CN106589245A - Modified terpolymer EP rubber and preparation method thereof - Google Patents
Modified terpolymer EP rubber and preparation method thereof Download PDFInfo
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- CN106589245A CN106589245A CN201510683768.8A CN201510683768A CN106589245A CN 106589245 A CN106589245 A CN 106589245A CN 201510683768 A CN201510683768 A CN 201510683768A CN 106589245 A CN106589245 A CN 106589245A
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Abstract
The invention discloses modified terpolymer EP rubber and a preparation method thereof. The method comprises the following steps: under a condition of an open loop cross-metathesis reaction of alkene, in the existence of an ion type catalyst with the structure shown in the formula (2), terpolymer EP rubber and nadic anhydride with the structure shown in formula (1) are contacted in an organic solvent. The preparation method of modified terpolymer EP rubber has the advantages of high grafting ratio, rapid reaction, simple steps, and easy enforcement. The grafting ratio of modified terpolymer EP rubber is 0.4-4wt%; compared with modified terpolymer EP rubber and unmodified terpolymer EP rubber, degree of unsaturation is 0.44-0.71mol/kg, and sulfuration speed is improved.
Description
Technical field
The present invention relates to a kind of modified EPT rubber and preparation method thereof.
Background technology
Ethylene propylene diene rubber (EPDM) has the physics such as excellent high resiliency, viscoplasticity, electrical insulating property
Chemical property is very prominent in the application of the aspect such as engineering plastics toughness reinforcing and ozone-resistant be aging.But, by
Belong to non-polar rubber in ethylene propylene diene rubber, its oil resistant, chemical-resistant reagent, tack and mutual viscosity compared with
Difference, it is difficult to be subject to certain restrictions with polar polymer blending, therefore its range of application.Therefore, to three
First EP rubbers is modified and is particularly important with the compatibility of polar polymer with strengthening it.
It is mainly by the way that ethylene propylene diene rubber is grafted with maleic anhydride (MAH) in prior art
Reaction, introduces highly polar group in rubber molecular chain, makes graft have highly polar and reactivity, from
And the graft for causing to prepare is poly- as a kind of multi-functional macromolecule interfacial compatilizer and filler filling
The coupling agent or dispersant of compound, is with a wide range of applications.
The graft reaction of rubber and MAH mainly based on radical reaction, can melt, emulsion and
Carry out in solution state, including the method such as fusion-grafting, irradiation grafting, solution graft copolymerization.Using different
Initiator system, the free radical mode of generation is different, and percent grafting and grafting efficiency are also different.
Melt grafting grafting MAH percent grafting it is not high, and after the completion of grafting remove residual monomer and
More difficult during initiator, products obtained therefrom smell is dense, and Color whiteness is low.Irradiation grafting method is grafted MAH
Percent grafting and grafting efficiency it is general all high than melt grafting.But irradiation grafting easily causes the friendship of rubber
Connection, side reaction is not easily controlled, and equipment cost is higher.Additionally, when reaction temperature exceeds certain limit
When, polymer molecular chain occurs degraded or crosslinking side reaction.
CN101402711B discloses a kind of using high-energy ray radiation ethylene propylene diene rubber grafted maleic
The method of acid anhydride, it with ethylene propylene diene rubber as raw material, with maleic anhydride as grafted monomers, add plasticizer,
Reinforcing agent and vulcanization retarder Jing melt blendings, carry out shooting high the prepared ternary second of beta radiation before melting extrusion
The graft of the third rubber and maleic anhydride, the percent grafting of the graft product is 1.2-3.6%.
The method that CN102643391B discloses a kind of to prepare grafting maleic anhydride with ethylene propylene terpolymer.Should
Method is by ethylene propylene diene rubber, initiator, maleic anhydride, styrene monomer, hexamethylphosphoric acid triamide
Composition produces grafting maleic anhydride with ethylene propylene terpolymer by melt grafting.The percent grafting of the method is
0.59-1.42%.
Solution grafting is grafted MAH compared with other grafting methods, and reaction condition temperature is low, accessory substance
Less, the percent grafting and utilization rate of MAH are all higher.But the reaction time of existing solution grafting is long,
Low production efficiency, and existing grafting method be modified the EP rubbers for obtaining pendant double bonds grafting
Just disappear after MAH so that the sulfuration of EP rubbers is more difficult.
The content of the invention
The purpose of the present invention is the drawbacks described above for overcoming prior art, there is provided a kind of modified EPT rubber
Preparation method and the modified EPT rubber that prepared by the method.
The present invention provides a kind of preparation method of modified EPT rubber, and the method is included in opening for alkene
Under the conditions of ring cross-metathesis, in the presence of the ionized catalyst of structure shown in formula (2), will
Ethylene propylene diene rubber is contacted in organic solvent with the carbic anhydride of structure shown in formula (1),
In formula (2), R1For hydrogen, the thiazolinyl of C2-C20, the alkynyl of C2-C20, the alkyl of C1-C20,
The aryl of C6-C20, the carboxylic acid ester groups of C2-C20, the alkoxyl of C1-C20, the alkene oxygen of C2-C20
Base, the chain oxy-acetylene of C2-C20, the aryloxy group of C6-C20, the alkylthio group of C1-C20, C1-C20
Alkyl sulphonyl or C1-C20 Alkylsulfinyls,
X1And X2It is each independently anion ligand,
L1And L2It is each independently neutral ligand, and alternatively L1And L2Can be interconnected to form
The neutral ligand of two coordinations；
Y is anion.
Present invention also offers a kind of modified EPT rubber prepared by said method.
The present invention by using structure shown in formula (2) ionized catalyst be catalyzed ethylene propylene diene rubber with
The ring opening cross-metathesis reaction of the alkene of the carbic anhydride of structure shown in formula (1) causes what is prepared to change
Property ethylene propylene diene rubber degree of unsaturation be 0.44-0.71mol/kg, and the modified EPT rubber also has
Have the advantages that percent grafting is high, specifically, on the basis of the weight of the modified EPT rubber, this
The percent grafting of the modified EPT rubber of bright offer is 0.4-4 weight %.What in addition the present invention was provided changes
Property ethylene propylene diene rubber preparation method have reaction quick and the characteristics of step simply easily implements.
The modified EPT rubber that the present invention is provided vulcanizes compared with unmodified ethylene propylene diene rubber
Speed improves, and is the present invention the reason for possible by the carbic anhydride of structure shown in formula (1)
With ethylene propylene diene rubber after alkene ring opening cross-metathesis reaction, ethylene propylene diene rubber can be increased
The double bond content of side chain, beneficial to sulfidation so that the curingprocess rate of modified EP rubbers is carried
It is high.
Additionally, the present invention by specific catalyst feed postition be obtained in that with higher degree of unsaturation with
The modified EPT rubber of higher percent grafting.Preferably, 2-6 addition reactant of the catalyst point
In system, and adjacent addition time interval twice is 3-15 minutes, and the amount of catalyst is arbitrarily added twice
Difference account for below 5 weight % of the total addition of catalyst, by this way add catalyst be conducive to carrying
The percent grafting and degree of unsaturation of high modified EPT rubber.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Description of the drawings
Accompanying drawing is, for providing a further understanding of the present invention, and to constitute the part of specification, with
Detailed description below is used to explain the present invention together, but is not construed as limiting the invention.
In accompanying drawing：
Fig. 1 is the infrared spectrogram of the modified EPT rubber that embodiments in accordance with the present invention 1 are obtained,
Wherein, a represents the infrared spectrum of unmodified ethylene propylene diene rubber, and b represents modified EPT rubber
Infrared spectrum.
Specific embodiment
The specific embodiment of the present invention is described in detail below.It should be appreciated that this place is retouched
The specific embodiment stated is merely to illustrate and explains the present invention, is not limited to the present invention.
The present invention provides a kind of preparation method of modified EPT rubber, and the method is included in opening for alkene
Under the conditions of ring cross-metathesis, in the presence of the ionized catalyst of structure shown in formula (2), will
Ethylene propylene diene rubber is contacted in organic solvent with the carbic anhydride of structure shown in formula (1),
In formula (2), R1For hydrogen, the thiazolinyl of C2-C20, the alkynyl of C2-C20, the alkyl of C1-C20,
The aryl of C6-C20, the carboxylic acid ester groups of C2-C20, the alkoxyl of C1-C20, the alkene oxygen of C2-C20
Base, the chain oxy-acetylene of C2-C20, the aryloxy group of C6-C20, the alkylthio group of C1-C20, C1-C20
Alkyl sulphonyl or C1-C20 Alkylsulfinyls,
X1And X2It is each independently anion ligand,
L1And L2It is each independently neutral ligand, and alternatively L1And L2Can be interconnected to form
The neutral ligand of two coordinations；
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 X2Can be common various anion ligands, for example, can be each
Halide ion, preferably chlorion；
In formula (2), L1And L2Can be each common various neutral ligands, its instantiation can
With including but not limited to：Phosphine, amine, thioether, Cabbeen or substituted or unsubstituted imidazolidine.It is preferred that
Ground, L1And L2For phosphine, Cabbeen or substituted or unsubstituted imidazolidine.It is highly preferred that L1To take
Generation or unsubstituted imidazolidine, L2For phosphine.
Phosphine can be the hydrogen partial in various phosphine molecules or all be replaced by organic group the change to be formed
Compound, preferably trialkyl phosphine, the organic group is identical or different, each can be selected from alkyl group (such as
The alkyl group of C1-C10) or substituted or unsubstituted cycloalkyl it is (substituted or unsubstituted such as C6-C12
Cycloalkyl), preferably it each is selected from substituted or unsubstituted cycloalkyl, more preferably cyclohexyl.Specifically,
The example of the phosphine can be including but not limited to：It is trimethyl-phosphine, triethyl phosphine, tri-n-butyl phosphine, three secondary
One kind in butyl phosphine, tripropyl phosphine, three amyl group phosphines, three hexyl phosphines, tri octyl phosphine and tricyclohexyl phosphine
Or it is various.
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；R2
And R3It is preferably independently of one anotherR4、R5、R6、R7And R8It is identical or different, respectively
From the alkyl that can be selected from hydrogen or C1-C5；R2And R3More preferablyR2And R3
More preferablyThe instantiation of the alkyl of C1-C5 can be including but not limited to：
Methyl, ethyl, n-propyl, isopropyl, normal-butyl, sec-butyl, isobutyl group, the tert-butyl group and n-pentyl.
In the preferred embodiment of the present invention, in formula (2), R1For phenyl, L1For replace or
Unsubstituted imidazolidine, L2For phosphine, X1And X2For chlorion, Y is iodide ion.The one of the present invention
In planting preferred embodiment, in formula (2), R1For phenyl, L1ForL2For trialkyl phosphine, X1And X2For chlorion, Y is I5 -。
According to the present invention, in order that the ionized catalyst has more preferable catalytic effect, the ion
Type catalyst is the ionized catalyst of structure shown in formula (5),
In above-mentioned formula (5), PCy3Tricyclohexyl phosphine is represented, Ph represents phenyl.
According to the present invention, the thiazolinyl of C2-C20 can be straight chain or side chain, and instantiation can be wrapped
Include but be not limited to：Vinyl, acrylic, cyclobutenyl, pentenyl, hexenyl, heptenyl, octenyl,
Nonenyl, decene base, undecenyl, dodecenyl succinic.
According to the present invention, the alkynyl of C2-C20 can be straight chain or side chain, and instantiation can be wrapped
Include but be 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 straight or branched, and specific example can be wrapped
Include but be not limited to：Methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl and
Decyl, undecyl, dodecyl, octadecyl.
According to the present invention, the instantiation of the aryl of C6-C20 can be including but not limited to：Phenyl, first
Base phenyl, naphthyl.
According to the present invention, the carboxylic acid ester groups of C2-C20 refers to contain in strand's
Group, instantiation can be including but not limited to：Methyl propionate base, ethyl acetate base, propyl formate base.
According to the present invention, the instantiation of the alkoxyl of C1-C20 can be including but not limited to：Methoxyl group,
Ethyoxyl, propoxyl group, isopropoxy, butoxy, sec-butoxy, tert-butoxy, amoxy, own oxygen
Base, epoxide in heptan, octyloxy, nonyl epoxide, decyloxy, octadecane epoxide.
According to the present invention, the instantiation of the alkenyloxy of C2-C20 can be including but not limited to：1- allyls
Epoxide, 2- alkene butoxy, 1- alkene pentyloxies.
According to the present invention, the instantiation of the chain oxy-acetylene of C2-C20 can be including but not limited to：1- alkynes third
Epoxide, 2- alkynes butoxy, 1- alkynes amoxys.
According to the present invention, the instantiation of the aryloxy group of C6-C20 can be including but not limited to：Phenoxy group,
Naphthyl epoxide.
According to the present invention, the alkylthio group of C1-C20 for the straight chain that is bonded by a sulphur atom or
The C1-C20 alkyl of chain, instantiation is included but is not limited to：Methyl mercapto (CH3- S-), ethylmercapto group, third
Sulfenyl, butylthio, penta sulfenyl, 1- methyl-prop sulfenyls, 2- methyl-props sulfenyl and 1,1- dimethylethylthios.
According to the present invention, the instantiation of the alkyl sulphonyl of C1-C20 can be including but not limited to：First
Base sulfonyl, ethylsulfonyl, sulfonyl propyl base, butyl sulfonyl, nonyl sulfonyl.
According to the present invention, the instantiation of the Alkylsulfinyl of C1-C20 can be including but not limited to：
Methyl sulfinyl, ethylsulfinyl-1 base.
The method according to the invention, the addition manner of the ionized catalyst is not particularly limited, can be with
By catalyst be added in the way of disposable addition or in the way of adding several times ethylene propylene diene rubber with
In the reaction system that the carbic anhydride of structure shown in formula (1) is contacted.In view of catalyst once
Property add and be easily caused carbic anhydride in reaction system side reaction, the side for preferably adding several times occur
Formula is added.It is highly preferred that the catalyst is added in reaction system point 2-6 time, and adjacent adding twice
The angle of incidence accounts for the total addition of catalyst at intervals of 3-15 minutes, the difference that the amount of catalyst is arbitrarily added twice
5 weight % below, add catalyst to be conducive to improving modified EPT rubber by this way
Degree of unsaturation and percent grafting.It is further preferred that in order that catalyst plays more preferable catalytic effect, will
The catalyst (is preferably dissolved in the organic solvent) as a solution the catalyst a point 2-6
In secondary addition reaction system, and adjacent addition time interval twice is 3-15 minutes, is arbitrarily added twice
The difference for entering the amount of catalyst is accounted for below 5 weight % of the total addition of catalyst.
The method according to the invention, the ionized catalyst of structure shown in formula (2) can adopt organic conjunction
Into the method synthesis that field is commonly used.For example：Lewis acid can be connect with the compound shown in formula (6)
Reaction is touched, so as to obtain the compound of structure shown in formula (2),
In formula (6), R1、L1、L2、X1And X2Definition it is identical with described previously, here is no longer detailed
State.
Lewis acid is not particularly limited with the catalytic condition of compound shown in formula (6).One
As, the temperature of the contact can be 20-100 DEG C, the compound shown in lewis acid and formula (6)
Mol ratio can be 1-5：1.The lewis acid can be conventional selection, such as iodine.The contact
Time appropriate selection can be carried out according to the temperature for being contacted.The contact is preferably in inert atmosphere
Under carry out, the inert atmosphere to be referred to and chemically interactive chemical combination does not occur with reactant and product
Thing, for example：One or more in nitrogen and the periodic table of elements in group 0 element gas, the described 0th
Race's elemental gas such as argon gas.Various methods commonly used in the art can be adopted to contact the mixture for obtaining
Purified, so as to obtain the ionized catalyst of structure shown in formula (2), for example：To can obtain
Mixture carry out pillar layer separation.Specifically, can by the mixture for obtaining alundum (Al2O3) post,
And eluted as eluant, eluent using dichloromethane, so as to the ionic for obtaining structure shown in formula (2) is urged
Agent.
According to the present invention, the ring opening cross-metathesis reaction of the alkene is preferably carried out under an inert atmosphere.
The inert atmosphere is consistent with described above, will not be described here.
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 selected with the routine of this area, for example, the condition of the ring opening cross-metathesis reaction of the alkene includes：
Reaction temperature is 20-150 DEG C, and the reaction time is 0.5-5 hours；Under preferable case, the alkene is opened
The condition of ring cross-metathesis includes：Reaction temperature is 40-130 DEG C, and the reaction time is 1-3 hours.
According to the present invention, the use of the ethylene propylene diene rubber, carbic anhydride and the ionized catalyst
Amount can change in wider scope, as long as can realize being swift in response and obtaining with target saturation degree
The purpose of the modified EPT rubber high with percent grafting, relative to the ternary of 100 weight portions
EP rubbers, the consumption of the carbic anhydride of structure shown in the formula (1) is 0.05-40 weight portions, excellent
Elect 0.5-20 weight portions as；The consumption of the ionized catalyst of structure shown in the formula (2) is 0.05-10
Weight portion, preferably 0.2-5 weight portions.
According to the present invention, the ethylene propylene diene rubber can be various ethylene-propylene-diene monomers commonly used in the art
Glue, such as on the basis of the gross weight of the ethylene propylene diene rubber, ethene knot in the ethylene propylene diene rubber
The content of structure unit is 50-70 weight %, the content of Third monomer is 4-6 weight %；The ternary second
The weight average molecular weight of the third rubber is 100,000-40 ten thousand；The Third monomer can be commonly used in the art each
Third monomer is planted, for example, can be Isosorbide-5-Nitrae-hexadiene, dicyclopentadiene (DCPD) and 5- ethylidene -2-
One or more in ENB, preferably 5- ethylidene -2- ENBs (ENB).
According to the present invention, prepare the organic solvent of modified EPT rubber for it is existing it is various can
Used as the organic substance of reaction media, under preferable case, the organic solvent is toluene, dimethylbenzene, chlorine
Benzene, the cycloalkane of C6-C12, the linear paraffin of C5-C10, tetrahydrofuran, acetone and 1,4- dioxies six
One or more in ring, further preferably in the case of, the organic solvent is toluene, dimethylbenzene, chlorine
One or more in benzene, hexamethylene, n-hexane, tetrahydrofuran, acetone and 1,4- dioxane；Most
Preferably toluene and/or dimethylbenzene.These solvents can be used alone, can also be used in mixed way.It is described
The consumption of organic solvent can be the conventional selection of this area, repeat no more herein.
According to the present invention, the preparation method of the modified EPT rubber also includes purification step.It is described
Purification step can be the conventional purification step in this area, for example, the reactant liquor that will be obtained after reaction
Filtered with nickel screen, and add acetone to form precipitation in filtrate, then the sediment of gained is filtered, washed
Wash and be dried.
According to the present invention, the carbic anhydride of structure shown in the formula (1) can pass through commercially available,
Can also be prepared by the method for prior art.For example, the Na Di of structure shown in the formula (1)
Gram acid anhydrides is prepared by the following method：Under the conditions of Diels-Alder reaction, will tie formula (4) Suo Shi
The cyclopentadiene of structure is contacted in organic solvent with maleic anhydride,
According to the consumption of the present invention, the cyclopentadiene of structure shown in the formula (4) and maleic anhydride
Can change in wider scope, as long as can be with the carbic anhydride of structure shown in production (1)
Can.Usually, the cyclopentadiene of structure shown in the formula (4) and the mol ratio of maleic anhydride can
Think 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 area,
For example can include：The temperature of reaction is 80-250 DEG C, preferably 100-230 DEG C；The time of reaction is
0.1-50 hours, preferably 0.5-10 hours.
According to the present invention, prepare the organic solvent in carbic anhydride for it is existing it is various being capable of conduct
The organic substance of reaction media, under preferable case, the organic solvent is selected from ether, tetrahydrofuran and first
One or more in benzene.The consumption of the organic solvent is referred to prior art and is reasonably selected
Select, will not be described here.
The preparation method of the carbic anhydride of structure shown in the formula (1) also includes purification step, described
Purification step is referred to prior art to be carried out, and be will not be described here.
Present invention also offers a kind of modified EPT rubber prepared by said method.
According to the present invention, on the basis of the weight of the modified EPT rubber, the modified ternary second
The percent grafting of the third rubber is 0.4-4 weight %.
According to the present invention, the degree of unsaturation of the modified EPT rubber can reach
0.44-0.71mol/kg, preferably 0.53-0.71mol/kg.
In accordance with the present invention it is preferred that, it is described when the Third monomer in ethylene propylene diene rubber is ENB
Modified EPT rubber contains construction unit A, construction unit B, construction unit C and construction unit D,
Wherein, the construction unit A is the unit with structure shown in formula (1 '), and the construction unit B is
Unit with structure shown in formula (2 '), the construction unit C is with structure shown in formula (3 ')
Unit, the construction unit D is the unit with structure shown in formula (4 ')；
The improvements of the present invention essentially consist in the modified EPT rubber of offer compared to unmodified
Ethylene propylene diene rubber, the double bond content in side chain increases, and with the weight of the modified EPT rubber
On the basis of, the percent grafting of the modified EPT rubber is modified EPT described in 0.4-4 weight %
The degree of unsaturation of rubber can reach 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 of the invention, it is preferable that the weight of the modified EPT rubber
Average molecular weight is 100,000-40 ten thousand.
The weight average molecular weight of modified EPT rubber is by gel permeation chromatography (GPC) side in the present invention
Method is determined.
Hereinafter will be described the present invention by embodiment.
In following preparation example and embodiment, the performance measurement being related to is as follows：
(1) measure of the ionic catalyst structure of preparation example 1：It is with tetramethylsilane (TMS)
Internal standard, on the INOVA500MHz type nuclear magnetic resonance spectrometers of VARIAN companies of the U.S. nuclear-magnetism is determined
Resonance hydrogen spectrum (1H-NMR) and carbon-13 nmr spectra (13C-NMR)；The crystal for selecting suitable dimension exists
X-ray single crystal diffraction measure is carried out on BRUKER SMART 1000CCD x-ray diffractometers；
(2) grafting samples after purification and ethylene propylene diene rubber are molded at 160 DEG C and make thickness about
The film of 0.1mm, is characterized with BRUKER company's T ENSOR-27 type Fourier infrared spectrographs；
(3) percent grafting (PG) is determined in accordance with the following methods：
1g grafts are accurately weighed, adds 50mL xylene solvents (limited purchased from Shanghai Yue Feng chemical industry
Company), after being heated to graft whole dissolving, room temperature is cooled to, 10mL concentration is added for 0.03mol/
The KOH- ethanol solutions (Jing oxalic acid-ethanol solution is demarcated) of L, it is molten with oxalic acid-ethanol after stirring 10min
Drop is determined, and using phenolphthalein as indicator, when indicator is aobvious red titration is stopped.It is calculated as follows grafting
Rate：
In formula, it is percent grafting that PG is the mass fraction of carbic anhydride in graft, %；M is grafting
The quality of thing, g；C1For the concentration of KOH- ethanol solutions, mol/L；V1For KOH- ethanol solutions
Volume, mL；C2For the concentration of oxalic acid-ethanol solution, mol/L；V2For the volume of oxalic acid-ethanol solution,
mL。
(4) fusing point of the carbic anhydride in preparation example is given birth to using Shanghai Shen Guang instrument and meters Co., Ltd
The WRS-1C melting point apparatus of product are determined, and the computing formula of yield is as follows：
In formula, Y：Yield, %；mIt is real：The actual production of carbic anhydride, g；mReason：With maleic
Dicarboxylic anhydride participates in the theoretical yield of the carbic anhydride that the amount of reaction is calculated, g.
(5) degree of unsaturation of modified EPT rubber is specific as follows by iodometric determination：Accurately
2g modified EPT rubber samples are weighed, in being placed in 250mL ground conical flasks, 50mL CCl is added4
Sample is dissolved, with pipette 20mL IBrs (IBr) solution is added, opened in dark place after fully shaking
1h, is subsequently adding the liquor kalii iodide that 10mL concentration is 10 weight %, shakes up, with the thio sulphur of 0.1N
When sour sodium standard solution is titrated to solution in yellow, 5mL starch indicators are added, continue to be titrated to indigo plant
Decoloration is terminal.Do blank test simultaneously.Degree of unsaturation is calculated as follows：
In formula, V0：Blank test consumes the volume of sodium thiosulfate standard solution, mL；V：Sample disappears
The volume of consumption sodium thiosulfate standard solution, mL；C：The concentration of sodium thiosulfate standard solution, mol/L；
m：Sample mass, g.The unit of degree of unsaturation is mol/kg in formula.
(6) weight average molecular weight of modified EPT rubber passes through gel permeation chromatography (GPC) method
Determine, instrument is the Isocratic HPLC gel permeation chrommatographs of Waters 1515.
Preparation example 1
The preparation example is used to illustrate the preparation of ionized catalyst.
Under nitrogen protection, 0.76g iodine, 0.85g formulas (7) institute are added in the there-necked flask of 100mL
The compound (commercially available from lark prestige Science and Technology Ltd.) for showing and 20mL dichloromethane, (be in room temperature
25 DEG C) stir 0.5 hour.Mixture alundum (Al2O3) column chromatography will be obtained and separated (expansion
Agent is dichloromethane), after the eluent for obtaining is concentrated, washed with hexamethylene, 1.31g is obtained for Huang
The catalyst of color solid.By the catalyst for obtaining carry out proton nmr spectra (1H-NMR) it is total to nuclear-magnetism
The carbon that shakes spectrum (13C-NMR) and X-ray single crystal diffraction determines analysis, confirm that the catalyst that obtains has
Structure shown in formula (5).
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
The preparation example is used for the preparation method of the carbic anhydride of structure shown in formula (1).
15.7 grams of maleic anhydride of the addition (0.16mol) in the reaction bulb of 100mL, toluene 40mL,
Reaction bulb is placed in into stirring in thermostated cooling bath and is cooled to 5 DEG C, cyclopentadiene is added dropwise by constant pressure funnel
14 grams (0.2mol), the temperature controlled in reaction bulb is less than 15 DEG C, is warmed up to reaction after completion of dropping
120 DEG C are continued to stir 1 hour, and cooling separates out white crystals, leaches carbic anhydride crude product, Ran Houzai
Recrystallized with toluene, filtration drying obtains 19.0 grams of carbic anhydride, the fusing point of carbic anhydride
(mp) it is 165.8 DEG C -167 DEG C, yield is 72.3%.
Embodiment 1
The present embodiment is used to illustrate modified EPT rubber of present invention offer and preparation method thereof.
By 5 grams of ethylene propylene diene rubbers (3280, purchased from Yanshan Petrochemical company, ethene in ethylene propylene diene rubber
It is 5 weight % that the content of construction unit is 55 weight %, the content of Third monomer, and weight average molecular weight is
300000, the Third monomer is 5- ethylidene -2- ENBs (ENB)), 0.8 gram of preparation example 2 is obtained
Carbic anhydride in N2Under protection, it is dissolved in 70mL xylene solutions to form reactant to being completely dissolved
System.The ionized catalyst of structure shown in formula (5) obtained in 0.05 gram of preparation example 1 is weighed simultaneously,
In being dissolved in 10mL xylene solutions, catalyst solution C1 is obtained.
Reaction system is heated to into 120 DEG C, 2mL catalyst solution C1 is added in reaction system, instead
After answering 10min, remaining 8mL catalyst solutions are uniformly divided into 4 parts, are added with every 10min a
Mode be added in reaction system, treat that last portion catalyst solution C1 adds reaction system 10min
Afterwards, reaction is stopped, altogether the reaction time is 1h.Reacting liquor while hot is filtered with nickel screen after completion of the reaction,
And add acetone to remove impurity in filtrate, and precipitated, sediment is isolated, clean heavy with acetone
Starch is clarified up to filtrate, is put the precipitate in 60 DEG C of vacuum drying ovens and is dried after 14h, obtains modified three
First EP rubbers A1.Infrared spectrum measurement is carried out to modified EPT rubber, Fig. 1 (a tables are as a result seen
Show the infrared spectrum of unmodified ethylene propylene diene rubber, b represents the infrared light of modified EPT rubber
Spectrum).Infrared spectrogram shows that carbic anhydride has been grafted on ethylene propylene diene rubber, additionally, respectively
Measure is analyzed to other performances of modified EPT rubber, 1 is the results are shown in Table.
Embodiment 2
Modified EPT rubber is prepared using method same as Example 1, except that, will be anti-
Answer system to be heated to 120 DEG C, then the catalyst solution C1 of 10mL is disposably added to into reactant
In system, 1h is reacted.Obtain modified EPT rubber A2.Product carries out infrared spectrum measurement, as a result
Show that carbic anhydride has been grafted on ethylene propylene diene rubber, in addition respectively to modified EPT rubber
Other performances be analyzed measure, the results are shown in Table 1.
Embodiment 3
Modified EPT rubber is prepared using method same as Example 1, except that, will be anti-
Answer system to be heated to 120 DEG C, then at twice catalyst solution C1 is added in reaction system, plus
The time for entering is respectively when reacting beginning when reaction system is heated to into 120 DEG C and reaction carries out 15min
Afterwards, each addition is 5mL, and reaction stops reaction after 1 hour.Obtain modified ethylene propylene diene rubber
A3.Infrared spectrum measurement is carried out to modified EPT rubber, as a result shows that carbic anhydride has been grafted
To on ethylene propylene diene rubber, additionally, being analyzed survey to other performances of modified EPT rubber respectively
It is fixed, the results are shown in Table 1.
Comparative example 1
Modified EPT rubber is prepared using method same as Example 1, except that, adopt
The maleic anhydride of identical weight replaces carbic anhydride.Obtain the modified EPT rubber D1 of reference.
Infrared spectrum measurement is carried out to the modified EPT rubber of reference, is as a result shown that maleic anhydride is non-grafted and is arrived
On ethylene propylene diene rubber.And measure is analyzed to reference ethylene propylene diene rubber D1, the results are shown in Table 1.
Comparative example 2
By ethylene propylene diene rubber (3280, purchased from Yanshan Petrochemical company, ethylene unit in ethylene propylene diene rubber
The content of unit be 55 weight %, the content of Third monomer be 5 weight %, weight average molecular weight be 300,000,
The Third monomer be ENB) be unmodified ethylene propylene diene rubber as reference EP rubbers D2, and
Measure is analyzed to reference ethylene propylene diene rubber D2,1 is the results are shown in Table.
Embodiment 4
The present embodiment is used to illustrate modified EPT rubber of present invention offer and preparation method thereof.
Modified EPT rubber is prepared using method same as Example 1, except that, reaction
Time is 2 hours, i.e., after last portion catalyst solution adds reaction system 70min, stop reaction.
Obtain modified EPT rubber A4.Infrared spectrum measurement is carried out to modified EPT rubber, as a result
Show that carbic anhydride has been grafted on ethylene propylene diene rubber, additionally, respectively to modified EPT rubber
Other performances of glue are analyzed measure, the results are shown in Table 1.
Embodiment 5
Modified EPT rubber is prepared using method same as Example 1, except that, will be anti-
Answer system to be heated to 80 DEG C, obtain modified EPT rubber A5.Modified EPT rubber is carried out
Infrared spectrum measurement, as a result shows that carbic anhydride has been grafted on ethylene propylene diene rubber.Additionally, point
Other other performances to modified EPT rubber are analyzed measure, the results are shown in Table 1.
Embodiment 6
Modified EPT rubber is prepared using method same as Example 1, except that, add
The carbic anhydride of 0.6g, obtains modified EPT rubber A6.Modified EPT rubber is carried out
Infrared spectrum measurement, as a result shows that carbic anhydride has been grafted on ethylene propylene diene rubber, additionally, point
Other other performances to modified EPT rubber are analyzed measure, the results are shown in Table 1.
Embodiment 7
Modified EPT rubber is prepared using method same as Example 1, except that, weigh
The ionized catalyst of structure shown in formula (5), is dissolved in 10mL obtained in 0.08g preparation examples 1
In xylene solution, 5 parts are divided into, per part of feed postition is same as Example 1, obtain modified three
First EP rubbers A7.Infrared spectrum measurement is carried out to modified EPT rubber, as a result shows Na Dike
Acid anhydrides has been grafted on ethylene propylene diene rubber.Additionally, respectively to other property of modified EPT rubber
Measure can be analyzed, 1 is the results are shown in Table.
Embodiment 8
The present embodiment is used to illustrate modified EPT rubber of present invention offer and preparation method thereof.
By 5 grams of ethylene propylene diene rubbers (3280, purchased from Yanshan Petrochemical company, ethene in ethylene propylene diene rubber
It is 5 weight % that the content of construction unit is 55 weight %, the content of Third monomer, and weight average molecular weight is
300000, the Third monomer is ENB), carbic anhydride obtained in 0.025 gram of preparation example 2 is in N2Protect
Under shield, it is dissolved in 70mL xylene solutions to form reaction system to being completely dissolved；Weigh 0.25 restraint simultaneously
The ionized catalyst of structure shown in formula (5), is dissolved in 10mL dimethylbenzene obtained in standby example 1
In solution, catalyst solution C8 is obtained.
Reaction system is heated to into 130 DEG C, 2mL catalyst solution C8 is added in reaction system, instead
After answering 10min, remaining 8mL catalyst solutions are uniformly divided into 4 parts, are added with every 10min a
Mode be added in reaction system, treat that last portion catalyst solution C8 adds reaction system 10min
Afterwards, reaction is stopped, altogether the reaction time is 1h.Reacting liquor while hot is filtered with nickel screen after completion of the reaction,
And add acetone to remove impurity in filtrate, and precipitated, sediment is isolated, clean heavy with acetone
Starch is clarified up to filtrate, is put the precipitate in 60 DEG C of vacuum drying ovens and is dried after 14h, obtains modified three
First EP rubbers A8.Infrared spectrum measurement is carried out to modified EPT rubber, as a result shows Na Dike
Acid anhydrides has been grafted on ethylene propylene diene rubber.Additionally, respectively to other property of modified EPT rubber
Measure can be analyzed, 1 is the results are shown in Table.
Embodiment 9
The present embodiment is used to illustrate modified EPT rubber of present invention offer and preparation method thereof.
By 5 grams of ethylene propylene diene rubbers (ESPRENE 305, purchased from SUMITOMO CHEMICAL, in ethylene propylene diene rubber
The content of ethylene unit unit be 65 weight %, the content of Third monomer be 7 weight %, weight average molecular weight
For 120,000, the Third monomer is dicyclopentadiene (DCPD)), the obtained enlightening of receiving of 1 gram of preparation example 2
Gram acid anhydrides is in N2Under protection, it is dissolved in 70mL xylene solutions forming reaction system to being completely dissolved；
The ionized catalyst of structure shown in formula (5) obtained in 0.01 gram of preparation example 1 is weighed simultaneously, its is molten
Solution obtains catalyst solution C9 in 10mL xylene solutions.
Reaction system is heated to into 40 DEG C, 2mL catalyst solution C9, reaction are added in reaction system
After 15min, remaining 8mL catalyst solutions are uniformly divided into 4 parts, and with every 15min a side is added
Formula is added in reaction system, after last portion catalyst solution C9 adds reaction system 105min,
Stop reaction, altogether the reaction time is 3h.Reacting liquor while hot is filtered with nickel screen after completion of the reaction, and to
Add acetone to remove impurity in filtrate, and precipitated, isolate sediment, with acetone sediment is cleaned
Until filtrate clarification, puts the precipitate in 60 DEG C of vacuum drying ovens and be dried after 14h, modified ternary second is obtained
Third rubber A9.Infrared spectrum measurement is carried out to modified EPT rubber, as a result shows carbic anhydride
It has been grafted on ethylene propylene diene rubber.Additionally, entering to other performances of modified EPT rubber respectively
Row analysis is determined, and the results are shown in Table 1.
Comparative example 3
By ethylene propylene diene rubber (ESPRENE 305, purchased from SUMITOMO CHEMICAL, ethene in ethylene propylene diene rubber
It is 7 weight % that the content of construction unit is 65 weight %, the content of Third monomer, and weight average molecular weight is
120000, the Third monomer is DCPD) it is unmodified ethylene propylene diene rubber as reference EP rubbers
D3, and measure is analyzed to reference ethylene propylene diene rubber D3, the results are shown in Table 1.
Table 1
Test case 1
The modified EPT rubber A1-A9 prepared in embodiment of the present invention 1-9 is entered by the following method
Row curability is determined.
Modified EPT rubber A1 prepared by the embodiment of the present invention 1 of 100 weight portions is placed on double roller
On cylinder rubber mixing machine, at 35 ± 5 DEG C of temperature, the activated zinc oxide of 5 weight portions, 1 weight portion are successively added
Stearic acid, the carbon black (N550, Shanghai Cabot Chemical Co., Ltd.) of 80 weight portions, 50 weight portions
ASTM103# oil (Ningbo co evolution work Co., Ltd), 1 weight portion Vulcanization accelerator TMTD (on
The rubber Science and Technology Ltd. of Nereid one), (Shijiazhuang is sharp to open up the limited public affairs of chemical science and technology to the Sulfur of 1.5 weight portions
Department), it is well mixed and is kneaded, the time of mixing is 21 minutes, obtains blend.Again will blending
Thing vulcanizes 15 minutes in 160 DEG C of temperature on the hydraulic flat vulcanizer of pressure 15MPa, is vulcanized
Ethylene propylene diene rubber film afterwards.
Method in GB/T16584-1996 is surveyed to the carrying out of the ethylene propylene diene rubber film after sulfuration
Examination, records curingprocess rate parameter sulfurizing time TC90, and test result is shown in Table 2.
Modified EPT rubber A2-A9 is carried out into according to the method described above the measure of curability, is tested
The results are shown in Table 2.
Contrast test example 1
Ethylene propylene diene rubber film is prepared using with the identical method of test case 1, except that, adopt
Commercially available ethylene propylene diene rubber (3280, purchased from Yanshan Petrochemical company, ethylene unit in ethylene propylene diene rubber
The content of unit be 55 weight %, the content of Third monomer be 5 weight %, weight average molecular weight be 300,000,
The Third monomer is ENB) replace modified EPT rubber.Test result is shown in Table 2.
Contrast test example 2
Ethylene propylene diene rubber film is prepared using with the identical method of test case 1, except that, adopt
Commercially available ethylene propylene diene rubber (ESPRENE 305, purchased from SUMITOMO CHEMICAL, ethene in ethylene propylene diene rubber
It is 7 weight % that the content of construction unit is 65 weight %, the content of Third monomer, and weight average molecular weight is
120000, the Third monomer is DCPD) replace modified EPT rubber.Test result is shown in Table 2.
Table 2
From table 1 it follows that by the way that carbic anhydride can be connect using ring opening cross-metathesis reaction
Branch is on ethylene propylene diene rubber, and percent grafting is higher, and reaction is quick.
By embodiment 1 and embodiment 9 respectively with comparative example 2 and (the unmodified EPDM of comparative example 3
Rubber) to compare, the degree of unsaturation of the modified EPT rubber that the present invention is obtained is 0.44-0.71mol/kg,
There is a certain degree of rising compared with the degree of unsaturation of unmodified ethylene propylene diene rubber, this is possibly due to
The present invention is by the carbic anhydride of structure shown in formula (1) and ethylene propylene diene rubber through alkene open loop crossover
After metathesis reaction, the pendant double bonds of ethylene propylene diene rubber can be increased.By embodiment 1 and embodiment 2
It is compared, it can be seen that the modified EPT rubber obtained using the method that catalyst is added dropwise by several times
Percent grafting is higher, and this is likely due to disposably add after catalyst, and catalyst concn is larger in system,
Easily there is ring-opening metathesis polymerization in carbic anhydride so that the carbic anhydride quantity for participating in graft reaction subtracts
It is few, ultimately result in degree of unsaturation and percent grafting declines.Additionally, by embodiment 2 to embodiment 9, can
Can efficiently control the degree of reaction by adjusting reaction condition to find out such that it is able to obtain with pre-
The modified EPT rubber of phase percent grafting.
The modified EPT rubber and unmodified three of present invention offer is can be seen that from the data of table 2
First EP rubbers is compared, and curingprocess rate improves.
The preferred embodiment of the present invention described in detail above, but, the present invention is not limited to above-mentioned reality
The detail in mode is applied, in the range of the technology design of the present invention, can be to the technical side of the present invention
Case carries out various simple variants, and these simple variants belong to protection scope of the present invention.
It is further to note that each particular technique described in above-mentioned specific embodiment is special
Levy, in the case of reconcilable, can be combined by any suitable means.In order to avoid need not
The repetition wanted, the present invention is no longer separately illustrated to various possible combinations.
Additionally, can also be combined between a variety of embodiments of the present invention, as long as its
Without prejudice to the thought of the present invention, it should equally be considered as content disclosed in this invention.
Claims (10)
1. a kind of preparation method of modified EPT rubber, the method is included in the open loop crossover of alkene
Under metathesis reaction conditions, in the presence of the ionized catalyst of structure shown in formula (2), by ternary second
Third rubber is contacted in organic solvent with the carbic anhydride of structure shown in formula (1),
In formula (2), R1For hydrogen, the thiazolinyl of C2-C20, the alkynyl of C2-C20, the alkyl of C1-C20,
The aryl of C6-C20, the carboxylic acid ester groups of C2-C20, the alkoxyl of C1-C20, the alkene oxygen of C2-C20
Base, the chain oxy-acetylene of C2-C20, the aryloxy group of C6-C20, the alkylthio group of C1-C20, C1-C20
Alkyl sulphonyl or C1-C20 Alkylsulfinyls,
X1And X2It is each independently anion ligand,
L1And L2It is each independently neutral ligand, and alternatively L1And L2Can be interconnected to form
The neutral ligand of two coordinations；
Y is anion.
2. method according to claim 1, wherein, R1For the aryl of C6-C20, preferably
Phenyl；
X1And X2It is each independently halide ion, preferably chlorion；
L1And L2It is each independently phosphine, amine, thioether, Cabbeen or substituted or unsubstituted imidazoles
Alkane, it is preferable that L1And L2It is each independently phosphine, Cabbeen or substituted or unsubstituted imidazolidine；
Y is halide ion, preferably iodide ion.
3. method according to claim 1, wherein, R1For phenyl, L1For replacement or unsubstituted
Imidazolidine, L2For phosphine, X1And X2For chlorion, Y is iodide ion；Preferably, the phosphine is three
Alkylphosphines.
4. according to the method in claim 2 or 3, wherein, the imidazolidine be formula (3) shown in
The imidazolidine of structure,
In formula (3), R2And R3It is each independently the aryl of substituted or unsubstituted C6-C20；R2
And R3It is preferably independently of one anotherR4、R5、R6、R7And R8It is each independently selected from
The alkyl of hydrogen or C1-C5；R2And R3More preferably
5. method according to claim 1, wherein, the open loop crossover double decomposition of the alkene is anti-
Should carry out under an inert atmosphere, the condition of the ring opening cross-metathesis reaction of the alkene includes：Reaction temperature
Spend for 20-150 DEG C, the reaction time is 0.5-5 hours.
6. method according to claim 1, wherein, relative to the ternary of 100 weight portions
EP rubbers, the consumption of the carbic anhydride is 0.05-40 weight portions, the ionized catalyst
Consumption is 0.05-10 weight portions；Preferably, in the ethylene propylene diene rubber ethylene unit unit content
It is 4-6 weight % for 50-70 weight %, the content of Third monomer；The weight of the ethylene propylene diene rubber is equal
Molecular weight is 100,000-40 ten thousand, and the Third monomer is Isosorbide-5-Nitrae-hexadiene, dicyclopentadiene and 5- ethylidene
One or more in -2- ENBs.
7. the method according to claim 1 or 6, wherein, the ionized catalyst is with once
Property the mode that adds or the mode that adds several times add in reaction system, it is preferable that the catalyst
Add in reaction system point 2-6 time, and the adjacent time interval for adding twice is 3-15 minutes, any two
The difference of the amount of secondary addition catalyst is accounted for below 5 weight % of the total addition of catalyst.
8. method according to claim 1, wherein, the organic solvent be toluene, dimethylbenzene,
Chlorobenzene, the cycloalkane of C6-C12, the linear paraffin of C5-C10, tetrahydrofuran, acetone and 1,4- dioxies
One or more in six rings.
9. the modified EPT rubber that the method in claim 1-8 described in any one is prepared.
10. modified EPT rubber according to claim 9, wherein, with the modified ternary
On the basis of the weight of EP rubbers, the percent grafting of the modified EPT rubber is 0.4-4 weight %；
The degree of unsaturation of the modified EPT rubber is 0.44-0.71mol/kg.
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| CN108864370A (en) * | 2017-05-15 | 2018-11-23 | 中国石油化工股份有限公司 | Ethylene propylene diene monomer graft polymer and halogen-free flame retardant ethylene propylene diene monomer (EPDM) material and preparation method thereof |
| 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 |
| 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 |
| CN109867896A (en) * | 2017-12-01 | 2019-06-11 | 中国石油化工股份有限公司 | Halogen-free flameproof EPDM/PP thermoplastic elastic material and its application |
| 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 |
| 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 |
| 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 |
| 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 |
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| CN108864370B (en) * | 2017-05-15 | 2020-10-23 | 中国石油化工股份有限公司 | Ethylene propylene diene monomer graft copolymer, halogen-free flame-retardant ethylene propylene diene monomer material and preparation method thereof |
| 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 |
| 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 |
| CN109867896A (en) * | 2017-12-01 | 2019-06-11 | 中国石油化工股份有限公司 | Halogen-free flameproof EPDM/PP thermoplastic elastic material and its application |
| 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 |
| CN109867750B (en) * | 2017-12-01 | 2024-08-06 | 中国石油化工股份有限公司 | Ethylene propylene diene monomer grafted copolymer 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 |
| 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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