WO2019096188A1 - 硅氧烷桥基硅烷封端的硅氧烷桥基梯形聚硅氧烷及其制备方法 - Google Patents

硅氧烷桥基硅烷封端的硅氧烷桥基梯形聚硅氧烷及其制备方法 Download PDF

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WO2019096188A1
WO2019096188A1 PCT/CN2018/115548 CN2018115548W WO2019096188A1 WO 2019096188 A1 WO2019096188 A1 WO 2019096188A1 CN 2018115548 W CN2018115548 W CN 2018115548W WO 2019096188 A1 WO2019096188 A1 WO 2019096188A1
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group
silane
siloxane
bridging
trapezoidal
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French (fr)
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潘赏
曹菁
张榕本
方世壁
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长兴（中国）投资有限公司
中国科学院化学研究所
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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
    • 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
    • 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
    • C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
    • 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

Definitions

  • This invention relates to silicone bridging ladder polysiloxanes, and more particularly to silicone bridging silane terminated siloxane bridging ladder polysiloxanes and methods of making same.
  • trapezoidal silicone polymers have a double-stranded ladder structure. Although the trapezoidal main chain is broken by external action, statistically speaking, there is little possibility that the upper and lower single chains of the same ladder will break at the same time. Therefore, it exhibits superior performance in heat resistance, radiation resistance, chemical resistance, mechanical and biological effects as compared with general single-chain silicone polymers.
  • trapezoidal organopolysiloxanes is divided into three stages according to the different bridging structure: the first generation is oxygen bridged trapezoidal polysiloxane (ie trapezoidal polysilsesquioxane, English abbreviation R-LPSQ, R Representing the side group); the second generation is the organic bridging trapezoidal polysiloxane (R-OLPS in English, R stands for the side group); the third generation is the silicone-based trapezoidal polysiloxane (English abbreviation R-SLPS, R Represents the side base).
  • the first generation is oxygen bridged trapezoidal polysiloxane (ie trapezoidal polysilsesquioxane, English abbreviation R-LPSQ, R Representing the side group); the second generation is the organic bridging trapezoidal polysiloxane (R-OLPS in English, R stands for the side group); the third generation is the silicone-based trapezoidal polysiloxane (English abbreviation R
  • the organic bridging trapezoidal polysiloxane has improved flexibility compared with the oxygen bridged trapezoidal polysilsesquioxane, and has good compatibility with common organic polymers, and is advantageous for improving the performance of organic polymers, but the heat resistance is less.
  • Oxygen agglomerate trapezoidal polysilsesquioxane In 2014, the group disclosed a silicone bridging trapezoidal polysiloxane homopolymer R-SLPS and a preparation method thereof (Chinese Patent CN10404583B).
  • the silicone bridging trapezoidal polysiloxane has the advantages of the above two types of trapezoidal polysiloxanes - excellent heat resistance, good mechanical properties, and good compatibility with other organic polymers.
  • the commonly used blocking agent is a monofunctional silane (such as trimethylsiloxy), which limits its heat resistance; the end cap is not easy to complete; and the degree of polymerization is difficult to control;
  • the single-layered structure of the blocking agent and the high price make the practical application face many difficulties.
  • the siloxane bridged silane-terminated silicone bridging trapezoidal polysiloxane of the present invention has more excellent heat resistance than the monofunctional silane-terminated silicone bridging trapezoidal polysiloxane, for example, Hydroxyl-terminated ladder polymer 4HO-blocked Ph-SLPS does not change color and does not crosslink at 400 ° C ⁇ 15 h, which is the highest heat resistance data of general polysiloxane reported in the literature so far, corresponding monofunctional silane (such as diphenylmethyl).
  • the silyl-terminated siloxane bridging trapezoidal polysiloxane MePh 2 SiO-blocked Ph-SLPS also showed better performance without cross-linking at 400 ° C for 15 h without discoloration.
  • the corresponding diphenylsiloxane bridyl silane-terminated siloxane bridging trapezoidal polysiloxane Ph 2 -I-Ph-SLPS showed better performance without cross-linking at 400 ° C ⁇ 24 h without discoloration.
  • the end capping is more complete.
  • the degree of polymerization of the ladder polymer can be effectively controlled by adjusting the molar ratio of the bifunctional I-type capping agent to the tetrafunctional I-shaped monomer.
  • the shuangguan type-type capping agent is easy to obtain raw materials, expands the diversity of the end groups, and the operation process is simplified, the cost is reduced, and the industrialization is more convenient.
  • One of the objects of the present invention is to provide a siloxane bridged silane-terminated silicone bridging trapezoidal polysiloxane, wherein the siloxane bridging trapezoidal polysiloxane has the following formula (1) molecule structure:
  • n 1 to 10
  • n is an integer from 1 to 1000
  • a 1 , A 2 , A 3 , A 4 , A 5 , A 6 are each independently selected from hydrogen, substituted or unsubstituted linear, branched or cyclic C 1-25 alkyl, substituted or unsubstituted straight a chain, branched or cyclic C 2-25 alkenyl group, a substituted or unsubstituted C 5-25 aryl group,
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 are each independently selected from hydrogen, hydroxy, substituted or unsubstituted straight, branched or cyclic.
  • the substituent is at least one selected from the group consisting of a linear, branched or cyclic C 1-25 alkyl group, a linear, branched or cyclic C 2 - 2 . a 25 -alkenyl group, a C 5-25 aryl group, a group containing at least one atom selected from the group consisting of an oxygen atom, a sulfur atom, a nitrogen atom and a phosphorus atom, a halogen atom,
  • Each of the above alkyl group, alkoxy group, alkenyl group, aryl group, and aryloxy group may have at least one hetero atom selected from the group consisting of O, S, P, and N as a chain constituent atom or ring in the chain or in the ring. Form an atom.
  • Another object of the present invention is to provide a process for preparing a siloxane bridging silane-terminated silicone bridging trapezoidal polysiloxane having the structure of the above formula (1).
  • the preparation method is characterized in that a tetrafunctional I-type siloxane bridging siloxane monomer is co-hydrolyzed with a bifunctional I-type siloxane bridging silane blocking agent, and a trapezoid is formed by synergistic action of a supramolecular weak bond.
  • the superstructure controls the polymerization and capping reaction to give a siloxane bridged silane-terminated siloxane bridging trapezoidal polysiloxane of the formula (1).
  • the siloxane bridging silane-terminated siloxane bridging ladder polysiloxane synthesis of the present invention involves the use of supramolecular chemistry to modulate the polymerization process. That is, the monomer is regulated by the synergistic action of supramolecular weak bonds (including ⁇ - ⁇ superposition, electron donor and acceptor, electrostatic, hydrophilic and hydrophobic, and hydrogen bonding interactions) during the hydrolysis process to form a trapezoidal superstructure.
  • supramolecular weak bonds including ⁇ - ⁇ superposition, electron donor and acceptor, electrostatic, hydrophilic and hydrophobic, and hydrogen bonding interactions
  • the temperature in the early stage is lower (-50 ° C to 50 ° C), to ensure the stability of the trapezoidal superstructure constructed by the weak interaction of supramolecules, and the need to properly raise the temperature (100 ° C) and the base with appropriate polarity and weak interaction for the end of the end-capping reaction.
  • the reaction solvent of the group thus obtains a trapezoidal polymer which is structurally regular and completely blocked.
  • a siloxane bridged silane-terminated silicone bridging ladder polysiloxane having the molecular structure of formula (1):
  • n 1 to 10
  • n is an integer from 1 to 1000
  • a 1 , A 2 , A 3 , A 4 , A 5 , A 6 are each independently selected from hydrogen, substituted or unsubstituted linear, branched or cyclic C 1-25 alkyl, substituted or unsubstituted straight a chain, branched or cyclic C 2-25 alkenyl group, a substituted or unsubstituted C 5-25 aryl group,
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 are each independently selected from hydrogen, hydroxy, substituted or unsubstituted straight, branched or cyclic.
  • the substituent is at least one selected from the group consisting of a linear, branched or cyclic C 1-25 alkyl group, a linear, branched or cyclic C 2 - 2 . a 25 -alkenyl group, a C 5-25 aryl group, a group containing at least one atom selected from the group consisting of an oxygen atom, a sulfur atom, a nitrogen atom and a phosphorus atom, a halogen atom,
  • Each of the above alkyl group, alkoxy group, alkenyl group, aryl group, and aryloxy group may have at least one hetero atom selected from the group consisting of O, S, P, and N as a chain constituent atom or ring in the chain or in the ring. Form an atom.
  • the group containing at least one atom selected from the group consisting of an oxygen atom, a sulfur atom, a nitrogen atom and a phosphorus atom is selected from the group consisting of a hydroxyl group, a glycidoxy group, and a C 5-25 epoxy naphthenic group.
  • the R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , A 1 , A 2 , A 3 , A 4 , A 5 and A 6 are each independently selected from the group consisting of hydrogen, hydroxy, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-hexyl, cyclohexyl, n-octyl Base, n-decyl, n-dodecyl, n-hexadecyl, n-octadecyl, n-docosyl, vinyl, allyl, phenyl, methylphenyl, chlorophenyl , p-vinylphenyl, 3-(2,3-epoxypropoxy)propyl, 2-(3,4-e
  • the second aspect of the present invention provides a method for preparing a siloxane bridging silane-terminated silicone bridging trapezoidal polysiloxane according to the above formula (1), characterized in that the tetrafunctional I-type silicon oxide
  • the alkane-based siloxane monomer is co-hydrolyzed with a bifunctional I-type siloxane bridging silane capping agent, and the super-molecular weak bond is synergistically formed to form a trapezoidal superstructure to regulate polymerization and capping reaction to obtain formula (1)
  • a structure of a silicone bridged silane terminated ladder polysiloxane A structure of a silicone bridged silane terminated ladder polysiloxane.
  • the method for preparing a siloxane bridged silane-terminated silicone bridging trapezoidal polysiloxane comprises the steps of:
  • silanes of structural formulas (2), (3) and (4) are added to the reactor, and the organic solvent, water and catalyst are subjected to hydrolysis and condensation reaction, while vacuuming is continuously or intermittently removed to remove condensation by-products;
  • the product is isolated and purified to obtain a siloxane bridged silane-terminated silicone bridging trapezoidal polysiloxane having the structure of the above formula (1).
  • the tetrafunctional I-shaped monomer is represented by the structural formula (2)
  • X is one selected from the group consisting of OH, halogen, C 1-25 alkoxy or C 1-25 acyloxy;
  • the difunctional I-shaped silane blocking agent is represented by the structural formula (3)
  • X is one selected from the group consisting of OH, halogen, C 1-25 alkoxy or C 1-25 acyloxy;
  • the difunctional I-shaped silane capping agent structural formula (4) represents
  • X is one selected from the group consisting of OH, halogen, C 1-25 alkoxy or C 1-25 acyloxy;
  • the tetrafunctional I-shaped monomer of the formula (2) is prepared by condensing a trifunctional silane coupling agent with a silicon diol in the presence of a catalyst.
  • the trifunctional silane coupling agent is represented by the formula -RSiX 3
  • R R 1 , R 2 ;
  • X halogen, C 1-25 alkoxy, C 1-25 acyloxy.
  • the difunctional I-form silane blocking agent of the formula (3) is prepared by condensing a difunctional silane coupling agent with a silicon diol in the presence of a catalyst.
  • the difunctional silane coupling agent is represented by the formula R'R"SiX 2 ,
  • R ', R " R 3 in combination with R 5, R 4 and R 6 in combination;
  • X halogen, C 1-25 alkoxy, C 1-25 acyloxy.
  • the difunctional I-shaped silane blocking agent of the formula (4) is prepared by condensing a difunctional silane coupling agent with a silicon diol in the presence of a catalyst.
  • the difunctional silane coupling agent is represented by the formula R'R"SiX 2 ,
  • R ', R " R 7 in combination with R 9, R 8 in combination with R 10;
  • X halogen, C 1-25 alkoxy, C 1-25 acyloxy.
  • the reaction temperature is from -50 ° C to 150 ° C, usually from -45 ° C to 100 ° C.
  • the hydrolysis and condensation reaction temperature is -50 ° C to 50 ° C; the end-capping reaction temperature is -50 ° C to 50 ° C in the early stage, and the complete reaction temperature can be raised to 100 ° C in the later stage.
  • the organic solvent is one selected from the group consisting of an alkane, a substituted alkane, an alcohol, an ether, a ketone, an ester, an amide, a nitrile, a pyrrolidone, and a sulfoxide.
  • an alkane a substituted alkane
  • an alcohol an ether
  • a ketone an ester
  • an amide an amide
  • a nitrile a pyrrolidone
  • a sulfoxide sulfoxide
  • the organic solvent is selected from the group consisting of: n-hexane, cyclohexane, dichloroethane, chloroform, tetrachloroethane, methanol, ethanol, isopropanol, ethylene glycol monomethyl Ether, diethylene glycol dimethyl ether, tetrahydrofuran, 1,4-dioxane, acetone, cyclohexanone, methyl isobutyl ketone, ethyl acetate, N,N-dimethylformamide, N,N One or more of dimethylacetamide, acetonitrile, N-methylpyrrolidone (NMP), dimethyl sulfoxide (DMSO).
  • NMP N-methylpyrrolidone
  • DMSO dimethyl sulfoxide
  • reaction time is from 30 minutes to 120 hours.
  • the number of moles of water added to the silane of the formula (2) is from 0.001 to 50 times the number of moles of the silane of the formula (2).
  • the number of moles of the silane of the formula (3) or (4) added to the silane of the formula (2) is 0.001 to 20 times the number of moles of the silane of the formula (2).
  • the number of moles of the catalyst added to the silane of the formula (2) is from 0 to 10 times the number of moles of the silane of the formula (2).
  • the number of moles of solvent added to the silane of the formula (2) is from 1 to 1000% by weight of the silane of the formula (2)(3)(4).
  • the vacuum reaction may be carried out continuously or indirectly at -50 ° C to 150 ° C for 0 minutes - 120 hour.
  • the yield of the siloxane bridged silane-terminated silicone bridging ladder polysiloxane of the formula (1) is from 70% to 100%.
  • the catalyst is selected from one or more of an acid, an oxide and a hydroxide, an ammonia or an amine, a transition metal compound, and an ion exchange resin, in order to obtain a structural regularity and complete termination.
  • the trapezoidal polymers are preferably organic amines and oxides as well as hydroxide catalysts.
  • the acid catalyst is one or more of an inorganic acid or an organic acid.
  • the oxide is one or more selected from the group consisting of metal oxides.
  • the hydroxide is selected from the group consisting of tetramethylammonium hydroxide, tetrabutylphosphoric acid hydroxide, lithium hydroxide, sodium hydroxide, potassium hydroxide, barium hydroxide, calcium hydroxide, and hydroxide.
  • tetramethylammonium hydroxide tetrabutylphosphoric acid hydroxide
  • lithium hydroxide lithium hydroxide
  • sodium hydroxide potassium hydroxide
  • barium hydroxide calcium hydroxide
  • hydroxide a hydroxide
  • magnesium and barium hydroxide is selected from the group consisting of magnesium and barium hydroxide.
  • the transition metal compound is one or more selected from the group consisting of organotins and titanates.
  • the amine is one or more selected from the group consisting of tertiary amines.
  • the ion exchange resin is a sulfonic acid type ion exchange resin selected from the group consisting of a quaternary ammonium ion exchange resin having a styrene divinylbenzene copolymer as a matrix and a styrene divinylbenzene copolymer as a matrix.
  • the styrene-divinylbenzene copolymer is one or more of a carboxylic acid-type ion exchange resin having a matrix and a carboxylic acid-type ion exchange resin having a polyacrylic acid as a matrix.
  • the acid catalyst is one or more of hydrochloric acid, sulfuric acid, formic acid, and acetic acid.
  • the oxide is one or more selected from the group consisting of calcium oxide and magnesium oxide.
  • the transition metal compound is one or more selected from the group consisting of dibutyltin laurate, dibutyltin diacetate, dibutyltin oxide, and butyl titanate.
  • the amine is selected from the group consisting of ammonia, n-butylamine, t-butylamine, dimethylamine, diethylamine, diisopropylamine, ethylenediamine, tetramethylammonium hydroxide, 1,8 One or several of diazabicyclo[5.4.0]undec-7-ene, 1,5-diazabicyclo[4.3.0]-5-nonene, triethylamine, pyridine, triethanolaminekind.
  • the siloxane bridging silane-terminated silicone bridging ladder polysiloxane of the present invention can effectively control the degree of polymerization by adjusting the amount of the bifunctional I-type blocking agent, and can continuously purify by-products under high vacuum. Make the end cap reaction more complete. It exhibits superior heat resistance, chemical stability and mechanical properties compared to the monofunctional end-capping method.
  • the bridging group, terminal group and side group of the siloxane bridging silane-terminated silicone bridging ladder polysiloxane of the invention are all organic groups, and have good compatibility with general-purpose polymers, due to sealing
  • the diversity of the terminal agent and the uniqueness of the preparation method solve the problem that the degree of polymerization of the monofunctional siloxane-terminated bridging trapezoidal polysiloxane is currently uncontrollable, the structure of the terminal functional group is single, the price is high, and the end cap is incomplete.
  • the problem is to adjust the optical properties, light transmittance, adhesion, airtightness, strength, etc. by changing the bridging group, side groups, end groups and degree of polymerization to make the application range wider.
  • the siloxane bridging silane-terminated silicone bridging trapezoidal polysiloxane of the present invention has excellent high temperature resistance, high weather resistance, high radiation resistance, and good optical and mechanical properties.
  • New materials such as new high temperature resistant silicone rubber, high heat and high weathering coatings, photocurable coatings, light emitting diodes and electronic packaging materials, high temperature resistant high vacuum diffusion pump oil, high temperature resistant lubricants and special coupling agents Will be widely used.
  • Figure 1 is a 29 Si-NMR chart of the product obtained in Example 1 of the present invention.
  • Figure 2 is a FTIR spectrum of the product obtained in Example 1 of the present invention.
  • Figure 3 is a 29 Si-NMR chart of the product obtained in Example 3 of the present invention.
  • Figure 4 is a FTIR spectrum of the product obtained in Example 5 of the present invention.
  • Figure 5 is a 29 Si-NMR chart of the product obtained in Example 5 of the present invention.
  • Figure 6 is a DSC chart of the product obtained in Example 5 of the present invention.
  • Figure 7 is a TGA spectrum of the product obtained in Example 5 of the present invention.
  • Figure 8 is a TGA spectrum of the product obtained in Example 6 of the present invention.
  • Figure 9 is a DSC chart of the product obtained in Example 6 of the present invention.
  • Figure 10 is a TGA spectrum of a comparative product used in Example 6 of the present invention.
  • Figure 11 is a DSC chart of a comparative product used in Example 6 of the present invention.
  • the siloxane bridging silane-terminated silicone bridging trapezoidal polysiloxane of the present embodiment has a molecular structure represented by the following formula (1):
  • n 1 to 10
  • n is an integer from 1 to 1000
  • a 1 , A 2 , A 3 , A 4 , A 5 , A 6 are each independently selected from hydrogen, substituted or unsubstituted linear, branched or cyclic C 1-25 alkyl, substituted or unsubstituted straight a chain, branched or cyclic C 2-25 alkenyl group, a substituted or unsubstituted C 5-25 aryl group,
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 are each independently selected from hydrogen, hydroxy, substituted or unsubstituted straight, branched or cyclic.
  • the substituent is at least one selected from the group consisting of a linear, branched or cyclic C 1-25 alkyl group, a linear, branched or cyclic C 2 - 2 . a 25 -alkenyl group, a C 5-25 aryl group, a group containing at least one atom selected from the group consisting of an oxygen atom, a sulfur atom, a nitrogen atom and a phosphorus atom, a halogen atom,
  • Each of the above alkyl group, alkoxy group, alkenyl group, aryl group, and aryloxy group may have at least one hetero atom selected from the group consisting of O, S, P, and N as a chain constituent atom or ring in the chain or in the ring. Form an atom.
  • C 1-25 alkyl group means an alkyl group having 1 to 25 carbon atoms.
  • Other similar terms are also the same.
  • the linear, branched or cyclic C 1-25 alkyl group may, but not limited to, a linear C 1-25 alkyl group, a branched C 1-25 alkyl group, a cyclic C 3-25 alkyl group, preferably a linear C group. 1-25 alkyl.
  • the alkyl group may have 1 to 22 carbon atoms, 1 to 20, 1 to 18, 1 to 16, 1 to 12, 1 to 10, 1 to 6, and 1 to 4, preferably 1 carbon atom. ⁇ 6.
  • n-propyl isopropyl
  • n-butyl isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, n-heptyl, N-octyl, n-decyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n.
  • the linear, branched or cyclic C 2-25 alkenyl group may be exemplified by, but not limited to, a linear C 2-25 alkenyl group, a branched C 2-25 alkenyl group, a cyclic C 3-25 alkenyl group, preferably a linear chain.
  • the alkenyl group may have 2 to 22 carbon atoms, 2 to 20, 2 to 18, 2 to 16, 2 to 12, 2 to 10, 2 to 6, 2 to 4, preferably 2 carbon atoms. ⁇ 3. Specific examples thereof include a vinyl group, a propylene group, and an allyl group.
  • C 5-25 aryl groups include but are not limited to, C 5 ⁇ 20 aryl group, C 5-18 aryl, C 5-14 aryl group. Specific examples thereof include a pyridyl group, a phenyl group, and a naphthyl group.
  • a linear, branched or cyclic C 1-25 alkoxy group is a group of a straight, branched or cyclic C 1-25 alkyl group bonded to an oxygen (O) atom, wherein the straight chain or the branched chain
  • O oxygen
  • Examples of the cyclic C 1-25 alkyl group are as described above.
  • C 5-25 aryloxy group is a C 5-25 aryl group and oxygen (O) atoms connected to each group, examples of which are C 5-25 aryl groups described above.
  • Each of the above alkyl group, alkoxy group, alkenyl group, aryl group, and aryloxy group may have at least one hetero atom selected from the group consisting of O, S, P, and N as a chain constituent atom or ring in the chain or in the ring.
  • the atom is formed to form a heteroalkyl group, a heteroalkoxy group, a heteroalkenyl group, a heteroaryl group or a heteroaryloxy group.
  • the halogen atom may, for example, be fluorine, chlorine, bromine or iodine, preferably fluorine or chlorine.
  • the preparation method of the siloxane bridging silane-terminated silicone bridging trapezoid polysiloxane of the present embodiment comprises: a tetrafunctional I-type siloxane bridging siloxane monomer and a bifunctional I-shaped siloxane
  • the alkane-based silane capping agent is co-hydrolyzed, and the siloxane-based silane-terminated trapezoidal polysiloxane having the structure of the formula (1) is obtained by synthesizing a trapezoidal superstructure by a synergistic action of a supramolecular weak bond to regulate polymerization and blocking reaction.
  • the method for preparing a siloxane bridging silane-terminated silicone bridging trapezoidal polysiloxane of the present embodiment comprises the steps of: silanes of structural formulae (2), (3) and (4) (ie, four Functional I-type siloxane bridging siloxane monomer and bifunctional I-type siloxane bridging silane capping agent) co-hydrolyzed in the presence of solvent, catalyst, water, relying on supramolecular weak bond interactions (including ⁇ - ⁇ superposition, electron donor and acceptor, electrostatic, hydrophilic and hydrophobic, and hydrogen bonding, etc.) form trapezoidal superstructure to regulate the polymerization and end-capping reaction of hydrolyzate to obtain siloxane bridging silane-terminated silicon oxygen Alkane bridged trapezoidal polysiloxane.
  • the preparation method comprises the following steps:
  • the structural formula (2) (3) and (4) silane, solvent, water and catalyst are added to the reactor by dropwise addition or "one-pot” method for hydrolysis and condensation reaction, intermittent or continuous vacuum reaction, and the product obtained by the reaction is passed through The separation and purification treatment is carried out to obtain a siloxane bridged silane-terminated silicone bridging trapezoidal polysiloxane having the structure of the above formula (1) in a yield of 70% to 100%.
  • the tetrafunctional I-shaped monomer is represented by the structural formula (2):
  • R 1 , R 2 , A 1 , A 2 have the same meanings as defined above;
  • X is one selected from the group consisting of OH, halogen, C 1-25 alkoxy or C 1-25 acyloxy;
  • the difunctional I-shaped monomer is represented by the structural formula (3):
  • R 3 , R 4 , R 5 , R 6 , A 3 , A 4 have the same meanings as defined above;
  • X is one selected from the group consisting of OH, halogen, C 1-25 alkoxy or C 1-25 acyloxy;
  • the difunctional I-shaped monomer is represented by the structural formula (4):
  • R 7 , R 8 , R 9 , R 10 , A 5 , A 6 have the same meanings as defined above;
  • X is one selected from the group consisting of OH, halogen, C 1-25 alkoxy or C 1-25 acyloxy;
  • a catalyst including dealcoholation, dehydration, dehydrohalogenation,
  • a catalyst including dealcoholation, dehydration, dehydrohalogenation, deacidification
  • deesterification reaction including dealco
  • R 3 - R 10 , A 3 , A 4 , A 5 , and A 6 are as defined above, and R 3 and R 5 may be the same or different, and R 4 and R 6 may be the same or different.
  • R 7 and R 9 may be the same or different, and R 8 and R 10 may be the same or different, and the A 3 and A 4 may be the same or different, and the A 5 and A 6 may be the same or different, and the R may be the same or different.
  • 3 in combination with R 5, R 4 and R 6 may be the same or different composition, the composition R 7 and R 9, R 8 R 10 may be the same or different compositions.
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 in the above formula (1), formula (2), formula (3) and formula (4) , R 9 , R 10 , A 1 , A 2 , A 3 , A 4 , A 5 , and A 6 are each independently selected from hydrogen, a hydroxyl group, a substituted or unsubstituted linear or branched chain having 1 to 25 carbon atoms.
  • a cyclic alkyl group, an alkenyl group, and an aryl group such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, hexyl, cyclohexyl, octyl, or Mercapto, n-dodecyl, n-hexadecyl, n-octadecyl, n-docosyl, vinyl, allyl, phenyl, methylphenyl, chlorophenyl, vinyl Phenyl, 3-(2,3-epoxypropoxy)propyl, 2-(3,4-epoxycyclohexane)ethyl, acryloxypropyl, 3-methacryloyloxy Propyl, propylpropyl, aminopropyl, 3-(2-aminoethyl)-aminopropyl, 4-amino-3,3-
  • the reaction temperature is not particularly limited and is usually -50 ° C to 150 ° C, for example, -45 ° C to 100 ° C.
  • the hydrolysis and condensation reaction temperature is -50 ° C to 50 ° C; the end-capping reaction temperature is -50 ° C to 50 ° C in the early stage, and the complete reaction temperature can be raised to 100 ° C in the later stage.
  • the reaction time is not particularly limited and is usually from 30 minutes to 120 hours, for example, from 1 hour to 80 hours.
  • the amount of water to be added to the silane of the structural formula (2) is not particularly limited, and usually the number of moles of water is 0.001 to 50 times the number of moles of the structural formula (2), for example, 0.01 to 30 times.
  • the amount of the silane of the structural formula (3) or (4) to be added to the silane of the structural formula (2) is not particularly limited, and usually the number of moles of the silane of the structural formula (3) or (4) is 0.001 of the number of moles of the silane of the formula (2) -20 times, for example, 0.01-10 times.
  • the amount of the catalyst to be added to the silane of the structural formula (2) is not particularly limited, and usually the number of moles of the catalyst is from 0 to 10 times the mole of the silane of the structural formula (2), for example, from 0.01 to 5 times.
  • the amount of the solvent to be added to the silane of the structural formula (2) is not particularly limited, and usually the weight of the solvent is from 1 to 1000%, for example, from 2 to 500%, based on the total weight of the structural formula (2)(3)(4).
  • the dropping or "one-pot cooking” is added to the structural formula (3) and (4) silane and then continuously or indirectly vacuum-reacting at -50 ° C to 150 ° C for 0 minutes - 120 hours, for example 1 minute - 72 hours .
  • the organic solvent is preferably selected from the group consisting of: alkanes (eg, n-hexane, cyclohexane, etc.), substituted alkanes (eg, chloroform, tetrachloroethane, etc.), alcohols (eg, methanol, ethanol, etc.) ), ethers (eg diethylene glycol dimethyl ether, tetrahydrofuran, 1,4-dioxane, etc.), ketones (eg acetone, cyclohexanone, etc.), esters (eg ethyl acetate, etc.) ), amide (such as dimethylacetamide, etc.), nitriles (such as acetonitrile, etc.), pyrrolidone (such as N-methylpyrrolidone (NMP)), sulfoxides (such as dimethyl sulfoxide (DMSO), etc.
  • alkanes eg, n-hexan
  • the supramolecular weak bond synergy between the tetrafunctional end-group polymer and the galvanic silane capping agent molecule is significantly affected by the polarity of the solvent, so it is necessary to select a group having appropriate polarity and weak interaction.
  • the reaction solvent of the group thus obtains a trapezoidal polymer having a structurally regular and completely blocked end.
  • the organic solvent is selected from the group consisting of n-hexane, cyclohexane, dichloroethane, chloroform, tetrachloroethane, methanol, Ethanol, isopropanol, ethylene glycol monomethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, 1,4-dioxane, acetone, cyclohexanone, methyl isobutyl ketone, ethyl acetate, N, One or more of N-dimethylformamide, N,N-dimethylacetamide, acetonitrile, N-methylpyrrolidone (NMP), dimethyl sulfoxide (DMSO).
  • NMP N-methylpyrrolidone
  • DMSO dimethyl sulfoxide
  • the catalyst is preferably one or more selected from the group consisting of an acid, an oxide and a hydroxide, an ammonia or an amine, a transition metal compound, and an ion exchange resin.
  • Preferred are amines and oxides and hydroxide-based catalysts.
  • a silane coupling agent may be condensed in the presence of the above catalyst.
  • the acid catalyst is preferably one or more selected from the group consisting of inorganic acids (such as hydrochloric acid, sulfuric acid, etc.) and organic acids (such as formic acid, acetic acid, etc.);
  • the oxide is preferably one or more selected from the group consisting of metal oxides (eg, calcium oxide, magnesium oxide, etc.);
  • the hydroxide is preferably selected from the group consisting of tetramethylammonium hydroxide, tetrabutylphosphoric acid hydroxide, lithium hydroxide, sodium hydroxide, potassium hydroxide, barium hydroxide, calcium hydroxide, magnesium hydroxide, barium hydroxide.
  • titanates eg, butyl titanate, etc.
  • the ammonia or amine is preferably selected from the group consisting of ammonia, n-butylamine, tert-butylamine, dimethylamine, diethylamine, diisopropylamine, ethylenediamine, tetramethylammonium hydroxide, 1,8-diaza One or more of bicyclo [5.4.0]undec-7-ene, 1,5-diazabicyclo[4.3.0]-5-nonene, triethylamine, pyridine, triethanolamine;
  • the ion exchange resin is preferably a quaternary ammonium type ion exchange resin selected from the group consisting of styrene divinylbenzene copolymer, a sulfonic acid type ion exchange resin having a styrene divinylbenzene copolymer as a matrix, and a styrene divinylbenzene copolymer.
  • a carboxylic acid type ion exchange resin having a matrix and a carboxylic acid type ion exchange resin having a polyacrylic acid as a matrix.
  • the siloxane bridging silane-terminated siloxane bridging trapezoidal polysiloxane of the present invention has excellent light transmittance from a colorless transparent liquid to a solid depending on the molecular weight and the different appearance of the terminal group side bridging group. Excellent temperature resistance and flexibility. Good solubility in solvents such as tetrahydrofuran, 1,4-dioxane, toluene, N-methylpyrrolidone, acetone, DMA, etc.
  • the glass transition temperature (T g ) is measured by a scanning calorimetry (DSC).
  • the DSC is tested at 20 ° C / min from the lowest temperature to be tested to the highest temperature to be tested, and then rapidly cooled from the highest temperature. At the lowest temperature, a second temperature rise test was performed at 10 ° C / min.
  • the refractive index was measured by an Abbe refractometer, and the test conditions of the refractive index were measured at a constant temperature of 298 K.
  • the viscosity is measured by melting the sample at a high temperature by a high temperature type cone and plate viscometer and selecting a suitable rotation speed.
  • the thermal decomposition temperature is measured by a thermogravimetric analyzer (TGA).
  • TGA thermogravimetric analyzer
  • the TGA is tested under the air atmosphere at 20 ° C / min from 30 ° C to 900 ° C; or, under a nitrogen atmosphere, at 20 ° C / min from 30 ° C
  • the temperature was raised from 600 ° C to 900 ° C at 20 ° C / min in an air atmosphere at 600 ° C.
  • R'R"-IR-SLPS I-type silane-terminated siloxane bridging polysiloxanes
  • R is the pendant group of the polysiloxane R-SLPS.
  • the font silane is capped;
  • R'R" represents the two end groups of the I-form silane.
  • a siloxane bridged silane terminated siloxane bridging ladder polysiloxane is prepared by phenyltrimethoxysilane, diphenyldimethoxysilane, and diphenylsilyl glycol.
  • siloxane bridging silane-terminated siloxane bridging trapezoidal polysiloxane is a colorless transparent solid, and the average degree of polymerization n is 14, the refractive index is 1.59 (25 ° C), and the glass transition temperature is 48.51. °C, 230 ° C, 800 rpm, the viscosity is 133 poise.
  • the air-tolerant thermal oxidation resistance is as follows: its hydroxyl terminated ladder polymer 4HO-blocked Ph-SLPS does not change color and does not crosslink at 400 ° C ⁇ 15 h; and the corresponding monofunctional silane (such as diphenylmethylsilyl) is capped The siloxane bridging trapezoidal polysiloxane MePh 2 SiO-I-blocked Ph-SLPS does not crosslink at 400 ° C for 15 h without discoloration.
  • a siloxane bridging silane terminated siloxane bridging ladder polysiloxane is prepared by phenyltrimethoxysilane, methylphenyldimethoxysilane, and diphenylsilyl diol.
  • the resulting siloxane bridged silane-terminated siloxane bridging trapezoidal polysiloxane is a colorless transparent solid having an average degree of polymerization of 80, a refractive index of 1.57 (25 ° C), and a glass transition temperature of 39.45. °C, 230 ° C, 50 rpm, the viscosity is 2430 poise.
  • the air-tolerant thermal oxidation resistance is as follows: its hydroxyl terminated ladder polymer 4HO-blocked Ph-SLPS does not change color and does not crosslink at 400 ° C ⁇ 15 h; and the corresponding monofunctional silane (such as diphenylmethylsilyl) is capped The siloxane bridging trapezoidal polysiloxane MePh 2 SiO-I-blocked Ph-SLPS does not crosslink at 400 ° C for 15 h without discoloration.
  • a siloxane bridging silane-terminated silicone bridging ladder polysiloxane is prepared by methyltrimethoxysilane, diphenyldimethoxysilane, and diphenylsilyl glycol.
  • the resulting siloxane bridged silane-terminated siloxane bridging trapezoidal polysiloxane colorless transparent solid has an average degree of polymerization of 12, a refractive index of 1.55 (25 ° C), and a glass transition temperature of 34.31 ° C.
  • the viscosity is 973 Poise at 230 ° C and 100 rpm.
  • the air-tolerant thermal oxidation resistance is as follows: its hydroxyl terminated ladder polymer 4HO-blocked Me-SLPS does not change color and does not crosslink at 300 ° C ⁇ 15 h; and the corresponding monofunctional silane (such as diphenylmethylsilyl) is capped The siloxane bridging trapezoidal polysiloxane MePh 2 SiO-I-blocked Me-SLPS does not crosslink at 300 ° C for 15 h without discoloration.
  • a siloxane bridged silane terminated siloxane bridging ladder polysiloxane is prepared by methyltrimethoxysilane, methylphenyldimethoxysilane, and diphenylsilyl glycol.
  • the resulting siloxane bridged silane-terminated siloxane bridging trapezoidal polysiloxane colorless transparent solid has an average degree of polymerization of 80, a refractive index of 1.54 (25 ° C), and a glass transition temperature of 28.51 ° C.
  • the viscosity is 365 Poise at 230 ° C and 50 rpm.
  • the air-tolerant thermal oxidation resistance is as follows: its hydroxyl terminated ladder polymer 4HO-blocked Me-SLPS does not change color and does not crosslink at 300 ° C ⁇ 15 h; and the corresponding monofunctional silane (such as dimethylphenylsilyl) is capped The siloxane bridging trapezoidal polysiloxane Me 2 PhSiO-I-blocked Me-SLPS does not crosslink at 300 ° C for 15 h without discoloration.
  • the three-necked flask of the condenser was stirred at room temperature uniformly, and 0.3 g of styrene-divinylbenzene copolymer was added as a base of ammonia water at 0 ° C, and the reaction was carried out for 15 hours to obtain an intermediate 1; 23.6 g of 3-((2,3)-glycidoxy)propylmethyldiethoxysilane (0.10 mol), 20 g of acetone, were added to a stirred, constant pressure dropping funnel and a reflux condenser.
  • the resulting siloxane bridged silane-terminated siloxane bridging trapezoidal polysiloxane colorless transparent solid has an average degree of polymerization of 34, a refractive index of 1.56 (25 ° C), and a glass transition temperature of 40.28 ° C. .
  • the TGA measured a 5% thermal decomposition temperature of 400 °C.
  • the viscosity is 8550 poise at 230 ° C and 30 rpm.
  • a silane bridged silane-terminated silicone bridging ladder polysiloxane is prepared by phenyltrimethoxysilane, methylvinyldimethoxysilane, and diphenylsilyl glycol.
  • the ene was reacted for 12 hours to obtain the intermediate 2, and the intermediate 2 was all added to the intermediate 1, and 33.6 g (1.86 mol) of water was added thereto, and the mixture was reacted at 0 ° C for 15 hours; then the resulting mixture was neutralized with hydrochloric acid, and added.
  • the resulting siloxane bridged silane-terminated silicone bridging trapezoidal polysiloxane was a colorless, transparent, soft solid having an average degree of polymerization of 6 and a refractive index of 1.57 (25 ° C).
  • the glass transition temperature was 28.83 ° C, compared to 0.47 ° C of the product dimethyl vinyl terminated phenyl homopolymer.
  • the TGA measured a 5% thermal decomposition temperature of 390 ° C, and the comparative product dimethyl vinyl terminated phenyl homopolymer had a 5% thermal decomposition temperature of 330 ° C.
  • the viscosity at 230 ° C, 100 rpm was 1973 Poise.
  • a siloxane bridging silane-terminated silicone bridging ladder polysiloxane is prepared by methyltrimethoxysilane, methylvinyldimethoxysilane, and diphenylsilyl glycol.
  • the resulting siloxane bridged silane-terminated silicone bridging trapezoidal polysiloxane colorless transparent solid has an average degree of polymerization of 12, a refractive index of 1.53 (25 ° C), and a glass transition temperature of 47.51 ° C. .
  • the viscosity is 718 Poise at 230 ° C and 100 rpm.
  • siloxane bridged silane-terminated siloxanes by vinyltrimethoxysilane, 3-((2,3)-glycidoxy)propylmethyldiethoxysilane and diphenylsilyl glycol Bridge-based trapezoidal polysiloxane.
  • the resulting siloxane bridging siloxane-terminated siloxane bridging trapezoidal polysiloxane is a colorless transparent solid having an average degree of polymerization of 15, a refractive index of 1.55 (25 ° C), and a glass transition temperature. It is 34.66 °C. The viscosity is 3,701 poise at 230 ° C and 50 rpm.
  • siloxane bridging silane-terminated siloxane bridging ladder polysiloxane by methyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane and diphenylsilyl glycol alkyl.
  • siloxane bridging siloxane-terminated silane bridging trapezoidal polysiloxane is a colorless transparent viscous liquid having an average degree of polymerization n of 120, a refractive index of 1.53 (25 ° C), and a glass transition temperature. It is 10.32 °C. The viscosity is 9490 poise at 230 ° C and 30 rpm.
  • siloxane bridged silane-terminated silicon oxide by 3-(methacryloyloxy)propyltrimethoxysilane, phenyltrimethoxysilane, dimethyldimethoxysilane and diphenylsilyl glycol Alkane bridged trapezoidal polysiloxane.
  • the resulting siloxane bridged silane-terminated siloxane bridging trapezoidal polysiloxane is a colorless transparent viscous liquid having an average degree of polymerization of 300, a refractive index of 1.53 (25 ° C), and a glass transition temperature. It is -12.34 °C. The viscosity was 61.62 Poise at 230 ° C and 100 rpm.
  • siloxane bridging groups by 3-((2,3)-glycidoxy)propyltrimethoxysilane, vinyltrimethoxysilane, diphenyldimethoxysilane and diphenylsilyl diol Silane-terminated siloxane bridging trapezoidal polysiloxane.
  • the resulting siloxane bridged silane-terminated silane bridging trapezoidal polysiloxane colorless transparent viscous liquid has an average degree of polymerization of 90, a refractive index of 1.55 (25 ° C), and a glass transition temperature of -3.4. °C.
  • the viscosity at 94 ° C, 100 rpm is 94.54 Poise.
  • the resulting siloxane bridged silane-terminated silicone bridging trapezoidal polysiloxane colorless transparent viscous liquid has a polymerization degree n of 320, a refractive index of 1.53 (25 ° C), and a glass transition temperature of -37.3 °C.
  • the viscosity at 32 ° C, 100 rpm is 32.65 Poise.
  • the resulting siloxane bridged silane-terminated siloxane bridging trapezoidal polysiloxane is a colorless transparent solid having an average degree of polymerization of 75, a refractive index of 1.53 (25 ° C), and a glass transition temperature of 27.54. °C.
  • the viscosity is 8490 Poise at 230 ° C and 30 rpm.
  • a siloxane bridged silane terminated siloxane bridging ladder polysiloxane is prepared by methyltrimethoxysilane, diphenyldimethoxysilane, and diisobutylsilyl glycol.
  • the obtained siloxane bridged silane-terminated silicone bridging trapezoidal polysiloxane colorless transparent solid has a polymerization degree n of 12, a refractive index of 1.52, a glass transition temperature of 14.82 ° C, 210 ° C, The viscosity is 345 Poise at 100 rpm.
  • a siloxane bridged silane terminated siloxane bridging ladder polysiloxane is prepared by methyltrimethoxysilane, dimethyldimethoxysilane, and dipropylsilyl glycol.
  • the resulting siloxane bridged silane-terminated siloxane bridging trapezoidal polysiloxane colorless transparent solid has an average degree of polymerization of 450, a refractive index of 1.52 (25 ° C), and a glass transition temperature of 13.51 ° C.
  • the viscosity is 134 poise at 210 ° C and 50 rpm.

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Abstract

本发明涉及硅氧烷桥基硅烷封端的硅氧烷桥基梯形聚硅氧烷及其制备方法。本发明提供硅氧烷桥基硅烷(即双官能工字型硅烷)封端的硅氧烷桥基梯形聚硅氧烷及其制备方法。通过将四官能工字型硅氧桥基硅氧烷单体与双官能工字型硅氧烷桥基硅烷封端剂共水解，依靠超分子弱键协同作用形成梯形超结构来调控水解产物的聚合和封端反应，得到具有以下通式的硅氧烷桥基封端梯形聚硅氧烷。与一般单官能封端硅氧烷桥基梯形聚硅氧烷相比，这种双官能工字型硅烷封端梯形聚硅氧烷的聚合度及封端完全程度可以得到有效控制。该聚合物具有优良的耐热性、良好的力学性能以及与通用有机高分子良好的兼容性。并且这种封端方式所用原料简单易得，成本低廉，适于产业化。 (I)

Description

硅氧烷桥基硅烷封端的硅氧烷桥基梯形聚硅氧烷及其制备方法 技术领域
本发明涉及硅氧烷桥基梯形聚硅氧烷，特别涉及硅氧烷桥基硅烷封端硅氧烷桥基梯形聚硅氧烷及其制备方法。
背景技术
一般梯形有机硅聚合物具有双链的梯形结构。虽然其梯形主链受到外界作用会发生断裂，但从统计学来讲，在同一梯撑的上、下两条单链同时发生断裂的可能性很少。因此与一般单链有机硅聚合物相比在耐热、耐辐射、耐化学、力学和生物作用方面显示出更优异的性能。
梯形有机聚硅氧烷的发展依据其桥基结构的不同分为三个阶段：第一代为氧桥基梯形聚硅氧烷(即梯形聚倍半硅氧烷，英文简写R-LPSQ，R代表侧基)；第二代为有机桥基梯形聚硅氧烷(英文简写R-OLPS，R代表侧基)；第三代为硅氧桥基梯形聚硅氧烷(英文简写R-SLPS，R代表侧基)。
早在1960年，前苏联K.A.Andrianov et.al(Izu.Akad.Nauk.S.S.S.R.，Otdel Khim.Nauk，1960，1266)曾尝试合成苯桥基梯形聚硅氧烷(Ph-OLPS)，未能成功，仅得到无规低聚物。同年，R-SLPS美国J.F.Brown et.al(J.Am.Chem.Soc.1960，82，6194)报导了采用“平衡热缩聚”方法合成了梯形聚苯基倍半硅氧烷(Ph-LPSQ)。随即在国际上引起很大的轰动，并出现了大量涉及不同侧基的梯形聚倍半硅氧烷的文章和专利。但是，1971年美国C.L.Frey等著文否认上述梯形聚苯基倍半硅氧烷的存在，指出实际上聚合反应并未达到平衡，产物是部分开环的多环笼状物(J.Am.Chem.Soc.1971，93，4599)。自此，欧美化学核心期刊不再发表有关梯形聚硅氧烷的文章。1983年以来，张榕本小组首先采用超分子化学方法分别合成了氧桥基梯形聚硅氧烷 R-LPSQ(国际专利WO2010034161-A1；Angew.Chem.Int.Ed.2006，45，3112和Chem.Commun.2009，4079)和有机桥基的梯形聚硅氧烷R-OLPS(中国专利CN 1280995A、美国专利US6423772 B1；J.Am.Chem.Soc.2002，124，10482)。一般来说，氧桥基梯形聚倍半硅氧烷耐热性能更好，可溶于一定的溶剂中，但其本身柔韧性能差，应用受到限制。而有机桥基梯形聚硅氧烷较氧桥基梯形聚倍半硅氧烷柔韧性有所提高，并且与一般有机高分子兼容性好，对改善有机高分子性能有利，但耐热性能稍逊于氧桥基梯形聚倍半硅氧烷。2014年，该组公开了硅氧烷桥基梯形聚硅氧烷均聚物R-SLPS及其制备方法(中国专利CN10404583B)。这种硅氧烷桥基梯形聚硅氧烷具有上述两类梯形聚硅氧烷的优点-优良的耐热性、良好的力学性能，与其他有机高分子的良好的兼容性。这些特点使其成为综合性能优良的新一代梯形聚硅氧烷的代表。然而目前存在以下问题，包括：一般所用封端剂为单官能硅烷(如三甲基硅氧基等)，使其耐热性受到限制；封端不易完全；并且聚合度难于控制；加之这类封端剂的结构单一、价格昂贵等因素造成实际应用面临诸多困难。本发明所述硅氧烷桥基硅烷封端硅氧烷桥基梯形聚硅氧烷较之单官能硅烷封端硅氧烷桥基梯形聚硅氧烷具有更优良的耐热性能，例如，其羟基封端梯形聚合物4HO-blocked Ph-SLPS在400℃×15h不变色和不交联，成为至今文献报导的一般聚硅氧烷最高耐热数据，相应单官能硅烷(如二苯基甲基硅烷基)封端硅氧烷桥基梯形聚硅氧烷MePh 2SiO-blocked Ph-SLPS也显示出较佳性能在400℃×15h不交联不变色。而相应二苯基硅氧烷桥基硅烷封端硅氧烷桥基梯形聚硅氧烷Ph 2-I-Ph-SLPS显示出更佳性能在400℃×24h不交联不变色。而且由于采用高沸点双官能硅烷封端剂在高真空条件下不易逸失，使封端更完全。通过调节双官能工字型封端剂与四官能工字型单体的克分子比可以有效控制梯形聚合物的聚合度。这种双官工字型封端剂，原料易得，扩大了端基的多样性，而且操作工艺简化，成本下降，更便于产业化。
发明内容
本发明的目的之一在于提供一种硅氧烷桥基硅烷封端硅氧烷桥基梯形聚硅氧烷，其中，所述硅氧烷桥基梯形聚硅氧烷具有以下式(1)分子结构：
Figure PCTCN2018115548-appb-000001
其中：
m为1-10的整数，
n为1-1000的整数，
A 1、A 2、A 3、A 4、A 5、A 6分别独立地选自氢、取代或未取代的直链、支链或环状C 1-25烷基、取代或未取代的直链、支链或环状C 2-25烯基、取代或未取代的C 5-25芳基，
R 1、R 2、R 3、R 4、R 5、R 6、R 7、R 8、R 9、R 10分别独立地选自氢、羟基、取代或未取代的直链、支链或环状C 1-25烷基、取代或未取代的直链、支链或环状C 2-25烯基、取代或未取代的C 5-25芳基、取代或未取代的直链、支链或环状C 1-25烷氧基、取代或未取代的C 5-25芳氧基，
在上述基团具有取代基时，所述取代基为选自如下的至少一种：直链、支链或环状的C 1-25烷基、直链、支链或环状的C 2-25烯基、C 5-25芳基、含有选自氧原子、硫原子、氮原子和磷原子中的至少一个原子的基团、卤素原子，
上述烷基、烷氧基、烯基、芳基、芳氧基各自在链中或环中可以具有至少一个选自由O、S、P、N构成的组中的杂原子作为链构成原子或环构成原子。
本发明的另一目的提供一种如上述式(1)结构的硅氧烷桥基硅烷封端的硅氧烷桥基梯形聚硅氧烷的制备方法。
所述制备方法的特征在于，四官能工字型硅氧烷桥基硅氧烷单体 与双官能工字型硅氧烷桥基硅烷封端剂共水解，依靠超分子弱键协同作用形成梯形超结构来调控聚合与封端反应而得到式(1)结构的硅氧烷桥基硅烷封端的硅氧烷桥基梯形聚硅氧烷。
由于聚合所用工字型单体为四官能化合物，在水解和缩合条件下极易发生支化和交联，生成不溶不熔的凝胶。为此，与一般聚合物合成方法不同，本发明所述硅氧烷桥基硅烷封端硅氧烷桥基梯形聚硅氧烷合成涉及到利用超分子化学方法来调控聚合过程。即单体在水解过程中通过超分子弱键的协同作用(包括π-π迭加、电子给体与受体、静电、亲水与疏水和氢键等相互作用等)形成梯形超结构来调控聚合反应，抑制支化和交联的发生从而得到结构规整的梯形聚合物；同时借助四官能端基聚合物与双官工字型硅烷封端剂分子彼此间的超分子弱键协同作用形成梯形超结构使封端反应顺利进行。考虑到反应过程中形成的超分子弱键协同作用受反应温度和溶剂极性的显著影响，因此需选择合适的反应温度(包括水解、缩合及封端反应前期温度要较低(-50℃至50℃)，以保证超分子弱相互作用构筑的梯形超结构的稳定性，以及封端反应后期为了封端完全而需要适当升高温度(100℃)和具有适当极性和弱相互作用的基团的反应溶剂从而得到结构规整、封端完全的梯形聚合物。
具体而言，本申请提供如下各项发明
在本发明的第一方面中，提供了一种硅氧烷桥基硅烷封端的硅氧烷桥基梯形聚硅氧烷，其具有以下式(1)分子结构：
Figure PCTCN2018115548-appb-000002
其中：
m为1-10的整数，
n为1-1000的整数，
A 1、A 2、A 3、A 4、A 5、A 6分别独立地选自氢、取代或未取代的直链、支链或环状C 1-25烷基、取代或未取代的直链、支链或环状C 2-25烯基、取代或未取代的C 5-25芳基，
R 1、R 2、R 3、R 4、R 5、R 6、R 7、R 8、R 9、R 10分别独立地选自氢、羟基、取代或未取代的直链、支链或环状C 1-25烷基、取代或未取代的直链、支链或环状C 2-25烯基、取代或未取代的C 5-25芳基、取代或未取代的直链、支链或环状C 1-25烷氧基、取代或未取代的C 5-25芳氧基，
在上述基团具有取代基时，所述取代基为选自如下的至少一种：直链、支链或环状的C 1-25烷基、直链、支链或环状的C 2-25烯基、C 5-25芳基、含有选自氧原子、硫原子、氮原子和磷原子中的至少一个原子的基团、卤素原子，
上述烷基、烷氧基、烯基、芳基、芳氧基各自在链中或环中可以具有至少一个选自由O、S、P、N构成的组中的杂原子作为链构成原子或环构成原子。
在另一优选例中，所述的含有选自氧原子、硫原子、氮原子和磷原子中的至少一个原子的基团选自羟基、环氧丙氧基、C 5-25环氧环烷基、丙烯酰氧基、C 1-25烷基取代的丙烯酰氧基、巯基、氨基、氨基-直链、支链或环状的C 1-25烷基、C 6-25芳基氨基、氰基、脲基、膦基。
在另一优选例中，所述的R 1、R 2、R 3、R 4、R 5、R 6、R 7、R 8、R 9、R 10、A 1、A 2、A 3、A 4、A 5、A 6分别独立地选自氢、羟基、甲基、乙基、正丙基、异丙基、正丁基、异丁基、叔丁基、正己基、环己基、正辛基、正癸基、正十二烷基、正十六烷基、正十八烷基、正二十二烷基、乙烯基、烯丙基、苯基、甲基苯基、氯代苯基、对乙烯基苯基、3-(2，3-环氧丙氧基)丙基、2-(3，4-环氧环己基)乙基、丙烯酰氧基丙基、3-甲基丙烯酰氧基丙基、巯丙基、氨丙基、3-(2-氨乙基)-氨丙基、4-氨基-3，3-二甲基丁基、N-正丁基-3-氨基丙基、2-氰基乙基、3-氰基丙基、3，3，3- 三氟丙基、1H，1H，2H，2H-全氟辛基、1H，1H，2H，2H-全氟癸基、氯丙基、脲丙基、甲氧基、乙氧基。
本发明第二方面提供了一种根据上述式(1)结构的硅氧烷桥基硅烷封端的硅氧烷桥基梯形聚硅氧烷的制备方法，其特征在于，四官能工字型硅氧烷桥基硅氧烷单体与双官能工字型硅氧烷桥基硅烷封端剂共水解，依靠超分子弱键协同作用形成梯形超结构来调控聚合与封端反应而得到式(1)结构的硅氧烷桥基硅烷封端梯形聚硅氧烷。
在另一优选例中，所述的硅氧烷桥基硅烷封端的硅氧烷桥基梯形聚硅氧烷的制备方法，其包括以下步骤：
在反应器中加入结构式(2)、(3)和(4)的硅烷，有机溶剂、水和催化剂进行水解和缩合反应，同时可持续或间断地抽真空，去除缩合副产物；之后将反应所得产物分离提纯，得到上述式(1)结构的硅氧烷桥基硅烷封端的硅氧烷桥基梯形聚硅氧烷。
所述的四官能工字型单体由结构式(2)表示
Figure PCTCN2018115548-appb-000003
其中，
m、R 1、R 2、A 1、A 2的含义各自与权利要求1所述相同；
X选自OH、卤素、C 1-25烷氧基或C 1-25酰氧基中的一种；
所述的二官能工字型硅烷封端剂由结构式(3)表示
Figure PCTCN2018115548-appb-000004
其中，
m、R 3、R 4、R 5、R 6、A 3、A 4的含义各自与权利要求1所述相同；
X选自OH、卤素、C 1-25烷氧基或C 1-25酰氧基中的一种；
所述的二官能工字型硅烷封端剂结构式(4)表示
Figure PCTCN2018115548-appb-000005
其中，
m、R 7、R 8、R 9、R 10、A 5、A 6的含义各自与权利要求1中的含义相同；
X选自OH、卤素、C 1-25烷氧基或C 1-25酰氧基中的一种；
在另一优选例中，所述的式(2)的四官能工字型单体由三官能硅烷偶联剂与硅二醇在催化剂存在下缩合制备，
所述三官能硅烷偶联剂由式-RSiX 3表示，
式中，R＝R 1，R 2；X＝卤素、C 1-25烷氧基、C 1-25酰氧基。
在另一优选例中，所述的式(3)的二官能工字型硅烷封端剂由双官能硅烷偶联剂与硅二醇在催化剂存在下缩合制备，
所述双官能硅烷偶联剂由式R’R”SiX 2表示，
式中，R’、R”＝R 3与R 5组合、R 4与R 6组合；X＝卤素、C 1-25烷氧基、C 1-25酰氧基。
式(4)的二官能工字型硅烷封端剂由双官能硅烷偶联剂与硅二醇在催化剂存在下缩合制备，
所述双官能硅烷偶联剂由式R’R”SiX 2表示，
式中，R’、R”＝R 7与R 9组合、R 8与R 10组合；X＝卤素、C 1-25烷氧基、C 1-25酰氧基。
在另一优选例中，
所述的反应温度为-50℃至150℃，通常为-45℃-100℃。其中水解和缩合反应温度为-50℃至50℃；封端反应温度前期为-50℃至50℃，后期为封端完全反应温度可升至100℃。
在另一优选例中，所述的有机溶剂为选自：烷烃类、取代烷烃类、 醇类、醚类、酮类、酯类、酰胺类、腈类、吡咯烷酮类、亚砜类中的一种或几种。
在另一优选例中，所述的有机溶剂为选自：正己烷、环己烷、二氯乙烷、三氯甲烷、四氯乙烷、甲醇、乙醇、异丙醇、乙二醇单甲醚、二乙二醇二甲醚、四氢呋喃、1，4-二氧六环、丙酮、环己酮、甲基异丁酮、乙酸乙酯、N，N-二甲基甲酰胺、N，N-二甲基乙酰胺、乙腈、N-甲基吡咯烷酮(NMP)、二甲基亚砜(DMSO)中的一种或几种。
在另一优选例中，所述的反应时间为30分钟至120小时。
在另一优选例中，向所述的结构式(2)硅烷中加入水的摩尔数是结构式(2)硅烷的摩尔数的0.001-50倍。
在另一优选例中，向所述的结构式(2)硅烷中加入结构式(3)或(4)硅烷的摩尔数是结构式(2)硅烷摩尔数的0.001-20倍。
在另一优选例中，向所述的结构式(2)硅烷中加入催化剂的摩尔数是结构式(2)硅烷的摩尔数0-10倍。
在另一优选例中，向所述的结构式(2)硅烷中加入溶剂的摩尔数是结构式(2)(3)(4)硅烷重量的1-1000％。
在另一优选例中，所述的滴加法或“一锅”法中，加入结构式(3)和(4)硅烷后可持续或间接在-50℃至150℃下抽真空反应0分钟-120小时。
在另一优选例中，所述的式(1)结构的硅氧烷桥基硅烷封端的硅氧烷桥基梯形聚硅氧烷的产率为70％～100％。
在另一优选例中，所述的催化剂选自酸、氧化物和氢氧化物、氨或胺类、过渡金属化合物、离子交换树脂中的一种或几种，为了得到结构规整、封端完全的梯形聚合物优选是有机胺类和氧化物以及氢氧化物类催化剂。
在另一优选例中，所述的酸催化剂为无机酸类、有机酸类的一种或几种。
在另一优选例中，所述的氧化物为选自金属氧化物的一种或几种。
在另一优选例中，所述的氢氧化物为选自四甲基氢氧化铵、四丁基氢氧化磷、氢氧化锂、氢氧化钠、氢氧化钾、氢氧化铯、氢氧化钙、氢氧化镁、氢氧化钡中的一种或几种。
在另一优选例中，所述的过渡金属化合物为选自有机锡类、钛酸酯类中的一种或几种。
在另一优选例中，所述的胺类为选自叔胺类中的一种或几种。
在另一优选例中，所述的离子交换树脂为选自苯乙烯二乙烯苯共聚物为基体的季铵型离子交换树脂、苯乙烯二乙烯苯共聚物为基体的磺酸型离子交换树脂、苯乙烯二乙烯苯共聚物为基体的羧酸型离子交换树脂、聚丙烯酸为基体的羧酸型离子交换树脂中的一种或几种。
在另一优选例中，所述的酸催化剂为盐酸、硫酸、甲酸、醋酸的一种或几种。
在另一优选例中，所述的氧化物为选自氧化钙、氧化镁的一种或几种。
在另一优选例中，所述的过渡金属化合物为选自二丁基二月桂酸锡、二丁基二醋酸锡、二丁基氧化锡、钛酸丁酯中的一种或几种。
在另一优选例中，所述的胺类为选自氨气、正丁胺、叔丁胺、二甲胺、二乙胺、二异丙胺、乙二胺、四甲基氢氧化铵、1，8-二氮杂双环[5.4.0]十一碳-7-烯、1，5-二氮杂双环[4.3.0]-5-壬烯、三乙胺、吡啶、三乙醇胺的一种或几种。
本发明的有益效果：
a)本发明硅氧烷桥基硅烷封端的硅氧烷桥基梯形聚硅氧烷通过调节双官能工字型封端剂用量可有效控制聚合度，并且可在高真空下持续蒸除副产物使得封端反应更完全。与单官能封端方式相比显示出更优良的耐热性、化学稳定性和力学性能。
b)本发明的硅氧烷桥基硅烷封端的硅氧烷桥基梯形聚硅氧烷的桥基、端基和侧基均为有机基团，与通用高分子具有良好的兼容性，由于封端剂的多样性和制备方法的独特性解决了目前已知单官能硅氧烷封端桥基梯形聚硅氧烷聚合度不可控、封端官能基结构单一、价格高、封端不完全的问题，通过对桥基、侧基、端基和聚合度的改变来调整折旋光性、透光性，粘接性、气密性、强度等使应用范围更广泛。
c)本发明的硅氧烷桥基硅烷封端的硅氧烷桥基梯形聚硅氧烷具有优良的高耐温性、高耐候性、高耐辐射性、以及良好的光学和力学性能。作为新型耐高温硅橡胶、高耐热和高耐候涂料、光固化涂料、发光二极管和电子封装材料、耐高温高真空扩散泵油、耐高温润滑剂和特种偶联剂等新材料在高技术领域将获得广泛应用。
附图说明
图1为本发明实施例1所得产物的 29Si-NMR谱图。
图2为本发明实施例1所得产物的FTIR谱图。
图3为本发明实施例3所得产物的 29Si-NMR谱图。
图4为本发明实施例5所得产物的FTIR谱图。
图5为本发明实施例5所得产物的 29Si-NMR谱图。
图6为本发明实施例5所得产物的DSC谱图。
图7为本发明实施例5所得产物的TGA谱图。
图8为本发明实施例6所得产物的TGA谱图。
图9为本发明实施例6所得产物的DSC谱图。
图10为本发明实施例6所用对比产物的TGA谱图。
图11为本发明实施例6所用对比产物的DSC谱图。
具体实施方式
以下对本申请的具体实施方式进行说明。但是，这些实施方式仅仅是例示，无意限制本申请发明的范围。
本实施方式的硅氧烷桥基硅烷封端的硅氧烷桥基梯形聚硅氧烷具有以下式(1)所示分子结构：
Figure PCTCN2018115548-appb-000006
其中：
m为1-10的整数，
n为1-1000的整数，
A 1、A 2、A 3、A 4、A 5、A 6分别独立地选自氢、取代或未取代的直链、支链或环状C 1-25烷基、取代或未取代的直链、支链或环状C 2-25烯基、取代或未取代的C 5-25芳基，
R 1、R 2、R 3、R 4、R 5、R 6、R 7、R 8、R 9、R 10分别独立地选自氢、羟基、取代或未取代的直链、支链或环状C 1-25烷基、取代或未取代的 直链、支链或环状C 2-25烯基、取代或未取代的C 5-25芳基、取代或未取代的直链、支链或环状C 1-25烷氧基、取代或未取代的C 5-25芳氧基，
在上述基团具有取代基时，所述取代基为选自如下的至少一种：直链、支链或环状的C 1-25烷基、直链、支链或环状的C 2-25烯基、C 5-25芳基、含有选自氧原子、硫原子、氮原子和磷原子中的至少一个原子的基团、卤素原子，
上述烷基、烷氧基、烯基、芳基、芳氧基各自在链中或环中可以具有至少一个选自由O、S、P、N构成的组中的杂原子作为链构成原子或环构成原子。
在本发明中，C 1-25烷基表示碳原子数为1～25的烷基。其它类似的术语也同样。
直链、支链或环状C 1-25烷基可以列举但不限于直链C 1-25烷基、支链C 1-25烷基、环状C 3-25烷基，优选直链C 1-25烷基。烷基的碳原子数可以为1～22个，1～20个，1～18个，1～16个，1～12个，1～10个，1～6个，1～4个，优选1～6个。具体地可以列举：甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基、叔丁基、正戊基、异戊基、正己基、正庚基、正辛基、正壬基、正癸基、正十一烷基、正十二烷基、正十三烷基、正十四烷基、正十五烷基、正十六烷基、正十七烷基、正十八烷基、正十九烷基、正二十烷基、正二十一烷基、正二十二烷基、正二十三烷基、正二十四烷基、正二十五烷基、环丙基、环丁基、环戊基、环己基、环庚基、环辛基、环壬基、环癸基、环十一烷基、环二十烷基、环十三烷基、环十四烷基、环十五烷基、环十六烷基、环十七烷基、环十八烷基、环十九烷基、环二十烷基、环二十一烷基、环二十二烷基、环二十三烷基、环二十四烷基、环二十五烷基。
直链、支链或环状C 2-25烯基可以列举但不于限直链C 2-25烯基、支链C 2-25烯基、环状C 3-25烯基，优选直链C 2-25烯基。烯基的碳原子数可 以为2～22个，2～20个，2～18个，2～16个，2～12个，2～10个，2～6个，2～4个，优选2～3个。具体地可以列举：乙烯基、丙烯基、烯丙基。
C 5-25芳基可以列举但不限于C 5～20芳基、C 5-18芳基、C 5-14芳基。具体地可以列举吡啶基、苯基、萘基。
直链、支链或环状C 1-25烷氧基为直链、支链或环状C 1-25烷基与氧(O)原子连接而成的基团，其中的直链、支链或环状C 1-25烷基的例子如上所述。
C 5-25芳氧基为C 5-25芳基与氧(O)原子连接而成的基团，其中的C 5-25芳基的例子如上所述。
上述烷基、烷氧基、烯基、芳基、芳氧基各自在链中或环中可以具有至少一个选自由O、S、P、N构成的组中的杂原子作为链构成原子或环构成原子，从而成为杂烷基、杂烷氧基、杂烯基、杂芳基、杂芳氧基。
含有选自氧原子、硫原子、氮原子和磷原子中的至少一个原子的基团可以列举但是不限于羟基、羰基、氧代(＝O)、直链、支链或环状的C 1-25烷氧基、C 5-25芳氧基、环氧丙氧基、C 5-25环氧环烷基、丙烯酰氧基、直链、支链或环状的C 1-25烷基取代的丙烯酰氧基、巯基、直链、支链或环状的C 1-25烷基硫基、磺基、硝基、氨基、氨基-直链、支链或环状的C 1-25烷基、C 5-25芳基氨基、氰基、脲基、膦基、直链、支链或环状的C 1-25烷基取代的膦基。
卤素原子可以列举氟、氯、溴、碘，优选氟、氯。
本实施方式的硅氧烷桥基硅烷封端的硅氧烷桥基梯形聚硅氧烷的 制备方法包含：四官能工字型硅氧烷桥基硅氧烷单体与双官能工字型硅氧烷桥基硅烷封端剂共水解，依靠超分子弱键协同作用形成梯形超结构来调控聚合与封端反应而得到式(1)结构的硅氧烷桥基硅烷封端梯形聚硅氧烷。
优选地，本实施方式的硅氧烷桥基硅烷封端的硅氧烷桥基梯形聚硅氧烷的制备方法其包含以下步骤：将结构式(2)、(3)和(4)硅烷(即四官能工字型硅氧烷桥基硅氧烷单体与双官能工字型硅氧烷桥基硅烷封端剂)在溶剂、催化剂、水存在下共水解，依靠超分子弱键相互作用(包括π-π迭加、电子给体与受体、静电、亲水与疏水和氢键等相互作用)形成梯形超结构调控水解产物的聚合和封端反应得到硅氧烷桥基硅烷封端的硅氧烷桥基梯形聚硅氧烷。该制备方法包括以下步骤：
向反应器中以滴加或“一锅煮”方式加入结构式(2)(3)和(4)硅烷、溶剂、水和催化剂进行水解和缩合反应，间断或持续性抽真空反应，将反应所得产物经过分离提纯等处理，得到上述式(1)结构的硅氧烷桥基硅烷封端的硅氧烷桥基梯形聚硅氧烷，其产率为70％-100％。
所述的四官能工字型单体由结构式(2)表示：
Figure PCTCN2018115548-appb-000007
其中，
m、R 1、R 2、A 1、A 2的含义各自与前述之定义相同；
X选自OH、卤素、C 1-25烷氧基或C 1-25酰氧基中的一种；
所述的二官能工字型单体由结构式(3)表示：
Figure PCTCN2018115548-appb-000008
其中，
m、R 3、R 4、R 5、R 6、A 3、A 4的含义各自与前述之定义相同；
X选自OH、卤素、C 1-25烷氧基或C 1-25酰氧基中的一种；
所述的二官能工字型单体由结构式(4)表示：
Figure PCTCN2018115548-appb-000009
其中，
m、R 7、R 8、R 9、R 10、A 5、A 6的含义各自与前述之定义相同；
X选自OH、卤素、C 1-25烷氧基或C 1-25酰氧基中的一种；
上述四官能工字型单体(2)优选是由三官能硅烷偶联剂-RSiX 3(R＝R 1，R 2；X＝卤素，C 1-25烷氧基，C 1-25酰氧基等；如甲基三甲氧基硅烷、苯基三甲氧基硅烷、乙烯基三甲氧基硅烷、甲基丙烯酸丙基三甲氧基硅烷、3-环氧丙氧丙基三甲氧基硅烷和3-氨丙基三甲氧基硅烷等)与硅二醇(如二苯基硅二醇，二叔丁基硅二醇等)在催化剂存在下缩合(包括脱醇、脱水、脱卤化氢、脱酸或脱酯反应)制备。
上述二官能工字型硅烷封端剂(3)和(4)优选是由双官能硅烷偶联剂-R’R”SiX 2(R’R”＝R 3与R 5组合、R 4与R 6组合或R 7与R 9组合、R 8与R 10组合；X＝卤素，烷氧基，酰氧基等)与硅二醇(A 3A 4Si(OH) 2，A 5A 6Si(OH) 2，具体实例如二苯基硅二醇，甲基苯基硅二醇，二叔丁基硅二醇等)在催化剂存在下缩合(包括脱醇、脱水、脱卤化氢、脱酸或脱酯反应)制备。所述R 3-R 10、A 3、A 4、A 5、A 6分别如前所述，所述R 3、R 5可相同或不同，所述R 4、R 6可相同或不同，所述R 7、R 9可相同或不同，所述R 8、R 10可相同或不同，所述A 3、A 4可相同或不同，所述A 5、A 6可相同或不同，所述R 3与R 5组合、R 4与R 6组合可相同或不同，所述R 7与R 9组合、R 8与R 10组合可相同或不同。
优选地，所述的式(1)、式(2)、式(3)以及式(4)中的R 1、 R 2、R 3、R 4、R 5、R 6、R 7、R 8、R 9、R 10、A 1、A 2、A 3、A 4、A 5、A 6分别独立选自氢、羟基、碳原子数为1-25的取代或未取代的直链、支链或环状烷基、烯基、芳基中的一种，如甲基、乙基、丙基、异丙基、丁基、异丁基、叔丁基、己基、环己基、辛基、正癸基、正十二烷基、正十六烷基、正十八烷基、正二十二烷基、乙烯基、烯丙基、苯基、甲基苯基、氯代苯基、对乙烯基苯基、3-(2，3-环氧丙氧)丙基、2-(3，4-环氧环己烷基)乙基、丙烯酰氧基丙基、3-甲基丙烯酰氧基丙基、巯丙基、氨丙基、3-(2-氨乙基)-氨丙基、4-氨基-3，3-二甲基丁基、N-正丁基-3-氨丙基、2-氰基乙基、3-氰基丙基、3，3，3-三氟丙基、1H，1H，2H，2H-全氟辛基、1H，1H，2H，2H-全氟癸基、氯丙基、脲丙基、甲氧基、乙氧基中的一种。
所述的反应温度没有特别限制，通常为-50℃至150℃，例如为-45℃-100℃。其中水解和缩合反应温度为-50℃至50℃；封端反应温度前期为-50℃至50℃，后期为封端完全反应温度可升至100℃。
所述的反应时间没有特别限制，通常为30分钟至120小时，例如为1小时-80小时。
向所述的结构式(2)硅烷中加入水的量没有特别限制，通常水的摩尔数是结构式(2)的摩尔数的0.001-50倍，例如为0.01-30倍。
向所述的结构式(2)硅烷中加入结构式(3)或(4)硅烷的量没有特别限制，通常结构式(3)或(4)硅烷各自的摩尔数是结构式(2)硅烷摩尔数的0.001-20倍，例如为0.01-10倍。
向所述的结构式(2)硅烷中加入催化剂的量没有特别限制，通常催化剂的摩尔数是结构式(2)硅烷的摩尔数0-10倍，例如为0.01-5倍。
向所述的结构式(2)硅烷中加入溶剂的量没有特别限制，通常溶剂的重量是结构式(2)(3)(4)的合计重量的1-1000％，例如为2-500％。
优选地，所述的滴加或“一锅煮法”加入结构式(3)和(4)硅烷后持续或间接在-50℃至150℃下抽真空反应0分钟-120小时，例如1分钟-72小时。
所述的有机溶剂优选为选自：烷烃类(如：正己烷、环己烷等)、取代烷烃类(如：三氯甲烷、四氯乙烷等)、醇类(如：甲醇、乙醇等)、醚类(如：二乙二醇二甲醚、四氢呋喃、1，4-二氧六环等)、酮类(如：丙酮、环己酮等)、酯类(如：乙酸乙酯等)、酰胺(如二甲基乙酰胺等)、腈类(如：乙腈等)、吡咯烷酮类(如N-甲基吡咯烷酮(NMP))，亚砜类(如二甲基亚砜(DMSO)等)中的一种或几种。反应过程中四官能端基聚合物与双官工字型硅烷封端剂分子彼此间的超分子弱键协同作用受溶剂极性的显著影响，因此需选择具有适当极性和弱相互作用的基团的反应溶剂从而得到结构规整、封端完全的梯形聚合物，优选所述的有机溶剂为选自：正己烷、环己烷、二氯乙烷、三氯甲烷、四氯乙烷、甲醇、乙醇、异丙醇、乙二醇单甲醚、二乙二醇二甲醚、四氢呋喃、1，4-二氧六环、丙酮、环己酮、甲基异丁酮、乙酸乙酯、N，N-二甲基甲酰胺、N，N-二甲基乙酰胺、乙腈、N-甲基吡咯烷酮(NMP)、二甲基亚砜(DMSO)中的一种或几种。
所述的催化剂优选为选自酸、氧化物和氢氧化物、氨或胺类、过渡金属化合物、离子交换树脂中的一种或几种，为了得到结构规整、封端完全的梯形聚合物，优选是胺类和氧化物以及氢氧化物类催化剂。另外为了制备结构式(2)(3)和(4)硅烷可选硅烷偶联剂在上述催化剂存在下缩合。
所述的酸催化剂优选为选自无机酸类(如：盐酸、硫酸等)、有 机酸类(如：甲酸、醋酸等)的一种或几种；
所述的氧化物优选为选自金属氧化物(如：氧化钙、氧化镁等)的一种或几种；
所述的氢氧化物优选为选自四甲基氢氧化铵、四丁基氢氧化磷、氢氧化锂、氢氧化钠、氢氧化钾、氢氧化铯、氢氧化钙、氢氧化镁、氢氧化钡中的一种或几种；
所述的过渡金属化合物优选为选自有机锡类(如：二丁基二月桂酸锡、二丁基二醋酸锡等)、钛酸酯类(如：钛酸丁酯等)中的一种或几种；
所述的氨或胺类优选为选自氨气、正丁胺、叔丁胺、二甲胺、二乙胺、二异丙胺、乙二胺、四甲基氢氧化铵、1，8-二氮杂双环[5.4.0]十一碳-7-烯、1，5-二氮杂双环[4.3.0]-5-壬烯、三乙胺、吡啶、三乙醇胺的一种或几种；
所述的离子交换树脂优选为选自苯乙烯二乙烯苯共聚物为基体的季铵型离子交换树脂、苯乙烯二乙烯苯共聚物为基体的磺酸型离子交换树脂、苯乙烯二乙烯苯共聚物为基体的羧酸型离子交换树脂、聚丙烯酸为基体的羧酸型离子交换树脂中的一种或几种。
本发明的硅氧烷桥基硅烷封端的硅氧烷桥基梯形聚硅氧烷根据分子量大小、端基侧基桥基的不同外观可从无色透明液体到固体，具有极好的透光率，优良的耐温性和柔韧性。在四氢呋喃、1，4-二氧六环、甲苯、N-甲基吡咯烷酮、丙酮、DMA等溶剂中具有良好的溶解性.通过核磁氢谱、核磁硅谱、红外光谱、示热扫描量热仪(DSC)等测试证明其组成结构，又通过核磁硅谱、蒸汽压渗透法(VPO)等可以推算其平均聚合度，通过测试高温熔融下的粘度值则可从另一个角度反映聚合度差异带来的粘度变化。
玻璃化转变温度(T g)通过示热扫描量热仪(DSC)进行测定，DSC的测试条件为20℃/分钟从需要测试的最低温升至需要测试的最高温，然后从最高温快速冷却至最低温，再以10℃/分钟进行第二次升温检测。
折光率通过阿贝折光仪进行测定，折光率的测试条件为在298K的恒温条件下，涂膜进行测定。
粘度通过高温型锥板粘度计将样品在高温下进行熔融再选择合适的转速进行测定。
热分解温度通过热重分析仪(TGA)进行测定，TGA的测试条件为空气气氛下，20℃/分钟从30℃升温至900℃；或者是，氮气气氛下，20℃/分钟从30℃升温至600℃，再在空气气氛下，20℃/分钟从600℃升温至900℃。
以下列举实施例对本本实施方式进行更详细的说明。但是，本发明不限于这些例子。
为简化起见，以下工字型硅烷封端硅氧烷桥基聚硅氧烷简写为R’R”-I-R-SLPS，其中：R为聚硅氧烷R-SLPS的侧基。I-代表工字型硅烷封端之意；R’R”代表工字型硅烷的两个端基。
实施例1：Ph 2-I-Ph-SLPS合成
通过苯基三甲氧基硅烷、二苯基二甲氧基硅烷和二苯基硅二醇制备硅氧烷桥基硅烷封端硅氧烷桥基梯形聚硅氧烷。
在干燥的氮气保护下将39.6克苯基三甲氧基硅烷(0.20mol)、21.6克二苯基硅二醇(0.01mol)以及乙酸乙酯15克置于装有机械搅拌、恒 压滴液漏斗及回流冷凝器的三口烧瓶中，室温搅拌均匀，在0℃下加入0.02克三乙醇胺，反应8小时得中间体1；同时在另一个有干燥的氮气保护，装有机械搅拌、恒压滴液漏斗及回流冷凝器的三口烧瓶中加入41.9克二苯基二甲氧基硅烷(0.17mol)、10克乙酸乙酯、18.6克二苯基硅二醇(0.09mol)搅拌均匀，在0℃下加入0.04克三乙醇胺，反应10小时，得中间体2，将中间体2全部加入到中间体1中，加入水12.6克(0.70mol)，在-10℃下反应5小时，升温至0℃继续反应10小时；然后将所得混合物用盐酸中和，加入50mL甲苯，水洗分离减压浓缩，得到式(1)结构的硅氧烷桥基硅烷封端硅氧烷桥基梯形聚硅氧烷，其中R 1-R 10为苯基，A 1-A 6为苯基，m＝1，n＝14，所得产率为95％。
所得的硅氧烷桥基硅烷封端硅氧烷桥基梯形聚硅氧烷为无色透明固体，聚合度n的平均值为14，折光率为1.59(25℃)，玻璃化转变温度为48.51℃，230℃、800rpm转速下黏度为133泊(poise)。耐空气热氧化性分别为：其羟基封端梯形聚合物4HO-blocked Ph-SLPS在400℃×15h不变色和不交联；而相应单官能硅烷(如二苯基甲基硅烷基)封端硅氧烷桥基梯形聚硅氧烷MePh 2SiO-I-blocked Ph-SLPS在400℃×15h不交联不变色。而相应二苯基硅氧烷桥基硅烷封端硅氧烷桥基梯形聚硅氧烷Ph 2-I-Ph-SLPS显示出更佳性能在400℃×24h不交联不变色。 1H NMR(400MHz，CDCl 3，298K)：δ7.14-7.53ppm； 29Si NMR(80MHz，CDCl 3，298K)：δ-79.16，-43.46ppm。
实施例2：PhMe-I-Ph-SLPS合成
通过苯基三甲氧基硅烷、甲基苯基二甲氧基硅烷和二苯基硅二醇制备硅氧烷桥基硅烷封端硅氧烷桥基梯形聚硅氧烷。
在干燥的氮气保护下将39.6克苯基三甲氧基硅烷(0.20mol)、21.6克二苯基硅二醇(0.10mol)以及10克N，N-二甲基乙酰胺置于装有机械搅拌、恒压滴液漏斗及回流冷凝器的三口烧瓶中，室温搅拌均匀，在-5℃下加入0.10克液氨，反应12小时得中间体1；同时在另一个有 干燥的氮气保护装有机械搅拌、恒压滴液漏斗及回流冷凝器的三口烧瓶中加入3.65克甲基苯基二甲氧基硅烷(0.02mol)、10克N，N-二甲基乙酰胺、2.16克二苯基硅二醇(0.01mol)搅拌均匀，在0℃下加入0.02克液氨，反应18小时，得中间体2，将中间体2全部加入到中间体1中，加入水9.00克(0.50mol)，在0℃下反应15小时；然后将所得混合物用盐酸中和，加入20mL甲苯，水洗分离减压浓缩，得到式(1)结构的硅氧烷桥基硅烷封端硅氧烷桥基梯形聚硅氧烷，其中R 1＝R 2＝R 3＝R 4＝R 7＝R 8为苯基，R 5＝R 6＝R 9＝R 10为甲基，A 1-A 6为苯基，m＝1，n＝80，所得产率为92％。
所得的硅氧烷桥基硅烷封端硅氧烷桥基梯形聚硅氧烷为无色透明固体，聚合度n的平均值为80，折光率为1.57(25℃)，玻璃化转变温度为39.45℃，230℃、50rpm转速下黏度为2430泊(poise)。耐空气热氧化性分别为：其羟基封端梯形聚合物4HO-blocked Ph-SLPS在400℃×15h不变色和不交联；而相应单官能硅烷(如二苯基甲基硅烷基)封端硅氧烷桥基梯形聚硅氧烷MePh 2SiO-I-blocked Ph-SLPS在400℃×15h不交联不变色。而相应甲基苯基硅氧烷桥基硅烷封端硅氧烷桥基梯形聚硅氧烷PhMe-I-Ph-SLPS显示出更佳性能在400℃×20h不交联不变色。 1H NMR(400MHz，CDCl 3，298K)：δ-0.06-0.11，7.14-7.53ppm； 29Si NMR(80MHz，CDCl 3，298K)：δ-80.02，-43.96，-27.23ppm。
实施例3：Ph 2-I-Me-SLPS合成
通过甲基三甲氧基硅烷、二苯基二甲氧基硅烷和二苯基硅二醇制备硅氧烷桥基硅烷封端硅氧烷桥基梯形聚硅氧烷。
在干燥的氮气保护下将27.2克甲基三甲氧基硅烷(0.20mol)、21.6克二苯基硅二醇(0.10mol)以及20克三氯甲烷置于装有机械搅拌、恒压滴液漏斗及回流冷凝器的三口烧瓶中，室温搅拌均匀，在-10℃下加入0.08克四丁基氢氧化膦，反应8小时得中间体1；同时在另一个有 干燥的氮气保护装有机械搅拌、恒压滴液漏斗及回流冷凝器的三口烧瓶中加入48.9克二苯基二甲氧基硅烷(0.20mol)、40克三氯甲烷、21.6克二苯基硅二醇(0.10mol)搅拌均匀，在5℃下加入0.3克四丁基氢氧化膦，反应24小时，得中间体2，将中间体2全部加入到中间体1中，加入水10.8克(0.60mol)，在5℃下反应15小时；然后将所得混合物用盐酸中和，加入60mL甲苯，水洗分离减压浓缩，得到式(1)结构的硅氧烷桥基硅烷封端硅氧烷桥基梯形聚硅氧烷，其中R 1＝R 2为甲基，R 3-R 10为苯基，A 1-A 6为苯基，m＝1，n＝12，所得产率为96％。
所得的硅氧烷桥基硅烷封端硅氧烷桥基梯形聚硅氧烷无色透明固体，聚合度n的平均值为12，折光率为1.55(25℃)，玻璃化转变温度为34.31℃，230℃、100rpm转速下黏度为973泊(Poise)。耐空气热氧化性分别为：其羟基封端梯形聚合物4HO-blocked Me-SLPS在300℃×15h不变色和不交联；而相应单官能硅烷(如二苯基甲基硅烷基)封端硅氧烷桥基梯形聚硅氧烷MePh 2SiO-I-blocked Me-SLPS在300℃×15h不交联不变色。而相应二苯基硅氧烷桥基硅烷封端硅氧烷桥基梯形聚硅氧烷Ph 2-I-Me-SLPS显示出更佳性能在300℃×24h不交联不变色。 1H NMR(400MHz，CDCl 3，298K)：δ-0.06-0.12，7.14-7.53ppm； 29Si NMR(80MHz，CDCl 3，298K)：δ-65.28，-43.35ppm。
实施例4：PhMe-I-Me-SLPS合成
通过甲基三甲氧基硅烷、甲基苯基二甲氧基硅烷和二苯基硅二醇制备硅氧烷桥基硅烷封端硅氧烷桥基梯形聚硅氧烷。
在干燥的氮气保护下将27.2克甲基三甲氧基硅烷(0.20mol)、21.6克二苯基硅二醇(0.10mol)以及20克N，N-二甲基甲酰胺置于装有机械搅拌、恒压滴液漏斗及回流冷凝器的三口烧瓶中，室温搅拌均匀，在-10℃下加入0.10克乙醇胺，反应8小时得中间体1；同时在另一个有干燥的氮气保护装有机械搅拌、恒压滴液漏斗及回流冷凝器的三口烧瓶中加入0.81克甲基苯基二甲氧基硅烷(0.0044mol)、2克N，N-二 甲基甲酰胺、0.476克二苯基硅二醇(0.0022mol)搅拌均匀，在0℃下加入0.02克乙醇胺，反应18小时，得中间体2，将中间体2全部加入到中间体1中，加入水7.2克(0.40mol)，在-5℃下反应5小时再抽真空反应12小时；然后将所得混合物用盐酸中和，加入40mL甲苯，水洗分离减压浓缩，得到式(1)结构的硅氧烷桥基硅烷封端硅氧烷桥基梯形聚硅氧烷，其中R 1＝R 2＝R 5＝R 6＝R 9＝R 10为甲基，R 3＝R 4＝R 7＝R 8为苯基，A 1-A 6为苯基，m＝1，n＝80，所得产率为94％。
所得的硅氧烷桥基硅烷封端硅氧烷桥基梯形聚硅氧烷无色透明固体，聚合度n的平均值为80，折光率为1.54(25℃)，玻璃化转变温度为28.51℃，230℃、50rpm转速下黏度为365泊(Poise)。耐空气热氧化性分别为：其羟基封端梯形聚合物4HO-blocked Me-SLPS在300℃×15h不变色和不交联；而相应单官能硅烷(如二甲基苯基硅烷基)封端硅氧烷桥基梯形聚硅氧烷Me 2PhSiO-I-blocked Me-SLPS在300℃×15h不交联不变色。而相应甲基苯基硅氧烷桥基硅烷封端硅氧烷桥基梯形聚硅氧烷PhMe-I-Me-SLPS显示出更佳性能在300℃×24h不交联不变色。 1H NMR(400MHz，CDCl 3，298K)：δ-0.06-0.12，7.14-7.53ppm； 29Si NMR(80MHz，CDCl 3，298K)：δ-64.32，-43.02，-28.73ppm。
实施例5：MeEpoxy-I-Ph-SLPS合成
通过苯基三甲氧基硅烷、3-((2，3)-环氧丙氧)丙基甲基二乙氧基硅烷和二苯基硅二醇制备硅氧烷桥基硅烷封端硅氧烷桥基梯形聚硅氧烷。
在干燥的氮气保护下将39.7克苯基三甲氧基硅烷(0.20mol)、21.6克二苯基硅二醇(0.10mol)以及10克丙酮置于装有机械搅拌、恒压滴液漏斗及回流冷凝器的三口烧瓶中，室温搅拌均匀，在0℃下加入0.3克苯乙烯二乙烯苯共聚物为基体的氨水，反应15小时得中间体1；同时在另一个有干燥的氮气保护装有机械搅拌、恒压滴液漏斗及回流冷凝器的三口烧瓶中加入23.6克3-((2，3)-环氧丙氧)丙基甲基二乙 氧基硅烷(0.10mol)、20克丙酮、10.8克二苯基硅二醇(0.05mol)搅拌均匀，在10℃下加入0.60克氨水，反应20小时，得中间体2，将中间体2全部加入到中间体1中，加入水27.0克(1.50mol)，在0℃下反应20小时；然后将所得混合物用盐酸中和，加入40ml甲苯，水洗分离减压浓缩，得到式(1)结构的硅氧烷桥基硅烷封端硅烷桥基梯形聚硅氧烷，其中R 1＝R 2为苯基，R 3＝R 4＝R 7＝R 8为甲基，R 5＝R 6＝R 9＝R 10为3-((2，3)-环氧丙氧)丙基，A 1-A 6为苯基，m＝1，n＝34，所得产率为92％。
所得的硅氧烷桥基硅烷封端硅氧烷桥基梯形聚硅氧烷无色透明固体，聚合度n的平均值为34，折光率为1.56(25℃)，玻璃化转变温度为40.28℃。TGA测得5％热分解温度为400℃。230℃、30rpm转速下黏度为8550泊(Poise)。 1H NMR(400MHz，CDCl 3，298K)：δ-0.06-0.12，0.21-0.44，1.41-1.73，2.52-3.64，7.02-7.53ppm； 29Si NMR(80MHz，CDCl 3，298K)：δ-78.6，-45.16，-17.87ppm。
实施例6：MeVi-I-Ph-SLPS合成
通过苯基三甲氧基硅烷、甲基乙烯基二甲氧基硅烷和二苯基硅二醇制备硅烷桥基硅烷封端硅氧烷桥基梯形聚硅氧烷。
在干燥的氮气保护下将39.7克苯基三甲氧基硅烷(0.20mol)、21.6克二苯基硅二醇(0.10mol)以及二乙二醇二甲醚30克置于装有机械搅拌、恒压滴液漏斗及回流冷凝器的三口烧瓶中，室温搅拌均匀，在-20℃下加入0.30克1，8-二氮杂双环[5.4.0]十一碳-7-烯，反应5小时得中间体1；同时在另一个有干燥的氮气保护装有机械搅拌、恒压滴液漏斗及回流冷凝器的三口烧瓶中加入8.8克甲基乙烯基二甲氧基硅烷(0.067mol)、40克二乙二醇二甲醚、7.2克二苯基硅二醇(0.033mol)搅拌均匀，在-20℃下加入0.30克1，8-二氮杂双环[5.4.0]十一碳-7-烯，反应12小时，得中间体2，将中间体2全部加入到中间体1中，加入水33.6克(1.86mol)，在0℃下反应15小时；然后将所得混合物用盐 酸中和，加入50mL甲苯水洗分离减压浓缩，得到式(1)结构的硅氧烷桥基硅烷封端硅氧烷桥基梯形聚硅氧烷，其中R 3＝R 4＝R 7＝R 8为乙烯基，R 1＝R 2为苯基，R 5＝R 6＝R 9＝R 10为甲基，A 1-A 6为苯基，m＝1，n＝6，所得产率为83％。
所得的硅氧烷桥基硅烷封端硅氧烷桥基梯形聚硅氧烷无色透明软固体，聚合度n的平均值为6，折光率为1.57(25℃)。玻璃化转变温度为28.83℃，对比产物二甲基乙烯基封端苯基均聚物的0.47℃。TGA测得5％热分解温度为390℃，对比产物二甲基乙烯基封端苯基均聚物的5％热分解温度为330℃。230℃、100rpm转速下黏度为1973泊(Poise)。 1H NMR(400MHz，CDCl 3，298K)：δ-0.06-0.13，5.51-6.02，7.01-7.56ppm； 29Si NMR(80MHz，CDCl 3，298K)：δ-78.27，-44.75，-32.76ppm。
实施例7：MeVi-I-Me-SLPS合成
通过甲基三甲氧基硅烷、甲基乙烯基二甲氧基硅烷和二苯基硅二醇制备硅氧烷桥基硅烷封端硅氧烷桥基梯形聚硅氧烷。
在干燥的氮气保护下将27.2克甲基三甲氧基硅烷(0.20mol)、21.6克二苯基硅二醇(0.10mol)以及环己烷20克置于装有机械搅拌、恒压滴液漏斗及回流冷凝器的三口烧瓶中，室温搅拌均匀，在-10℃下加入0.40克1，5-二氮杂双环[4.3.0]-5-壬烯，反应8小时得中间体1；同时在另一个有干燥的氮气保护装有机械搅拌、恒压滴液漏斗及回流冷凝器的三口烧瓶中加入21.9克甲基乙烯基二甲氧基硅烷(0.17mol)、30克二氧六环、18克二苯基硅二醇(0.083mol)搅拌均匀，在0℃下加入0.40克1，5-二氮杂双环[4.3.0]-5-壬烯，反应18小时，得中间体2，将中间体2全部加入到中间体1中，加入水18克(1.0mol)，加入20克二乙二醇二甲醚在0℃下反应15小时；然后将所得混合物用盐酸中和，加入35mL甲苯，水洗分离减压浓缩，得到式(1)结构的硅氧烷桥基硅烷封端硅氧烷桥基梯形聚硅氧烷，其中R 1＝R 2＝R 3＝R 4＝R 7＝R 8为甲 基，R 5＝R 6＝R 9＝R 10为乙烯基，A 1-A 6为苯基，m＝1，n＝12，所得产率为97％。
所得的硅氧烷桥基硅烷封端硅氧烷桥基梯形聚硅氧烷无色透明固体，聚合度n的平均值为12，折光率为1.53(25℃)，玻璃化转变温度为47.51℃。230℃、100rpm转速下黏度为718泊(Poise)。 1H NMR(400MHz，CDCl 3，298K)：δ-0.06-0.11，5.51-6.02，7.02-7.53ppm； 29Si NMR(80MHz，CDCl 3，298K)：δ-65.12，-44.47，-31.87ppm。
实施例8：MeEpoxy-I-Vi-SLPS合成
通过乙烯基三甲氧基硅烷、3-((2，3)-环氧丙氧)丙基甲基二乙氧基硅烷和二苯基硅二醇制备硅氧烷桥基硅烷封端硅氧烷桥基梯形聚硅氧烷。
在干燥的氮气保护下将29.7克乙烯基三甲氧基硅烷(0.20mol)、21.6克二苯基硅二醇(0.10mol)以及5克N，N-二甲基甲酰胺置于装有机械搅拌、恒压滴液漏斗及回流冷凝器的三口烧瓶中，室温搅拌均匀，在5℃下加入2克二乙醇胺，反应16小时得中间体1；同时在另一个有干燥的氮气保护装有机械搅拌、恒压滴液漏斗及回流冷凝器的三口烧瓶中加入4.97克3-((2，3)-环氧丙氧)丙基甲基二乙氧基硅烷(0.02mol)、10克N，N-二甲基甲酰胺、2.2克二苯基硅二醇(0.01mol)搅拌均匀，在10℃下加入0.40克二乙醇胺，反应18小时，得中间体2，将中间体2全部加入到中间体1中，加入水9克(0.50mol)，加入5克N，N-二甲基甲酰胺，在5℃下抽真空反应15小时；然后将所得混合物用甲酸中和，加入40mL甲苯，水洗分离减压浓缩，得到式(1)结构的硅氧烷桥基硅烷封端硅氧烷桥基梯形聚硅氧烷，其中R 1＝R 2为乙烯基，R 3＝R 4＝R 7＝R 8为甲基，R 5＝R 6＝R 9＝R 10为3-((2，3)-环氧丙氧)丙基，A 1-A 6为苯基，m＝1，n＝15，所得产率为77％。
所得的硅氧烷桥基硅氧烷封端硅氧烷桥基梯形聚硅氧烷为无色透 明固体，聚合度n的平均值为15，折光率为1.55(25℃)，玻璃化转变温度为34.66℃。230℃、50rpm转速下黏度为3701泊(Poise)。 1H NMR(400MHz，CDCl 3，298K)：δ-0.06-0.13，0.24-0.43，1.40-1.74，2.52-3.62，5.55-6.02，7.14-7.53ppm； 29Si NMR(80MHz，CDCl 3，298K)：δ-79.46，-44.87，-17.94ppm。
实施例9：MeAcryl-I-Me-SLPS合成
通过甲基三甲氧基硅烷、3-甲基丙烯酰氧基丙基甲基二甲氧基硅烷和二苯基硅二醇制备硅氧烷桥基硅烷封端硅氧烷桥基梯形聚硅氧烷。
在干燥的氮气保护下将27.2克甲基三甲氧基硅烷(0.20mol)、21.6克二苯基硅二醇(0.10mol)以及二氧六环25克置于装有机械搅拌、恒压滴液漏斗及回流冷凝器的三口烧瓶中，室温搅拌均匀，在-30℃下加入0.20克乙醇胺，反应16小时得中间体1；同时在另一个有干燥的氮气保护装有机械搅拌、恒压滴液漏斗及回流冷凝器的三口烧瓶中加入3.9克3-甲基丙烯酰氧基丙基甲基二甲氧基硅烷(0.017mol)、10克二氧六环、1.8克二苯基硅二醇(0.0083mol)搅拌均匀，在-20℃下加入0.04克乙醇胺，反应18小时，得中间体2，在-20℃下向中间体1中加入水12.6克(0.70mol)，将中间体2滴加入中间体1和水的混合液中，滴加3小时完毕继续反应10小时；然后将所得混合物用甲酸中和，加入50mL甲苯，水洗分离减压浓缩，得到式(1)结构的硅氧烷桥基硅烷封端硅氧烷桥基梯形聚硅氧烷，其中R 1＝R 2＝R 3＝R 4＝R 7＝R 8为甲基，R 5＝R 6＝R 9＝R 10为3-甲基丙烯酰氧基丙基，A 1-A 6为苯基，m＝1，n＝120，所得产率为87％。
所得的硅氧烷桥基硅氧烷封端硅烷桥基梯形聚硅氧烷为无色透明粘稠液体，聚合度n的平均值为120，折光率为1.53(25℃)，玻璃化转变温度为10.32℃。230℃、30rpm转速下黏度为9490泊(Poise)。 1H NMR(400MHz，CDCl 3，298K)：δ-0.06-0.11，-0.25-0.66，1.72-1.91， 5.51-5.53，5.98-6.04，7.02-7.53ppm； 29Si NMR(80MHz，CDCl 3，298K)：δ-65.02，-45.15，-17.94ppm。
实施例10：Me 2-I-Ph/Acryl-SLPS合成
通过3-(甲基丙烯酰氧)丙基三甲氧基硅烷、苯基三甲氧基硅烷、二甲基二甲氧基硅烷和二苯基硅二醇制备硅氧烷桥基硅烷封端硅氧烷桥基梯形聚硅氧烷。
在干燥的氮气保护下将19.8克苯基三甲氧基硅烷(0.10mol)、24.8克3-(甲基丙烯酰氧)丙基三甲氧基硅烷(0.10mol)、21.6克二苯基硅二醇(0.10mol)以及40克二乙二醇二甲醚置于装有机械搅拌、恒压滴液漏斗及回流冷凝器的三口烧瓶中，室温搅拌均匀，在-20℃下加入0.20克四甲基氢氧化铵，反应14小时得中间体1；同时在另一个有干燥的氮气保护装有机械搅拌、恒压滴液漏斗及回流冷凝器的三口烧瓶中加入0.15克二甲基二甲氧基硅烷(0.0012mol)、5克二乙二醇二甲醚、0.14克二苯基硅二醇(0.00062mol)搅拌均匀，在-20℃下加入0.02克四甲基氢氧化胺，反应18小时，得中间体2，将中间体2全部加入到中间体1中，加入水9克(0.50mol)，在-20℃下反应5小时；然后将所得混合物用盐酸中和，加入80mL甲苯，水洗分离减压浓缩，得到式(1)结构的硅氧烷桥基硅烷封端硅氧烷桥基梯形聚硅氧烷，其中R 1为3-(甲基丙烯酰氧)丙基，R 2为苯基，R 3＝R 4＝R 7＝R 8＝R 5＝R 6＝R 9＝R 10为甲基，A 1-A 6为苯基，m＝1，n＝300，所得产率为87％。
所得的硅氧烷桥基硅烷封端硅氧烷桥基梯形聚硅氧烷为无色透明粘稠液体，聚合度n的平均值为300，折光率为1.53(25℃)，玻璃化转变温度为-12.34℃。230℃、100rpm转速下黏度为61.62泊(Poise)。 1H NMR(400MHz，CDCl 3，298K)：δ-0.06-0.11，0.64-0.66，1.72-1.91，5.51-5.53，5.99-6.03，7.02-7.53ppm； 29Si NMR(80MHz，CDCl 3，298K)：δ-79.22，-64.85，-45.21，-18.02ppm。
实施例11：Ph 2-I-Vi/Epoxy-SLPS合成
通过3-((2，3)-环氧丙氧)丙基三甲氧基硅烷、乙烯基三甲氧基硅烷、二苯基二甲氧基硅烷和二苯基硅二醇制备硅氧烷桥基硅烷封端硅氧烷桥基梯形聚硅氧烷。
在干燥的氮气保护下将14.82克苯基三甲氧基硅烷(0.10mol)、23.6克3-((2，3)-环氧丙氧)丙基三甲氧基硅烷(0.10mol)、21.6克二苯基硅二醇(0.10mol)以及10克四氢呋喃置于装有机械搅拌、恒压滴液漏斗及回流冷凝器的三口烧瓶中，室温搅拌均匀，在0℃下加入0.70克DBN，反应10小时得中间体1；同时在另一个有干燥的氮气保护装有机械搅拌、恒压滴液漏斗及回流冷凝器的三口烧瓶中加入0.92克二苯基二甲氧基硅烷(0.0038mol)、2克三氯甲烷、0.40克二苯基硅二醇(0.0019mol)搅拌均匀，在0℃下加入0.02克DBN反应18小时，得中间体2，将中间体2全部加入到中间体1中，加入水8克(0.44mol)，在-10℃下反应15小时；然后将所得混合物用盐酸中和，加入30mL甲苯，水洗分离减压浓缩，得到式(1)结构的硅氧烷桥基硅烷封端硅氧烷桥基梯形聚硅氧烷，其中R 1为3-((2，3)-环氧丙氧)丙基，R 2为乙烯基，R 3＝R 4＝R 7＝R 8＝R 5＝R 6＝R 9＝R 10为苯基，A 1-A 6为苯基，m＝1，n＝90，所得产率为80％。
所得的硅氧烷桥基硅烷封端硅烷桥基梯形聚硅氧烷无色透明粘稠液体，聚合度n的平均值为90，折光率为1.55(25℃)，玻璃化转变温度为-3.4℃。230℃、100rpm转速下黏度为94.54泊(Poise)。 1H NMR(400MHz，CDCl 3，298K)：δ-0.04-0.13，0.20-0.41，1.40-1.73，2.52-3.64，7.02-7.53ppm； 29Si NMR(80MHz，CDCl 3，298K)：δ-78.72，-64.18，-45.28ppm。
实施例12：MePh-I-AE/AP-SLPS
通过N-(2-氨乙基)-3-氨丙基三甲氧基硅烷、甲基苯基二甲氧基硅烷和HO(Ph 2SiO) 2H制备硅氧烷桥基硅烷封端硅氧烷桥基梯形聚硅氧 烷。
在干燥的氮气保护下将44.5克N-(2-氨乙基)-3-氨丙基三甲氧基硅烷(0.20mol)、41.4克HO(Ph 2SiO) 2H(0.10mol)以及40克四氢呋喃置于装有机械搅拌、恒压滴液漏斗及回流冷凝器的三口烧瓶中，室温搅拌均匀，在0℃下加入0.20克吡啶，反应6小时得中间体1；同时在另一个有干燥的氮气保护装有机械搅拌、恒压滴液漏斗及回流冷凝器的三口烧瓶中加入11.5克甲基苯基二甲氧基硅烷(0.063mol)、20克四氢呋喃、12.9克HO(Ph 2SiO) 2H(0.031mol)搅拌均匀，在0℃下加入0.20克三乙醇胺，反应13小时，得中间体2，将中间体2全部加入到中间体1中，加入水9克(0.50mol)，在-10℃下反应15小时；然后将所得混合物用盐酸中和，加入40mL甲苯，水洗分离减压浓缩，得到式(1)结构的硅氧烷桥基硅烷封端硅氧烷桥基梯形聚硅氧烷，其中R 1＝R 2为N-(2-氨乙基)-3-氨丙基，R 3＝R 4＝R 7＝R 8为甲基，R 5＝R 6＝R 9＝R 10为苯基，A 1-A 6为苯基，m＝2，n＝320，所得产率为86％。
所得的硅氧烷桥基硅烷封端硅氧烷桥基梯形聚硅氧烷无色透明粘稠液体，聚合度n的平均值为320，折光率为1.53(25℃)，玻璃化转变温度为-37.3℃。230℃、100rpm转速下黏度为32.65泊(Poise)。 1H NMR(400MHz，CDCl 3，298K)：δ-0.04-0.13，1.15-1.22，2.52-2.58，3.70-3.85，7.02-7.53ppm； 29Si NMR(80MHz，CDCl 3，298K)：δ-64.67，-44.81，-28.65ppm。
实施例13：MeEpoxy-I-Pr-SLPS合成
通过丙基三甲氧基硅烷、3-((2，3)-环氧丙氧)丙基甲基二乙氧基硅烷、二甲基二甲氧基硅烷和二苯基硅二醇制备硅氧烷桥基硅烷封端硅氧烷桥基梯形聚硅氧烷。
在干燥的氮气保护下将32.9克丙基三甲氧基硅烷(0.20mol)、21.6克二苯基硅二醇(0.10mol)以及10克二氧六环置于装有机械搅拌、恒 压滴液漏斗及回流冷凝器的三口烧瓶中，室温搅拌均匀，在-5℃下加入0.20克三乙胺，反应12小时得中间体1；同时在另一个有干燥的氮气保护装有机械搅拌、恒压滴液漏斗及回流冷凝器的三口烧瓶中加入3.3克3-((2，3)-环氧丙氧)丙基甲基二乙氧基硅烷(0.013mol)、1.6克二甲基二甲氧基硅烷(0.013mol)和2.9克二苯基硅二醇(0.013mol)、10克二氧六环搅拌均匀，在-5℃下加入0.2克三乙胺，反应16小时，得中间体2，将中间体2全部加入到中间体1中，加入水12.6克(0.70mol)，在0℃下反应10小时；然后将所得混合物用盐酸中和，加入30mL甲苯，水洗分离减压浓缩，得到式(1)结构的硅氧烷桥基硅烷封端硅氧烷桥基梯形聚硅氧烷，其中R 1＝R 2为丙基，R 3＝R 4＝R 5＝R 7＝R 8＝R 9为甲基，R 6＝R 10为3-((2，3)-环氧丙氧)丙基，A 1-A 6为苯基，m＝1，n＝75，所得产率为89％。
所得的硅氧烷桥基硅烷封端硅氧烷桥基梯形聚硅氧烷为无色透明固体，聚合度n的平均值为75，折光率为1.53(25℃)，玻璃化转变温度为27.54℃。230℃、30rpm转速下黏度为8490泊(Poise)。 1H NMR(400MHz，CDCl 3，298K)：δ-0.04-0.13，0.19-0.41，1.42-1.74，2.52-3.64，7.01-7.57ppm； 29Si NMR(80MHz，CDCl 3，298K)：δ-64.85，-45.24，-18.32ppm。
实施例14：Ph 2-I-Me-SLBuS合成
通过甲基三甲氧基硅烷、二苯基二甲氧基硅烷和二异丁基硅二醇制备硅氧烷桥基硅烷封端硅氧烷桥基梯形聚硅氧烷。
在干燥的氮气保护下将27.2克甲基三甲氧基硅烷(0.20mol)、17.6克二异丁基硅二醇(0.10mol)以及20克三氯甲烷置于装有机械搅拌、恒压滴液漏斗及回流冷凝器的三口烧瓶中，室温搅拌均匀，在-20℃下加入0.08克液氨，反应6小时得中间体1；同时在另一个有干燥的氮气保护装有机械搅拌、恒压滴液漏斗及回流冷凝器的三口烧瓶中加入48.9克二苯基二甲氧基硅烷(0.20mol)、40克三氯甲烷、17.6克二异 丁基硅二醇(0.10mol)搅拌均匀，在0℃下加入0.30克液氨，反应20小时，得中间体2，将中间体2全部加入到中间体1中，加入水10.8克(0.60mol)，在0℃下反应10小时；然后将所得混合物用盐酸中和，加入40mL甲苯，水洗分离减压浓缩，得到式(1)结构的硅氧烷桥基硅烷封端硅氧烷桥基梯形聚硅氧烷，其中R 1＝R 2为甲基，R 3-R 10为苯基，A 1-A 6为异丁基，m＝1，n＝12，所得产率为94％。
所得的硅氧烷桥基硅烷封端硅氧烷桥基梯形聚硅氧烷无色透明固体，聚合度n的平均值为12，折光率为1.52，玻璃化转变温度为14.82℃，210℃、100rpm转速下黏度为345泊(Poise)。 1H NMR(400MHz，CDCl 3，298K)：δ-0.06-0.12，0.89-1.02，1.52-1.71，7.12-7.51ppm； 29Si NMR(80MHz，CDCl 3，298K)：δ-63.28，-44.23，-21.25ppm。
实施例15：Me 2-I-Me-SLPrS合成
通过甲基三甲氧基硅烷、二甲基二甲氧基硅烷和二丙基硅二醇制备硅氧烷桥基硅烷封端硅氧烷桥基梯形聚硅氧烷。
在干燥的氮气保护下将27.2克甲基三甲氧基硅烷(0.20mol)、14.8克二丙基硅二醇(0.10mol)以及15克N，N-二甲基甲酰胺置于装有机械搅拌、恒压滴液漏斗及回流冷凝器的三口烧瓶中，室温搅拌均匀，在-10℃下加入0.10克DBU，反应10小时得中间体1；同时在另一个有干燥的氮气保护装有机械搅拌、恒压滴液漏斗及回流冷凝器的三口烧瓶中加入0.53克二甲基苯基二甲氧基硅烷(0.0044mol)、2克N，N-二甲基甲酰胺、0.33克二丙基硅二醇(0.0022mol)搅拌均匀，在0℃下加入0.02克DBU，反应20小时，得中间体2，将中间体2全部加入到中间体1中，加入水7.2克(0.40mol)，然后将所得混合物用盐酸中和，加入40mL甲苯，水洗分离减压浓缩，得到式(1)结构的硅氧烷桥基硅烷封端硅氧烷桥基梯形聚硅氧烷，其中R 1-R 10为甲基，A 1-A 6为丙基，m＝1，n＝450，所得产率为92％。
所得的硅氧烷桥基硅烷封端硅氧烷桥基梯形聚硅氧烷无色透明固体，聚合度n的平均值为450，折光率为1.52(25℃)，玻璃化转变温度为13.51℃，210℃、50rpm转速下黏度为134泊(Poise)。 1H NMR(400MHz，CDCl 3，298K)：δ-0.06-0.11ppm； 29Si NMR(80MHz，CDCl 3，298K)：δ-56.43，-21.73ppm。
以上参考特定的实施方式和实施例对本申请发明进行了详细说明，但是对于本领域技术人员来说，在不脱离本申请发明的本质和主旨特征的范围内，可以对上述实施方式和实施例进行各种变更、修正、替换等来实施。通过变更、修正、替换而得到的实施方式也均在本申请发明的保护范围内。

Claims (10)

  1. 一种硅氧烷桥基硅烷封端的硅氧烷桥基梯形聚硅氧烷，其特征在于，所述硅氧烷桥基梯形聚硅氧烷具有以下式(1)所示分子结构：
    Figure PCTCN2018115548-appb-100001
    其中：
    m为1-10的整数，
    n为1-1000的整数，
    A 1、A 2、A 3、A 4、A 5、A 6分别独立地选自氢、取代或未取代的直链、支链或环状C 1-25烷基、取代或未取代的直链、支链或环状C 2-25烯基、取代或未取代的C 5-25芳基，
    R 1、R 2、R 3、R 4、R 5、R 6、R 7、R 8、R 9、R 10分别独立地选自氢、羟基、取代或未取代的直链、支链或环状C 1-25烷基、取代或未取代的直链、支链或环状C 2-25烯基、取代或未取代的C 5-25芳基、取代或未取代的直链、支链或环状C 1-25烷氧基、取代或未取代的C 5-25芳氧基，
    在上述基团具有取代基时，所述取代基为选自如下的至少一种：直链、支链或环状的C 1-25烷基、直链、支链或环状的C 2-25烯基、C 5-25芳基、含有选自氧原子、硫原子、氮原子和磷原子中的至少一个原子的基团、卤素原子，
    上述烷基、烷氧基、烯基、芳基、芳氧基各自在链中或环中可以具有至少一个选自由O、S、P、N构成的组中的杂原子作为链构成原子或环构成原子。
  2. 根据权利要求1所述的硅氧烷桥基硅烷封端的硅氧烷桥基梯形聚硅氧烷，其特征在于，
    所述含有选自氧原子、硫原子、氮原子和磷原子中的至少一个原子的基团选自羟基、环氧丙氧基、C 5-25环氧环烷基、丙烯酰氧基、C 1-25烷基取代的丙烯酰氧基、巯基、氨基、氨基-直链、支链或环状的C 1-25烷基、C 6-25芳基氨基、氰基、脲基、膦基。
  3. 根据权利要求1所述的硅氧烷桥基硅烷封端的硅氧烷桥基梯形聚硅氧烷，其特征在于，所述R 1、R 2、R 3、R 4、R 5、R 6、R 7、R 8、R 9、R 10、A 1、A 2、A 3、A 4、A 5、A 6分别独立地选自氢、羟基、甲基、乙基、正丙基、异丙基、正丁基、异丁基、叔丁基、正己基、环己基、正辛基、正癸基、正十二烷基、正十六烷基、正十八烷基、正二十二烷基、乙烯基、烯丙基、苯基、甲基苯基、氯代苯基、对乙烯基苯基、3-(2，3-环氧丙氧基)丙基、2-(3，4-环氧环己基)乙基、丙烯酰氧基丙基、3-甲基丙烯酰氧基丙基、巯丙基、氨丙基、3-(2-氨乙基)-氨丙基、4-氨基-3，3-二甲基丁基、N-正丁基-3-氨基丙基、2-氰基乙基、3-氰基丙基、3，3，3-三氟丙基、1H，1H，2H，2H-全氟辛基、1H，1H，2H，2H-全氟癸基、氯丙基、脲丙基、甲氧基、乙氧基中的一种。
  4. 一种根据权利要求1所述的硅氧烷桥基硅烷封端的硅氧烷桥基梯形聚硅氧烷的制备方法，其特征在于，四官能工字型硅氧烷桥基硅氧烷单体与双官能工字型硅氧烷桥基硅烷封端剂共水解，依靠超分子弱键协同作用形成梯形超结构来调控聚合与封端反应而得到式(1)结构的硅氧烷桥基硅烷封端的硅氧烷桥基梯形聚硅氧烷。
  5. 根据权利要求4所述的硅氧烷桥基硅烷封端的硅氧烷桥基梯形聚硅氧烷制备方法，其特征在于包含以下步骤：
    在反应器中加入结构式(2)、(3)和(4)的硅烷，有机溶剂、水和催化剂进行水解和缩合反应，同时可持续或间断地抽真空，去除缩合副产物；之后将反应所得产物分离提纯，得到上述式(1)结构的 硅氧烷桥基硅烷封端的硅氧烷桥基梯形聚硅氧烷，
    所述的四官能工字型单体结构式(2)表示
    Figure PCTCN2018115548-appb-100002
    其中，
    m、R 1、R 2、A 1、A 2的含义各自与权利要求1中的含义相同；
    X为选自OH、卤素、C 1-25烷氧基或C 1-25酰氧基中的一种；
    所述二官能工字型硅烷封端剂结构式(3)表示
    Figure PCTCN2018115548-appb-100003
    其中，
    m、R 3、R 4、R 5、R 6、A 3、A 4的含义各自与权利要求1中的含义相同；
    X为选自OH、卤素、C 1-25烷氧基或C 1-25酰氧基中的一种；
    所述二官能工字型硅烷封端剂结构式(4)表示
    Figure PCTCN2018115548-appb-100004
    其中，
    m、R 7、R 8、R 9、R 10、A 5、A 6的含义各自与权利要求1中的含义相同；
    X为选自OH、卤素、C 1-25烷氧基或C 1-25酰氧基中的一种。
  6. 根据权利要求5所述的硅氧烷桥基硅烷封端的硅氧烷桥基梯形聚硅氧烷制备方法，其特征在于，
    所述式(2)的四官能工字型单体是由三官能硅烷偶联剂与硅二醇在催化剂存在下缩合制备，
    所述三官能硅烷偶联剂由式-RSiX 3表示，
    式中，R＝R 1，R 2；X＝卤素、C 1-25烷氧基、C 1-25酰氧基。
  7. 根据权利要求5所述的硅氧烷桥基硅烷封端的硅氧烷桥基梯形聚硅氧烷制备方法，其特征在于，
    所述式(3)的二官能工字型硅烷封端剂由双官能硅烷偶联剂与硅二醇在催化剂存在下缩合制备，
    所述双官能硅烷偶联剂由式R’R”SiX 2表示，
    式中，R’、R”＝R 3与R 5组合、R 4与R 6组合；X＝卤素、C 1-25烷氧基、C 1-25酰氧基；
    所述式(4)的二官能工字型硅烷封端剂由双官能硅烷偶联剂与硅二醇在催化剂存在下缩合制备，
    所述双官能硅烷偶联剂由式R’R”SiX 2表示，
    式中，R’、R”＝R 7与R 9组合、R 8与R 10组合；X＝卤素、C 1-25烷氧基、C 1-25酰氧基。
  8. 根据权利要求5所述的硅氧烷桥基硅烷封端的硅氧烷桥基梯形聚硅氧烷制备方法，其特征在于所述的反应温度为-50℃至150℃；所述水解和缩合反应温度为-50℃至50℃；封端反应温度前期为-50℃至50℃，后期为封端完全反应温度可升至100℃。
  9. 根据权利要求5所述硅氧烷桥基硅烷封端的硅氧烷桥基梯形聚硅氧烷制备方法，其特征在于，所述有机溶剂为选自：烷烃类、取代烷烃类、醇类、醚类、酮类、酯类、酰胺类、腈类、吡咯烷酮类、亚砜类中的一种或几种。
  10. 根据权利要求5所述硅氧烷桥基硅烷封端的硅氧烷桥基梯形聚硅氧烷制备方法，其特征在于，
    所述催化剂为选自酸、氧化物和氢氧化物、氨或胺类、过渡金属化合物、离子交换树脂中的一种或几种。
PCT/CN2018/115548 2017-11-17 2018-11-15 硅氧烷桥基硅烷封端的硅氧烷桥基梯形聚硅氧烷及其制备方法 WO2019096188A1 (zh)

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