WO2019237582A1 - Complex of silica and ethylene propylene rubber and preparation method therefor - Google Patents

Complex of silica and ethylene propylene rubber and preparation method therefor Download PDF

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WO2019237582A1
WO2019237582A1 PCT/CN2018/109104 CN2018109104W WO2019237582A1 WO 2019237582 A1 WO2019237582 A1 WO 2019237582A1 CN 2018109104 W CN2018109104 W CN 2018109104W WO 2019237582 A1 WO2019237582 A1 WO 2019237582A1
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ethylene
silica
propylene rubber
propylene
bond
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PCT/CN2018/109104
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French (fr)
Chinese (zh)
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牛慧
荆彦宽
何宗科
李杨
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大连理工大学
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/06—Polymer mixtures characterised by other features having improved processability or containing aids for moulding methods

Definitions

  • the invention relates to the field of new ethylene-propylene rubber materials, in particular to a method for preparing a composite of silicon dioxide and ethylene-propylene rubber, a silicon dioxide and ethylene-propylene rubber composite material prepared by the method, and applications thereof .
  • Ethylene-propylene rubber (ethylene / propylene copolymer) is an important variety of synthetic rubber and has been widely used in the fields of automobile manufacturing, construction materials, sealing parts and the like.
  • Ethylene-propylene rubber has excellent properties such as heat resistance, ozone resistance, chemical resistance, and stress cracking resistance, but its strength is insufficient. Therefore, it must be reinforced in practical applications.
  • Most rubber products contain a large amount of fillers. Adding fillers can not only improve the physical and mechanical properties of rubber products, reduce product costs, but also improve the processing performance of rubber materials. Among them, fillers based on reinforcement can obviously improve the abrasion resistance, tear strength and tensile stress of rubber.
  • Silica also known as white carbon black
  • Silica is the main light-colored reinforcing filler of ethylene-propylene rubber, which can give rubber products good physical properties and insulation properties.
  • the surface of silica has a strong polarity due to the large amount of silicon hydroxyl groups (Si-OH), the surface energy is very high, and it is easy to produce agglomeration.
  • Silica without surface treatment is usually difficult to disperse, and often exists in the form of agglomerates in the rubber matrix, which cannot fully exert the reinforcing effect on the rubber. People can modify the surface of silica by adding small molecule modifiers to improve the dispersion of silica in ethylene-propylene rubber and improve the physical and mechanical properties of rubber.
  • Modifier small molecules usually contain an alkyl group at one end (ethylene-propylene-acid end) and a reactive group at the other end (a Si-OH end).
  • Many groups including amino (-NH 3 ), carboxyl (-COOH), and ethoxy (-OC 2 H 5 ), can be hydrogen bonded, esterified, and polarized with Si-OH on the surface of silica. Strong interactions, such as attractivity, form a bonding layer on the surface of the filler powder, transforming the polar Si-OH surface to a less polar alkyl surface, thereby weakening the easy agglomeration of silica, and Improve its compatibility with rubber.
  • the object of the present invention is to provide a composite of silica and ethylene-propylene rubber, the composition of which is: the mass content of ethylene-propylene rubber is 5 to 98%, and the mass content of silica is 2 to 95%; Ethylene-propylene rubber is a copolymer of ethylene, propylene and Si-Cl bond-containing olefin monomers.
  • the molar content of ethylene units in the copolymer is 5 to 94%, and the molar content of propylene units is 5 to 94. %,
  • the molar content of Si-Cl bond-containing olefin monomer units is 0.01-50%;
  • the Si-Cl bond-containing olefin monomer has the following structure:
  • R 1 and R 2 may be the same or different, and each is independently selected from Cl, methyl, ethyl, isopropyl, methoxy, ethoxy, isopropoxy, and hydrogen; n is 1 to 12 Integer.
  • Another object of the present invention is to provide a method for preparing the above-mentioned composite of silica and ethylene-propylene rubber.
  • the composite of silica and ethylene-propylene rubber is prepared by a solution polymerization method. The specific steps are as follows:
  • the organic solvent is an alkane having 5 to 10 carbon atoms and / or an aromatic hydrocarbon having 6 to 10 carbon atoms;
  • the mass ratio of the total mass of the ethylene, propylene, and Si-Cl bond-containing olefin monomer to the mass of the organic solvent is 1 to 1000: 100.
  • the ratio of sum is 0.01 to 5: 1;
  • the polymerization temperature is from 0 ° C to 100 ° C, the polymerization pressure is from 0.01 to 6 MPa, and the polymerization time is from 0.1 to 12 hours;
  • the main catalyst is selected from Ziegler-Natta catalyst or metallocene catalyst, and the co-catalyst is selected from alkyl aluminum compound or alkyl alumoxane compound;
  • Step (1) After the polymerization reaction is completed, silica is added to the reaction product for reaction.
  • the mass ratio of silica to the polymerization product is 0.02 to 19: 1, the reaction time is 0.1 to 24 hours, and the reaction temperature is 0. °C ⁇ 100 °C; after the reaction is completed, the remaining solvent is removed to obtain a composite of silica and ethylene-propylene rubber.
  • the total mass of the ethylene, propylene, and Si-Cl bond-containing olefin monomers to be reacted with the mass ratio of the organic solvent is preferably 5 to 100: 100; the Si-Cl bond-containing
  • the ratio of the olefin monomer to the sum of the mass of ethylene and propylene added is preferably 0.1 to 3: 1;
  • the polymerization reaction temperature is preferably 30 ° C to 80 ° C, the polymerization pressure is 0.1 to 4 MPa; and the polymerization time is 0.5 to 5 hours.
  • the Ziegler-Natta main catalyst is a transition metal chloride or oxychloride; the transition metal is selected from Ti (titanium), V (vanadium); further preferably, the titanium chloride or chlorine The oxide is selected from at least one of TiCl 3 , TiCl 4 and TiOCl 2 , and the chloride or chlorine oxide of V is selected from at least one of VCl 3 , VCl 4 and VOCl 3 .
  • the metallocene catalyst is selected from a transition metal- ⁇ bond compound with a transition metal M as a central atom, and M is Ti, Zr, or Hf; further preferably, a transition with a transition metal M as a central atom
  • the metal- ⁇ bond compound is selected from Cp 2 TiCl 2 , C 2 H 4 (Me 4 Cp) 2 MCl 2 , C 2 H 4 (Ind) 2 MCl 2 , C 2 H 4 ( 2 , 4 , 7-Me 3- Ind) 2 MCl 2 , Me 2 Si (Flu) 2 MCl 2 , Me 2 SiCH 2 (Ind) 2 MCl 2 , Me 2 Si (2-MeInd) 2 MCl 2 , Me 2 Si (2,5-Me-Cp ) 2 MCl 2 , Me 2 Si (4,7-Me 2 -Ind) 2 MCl 2 , Me 2 Si (2-Me-4-Naph-Ind) 2
  • the cocatalyst when the main catalyst is a Ziegler-Natta catalyst, the cocatalyst is selected from an alkyl aluminum compound; when the main catalyst is a metallocene catalyst, the cocatalyst is selected from an alkyl alumoxane compound.
  • the alkyl aluminum is a trialkyl aluminum or a mixture consisting of a trialkyl aluminum and a haloalkyl aluminum or a polyhaloalkyl aluminum, wherein the trialkyl aluminum is preferably triethyl At least one of aluminum, triisobutylaluminum, tri-n-butylaluminum, tri-n-hexylaluminum, and tri-n-octylaluminum, the haloalkylaluminum is preferably diethylaluminum chloride; the polyhaloalkylaluminum is preferably Triethyldichloro aluminum.
  • the alkylalumoxane is preferably at least one of methylalumoxane and isobutylalumoxane.
  • / V 10 to 20,000: 1, preferably 50 to 1000: 1;
  • Al: M 10 to 20,000: 1, preferably 500 to 10,000: 1.
  • the alkane having 5 to 10 carbon atoms is selected from at least one of n-pentane, n-hexane, cyclohexane, n-heptane, n-octane, and n-decane.
  • the aromatic hydrocarbon organic solvent having 6 to 10 carbon atoms is selected from at least one of benzene, toluene, xylene, ethylbenzene, n-propylbenzene, and cumene.
  • silica is added to the reaction product, and the silica solid powder may be directly added, or the silica may be dispersed in an organic solvent to be added.
  • the silica may be dispersed Add in organic solvent.
  • the silica is preferably a granular silica having a particle size ranging from 0.05 to 50 ⁇ m, and more preferably a granular silica having a particle size ranging from 0.1 to 20 ⁇ m;
  • the reaction time between the polymerization product and the silica is 0.5 to 12 hours.
  • the organic solvent for dispersing the silica may be the same as or different from the polymerization solvent, and is selected from n-pentane, n-hexane, cyclohexane, n-heptane, n-octane, n- At least one kind of decane, or at least one kind selected from benzene, toluene, xylene, ethylbenzene, n-propylbenzene, and cumene.
  • the composite of silica and ethylene-propylene rubber according to the present invention has the characteristics of simple preparation process, uniform silica dispersion, and can completely avoid the phenomenon of silica agglomeration.
  • the invention also provides the application of the composite material of the above silica and ethylene-propylene rubber as a reinforcement of ethylene-propylene rubber.
  • the ethylene-propylene rubber prepared by the invention has high strength, good toughness and stable performance.
  • Si-Cl bonds are introduced into the side chain of the molecular chain of ethylene-propylene rubber, and a large amount of silicon existing on the surfaces of the Si-Cl bonds and silicon dioxide is introduced.
  • Figure 1 shows the thermal weight loss (TGA) curve of the polymer product.
  • FIG. 2 is a scanning electron microscope (SEM) photograph of the morphology of the polymerized product from Example 3 of the present invention.
  • FIG. 3 is a scanning electron microscope (SEM) photograph of the quenched surface morphology of the polymerized product from Example 1 of the present invention after melt processing.
  • Si-Cl bond-containing olefin monomers can be purchased from commercial sources or synthesized directly.
  • this application provides a conventional synthesis method, and is not a limitation on the Si-Cl bond-containing monomer.
  • a three-necked round-bottomed flask equipped with a constant-pressure dropping funnel and a reflux condenser was charged with 24.3 g of a sandpaper-polished magnesium band.
  • a constant-pressure dropping funnel was charged with 100 mL of dry tetrahydrofuran (THF) and 12.5 g 4-chloromethylstyrene was then added dropwise to a three-necked round-bottomed flask and reacted for 2 hours to obtain a dark gray suspension; under nitrogen protection, the suspension was added dropwise to 50 mL of dry solution.
  • THF dry tetrahydrofuran
  • the polymer has an ethylene content of 40.3 mol% and a propylene content of 59.7 mol%.
  • Polymer composition is shown in Table 1.
  • the mass content of ethylene-propylene rubber in the product is 52.8 wt%, and the mass content of silica is 47.2 wt%; in the ethylene-propylene rubber, the ethylene content is 40.3 mol% and the propylene content is 59.7 mol%.
  • the polymer composition is shown in Table 1.
  • the ethylene content in the polymer is 34.9 mol%, the propylene content is 55.4 mol%, and the Si-Cl bond-containing olefin monomer A content is 9.7 mol%.
  • the polymer composition is shown in Table 1.
  • the polymer solution was transferred to a dispersion of 1.62 In a 50 mL hexane solution of g of silica, the reaction was stirred at room temperature for 2 hours. The product was collected, washed and dried to obtain 6.95 g of product.
  • the mass content of ethylene-propylene rubber in the product is 76.7 wt% and the mass content of silica is 23.3 wt%; in the ethylene-propylene rubber, the ethylene content is 34.9 mol%, the propylene content is 55.4 mol%, and the monomer A containing Si-Cl bonds The content is 9.7 mol%, and the polymer composition is shown in Table 1.
  • the mass content of ethylene-propylene rubber in the product is 51.7% by weight and the mass content of silica is 48.3% by weight; in the ethylene-propylene rubber, the ethylene content is 39.3mol%, the propylene content is 49.1mol%, and the monomer B containing Si-Cl bonds The content is 11.6 mol%, and the polymer composition is shown in Table 1.
  • the material solution was transferred to a 100 mL hexane solution in which 9.05 g of silica was dispersed, and the reaction was stirred at room temperature for 4 hours. The product was collected, washed and dried to obtain 9.90 g of the product.
  • the mass content of ethylene-propylene rubber in the product is 8.6% by weight and the mass content of silica is 91.4% by weight; in the ethylene-propylene rubber, the ethylene content is 45.5 mol%, the propylene content is 29.4 mol%, and the monomer B containing Si-Cl bonds The content is 25.1 mol%, and the polymer composition is shown in Table 1.
  • the mass content of ethylene-propylene rubber in the product is 55.8wt%, and the mass content of silica is 44.2wt%; in ethylene-propylene rubber, the ethylene content is 70.8mol%, the propylene content is 21.0mol%, and the monomer B containing Si-Cl bonds The content is 8.2 mol%, and the polymer composition is shown in Table 1.
  • the polymer solution is transferred to 1.10 g of dioxide dispersed In a 50 mL hexane solution of silicon, the reaction was stirred at room temperature for 2 hours. The product was collected, washed and dried to obtain 1.50 g of the product.
  • the mass content of ethylene-propylene rubber in the product is 27.3 wt%, and the mass content of silica is 72.7 wt%; in the ethylene-propylene rubber, the ethylene content is 58.2 mol%, the propylene content is 33.7 mol%, and the monomer B containing Si-Cl bonds The content is 8.1 mol%, and the polymer composition is shown in Table 1.
  • the mass content of ethylene-propylene rubber in the product is 82.6 wt% and the mass content of silica is 17.4 wt%; in ethylene-propylene rubber, the ethylene content is 51.3 mol%, the propylene content is 39.8 mol%, and the monomer C containing Si-Cl bonds The content is 8.9 mol%, and the polymer composition is shown in Table 1.
  • the polymer solution was transferred to a dispersion of 1.50 In a 100 mL hexane solution of g of silica, the reaction was stirred at room temperature for 4 hours. The product was collected, washed and dried to obtain 7.18 g of the product.
  • the mass content of ethylene-propylene rubber in the product is 79.2 wt%, and the mass content of silica is 20.8 wt%; in the ethylene-propylene rubber, the ethylene content is 40.3 mol%, the propylene content is 48.0 mol%, and the monomer D containing Si-Cl bonds The content is 11.7 mol%, and the polymer composition is shown in Table 1.
  • the solution was transferred to 100 mL of a hexane solution in which 1.59 g of silica was dispersed, and the reaction was stirred at room temperature for 4 hours.
  • the product was collected, washed and dried to obtain 7.06 g of product.
  • the mass content of ethylene-propylene rubber in the product is 77.5 wt%, and the mass content of silica is 22.5 wt%; in ethylene-propylene rubber, the ethylene content is 34.4 mol%, the propylene content is 53.4 mol%, and the monomer E containing Si-Cl bonds The content is 12.2 mol%, and the polymer composition is shown in Table 1.
  • the polymer solution was transferred to a dispersion of 1.78 In a 100 mL hexane solution of g of silica, the reaction was stirred at room temperature for 4 hours. The product was collected, washed and dried to obtain 9.06 g of the product.
  • the mass content of ethylene-propylene rubber in the product is 80.3 wt%, and the mass content of silica is 19.7 wt%; in the ethylene-propylene rubber, the ethylene content is 37.5 mol%, the propylene content is 50.4 mol%, and the monomer E containing Si-Cl bonds The content is 12.1 mol%, and the polymer composition is shown in Table 1.
  • the Si-Cl bond in the olefin monomer containing Si-Cl bond is introduced into the ethylene-propylene copolymer side group through copolymerization reaction, and the content is adjustable; Si-Cl of the ethylene-propylene copolymer side group It is easy to react with a large amount of Si-OH existing on the surface of silica particles to form Si-O-Si bonds, thereby firmly combining ethylene-propylene rubber and silica particles through chemical bonds, which fundamentally solves the problem of silica. Problems with compatibility with ethylene-propylene rubber, and stability of dispersion of silica particles in ethylene-propylene rubber.
  • the mass content of silica and ethylene-propylene rubber in the product can be determined through the thermal weight loss curve of the material (as shown in Figure 1).
  • the remaining material above 500 ° C is silica.
  • scanning electron microscope observation of the morphology of the direct polymerization product it can be seen that the surface of the silica particles is uniformly coated with ethylene-propylene rubber, and the particle diameter is about 50 nm, which is equivalent to the size of the selected silica particles (as shown in Figure 2). (Shown), indicating that the polymerization method can effectively achieve the coating of silica particles with ethylene-propylene rubber.

Abstract

Disclosed are a complex of silica and an ethylene propylene rubber and a preparation method therefor. In the copolymer, the mass content of the ethylene propylene rubber is 5%-98%, and the mass content of the silica is 2%-95%, wherein the ethylene propylene rubber is a copolymer made by the polymerization of ethylene, propylene and an olefin monomer containing an Si-Cl bond. A silicon-chlorine group contained in the olefin monomer containing an Si-Cl bond is introduced into the pendant group of the ethylene propylene copolymer by a copolymerization reaction, and then is chemically reacted with a large number of silicon-hydroxyl groups present on the surface of silica particles, thus the ethylene propylene rubber is firmly bonded with the silica particles by means of chemical bonds, which fundamentally solves the compatibility problem between silica and the ethylene propylene rubber and the stability problem of dispersing the silica particles in the ethylene propylene rubber.

Description

二氧化硅和乙丙橡胶复合物及其制备方法Silica and ethylene-propylene rubber composite and preparation method thereof 技术领域Technical field
本发明涉及一种新型乙丙橡胶材料领域，特别涉及一种二氧化硅和乙丙橡胶的复合物的制备方法，以及由该方法制备得到的二氧化硅和乙丙橡胶复合物材料和其应用。The invention relates to the field of new ethylene-propylene rubber materials, in particular to a method for preparing a composite of silicon dioxide and ethylene-propylene rubber, a silicon dioxide and ethylene-propylene rubber composite material prepared by the method, and applications thereof .
背景技术Background technique
乙丙橡胶(乙烯/丙烯共聚物)是合成橡胶的重要品种，在汽车制造、建筑材料、密封制件等领域都有广泛应用。乙丙橡胶具有耐热、耐臭氧、耐化学品、耐应力开裂等优良的性能，但是强度不足，因此在实际应用中必须进行补强，绝大多数橡胶制品中都含有大量填料。加入填料不仅可以提高橡胶制品的物理机械性能，降低制品成本，还能改善橡胶材料的加工性能。其中，以补强为主的填充剂能明显提高橡胶的耐磨性、撕裂强度及拉伸应力。二氧化硅(也称白炭黑)是乙丙橡胶主要的浅色补强填料，能赋予橡胶制品良好的物性和绝缘性。然而，二氧化硅表面由于含有大量的硅羟基(Si-OH)而具有较强的极性，表面能很高，极易产生团聚现象。未经表面处理的二氧化硅通常较难分散，往往以团聚体的形态存在于橡胶基体中，不能充分发挥对橡胶的增强作用。人们通过加入小分子改性剂可对二氧化硅表面进行改性，以提高二氧化硅在乙丙橡胶中的分散性，改善橡胶的物理机械性能。改性剂小分子通常一端含有烷基(亲乙丙橡胶端)、另一端含有反应性基团(亲Si-OH端)。包括氨基(-NH 3)、羧基(-COOH)、乙氧基(-OC 2H 5)等在内的许多基团都能与二氧化硅表面的Si-OH发生氢键、酯化、极性相吸等较强的相互作用，在填料粉体的表面形成结合层，将极性的Si-OH表面转变为极性较弱的烷基表面，从而削弱二氧化硅的易团聚性，并提高其与橡胶之间的相容性。目前报道的这类改性剂均为小分子化合物，需要预先与二氧化硅进行反应，得到表面改性的二氧化硅，然后再与乙丙橡胶进行混合。此外，表面改性的二氧化硅与乙丙橡胶之间相容性还取决于改性剂小分子中所含烷基与乙丙共聚物的相容程度。如能在乙丙橡胶合成过程中即实现二氧化硅的分散，直接在聚合釜中制备出二氧化硅分散稳定、性能优异的乙丙橡胶，具有重要的实用价值和长远的环保意义。 Ethylene-propylene rubber (ethylene / propylene copolymer) is an important variety of synthetic rubber and has been widely used in the fields of automobile manufacturing, construction materials, sealing parts and the like. Ethylene-propylene rubber has excellent properties such as heat resistance, ozone resistance, chemical resistance, and stress cracking resistance, but its strength is insufficient. Therefore, it must be reinforced in practical applications. Most rubber products contain a large amount of fillers. Adding fillers can not only improve the physical and mechanical properties of rubber products, reduce product costs, but also improve the processing performance of rubber materials. Among them, fillers based on reinforcement can obviously improve the abrasion resistance, tear strength and tensile stress of rubber. Silica (also known as white carbon black) is the main light-colored reinforcing filler of ethylene-propylene rubber, which can give rubber products good physical properties and insulation properties. However, the surface of silica has a strong polarity due to the large amount of silicon hydroxyl groups (Si-OH), the surface energy is very high, and it is easy to produce agglomeration. Silica without surface treatment is usually difficult to disperse, and often exists in the form of agglomerates in the rubber matrix, which cannot fully exert the reinforcing effect on the rubber. People can modify the surface of silica by adding small molecule modifiers to improve the dispersion of silica in ethylene-propylene rubber and improve the physical and mechanical properties of rubber. Modifier small molecules usually contain an alkyl group at one end (ethylene-propylene-acid end) and a reactive group at the other end (a Si-OH end). Many groups, including amino (-NH 3 ), carboxyl (-COOH), and ethoxy (-OC 2 H 5 ), can be hydrogen bonded, esterified, and polarized with Si-OH on the surface of silica. Strong interactions, such as attractivity, form a bonding layer on the surface of the filler powder, transforming the polar Si-OH surface to a less polar alkyl surface, thereby weakening the easy agglomeration of silica, and Improve its compatibility with rubber. These modifiers reported so far are all small molecule compounds, which need to be reacted with silica in advance to obtain surface modified silica, and then mixed with ethylene-propylene rubber. In addition, the compatibility between surface-modified silica and ethylene-propylene rubber also depends on the compatibility of the alkyl group contained in the small molecule of the modifier with the ethylene-propylene copolymer. If the dispersion of silica can be achieved during the synthesis of ethylene-propylene rubber, it is of great practical value and long-term environmental significance to prepare ethylene-propylene rubber with stable silica dispersion and excellent performance directly in the polymerization kettle.
发明内容Summary of the Invention
本发明的目的是提供一种二氧化硅和乙丙橡胶的复合物，该复合物的组成为：乙丙橡胶质量含量为5～98％，二氧化硅质量含量为2～95％；所述乙丙橡胶为一种由乙烯、丙烯和含Si-Cl键的烯烃单体聚合而成的共聚物，共聚物中乙烯单元的摩尔含量为5～94％，丙烯单元的摩尔含量为5～94％，含Si-Cl键的烯烃单体单元的摩尔含量为0.01～50％；The object of the present invention is to provide a composite of silica and ethylene-propylene rubber, the composition of which is: the mass content of ethylene-propylene rubber is 5 to 98%, and the mass content of silica is 2 to 95%; Ethylene-propylene rubber is a copolymer of ethylene, propylene and Si-Cl bond-containing olefin monomers. The molar content of ethylene units in the copolymer is 5 to 94%, and the molar content of propylene units is 5 to 94. %, The molar content of Si-Cl bond-containing olefin monomer units is 0.01-50%;
其中，含Si-Cl键的烯烃单体具有如下结构：Among them, the Si-Cl bond-containing olefin monomer has the following structure:
Figure PCTCN2018109104-appb-000001
Figure PCTCN2018109104-appb-000001
其中，R 1和R 2可以相同或者不同，各自独立的选自Cl、甲基、乙基、异丙基、甲氧基、乙氧基、异丙氧基和氢；n为1～12之间的整数。 Wherein, R 1 and R 2 may be the same or different, and each is independently selected from Cl, methyl, ethyl, isopropyl, methoxy, ethoxy, isopropoxy, and hydrogen; n is 1 to 12 Integer.
本发明的另一目的在于提供上述二氧化硅和乙丙橡胶的复合物的制备方法，该二氧化硅和乙丙橡胶的复合物通过溶液聚合方法制备，具体步骤如下：Another object of the present invention is to provide a method for preparing the above-mentioned composite of silica and ethylene-propylene rubber. The composite of silica and ethylene-propylene rubber is prepared by a solution polymerization method. The specific steps are as follows:
(1)向反应容器中依次加入有机溶剂、助催化剂、含Si-Cl键的烯烃单体，再通入乙烯、丙烯气体，最后加入主催化剂进行聚合反应；(1) Add an organic solvent, a cocatalyst, and an Si-Cl bond-containing olefin monomer to the reaction vessel in order, and then pass in ethylene and propylene gas, and finally add a main catalyst for polymerization reaction;
所述有机溶剂为5～10个碳原子的烷烃和/或6～10个碳原子的芳香烃；The organic solvent is an alkane having 5 to 10 carbon atoms and / or an aromatic hydrocarbon having 6 to 10 carbon atoms;
所述乙烯、丙烯和含Si-Cl键的烯烃单体的总质量与有机溶剂的质量比为1～1000∶100，所述含Si-Cl键的烯烃单体与加入的乙烯、丙烯质量之和的比为0.01～5∶1；The mass ratio of the total mass of the ethylene, propylene, and Si-Cl bond-containing olefin monomer to the mass of the organic solvent is 1 to 1000: 100. The ratio of sum is 0.01 to 5: 1;
聚合反应温度为0℃～100℃，聚合压力为0.01～6MPa，聚合时间为0.1～12小时；The polymerization temperature is from 0 ° C to 100 ° C, the polymerization pressure is from 0.01 to 6 MPa, and the polymerization time is from 0.1 to 12 hours;
主催化剂选自Ziegler-Natta催化剂或茂金属催化剂，助催化剂选自烷基铝化合物或烷基铝氧烷化合物；The main catalyst is selected from Ziegler-Natta catalyst or metallocene catalyst, and the co-catalyst is selected from alkyl aluminum compound or alkyl alumoxane compound;
(2)步骤(1)聚合反应结束后，向反应产物中加入二氧化硅进行反应，二氧化硅与聚合产物质量之比为0.02～19∶1，反应时间0.1～24小时，反应温度为0℃～100℃；反应结束后将剩余溶剂脱除得到二氧化硅和乙丙橡胶的复合物。(2) Step (1) After the polymerization reaction is completed, silica is added to the reaction product for reaction. The mass ratio of silica to the polymerization product is 0.02 to 19: 1, the reaction time is 0.1 to 24 hours, and the reaction temperature is 0. ℃ ~ 100 ℃; after the reaction is completed, the remaining solvent is removed to obtain a composite of silica and ethylene-propylene rubber.
进一步地，在上述技术方案中，进行反应的乙烯、丙烯和含Si-Cl键的烯烃单体的总质量与有机溶剂的质量比优选为5～100∶100；加入的含Si-Cl键的烯烃单体与加入的乙烯、丙烯质量之和的比优选为0.1～3∶1；聚合反应温度优选为30℃～80℃，聚合压力为0.1～4MPa；聚合时间为0.5～5小时。Further, in the above technical scheme, the total mass of the ethylene, propylene, and Si-Cl bond-containing olefin monomers to be reacted with the mass ratio of the organic solvent is preferably 5 to 100: 100; the Si-Cl bond-containing The ratio of the olefin monomer to the sum of the mass of ethylene and propylene added is preferably 0.1 to 3: 1; the polymerization reaction temperature is preferably 30 ° C to 80 ° C, the polymerization pressure is 0.1 to 4 MPa; and the polymerization time is 0.5 to 5 hours.
进一步地，在上述技术方案中，Ziegler-Natta主催化剂是过渡金属氯化物或氯氧化物；过渡金属选自Ti(钛)、V(钒)；进一步优选地，所述钛的氯化物或氯氧化物选自TiCl 3、TiCl 4和TiOCl 2中的至少一种，所述V的氯化物或氯氧化物选自VCl 3、VCl 4和VOCl 3中的至少一种。 Further, in the above technical solution, the Ziegler-Natta main catalyst is a transition metal chloride or oxychloride; the transition metal is selected from Ti (titanium), V (vanadium); further preferably, the titanium chloride or chlorine The oxide is selected from at least one of TiCl 3 , TiCl 4 and TiOCl 2 , and the chloride or chlorine oxide of V is selected from at least one of VCl 3 , VCl 4 and VOCl 3 .
进一步地，在上述技术方案中，茂金属催化剂选自以过渡金属M为中心原子的过渡金属-π键化合物，M为Ti、Zr或Hf；进一步优选地，以过渡金属M为中心原子的过渡金属-π键化合物选自Cp 2TiCl 2，C 2H 4(Me 4Cp) 2MCl 2，C 2H 4(Ind) 2MCl 2，C 2H 4(2，4，7-Me 3-Ind) 2MCl 2，Me 2Si(Flu) 2MCl 2，Me 2SiCH 2(Ind) 2MCl 2，Me 2Si(2-MeInd) 2MCl 2，Me 2Si(2，5-Me-Cp) 2MCl 2，Me 2Si(4，7-Me 2-Ind) 2MCl 2，Me 2Si(2-Me-4-Naph-Ind) 2ZrCl 2；上述化合物中，Me＝甲基，Ph＝苯基，Cp＝环戊二烯基，Ind＝茚基，H 4Ind＝4，5，6，7-四氢化茚， Flu＝芴基，Naph＝萘基。 Further, in the above technical solution, the metallocene catalyst is selected from a transition metal-π bond compound with a transition metal M as a central atom, and M is Ti, Zr, or Hf; further preferably, a transition with a transition metal M as a central atom The metal-π bond compound is selected from Cp 2 TiCl 2 , C 2 H 4 (Me 4 Cp) 2 MCl 2 , C 2 H 4 (Ind) 2 MCl 2 , C 2 H 4 ( 2 , 4 , 7-Me 3- Ind) 2 MCl 2 , Me 2 Si (Flu) 2 MCl 2 , Me 2 SiCH 2 (Ind) 2 MCl 2 , Me 2 Si (2-MeInd) 2 MCl 2 , Me 2 Si (2,5-Me-Cp ) 2 MCl 2 , Me 2 Si (4,7-Me 2 -Ind) 2 MCl 2 , Me 2 Si (2-Me-4-Naph-Ind) 2 ZrCl 2 ; In the above compounds, Me = methyl, Ph = phenyl, Cp = cyclopentadienyl, Ind = indenyl, H 4 Ind = 4,5,6,7- tetrahydroindenyl, Flu = fluorenyl, Naph = naphthyl.
进一步地，在上述技术方案中，当主催化剂采用Ziegler-Natta催化剂时，助催化剂选自烷基铝化合物；当主催化剂采用茂金属催化剂时，助催化剂选自烷基铝氧烷化合物。Further, in the above technical scheme, when the main catalyst is a Ziegler-Natta catalyst, the cocatalyst is selected from an alkyl aluminum compound; when the main catalyst is a metallocene catalyst, the cocatalyst is selected from an alkyl alumoxane compound.
进一步地，在上述技术方案中，所述烷基铝为三烷基铝或由三烷基铝与卤代烷基铝或多卤代烷基铝组成的混合物，其中，所述三烷基铝优选三乙基铝、三异丁基铝、三正丁基铝、三正己基铝、三正辛基铝中的至少一种，所述卤代烷基铝优选二乙基氯化铝；所述多卤代烷基铝优选三乙基三氯化二铝。Further, in the above technical solution, the alkyl aluminum is a trialkyl aluminum or a mixture consisting of a trialkyl aluminum and a haloalkyl aluminum or a polyhaloalkyl aluminum, wherein the trialkyl aluminum is preferably triethyl At least one of aluminum, triisobutylaluminum, tri-n-butylaluminum, tri-n-hexylaluminum, and tri-n-octylaluminum, the haloalkylaluminum is preferably diethylaluminum chloride; the polyhaloalkylaluminum is preferably Triethyldichloro aluminum.
进一步地，在上述技术方案中，烷基铝氧烷优选甲基铝氧烷和异丁基铝氧烷中的至少一种。Further, in the above technical solution, the alkylalumoxane is preferably at least one of methylalumoxane and isobutylalumoxane.
助催化剂的添加量以Al与所述Ziegler-Natta催化剂中的Ti或V、或者Al与所述茂金属催化剂中的M(M＝Ti、Zr或Hf)的摩尔比计，分别为Al∶Ti/V＝10～20000∶1，优选50～1000∶1；Al∶M＝10～20000∶1，优选500～10000∶1。The cocatalyst is added in terms of molar ratios of Al to Ti or V in the Ziegler-Natta catalyst, or Al (M = Ti, Zr, or Hf) in the metallocene catalyst. / V = 10 to 20,000: 1, preferably 50 to 1000: 1; Al: M = 10 to 20,000: 1, preferably 500 to 10,000: 1.
进一步地，在上述技术方案中，作为优选地，5～10个碳原子的烷烃选自正戊烷、正己烷、环己烷、正庚烷、正辛烷、正癸烷中的至少一种，6～10个碳原子的芳香烃有机溶剂选自苯、甲苯、二甲苯、乙苯、正丙苯、异丙苯中的至少一种。Further, in the above technical solution, preferably, the alkane having 5 to 10 carbon atoms is selected from at least one of n-pentane, n-hexane, cyclohexane, n-heptane, n-octane, and n-decane. The aromatic hydrocarbon organic solvent having 6 to 10 carbon atoms is selected from at least one of benzene, toluene, xylene, ethylbenzene, n-propylbenzene, and cumene.
进一步地，在上述技术方案中，在反应产物中加入二氧化硅，可以直接加入二氧化硅固体粉末，也可以将二氧化硅分散于有机溶剂中加入；作为优选地，可将二氧化硅分散于有机溶剂中加入。Further, in the above technical solution, silica is added to the reaction product, and the silica solid powder may be directly added, or the silica may be dispersed in an organic solvent to be added. As a preferred embodiment, the silica may be dispersed Add in organic solvent.
进一步地，在上述技术方案中，优选二氧化硅为粒径范围在0.05～50μm的颗粒状二氧化硅，更优选地为粒径范围在0.1～20μm的颗粒状二氧化硅；作为优选地，聚合产物与二氧化硅的反应时间为0.5～12小时。Further, in the above technical solution, the silica is preferably a granular silica having a particle size ranging from 0.05 to 50 μm, and more preferably a granular silica having a particle size ranging from 0.1 to 20 μm; The reaction time between the polymerization product and the silica is 0.5 to 12 hours.
进一步地，在上述技术方案中，所述用于分散二氧化硅的有机溶剂可以与聚合溶剂相同或不同，选自正戊烷、正己烷、环己烷、正庚烷、正辛烷、正癸烷中的至少一种，或选自苯、甲苯、二甲苯、乙苯、正丙苯、异丙苯中的至少一种。Further, in the above technical solution, the organic solvent for dispersing the silica may be the same as or different from the polymerization solvent, and is selected from n-pentane, n-hexane, cyclohexane, n-heptane, n-octane, n- At least one kind of decane, or at least one kind selected from benzene, toluene, xylene, ethylbenzene, n-propylbenzene, and cumene.
本发明所述的二氧化硅和乙丙橡胶的复合物，具有制备工艺简单、二氧化硅分散均匀的特点，且能够完全避免二氧化硅团聚的现象。The composite of silica and ethylene-propylene rubber according to the present invention has the characteristics of simple preparation process, uniform silica dispersion, and can completely avoid the phenomenon of silica agglomeration.
本发明还提供上述二氧化硅和乙丙橡胶的复合物材料作为增强乙丙橡胶的应用，本发明所制备的乙丙橡胶，强度高，韧性好，性能稳定。The invention also provides the application of the composite material of the above silica and ethylene-propylene rubber as a reinforcement of ethylene-propylene rubber. The ethylene-propylene rubber prepared by the invention has high strength, good toughness and stable performance.
本发明通过乙烯、丙烯、含Si-Cl键的烯烃单体聚合方法，在乙丙橡胶的分子链侧基上引入了Si-Cl键，而Si-Cl键与二氧化硅表面存在的大量硅羟基(Si-OH)之间可以进行化学反应，生成Si-O-Si键，从而使乙丙橡胶分子链以化学键的形式牢固地结合在二氧化硅表面，从根本上解决了乙丙橡胶与二氧化硅之间相互作用弱的问题；同时，由于乙丙橡胶对二氧化硅颗粒的包裹，也使得二氧化硅颗粒之间完全被乙丙橡胶隔开，从根本上解决了二氧化硅易团聚的问题。In the present invention, through the polymerization method of ethylene, propylene, and olefin monomers containing Si-Cl bonds, Si-Cl bonds are introduced into the side chain of the molecular chain of ethylene-propylene rubber, and a large amount of silicon existing on the surfaces of the Si-Cl bonds and silicon dioxide is introduced. Chemical reactions can occur between hydroxyl groups (Si-OH) to form Si-O-Si bonds, so that the molecular chain of ethylene-propylene rubber is firmly bonded to the surface of silicon dioxide in the form of chemical bonds, which fundamentally solves the problem of ethylene-propylene rubber and The problem of weak interaction between silica; at the same time, because of the encapsulation of silica particles by ethylene-propylene rubber, the silica particles are completely separated by ethylene-propylene rubber, which fundamentally solves the problem of silica The problem of reunion.
附图说明BRIEF DESCRIPTION OF THE DRAWINGS
图1为聚合产物热失重(TGA)曲线。Figure 1 shows the thermal weight loss (TGA) curve of the polymer product.
图2为由本发明实施例3聚合产物形貌扫描电镜(SEM)照片。FIG. 2 is a scanning electron microscope (SEM) photograph of the morphology of the polymerized product from Example 3 of the present invention.
图3为由本发明实施例1聚合产物经过熔融加工后淬断面形貌扫描电镜(SEM)照片。FIG. 3 is a scanning electron microscope (SEM) photograph of the quenched surface morphology of the polymerized product from Example 1 of the present invention after melt processing.
具体实施方式detailed description
本发明提出以下实施例作为进一步的说明，但并非限制本发明权利要求保护的范围。The present invention provides the following embodiments as further description, but does not limit the scope of protection of the claims of the present invention.
含Si-Cl键的烯烃单体：Si-Cl bond-containing olefin monomer:
含Si-Cl键的烯烃单体可以购自商品，也可以直接合成。对于合成的含Si-Cl键的单体，本申请提供一种常规合成方法，并非对含Si-Cl键的单体的限定。Si-Cl bond-containing olefin monomers can be purchased from commercial sources or synthesized directly. For the synthesized Si-Cl bond-containing monomer, this application provides a conventional synthesis method, and is not a limitation on the Si-Cl bond-containing monomer.
(1)含Si-Cl键的烯烃单体A：(1) Si-Cl bond-containing olefin monomer A:
烯丙基二甲基氯硅烷，购自百灵威化学(CAS号：4028-23-3)。结构式为：Allyldimethylchlorosilane was purchased from Blackwell Chemical (CAS No. 4028-23-3). The structural formula is:
Figure PCTCN2018109104-appb-000002
Figure PCTCN2018109104-appb-000002
(2)含Si-Cl键的烯烃单体B：(2) Si-Cl bond-containing olefin monomer B:
将9.4g(0.142mol)环戊二烯加入充满氮气的反应釜中，缓慢加入24.8g(0.172mol)乙烯基三氯硅烷；在80℃反应3小时，然后升温至120℃反应1小时，再降温至80℃反应10小时；产物经减压蒸馏得到含Si-Cl键的烯烃单体B。结构式为：Add 9.4 g (0.142 mol) of cyclopentadiene to a reactor filled with nitrogen, and slowly add 24.8 g (0.172 mol) of vinyltrichlorosilane; react at 80 ° C for 3 hours, then heat to 120 ° C for 1 hour, and then The temperature was lowered to 80 ° C for 10 hours, and the product was distilled under reduced pressure to obtain an Si-Cl bond-containing olefin monomer B. The structural formula is:
Figure PCTCN2018109104-appb-000003
Figure PCTCN2018109104-appb-000003
(3)含Si-Cl键的烯烃单体C：(3) Si-Cl bond-containing olefin monomer C:
氮气保护下，在装有恒压滴液漏斗和回流冷凝管的三口圆底烧瓶中加入用砂纸打磨过的镁带24.3g，恒压滴液漏斗中加入100mL干燥的四氢呋喃(THF)和9.7g对氯苯乙烯，然后逐滴滴加至三口圆底烧瓶中，反应2小时，得到暗灰色的悬浊液；氮气保护下，将该悬浊液逐滴滴加到含50mL干燥的THF和11.21g甲基三氯化硅的圆底烧瓶中，室温下反应16小时；最后减压去除THF，加入干燥的正己烷溶解出产物，过滤，得到粗产品；加入0.3g的4-甲氧基酚在110～120℃减压蒸馏得到中间体，再逐滴加入等摩尔的无水甲醇溶液，最终得到含Si-Cl键的烯烃单体C。结构式为：Under nitrogen protection, a three-necked round-bottomed flask equipped with a constant-pressure dropping funnel and a reflux condenser was charged with 24.3 g of a sandpaper-polished magnesium belt. A constant-pressure dropping funnel was charged with 100 mL of dry tetrahydrofuran (THF) and 9.7 g. P-chlorostyrene was then added dropwise to a three-necked round-bottomed flask and reacted for 2 hours to obtain a dark gray suspension; under the protection of nitrogen, the suspension was added dropwise to 50 mL of dry THF and 11.21 g methyl methyl trichloride in a round bottom flask, react at room temperature for 16 hours; finally, remove THF under reduced pressure, add dry n-hexane to dissolve the product, and filter to obtain a crude product; add 0.3 g of 4-methoxyphenol The intermediate was distilled under reduced pressure at 110 to 120 ° C, and an equimolar anhydrous methanol solution was added dropwise to finally obtain an Si-Cl bond-containing olefin monomer C. The structural formula is:
Figure PCTCN2018109104-appb-000004
Figure PCTCN2018109104-appb-000004
(4)含Si-Cl键的烯烃单体D：(4) Si-Cl bond-containing olefin monomer D:
将9.4g(0.142mol)环戊二烯加入充满氮气的反应釜中，缓慢加入30.2g(0.172mol)丙烯基三氯硅烷；在80℃反应3小时，然后升温至120℃反应1小时，再降温至80℃反应10小时；产物经减压蒸馏得到含Si-Cl键的烯烃单体D。结构式为：Add 9.4 g (0.142 mol) of cyclopentadiene to a reactor filled with nitrogen, and slowly add 30.2 g (0.172 mol) of acryltrichlorosilane; react at 80 ° C for 3 hours, then heat to 120 ° C for 1 hour, then The temperature was lowered to 80 ° C. for 10 hours, and the product was distilled under reduced pressure to obtain an Si-Cl bond-containing olefin monomer D. The structural formula is:
Figure PCTCN2018109104-appb-000005
Figure PCTCN2018109104-appb-000005
(5)含Si-Cl键的烯烃单体E：(5) Si-Cl bond-containing olefin monomer E:
氮气保护下，在装有恒压滴液漏斗和回流冷凝管的三口圆底烧瓶中加入用砂纸打磨过的镁带24.3g，恒压滴液漏斗中加入100mL干燥的四氢呋喃(THF)和12.5g的4-氯甲基苯乙烯，然后逐滴滴加至三口圆底烧瓶中，反应2小时，得到暗灰色的悬浊液；氮气保护下，将该悬浊液逐滴滴加到含50mL干燥的THF和13.0g四氯化硅的圆底烧瓶中，室温下反应16小时；最后减压去除THF，加入干燥的正己烷溶解出产物，过滤，得到粗产品；加入0.3g的4-甲氧基酚在110～120℃减压蒸馏得到含Si-Cl键的烯烃单体E。结构式为：Under nitrogen protection, a three-necked round-bottomed flask equipped with a constant-pressure dropping funnel and a reflux condenser was charged with 24.3 g of a sandpaper-polished magnesium band. A constant-pressure dropping funnel was charged with 100 mL of dry tetrahydrofuran (THF) and 12.5 g 4-chloromethylstyrene was then added dropwise to a three-necked round-bottomed flask and reacted for 2 hours to obtain a dark gray suspension; under nitrogen protection, the suspension was added dropwise to 50 mL of dry solution. THF and 13.0 g of silicon tetrachloride in a round-bottomed flask, reacted at room temperature for 16 hours; finally, the THF was removed under reduced pressure, dried n-hexane was added to dissolve the product, and filtered to obtain a crude product; 0.3 g of 4-methoxy was added The phenol was distilled under reduced pressure at 110 to 120 ° C to obtain an Si-Cl bond-containing olefin monomer E. The structural formula is:
Figure PCTCN2018109104-appb-000006
Figure PCTCN2018109104-appb-000006
(6)含Si-Cl键的烯烃单体F：(6) Si-Cl bond-containing olefin monomer F:
将9.4g(0.142mol)环戊二烯加入充满氮气的反应釜中，缓慢加入32.4g(0.172mol)丁二烯基三氯硅烷；在80℃反应3小时，然后升温至120℃反应1小时，再降温至80℃反应10小时；产物经减压蒸馏得到含Si-Cl键的烯烃单体F。结构式为：Add 9.4 g (0.142 mol) of cyclopentadiene to a reactor filled with nitrogen, and slowly add 32.4 g (0.172 mol) of butadienyl trichlorosilane; react at 80 ° C for 3 hours, then raise the temperature to 120 ° C for 1 hour Then, the temperature was lowered to 80 ° C. for 10 hours, and the product was distilled under reduced pressure to obtain an Si-Cl bond-containing olefin monomer F. The structural formula is:
Figure PCTCN2018109104-appb-000007
Figure PCTCN2018109104-appb-000007
对比实验1Comparative Experiment 1
在250mL的反应釜中，加入50mL甲苯，在搅拌下加入1.0mol/L的甲基铝氧烷溶 液4mL，2μmol茂金属催化剂C 2H 4(Ind) 2ZrCl 2，通入乙烯/丙烯混合气0.1MPa，其中，乙烯∶丙烯＝1∶1(v/v)，40℃反应0.5小时。收集聚合产物，洗涤、干燥后得到乙丙橡胶5.60g。 In a 250mL reaction kettle, add 50mL of toluene, add 1.0mL / L methylalumoxane solution 4mL, 2μmol metallocene catalyst C 2 H 4 (Ind) 2 ZrCl 2 under stirring, and pass in an ethylene / propylene gas mixture. 0.1 MPa, where ethylene: propylene = 1: 1 (v / v), and reacted at 40 ° C for 0.5 hours. The polymerization product was collected, washed and dried to obtain 5.60 g of ethylene-propylene rubber.
该聚合物中乙烯含量为40.3mol％，丙烯含量为59.7mol％。聚合物组成见表1。The polymer has an ethylene content of 40.3 mol% and a propylene content of 59.7 mol%. Polymer composition is shown in Table 1.
对比实验2Comparative Experiment 2
在250mL的反应釜中，加入50mL甲苯，在搅拌下加入1.0mol/L的甲基铝氧烷溶液4mL，2μmol茂金属催化剂C 2H 4(Ind) 2ZrCl 2，通入乙烯/丙烯混合气0.1MPa，其中，乙烯∶丙烯＝1∶1(v/v)，40℃反应0.5小时；反应结束后将聚合物溶液转移至分散有5.00g二氧化硅的100mL己烷溶液中，室温搅拌反应2小时。收集产物，洗涤、干燥后得到产物10.60g。 In a 250mL reaction kettle, add 50mL of toluene, add 1.0mL / L methylalumoxane solution 4mL, 2μmol metallocene catalyst C 2 H 4 (Ind) 2 ZrCl 2 under stirring, and pass in an ethylene / propylene gas mixture. 0.1 MPa, of which ethylene: propylene = 1: 1 (v / v), reacted at 40 ° C for 0.5 hours; after the reaction, the polymer solution was transferred to 100 mL of a hexane solution in which 5.00 g of silica was dispersed, and the reaction was stirred at room temperature 2 hours. The product was collected, washed and dried to obtain 10.60 g of the product.
产物中乙丙橡胶质量含量为52.8wt％，二氧化硅质量含量为47.2wt％；乙丙橡胶中，乙烯含量为40.3mol％，丙烯含量为59.7mol％，聚合物组成见表1。The mass content of ethylene-propylene rubber in the product is 52.8 wt%, and the mass content of silica is 47.2 wt%; in the ethylene-propylene rubber, the ethylene content is 40.3 mol% and the propylene content is 59.7 mol%. The polymer composition is shown in Table 1.
对比实验3Comparative Experiment 3
在250mL的反应釜中，加入50mL甲苯，在搅拌下加入1.0mol/L的甲基铝氧烷溶液4mL，加入25mmol含Si-Cl键的烯烃单体A，通入乙烯/丙烯混合气0.1MPa，其中，乙烯∶丙烯＝1∶1(v/v)，加入2μmol茂金属催化剂C 2H 4(Ind) 2ZrCl 2，40℃反应0.5小时；收集聚合产物，洗涤、干燥后得到乙丙橡胶5.05g。 In a 250 mL reaction kettle, add 50 mL of toluene, add 4 mL of a 1.0 mol / L methylalumoxane solution under stirring, add 25 mmol of Si-Cl bond-containing olefin monomer A, and pass in an ethylene / propylene mixed gas 0.1 MPa In which, ethylene: propylene = 1: 1 (v / v), 2 μmol metallocene catalyst C 2 H 4 (Ind) 2 ZrCl 2 was added , and reacted at 40 ° C. for 0.5 hours; the polymerization product was collected, washed and dried to obtain ethylene-propylene rubber 5.05g.
该聚合物中乙烯含量为34.9mol％，丙烯含量为55.4mol％，含Si-Cl键的烯烃单体A含量为9.7mol％，聚合物组成见表1。The ethylene content in the polymer is 34.9 mol%, the propylene content is 55.4 mol%, and the Si-Cl bond-containing olefin monomer A content is 9.7 mol%. The polymer composition is shown in Table 1.
实施例1Example 1
在250mL的反应釜中，加入50mL甲苯，在搅拌下加入1.0mol/L的甲基铝氧烷溶液4mL，加入25mmol含Si-Cl键的烯烃单体A，通入乙烯/丙烯混合气0.1MPa，其中，乙烯∶丙烯＝1∶1(v/v)，加入2μmol茂金属催化剂C 2H 4(Ind) 2ZrCl 2，40℃反应0.5小时；反应结束后将聚合物溶液转移至分散有1.62g二氧化硅的50mL己烷溶液中，室温搅拌反应2小时。收集产物，洗涤、干燥后得到产物6.95g。 In a 250 mL reaction kettle, add 50 mL of toluene, add 4 mL of a 1.0 mol / L methylalumoxane solution under stirring, add 25 mmol of Si-Cl bond-containing olefin monomer A, and pass in an ethylene / propylene mixed gas 0.1 MPa Among them, ethylene: propylene = 1: 1 (v / v), 2 μmol metallocene catalyst C 2 H 4 (Ind) 2 ZrCl 2 was added , and the reaction was carried out at 40 ° C. for 0.5 hours. After the reaction, the polymer solution was transferred to a dispersion of 1.62 In a 50 mL hexane solution of g of silica, the reaction was stirred at room temperature for 2 hours. The product was collected, washed and dried to obtain 6.95 g of product.
产物中乙丙橡胶质量含量为76.7wt％，二氧化硅质量含量为23.3wt％；乙丙橡胶中，乙烯含量为34.9mol％，丙烯含量为55.4mol％，含Si-Cl键的单体A含量为9.7mol％，聚合物组成见表1。The mass content of ethylene-propylene rubber in the product is 76.7 wt% and the mass content of silica is 23.3 wt%; in the ethylene-propylene rubber, the ethylene content is 34.9 mol%, the propylene content is 55.4 mol%, and the monomer A containing Si-Cl bonds The content is 9.7 mol%, and the polymer composition is shown in Table 1.
实施例2Example 2
在250mL的反应釜中，加入50mL甲苯，在搅拌下加入1.0mol/L的甲基铝氧烷溶液4mL，加入25mmol含Si-Cl键的烯烃单体B，通入乙烯/丙烯混合气0.1MPa，其中，乙烯∶丙烯＝1∶1(v/v)，加入2μmol茂金属催化剂C 2H 4(Ind) 2ZrCl 2，40℃反应0.5小时；反应结束后将聚合物溶液转移至分散有5.22g二氧化硅的100mL己烷溶液中， 室温搅拌反应4小时。收集产物，洗涤、干燥后得到产物10.80g。 In a 250 mL reaction kettle, add 50 mL of toluene, add 4 mL of a 1.0 mol / L methylalumoxane solution under stirring, add 25 mmol of Si-Cl bond-containing olefin monomer B, and pass in an ethylene / propylene mixed gas 0.1 MPa Among them, ethylene: propylene = 1: 1 (v / v), 2 μmol metallocene catalyst C 2 H 4 (Ind) 2 ZrCl 2 was added , and the reaction was carried out at 40 ° C. for 0.5 hours; after the reaction was completed, the polymer solution was transferred to a dispersion of 5.22 In 100 mL of a hexane solution of g of silica, the reaction was stirred at room temperature for 4 hours. The product was collected, washed and dried to obtain 10.80 g of the product.
产物中乙丙橡胶质量含量为51.7wt％，二氧化硅质量含量为48.3wt％；乙丙橡胶中，乙烯含量为39.3mol％，丙烯含量为49.1mol％，含Si-Cl键的单体B含量为11.6mol％，聚合物组成见表1。The mass content of ethylene-propylene rubber in the product is 51.7% by weight and the mass content of silica is 48.3% by weight; in the ethylene-propylene rubber, the ethylene content is 39.3mol%, the propylene content is 49.1mol%, and the monomer B containing Si-Cl bonds The content is 11.6 mol%, and the polymer composition is shown in Table 1.
实施例3Example 3
在250mL的反应釜中，加入50mL甲苯，在搅拌下加入1.0mol/L的甲基铝氧烷溶液4mL，加入50mmol含Si-Cl键的烯烃单体B，通入乙烯/丙烯混合气0.1MPa，其中，乙烯∶丙烯＝1∶1(v/v)，加入1μmol茂金属催化剂Me 2Si(2-Me-4-Naph-Ind) 2ZrCl 2，65℃反应0.25小时；反应结束后将聚合物溶液转移至分散有9.05g二氧化硅的100mL己烷溶液中，室温搅拌反应4小时。收集产物，洗涤、干燥后得到产物9.90g。 In a 250 mL reaction kettle, add 50 mL of toluene, add 4 mL of a 1.0 mol / L methylalumoxane solution under stirring, add 50 mmol of Si-Cl bond olefin monomer B, and pass in an ethylene / propylene mixed gas 0.1 MPa In which, ethylene: propylene = 1: 1 (v / v), 1 μmol metallocene catalyst Me 2 Si (2-Me-4-Naph-Ind) 2 ZrCl 2 was added , and the reaction was performed at 65 ° C. for 0.25 hours; after the reaction was completed, polymerization was performed. The material solution was transferred to a 100 mL hexane solution in which 9.05 g of silica was dispersed, and the reaction was stirred at room temperature for 4 hours. The product was collected, washed and dried to obtain 9.90 g of the product.
产物中乙丙橡胶质量含量为8.6wt％，二氧化硅质量含量为91.4wt％；乙丙橡胶中，乙烯含量为45.5mol％，丙烯含量为29.4mol％，含Si-Cl键的单体B含量为25.1mol％，聚合物组成见表1。The mass content of ethylene-propylene rubber in the product is 8.6% by weight and the mass content of silica is 91.4% by weight; in the ethylene-propylene rubber, the ethylene content is 45.5 mol%, the propylene content is 29.4 mol%, and the monomer B containing Si-Cl bonds The content is 25.1 mol%, and the polymer composition is shown in Table 1.
实施例4Example 4
在250mL的反应釜中，加入50mL甲苯，在搅拌下加入1.0mol/L的甲基铝氧烷溶液4mL，加入25mmol含Si-Cl键的烯烃单体B，通入乙烯/丙烯混合气0.1MPa，其中，乙烯∶丙烯＝2∶1(v/v)，加入1μmol茂金属催化剂C 2H 4(Ind) 2ZrCl 2，40℃反应2小时；反应结束后将聚合物溶液转移至分散有5.00g二氧化硅的100mL己烷溶液中，室温搅拌反应1小时。收集产物，洗涤、干燥后得到产物11.30g。 In a 250 mL reaction kettle, add 50 mL of toluene, add 4 mL of a 1.0 mol / L methylalumoxane solution under stirring, add 25 mmol of Si-Cl bond-containing olefin monomer B, and pass in an ethylene / propylene mixed gas 0.1 MPa Among them, ethylene: propylene = 2: 1 (v / v), 1 μmol metallocene catalyst C 2 H 4 (Ind) 2 ZrCl 2 was added , and reacted at 40 ° C. for 2 hours; after the reaction, the polymer solution was transferred to a dispersion of 5.00 In 100 mL of a hexane solution of g of silica, the reaction was stirred at room temperature for 1 hour. The product was collected, washed and dried to obtain 11.30 g of the product.
产物中乙丙橡胶质量含量为55.8wt％，二氧化硅质量含量为44.2wt％；乙丙橡胶中，乙烯含量为70.8mol％，丙烯含量为21.0mol％，含Si-Cl键的单体B含量为8.2mol％，聚合物组成见表1。The mass content of ethylene-propylene rubber in the product is 55.8wt%, and the mass content of silica is 44.2wt%; in ethylene-propylene rubber, the ethylene content is 70.8mol%, the propylene content is 21.0mol%, and the monomer B containing Si-Cl bonds The content is 8.2 mol%, and the polymer composition is shown in Table 1.
实施例5Example 5
在250mL的反应釜中，加入50mL己烷，在搅拌下加入1.0mol/L的三乙基三氯二铝溶液2mL，加入1mmol含Si-Cl键的烯烃单体B，通入乙烯/丙烯混合气0.1MPa，其中，乙烯∶丙烯＝1∶2(v/v)，加入50μmol的Ziegler-Natta催化剂VOCl 3，30℃反应0.5小时；反应结束后将聚合物溶液转移至分散有1.10g二氧化硅的50mL己烷溶液中，室温搅拌反应2小时。收集产物，洗涤、干燥后得到产物1.50g。 In a 250 mL reaction kettle, add 50 mL of hexane, add 2 mL of a 1.0 mol / L triethyltrichlorodialuminum solution with stirring, add 1 mmol of Si-Cl bond-containing olefin monomer B, and pass in ethylene / propylene mixture The gas is 0.1 MPa, in which ethylene: propylene = 1: 2 (v / v), 50 μmol of Ziegler-Natta catalyst VOCl 3 is added , and the reaction is performed at 30 ° C. for 0.5 hours. After the reaction, the polymer solution is transferred to 1.10 g of dioxide dispersed In a 50 mL hexane solution of silicon, the reaction was stirred at room temperature for 2 hours. The product was collected, washed and dried to obtain 1.50 g of the product.
产物中乙丙橡胶质量含量为27.3wt％，二氧化硅质量含量为72.7wt％；乙丙橡胶中，乙烯含量为58.2mol％，丙烯含量为33.7mol％，含Si-Cl键的单体B含量为8.1mol％，聚合物组成见表1。The mass content of ethylene-propylene rubber in the product is 27.3 wt%, and the mass content of silica is 72.7 wt%; in the ethylene-propylene rubber, the ethylene content is 58.2 mol%, the propylene content is 33.7 mol%, and the monomer B containing Si-Cl bonds The content is 8.1 mol%, and the polymer composition is shown in Table 1.
实施例6Example 6
在250mL的反应釜中，加入100mL甲苯，在搅拌下加入1.0mol/L的异丁基铝氧 烷溶液4mL，加入20mmol含Si-Cl键的烯烃单体C，通入乙烯/丙烯混合气0.4MPa，其中，乙烯∶丙烯＝1∶1(v/v)，加入1μmol茂金属催化剂C 2H 4(Ind) 2ZrCl 2，50℃反应0.5小时；反应结束后将聚合物溶液转移至分散有1.50g二氧化硅的50mL己烷溶液中，室温搅拌反应2小时。收集产物，洗涤、干燥后得到产物8.60g。 In a 250 mL reaction kettle, add 100 mL of toluene, add 4 mL of a 1.0 mol / L isobutylaluminoxane solution under stirring, add 20 mmol of Si-Cl bond-containing olefin monomer C, and pass in an ethylene / propylene mixed gas 0.4 MPa, where ethylene: propylene = 1: 1 (v / v), 1 μmol metallocene catalyst C 2 H 4 (Ind) 2 ZrCl 2 was added , and reacted at 50 ° C. for 0.5 hours; after the reaction, the polymer solution was transferred to In a 50 mL hexane solution of 1.50 g of silica, the reaction was stirred at room temperature for 2 hours. The product was collected, washed and dried to obtain 8.60 g of the product.
产物中乙丙橡胶质量含量为82.6wt％，二氧化硅质量含量为17.4wt％；乙丙橡胶中，乙烯含量为51.3mol％，丙烯含量为39.8mol％，含Si-Cl键的单体C含量为8.9mol％，聚合物组成见表1。The mass content of ethylene-propylene rubber in the product is 82.6 wt% and the mass content of silica is 17.4 wt%; in ethylene-propylene rubber, the ethylene content is 51.3 mol%, the propylene content is 39.8 mol%, and the monomer C containing Si-Cl bonds The content is 8.9 mol%, and the polymer composition is shown in Table 1.
实施例7Example 7
在250mL的反应釜中，加入50mL甲苯，在搅拌下加入1.0mol/L的甲基铝氧烷溶液4mL，加入25mmol含Si-Cl键的烯烃单体D，通入乙烯/丙烯混合气0.1MPa，其中，乙烯∶丙烯＝1∶1(v/v)，加入2μmol茂金属催化剂C 2H 4(Ind) 2ZrCl 2，40℃反应0.5小时；反应结束后将聚合物溶液转移至分散有1.50g二氧化硅的100mL己烷溶液中，室温搅拌反应4小时。收集产物，洗涤、干燥后得到产物7.18g。 In a 250 mL reaction kettle, add 50 mL of toluene, add 4 mL of a 1.0 mol / L methylalumoxane solution under stirring, add 25 mmol of Si-Cl bond-containing olefin monomer D, and pass in an ethylene / propylene mixed gas 0.1 MPa In which, ethylene: propylene = 1: 1 (v / v), 2 μmol metallocene catalyst C 2 H 4 (Ind) 2 ZrCl 2 was added , and the reaction was carried out at 40 ° C. for 0.5 hours. After the reaction, the polymer solution was transferred to a dispersion of 1.50 In a 100 mL hexane solution of g of silica, the reaction was stirred at room temperature for 4 hours. The product was collected, washed and dried to obtain 7.18 g of the product.
产物中乙丙橡胶质量含量为79.2wt％，二氧化硅质量含量为20.8wt％；乙丙橡胶中，乙烯含量为40.3mol％，丙烯含量为48.0mol％，含Si-Cl键的单体D含量为11.7mol％，聚合物组成见表1。The mass content of ethylene-propylene rubber in the product is 79.2 wt%, and the mass content of silica is 20.8 wt%; in the ethylene-propylene rubber, the ethylene content is 40.3 mol%, the propylene content is 48.0 mol%, and the monomer D containing Si-Cl bonds The content is 11.7 mol%, and the polymer composition is shown in Table 1.
实施例8Example 8
在250mL的反应釜中，加入50mL甲苯，在搅拌下加入1.0mol/L的甲基铝氧烷溶液4mL，加入25mmol含Si-Cl键的烯烃单体E，通入乙烯/丙烯混合气0.1MPa，其中，乙烯∶丙烯＝1∶1(v/v)，加入2μmol茂金属催化剂Me 2Si(2，5-Me-Cp) 2MCl 2，40℃反应0.5小时；反应结束后将聚合物溶液转移至分散有1.59g二氧化硅的100mL己烷溶液中，室温搅拌反应4小时。收集产物，洗涤、干燥后得到产物7.06g。 In a 250 mL reaction kettle, add 50 mL of toluene, add 4 mL of a 1.0 mol / L methylalumoxane solution under stirring, add 25 mmol of Si-Cl bond-containing olefin monomer E, and pass in an ethylene / propylene mixed gas 0.1 MPa In which, ethylene: propylene = 1: 1 (v / v), 2 μmol metallocene catalyst Me 2 Si (2,5-Me-Cp) 2 MCl 2 was added , and the reaction was performed at 40 ° C. for 0.5 hours. After the reaction was completed, the polymer solution was added. The solution was transferred to 100 mL of a hexane solution in which 1.59 g of silica was dispersed, and the reaction was stirred at room temperature for 4 hours. The product was collected, washed and dried to obtain 7.06 g of product.
产物中乙丙橡胶质量含量为77.5wt％，二氧化硅质量含量为22.5wt％；乙丙橡胶中，乙烯含量为34.4mol％，丙烯含量为53.4mol％，含Si-Cl键的单体E含量为12.2mol％，聚合物组成见表1。The mass content of ethylene-propylene rubber in the product is 77.5 wt%, and the mass content of silica is 22.5 wt%; in ethylene-propylene rubber, the ethylene content is 34.4 mol%, the propylene content is 53.4 mol%, and the monomer E containing Si-Cl bonds The content is 12.2 mol%, and the polymer composition is shown in Table 1.
实施例9Example 9
在250mL的反应釜中，加入50mL甲苯，在搅拌下加入1.0mol/L的甲基铝氧烷溶液4mL，加入25mmol含Si-Cl键的烯烃单体F，通入乙烯/丙烯混合气0.1MPa，其中，乙烯∶丙烯＝1∶1(v/v)，加入2μmol茂金属催化剂C 2H 4(Ind) 2ZrCl 2，40℃反应0.5小时；反应结束后将聚合物溶液转移至分散有1.78g二氧化硅的100mL己烷溶液中，室温搅拌反应4小时。收集产物，洗涤、干燥后得到产物9.06g。 In a 250 mL reaction kettle, add 50 mL of toluene, add 4 mL of a 1.0 mol / L methylalumoxane solution under stirring, add 25 mmol of Si-Cl bond-containing olefin monomer F, and pass in an ethylene / propylene mixed gas 0.1 MPa Among them, ethylene: propylene = 1: 1 (v / v), 2 μmol metallocene catalyst C 2 H 4 (Ind) 2 ZrCl 2 was added , and the reaction was carried out at 40 ° C. for 0.5 hours. After the reaction was completed, the polymer solution was transferred to a dispersion of 1.78 In a 100 mL hexane solution of g of silica, the reaction was stirred at room temperature for 4 hours. The product was collected, washed and dried to obtain 9.06 g of the product.
产物中乙丙橡胶质量含量为80.3wt％，二氧化硅质量含量为19.7wt％；乙丙橡胶中，乙烯含量为37.5mol％，丙烯含量为50.4mol％，含Si-Cl键的单体E含量为12.1mol％，聚合物组成见表1。The mass content of ethylene-propylene rubber in the product is 80.3 wt%, and the mass content of silica is 19.7 wt%; in the ethylene-propylene rubber, the ethylene content is 37.5 mol%, the propylene content is 50.4 mol%, and the monomer E containing Si-Cl bonds The content is 12.1 mol%, and the polymer composition is shown in Table 1.
上述聚合物的性能列于表2。The properties of the above polymers are listed in Table 2.
含Si-Cl键的烯烃单体中所含硅氯基团(Si-Cl)通过共聚合反应引入到乙丙共聚物侧基上，且含量可调；乙丙共聚物侧基的Si-Cl很容易与二氧化硅颗粒表面存在的大量Si-OH发生反应，生成Si-O-Si键，从而将乙丙橡胶与二氧化硅颗粒通过化学键牢固地结合起来，从根本上解决了二氧化硅与乙丙橡胶之间相容性的问题，以及二氧化硅颗粒在乙丙橡胶中分散的稳定性问题。The Si-Cl bond in the olefin monomer containing Si-Cl bond is introduced into the ethylene-propylene copolymer side group through copolymerization reaction, and the content is adjustable; Si-Cl of the ethylene-propylene copolymer side group It is easy to react with a large amount of Si-OH existing on the surface of silica particles to form Si-O-Si bonds, thereby firmly combining ethylene-propylene rubber and silica particles through chemical bonds, which fundamentally solves the problem of silica. Problems with compatibility with ethylene-propylene rubber, and stability of dispersion of silica particles in ethylene-propylene rubber.
从表2中的己烷溶出物数据可以看出，简单共混的样品(对比实验2)中含有52.8％的乙丙橡胶，其中51.3％可以被己烷溶出，说明乙丙橡胶与二氧化硅之间是物理共混状态；而聚合样品(实施例2)中含有51.7％的乙丙橡胶，己烷溶出物仅为9.2％，说明绝大部分乙丙共聚物与二氧化硅之间具有化学连接，而非物理混合状态。From the hexane eluate data in Table 2, it can be seen that the simple blended sample (Comparative Experiment 2) contained 52.8% ethylene-propylene rubber, of which 51.3% could be eluted by hexane, indicating that ethylene-propylene rubber and silica There is a physical blending state between them; and the polymer sample (Example 2) contains 51.7% of ethylene-propylene rubber, and the hexane eluate is only 9.2%, indicating that most of the ethylene-propylene copolymers have a chemical relationship with silica. Connected, not physically mixed.
通过材料的热失重曲线可以测定产物中二氧化硅和乙丙橡胶的质量含量(如附图1所示)，500℃以上剩余物质为二氧化硅。通过对直接聚合产物形貌进行扫描电镜观察，可以看到二氧化硅颗粒表面均匀地包覆着乙丙橡胶，颗粒直径约50nm左右，与选用的二氧化硅颗粒尺寸相当(如附图2所示)，说明聚合方法可以有效地实现乙丙橡胶对二氧化硅颗粒的包覆。通过将聚合产物进行熔融加工，可以看到乙丙橡胶中分散的二氧化硅始终保持良好的分散，没有出现聚集现象(如附图3所示)，证明乙丙橡胶和二氧化硅之间的化学连接能够实现二氧化硅稳定分散。The mass content of silica and ethylene-propylene rubber in the product can be determined through the thermal weight loss curve of the material (as shown in Figure 1). The remaining material above 500 ° C is silica. By scanning electron microscope observation of the morphology of the direct polymerization product, it can be seen that the surface of the silica particles is uniformly coated with ethylene-propylene rubber, and the particle diameter is about 50 nm, which is equivalent to the size of the selected silica particles (as shown in Figure 2). (Shown), indicating that the polymerization method can effectively achieve the coating of silica particles with ethylene-propylene rubber. Through the melt processing of the polymerization product, it can be seen that the dispersed silica in the ethylene-propylene rubber has always maintained a good dispersion, and there is no aggregation phenomenon (as shown in Figure 3), which proves that the Chemical bonding enables stable dispersion of silica.
表1聚合物组成列表Table 1 polymer composition list
Figure PCTCN2018109104-appb-000008
Figure PCTCN2018109104-appb-000008
表2聚合物性能列表Table 2 List of polymer properties
Figure PCTCN2018109104-appb-000009
Figure PCTCN2018109104-appb-000009

Claims (10)

  1. 二氧化硅和乙丙橡胶复合物，包括二氧化硅与乙丙橡胶，其特征在于：所述二氧化硅和乙丙橡胶复合物中，乙丙橡胶质量含量为5～98％，二氧化硅质量含量为2～95％；其中，所述乙丙橡胶为一种由乙烯、丙烯和含Si-Cl键的烯烃单体聚合而成的共聚物，其中乙烯单元的摩尔含量为5～94％，丙烯单元的摩尔含量为5～94％，含Si-Cl键的烯烃单体单元的摩尔含量为0.01～50％。A composite of silicon dioxide and ethylene-propylene rubber, including silicon dioxide and ethylene-propylene rubber, is characterized in that: in the silicon dioxide and ethylene-propylene rubber composite, the mass content of ethylene-propylene rubber is 5 to 98%, and the silicon dioxide The mass content is 2 to 95%; wherein, the ethylene-propylene rubber is a copolymer obtained by polymerizing ethylene, propylene, and an olefin monomer containing a Si-Cl bond, wherein the molar content of ethylene units is 5 to 94% The molar content of propylene units is 5 to 94%, and the molar content of Si-Cl bond-containing olefin monomer units is 0.01 to 50%.
  2. 根据权利要求1所述的二氧化硅和乙丙橡胶复合物，其特征在于：所述含Si-Cl键的烯烃单体具有如下结构：The composite of silica and ethylene-propylene rubber according to claim 1, wherein the Si-Cl bond-containing olefin monomer has the following structure:
    Figure PCTCN2018109104-appb-100001
    Figure PCTCN2018109104-appb-100001
    其中，R 1和R 2可以相同或者不同，R 1和R 2各自独立的选自氯、甲基、乙基、异丙基、甲氧基、乙氧基、异丙氧基和氢；n为1～12之间的整数。 Wherein, R 1 and R 2 may be the same or different, and R 1 and R 2 are each independently selected from the group consisting of chlorine, methyl, ethyl, isopropyl, methoxy, ethoxy, isopropoxy, and hydrogen; n It is an integer between 1 and 12.
  3. 权利要求1所述的二氧化硅和乙丙橡胶复合物的制备方法，其特征在于包括以下步骤：The method for preparing a silica and ethylene-propylene rubber composite according to claim 1, comprising the following steps:
    (1)向反应容器中依次加入有机溶剂、助催化剂、含Si-Cl键的烯烃单体，再通入乙烯、丙烯气体，最后加入主催化剂进行聚合反应；上述聚合反应中，(1) Add an organic solvent, a cocatalyst, and an Si-Cl bond-containing olefin monomer to the reaction vessel in order, and then pass in ethylene and propylene gas, and finally add a main catalyst to perform a polymerization reaction. In the above polymerization reaction,
    所述有机溶剂为5～10个碳原子的烷烃和/或6～10个碳原子的芳香烃；The organic solvent is an alkane having 5 to 10 carbon atoms and / or an aromatic hydrocarbon having 6 to 10 carbon atoms;
    所述乙烯、丙烯和含Si-Cl键的烯烃单体的总质量与有机溶剂的质量比为1～1000：100，所述含Si-Cl键的烯烃单体与乙烯、丙烯质量之和的比为0.01～5：1；聚合反应温度为0℃～100℃，聚合压力为0.01～6MPa，聚合时间为0.1～12小时；The total ratio of the total mass of the ethylene, propylene, and Si-Cl bond-containing olefin monomer to the mass of the organic solvent is 1 to 1000: 100. The sum of the mass of the Si-Cl bond-containing olefin monomer and the mass of ethylene and propylene is The ratio is 0.01 to 5: 1; the polymerization temperature is 0 ° C to 100 ° C, the polymerization pressure is 0.01 to 6MPa, and the polymerization time is 0.1 to 12 hours;
    所述主催化剂选自Ziegler-Natta催化剂或茂金属催化剂，所述助催化剂选自烷基铝化合物或烷基铝氧烷化合物；The main catalyst is selected from a Ziegler-Natta catalyst or a metallocene catalyst, and the co-catalyst is selected from an aluminum alkyl compound or an alkylalumoxane compound;
    (2)步骤(1)聚合反应结束后，向聚合产物中加入二氧化硅进行反应，二氧化硅与聚合产物质量之比为0.02～19：1，反应时间0.1～24小时，反应温度0～100℃；反应结束后将剩余溶剂脱除得到二氧化硅和乙丙橡胶的复合物。(2) Step (1) After the polymerization reaction is completed, silica is added to the polymerization product for reaction. The mass ratio of silica to the polymerization product is 0.02 to 19: 1, the reaction time is 0.1 to 24 hours, and the reaction temperature is 0 to 100 ° C; after the reaction is completed, the remaining solvent is removed to obtain a composite of silica and ethylene-propylene rubber.
  4. 根据权利要求3所述的制备方法，其特征在于：所述Ziegler-Natta催化剂是过渡金属氯化物或氯氧化物，所述过渡金属为钛或钒。The method according to claim 3, wherein the Ziegler-Natta catalyst is a transition metal chloride or oxychloride, and the transition metal is titanium or vanadium.
  5. 根据权利要求3所述的制备方法，其特征在于：所述茂金属催化剂为以过渡金属M为中心原子的过渡金属-π键化合物，所述过渡金属M为Ti、Zr或Hf；所述以过渡金属M为中心原子的过渡金属-π键化合物选自Cp 2TiCl 2，C 2H 4(Me 4Cp) 2MCl 2，C 2H 4(Ind) 2MCl 2，C 2H 4(2,4,7-Me 3-Ind) 2MCl 2，Me 2Si(Flu) 2MCl 2，Me 2SiCH 2(Ind) 2MCl 2，Me 2Si(2-MeInd) 2MCl 2，Me 2Si(2,5-Me-Cp) 2MCl 2，Me 2Si(4,7-Me 2-Ind) 2MCl 2，Me 2Si(2-Me-4-Naph-Ind) 2ZrCl 2。 The method according to claim 3, wherein the metallocene catalyst is a transition metal-π bond compound with a transition metal M as a central atom, and the transition metal M is Ti, Zr, or Hf; Transition metal-π bond compounds with transition metal M as the central atom are selected from Cp 2 TiCl 2 , C 2 H 4 (Me 4 Cp) 2 MCl 2 , C 2 H 4 (Ind) 2 MCl 2 , C 2 H 4 (2 , 4,7-Me 3 -Ind) 2 MCl 2 , Me 2 Si (Flu) 2 MCl 2 , Me 2 SiCH 2 (Ind) 2 MCl 2 , Me 2 Si (2-MeInd) 2 MCl 2 , Me 2 Si (2,5-Me-Cp) 2 MCl 2 , Me 2 Si (4,7-Me 2 -Ind) 2 MCl 2 , Me 2 Si (2-Me-4-Naph-Ind) 2 ZrCl 2 .
  6. 根据权利要求3所述的制备方法，其特征在于：步骤(1)所述助催化剂中的烷基铝为三烷基铝，或由三烷基铝与卤代烷基铝或多卤代烷基铝组成的混合物；其中，所述三烷基铝选自三乙基铝、三异丁基铝、三正丁基铝、三正己基铝、三正辛基铝中的至少一种，所述卤代烷基铝为二乙基氯化铝，所述多卤代烷基铝为三乙基三氯化二铝；所述助催化剂中的烷基铝氧烷选自甲基铝氧烷和异丁基铝氧烷中的至少一种。The preparation method according to claim 3, characterized in that: the alkyl aluminum in the co-catalyst in step (1) is trialkyl aluminum, or is composed of trialkyl aluminum and haloalkyl aluminum or polyhaloalkyl aluminum A mixture; wherein the trialkylaluminum is at least one selected from the group consisting of triethylaluminum, triisobutylaluminum, tri-n-butylaluminum, tri-n-hexylaluminum, and tri-n-octylaluminum, and the halogenated alkylaluminum Is diethylaluminum chloride, the polyhaloalkylaluminum is triethyldialuminum chloride; the alkylalumoxane in the cocatalyst is selected from methylalumoxane and isobutylalumoxane At least one.
  7. 根据权利要求3所述的制备方法，其特征在于：所述助催化剂的添加量以Al与主催化剂中过渡金属的摩尔比计，分别为Al：Ti或V＝10～20000：1；Al：M＝10～20000：1。The preparation method according to claim 3, characterized in that the added amount of the cocatalyst is based on the molar ratio of Al to the transition metal in the main catalyst, and is respectively Al: Ti or V = 10 to 20000: 1; Al: M = 10 to 20000: 1.
  8. 根据权利要求3所述的制备方法，其特征在于：所述5～10个碳原子的烷烃选自正戊烷、正己烷、环己烷、正庚烷、正辛烷、正癸烷中的至少一种；所述6～10个碳原子的芳香烃选自苯、甲苯、二甲苯、乙苯、正丙苯、异丙苯中的至少一种。The preparation method according to claim 3, wherein the alkane having 5 to 10 carbon atoms is selected from the group consisting of n-pentane, n-hexane, cyclohexane, n-heptane, n-octane, and n-decane. At least one; the aromatic hydrocarbon having 6 to 10 carbon atoms is selected from at least one of benzene, toluene, xylene, ethylbenzene, n-propylbenzene, and cumene.
  9. 根据权利要求3所述的制备方法，其特征在于：步骤(2)所述二氧化硅，可以直接加入二氧化硅固体粉末，也可以将二氧化硅分散于有机溶剂中加入；所述用于分散二氧化硅的有机溶剂可以与聚合溶剂相同或不同，选自正戊烷、正己烷、环己烷、正庚烷、正辛烷、正癸烷中的至少一种，或选自苯、甲苯、二甲苯、乙苯、正丙苯、异丙苯中的至少一种。The preparation method according to claim 3, characterized in that: the silica in step (2) can be directly added to the silica solid powder, or the silica can be dispersed in an organic solvent and added; The organic solvent in which the silica is dispersed may be the same as or different from the polymerization solvent, and is selected from at least one of n-pentane, n-hexane, cyclohexane, n-heptane, n-octane, and n-decane, or selected from benzene, At least one of toluene, xylene, ethylbenzene, n-propylbenzene, and cumene.
  10. 根据权利要求3～9任意一项所述的制备方法得到的二氧化硅和乙丙橡胶的复合物，作为增强乙丙橡胶材料的应用。Use of the composite of silica and ethylene-propylene rubber obtained by the preparation method according to any one of claims 3 to 9 as a reinforced ethylene-propylene rubber material.
PCT/CN2018/109104 2018-06-13 2018-09-30 Complex of silica and ethylene propylene rubber and preparation method therefor WO2019237582A1 (en)

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