CN108570129B - Modified ethylene propylene diene monomer and preparation method thereof - Google Patents
Modified ethylene propylene diene monomer and preparation method thereof Download PDFInfo
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- CN108570129B CN108570129B CN201710141658.8A CN201710141658A CN108570129B CN 108570129 B CN108570129 B CN 108570129B CN 201710141658 A CN201710141658 A CN 201710141658A CN 108570129 B CN108570129 B CN 108570129B
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Abstract
The invention relates to the field of rubber, and discloses modified ethylene propylene diene monomer rubber and a preparation method thereof. The modified ethylene propylene diene monomer rubber contains a third structural unit derived from a third monomer, the third monomer is non-conjugated diene, at least part of the third structural unit contains a grafting group derived from a compound with a structure shown in a formula (1), and the grafting rate of the modified ethylene propylene diene monomer rubber is 0.4-4.3 wt% based on the weight of the modified ethylene propylene diene monomer rubber. The preparation method comprises the step of contacting ethylene propylene diene rubber with a compound with a structure shown in a formula (1) in an organic solvent in the presence of an ionic catalyst with a structure shown in a formula (2) under the condition of olefin ring-opening cross double decomposition reaction, wherein the ethylene propylene diene rubber contains a structural unit derived from a third monomer, and the third monomer is non-conjugated diene. The method has the advantages of high grafting rate, quick reaction, simple steps and easy implementation, and the vulcanization speed of the modified ethylene propylene diene monomer is improved.
Description
Technical Field
The invention relates to the field of rubber, in particular to modified ethylene propylene diene monomer, a preparation method of the modified ethylene propylene diene monomer and ethylene propylene diene monomer prepared by the method.
Background
Ethylene Propylene Diene Monomer (EPDM) has excellent physical and chemical properties such as high elasticity, viscoelasticity, electrical insulation and the like, and is very prominent in application in aspects such as engineering plastic toughening, ozone aging resistance and the like. However, since ethylene propylene diene monomer is a non-polar rubber, it has poor resistance to oil, chemicals, self-adhesion and mutual adhesion, and is difficult to blend with polar polymers, so its application range is limited. Therefore, it is important to modify the epdm rubber to enhance its compatibility with polar polymers.
In the prior art, ethylene propylene diene monomer and Maleic Anhydride (MAH) are subjected to grafting reaction, and a strong polar group is introduced into a rubber molecular chain, so that a graft has strong polarity and reactivity, and the prepared graft is used as a multifunctional polymer interface compatilizer and a coupling agent or a dispersing agent of a filler filled polymer, and has wide application prospect.
The grafting reaction of the rubber and the MAH is mainly a free radical reaction and can be carried out in a melt, emulsion and solution state, and the grafting reaction comprises methods such as melt grafting, irradiation grafting, solution grafting and the like. Different initiating systems are adopted, the generated free radicals have different modes, and the grafting rate and the grafting efficiency are different.
The grafting rate of MAH grafted by the melt grafting method is not high, and it is difficult to remove residual monomers and initiators after grafting is completed, and the obtained product has strong smell and low color and whiteness. The grafting rate and grafting efficiency of MAH grafted by the irradiation grafting method are generally higher than those grafted by the melt grafting method. However, irradiation grafting easily causes crosslinking of rubber, side reactions are not easy to control, and equipment cost is high. In addition, when the reaction temperature is out of a certain range, degradation or crosslinking side reactions of polymer molecular chains may occur.
CN101402711B discloses a method for grafting maleic anhydride by using high-energy ray radiation ethylene propylene diene rubber, which takes ethylene propylene diene rubber as a raw material and maleic anhydride as a grafting monomer, adds a plasticizer, a reinforcing agent and a vulcanization retarder, and carries out melt blending, and high-ray radiation is carried out before melt extrusion to prepare a graft of the ethylene propylene diene rubber and the maleic anhydride, wherein the grafting rate of the graft product is 1.2-3.6%.
CN102643391B discloses a method for preparing ethylene propylene diene monomer grafted maleic anhydride. The method produces the ethylene propylene diene monomer grafted maleic anhydride by the melt grafting method of the composition of ethylene propylene diene monomer, initiator, maleic anhydride, styrene monomer and hexamethylphosphoric triamide. The grafting rate of the method is 0.59-1.42%.
Compared with other grafting methods, the reaction temperature of the solution grafting method for grafting the MAH is low, the byproducts are few, and the grafting rate and the utilization rate of the MAH are high. However, the reaction time of the existing solution grafting method is too long, the production efficiency is low, and the double bonds of the side chains of the ethylene propylene rubber obtained by modification of the existing grafting method disappear after MAH is grafted, so that the vulcanization of the ethylene propylene rubber is more difficult.
Disclosure of Invention
The invention aims to provide modified ethylene propylene diene monomer, a preparation method of the modified ethylene propylene diene monomer and the modified ethylene propylene diene monomer prepared by the method.
According to a first aspect of the present invention, there is provided a modified ethylene-propylene-diene monomer, wherein the modified ethylene-propylene-diene monomer contains a third structural unit derived from a third monomer, the third monomer is a non-conjugated diene, at least a part of the third structural unit contains a graft group derived from a compound having a structure represented by formula (1), the modified ethylene-propylene-diene monomer has a graft ratio of 0.4 to 4.3% by weight based on the weight of the modified ethylene-propylene-diene monomer,
r is a substituted or unsubstituted alkyl group of C1-C10 or a substituted or unsubstituted aryl group of C6-C20.
According to a second aspect of the present invention, there is provided a process for the preparation of a modified ethylene propylene diene monomer, the process comprising: under the condition of olefin ring-opening cross double decomposition reaction, in the presence of an ionic catalyst with a structure shown in a formula (2), contacting ethylene propylene diene monomer with a compound with a structure shown in a formula (1) in an organic solvent, wherein the ethylene propylene diene monomer contains a structural unit derived from a third monomer, and the third monomer is non-conjugated diene,
in the formula (1), R is substituted or unsubstituted alkyl of C1-C10 or substituted or unsubstituted aryl of C6-C20;
in the formula (2), R1Is hydrogen, substituted or unsubstituted alkenyl of C2-C20, substituted or unsubstituted alkynyl of C2-C20, substituted or unsubstituted alkyl of C1-C20, substituted or unsubstituted aryl of C6-C20, substituted or unsubstituted carboxylate of C2-C20, substituted or unsubstituted alkoxy of C1-C20, substituted or unsubstituted alkenyloxy of C2-C20, substituted or unsubstituted alkynyloxy of C2-C20, substituted or unsubstituted aryloxy of C6-C20, substituted or unsubstituted alkylthio of C1-C20, substituted or unsubstituted alkylsulfonyl of C1-C20, or substituted or unsubstituted alkylsulfinyl of C1-C20;
X1and X2Each independently of the other, is an anionic ligand,
L1and L2Each independently is a neutral ligand, and optionally L1And L2Neutral ligands capable of being linked to each other to form a bidentate ligand;
y is an anion;
n is an integer of 1 to 6.
According to a third aspect of the invention, the invention also provides a modified ethylene propylene diene monomer prepared by the method.
The invention adopts the ionic catalyst with the structure shown in the formula (2) to catalyze the olefin ring-opening cross double decomposition reaction of the ethylene propylene diene monomer and the compound with the structure shown in the formula (1), so that the unsaturation degree of the prepared modified ethylene propylene diene monomer is 0.44-0.7mol/kg, and the modified ethylene propylene diene monomer also has the advantage of high grafting rate. Specifically, the grafting ratio of the modified ethylene propylene diene monomer provided by the invention is 0.4-4.3 wt% based on the weight of the modified ethylene propylene diene monomer. Moreover, the preparation method of the modified ethylene propylene diene monomer provided by the invention has the characteristics of quick reaction, simplicity and easiness in implementation.
In addition, compared with unmodified ethylene propylene diene monomer, the modified ethylene propylene diene monomer provided by the invention has a certain improvement in vulcanization speed, and the possible reason is that after the compound with the structure shown in the formula (1) and the ethylene propylene diene monomer are subjected to an olefin ring-opening cross metathesis reaction, the double bond content of a side chain of the ethylene propylene diene monomer can be increased, so that the vulcanization process is facilitated, and the vulcanization speed of the modified ethylene propylene diene monomer is improved.
According to a preferred embodiment of the invention, the catalyst is added into the reaction system in 2-6 times, the time interval between two adjacent times of addition is 3-15 minutes, and the difference between the catalyst addition amounts of any two times of addition accounts for less than 5 weight percent of the total catalyst addition amount, so that the catalyst is added in such a way to be beneficial to improving the grafting rate and the unsaturation degree of the modified ethylene propylene diene rubber.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention. In the drawings:
FIG. 1 is an infrared spectrum of a modified ethylene-propylene-diene rubber obtained in example 1 according to the present invention, wherein a represents an infrared spectrum of an unmodified ethylene-propylene-diene rubber and b represents an infrared spectrum of a modified ethylene-propylene-diene rubber.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
According to a first aspect of the present invention, there is provided a modified ethylene-propylene-diene monomer, wherein the modified ethylene-propylene-diene monomer contains a third structural unit derived from a third monomer, the third monomer is a non-conjugated diene, at least a part of the third structural unit contains a graft group derived from a compound having a structure represented by formula (1), the graft ratio of the modified ethylene-propylene-diene monomer is 0.4 to 4.3% by weight based on the weight of the modified ethylene-propylene-diene monomer,
r is a substituted or unsubstituted alkyl group of C1-C10 or a substituted or unsubstituted aryl group of C6-C20.
The improvement of the invention is that compared with the unmodified ethylene propylene diene monomer, the double bond content in the side chain of the modified ethylene propylene diene monomer provided by the invention is increased, and the vulcanization speed is improved.
In the modified ethylene propylene diene monomer of the present invention, in formula (1), preferably, R is a substituted or unsubstituted alkyl group of C1 to C6 or a substituted or unsubstituted aryl group of C6 to C10, more preferably one of a methyl group, a tert-butyl group and a phenyl group, and further preferably a methyl group.
According to the modified ethylene propylene diene monomer rubber, the unsaturation degree of the modified ethylene propylene diene monomer rubber can be 0.44-0.7mol/kg, and preferably 0.53-0.7mol/kg, from the viewpoint of further improving the vulcanization speed of the modified ethylene propylene diene monomer rubber.
The unsaturation degree of the modified ethylene propylene diene monomer rubber is measured by an iodometry method.
According to the modified ethylene propylene diene monomer, the weight average molecular weight of the modified ethylene propylene diene monomer is preferably 10-40 ten thousand.
The weight average molecular weight of the modified ethylene propylene diene rubber of the present invention is measured by a Gel Permeation Chromatography (GPC) method.
In the present invention, the structural units in the ethylene-propylene-diene monomer rubber are mainly an ethylene structural unit having a structure represented by formula (III) and a propylene structural unit having a structure represented by formula (IV), and a structural unit derived from a third monomer is referred to as a third structural unit,
-CH2-CH2-a compound of formula (III),
according to the modified ethylene-propylene-diene rubber of the present invention, the third monomer may be a non-conjugated diene commonly used in the art, such as one or more of 1, 4-hexadiene, dicyclopentadiene (DCPD) and 5-ethylidene-2-norbornene (ENB), in order to obtain higher grafting ratio and unsaturation, based on the capability of subjecting the ethylene-propylene-diene rubber to olefin ring-opening cross metathesis with a compound having a structure represented by formula (1).
In the present invention, the third structural unit may contain all of the graft groups, or a part of the third structural units may contain the graft groups. From the viewpoint of further improving the vulcanization speed of the modified ethylene propylene diene monomer, the graft ratio of the modified ethylene propylene diene monomer is preferably 0.4 to 4.3%, more preferably 3.0 to 4.3% by weight, based on the weight of the modified ethylene propylene diene monomer.
In the present invention, the graft ratio is the mass content of the graft group derived from the compound having the structure represented by formula (1) in the modified ethylene-propylene-diene rubber.
According to the modified ethylene propylene diene monomer, when the third monomer is 5-ethylidene-2-norbornene (ENB), the third structural unit containing the grafting group has a structure shown in a formula (I),
in formula (I), R is as defined above and will not be described herein.
When the third monomer is 5-ethylidene-2-norbornene (ENB), part of the third structural units are structural units shown in a formula (II) from the viewpoint of further improving the vulcanization speed of the modified ethylene propylene diene monomer,
according to the modified ethylene propylene diene monomer rubber, the modified ethylene propylene diene monomer rubber is preferably obtained by contacting the ethylene propylene diene monomer rubber with a compound with a structure shown as a formula (1) under the condition of olefin ring-opening cross metathesis reaction.
According to the modified ethylene propylene diene monomer disclosed by the invention, the ethylene propylene diene monomer is subject to an olefin ring-opening cross metathesis reaction with a compound with a structure shown in a formula (1), for example, the ethylene propylene diene monomer contains 50-70 wt% of ethylene structural units and 4-6 wt% of structural units derived from a third monomer based on the total weight of the ethylene propylene diene monomer; the weight average molecular weight of the ethylene propylene diene monomer is 10-40 ten thousand.
The above-mentioned modified ethylene-propylene-diene rubber is produced by the method described later.
According to a second aspect of the present invention, there is provided a process for the preparation of a modified ethylene propylene diene monomer, the process comprising: under the condition of olefin ring-opening cross double decomposition reaction, in the presence of an ionic catalyst with a structure shown in a formula (2), contacting ethylene propylene diene monomer with a compound with a structure shown in a formula (1) in an organic solvent, wherein the ethylene propylene diene monomer contains a structural unit derived from a third monomer, and the third monomer is non-conjugated diene,
formula (1), R is C1-C10 substituted or unsubstituted alkyl or C6-C20 substituted or unsubstituted aryl;
in the formula (2), R1Is hydrogen, substituted or unsubstituted alkenyl of C2-C20, substituted or unsubstituted alkynyl of C2-C20, substituted or unsubstituted alkyl of C1-C20, substituted or unsubstituted aryl of C6-C20, substituted or unsubstituted carboxylate of C2-C20, substituted or unsubstituted alkoxy of C1-C20, substituted or unsubstituted alkenyloxy of C2-C20, substituted or unsubstituted alkynyloxy of C2-C20, substituted or unsubstituted aryloxy of C6-C20, substituted or unsubstituted alkylthio of C1-C20, substituted or unsubstituted alkylsulfonyl of C1-C20, or substituted or unsubstituted alkylsulfinyl of C1-C20;
X1and X2Each independently of the other, is an anionic ligand,
L1and L2Each independently is a neutral ligand, and optionally L1And L2Neutral ligands capable of being linked to each other to form a bidentate ligand;
y is an anion, preferably a halide, more preferably an iodide;
n is an integer of 1 to 6, and can be selected according to the type of Y.
According to the method of the present invention, preferably, in formula (1), R is a substituted or unsubstituted alkyl group of C1 to C6 or a substituted or unsubstituted aryl group of C6 to C10, more preferably one of a methyl group, a tert-butyl group, and a phenyl group, and further preferably a methyl group.
In the formula (2), R1Preferably a C6-C20 substituted or unsubstituted aryl group, more preferably phenyl.
In the formula (2), X1And X2Various anionic ligands which may be conventional, for example each may be a halide ion, preferably chloride;
in the formula (2), L1And L2Each may be a common variety of neutral ligands, specific examples of which may include, but are not limited to: a phosphine, amine, thioether, carbene, or a substituted or unsubstituted imidazolidine. Preferably, L1And L2Is a phosphine, carbene, or substituted or unsubstituted imidazolidine. More excellentOptionally, L1Is a substituted or unsubstituted imidazolidine, L2Is a phosphine.
The phosphine may be a compound formed by partially or totally substituting hydrogen in each phosphine molecule with an organic group, preferably a trialkylphosphine, which may be the same or different, each of which may be selected from an alkanyl group (e.g. C1-C10) or a substituted or unsubstituted cycloalkyl group (e.g. C6-C12), preferably each of which is selected from a substituted or unsubstituted cycloalkyl group, more preferably a cyclohexyl group. Specifically, examples of the phosphine may include, but are not limited to: one or more of trimethylphosphine, triethylphosphine, tri-n-butylphosphine, tri-sec-butylphosphine, tripropylphosphine, tripentylphosphine, trihexylphosphine, trioctylphosphine and tricyclohexylphosphine.
The substituted or unsubstituted imidazolidine may be an imidazolidine having a structure represented by the formula (3),
in the formula (3), R2And R3Each independently is a substituted or unsubstituted aryl group of C6-C20; r2And R3Each independently preferably
R4、R5、R6、R7And R8The same or different, each may be selected from hydrogen or substituted or unsubstituted alkyl of C1-C5; r2And R3More preferably
R2And R3Further preferred is
Specific examples of the C1-C5 alkyl group may include, but are not limited to: methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl and n-pentyl.
In a preferred embodiment of the present invention,in the formula (1), R is one of methyl, tert-butyl and phenyl; in the formula (2), R1Is phenyl, L1Is a substituted or unsubstituted imidazolidine, L2Is phosphine, X1And X2Is chloride ion and Y is iodide ion. In a more preferred embodiment of the present invention, in formula (1), R is one of methyl, t-butyl and phenyl; in the formula (2), R1Is phenyl, L1Is composed of
L2Is a trialkylphosphine, X1And X2Is chloride, Y is iodide and n is 5.
According to the method of the present invention, in order to make the ionic catalyst have higher reactivity under high temperature conditions, it is further preferred that the ionic catalyst is an ionic catalyst having a structure represented by formula (5),
in the above formula (5), PCy3Represents tricyclohexylphosphine, Ph represents phenyl.
According to the method of the present invention, the substituted or unsubstituted alkenyl group of C2-C20 may be straight-chain or branched, and specific examples may include, but are not limited to: vinyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl.
According to the method of the present invention, the substituted or unsubstituted alkynyl group of C2 to C20 may be linear or branched, and specific examples may include, but are not limited to: ethynyl, propynyl, butynyl, pentynyl, hexynyl, heptynyl, octynyl, nonynyl and decynyl.
According to the present invention, the substituted or unsubstituted alkyl group of C1-C20 may be straight or branched, and specific examples may include, but are not limited to: methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl and decyl, undecyl, dodecyl, octadecyl.
Specific examples of substituted or unsubstituted aryl groups of C6-C20 according to the present invention may include, but are not limited to: phenyl, methylphenyl, naphthyl.
According to the invention, the substituted or unsubstituted carboxylic ester group of C2-C20 means a group containing a carboxylic acid in the molecular chain
Specific examples may include, but are not limited to: methyl propionate, ethyl acetate and propyl formate.
Specific examples of substituted or unsubstituted alkoxy groups of C1-C20 according to the present invention may include, but are not limited to: methoxy, ethoxy, propoxy, isopropoxy, butoxy, sec-butoxy, tert-butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, nonyloxy, decyloxy, octadecyloxy.
Specific examples of substituted or unsubstituted alkenyloxy groups of C2-C20 according to the present invention may include, but are not limited to: 1-allyloxy, 2-alkenylbutoxy, 1-alkenylpentoxy.
Specific examples of substituted or unsubstituted alkynyloxy groups of C2-C20 according to the present invention may include, but are not limited to: 1-alkynylpropoxy, 2-alkynylbutoxy, 1-alkynylpentyloxy.
Specific examples of substituted or unsubstituted aryloxy groups of C6-C20 according to the present invention may include, but are not limited to: phenoxy, naphthyloxy.
According to the present invention, the substituted or unsubstituted alkylthio group of C1 to C20 is a straight or branched C1 to C20 alkyl group bonded through one sulfur atom, and specific examples include, but are not limited to: methylthio (CH)3-S-), ethylthio, propylthio, butylthio, pentylthio, 1-methylpropylthio, 2-methylpropylthio and 1, 1-dimethylethylthio.
Specific examples of the substituted or unsubstituted alkylsulfonyl group of C1 to C20 according to the present invention may include, but are not limited to: methylsulfonyl, ethylsulfonyl, propylsulfonyl, butylsulfonyl, nonylsulfonyl.
According to the present invention, specific examples of the substituted or unsubstituted alkylsulfinyl group of C1 to C20 may include, but are not limited to: methylsulfinyl, ethylsulfinyl.
According to the method of the present invention, the method of adding the ionic catalyst is not particularly limited, and the catalyst may be added to the reaction system of the ethylene propylene diene monomer and the compound having the structure represented by formula (1) in a single addition manner or in a plurality of additions. In view of the fact that the addition of the catalyst at one time is likely to cause a side reaction of the compound having the structure represented by formula (1) in the reaction system, it is preferable to add the catalyst in divided portions. More preferably, the catalyst is added into the reaction system in 2-6 times, the time interval between two adjacent times of addition is 3-15 minutes, and the difference between the catalyst addition amounts in any two times accounts for less than 5 wt% of the total catalyst addition amount, so that the catalyst is added in such a way to be beneficial to improving the unsaturation degree and the grafting rate of the modified ethylene propylene diene rubber. Further preferably, in order to make the catalyst have better catalytic effect, the catalyst is added into the reaction system in the form of solution (preferably, the catalyst is dissolved in the organic solvent) in 2-6 times, the time interval between two adjacent times of addition is 3-15 minutes, and the difference between the two catalyst additions accounts for less than 5 wt% of the total catalyst addition.
According to the method of the present invention, the ionic catalyst having the structure represented by formula (2) can be synthesized by a method commonly used in the field of organic synthesis. For example: the Lewis acid can be contacted and reacted with the compound shown in the formula (6) to obtain the compound shown in the formula (2),
in the formula (6), R1、L1、L2、X1And X2The definitions of (a) and (b) are the same as those described above and are not described in detail herein.
The conditions for the contact reaction of the Lewis acid and the compound represented by the formula (6) are not particularly limited. Generally, the contacting temperature may be 20 to 100 ℃, and the molar ratio of the lewis acid to the compound represented by formula (6) may be 1 to 5: 1. the lewis acid may be of conventional choice, such as iodine. The time of the contact may be appropriately selected depending on the temperature at which the contact is performed. The contacting is preferably carried out under an inert atmosphere, which refers to compounds that do not chemically interact with the reactants and reaction products, such as: nitrogen and one or more of a group zero element gas of the periodic table, such as argon. The mixture resulting from the contacting may be purified by various methods commonly used in the art to obtain an ionic catalyst having the structure represented by formula (2), for example: the resulting mixture may be subjected to column chromatography. Specifically, the obtained mixture may be subjected to alumina column elution with dichloromethane as an eluent, thereby obtaining the ionic catalyst having the structure represented by formula (2).
According to the present invention, the conditions for the ring-opening cross-metathesis reaction of the olefin are not particularly limited and may be conventionally selected in the art, and for example, the ring-opening cross-metathesis reaction of the olefin is preferably carried out under an inert atmosphere. The inert atmosphere is identical to that described above and will not be described in further detail here. The conditions for the ring-opening cross-metathesis reaction of the olefin include: the reaction temperature is 20-150 deg.C, preferably 40-130 deg.C, more preferably 100-130 deg.C. The reaction time is appropriately selected depending on the reaction temperature, and for example, the reaction time is 0.5 to 5 hours, preferably 1 to 3 hours.
According to the invention, the amount of the ethylene propylene diene monomer, the compound of the structure shown in the formula (1) and the ionic catalyst can be changed in a wide range, as long as the purpose of obtaining the modified ethylene propylene diene monomer with high target saturation and grafting ratio by rapid reaction can be realized, and the amount of the compound of the structure shown in the formula (1) is 0.05-40 parts by weight, preferably 0.5-22 parts by weight, relative to 100 parts by weight of the ethylene propylene diene monomer; the ionic catalyst is used in an amount of 0.05 to 10 parts by weight, preferably 0.2 to 5 parts by weight.
According to the invention, the third monomer may be a non-conjugated diene commonly used in the art, such as one or more of 1, 4-hexadiene, dicyclopentadiene (DCPD) and 5-ethylidene-2-norbornene (ENB), to enable the ring-opening cross-metathesis of an ethylene-propylene-diene monomer with a compound having a structure represented by formula (1), preferably 5-ethylidene-2-norbornene (ENB), to obtain higher grafting and unsaturation.
According to the invention, the ethylene-propylene-diene monomer rubber is subject to an olefin ring-opening cross metathesis reaction with a compound having a structure shown in formula (1), for example, the ethylene-propylene-diene monomer rubber contains 50-70 wt% of ethylene structural units and 4-6 wt% of structural units derived from a third monomer, based on the total weight of the ethylene-propylene-diene monomer rubber; the weight average molecular weight of the ethylene propylene diene monomer is 10-40 ten thousand.
According to the invention, the organic solvent for preparing the modified ethylene propylene diene monomer rubber is various organic substances capable of being used as a reaction medium, preferably, the organic solvent is one or more of toluene, xylene, chlorobenzene, C6-C12 naphthenic hydrocarbon, C5-C10 straight-chain alkane, tetrahydrofuran, acetone and 1, 4-dioxane, and more preferably, the organic solvent is one or more of toluene, xylene, chlorobenzene, cyclohexane, n-hexane, tetrahydrofuran, acetone and 1, 4-dioxane; most preferred is toluene and/or xylene. These solvents may be used alone or in combination. The amount of the organic solvent may be selected conventionally in the art and will not be described herein.
According to the invention, the preparation method of the modified ethylene propylene diene monomer further comprises a purification step. The purification step may be a conventional purification step in the art, for example, a reaction solution obtained after the reaction is filtered with a nickel mesh, and acetone is added to the filtrate to form a precipitate, and then the resulting precipitate is filtered, washed and dried.
According to the present invention, the compound having the structure represented by the formula (1) can be prepared by a method of the prior art. For example, the compound having the structure represented by the formula (1) is prepared by the following method: under the Diels-Alder reaction condition, cyclopentadiene with the structure shown in formula (4) is contacted with maleic anhydride in an organic solvent,
r in the formula (4) is the same as described above, and is not described in detail.
According to the process of the present invention, the amounts of cyclopentadiene and maleic anhydride in the structure of formula (4) may vary within wide ranges, as long as the compound of formula (1) can be produced. Generally, the molar ratio of cyclopentadiene to maleic anhydride of the structure represented by formula (4) may be 1: 0.4 to 1.2, preferably 1: 0.6-1.
According to the present invention, the diels-alder reaction conditions may be conventional in the art and may include, for example: the reaction temperature is 80-250 ℃, preferably 100-230 ℃; the reaction time is 0.1 to 50 hours, preferably 0.5 to 10 hours.
According to the present invention, the organic solvent used in the preparation of the compound having the structure represented by formula (1) is any of various organic substances that can be used as a reaction medium, and preferably, the organic solvent is one or more selected from the group consisting of diethyl ether, tetrahydrofuran, and toluene. The amount of the organic solvent can be reasonably selected by referring to the prior art, and is not described in detail herein.
The preparation method of the compound with the structure shown in the formula (1) further comprises a purification step, and the purification step can be carried out by referring to the prior art and is not described in detail herein.
The invention also provides the modified ethylene propylene diene monomer prepared by the method.
According to the invention, the grafting ratio of the modified ethylene propylene diene monomer is 0.4-4.3 wt%, preferably 3.0-4.3 wt%, based on the weight of the modified ethylene propylene diene monomer.
According to the invention, the unsaturation degree of the modified ethylene-propylene-diene rubber can be 0.44-0.7mol/kg, preferably 0.53-0.7mol/kg, in order to obtain a higher vulcanization speed.
According to the modified ethylene propylene diene monomer, the weight average molecular weight of the modified ethylene propylene diene monomer is preferably 10-40 ten thousand.
The following preparations and examples relate to the following measurements of properties:
(1) determination of the Structure of the Ionic catalyst in preparation example 1: hydrogen nuclear magnetic resonance spectroscopy (NMR) was measured on an INOVA500MHz NMR spectrometer manufactured by VARIAN, USA using Tetramethylsilane (TMS) as an internal standard (1H-NMR) and nuclear magnetic resonance carbon Spectroscopy (C13C-NMR); selecting crystals with proper size to perform X-ray single crystal diffraction measurement on a BRUKER SMART 1000CCD X-ray diffractometer;
(2) molding and pressing the purified grafting sample and ethylene propylene diene monomer rubber at 160 ℃ to form a film with the thickness of about 0.1mm, and characterizing by a TENSOR-27 Fourier infrared spectrometer of BRUKER company;
(3) the graft ratio (PG) was measured according to the following method:
accurately weighing 1g of graft, adding 50mL of xylene solvent (purchased from Shanghai Yueyeng chemical Co., Ltd.), heating until the graft is completely dissolved, cooling to room temperature, adding 10mL of 0.03mol/L KOH-ethanol solution (calibrated by oxalic acid-ethanol solution), stirring for 10min, titrating with the oxalic acid-ethanol solution, taking phenolphthalein as an indicator, and stopping titration when the indicator shows red. The grafting rate was calculated as follows:
in the formula, PG is the mass content of the grafting group derived from the compound with the structure shown in the formula (1) in the graft, namely the grafting rate,%; m is the mass of the graft, g; m is the molecular weight of the grafting monomer; c1The concentration of KOH-ethanol solution, mol/L; v1Volume of KOH-ethanol solution, mL; c2The concentration of the oxalic acid-ethanol solution is mol/L; v2Volume of oxalic acid-ethanol solution, mL.
(4) The melting point of methylnadic anhydride in the preparation examples was measured using WRS-1C melting point apparatus manufactured by Shanghai Shenke apparatus instruments, Ltd., and the yield was calculated as follows:
in the formula, Y: yield,%; m isFruit of Chinese wolfberry: actual yield of methylnadic anhydride, g; m isTheory of things: theoretical yield of methylnadic anhydride, g, calculated as the amount of maleic anhydride reacted.
(5) The unsaturation degree of the modified ethylene propylene diene monomer is determined by an iodometry method, and specifically comprises the following steps: accurately weighing 2g of modified ethylene propylene diene monomer sample, placing the sample in a 250mL ground conical flask, adding 50mL CCl4Dissolving the sample, adding 20mL of iodine bromide (IBr) solution by a pipette, fully shaking, standing in the dark for 1h, then adding 10mL of 10 wt% potassium iodide solution, shaking up, titrating with 0.1N sodium thiosulfate standard solution until the solution is yellow, adding 5mL of starch indicator, and continuing to titrate until the blue color disappears, namely the end point. And simultaneously performing a blank test. The degree of unsaturation (U) is calculated as follows:
in the formula, V0: the blank test consumes the volume, mL, of the sodium thiosulfate standard solution; v: the sample consumed the volume of sodium thiosulfate standard solution, mL; c: concentration of sodium thiosulfate standard solution, mol/L; m: sample mass, g. The unit of unsaturation in the formula is mol/kg.
(6) The weight average molecular weight of the modified ethylene propylene diene rubber was determined by means of Gel Permeation Chromatography (GPC) using a Waters 1515Isocratic HPLC gel chromatograph.
Preparation example 1
This preparation is illustrative of the preparation of the ionic catalyst.
In a 100mL three-necked flask, 0.76g of iodine, 0.85g of the compound represented by the formula (7) (commercially available from carbofuran technologies, Ltd.), and 20mL of methylene chloride were placed under nitrogen, and the mixture was stirred at room temperature (25 ℃ C.) for 0.5 hour. The obtained mixture was separated by alumina column chromatography (dichloromethane was used as a developing solvent), and the obtained eluate was concentrated and washed with cyclohexane to obtain 1.31g of a catalyst as a yellow solid. Subjecting the obtained catalyst to nuclear magnetic resonance hydrogen spectroscopy (1H-NMR) and nuclear magnetic resonance carbon Spectroscopy (C13C-NMR) and X-ray single crystal diffraction measurement analysis, and it was confirmed that the obtained catalyst had a structure represented by formula (5).
1H-NMR(400MHz,DMSO)(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)(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 the formulae (5) and (7), Cy is cyclohexyl.
Preparation example 2
This preparation example is intended to illustrate the preparation of methylnadic anhydride.
Adding 15.7 g (0.16mol) of maleic anhydride and 40mL of toluene into a 100mL reaction bottle, placing the reaction bottle in a constant-temperature cold bath, stirring and cooling to 5 ℃, dropwise adding 16 g (0.2mol) of methyl cyclopentadiene through a constant-pressure dropping funnel, controlling the temperature in the reaction bottle not to exceed 15 ℃, after the dropwise adding is finished, heating the reaction to 120 ℃, continuing stirring for 1 hour, cooling to separate out white crystals, filtering out a crude product of the methyl nadic anhydride, then recrystallizing with toluene, filtering and drying to obtain 20.5 g of the methyl nadic anhydride, wherein the melting point (mp) of the methyl nadic anhydride is 164-165 ℃, and the yield is 71.9%.
Example 1
This example is used to illustrate the modified ethylene propylene diene monomer and the preparation method thereof provided by the present invention.
5g of ethylene-propylene-diene monomer (3280, available from Yanshan petrochemical company, having an ethylene structural unit content of 55 wt% and a structural unit derived from a third monomer of 5-ethylidene-2-norbornene (ENB)) and 0.87g of methylnadic anhydride prepared in preparation example 2 in N, the weight average molecular weight of the rubber composition was 30 ten thousand2Under protection, the mixture is dissolved in 70mL of xylene solution until the mixture is completely dissolved to form a reaction system. 0.05 g of the product of preparation example 1 was weighed out simultaneouslyThe obtained ionic catalyst having a structure represented by formula (5) was dissolved in 10mL of a xylene solution to obtain a catalyst solution C1.
Heating the reaction system to 120 ℃, adding 2mL of catalyst solution C1 into the reaction system, after reacting for 10min, uniformly dividing the rest 8mL of catalyst solution into 4 parts, adding one part of catalyst solution into the reaction system every 10min, and after adding the last part of catalyst solution C1 into the reaction system for 10min, stopping the reaction, wherein the total reaction time is 1 h. And after the reaction is finished, filtering the reaction solution with a nickel screen while the reaction solution is hot, adding acetone into the filtrate to remove impurities, carrying out precipitation, separating out a precipitate, washing the precipitate with acetone until the filtrate is clear, and drying the precipitate in a vacuum oven at 60 ℃ for 14 hours to obtain the modified ethylene propylene diene monomer A1. The infrared spectrum of the modified ethylene propylene diene rubber was measured and the results are shown in FIG. 1(a represents the infrared spectrum of the unmodified ethylene propylene diene rubber and b represents the infrared spectrum of the modified ethylene propylene diene rubber). The infrared spectrogram shows that the methyl nadic anhydride is grafted onto the ethylene propylene diene monomer, and the results of the analysis and the measurement on other properties of the modified ethylene propylene diene monomer are shown in the table 1.
Example 2
A modified ethylene-propylene-diene monomer was prepared in the same manner as in example 1, except that the reaction system was heated to 120 ℃ and then 10mL of the catalyst solution C1 was added to the reaction system at once, followed by reaction for 1 hour. Obtaining the modified ethylene propylene diene monomer A2. The infrared spectrum measurement of the product shows that the methyl nadic anhydride is grafted to the ethylene propylene diene monomer, and the analysis and measurement are respectively carried out on other performances of the modified ethylene propylene diene monomer, and the results are shown in table 1.
Example 3
Modified ethylene propylene diene monomer was prepared in the same manner as in example 1, except that the reaction system was heated to 120 ℃ and then the catalyst solution C1 was added to the reaction system in two portions, the addition time was 5mL each time when the reaction system was heated to 120 ℃ i.e. at the start of the reaction and after the reaction was carried out for 15min, and the reaction was stopped after 1 hour of reaction. Modified ethylene propylene diene monomer A3 is obtained. The infrared spectroscopic measurement of the modified ethylene propylene diene monomer rubber shows that the methyl nadic anhydride is grafted to the ethylene propylene diene monomer rubber, and in addition, the analysis and measurement of other properties of the modified ethylene propylene diene monomer rubber are respectively carried out, and the results are shown in table 1.
Comparative example 1
A modified ethylene-propylene-diene rubber was prepared in the same manner as in example 1, except that the same weight of maleic anhydride was used in place of the methyl nadic anhydride. A reference modified ethylene propylene diene monomer D1 was obtained. And infrared spectroscopic measurement is carried out on the reference modified ethylene propylene diene monomer rubber, and the result shows that maleic anhydride is not grafted to the ethylene propylene diene monomer rubber. And the reference ethylene propylene diene monomer D1 was analyzed and determined, and the results are shown in Table 1.
Comparative example 2
Ethylene propylene diene monomer (3280, available from Yanshan petrochemical company, having an ethylene structural unit content of 55 wt%, a structural unit content derived from a third monomer of 5 wt%, a weight average molecular weight of 30 ten thousand, and the third monomer being ENB), i.e., unmodified ethylene propylene diene monomer, was used as reference ethylene propylene monomer D2, and analysis and measurement were performed on reference ethylene propylene diene monomer D2, and the results are shown in Table 1.
Example 4
This example is used to illustrate the modified ethylene propylene diene monomer and the preparation method thereof provided by the present invention.
A modified ethylene-propylene-diene monomer was prepared in the same manner as in example 1, except that the reaction time was 2 hours, that is, the reaction was stopped after the last portion of the catalyst solution was added to the reaction system for 70 minutes. Obtaining the modified ethylene propylene diene monomer A4. The infrared spectroscopic measurement of the modified ethylene propylene diene monomer rubber shows that the methyl nadic anhydride is grafted to the ethylene propylene diene monomer rubber, and in addition, the analysis and measurement of other properties of the modified ethylene propylene diene monomer rubber are respectively carried out, and the results are shown in table 1.
Example 5
Modified ethylene propylene diene monomer was prepared in the same manner as in example 1, except that the reaction system was heated to 80 ℃ to obtain modified ethylene propylene diene monomer A5. The infrared spectroscopic measurement is carried out on the modified ethylene propylene diene monomer rubber, and the result shows that the methyl nadic anhydride is grafted to the ethylene propylene diene monomer rubber. In addition, the other properties of the modified ethylene propylene diene monomer rubber were analyzed and determined, respectively, and the results are shown in table 1.
Example 6
A modified ethylene-propylene-diene rubber was produced in the same manner as in example 1, except that 0.65g of methyl nadic anhydride was added to obtain a modified ethylene-propylene-diene rubber A6. The infrared spectroscopic measurement of the modified ethylene propylene diene monomer rubber shows that the methyl nadic anhydride is grafted to the ethylene propylene diene monomer rubber, and in addition, the analysis and measurement of other properties of the modified ethylene propylene diene monomer rubber are respectively carried out, and the results are shown in table 1.
Example 7
Modified ethylene-propylene-diene monomer was prepared in the same manner as in example 1, except that 0.08g of the ionic catalyst having the structure represented by formula (5) prepared in preparation example 1 was weighed and dissolved in 10mL of a xylene solution and divided into 5 parts, and the modified ethylene-propylene-diene monomer A7 was obtained in the same manner as in example 1. The infrared spectroscopic measurement is carried out on the modified ethylene propylene diene monomer rubber, and the result shows that the methyl nadic anhydride is grafted to the ethylene propylene diene monomer rubber. In addition, the other properties of the modified ethylene propylene diene monomer rubber were analyzed and determined, respectively, and the results are shown in table 1.
Example 8
This example is used to illustrate the modified ethylene propylene diene monomer and the preparation method thereof provided by the present invention.
5g of ethylene-propylene-diene monomer (3280, available from Yanshan petrochemical company, having an ethylene structural unit content of 55% by weight, a structural unit derived from a third monomer (ENB) having a weight average molecular weight of 30 ten thousand, the content of the ethylene structural unit in the ethylene-propylene-diene monomer being 55% by weight, and 0.027 g of methylnadic anhydride prepared in preparation example 2 in N2Under protection, dissolving the mixture in 70mL of dimethylbenzene solution until the mixture is completely dissolved to form a reaction system; at the same time, 0.25 g of the ionic catalyst having the structure represented by the formula (5) prepared in preparation example 1 was weighed out and dissolved in 10mL of a xylene solution to obtain a catalyst solution C8.
Heating the reaction system to 40 ℃, adding 2mL of catalyst solution C8 into the reaction system, after reacting for 10min, uniformly dividing the rest 8mL of catalyst solution into 4 parts, adding one part of catalyst solution into the reaction system every 10min, and after adding the last part of catalyst solution C8 into the reaction system for 10min, stopping the reaction, wherein the total reaction time is 1 h. And after the reaction is finished, filtering the reaction solution with a nickel screen while the reaction solution is hot, adding acetone into the filtrate to remove impurities, carrying out precipitation, separating out a precipitate, washing the precipitate with acetone until the filtrate is clear, and drying the precipitate in a vacuum oven at 60 ℃ for 14 hours to obtain the modified ethylene propylene diene monomer A8. The infrared spectroscopic measurement is carried out on the modified ethylene propylene diene monomer rubber, and the result shows that the methyl nadic anhydride is grafted to the ethylene propylene diene monomer rubber. In addition, the other properties of the modified ethylene propylene diene monomer rubber were analyzed and determined, respectively, and the results are shown in table 1.
Example 9
This example is used to illustrate the modified ethylene propylene diene monomer and the preparation method thereof provided by the present invention.
5g of ethylene-propylene-diene monomer (ESPRENE 305, available from Sumitomo, Japan, having an ethylene structural unit content of 65% by weight and a structural unit content derived from a third monomer of dicyclopentadiene (DCPD) of 7% by weight and a weight-average molecular weight of 12 ten thousand, 1.1 g of methylnadic anhydride prepared in preparation example 2 in N2Under protection, dissolving the mixture in 70mL of dimethylbenzene solution until the mixture is completely dissolved to form a reaction system; at the same time, 0.01 g of the ionic catalyst having the structure represented by the formula (5) prepared in preparation example 1 was weighed out and dissolved in 10mL of a xylene solution to obtain a catalyst solution C9.
Heating the reaction system to 130 ℃, adding 2mL of catalyst solution C9 into the reaction system, after reacting for 15min, uniformly dividing the rest 8mL of catalyst solution into 4 parts, adding one part of catalyst solution into the reaction system every 15min, and after adding the last part of catalyst solution C9 into the reaction system for 105min, stopping the reaction, wherein the total reaction time is 3 h. And after the reaction is finished, filtering the reaction solution with a nickel screen while the reaction solution is hot, adding acetone into the filtrate to remove impurities, carrying out precipitation, separating out a precipitate, washing the precipitate with acetone until the filtrate is clear, and drying the precipitate in a vacuum oven at 60 ℃ for 14 hours to obtain the modified ethylene propylene diene monomer A9. The infrared spectroscopic measurement is carried out on the modified ethylene propylene diene monomer rubber, and the result shows that the methyl nadic anhydride is grafted to the ethylene propylene diene monomer rubber. In addition, the other properties of the modified ethylene propylene diene monomer rubber were analyzed and determined, respectively, and the results are shown in table 1.
Comparative example 3
Ethylene-propylene-diene monomer (ESPRENE 305, available from sumitomo, japan, in which the content of ethylene structural units is 65% by weight, the content of structural units derived from a third monomer is 7% by weight, and the weight average molecular weight is 12 ten thousand, the third monomer being DCPD), i.e., unmodified ethylene-propylene-diene monomer, was used as a reference ethylene-propylene-diene monomer D3, and the results of analytical measurement were carried out on the reference ethylene-propylene-diene monomer D3, and are shown in table 1.
Example 10
A modified ethylene-propylene-diene rubber was prepared in the same manner as in example 1, except that 0.87g of t-butyl nadic anhydride represented by the formula (8) (CAS No: 97024-52-7, commercially available from Bailingwei science Co., Ltd.) was added to obtain a modified ethylene-propylene-diene rubber A10. The infrared spectroscopic measurement of the modified ethylene propylene diene monomer rubber shows that the tert-butyl nadic anhydride is grafted to the ethylene propylene diene monomer rubber, and in addition, the analysis and measurement of other properties of the modified ethylene propylene diene monomer rubber are respectively carried out, and the results are shown in table 1.
Example 11
A modified ethylene-propylene-diene rubber was prepared in the same manner as in example 1, except that 0.87g of phenyl nadic anhydride represented by the formula (9) (CAS No: 69248-38-0, commercially available from Bailingwei science Co., Ltd.) was added to obtain a modified ethylene-propylene-diene rubber A11. The infrared spectroscopic measurement of the modified ethylene propylene diene monomer rubber shows that the phenyl nadic anhydride is grafted to the ethylene propylene diene monomer rubber, and in addition, the analysis and measurement of other properties of the modified ethylene propylene diene monomer rubber are respectively carried out, and the results are shown in table 1.
Example 12
This example is used to illustrate the modified ethylene propylene diene monomer and the preparation method thereof provided by the present invention.
5g of ethylene-propylene-diene monomer (3280, available from Yanshan petrochemical company, having an ethylene structural unit content of 55 wt% and a structural unit content derived from a third monomer of 5-ethylidene-2-norbornene (ENB)) and 0.5 g of methylnadic anhydride prepared in preparation example 2 in N, the weight average molecular weight was 30 ten thousand2Under protection, the mixture is dissolved in 70mL of xylene solution until the mixture is completely dissolved to form a reaction system. 0.15 g of the ionic catalyst having the structure represented by the formula (5) prepared in preparation example 1 was weighed out and dissolved in 10mL of a xylene solution to obtain a catalyst solution C1.
Heating the reaction system to 100 ℃, adding 2mL of catalyst solution C1 into the reaction system, after reacting for 10min, uniformly dividing the rest 8mL of catalyst solution into 4 parts, adding one part of catalyst solution into the reaction system every 10min, and after adding the last part of catalyst solution C1 into the reaction system for 10min, stopping the reaction, wherein the total reaction time is 1 h. And after the reaction is finished, filtering the reaction solution with a nickel screen while the reaction solution is hot, adding acetone into the filtrate to remove impurities, carrying out precipitation, separating out a precipitate, washing the precipitate with acetone until the filtrate is clear, and drying the precipitate in a vacuum oven at 60 ℃ for 14 hours to obtain the modified ethylene propylene diene monomer A12. The infrared spectroscopic measurement of the modified ethylene propylene diene monomer rubber shows that the methyl nadic anhydride is grafted to the ethylene propylene diene monomer rubber, and in addition, the analysis and measurement of other properties of the modified ethylene propylene diene monomer rubber are respectively carried out, and the results are shown in table 1.
TABLE 1
Test example 1
The modified ethylene-propylene-diene rubbers A1-A12 prepared in examples 1 to 12 of the present invention were subjected to vulcanization property measurement in accordance with the following methods.
100 parts by weight of the modified ethylene propylene diene monomer A1 prepared in example 1 of the present invention was placed on a two-roll kneader, and 5 parts by weight of activated zinc oxide, 1 part by weight of stearic acid, 80 parts by weight of carbon black (N550, Shanghai Kabot chemical Co., Ltd.), 50 parts by weight of ASTM103# oil (Ningbo Co., Ltd.), 1 part by weight of accelerator TMTD (Shanghai rubber science Co., Ltd.), and 1.5 parts by weight of sulfur (Shijiazhuang Ruitou chemical science Co., Ltd.) were added successively at a temperature of 35. + -. 5 ℃ to obtain a blend. And vulcanizing the blend for 15 minutes on a hydraulic flat vulcanizing machine with the temperature of 160 ℃ and the pressure of 15MPa to obtain the vulcanized ethylene propylene diene monomer rubber sheet.
The vulcanized ethylene propylene diene monomer rubber sheets were tested according to the method of GB/T16584-1996, and the vulcanization speed parameter, positive vulcanization time TC90, was recorded, and the test results are shown in Table 2.
The modified ethylene propylene diene monomer A2-A12 was subjected to vulcanization performance measurement in the manner described above, and the test results are shown in Table 2.
Comparative test example 1
An ethylene propylene diene rubber sheet was prepared in the same manner as in test example 1, except that a commercially available ethylene propylene diene rubber D2(3280, available from delphin petrochemical company, having an ethylene structural unit content of 55 wt%, a structural unit derived from a third monomer having a weight average molecular weight of 30 ten thousand, which was ENB) was used in place of the modified ethylene propylene diene rubber. The test results are shown in Table 2.
Comparative test example 2
An ethylene-propylene-diene rubber sheet was produced in the same manner as in test example 1, except that a commercially available ethylene-propylene-diene rubber D3(ESPRENE 305, available from sumitomo in japan, having an ethylene structural unit content of 65 wt%, a structural unit derived from a third monomer having a weight average molecular weight of 12 ten thousand, which is DCPD) was used in place of the modified ethylene-propylene-diene rubber. The test results are shown in Table 2.
TABLE 2
As can be seen from Table 1, methyl nadic anhydride can be grafted onto ethylene-propylene-diene rubber by using a ring-opening cross metathesis reaction, and the grafting ratio is relatively high and the reaction is rapid.
Comparing example 1 and example 9 with comparative example 2 and comparative example 3 (unmodified ethylene propylene diene monomer), respectively, the unsaturation degree of the modified ethylene propylene diene monomer obtained by the invention is 0.44-0.7mol/kg, and is increased to a certain extent compared with the unsaturation degree of the unmodified ethylene propylene diene monomer, which is probably because the side chain double bonds of the ethylene propylene diene monomer can be increased after the methyl nadic anhydride and the ethylene propylene diene monomer are subjected to the olefin ring-opening cross metathesis reaction.
Comparing example 1 with example 2, it can be seen that the grafting ratio of the modified ethylene propylene diene monomer obtained by the method of dropping the catalyst in several times is higher, which is probably because the catalyst concentration in the system is higher after adding the catalyst once, and the methyl nadic anhydride is easy to generate ring-opening metathesis polymerization, so that the number of the methyl nadic anhydride participating in the grafting reaction is reduced, and finally the unsaturation degree and the grafting ratio are reduced. Further, from examples 2 to 12, it can be seen that the degree of reaction can be effectively controlled by adjusting the reaction conditions, so that a modified ethylene-propylene-diene rubber having a desired graft ratio can be obtained.
As can be seen from the data in Table 2, the modified EPDM provided by the invention has a certain improvement in vulcanization speed compared with unmodified EPDM.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various features described in the above embodiments may be combined in any suitable manner without departing from the scope of the invention. The invention is not described in detail in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (26)
1. A modified ethylene propylene diene monomer is characterized in that the modified ethylene propylene diene monomer contains a third structural unit derived from a third monomer, the third monomer is non-conjugated diene, at least part of the third structural unit contains a grafting group derived from a compound with a structure shown in a formula (1), and the grafting ratio of the modified ethylene propylene diene monomer is 0.4-4.3 wt% based on the weight of the modified ethylene propylene diene monomer,
r is a substituted or unsubstituted alkyl group of C1-C10 or a substituted or unsubstituted aryl group of C6-C20.
2. The modified ethylene-propylene-diene monomer of claim 1, wherein the third monomer is one or more of 1, 4-hexadiene, dicyclopentadiene, and 5-ethylidene-2-norbornene.
3. The modified ethylene propylene diene rubber of claim 1, wherein R is a substituted or unsubstituted alkyl group of C1-C6 or a substituted or unsubstituted aryl group of C6-C10.
4. The modified ethylene propylene diene monomer of claim 1, wherein R is one of methyl, t-butyl and phenyl.
5. The modified ethylene-propylene-diene monomer according to claim 1 or 2, wherein the third monomer is 5-ethylidene-2-norbornene, the third structural unit containing the grafting group has a structure represented by formula (I),
6. the modified ethylene-propylene-diene monomer rubber of claim 1, wherein the unsaturation degree of the modified ethylene-propylene-diene monomer rubber is 0.44-0.7 mol/kg.
7. The modified ethylene propylene diene monomer of claim 1, wherein the unsaturation level of the modified ethylene propylene diene monomer is 0.53-0.7 mol/kg.
8. The modified ethylene propylene diene rubber according to any one of claims 1 to 4, 6 and 7, wherein the modified ethylene propylene diene rubber is obtained by contacting the ethylene propylene diene rubber with a compound having a structure represented by formula (1) under an olefin ring opening cross metathesis reaction condition.
9. A preparation method of modified ethylene propylene diene monomer comprises the following steps: under the condition of olefin ring-opening cross double decomposition reaction, in the presence of an ionic catalyst with a structure shown in a formula (2), contacting ethylene propylene diene monomer with a compound with a structure shown in a formula (1) in an organic solvent, wherein the ethylene propylene diene monomer contains a structural unit derived from a third monomer, and the third monomer is non-conjugated diene,
formula (1), R is C1-C10 substituted or unsubstituted alkyl or C6-C20 substituted or unsubstituted aryl;
in the formula (2), R1Is hydrogen, substituted or unsubstituted alkenyl of C2-C20, substituted or unsubstituted alkynyl of C2-C20, substituted or unsubstituted alkyl of C1-C20, substituted or unsubstituted aryl of C6-C20, substituted or unsubstituted carboxylate of C2-C20, substituted or unsubstituted alkoxy of C1-C20, substituted or unsubstituted alkenyloxy of C2-C20, substituted or unsubstituted alkynyloxy of C2-C20, substituted or unsubstituted aryloxy of C6-C20, substituted or unsubstituted alkylthio of C1-C20, substituted or unsubstituted alkylsulfonyl of C1-C20, or substituted or unsubstituted alkylsulfinyl of C1-C20;
X1and X2Each independently of the other, is an anionic ligand,
L1and L2Each independently a neutral ligand;
y is an anion;
n is an integer of 1 to 6.
10. The method of claim 9, wherein R is a C1-C6 substituted or unsubstituted alkyl group or a C6-C10 substituted or unsubstituted aryl group.
11. The method of claim 9, wherein R is one of methyl, t-butyl, and phenyl.
12. The method of claim 9, wherein R1Substituted or unsubstituted aryl of C6 to C20;
X1and X2Each independently is a halide ion;
L1and L2Each independently a phosphine, amine, thioether, carbene, or a substituted or unsubstituted imidazolidine;
y is a halogen ion.
13. The method of claim 9, wherein R1Is phenyl; x1And X2Each independently is chloride; l is1And L2Each independently of the others is a phosphine, carbene,Or a substituted or unsubstituted imidazolidine; y is iodide ion.
14. The method of claim 9, wherein R1Is phenyl, L1Is a substituted or unsubstituted imidazolidine, L2Is phosphine, X1And X2Is chloride ion and Y is iodide ion.
15. The method of claim 14, wherein the phosphine is a trialkyl phosphine.
16. The method according to any one of claims 12 to 14, wherein the imidazolidine is an imidazolidine having a structure represented by formula (3),
in the formula (3), R2And R3Each independently is a substituted or unsubstituted aryl group of C6-C20.
17. The method of claim 16, wherein R2And R3Each independently is
R4、R5、R6、R7And R8Each independently selected from hydrogen or a substituted or unsubstituted alkyl group of C1-C5.
18. The method of claim 17, wherein R2And R3Is composed of
19. The method of claim 9, wherein the third monomer is one or more of 1, 4-hexadiene, dicyclopentadiene, and 5-ethylidene-2-norbornene.
20. The process of claim 9, wherein the conditions for the olefin ring opening cross metathesis reaction comprise: the olefin ring-opening cross metathesis reaction is carried out in inert atmosphere, the reaction temperature is 20-150 ℃, and the reaction time is 0.5-5 hours.
21. The method according to claim 9, wherein the compound having the structure represented by formula (1) is used in an amount of 0.05 to 40 parts by weight and the ionic catalyst is used in an amount of 0.05 to 10 parts by weight, relative to 100 parts by weight of the ethylene-propylene-diene monomer.
22. The method according to claim 9, wherein the ethylene-propylene-diene rubber has a content of ethylene structural units of 50 to 70 wt% and a content of structural units derived from a third monomer of 4 to 6 wt%; the weight average molecular weight of the ethylene propylene diene monomer is 10-40 ten thousand.
23. The method according to claim 9, wherein the ionic catalyst is added to the reaction system in a single addition or in multiple additions.
24. The method of claim 9, wherein the catalyst is added into the reaction system in 2-6 times, the time interval between two adjacent times is 3-15 minutes, and the difference between the two catalyst additions accounts for less than 5 wt% of the total catalyst addition.
25. The method of claim 9, wherein the organic solvent is one or more of toluene, xylene, chlorobenzene, C6-C12 cycloalkanes, C5-C10 linear alkanes, tetrahydrofuran, acetone, and 1, 4-dioxane.
26. A modified ethylene propylene diene rubber prepared by the process of any one of claims 9 to 25.
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| 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 |
| CN112961292B (en) * | 2021-03-17 | 2022-04-05 | 山东京博中聚新材料有限公司 | Preparation method of branched butyl rubber |
| CN115368489A (en) * | 2021-05-21 | 2022-11-22 | 中国石油化工股份有限公司 | Preparation method of ester-based modified ethylene propylene diene monomer rubber and modified ethylene propylene diene monomer rubber |
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