and formula (6) compound represented can be 1-5：1.The road
Lewis acid can be conventional selection, such as iodine.The time of the contact can carry out choosing appropriate according to the temperature contacted
It selects.The contact preferably carries out under an inert atmosphere, and the inert atmosphere, which refers to, does not occur chemistry with reactant and reaction product
The compound of interaction, such as：One of group 0 element gas or a variety of in nitrogen and the periodic table of elements, the described 0th
Race's elemental gas such as argon gas.The mixture that contact obtains can be purified using various methods commonly used in the art, from
And the ionized catalyst of structure shown in formula (2) is obtained, such as：Obtained mixture can be subjected to pillar layer separation.Specifically
Ground, can be by obtained mixture aluminum oxide column, and is eluted using methylene chloride as eluant, eluent, to obtain formula
(2) ionized catalyst of structure shown in.
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 20-150 DEG C,
Reaction time is 0.5-5 hours；Under preferable case, the condition of the ring opening cross-metathesis reaction of the alkene includes：Reaction temperature
Degree is 40-130 DEG C, and the reaction time is 1-3 hours.
According to the present invention, the dosage of the ethylene propylene diene rubber, carbic anhydride and the ionized catalyst can be
It changes in wider range, as long as may be implemented to be swift in response and obtain having target saturation degree and the high modification ternary of grafting rate
The purpose of EP rubbers, relative to the ethylene propylene diene rubber of 100 parts by weight, the Na Di of structure shown in the formula (1)
The dosage of gram acid anhydrides is 0.05-40 parts by weight, preferably 0.5-20 parts by weight；The ionic of structure shown in the formula (2) is catalyzed
The dosage of agent 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).
According to the present invention, the organic solvent for preparing modified EPT rubber is that existing various can be used as is reacted
The organic substance of medium, under preferable case, the organic solvent is toluene, dimethylbenzene, chlorobenzene, the cycloalkane of C6-C12, C5-
One of linear paraffin, tetrahydrofuran, acetone and Isosorbide-5-Nitrae-dioxane of C10 are a variety of, described in further preferred situation
Organic solvent is one of toluene, dimethylbenzene, chlorobenzene, hexamethylene, n-hexane, tetrahydrofuran, acetone and 1,4- dioxane
Or it is a variety of；Most preferably toluene and/or dimethylbenzene.These solvents can be used alone, can also be used in mixed way.It is described organic
The dosage of solvent can be the conventional selection of this field, and repeats no more herein.
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 (1) 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.
The present invention also provides a kind of modified EPT rubber prepared by the above method.
According to the present invention, on the basis of the weight of the modified EPT rubber, the modified EPT rubber
Grafting rate is 0.4-4 weight %.
According to the present invention, the degree of unsaturation of the modified EPT rubber can achieve 0.44-0.71mol/kg, preferably
For 0.53-0.71mol/kg.
In accordance with the present invention it is preferred that when the Third monomer in ethylene propylene diene rubber is ENB, the modified EPT
Rubber contains structural unit A, structural unit B, structural unit C and structural unit D, wherein the structural unit A is with formula
The unit of structure shown in (1 '), the structural unit B are the unit with structure shown in formula (2 '), and the structural unit C is tool
There is the unit of structure shown in formula (3 '), the structural unit D is the unit with structure shown in formula (4 ')；
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 that the degree of unsaturation of modified EPT rubber described in 0.4-4 weight % can achieve 0.44-
0.71mol/kg。
The degree of unsaturation of modified EPT rubber is measured by iodimetric titration in the present invention.
Modified EPT rubber according to the present invention, it is preferable that the weight average molecular weight of the modified EPT rubber
It is 100,000-40 ten thousand.
The weight average molecular weight of modified EPT rubber is measured by gel permeation chromatography (GPC) method in the present invention.
The present invention will be described in detail by way of examples below.
In following preparation example and embodiment, the performance measurement being related to is as follows：
(1) measurement of 1 ionic catalyst structure of preparation example：With tetramethylsilane (TMS) for internal standard, in the U.S.
On the INOVA500MHz type nuclear magnetic resonance spectrometer of VARIAN company measure nuclear magnetic resonance spectroscopy (1) and carbon-13 nmr spectra H-NMR
(13C-NMR)；The crystal of selection suitable dimension carries out X-ray list on BRUKER SMART 1000CCD x-ray diffractometer
Brilliant diffraction；
(2) 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；
(3) 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.
(4) fusing point of the carbic anhydride in preparation example uses the WRS-1C of Shanghai Shen Guang instrument and meter Co., Ltd production
Melting point apparatus 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.
(5) degree of unsaturation of modified EPT rubber is specific as follows by iodometric determination：Accurately weigh 2g modified three
First EP rubbers sample is placed in 250mL ground conical flask, and 50mL CCl is added4Sample is dissolved, 20mL is added with pipette
Iodide Bromide (IBr) solution, open in dark place 1h after fulling shake, and the liquor kalii iodide that 10mL concentration is 10 weight % is then added,
It shakes up, when being titrated to solution in yellow with 0.1N sodium thiosulfate standard solution, 5mL starch indicator is added, continues to be titrated to
It is terminal that blue, which disappears,.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.
(6) weight average molecular weight of modified EPT rubber is measured by gel permeation chromatography (GPC) method, and instrument is
1515 Isocratic HPLC gel permeation chrommatograph of Waters.
Preparation example 1
The preparation example is used to illustrate the preparation of ionized catalyst.
Under nitrogen protection, 0.76g iodine, 0.85g formula (7) compound represented (quotient are added in the three-necked flask of 100mL
Purchased from lark prestige Science and Technology Ltd.) and 20mL methylene chloride, it is stirred 0.5 hour in room temperature (for 25 DEG C).It will obtain mixture
(solvent is methylene chloride) is separated with aluminum oxide column chromatography, after obtained eluent is concentrated, uses hexamethylene
Alkane washing obtains the catalyst that 1.31g is yellow solid.By obtained catalyst carry out nuclear magnetic resonance spectroscopy (1) and core H-NMR
Magnetic resonance carbon spectrum (13C-NMR) and the measurement analysis of X-ray single crystal diffraction, the catalyst confirmed have knot shown in formula (5)
Structure.
1H-NMR(400MHz,DMSO)δ(ppm):1.35-2.06(m,33H),1.81(s,18H),2.62(m,4H),
6.11(d,1H),7.38-7.50(m,5H),7.59-7.67(m,3H)。
13C-NMR(100MHz,DMSO)δ(ppm):24.8,25.5,26.2,26.3,26.4,26.6,31.9,32.1,
129.1,129.2,129.3,129.5,130.7,134.2,134.3,193.0。
In formula (5) and formula (7), Cy is cyclohexyl.
Preparation example 2
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 5 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 0.8 gram of preparation example 2 is in N2Under protection, it is dissolved in 70mL xylene solution
Reaction system is formed to being completely dissolved.The ionic catalysis of structure shown in formula (5) made from 0.05 gram of preparation example 1 is weighed simultaneously
Agent is dissolved in 10mL xylene solution, obtains catalyst solution C1.
Reaction system is heated to 120 DEG C, 2mL catalyst solution C1 is added into reaction system, after reacting 10min, is remained
Remaining 8mL catalyst solution is uniformly divided into 4 parts, is added in reaction system in such a way that portion is added in every 10min, to last
After reaction system 10min is added in part catalyst solution C1, stop reaction, the reaction time is 1h in total.It after completion of the reaction will reaction
Liquid is filtered with nickel screen while hot, and acetone is added into filtrate and removes impurity, and is precipitated, and isolates sediment, clear with acetone
Sediment is washed until filtrate clarification, puts the precipitate in 60 DEG C of vacuum drying ovens after drying 14h, obtain modified EPT rubber
A1.Infrared spectrum measurement is carried out to modified EPT rubber, (a indicates the red of unmodified ethylene propylene diene rubber to the result is shown in Figure 1
External spectrum, b indicate the infrared spectroscopy of modified EPT rubber).Infrared spectrogram shows 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 2
Modified EPT rubber is prepared using method same as Example 1, the difference is that reaction system is heated
To 120 DEG C, then the catalyst solution C1 of 10mL is added at one time in reaction system, reacts 1h.Obtain modified ternary second
Third rubber A2.Product carries out infrared spectrum measurement, the results showed that carbic anhydride has been grafted on ethylene propylene diene rubber, furthermore
Analysis measurement is carried out to other performances of modified EPT rubber respectively, the results are shown in Table 1.
Embodiment 3
Modified EPT rubber is prepared using method same as Example 1, the difference is that reaction system is heated
To 120 DEG C, then catalyst solution C1 is added in two portions in reaction system, the time of addition is respectively to add reaction system
When reaction starts when heat is to 120 DEG C and after reaction carries out 15min, each additional amount is 5mL, stops reaction after reaction 1 hour.
Obtain modified ethylene propylene diene 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, in addition, analysis measurement is carried out to other performances of modified EPT rubber respectively,
It the results are 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 ethylene propylene diene 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 2 small
When, i.e., after reaction system 70min 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, in addition, carrying out analysis measurement to other performances of modified EPT rubber respectively, it 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 80 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.In addition, analyzing respectively other performances of modified EPT rubber
Measurement, 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 0.6g 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, in addition, analyzing respectively other performances of modified EPT rubber
Measurement, 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 preparation
The ionized catalyst of structure shown in formula made from example 1 (5), is dissolved in 10mL xylene solution, is divided into 5 parts, often
The adding manner of part is same as Example 1, obtains modified EPT rubber A7.Infrared light is carried out to modified EPT rubber
Spectrum measurement, the results showed that carbic anhydride has been grafted on ethylene propylene diene rubber.In addition, respectively to modified EPT rubber
Other performances carry out analysis measurement, 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 5 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 0.025 gram of preparation example 2 is in N2Under protection, it is dissolved in 70mL xylene solution to being completely dissolved to form reaction
System；The ionized catalyst for weighing structure shown in formula (5) made from 0.25 gram of preparation example 1 simultaneously, is dissolved in 10mL bis-
In toluene solution, catalyst solution C8 is obtained.
Reaction system is heated to 130 DEG C, 2mL catalyst solution C8 is added into reaction system, after reacting 10min, is remained
Remaining 8mL catalyst solution is uniformly divided into 4 parts, is added in reaction system in such a way that portion is added in every 10min, to last
After reaction system 10min is added in part catalyst solution C8, stop reaction, the reaction time is 1h in total.It after completion of the reaction will reaction
Liquid is filtered with nickel screen while hot, and acetone is added into filtrate and removes impurity, and is precipitated, and isolates sediment, clear with acetone
Sediment is washed 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 ethylene-propylene-diene monomer
On glue.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 5 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 gram of preparation example 2 is in N2Under protection, it is dissolved in 70mL xylene solution to complete
Dissolution forms reaction system；The ionized catalyst for weighing structure shown in formula (5) made from 0.01 gram of preparation example 1 simultaneously, by it
It is dissolved in 10mL xylene solution, obtains catalyst solution C9.
Reaction system is heated to 40 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 C9, stop reaction, the reaction time is 3h in total.After completion of the reaction by reaction solution
It is filtered while hot with nickel screen, and acetone is added into filtrate and removes impurity, and is precipitated, isolated sediment, cleaned with acetone
Sediment 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 monomer
On glue.In addition, carrying out analysis measurement to other performances of modified EPT rubber respectively, 1 the results are shown in Table.
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.
Table 1
Test case 1
The modified EPT rubber A1-A9 prepared in 1-9 of the embodiment of the present invention is subjected to cure by the following method
It can measurement.
Modified EPT rubber A1 prepared by the embodiment of the present invention 1 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-A9 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 to ternary by using ring opening cross-metathesis reaction
On EP rubbers, 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 0.44-0.71mol/kg, with unmodified ethylene propylene diene rubber
Degree of unsaturation compared to there is a degree of raising, this may be because the present invention is by the carbic anhydride of structure shown in formula (1)
With ethylene propylene diene rubber after alkene ring opening cross-metathesis reaction, the pendant double bonds of ethylene propylene diene rubber can be increased.It will
Embodiment 1 and embodiment 2 are compared, it can be seen that the modified EPT rubber obtained using the method that catalyst is added dropwise by several times
The grafting rate of glue is higher, this may be due to being added at one time catalyst after, catalyst concn is larger in system, carbic anhydride
Ring-opening metathesis polymerization easily occurs, so that the carbic anhydride quantity for participating in graft reaction is reduced, eventually leads to degree of unsaturation and connects
Branch rate decline.In addition, passing through embodiment 2 to embodiment 9, 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 (16)
1. a kind of preparation method of modified EPT rubber, this method includes the ring opening cross-metathesis reaction condition in alkene
Under, in the presence of the ionized catalyst of the structure shown in formula (2), by the nadik of structure shown in ethylene propylene diene rubber and formula (1)
Acid anhydrides 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；
Y is anion.
2. according to the method described in claim 1, 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；
Y is halide ion.
3. according to the method described in claim 1, wherein, R1For phenyl；
X1And X2It is each independently chloride ion；
L1And L2It is each independently phosphine, Cabbeen or substituted or unsubstituted imidazolidine；
Y is iodide ion.
4. according to the method described in claim 1, wherein, R1For phenyl, L1For substituted or unsubstituted imidazolidine, L2For phosphine, X1
And X2For chloride ion, Y is iodide ion.
5. according to the method described in claim 4, wherein, the phosphine is trialkyl phosphine.
6. according to the method in claim 2 or 3, wherein 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.
7. according to the method described in claim 6, wherein, R2And R3It is each independentlyR4、R5、R6、R7And R8
It is each independently selected from hydrogen or the alkyl of C1-C5.
8. according to the method described in claim 7, wherein, R2And R3For
9. according to the method described in claim 1, wherein, the ring opening cross-metathesis reaction of the alkene under an inert atmosphere into
Row, the condition of the ring opening cross-metathesis reaction of the alkene include：Reaction temperature is 20-150 DEG C, reaction time 0.5-5
Hour.
10. described to receive relative to the ethylene propylene diene rubber of 100 parts by weight according to the method described in claim 1, wherein
The dosage of Dick acid anhydrides is 0.05-40 parts by weight, and the dosage of the ionized catalyst is 0.05-10 parts by weight.
11. according to the method described in claim 1, wherein, the content of ethylene unit unit is 50- in the ethylene propylene diene rubber
70 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, institute
Stating Third monomer is one of 1,4- hexadiene, dicyclopentadiene and 5- ethylidene -2- norbornene or a variety of.
12. according to claim 1 or method described in 10, wherein the ionized catalyst in a manner of being added at one time or
The mode that person is added several times is added in reaction system.
13. according to the method for claim 12, 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.
14. according to the method described in claim 1, wherein, the organic solvent is the ring of toluene, dimethylbenzene, chlorobenzene, C6-C12
One of alkane, the linear paraffin of C5-C10, tetrahydrofuran, acetone and 1,4- dioxane are a variety of.
15. the modified EPT rubber that method described in any one of claim 1-14 is prepared.
16. modified EPT rubber according to claim 15, wherein with the weight of the modified EPT rubber
On the basis of, the grafting rate of the modified EPT rubber is 0.4-4 weight %；The unsaturation of the modified EPT rubber
Degree is 0.44-0.71mol/kg.
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| CN109867748A (en) * | 2017-12-01 | 2019-06-11 | 中国石油化工股份有限公司 | Ethylene propylene diene monomer graft polymer and preparation method thereof |
| CN109867896B (en) * | 2017-12-01 | 2021-07-02 | 中国石油化工股份有限公司 | Halogen-free flame-retardant EPDM/PP thermoplastic elastomer material and application thereof |
| CN109867750A (en) * | 2017-12-01 | 2019-06-11 | 中国石油化工股份有限公司 | Ethylene propylene diene monomer graft polymer and preparation method thereof |
| CN112409523A (en) * | 2019-08-22 | 2021-02-26 | 中国石油化工股份有限公司 | Modified ethylene propylene diene monomer and preparation method thereof |
| CN113896836A (en) * | 2020-06-22 | 2022-01-07 | 中国石油化工股份有限公司 | Modified ethylene propylene diene monomer and preparation method thereof |
| CN113896816A (en) * | 2020-06-22 | 2022-01-07 | 中国石油化工股份有限公司 | Modified ethylene propylene diene monomer and preparation method thereof |
| CN113896837A (en) * | 2020-06-22 | 2022-01-07 | 中国石油化工股份有限公司 | Modified ethylene propylene diene monomer and preparation method thereof |
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| EP2835381A1 (en) * | 2013-08-09 | 2015-02-11 | Lanxess Elastomers B.V. | Functionalized olefinic copolymers |
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