WO2023130551A1 - 一种改性乙烯基硅烷及其制备方法和应用 - Google Patents

一种改性乙烯基硅烷及其制备方法和应用 Download PDF

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WO2023130551A1
WO2023130551A1 PCT/CN2022/078517 CN2022078517W WO2023130551A1 WO 2023130551 A1 WO2023130551 A1 WO 2023130551A1 CN 2022078517 W CN2022078517 W CN 2022078517W WO 2023130551 A1 WO2023130551 A1 WO 2023130551A1
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vinylsilane
modified
preparation
vinyl silane
mass
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French (fr)
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孔凡振
渠源
杨甜甜
孔令刚
李杭杭
卢海峰
齐士林
李朋涛
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山东硅科新材料有限公司
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Publication of WO2023130551A1 publication Critical patent/WO2023130551A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
    • C07F7/1804—Compounds having Si-O-C linkages
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
    • C07F7/1804—Compounds having Si-O-C linkages
    • C07F7/1872—Preparation; Treatments not provided for in C07F7/20
    • C07F7/188—Preparation; Treatments not provided for in C07F7/20 by reactions involving the formation of Si-O linkages
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/06—Preparatory processes
    • C08G77/10—Equilibration processes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/38—Polysiloxanes modified by chemical after-treatment
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C08K5/541—Silicon-containing compounds containing oxygen
    • C08K5/5425—Silicon-containing compounds containing oxygen containing at least one C=C bond
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/02—Compounds of alkaline earth metals or magnesium
    • C09C1/028—Compounds containing only magnesium as metal
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/12—Treatment with organosilicon compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/045—Polysiloxanes containing less than 25 silicon atoms

Definitions

  • the invention relates to the technical field of organosilicon materials, in particular to a modified vinyl silane and its preparation method and application.
  • Vinyl silane coupling agent is relatively simple in structure, and its structural formula is R-Si-O-X. Calcium, titanium dioxide or white carbon black) are organically linked together.
  • the shortcomings of silane coupling agents are also obvious, such as insufficient oiliness. When it is applied to organic-inorganic hybrid materials, it will lead to weak dispersibility of the modified powder and unstable performance, thereby reducing some physical properties of the material. properties such as dielectric constant, toughness and elasticity.
  • the purpose of the present invention is to provide a modified vinyl silane and its preparation method and application.
  • the modified vinyl silane contains oily groups. After modifying the organic-inorganic hybrid material, the obtained modified material has good dispersibility , strong stability.
  • the invention provides a modified vinyl silane, which has a structure shown in formula I:
  • R includes
  • the modified vinylsilane has a viscosity of 2-50 mPa/s.
  • the structural formula of the modified vinylsilane is:
  • the present invention provides the preparation method of the modified vinyl silane described in the technical scheme, comprising the following steps:
  • the vinyl silane includes vinyltrialkoxysilane; the vinyltrialkoxysilane includes vinyltrimethoxysilane, vinyltriethoxysilane, vinyltripropoxysilane or vinyltri Isopropoxysilane;
  • the modifying reagent includes silicone oil or dimethylsiloxane ring body
  • Described silicone oil has the described structure of formula II:
  • the dimethylsiloxane ring body has a structure shown in formula III:
  • the mass ratio of the vinylsilane to the modifying agent is 1:(0.3-1.2).
  • the mass ratio of the vinylsilane to the modifying agent is 1:(0.5-1.0).
  • the catalyst includes caustic alkali or concentrated sulfuric acid.
  • the mass of the catalyst is 0.01-0.03% of the total mass of the vinylsilane and the modifying agent.
  • the mass of the catalyst is 0.015-0.02% of the total mass of the vinylsilane and the modifying agent.
  • the mass of the water is 5-20% of the mass of the vinylsilane.
  • the mass of the water is 8-15% of the mass of the vinylsilane.
  • the temperature of the modification reaction is 50-100° C., and the time is 1-12 hours.
  • the process of mixing vinylsilane, modifying agent, catalyst and water includes: After mixing vinylsilane and modifying agent, the temperature is raised to 50-100°C, and water and catalyst are simultaneously added to the obtained mixture, so that The adding time of the water and the catalyst is 0.5 ⁇ 2h.
  • the vinylsilane content in the product obtained from the modification reaction is less than ⁇ 10%, it is judged that the modification reaction is complete, and the product obtained is dealcoholized.
  • the dealcoholization temperature is 60-100°C.
  • the ethanol is extracted, and the obtained product is cooled and filtered to obtain the modified vinylsilane.
  • the present invention provides the application of the modified vinyl silane described in the above technical solution or the modified vinyl silane prepared by the preparation method described in the above technical solution in the synthesis of organic-inorganic hybrid materials.
  • the invention provides a modified vinyl silane, the modified vinyl silane of the invention is grafted with oily groups (silicone oil groups or ring-opening groups of dimethylsiloxane rings), which can increase the The oiliness of the obtained modified vinyl silane reduces the viscosity, thereby enhancing the dispersibility.
  • oily groups silicone oil groups or ring-opening groups of dimethylsiloxane rings
  • the modified powder has good dispersibility and can be uniformly It can be stably grafted onto organic and/or inorganic powders to improve the stability of modified materials.
  • the invention provides a preparation method of the modified vinyl silane, in which the vinyl silane and the modifying reagent are subjected to a rearrangement reaction under the action of a catalyst, the modifying reagent has high oiliness and high dispersibility, and can strengthen the modified vinyl silane.
  • the dispersion ability of silane can improve the grafting ability of modified vinyl silane in organic and/or inorganic powder, and enhance the binding force of modified vinyl silane with organic and/or inorganic powder when it is used as a coupling agent.
  • Fig. 1 is the nuclear magnetic spectrogram of the modified vinylsilane prepared by embodiment 1;
  • Fig. 2 is the infrared spectrogram of the modified vinylsilane prepared in embodiment 1;
  • Fig. 3 is the nuclear magnetic spectrum of the modified vinylsilane prepared by embodiment 2;
  • Fig. 4 is the infrared spectrogram of the modified vinylsilane prepared in embodiment 2;
  • Fig. 5 is the nuclear magnetic spectrogram of the modified vinylsilane prepared by embodiment 3;
  • Fig. 6 is the infrared spectrogram of the modified vinylsilane prepared in embodiment 3.
  • Fig. 7 is the nuclear magnetic spectrogram of the modified vinylsilane prepared in embodiment 4.
  • Fig. 8 is the infrared spectrogram of the modified vinylsilane prepared in Example 4.
  • the invention provides a modified vinyl silane, which has a structure shown in formula I:
  • R includes
  • the viscosity of the modified vinylsilane is preferably 2-50 mPa/s, more preferably 5-22 mPa/s, even more preferably 18-20 mPa/s.
  • the structural formula of the modified vinylsilane is preferably:
  • the present invention provides the preparation method of the modified vinyl silane described in the technical scheme, comprising the following steps:
  • the vinyl silane includes vinyltrialkoxysilane; the vinyltrialkoxysilane includes vinyltrimethoxysilane, vinyltriethoxysilane, vinyltripropoxysilane or vinyltri Isopropoxysilane;
  • the modifying reagent includes silicone oil or dimethylsiloxane ring body
  • Described silicone oil has the described structure of formula II:
  • the dimethylsiloxane ring body has a structure shown in formula III:
  • the invention mixes vinyl silane, modifying agent, catalyst and water.
  • the vinyl silane includes vinyltrialkoxysilane; the vinyltrialkoxysilane includes vinyltrimethoxysilane, vinyltriethoxysilane, vinyltripoxysilane Silane or Vinyltriisopropoxysilane.
  • the modifying reagent includes silicone oil or dimethylsiloxane ring body (DMC);
  • Described silicone oil has the described structure of formula II:
  • the dimethylsiloxane ring body has a structure shown in formula III:
  • n 2-8, more preferably 3-4.
  • the mass ratio of the vinylsilane to the modifying agent is preferably 1:(0.3-1.2), more preferably 1:(0.5-1.0), and even more preferably 1:(0.6-0.8).
  • the catalyst preferably includes caustic alkali or concentrated sulfuric acid; the mass concentration of the concentrated sulfuric acid is preferably 98%.
  • the mass of the catalyst is preferably 0.01-0.03%, more preferably 0.015-0.02%, of the total mass of the vinylsilane and the modifying agent.
  • the mass of the water is preferably 5-20% of the mass of the vinylsilane, more preferably 8-15%, and even more preferably 12-13%.
  • the invention increases the proportion of vinyl functional groups in the vinyl silane through the addition of the water phase, increases the vinyl content in the modified vinyl silane, and further improves the coupling characteristics of the modified vinyl silane.
  • the process of mixing vinylsilane, modifying reagent, catalyst and water preferably includes: after mixing vinylsilane and modifying reagent, the temperature is raised to 50-100°C, and water and Catalyst:
  • the present invention has no special limitation on the process of raising the temperature, and the temperature can be raised according to the process well known in the art.
  • the obtained catalyst solution is added dropwise to the mixture of the vinyl silane and the modifying agent.
  • the dropping time of the water and the catalyst is preferably 0.5-2 hours, more preferably 1.0-1.5 hours.
  • the present invention preferably carries out a modification reaction; the temperature of the modification reaction is preferably 50-100°C, more preferably 60-80°C, further preferably 65-70°C; the time is preferably 1-12h , more preferably 1.5 to 3 hours.
  • the present invention when the vinylsilane content in the product obtained from the modification reaction is less than ⁇ 10%, it is judged that the modification reaction is complete, and the product obtained is dealcoholized.
  • the present invention has no special limitation on the specific method for detecting the content of vinylsilane in the product, and it can be detected by methods well known in the art.
  • the temperature of the dealcoholization is preferably 60-100°C, more preferably 70-90°C; after the dealcoholization is completed, the present invention extracts ethanol, cools and filters the obtained product, and obtains modified vinyl silane .
  • the present invention has no special limitation on the process of extracting ethanol and cooling and filtering, and it can be carried out according to the process well known in the art.
  • the reaction formula of the modification reaction is:
  • the reaction formula of the modification reaction is:
  • the present invention provides the application of the modified vinyl silane described in the above technical solution or the modified vinyl silane prepared by the preparation method described in the above technical solution in the synthesis of organic materials and/or inorganic materials.
  • the modified vinyl silane is used as a coupling agent to synthesize organic materials and/or inorganic materials according to methods well known in the art.
  • Figures 2, 4, 6 and 8 are the infrared spectrograms of the modified vinylsilanes prepared in Examples 1 to 4 in turn.
  • 2885cm -1 and 2973cm -1 are CH vibration peaks
  • 1259cm -1 is the peak of CH 3 Si
  • 1031/1037/1047/1051cm -1 is the peak of Si-O-Si
  • 788/795/796cm -1 is CH 3- Si-CH 3 .
  • the verification principle is: only a small part of the unmodified high-purity magnesium hydroxide (blank sample) will float on the water surface, and the activation rate is low, but the magnesium hydroxide modified by the modified silane has some organic properties, which will increase the hydrogen oxidation rate.
  • the oily nature of the magnesium powder increases the activation rate, so that the magnesium hydroxide powder floats on the water surface without precipitation, and most of the modified powder does not precipitate during liquid separation.
  • magnesium hydroxide is modified by the method of above 1) with vinyltriethoxysilane, vinyltrimethoxysilane and 500 viscosity silicone oil respectively to obtain modified magnesium hydroxide powder; then according to 2) The method of activation rate verification experiment;
  • activation rate Modified rear magnesium hydroxide sample gross mass/magnesium hydroxide sample weight (5g)*100%, and with blank sample (do not carry out any modified hydrogen Magnesium oxide powder) as a comparison, the results are shown in Table 1.
  • the activation rate of unmodified magnesium hydroxide is low, and basically all precipitates in water, but the modified magnesium hydroxide has some organic properties, and the activation rate is improved, and compared with silane single body, the vinyl silane modified in Examples 1 to 4 has a greater performance improvement on magnesium hydroxide.

Abstract

改性乙烯基硅烷及其制备方法和应用，所述改性乙烯基硅烷是将油性基团硅油基团或二甲基硅氧烷环体的开环基团接枝于乙烯基硅烷，所得改性乙烯基硅烷油性增大、粘度较低、分散性增强，作为偶联剂用于有机和/或无机粉体时，改性后的粉体分散性好，能够均匀稳定地接枝到有机和/或无机粉体上，提高改性材料的稳定性。所述改性乙烯基硅烷通过乙烯基硅烷和改性试剂在催化剂的作用下进行重排反应制备得到，所述改性试剂的油性大，分散性高，能够增强改性乙烯基硅烷的分散能力，提高改性乙烯基硅烷在有机和/或无机粉体中的接枝能力，增强改性乙烯基硅烷作为偶联剂应用时与有机和/或无机粉体的结合力。

Description

一种改性乙烯基硅烷及其制备方法和应用
本申请要求于2022年1月7日提交中国专利局、申请号为202210011879.4、发明名称为“一种改性乙烯基硅烷及其制备方法和应用”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。
技术领域
本发明涉及有机硅材料技术领域，尤其涉及一种改性乙烯基硅烷及其制备方法和应用。
背景技术
乙烯基硅烷偶联剂在结构上较为简单，结构式为R-Si-O-X，其特点是具有两性能力，能将有机材料(例如聚乙烯或聚氯乙烯)和无机材料(例如氢氧化镁、碳酸钙、钛白粉或白炭黑)有机地链接在一起。然而，硅烷偶联剂的缺点也很明显，例如油性不足，将其应用于有机无机杂化材料时，会导致改性后的粉体分散能力弱，性能不稳定，从而降低了材料的一些物理性能，例如介电常数、韧性及弹性。
发明内容
本发明的目的在于提供一种改性乙烯基硅烷及其制备方法和应用，所述改性乙烯基硅烷含有油性基团，对有机无机杂化材料改性后，所得改性材料的分散性能好，稳定性强。
为了实现上述发明目的，本发明提供以下技术方案：
本发明提供了一种改性乙烯基硅烷，具有式I所示结构：
Figure PCTCN2022078517-appb-000001
其中，R包括
Figure PCTCN2022078517-appb-000002
Figure PCTCN2022078517-appb-000003
R 1包括甲基、乙基、丙基或异丙基；x＝2～8，y＝1～50。
优选的，所述改性乙烯基硅烷的粘度为2～50mPa/s。
优选的，所述改性乙烯基硅烷的结构式为：
Figure PCTCN2022078517-appb-000004
x＝2；
Figure PCTCN2022078517-appb-000005
x＝4；
Figure PCTCN2022078517-appb-000006
y＝3或
Figure PCTCN2022078517-appb-000007
x＝4。
本发明提供了上述技术方案所述改性乙烯基硅烷的制备方法，包括以下步骤：
将乙烯基硅烷、改性试剂、催化剂和水混合，进行改性反应，得到改性乙烯基硅烷；
所述乙烯基硅烷包括乙烯基三烷氧基硅烷；所述乙烯基三烷氧基硅烷包括乙烯基三甲氧基硅烷、乙烯基三乙氧基硅烷、乙烯基三丙氧基硅烷或乙烯基三异丙氧基硅烷；
所述改性试剂包括硅油或二甲基硅氧烷环体；
所述硅油具有式II所述结构：
Figure PCTCN2022078517-appb-000008
式II，m＝1～50；
所述二甲基硅氧烷环体具有式III所示结构：
Figure PCTCN2022078517-appb-000009
式III，n＝2～8。
优选的，所述乙烯基硅烷与改性试剂的质量比为1:(0.3～1.2)。
优选的，所述乙烯基硅烷与改性试剂的质量比为1:(0.5～1.0)。
优选的，所述催化剂包括苛性碱或浓硫酸。
优选的，所述催化剂的质量为所述乙烯基硅烷与改性试剂的总质量的0.01～0.03％。
优选的，所述催化剂的质量为所述乙烯基硅烷与改性试剂的总质量的0.015～0.02％。
优选的，所述水的质量为所述乙烯基硅烷质量的5～20％。
优选的，所述水的质量为所述乙烯基硅烷质量的8～15％。
优选的，所述改性反应的温度为50～100℃，时间为1～12h。
优选的，所述乙烯基硅烷、改性试剂、催化剂和水混合的过程包括： 将乙烯基硅烷和改性试剂混合后，升温至50～100℃，向所得混合物中同时加入水和催化剂，所述水和催化剂的加入时间为0.5～2h。
优选的，当所述改性反应所得产物中乙烯基硅烷含量低于＜10％，判断改性反应完成，将所得产物进行脱醇。
优选的，所述脱醇的温度为60～100℃。
优选的，完成所述脱醇后，抽出乙醇，将所得产物降温过滤，得到改性乙烯基硅烷。
本发明提供了上述技术方案所述改性乙烯基硅烷或上述技术方案所述制备方法制备得到的改性乙烯基硅烷在合成有机无机杂化材料中的应用。
本发明提供了一种改性乙烯基硅烷，本发明所述改性乙烯基硅烷接枝有油性基团(硅油基团或二甲基硅氧烷环体的开环基团)，能够增大所得改性乙烯基硅烷的油性，降低粘度，从而增强分散性，所得改性乙烯基硅烷作为偶联剂用于有机和/或无机粉体时，改性后的粉体分散性好，能够均匀稳定地接枝到有机和/或无机粉体上，提高改性材料的稳定性。
本发明提供了所述改性乙烯基硅烷的制备方法，将乙烯基硅烷和改性试剂在催化剂的作用下进行重排反应，改性试剂的油性大，分散性高，能够增强改性乙烯基硅烷的分散能力，提高改性乙烯基硅烷在有机和/或无机粉体中的接枝能力，增强改性乙烯基硅烷作为偶联剂应用时与有机和/或无机粉体的结合力。
说明书附图
图1为实施例1制备的改性乙烯基硅烷的核磁谱图；
图2为实施例1制备的改性乙烯基硅烷的红外谱图；
图3为实施例2制备的改性乙烯基硅烷的核磁谱图；
图4为实施例2制备的改性乙烯基硅烷的红外谱图；
图5为实施例3制备的改性乙烯基硅烷的核磁谱图；
图6为实施例3制备的改性乙烯基硅烷的红外谱图；
图7为实施例4制备的改性乙烯基硅烷的核磁谱图；
图8为实施例4制备的改性乙烯基硅烷的红外谱图。
具体实施方式
本发明提供了一种改性乙烯基硅烷，具有式I所示结构：
Figure PCTCN2022078517-appb-000010
其中，R包括
Figure PCTCN2022078517-appb-000011
Figure PCTCN2022078517-appb-000012
R 1包括甲基、乙基、丙基或异丙基；x＝2～8，y＝1～50。
在本发明中，所述改性乙烯基硅烷的粘度优选为2～50mPa/s，更优选为5～22mPa/s，进一步优选为18～20mPa/s。
在本发明中，所述改性乙烯基硅烷的结构式优选为：
Figure PCTCN2022078517-appb-000013
x＝2；
Figure PCTCN2022078517-appb-000014
x＝4；
Figure PCTCN2022078517-appb-000015
y＝3或
Figure PCTCN2022078517-appb-000016
x＝4。
本发明提供了上述技术方案所述改性乙烯基硅烷的制备方法，包括以下步骤：
将乙烯基硅烷、改性试剂、催化剂和水混合，进行改性反应，得到改性乙烯基硅烷；
所述乙烯基硅烷包括乙烯基三烷氧基硅烷；所述乙烯基三烷氧基硅烷包括乙烯基三甲氧基硅烷、乙烯基三乙氧基硅烷、乙烯基三丙氧基硅烷或乙烯基三异丙氧基硅烷；
所述改性试剂包括硅油或二甲基硅氧烷环体；
所述硅油具有式II所述结构：
Figure PCTCN2022078517-appb-000017
式II，m＝1～50；
所述二甲基硅氧烷环体具有式III所示结构：
Figure PCTCN2022078517-appb-000018
式III，n＝2～8。
在本发明中，若无特殊说明，所需制备原料均为本领域技术人员熟知的市售商品。
本发明将乙烯基硅烷、改性试剂、催化剂和水混合。在本发明中，所述乙烯基硅烷包括乙烯基三烷氧基硅烷；所述乙烯基三烷氧基硅烷包括乙烯基三甲氧基硅烷、乙烯基三乙氧基硅烷、乙烯基三丙氧基硅烷或乙烯基三异丙氧基硅烷。
在本发明中，所述改性试剂包括硅油或二甲基硅氧烷环体(DMC)；
所述硅油具有式II所述结构：
Figure PCTCN2022078517-appb-000019
式II，m＝1～50，更优选为3；
所述二甲基硅氧烷环体具有式III所示结构：
Figure PCTCN2022078517-appb-000020
式III，n＝2～8，更优选为3～4。
在本发明中，所述乙烯基硅烷与改性试剂的质量比优选为1:(0.3～1.2)，更优选为1:(0.5～1.0)，进一步优选为1:(0.6～0.8)。
在本发明中，所述催化剂优选包括苛性碱或浓硫酸；所述浓硫酸的质量浓度优选为98％。在本发明中，所述催化剂的质量优选为所述乙烯基硅烷与改性试剂的总质量的0.01～0.03％，更优选为0.015～0.02％。
在本发明中，所述水的质量优选为所述乙烯基硅烷质量的5～20％，更优选为8～15％，进一步优选为12～13％。本发明通过水相的加入，使得乙烯基硅烷中乙烯基官能团的比例提高，提高改性乙烯基硅烷中乙烯基的含量，进而提高改性乙烯基硅烷的偶联特性。
在本发明中，所述乙烯基硅烷、改性试剂、催化剂和水混合的过程优选包括：将乙烯基硅烷和改性试剂混合后，升温至50～100℃，向所得混合物中同时加入水和催化剂；本发明对所述升温的过程没有特殊的限定，按照本领域熟知的过程升温即可。本发明优选将水与催化剂混合后，将所得催化剂溶液滴加于所述乙烯基硅烷和改性试剂的混合物中。在本发明中，所述水和催化剂的滴加时间优选为0.5～2h，更优选为1.0～1.5h。
完成所述混合后，本发明优选进行改性反应；所述改性反应的温度优选为50～100℃，更优选为60～80℃，进一步优选为65～70℃；时间优选为1～12h，更优选为1.5～3h。
在本发明中，当改性反应所得产物中乙烯基硅烷含量低于＜10％，判断改性反应完成，将所得产物进行脱醇。本发明对检测产物中乙烯基硅烷含量的具体方法没有特殊的限定，按照本领域熟知的方法检测即可。在本发明中，所述脱醇的温度优选为60～100℃，更优选为70～90℃；完成所述脱醇后，本发明抽出乙醇，将所得产物降温过滤，得到改性乙烯基硅烷。本发明对所述抽出乙醇、降温过滤的过程没有特殊的限定，按照本领域熟知的过程进行即可。
在本发明中，当所述改性试剂为二甲基硅氧烷环体(DMC)时，所述改性反应的反应式为：
Figure PCTCN2022078517-appb-000021
当所述改性试剂为硅油时，所述改性反应的反应式为：
Figure PCTCN2022078517-appb-000022
本发明提供了上述技术方案所述改性乙烯基硅烷或上述技术方案所述制备方法制备得到的改性乙烯基硅烷在合成有机材料和/或无机材料中的应用。本发明对所述应用的方法没有特殊的限定，按照本领域熟知的方法将所述改性乙烯基硅烷作为偶联剂用于合成有机材料和/或无机材料即可。
下面将结合本发明中的实施例，对本发明中的技术方案进行清楚、完整地描述。显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。
实施例1
在500L反应釜中抽入100kg乙烯基三乙氧基硅烷，然后加入50kg DMC(二甲基硅氧烷环体)，升温到60℃，向所得混合物中同时滴加5kg水和0.015kg氢氧化钾的混合溶液，滴加时间为0.5h，保持温度70℃反应3h，取样分析，产物中乙烯基硅烷含量低于＜10％，升温到80℃，抽出乙醇总量25kg，将所得产物降温过滤，得到无色透明的改性乙烯基硅烷产品130kg，产品粘度为5mPa/s；
本实施例制备得到的改性乙烯基硅烷的结构式为：
Figure PCTCN2022078517-appb-000023
x＝2。
实施例2
在500L反应釜中抽入100kg乙烯基三乙氧基硅烷，然后加入50kg DMC(二甲基硅氧烷环体)，升温到60℃，向所得混合物中同时滴加10kg水和0.03kg氢氧化钾的混合溶液，滴加时间为1h；保持温度70℃，反应3h，取样分析，产物中乙烯基硅烷含量低于＜10％，升温至80℃，抽出乙醇总量50kg，将所得产物降温过滤，得到成品110kg，产品粘度为20mPa/s；
本实施例制备得到的改性乙烯基硅烷的结构式为：
Figure PCTCN2022078517-appb-000024
x＝4。
实施例3
在500L反应釜中抽入100kg乙烯基三乙氧基硅烷，然后加入50kg硅油(粘度为500mPa/s)，升温到60℃，向所得混合物中同时滴加10kg水和0.03kg氢氧化钾的混合溶液，滴加时间为1h；保持温度70℃反应3h，取样分析，产物中乙烯基硅烷含量低于＜10％，升温至80℃，抽出乙醇总量50kg，将所得产物降温过滤，得到成品110kg，产品粘度为18mPa/s；本实施例制备得到的改性乙烯基硅烷的结构式为：
Figure PCTCN2022078517-appb-000025
y＝3。
实施例4
在500L反应釜中抽入100kg乙烯基三甲氧基硅烷，然后加入50kg DMC(二甲基硅氧烷环体)，升温到60℃，向所得混合物中同时滴加12kg水和0.03kg浓硫酸(质量浓度98％)的混合溶液，滴加时间为1h；保持温度70℃，反应3h，取样分析，所得产物中乙烯基硅烷含量低于＜10％，升温至80℃，抽出甲醇总量42kg，将所得产物降温过滤，得到成品110kg，产品粘度为22mPa/s。
本实施例制备得到的改性乙烯基硅烷的结构式为：
Figure PCTCN2022078517-appb-000026
x＝4。
表征及性能测试
1)对实施例1～4制备的改性乙烯基硅烷进行核磁表征和红外表征，结果见图1～8；图1、3、5和7依次为实施例1～4制备的改性乙烯基硅烷的核磁谱图，由图1可知，5.80～5.93为CH 2＝CH峰；3.60～3.74为CH 3CH 2中CH 2的峰；1.09～1.14为CH 3CH 2中CH 3的峰；-0.1～0.06为CH 3Si中CH 3峰。由图3可知，5.81～5.95为CH 2＝CH峰；3.62～3.75为CH 3CH 2中CH 2的峰；1.10～1.16为CH 3CH 2中CH 3的峰；-0.09～0.07为CH 3Si中CH 3峰。由图5可知，5.84～6.02为CH 2＝CH峰；3.63～3.78为CH 3CH 2中CH 2的峰；1.10～1.16为CH 3CH 2中CH 3的峰；﹣0.07～0.05为CH 3Si中CH 3峰。由图7可知，5.791～5.94为CH 2＝CH峰；3.36～3.47为CH 3O中CH 3的峰；-0.11～0.05为CH 3Si中CH 3峰。
图2、4、6和8依次为实施例1～4制备的改性乙烯基硅烷的红外谱图，图2、4、6和8中，2885cm -1及2973cm -1是C-H振动峰，1259cm -1为CH 3Si的峰，1031/1037/1047/1051cm -1为Si-O-Si的峰，955/961/963cm -1为CH 2＝CH峰，788/795/796cm -1为CH 3-Si-CH 3。
应用效果验证
验证原理为：不经过修饰的高纯度氢氧化镁(空白样)只有少部分会漂浮在水面上，活化率低，但是经过改性硅烷修饰后的氢氧化镁具备部分有机物特性，会增加氢氧化镁粉体的油性，活化率提高，使得氢氧化镁粉体漂浮在水面，不会沉淀，分液时修饰好的粉体大部分不沉淀。
1)将50g研磨后的氢氧化镁分别加入到1.5g实施例1～4制备的改性乙烯基硅烷中，机械搅拌，在85℃反应1h，得到改性硅烷修饰的氢氧化镁粉体。
2)活化率验证：分别称取5g使用实施例1～4制备的改性乙烯基硅烷修饰的氢氧化镁粉体放入烧杯中，加入300g蒸馏水，充分搅拌，静置分液，放出下层液体和少量沉淀，修饰后氢氧化镁会漂浮在水面上，精滤出漂浮的固体，烘干，得到修饰后氢氧化镁样品；
同时，分别以乙烯基三乙氧基硅烷、乙烯基三甲氧基硅烷和500粘度硅油采用上述1)的方法对氢氧化镁进行改性，得到修饰后氢氧化镁粉体；然后分别按照2)的方法进行活化率验证实验；
分别测试不同改性剂修饰后氢氧化镁的活化率，活化率＝修饰后氢氧化镁样品总质量/氢氧化镁样品重量(5g)*100％，并以空白样(不进行任何修饰的氢氧化镁粉体)作为对比，所得结果见表1。
表1不同改性剂改性氢氧化镁后的活化率
改性剂 活化率
空白样 9.22％
乙烯基三乙氧基硅烷 47.01％
乙烯基三甲氧基硅烷 54.24％
500粘度硅油 41.06％
实施例1 89.87％
实施例2 87.62％
实施例3 88.34％
实施例4 89.75％
由表1可知，不进行修饰的氢氧化镁(空白样)的活化率低，基本上均在水中沉淀，但是经过修饰后的氢氧化镁具备部分有机物特性，活化率提高，而且相对于硅烷单体，经过实施例1～4改性的乙烯基硅烷对氢氧化镁的性能提升更大。
以上所述仅是本发明的优选实施方式，应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以做出若干改进和润饰，这些改进和润饰也应视为本发明的保护范围。

Claims (17)

  1. 一种改性乙烯基硅烷，其特征在于，具有式I所示结构：
    Figure PCTCN2022078517-appb-100001
    其中，R包括
    Figure PCTCN2022078517-appb-100002
    Figure PCTCN2022078517-appb-100003
    R 1包括甲基、乙基、丙基或异丙基；x＝2～8，y＝1～50。
  2. 根据权利要求1所述的改性乙烯基硅烷，其特征在于，所述改性乙烯基硅烷的粘度为2～50mPa/s。
  3. 根据权利要求1所述的改性乙烯基硅烷，其特征在于，所述改性乙烯基硅烷的结构式为：
    Figure PCTCN2022078517-appb-100004
    x＝2；
    Figure PCTCN2022078517-appb-100005
    x＝4；
    Figure PCTCN2022078517-appb-100006
    y＝3；
    Figure PCTCN2022078517-appb-100007
    x＝4。
  4. 权利要求1～3任一项所述改性乙烯基硅烷的制备方法，其特征在于，包括以下步骤：
    将乙烯基硅烷、改性试剂、催化剂和水混合，进行改性反应，得到改性乙烯基硅烷；
    所述乙烯基硅烷包括乙烯基三烷氧基硅烷；所述乙烯基三烷氧基硅烷包括乙烯基三甲氧基硅烷、乙烯基三乙氧基硅烷、乙烯基三丙氧基硅烷或乙烯基三异丙氧基硅烷；
    所述改性试剂包括硅油或二甲基硅氧烷环体；
    所述硅油具有式II所述结构：
    Figure PCTCN2022078517-appb-100008
    m＝1～50；
    所述二甲基硅氧烷环体具有式III所示结构：
    Figure PCTCN2022078517-appb-100009
    n＝2～8。
  5. 根据权利要求4所述的制备方法，其特征在于，所述乙烯基硅烷与改性试剂的质量比为1:(0.3～1.2)。
  6. 根据权利要求5所述的制备方法，其特征在于，所述乙烯基硅烷与改性试剂的质量比为1:(0.5～1.0)。
  7. 根据权利要求4所述的制备方法，其特征在于，所述催化剂包括苛性碱或浓硫酸。
  8. 根据权利要求4或7所述的制备方法，其特征在于，所述催化剂的质量为所述乙烯基硅烷与改性试剂的总质量的0.01～0.03％。
  9. 根据权利要求8所述的制备方法，其特征在于，所述催化剂的质量为所述乙烯基硅烷与改性试剂的总质量的0.015～0.02％。
  10. 根据权利要求4所述的制备方法，其特征在于，所述水的质量为所述乙烯基硅烷质量的5～20％。
  11. 根据权利要求10所述的制备方法，其特征在于，所述水的质量为所述乙烯基硅烷质量的8～15％。
  12. 根据权利要求4所述的制备方法，其特征在于，所述改性反应的温度为50～100℃，时间为1～12h。
  13. 根据权利要求4所述的制备方法，其特征在于，所述乙烯基硅烷、改性试剂、催化剂和水混合包括：将乙烯基硅烷和改性试剂混合后，升温至50～100℃，向所得混合物中同时加入水和催化剂，所述水和催化剂的加入时间为0.5～2h。
  14. 根据权利要求4或12所述的制备方法，其特征在于，当所述改性反应所得产物中乙烯基硅烷含量低于＜10％，判断改性反应完成，将所得产物进行脱醇。
  15. 根据权利要求14所述的制备方法，其特征在于，所述脱醇的温度为60～100℃。
  16. 根据权利要求15所述的制备方法，其特征在于，完成所述脱醇后，抽出乙醇，还包括：将所得产物降温过滤，得到改性乙烯基硅烷。
  17. 权利要求1～3任一项所述改性乙烯基硅烷或权利要求4～16任一项所述制备方法制备得到的改性乙烯基硅烷在合成有机无机杂化材料中的应用。
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