Side-group siloxane functionalized polyolefin elastomer and preparation method thereof

Abstract

The invention belongs to the field of high polymer materials, and relates to a side-group siloxane functionalized polyolefin elastomer and a preparation method thereof. The side group siloxane functionalized polyolefin elastomer contains an ethylene structural unit, an alpha-olefin structural unit and a structural unit derived from alkoxysilyl cycloolefin; the alkoxyl-containing silyl cycloolefin is selected from at least one of compounds shown in the formula 1, and in the # imgabs0 # formula 1, a is an integer of 0-5; r1 and R2 are respectively and independently selected from alkyl groups of C1 to C10, alkoxy groups of C1 to C10, naphthenic groups of C4 to C10 or naphthenic alkoxy groups of C4 to C10; r3 is an alkyl group of C1 to C10 or a cycloalkyl group of C4 to C10; and R4 is hydrogen or alkyl of C1-C10. According to the functionalized polyolefin elastomer with the side group containing the alkoxy silane substituent group, the molecular weight of a copolymer is high, and the molecular weight distribution is relatively narrow.

Description

Technical Field

[0001] The invention belongs to the field of polymer materials, and in particular relates to a side-group siloxane functionalized polyolefin elastomer and a preparation method thereof. Background Art

[0002] Polyolefin elastomers are a type of polyolefin material formed by copolymerization of ethylene and propylene or other α-olefins (such as 1-butene, 1-hexene or 1-octene), mainly including ethylene propylene diene monomer random copolymer (EPR), ethylene propylene diene monomer random copolymer (EPDM), ethylene / α-olefin copolymer (POE) and olefin block copolymer (OBC). Polyolefin elastomers have excellent weather resistance, chemical resistance, water resistance, etc., and are widely used in the fields of automobiles, cables, photovoltaic packaging, etc. However, non-polar polyolefin elastomers have poor adhesion to materials such as glass, inorganic fillers, and metals.

[0003] Introducing polar groups (such as hydroxyl, carboxyl, anhydride, alkoxysilyl, etc.) into the side groups of polymer molecular chains can improve the adhesion of materials while maintaining the original excellent performance, increase its adhesion to polar inorganic materials and metal materials, broaden the application range of polyolefin elastomers, and increase their added value. Compared with polar functional groups such as hydroxyl, carboxyl, and anhydride, alkoxysilyl has higher reactivity and stronger interaction with inorganic substances and metals. Introducing alkoxysilane functional groups into the side groups of polyolefin elastomers can give materials the ability to crosslink in moisture and improve the adhesion of materials to the surfaces of inorganic or metal materials. In particular, using such polymers as adhesive components can improve the bonding strength between polyolefin materials and metals (such as aluminum), glass, natural fibers, and polar polymers (such as methacrylate polymers, nylon, ABS, etc.). See: Rubber Industry, 2021, 68, 464-470; CN 102124041 A.

[0004] At present, there are two main methods for preparing alkoxysilyl functionalized polyolefin elastomers: one is through free radical grafting modification of polyolefin elastomers, which mainly includes solution grafting process and melt grafting process; the other is through copolymerization of ethylene, α-olefin and alkoxysilyl functional group-containing silane vinyl monomer or trichlorosilyl norbornene monomer.

[0005] For the polyolefin elastomer solution grafting process, the polymer needs to be dissolved in a solvent such as toluene or tetrahydrofuran, and vinyl alkoxysilane and an initiator that can generate free radicals are added to carry out the grafting reaction at a relatively high temperature. However, the grafting reaction efficiency is low, and there is also the problem of degradation of the macromolecular chain or cross-linking reaction causing the product quality to decrease. Moreover, the solvent and the unreacted vinyl alkoxysilane need to be separated and recovered, which leads to the increase of production processes and production costs. For example, in a 750g tetrahydrofuran solution containing 150g of ethylene / propylene copolymer elastomer (ethylene structural unit content 22mol%), 18.75g of vinyl dimethoxyethoxysilane and 1.85g of azobisisobutyronitrile initiator are continuously added within 120min at 85°C to synthesize vinyl dimethoxyethoxysilane grafted modified ethylene / propylene copolymer elastomer, but the grafting functionalization degree is only 0.51mol%. For the melt grafting process of polyolefin elastomers, the polymer, alkenyl alkoxy silane and free radical initiator are melt-blended and reacted at high temperature (160-200°C) to prepare a grafted modified copolymer. There are also problems such as low grafting reaction efficiency and degradation of macromolecular chains or cross-linking reactions that cause reduced product quality. For example, 100 parts of an ethylene / propylene copolymer containing 22 mol% of ethylene structural units are used as raw materials, mixed with 1.23 parts of a free radical initiator dicumyl peroxide and 12.5 parts of vinyl trimethoxysilane () at 165° C. to synthesize an ethylene / propylene copolymer elastomer modified by vinyl trimethoxysilane, and the degree of functionalization is only 0.38 mol%, and a large amount of unreacted vinyl trimethoxysilane small molecule compounds remain in the polymer melt, reducing the physical and mechanical properties of the material; 100 parts of ethylene propylene diene monomer rubber (ethylene structural unit content of 57.9 mol%, ethylene structural unit content of 40.4 mol%, ENB structural unit content of 1.7 mol%) are used as raw materials, mixed with 5 parts of vinyl triethoxysilane and 0.33 parts of diisopropylbenzene peroxide, and then banburying is performed at 160° C. to prepare a functionalized ethylene propylene rubber modified by vinyl triethoxysilane, and the grafting rate is only 0.48 mol%. See: CN 102124041 A; RubberChem.Technol.2021,94,759-773.

[0006] Polar functionalized polyolefins can be prepared by copolymerization of ethylene, α-olefins and vinyl alkoxysilane monomers. For example, under anhydrous and oxygen-free conditions, α-imino ketone nickel complex is used as a catalyst to react with B(C 6 F 5 ) 3 and LiB(C 6 F 5 ) 4As a cocatalyst, ethylene, 1-octene and vinyl trimethoxysilane are catalyzed for coordination copolymerization under a pressure of 3.45 MPa to prepare trimethoxysilyl side functionalized copolymers, and the polar monomer insertion rate is 0.6-2.1 mol%. However, the boron compound cocatalyst is expensive, the polymerization reaction is difficult to control, the molecular weight of the polymer product is relatively low, the molecular weight distribution is wide, the molecular weight distribution index is 4.3-15.4, and polymer gel is produced, resulting in poor product quality. See: WO03044066A2; Using α-diimine nickel complex as catalyst, B(C 6 F 5 ) 3 As a co-catalyst, ethylene and vinyl triethoxysilane copolymerization is catalyzed in toluene solution. The conversion rate of vinyl triethoxysilane is only 5.25%, the molecular weight of the polymer product is low, and it decreases significantly with the increase of the content of vinyl trimethoxysilane structural units. More vinyl trimethoxysilane structural units appear at the end of the molecular chain, and there are also problems such as expensive co-catalysts. See: J.Am.Chem.Soc.2017,139,16013-16022. In addition, because the nickel complex catalyst has "chain walking" when catalyzing olefin coordination polymerization, the polymer product contains methyl, ethyl, propyl, butyl, pentyl, hexyl and other branches of different lengths and uncertain numbers, and it is impossible to obtain a terpolymer of ethylene-α-olefin-vinyl siloxane with a clear structure, see: WO03044066A2; J.Am.Chem.Soc.2017,139,16013-16022.

[0007] Early transition metal catalyzed olefin polymerization has the characteristics of high catalytic activity and good copolymerization performance. However, early transition metal catalysts are sensitive to polar monomers and are easily poisoned by polar monomers. The active center is easily deactivated by chelation of polar groups, and it is impossible to directly copolymerize olefins with vinyl siloxane to obtain copolymer products. Therefore, when using early transition metal catalyzed monomer copolymerization to prepare polyolefin elastomers containing alkoxysilyl groups, a two-step method must be used: first, copolymerize olefin monomers containing chlorosilanes, and then convert the chlorine in the chlorosilane substituent into alkoxy groups. For example, using rac-C 2 H 4 (Ind) 2 ZrCl 2With methyl alkoxide aluminum (MAO) as the main catalyst and ethylene, propylene and 5-trichlorosilyl-2-norbornene as the co-catalyst, ethylene, propylene and 5-trichlorosilyl-2-norbornene are copolymerized to prepare ethylene-propylene copolymers with trichlorosilyl functionalized side groups, and then methanol is added for reaction to convert the trichlorosilyl group into a trimethoxysilyl group to obtain a functionalized ethylene-propylene copolymer containing a methoxysilyl substituent, and the functionalized group content is 0.71-4.68 mol%. The copolymerization product has a relatively low molecular weight, and the weight-average molecular weight is only 57.0-71.6 kg / mol. This two-step preparation process is cumbersome to operate, and hydrogen chloride is produced during the reaction, which corrodes the equipment. Zirconocene metal catalysts are required in the polymerization process, and their synthesis process is relatively complicated and costly, and the co-catalyst MAO is expensive. See: Polymer, 2019, 172, 117-125.

[0008] In summary, in the prior art, the functionalized polyolefin elastomer containing alkoxysilyl groups is prepared by free radical grafting modification of polyolefin elastomer, the grafting efficiency is low, and it is easy to produce chain breaking or cross-linking side reactions, resulting in reduced product quality, and the obtained polymer molecular chain does not contain alkoxysilyl norbornene structural units; when a nickel complex catalyst is used to prepare siloxane functionalized polyolefin by copolymerization of polar monomers, the process flow is short, but due to the "chain walking" polymerization mechanism, it is impossible to obtain a terpolymer of ethylene-α-olefin-vinylsiloxane with a clear structure, the product molecular weight is relatively low, and the molecular chain does not contain alkoxysilyl norbornene structural units, and the organic metal catalyst used is relatively complex to synthesize, requiring expensive MAO or boron compound co-catalysts, and the production cost is high. In addition, in the catalytic polymerization using an early transition metal catalyst, due to the easy poisoning by the polar monomer, only a relatively low molecular weight copolymer product must be obtained through a two-step reaction, and toxic and harmful substances (such as hydrogen chloride) are generated during the functional group conversion process.

[0009] To date, there has been no public report on high molecular weight ethylene / α-olefin / alkoxysilylcycloolefin terpolymers, nor has there been any public report on the use of vanadium-based catalysts to directly catalyze the coordination copolymerization of ethylene, α-olefins and alkoxysilylcycloolefins to prepare pendant siloxane-functionalized polyolefin elastomers. Summary of the invention

[0010] In order to solve the problems existing in the prior art, the present invention provides a side-siloxane functionalized polyolefin elastomer and a preparation method thereof, that is, ethylene, α-olefin and cycloolefin containing alkoxysilyl substitution are directly subjected to coordination copolymerization reaction under the action of a vanadium-based catalyst to prepare the side-siloxane functionalized polyolefin elastomer in a one-step process. The method has mild reaction conditions and a short process flow, can efficiently prepare the side-siloxane functionalized polyolefin elastomer, and the obtained copolymer has a high molecular weight.

[0011] In order to achieve the above object, the first aspect of the present invention provides a side-siloxane functionalized polyolefin elastomer, wherein the side-siloxane functionalized polyolefin elastomer contains an ethylene structural unit, an α-olefin structural unit and a structural unit derived from an alkoxy-containing silicon-based cycloolefin; the alkoxy-containing silicon-based cycloolefin is selected from at least one of the compounds shown in Formula 1,

[0012]

[0013] In Formula 1, a is an integer of 0-5, preferably an integer of 0-3, and more preferably an integer of 0-2; R 1 , R 2 Each independently selected from C 1 -C 10 Alkyl, C 1 -C 10 Alkoxy, C 4 -C 10 Cycloalkyl or C 4 -C 10 The cycloalkyloxy group is preferably C 1 -C 5 Alkyl or C 1 -C 5 Alkoxy; R 3 C 1 -C 10 Alkyl or C 4 -C 10 The cycloalkyl group is preferably C 1 -C 5 Alkyl; R 4 is hydrogen or C 1 -C 10 is preferably hydrogen or C 1 -C 5 of alkyl.

[0014] According to the present invention, preferably, the alkoxysilyl-containing cycloolefin is selected from 5-(dimethoxy-ethoxysilyl)-2-norbornene, 5-(methoxy-diethoxysilyl)-2-norbornene, 5-(trimethoxysilyl)-2-norbornene, 5-(triethoxysilyl)-2-norbornene, 5-(tri-n-propoxysilyl)-2-norbornene, 5-(triisopropoxysilyl)-2-norbornene, 5-(methyl-diethoxysilyl)-2-norbornene, 5-(ethyl-diethoxysilyl)-2-norbornene, 2-trimethoxysilyl-1,4:5,8-dimethyl-1,2,3,4,4a,5,8,8a-octahydro At least one of naphthalene and 2-triethoxysilyl-1,4:5,8-dimethyl-1,2,3,4,4a,5,8,8a-octahydronaphthalene, preferably one or more of 5-(trimethoxysilyl)-2-norbornene, 5-(methyl-diethoxysilyl)-2-norbornene, 5-(dimethyl-ethoxysilyl)-2-norbornene, 5-(triethoxysilyl)-2-norbornene, 2-trimethoxysilyl-1,4:5,8-dimethyl-1,2,3,4,4a,5,8,8a-octahydronaphthalene and 2-triethoxysilyl-1,4:5,8-dimethyl-1,2,3,4,4a,5,8,8a-octahydronaphthalene.

[0015] In the present invention, the alkoxy-containing silicon-based cycloolefin can be selected from commercially available products, or can be synthesized by reacting dicyclopentadiene with compounds such as vinyltrialkoxysilane or vinylalkyldialkoxysilane.

[0016] According to the present invention, preferably, the α-olefin is C 3 ~C 15 α-olefins, preferably C 3 ~C 10 of α-olefins.

[0017] According to the present invention, preferably, based on the molar number of all structural units in the side-group siloxane functionalized polyolefin elastomer, the molar content of the ethylene structural unit is 34% to 90%, preferably 38% to 88%, and more preferably 42% to 85%; the molar content of the structural unit of the α-olefin is 5% to 65%, preferably 10% to 60%, and more preferably 15% to 55%; the molar content of the structural unit containing alkoxysilyl cycloolefin is 0.01% to 1.5%, preferably 0.02 to 1.3%, and more preferably 0.03% to 1.2%.

[0018] According to the present invention, preferably, the weight average molecular weight of the pendant siloxane functionalized polyolefin elastomer is 100 to 1600 kg / mol, preferably 150 to 1400 kg / mol, and more preferably 200 to 1200 kg / mol.

[0019] The second aspect of the present invention provides a method for preparing the pendant siloxane functionalized polyolefin elastomer, comprising the following steps:

[0020] Under the action of a vanadium catalyst, ethylene, alpha-olefin and alkoxy-containing silicon-based cycloolefin are copolymerized to obtain the side-group siloxane functionalized polyolefin elastomer.

[0021] According to the present invention, preferably, the vanadium-based catalyst comprises the following components:

[0022] Component A: main catalyst, the main catalyst is selected from the general formula VOCl 2 OR 1 and VOCl(OR 1 )(OR 2 ) shown in at least one of the vanadium-containing compounds, wherein R 1 and R 2 The same or different, each independently selected from C 1 ~C 10 Alkyl, C 1 ~C 10 The halogenated alkyl, C 4 ~C 10 Cycloalkyl, C 4 ~C 10 halocycloalkyl or C 6 ~C 25 The aromatic group;

[0023] Component B: a co-catalyst, wherein the co-catalyst is an organic aluminum compound.

[0024] According to the present invention, preferably, R 1 and R 2 Each is independently selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, 2,2-dichloro-1-ethyl, 1,1-dichloro-2-propyl, 1,1-dichloro-2-methyl-2-propyl, 3,3-dichloro-1-propyl, 2,2-dichloro-1-propyl, 1,1-dichloro-2-butyl, 3,3-dichloro-1-butyl, 2,2-dichloro-1-butyl, 1,1-dichloro R is 1,1,1-trichloro-2-butyl, 1,1,1-trichloro-2-butyl, 1,1,1-trichloro-2-butyl, 2,2-dichloro-1-pentyl, 2,2-dichloro-1-hexyl, 2,2,2-trichloro-1-ethyl, 3,3,3-trichloro-1-propyl, 1,1,1-trichloro-2-propyl, 1,1,1-trichloro-2-methyl-2-propyl, 1,1,1-trichloro-2-butyl, or 1,1,1-trichloro-2-methyl-2-butyl. 2It can also be selected from p-methylphenoxy, 2-methylphenoxy, 2-ethylphenoxy, 4-ethylphenoxy, 2-isopropylphenoxy, 2-tert-butylphenoxy, 2-sec-butylphenoxy, 2,4-dimethylphenoxy, 2,6-dimethylphenoxy, 2,3,4-trimethylphenoxy, 2,3,5-trimethylphenoxy, 2,3,6-trimethylphenoxy, 2,4,6-trimethylphenoxy, 2,4-diethylphenoxy, 2,6-diethylphenoxy, 2,4,6 - at least one of triethylphenoxy, 2,3-di-tert-butylphenoxy, 2,4-di-tert-butylphenoxy, 2,5-di-tert-butylphenoxy, 2,6-di-tert-butylphenoxy, 2,3,4-tri-tert-butylphenoxy, 2,3,5-tri-tert-butylphenoxy, 2,3,6-tri-tert-butylphenoxy, 2,4,6-tri-tert-butylphenoxy, 2,6-di-tert-butyl-4-methylphenoxy, 4-tert-pentylphenoxy, 3-pentadecylphenoxy and 4-tert-octylphenoxy.

[0025] According to the present invention, preferably, the organoaluminum compound is selected from at least one of alkylaluminum and alkylaluminum halide; the alkylaluminum and the alkylaluminum halide are selected from the general formula R m AlX 3-m At least one of the compounds shown, wherein R is C 1 ~C 10 Alkyl, C 4 ~C 10 Cycloalkyl, C 7 ~C 10 Aralkyl and C 6 ~C 10 wherein X is a halogen, preferably Cl or Br, and m is 1, 1.5, 2 or 3; preferably, the alkylaluminum is selected from at least one of trimethylaluminum, triethylaluminum, tri-n-propylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-n-pentylaluminum, tri-n-hexylaluminum and tricyclohexylaluminum, and the alkylaluminum halide is selected from at least one of dimethylaluminum chloride, diethylaluminum chloride, di-n-butylaluminum chloride, diisobutylaluminum chloride, methylaluminum dichloride, ethylaluminum dichloride, n-butylaluminum dichloride, isobutylaluminum dichloride, sesquimethylaluminum chloride, sesquiethylaluminum chloride, sesqui-n-butylaluminum chloride and sesquiisobutylaluminum chloride.

[0026] According to the present invention, preferably, the molar ratio of component B calculated as Al element to component A calculated as V element is 10 to 80:1, preferably 15 to 70:1, and more preferably 25 to 65:1.

[0027] In the present invention, the amount of component B is related to factors such as the impurity content, the amount of the primary catalyst, the amount of monomer, the molecular weight and molecular weight distribution of the polymerized product in the system. Usually, increasing the amount of the cocatalyst in the polymerization system within a certain range can improve the polymerization activity. Too little cocatalyst produces a small number of active centers, low catalytic activity, and low monomer polymerization conversion. However, too much cocatalyst can cause the primary catalyst to be excessively reduced on the one hand, affecting the monomer conversion, and on the other hand, cause chain transfer, and the molecular weight of the polymer decreases. In addition, too much cocatalyst can also cause the catalyst cost to increase.

[0028] In the present invention, if the monomer concentration in the polymerization system is too high, the system viscosity will be too large, affecting the production process. If the monomer concentration is too low, the amount of solvent used will increase, the cost will increase, and the production efficiency will decrease. In the present invention, a suitable monomer concentration is necessary. Preferably, the monomer concentration is 10 to 180 g / L, preferably 20 to 150 g / L, and more preferably 30 to 120 g / L.

[0029] In the present invention, the polymerization reaction may be adiabatic polymerization or isothermal polymerization. It may be a batch polymerization operation mode, or a semi-continuous polymerization or a continuous polymerization operation mode. The starting temperature of the polymerization reaction is -60 to 60°C, preferably -50 to 50°C, and more preferably -40 to 40°C.

[0030] In the present invention, the polymerization conversion rate of monomers and the polymer yield will both increase by prolonging the polymerization reaction time. The polymerization reaction time is generally selected to be 1 to 60 minutes, preferably 2 to 50 minutes, and more preferably 4 to 40 minutes.

[0031] In the present invention, the polymerization reaction pressure is related to the polymerization temperature. The higher the temperature, the greater the pressure. In addition, increasing the pressure is conducive to the gas monomer dissolving in the solution for polymerization reaction, but too high a pressure will have high pressure resistance requirements for the polymerization reactor. Therefore, the polymerization pressure is generally selected to be 0.01 to 3.0 MPa, preferably 0.05 to 2.0 MPa, and more preferably 0.1 to 1.0 MPa.

[0032] According to the present invention, preferably, the copolymerization reaction adopts solution polymerization or slurry polymerization.

[0033] According to the present invention, preferably, the copolymerization reaction adopts solution polymerization, and the solvent used is selected from C 5 ~C 10 Saturated alkanes, C 5 ~C 10 Cycloalkanes or C 6 ~C 10At least one of the aromatic hydrocarbons is preferably selected from at least one of n-pentane, cyclopentane, n-hexane, cyclohexane, methylcyclopentane, methylcyclohexane, n-heptane, n-octane, isooctane, n-nonane, n-decane, toluene and xylene.

[0034] The present invention has the following beneficial effects:

[0035] (1) The use of vanadium-based catalysts has a certain tolerance to olefins containing alkoxysilane substituents, and does not require expensive MAO or boron compounds, so the catalyst cost is low.

[0036] (2) Using vanadium-based catalysts, functionalized polyolefin elastomers containing alkoxysilyl substituents on the side groups can be efficiently prepared in one step through direct copolymerization of olefins and cycloolefins containing alkoxysilane substituents. The reaction conditions are mild, the process flow is short, the production cost is low, the molecular weight of the copolymer is high, the molecular weight distribution is relatively narrow, and the product structure composition is adjustable, and the structure determines the performance.

[0037] (3) The copolymerization composition and functionality of the functionalized polyolefin can be regulated by directly controlling the addition amount of the three monomers during the monomer copolymerization reaction, which has great flexibility and strong controllability, and a high molecular weight side-group siloxane functionalized polyolefin elastomer can be directly prepared in one step, wherein: the molar content of the ethylene structural unit is in the range of 47 to 82%, the molar content of the α-olefin structural unit is in the range of 17 to 52%, and the molar content of the alkoxysilyl cycloolefin structural unit is in the range of 0.05 to 1.01%.

[0038] Other features and advantages of the present invention will be described in detail in the following detailed description. DETAILED DESCRIPTION

[0039] The preferred embodiments of the present invention will be described in more detail below. Although the preferred embodiments of the present invention are described below, it should be understood that the present invention can be implemented in various forms and should not be limited to the embodiments set forth herein.

[0040] For polymer 1 H NMR test, the molar contents of ethylene, propylene and alkoxysilyl-containing cycloolefin structural units in the copolymer were calculated according to the integrated areas of the characteristic peaks.

[0041] The number average molecular weight (M) of the polymer was measured by GPC at 150 °C using trichlorobenzene as solvent. n ), weight average molecular weight (M w ) and molecular weight distribution.

[0042] Example 1

[0043] In a -35°C cold bath, under the protection of high-purity nitrogen and under stirring, a propylene / ethylene mixed gas (molar ratio = 3.5:1) was introduced into a reactor containing 30 mL of hexane, 0.04 g of 5-(triethoxysilyl)-2-norbornene (VSi) was added, and after uniform mixing, 2.0 mmol of sesquiethylaluminum chloride and 0.05 mmol of trichlorotert-butyloxydichlorovanadium were added to start the polymerization reaction, and the propylene / ethylene mixed gas was continuously introduced during the reaction. After the polymerization reaction lasted for 10 minutes, ethanol was added to terminate the polymerization reaction, the polymer in the reaction solution was precipitated with ethanol, the liquid was filtered off, and the polymer product solid was vacuum dried to constant weight at 40°C to obtain 1.94 g of E / P / VSi terpolymer.

[0044] In the obtained E / P / VSi copolymer, the molar content of ethylene structural units (C E ) is 60.42%, and the molar content of propylene structural units (C P ) is 39.53%, and the molar content of 5-(triethoxysilyl)-2-norborneol structural unit (C VSi ) is 0.05%. The weight average molecular weight (M w ) is 521kg / mol, and the molecular weight distribution index (M w / M n ) is 3.07.

[0045] Example 2

[0046] The polymerization method and post-treatment method are the same as those in Example 1, except that 0.12 g of 5-(triethoxysilyl)-2-norbornene is added. 1.15 g of copolymer is obtained, wherein C E is 70.53%, C P 28.95%, C VSi The M w is 657 kg / mol, M w / M n is 3.02.

[0047] Example 3

[0048] The polymerization method and post-treatment method are the same as those in Example 1, except that 0.20 g of 5-(triethoxysilyl)-2-norbornene is added. 0.40 g of copolymer is obtained, wherein C E is 77.56%, C P is 21.43%, C VSi The M w is 302kg / mol, M w / M n is 2.80.

[0049] Example 4

[0050] The polymerization method and post-treatment method are the same as those in Example 1, except that 0.16 g of 5-(triethoxysilyl)-2-norbornene and 0.05 mmol of trichloro-tert-butyloxy-p-tert-octyl-phenylvanadium chloride are added. 0.99 g of copolymer is obtained, wherein C E is 67.56%, C P 32.08%, C VSi The M w is 1010kg / mol, M w / M n It is 2.81.

[0051] Example 5

[0052] The polymerization method and post-treatment method are the same as those in Example 1, except that 0.16 g of 5-(triethoxysilyl)-2-norbornene and 0.05 mmol of trichloro-tert-butyl-p-methylphenylvanadium chloride are added. 0.96 g of copolymer is obtained, wherein C E is 73.74%, C P is 25.97%, C VSi The M w is 537 kg / mol, M w / M n is 3.03.

[0053] Example 6

[0054] The polymerization method and post-treatment method are the same as those in Example 1, except that the molar ratio of the propylene / ethylene mixed gas used is 3:1, and 0.12 g of 5-(triethoxysilyl)-2-norbornene is added. 0.44 g of copolymer is obtained, wherein C E is 63.83%, C P is 35.66%, C VSi The M w is 307 kg / mol, M w / M n is 3.26.

[0055] Example 7

[0056] The polymerization method and post-treatment method are the same as those in Example 1, except that the molar ratio of the propylene / ethylene mixed gas used is 5:1, and 0.12 g of 5-(triethoxysilyl)-2-norbornene is added. 0.26 g of copolymer is obtained. E is 47.30%, C P is 52.19%, CVSi The M w is 242kg / mol, M w / M n is 3.08.

[0057] Example 8

[0058] In a -35°C cold bath and under the protection of high-purity nitrogen, ethylene was introduced into a reactor containing 30 mL of hexane and 4.3 g of 1-octene. After 3 minutes, ethylene was turned off, and 0.12 g of 5-(triethoxysilyl)-2-norbornene was added. After mixing evenly, 2.0 mmol of sesquiethylaluminum chloride and 0.05 mmol of trichlorotert-butyloxydichlorovanadium were added to start polymerization. The polymerization reaction lasted for 10 minutes. The post-treatment method was the same as in Example 1, and 1.0 g of terpolymer was obtained, wherein C E The molar content of 1-octene structural unit (C O ) is 25.16%, C VSi The M w is 217 kg / mol, M w / M n is 2.08.

[0059] Example 9

[0060] The polymerization method and post-treatment method were the same as those in Example 8, except that 4.0 g of 1-hexene was used instead of 4.3 g of 1-octene. 0.94 g of copolymer was obtained, wherein C E The molar content of 1-hexene structural unit (C H ) is 18.61%, C VSi The copolymer has a M w is 489 kg / mol, M w / M n is 2.75.

[0061] Example 10

[0062] The polymerization method and post-treatment method are the same as those in Example 1, except that the amount of sesquiethylaluminum chloride added is 3.0 mmol, and the amount of 5-(triethoxysilyl)-2-norbornene added is 0.20 g. 1.31 g of copolymer is obtained, wherein C E is 64.75%, C P is 34.71%, C VSi The M w is 571kg / mol, M w / M n It is 2.66.

[0063] Embodiment 11

[0064] The polymerization method and post-treatment method are the same as those in Example 1, except that the molar ratio of the ethylene / propylene mixed gas used is 2:1, the amount of 5-(triethoxysilyl)-2-norbornene added is 0.20 g, and the amount of sesquiethylaluminum chloride added is 3.0 mmol. 0.85 g of copolymer is obtained, wherein C E is 82.32%, C P is 17.10%, C VSi The M w is 534 kg / mol, M w / M n is 3.07.

[0065] Example 12

[0066] The polymerization method and post-treatment method were the same as those in Example 1, except that 0.23 g of 5-(diethoxy-methylsilyl)-2-norbornene was added, the ethylene / propylene molar ratio of the propylene / ethylene mixed gas was 3.0:1, and the amount of ES added was 3.0 mmol. 1.11 g of copolymer was obtained, of which C E is 64.21%, C P 35.05%, C VSi The M w is 378 kg / mol, M w / M n It is 2.41.

[0067] Comparative Example 1

[0068] The polymerization method was the same as in Example 1, except that 0.12 g of vinyltriethoxysilane was added. No polymerization reaction occurred, and no polymerization product was obtained.

[0069] The embodiments of the present invention have been described above, and the above description is exemplary, not exhaustive, and is not limited to the disclosed embodiments. Many modifications and changes will be apparent to those skilled in the art without departing from the scope and spirit of the described embodiments.

Claims

1. A pendant siloxane functionalized polyolefin elastomer, characterized in that: The pendant siloxane functionalized polyolefin elastomer contains ethylene structural units, α-olefin structural units and structural units derived from alkoxy-containing silicon-based cycloolefins; the alkoxy-containing silicon-based cycloolefins are selected from at least one of the compounds shown in Formula 1, In Formula 1, a is an integer of 0-5, preferably an integer of 0-3, and more preferably an integer of 0-2; R1 and R2 are each independently selected from C1-C 10 Alkyl, C1-C 10 Alkoxy, C4-C 10 Cycloalkyl or C4-C 10 The cycloalkyloxy group is preferably a C1-C5 alkyl group or a C1-C5 alkoxy group; R3 is a C1-C 10 Alkyl or C4-C 10 R4 is hydrogen or C1-C 10 The alkyl group is preferably hydrogen or a C1-C5 alkyl group.

2. The pendant siloxane functionalized polyolefin elastomer according to claim 1, wherein The alkoxysilyl-containing cycloolefin is selected from 5-(dimethoxy-ethoxysilyl)-2-norbornene, 5-(methoxy-diethoxysilyl)-2-norbornene, 5-(trimethoxysilyl)-2-norbornene, 5-(triethoxysilyl)-2-norbornene, 5-(tri-n-propoxysilyl)-2-norbornene, 5-(triisopropoxysilyl)-2-norbornene, 5-(methyl-diethoxysilyl)-2-norbornene, 5-(dimethyl-ethoxysilyl)-2-norbornene, 5-(ethyl-diethoxysilyl)-2-norbornene, 2-trimethoxysilyl-1,4:5,8-dimethyl-1,2, At least one of 3,4,4a,5,8,8a-octahydronaphthalene and 2-triethoxysilyl-1,4:5,8-dimethyl-1,2,3,4,4a,5,8,8a-octahydronaphthalene, preferably at least one of 5-(trimethoxysilyl)-2-norbornene, 5-(methyl-diethoxysilyl)-2-norbornene, 5-(triethoxysilyl)-2-norbornene, 2-trimethoxysilyl-1,4:5,8-dimethyl-1,2,3,4,4a,5,8,8a-octahydronaphthalene and 2-triethoxysilyl-1,4:5,8-dimethyl-1,2,3,4,4a,5,8,8a-octahydronaphthalene.

3. The pendant siloxane functionalized polyolefin elastomer according to claim 1, wherein The α-olefin is C3~C 15 α-olefins, preferably C3~C 10 of α-olefins.

4. The pendant siloxane functionalized polyolefin elastomer according to claim 1, wherein Based on the molar number of all structural units in the side-group siloxane functionalized polyolefin elastomer, the molar content of the ethylene structural unit is 34% to 90%, preferably 38% to 88%, and more preferably 42% to 85%; the molar content of the structural unit of the α-olefin is 5% to 65%, preferably 10% to 60%, and more preferably 15% to 55%; the molar content of the structural unit containing alkoxysilyl cycloolefin is 0.01% to 1.5%, preferably 0.02% to 1.3%, and more preferably 0.03% to 1.2%.

5. The pendant siloxane functionalized polyolefin elastomer according to claim 1, wherein The weight average molecular weight of the pendant siloxane functionalized polyolefin elastomer is 100 to 1600 kg / mol, preferably 150 to 1400 kg / mol, and more preferably 200 to 1200 kg / mol.

6. The method for preparing a pendant siloxane functionalized polyolefin elastomer according to any one of claims 1 to 5, characterized in that: The steps include: Under the action of a vanadium catalyst, ethylene, alpha-olefin and alkoxysilyl-containing cycloolefin are copolymerized to obtain the side-group siloxane functionalized polyolefin elastomer.

7. The preparation method according to claim 6, wherein: The vanadium-based catalyst comprises the following components: Component A: main catalyst, the main catalyst is selected from the general formula VOCl2OR 1 and VOCl(OR 1 )(OR 2 ) shown in at least one of the vanadium-containing compounds, wherein R 1 and R 2 The same or different, each independently selected from C1 to C 10 Alkyl, C1~C 10 haloalkyl, C4~C 10 Cycloalkyl, C4~C 10 Halogenated cycloalkyl or C6~C 25 Preferably, R 1 and R 2 Each is independently selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, 2,2-dichloro-1-ethyl, 1,1-dichloro-2-propyl, 1,1-dichloro-2-methyl-2-propyl, 3,3-dichloro-1-propyl, 2,2-dichloro-1-propyl, 1,1-dichloro-2-butyl, 3,3-dichloro-1-butyl, 2,2-dichloro-1-butyl, 1,1-dichloro-2-pentyl, 2,2-dichloro -1-pentyl, 1,1-dichloro-2-hexyl, 2,2-dichloro-1-hexyl, 2,2,2-trichloro-1-ethyl, 3,3,3-trichloro-1-propyl, 1,1,1-trichloro-2-propyl, 1,1,1-trichloro-2-methyl-2-propyl, 1,1,1-trichloro-2-butyl, 1,1,1-trichloro-2-methyl-2-butyl, methylphenoxy, 2-methylphenoxy, 2-ethylphenoxy, 4- Ethylphenoxy, 2-isopropylphenoxy, 2-tert-butylphenoxy, 2-sec-butylphenoxy, 2,4-dimethylphenoxy, 2,6-dimethylphenoxy, 2,3,4-trimethylphenoxy, 2,3,5-trimethylphenoxy, 2,3,6-trimethylphenoxy, 2,4,6-trimethylphenoxy, 2,4-diethylphenoxy, 2,6-diethylphenoxy, 2,4,6-triethylphenoxy, 2,3-ditert-butylphenoxy At least one of butylphenoxy, 2,4-di-tert-butylphenoxy, 2,5-di-tert-butylphenoxy, 2,6-di-tert-butylphenoxy, 2,3,4-tri-tert-butylphenoxy, 2,3,5-tri-tert-butylphenoxy, 2,3,6-tri-tert-butylphenoxy, 2,4,6-tri-tert-butylphenoxy, 2,6-di-tert-butyl-4-methylphenoxy, 4-tert-pentylphenoxy, 3-pentadecylphenoxy and 4-tert-octylphenoxy; Component B: a cocatalyst, wherein the cocatalyst is an organoaluminum compound; preferably, the organoaluminum compound is selected from at least one of an alkylaluminum and an alkylaluminum halide; the alkylaluminum and the alkylaluminum halide are selected from the general formula R m AlX 3-m At least one of the compounds shown, wherein R is C1~C 10 Alkyl, C4~C 10 Cycloalkyl, C7~C 10 Arylalkyl and C6~C 10 wherein X is a halogen, preferably Cl or Br, and m is 1, 1.5, 2 or 3; more preferably, the alkylaluminum is selected from at least one of trimethylaluminum, triethylaluminum, tri-n-propylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-n-pentylaluminum, tri-n-hexylaluminum and tricyclohexylaluminum, and the alkylaluminum halide is selected from at least one of dimethylaluminum chloride, diethylaluminum chloride, di-n-butylaluminum chloride, diisobutylaluminum chloride, methylaluminum dichloride, ethylaluminum dichloride, n-butylaluminum dichloride, isobutylaluminum dichloride, sesquimethylaluminum chloride, sesquiethylaluminum chloride, sesqui-n-butylaluminum chloride and sesquiisobutylaluminum chloride.

8. The preparation method according to claim 7, wherein: The molar ratio of component B calculated as Al element to component A calculated as V element is 10 to 80:1, preferably 15 to 70:1, and more preferably 25 to 65:

1.

9. The preparation method according to claim 6, wherein: The process conditions of the copolymerization reaction include: a monomer concentration of 10 to 180 g / L, preferably 20 to 150 g / L, and more preferably 30 to 120 g / L; a pressure of 0.01 to 3.0 MPa, preferably 0.05 to 2.0 MPa, and more preferably 0.1 to 1.0 MPa; an initial reaction temperature of -60 to 60°C, preferably -50 to 50°C, and more preferably -40 to 40°C; and a polymerization time of 1 to 60 min, preferably 2 to 50 min, and more preferably 4 to 40 min.

10. The preparation method according to claim 6, wherein: The copolymerization reaction adopts solution polymerization or slurry polymerization; Preferably, the copolymerization reaction is carried out by solution polymerization, and the solvent used is selected from C5 to C 10 Saturated alkanes, C5~C 10 Cycloalkanes or C6~C 10 At least one of the aromatic hydrocarbons is preferably selected from at least one of n-pentane, cyclopentane, n-hexane, cyclohexane, methylcyclopentane, methylcyclohexane, n-heptane, n-octane, isooctane, n-nonane, n-decane, toluene and xylene.

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