CN107880267A - Siloxanes abutting ladder poly-siloxane of siloxane bridge base silane end-blocking and preparation method thereof - Google Patents

Siloxanes abutting ladder poly-siloxane of siloxane bridge base silane end-blocking and preparation method thereof Download PDF

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CN107880267A
CN107880267A CN201711146924.2A CN201711146924A CN107880267A CN 107880267 A CN107880267 A CN 107880267A CN 201711146924 A CN201711146924 A CN 201711146924A CN 107880267 A CN107880267 A CN 107880267A
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siloxane
siloxanes
formula
bridge base
silane
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CN107880267B (en
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潘赏
曹菁
张榕本
方世壁
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CHANGXING (CHINA) INVESTMENT CO LTD
Institute of Chemistry CAS
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CHANGXING (CHINA) INVESTMENT CO LTD
Institute of Chemistry CAS
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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

Abstract

The present invention relates to siloxanes abutting ladder poly-siloxane of siloxane bridge base silane end-blocking and preparation method thereof.The present invention provides siloxanes abutting ladder poly-siloxane of siloxane bridge base silane (i.e. the I-shaped silane of difunctionality) end-blocking and preparation method thereof.By by the I-shaped silica abutment siloxanyl monomers of tetrafunctional and the I-shaped siloxane bridge base silane end-capping reagent cohydrolysis of difunctionality, act synergistically to form trapezoidal superstructure to regulate and control the polymerization of hydrolysate and end capping reaction by supermolecule weak bond, obtain the siloxanes abutment end-blocking ladder polysiloxane with below general formula.Compared with general simple function endcapped siloxanes abutting ladder poly-siloxane, the degree of polymerization and end-blocking completeness of this I-shaped Silante terminated ladder polysiloxane of difunctionality can be effectively controlled.The polymer has excellent heat resistance, good mechanical property and the compatibility good with general organic polymer.And this end-blocking mode is raw materials used simple and easy to get, and cost is cheap, suitable for industrialization.

Description

The siloxanes abutting ladder poly-siloxane of siloxane bridge base silane end-blocking and its preparation Method
Technical field
The present invention relates to siloxanes abutting ladder poly-siloxane, more particularly to siloxane bridge base silane endcapped siloxanes abutment Ladder polysiloxane and preparation method thereof.
Background technology
General trapezoidal organosilicon polymer has the trapezium structure of double-strand.Although its trapezoidal main chain can be sent out by external influence Raw fracture, but for statistics, it is seldom in upper and lower two possibilities that are single-stranded while being broken of same ladder brace.Therefore Shown compared with general single-stranded organosilicon polymer in terms of heat-resisting, radiation hardness, chemically-resistant, mechanics and biological agent more excellent Performance.
The difference of its abutment structure of the basis for development of trapezoidal organopolysiloxane is divided into three phases：First on behalf of oxygen bridge base Ladder polysiloxane (i.e. ladder-like polysiloxane, English write a Chinese character in simplified form R-LPSQ, and R represents side base)；Second on behalf of organic abutment ladder Shape polysiloxanes (English writes a Chinese character in simplified form R-OLPS, and R represents side base)；The third generation is that (English writes a Chinese character in simplified form R- to silica abutting ladder poly-siloxane SLPS, R represent side base).
Early in nineteen sixty, the former Soviet Union K.A.Andrianov et.al (Izu.Akad.Nauk.S.S.S.R., Otdel Khim.Nauk, 1960,1266) synthesis benzene abutting ladder poly-siloxane (Ph-OLPS) is once attempted, fail, only obtain random Oligomer.The same year, R-SLPS U.S. J.F.Brown et.al (J.Am.Chem.Soc.1960,82,6194) have reported use " balance thermal polycondensation " method has synthesized trapezoid polyphenylsilsesquioxane (Ph-LPSQ).Cause very big bang in the world immediately It is dynamic, and there is the article and patent of the ladder-like polysiloxane for being largely related to different side bases.But the U.S. in 1971 C.L.Frey etc. writes text and denies the presence of above-mentioned trapezoid polyphenylsilsesquioxane, it is indicated that actually polymerisation and not up to flat Weighing apparatus, product is the polycyclic cage (J.Am.Chem.Soc.1971,93,4599) of part open loop.Since then, the American-European chemical core phase Periodical no longer delivers the article about ladder polysiloxane.Since nineteen eighty-three, Zhang Rongben groups use supramolecular chemistry method first It has been respectively synthesized oxygen abutting ladder poly-siloxane R-LPSQ (international monopoly WO2010034161-A1； Angew.Chem.Int.Ed.2006,45,3112 and Chem.Commun.2009,4079) and organic abutment trapezoidal poly- silica Alkane R-OLPS (Chinese patent CN 1280995A, United States Patent (USP) US6423772B1；J.Am.Chem.Soc.2002,124, 10482).In general, oxygen bridge base ladder-like polysiloxane heat resistance is more preferable, dissolves in certain solvent, but its Body flexility is poor, using being restricted.And organic abutting ladder poly-siloxane is flexible compared with oxygen bridge base ladder-like polysiloxane Property increase, it is and good with general organic polymer compatibility, it is favourable to improving organic polymer performance, but heat resistance is slightly It is inferior to oxygen bridge base ladder-like polysiloxane.2014, the group disclosed siloxanes abutting ladder poly-siloxane homopolymer R- SLPS and preparation method thereof (Chinese patent CN10404583B).This siloxanes abutting ladder poly-siloxane has above-mentioned two class The advantages of ladder polysiloxane-excellent heat resistance, good mechanical property, with good compatible of other organic macromolecules Property.These features become the representative of the ladder polysiloxane of new generation of high comprehensive performance.But it presently, there are following ask Topic, including：General end-capping reagent used is monofunctional silanes' (such as trimethylsiloxy group), is restricted its heat resistance；End-blocking It is not easy completely；And the degree of polymerization is difficult to control；In addition the structure of this kind of end-capping reagent is single, the factor such as expensive cause it is actual should With facing many difficulties.Siloxane bridge base silane endcapped siloxanes abutting ladder poly-siloxane of the present invention is than simple function silicon Alkane endcapped siloxanes abutting ladder poly-siloxane has more excellent heat resistance, for example, its hydroxy-end capped ladder polymer 4HO-blockedPh-SLPS is non-discolouring and be not crosslinked in 400 DEG C × 15h, turns into the general polysiloxanes of reported in literature so far most High resistance to dsc data, corresponding monofunctional silanes' (such as diphenylmethylsilane base) endcapped siloxanes abutting ladder poly-siloxane MePh2It is non-discolouring that SiO-blocked Ph-SLPS also show that better performance is not crosslinked in 400 DEG C × 15h.And corresponding diphenyl Siloxane bridge base silane endcapped siloxanes abutting ladder poly-siloxane Ph2- I-Ph-SLPS show more best performance 400 DEG C × 24h is not crosslinked non-discolouring.And due to being not easy to escape in high vacuum conditions using higher boiling difunctional silane end-capping reagent, make envelope End is more complete.Ladder can effectively be controlled by the mole ratio for adjusting the I-shaped end-capping reagent of difunctionality and the I-shaped monomer of tetrafunctional The degree of polymerization of shape polymer.This double functionary-enterprise's font end-capping reagents, raw material are easy to get, and expand the diversity of end group, and operative employee Skill simplifies, and cost declines, industrialization of being more convenient for.
The content of the invention
An object of the present invention is to provide a kind of siloxane bridge base silane endcapped siloxanes abutting ladder poly-siloxane, Wherein, the siloxanes abutting ladder poly-siloxane has with following formula (1) molecular structure：
Wherein：
M is 1-10 integer,
N is 1-1000 integer,
A1、A2、A3、A4、A5、A6Separately it is selected from hydrogen, substituted or unsubstituted straight chain, side chain or ring-type C1-25Alkane Base, substituted or unsubstituted straight chain, side chain or ring-type C2-25Alkenyl, substituted or unsubstituted C5-25Aryl,
R1、R2、R3、R4、R5、R6、R7、R8、R9、R10Separately selected from hydrogen, hydroxyl, substituted or unsubstituted straight chain, branch Chain or ring-type C1-25Alkyl, substituted or unsubstituted straight chain, side chain or ring-type C2-25Alkenyl, substituted or unsubstituted C5-25Aryl, Substituted or unsubstituted straight chain, side chain or ring-type C1-25Alkoxy, substituted or unsubstituted C5-25Aryloxy group,
When above-mentioned group has substituent, the substituent is selected from following at least one：Straight chain, side chain or ring-type C1-25Alkyl, straight chain, the C of side chain or ring-type2-25Alkenyl, C5-25Aryl, containing selected from oxygen atom, sulphur atom, nitrogen-atoms and phosphorus Group, the halogen atom of at least one atom in atom,
There can be at least one be selected from each comfortable chain of abovementioned alkyl, alkoxy, alkenyl, aryl, aryloxy group or in ring Hetero atom in the group be made up of O, S, P, N is as chain constituting atom or ring atom.
Another object of the present invention provides the siloxane bridge that a kind of siloxane bridge base silane such as above-mentioned formula (1) structure blocks The preparation method of base ladder polysiloxane.
The preparation method is characterised by that the I-shaped siloxane bridge radical siloxane monomer of tetrafunctional and difunctionality are I-shaped Siloxane bridge base silane end-capping reagent cohydrolysis, act synergistically to form trapezoidal superstructure to regulate and control polymerization and envelope by supermolecule weak bond React and obtain the siloxanes abutting ladder poly-siloxane of the siloxane bridge base silane end-blocking of formula (1) structure in end.
Because I-shaped monomer used in polymerization is tetrafunctional compound, hydrolyze and condensation condition under easily occur it is branched and Crosslinking, generate insoluble insoluble gel.Therefore, of the present invention siloxanes abutment silicon different from general polymerization thing synthetic method The synthesis of alkane endcapped siloxanes abutting ladder poly-siloxane is related to regulating and controlling polymerization process using supramolecular chemistry method.That is monomer In hydrolytic process by the synergy of supermolecule weak bond (including π-π superpositions, electron donor and acceptor, electrostatic, it is hydrophilic with it is thin Interaction such as water and hydrogen bond etc.) form trapezoidal superstructure to regulate and control polymerisation, suppress branched and crosslinking generation so as to To the ladder polymer of compound with regular structure；Simultaneously agent molecule by tetrafunctional end group polymer and Silante terminated of double functionary-enterprise's fonts each other Between supermolecule weak bond act synergistically to form trapezoidal superstructure and be smoothed out end capping reaction.In view of what is formed in course of reaction Supermolecule weak bond synergy is significantly affected by reaction temperature and solvent polarity, therefore need to select suitable reaction temperature (bag It is relatively low (- 50 DEG C to 50 DEG C) to include hydrolysis, condensation and end capping reaction temperature early stage, is constructed with to ensure supermolecule weak interaction The stability of trapezoidal superstructure, and end capping reaction later stage need appropriate rise temperature (100 DEG C) and tool to block completely There is the reaction dissolvent of the group of appropriate polarity and weak interaction so as to obtain compound with regular structure, the complete ladder polymer of end-blocking.
Specifically, the application provides following every invention
In the first aspect of the present invention, there is provided a kind of poly- silicon of siloxanes abutting ladder poly of siloxane bridge base silane end-blocking Oxygen alkane, it has with following formula (1) molecular structure：
Wherein：
M is 1-10 integer,
N is 1-1000 integer,
A1、A2、A3、A4、A5、A6Separately it is selected from hydrogen, substituted or unsubstituted straight chain, side chain or ring-type C1-25Alkane Base, substituted or unsubstituted straight chain, side chain or ring-type C2-25Alkenyl, substituted or unsubstituted C5-25Aryl,
R1、R2、R3、R4、R5、R6、R7、R8、R9、R10Separately selected from hydrogen, hydroxyl, substituted or unsubstituted straight chain, branch Chain or ring-type C1-25Alkyl, substituted or unsubstituted straight chain, side chain or ring-type C2-25Alkenyl, substituted or unsubstituted C5-25Aryl, Substituted or unsubstituted straight chain, side chain or ring-type C1-25Alkoxy, substituted or unsubstituted C5-25Aryloxy group,
When above-mentioned group has substituent, the substituent is selected from following at least one：Straight chain, side chain or ring-type C1-25Alkyl, straight chain, the C of side chain or ring-type2-25Alkenyl, C5-25Aryl, containing selected from oxygen atom, sulphur atom, nitrogen-atoms and phosphorus Group, the halogen atom of at least one atom in atom,
There can be at least one be selected from each comfortable chain of abovementioned alkyl, alkoxy, alkenyl, aryl, aryloxy group or in ring Hetero atom in the group be made up of O, S, P, N is as chain constituting atom or ring atom.
In another preference, described containing is at least one in oxygen atom, sulphur atom, nitrogen-atoms and phosphorus atoms The group of atom is selected from hydroxyl, glycidoxy, C5-25Epoxy cycloalkyl, acryloxy, C1-25Alkyl-substituted acryloyl-oxy Base, sulfydryl, amino, amino-straight chain, the C of side chain or ring-type1-25Alkyl, C6-25Arylamino, cyano group, urea groups, phosphino-.
In another preference, described R1、R2、R3、R4、R5、R6、R7、R8、R9、R10、A1、A2、A3、A4、A5、A6It is only respectively On the spot selected from hydrogen, hydroxyl, methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, the tert-butyl group, n-hexyl, cyclohexyl, just Octyl group, positive decyl, dodecyl, n-hexadecyl, n-octadecane base, n-docosane base, vinyl, pi-allyl, phenyl, Aminomethyl phenyl, chlorophenyl, to ethenylphenyl, 3- (2,3- glycidoxies) propyl group, 2- (3,4- epoxycyclohexyls) ethyl, Acryloxypropyl, 3- methacryloxypropyls, mercapto propyl group, aminopropyl, 3- (2- aminoethyls)-aminopropyl, 4- amino- 3,3- dimethylbutyls, N- normal-butyl -3- aminopropyls, 2- cyano ethyls, 3- cyanopropyls, 3,3,3- trifluoro propyls, 1H, 1H, 2H, 2H- perfluoro capryl, 1H, 1H, 2H, 2H- perfluoro decyls, chloropropyl, urea propyl group, methoxyl group, ethyoxyl.
Second aspect of the present invention provides a kind of siloxanes blocked according to the siloxane bridge base silane of above-mentioned formula (1) structure The preparation method of abutting ladder poly-siloxane, it is characterised in that the I-shaped siloxane bridge radical siloxane monomer of tetrafunctional and double officials The I-shaped siloxane bridge base silane end-capping reagent cohydrolysis of energy, acts synergistically to form trapezoidal superstructure to regulate and control by supermolecule weak bond Polymerization with end capping reaction and obtain formula (1) structure siloxane bridge base silane end-blocking ladder polysiloxane.
In another preference, the preparation of the siloxanes abutting ladder poly-siloxane of described siloxane bridge base silane end-blocking Method, it comprises the following steps：
In the reactor add structural formula (2), (3) and (4) silane, organic solvent, water and catalyst be hydrolyzed and Condensation reaction, at the same it is sustainable or discontinuously vacuumize, remove condensation by-product；Products therefrom separating-purifying will be reacted afterwards, Obtain the siloxanes abutting ladder poly-siloxane of the siloxane bridge base silane end-blocking of above-mentioned formula (1) structure.
The I-shaped monomer of described tetrafunctional is represented by structural formula (2)
Wherein,
m、R1、R2、A1、A2Implication it is each identical with described in claim 1；
X is selected from OH, halogen, C1-25Alkoxy or C1-25One kind in acyloxy；
The described I-shaped silane end-cappers of two functions are represented by structural formula (3)
Wherein,
m、R3、R4、R5、R6、A3、A4Implication it is each identical with described in claim 1；
X is selected from OH, halogen, C1-25Alkoxy or C1-25One kind in acyloxy；
The I-shaped silane end-cappers structural formula (4) of two described functions represents
Wherein,
m、R7、R8、R9、R10、A5、A6Implication it is each identical with the implication in claim 1；
X is selected from OH, halogen, C1-25Alkoxy or C1-25One kind in acyloxy；
In another preference, the I-shaped monomer of tetrafunctional of described formula (2) is by trifunctional silane coupler and silicon two Alcohol is condensed preparation in the presence of a catalyst,
The trifunctional silane coupler is by formula-RSiX3Represent,
In formula, R=R1,R2；X=halogens, C1-25Alkoxy, C1-25Acyloxy.
In another preference, the I-shaped silane end-cappers of two functions of described formula (3) are by difunctional silane coupling agent It is condensed preparation in the presence of a catalyst with silicon diol,
The difunctional silane coupling agent is by formula R ' R " SiX2Represent,
In formula, R ', R "=R3With R5Combination, R4With R6Combination；X=halogens, C1-25Alkoxy, C1-25Acyloxy.
The I-shaped silane end-cappers of two functions of formula (4) by difunctional silane coupling agent and silicon diol in the presence of a catalyst It is prepared by condensation,
The difunctional silane coupling agent is by formula R ' R " SiX2Represent,
In formula, R ', R "=R7With R9Combination, R8With R10Combination；X=halogens, C1-25Alkoxy, C1-25Acyloxy.
In another preference,
Described reaction temperature is -50 DEG C to 150 DEG C, is usually -45 DEG C -100 DEG C.Wherein hydrolysis and setting-up point For -50 DEG C to 50 DEG C；End capping reaction temperature early stage is -50 DEG C to 50 DEG C, and the later stage can rise to 100 to block complete reaction temperature ℃。
In another preference, described organic solvent be selected from：Alkanes, alkane substitute class, alcohols, ethers, ketone, One or more in esters, amide-type, nitrile, pyrrolidinone compounds, sulfoxide type.
In another preference, described organic solvent be selected from：N-hexane, hexamethylene, dichloroethanes, chloroform, Tetrachloroethanes, methanol, ethanol, isopropanol, glycol monoethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, 1,4- dioxane, Acetone, cyclohexanone, methylisobutylketone, ethyl acetate, N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, acetonitrile, N- methyl One or more in pyrrolidones (NMP), dimethyl sulfoxide (DMSO) (DMSO).
In another preference, the described reaction time is 30 minutes to 120 hours.
In another preference, the molal quantity that water is added into described structural formula (2) silane is structural formula (2) silane 0.001-50 times of molal quantity.
In another preference, the molal quantity of structural formula (3) or (4) silane is added into described structural formula (2) silane It is 0.001-20 times of structural formula (2) silane molal quantity.
In another preference, the molal quantity that catalyst is added into described structural formula (2) silane is structural formula (2) silicon 0-10 times of the molal quantity of alkane.
In another preference, the molal quantity that solvent is added into described structural formula (2) silane is structural formula (2) (3) (4) 1-1000% of silane weight.
In another preference, in described dripping method or " one pot " method, it can be held after adding structural formula (3) and (4) silane It is continuous or be connected at -50 DEG C to 150 DEG C and to vacuumize reaction -120 hours 0 minute.
In another preference, the siloxanes abutting ladder poly of the siloxane bridge base silane end-blocking of described formula (1) structure gathers The yield of siloxanes is 70%~100%.
In another preference, described catalyst is selected from acid, oxide and hydroxide, ammonia or amine, transition metal One or more in compound, ion exchange resin, in order to obtain compound with regular structure, the complete ladder polymer of end-blocking is preferably Organic amine and oxide and hydroxide species catalyst.
In another preference, described acid catalyst is inorganic acids, the one or more of organic acid.
In another preference, described oxide is the one or more selected from metal oxide.
In another preference, described hydroxide is selected from TMAH, tetrabutylammonium hydroxide phosphorus, hydrogen-oxygen Change the one or more in lithium, sodium hydroxide, potassium hydroxide, cesium hydroxide, calcium hydroxide, magnesium hydroxide, barium hydroxide.
In another preference, described transistion metal compound in organic tin, titanate ester one kind or It is several.
In another preference, described amine is the one or more in tertiary amines.
In another preference, described ion exchange resin is selected from the season that styrene divinylbenzene copolymer is matrix Ammonium type ion exchange resin, sulfonic acid ion exchange resin, the styrene divinyl that styrene divinylbenzene copolymer is matrix Benzene copolymer is that carboxylic acid type ion exchange resin, the polyacrylic acid of matrix are one kind in the carboxylic acid type ion exchange resin of matrix It is or several.
In another preference, described acid catalyst is hydrochloric acid, sulfuric acid, formic acid, the one or more of acetic acid.
In another preference, described oxide is the one or more selected from calcium oxide, magnesia.
In another preference, described transistion metal compound is selected from dibutyl tin dilaurate, the vinegar of dibutyl two One or more in sour tin, Dibutyltin oxide, butyl titanate.
In another preference, described amine is selected from ammonia, n-butylamine, tert-butylamine, dimethylamine, diethylamine, two different Propylamine, ethylenediamine, TMAH, the carbon -7- alkene of 1,8- diazabicyclos [5.4.0] 11,1,5- diazabicyclos [4.3.0] -5- nonenes, triethylamine, pyridine, the one or more of triethanolamine.
Beneficial effects of the present invention：
A) the siloxanes abutting ladder poly-siloxane of siloxane bridge base silane end-blocking of the present invention is by adjusting difunctionality I-shaped Type end-capping reagent dosage can effectively control the degree of polymerization, and accessory substance can persistently be evaporated off under a high vacuum and make it that end capping reaction is completeer Entirely.More excellent heat resistance, chemical stability and mechanical property are shown compared with simple function blocks mode.
B) abutment, end group and the side base of the siloxanes abutting ladder poly-siloxane of siloxane bridge base silane of the invention end-blocking It is organic group, there is good compatibility with commodity polymer, due to the diversity of end-capping reagent and the uniqueness of preparation method Property solve be currently known Mono-functional siloxanes block the abutting ladder poly-siloxane degree of polymerization it is uncontrollable, end-blocking function based structures list First, price is high, the incomplete problem of end-blocking, by the change to abutment, side base, end group and the degree of polymerization come adjust folding optical activity, Translucency, cementability, air-tightness, intensity etc. makes application more extensive.
C) the siloxanes abutting ladder poly-siloxane of siloxane bridge base silane of the invention end-blocking has excellent high-temperature resistant Property, high-weatherability, high radiation resistance and good optics and mechanical property.As novel fire resistant silicon rubber, it is high heat-resisting and Coatings with high weatherability, photocureable coating, light emitting diode and electronic package material, high temperature resistant high vacuum diffusion pump oil, high temperature resistant profit The new material such as lubrication prescription and extraordinary coupling agent will obtain extensive use in high-tech sector.
Brief description of the drawings
Fig. 1 is the products therefrom of the embodiment of the present invention 129Si-NMR spectrograms.
Fig. 2 is the FTIR spectrograms of the products therefrom of the embodiment of the present invention 1.
Fig. 3 is the products therefrom of the embodiment of the present invention 329Si-NMR spectrograms.
Fig. 4 is the FTIR spectrograms of the products therefrom of the embodiment of the present invention 5.
Fig. 5 is the products therefrom of the embodiment of the present invention 529Si-NMR spectrograms.
Fig. 6 is the DSC spectrograms of the products therefrom of the embodiment of the present invention 5.
Fig. 7 is the TGA spectrograms of the products therefrom of the embodiment of the present invention 5.
Fig. 8 is the TGA spectrograms of the products therefrom of the embodiment of the present invention 6.
Fig. 9 is the DSC spectrograms of the products therefrom of the embodiment of the present invention 6.
Figure 10 is the TGA spectrograms of the contrast product used of the embodiment of the present invention 6.
Figure 11 is the DSC spectrograms of the contrast product used of the embodiment of the present invention 6.
Embodiment
The embodiment of the application is illustrated below.But these embodiments are only to illustrate, it is not intended to are limited The scope of the present application processed.
The siloxanes abutting ladder poly-siloxane of the siloxane bridge base silane end-blocking of present embodiment has with following formula (1) institute Show molecular structure：
Wherein：
M is 1-10 integer,
N is 1-1000 integer,
A1、A2、A3、A4、A5、A6Separately it is selected from hydrogen, substituted or unsubstituted straight chain, side chain or ring-type C1-25Alkane Base, substituted or unsubstituted straight chain, side chain or ring-type C2-25Alkenyl, substituted or unsubstituted C5-25Aryl,
R1、R2、R3、R4、R5、R6、R7、R8、R9、R10Separately selected from hydrogen, hydroxyl, substituted or unsubstituted straight chain, branch Chain or ring-type C1-25Alkyl, substituted or unsubstituted straight chain, side chain or ring-type C2-25Alkenyl, substituted or unsubstituted C5-25Aryl, Substituted or unsubstituted straight chain, side chain or ring-type C1-25Alkoxy, substituted or unsubstituted C5-25Aryloxy group,
When above-mentioned group has substituent, the substituent is selected from following at least one：Straight chain, side chain or ring-type C1-25Alkyl, straight chain, the C of side chain or ring-type2-25Alkenyl, C5-25Aryl, containing selected from oxygen atom, sulphur atom, nitrogen-atoms and phosphorus Group, the halogen atom of at least one atom in atom,
There can be at least one be selected from each comfortable chain of abovementioned alkyl, alkoxy, alkenyl, aryl, aryloxy group or in ring Hetero atom in the group be made up of O, S, P, N is as chain constituting atom or ring atom.
In the present invention, C1-25Alkyl represents the alkyl that carbon number is 1~25.Other similar terms are similarly.
Straight chain, side chain or ring-type C1-25Alkyl can be enumerated but be not limited to straight chain C1-25Alkyl, side chain C1-25Alkyl, ring-type C3-25Alkyl, preferably straight chain C1-25Alkyl.The carbon number of alkyl can be 1~22,1~20,1~18,1~16, 1~12,1~10,1~6,1~4, preferably 1~6.It can specifically enumerate：Methyl, ethyl, n-propyl, isopropyl Base, normal-butyl, isobutyl group, sec-butyl, the tert-butyl group, n-pentyl, isopentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, the positive last of the ten Heavenly stems Base, n-undecane base, dodecyl, n-tridecane base, n-tetradecane base, n-pentadecane base, n-hexadecyl, n-heptadecane Base, n-octadecane base, NSC 77136 base, n-eicosane base, Heneicosane base, n-docosane base, n-tricosane base, just Tetracosyl, pentacosane base, cyclopropyl, cyclobutyl, cyclopenta, cyclohexyl, suberyl, cyclooctyl, cyclononyl, the ring last of the ten Heavenly stems Base, ring undecyl, ring eicosyl, ring tridecyl, ring myristyl, cyclopentadecane base, ring cetyl, ring heptadecane Base, ring octadecyl, ring nonadecyl, ring eicosyl, ring heneicosyl, ring docosyl, ring tricosyl, ring Tetracosyl, ring pentacosyl.
Straight chain, side chain or ring-type C2-25Alkenyl can be enumerated but not in limit straight chain C2-25Alkenyl, side chain C2-25Alkenyl, ring-type C3-25Alkenyl, preferably straight chain C2-25Alkenyl.The carbon number of alkenyl can be 2~22,2~20,2~18,2~16, 2~12,2~10,2~6,2~4, preferably 2~3.It can specifically enumerate：Vinyl, acrylic, pi-allyl.
C5-25Aryl can be enumerated but be not limited to C5~20Aryl, C5-18Aryl, C5-14Aryl.Pyridine can specifically be enumerated Base, phenyl, naphthyl.
Straight chain, side chain or ring-type C1-25Alkoxy is straight chain, side chain or ring-type C1-25Alkyl is formed by connecting with oxygen (O) atom Group, straight chain, side chain or ring-type C therein1-25The example of alkyl is as described above.
C5-25Aryloxy group is C5-25The group that aryl is formed by connecting with oxygen (O) atom, C therein5-25The example of aryl is as above It is described.
There can be at least one be selected from each comfortable chain of abovementioned alkyl, alkoxy, alkenyl, aryl, aryloxy group or in ring Hetero atom in the group be made up of O, S, P, N is as chain constituting atom or ring atom, so as to as miscellaneous alkyl, miscellaneous alcoxyl Base, miscellaneous thiazolinyl, heteroaryl, heteroaryloxy.
Group containing at least one atom in oxygen atom, sulphur atom, nitrogen-atoms and phosphorus atoms can enumerate but It is not limited to the C of hydroxyl, carbonyl, oxo (=O), straight chain, side chain or ring-type1-25Alkoxy, C5-25Aryloxy group, glycidoxy, C5-25Epoxy cycloalkyl, acryloxy, straight chain, the C of side chain or ring-type1-25Alkyl-substituted acryloxy, sulfydryl, straight chain, The C of side chain or ring-type1-25Alkyl sulfenyl, sulfo group, nitro, amino, amino-straight chain, the C of side chain or ring-type1-25Alkyl, C5-25Virtue Base amino, cyano group, urea groups, phosphino-, straight chain, the C of side chain or ring-type1-25Alkyl-substituted phosphino-.
Halogen atom can enumerate fluorine, chlorine, bromine, iodine, preferably fluorine, chlorine.
The preparation method of the siloxanes abutting ladder poly-siloxane of the siloxane bridge base silane end-blocking of present embodiment includes： The I-shaped siloxane bridge radical siloxane monomer of tetrafunctional and the I-shaped siloxane bridge base silane end-capping reagent cohydrolysis of difunctionality, are relied on Supermolecule weak bond act synergistically to be formed trapezoidal superstructure come regulate and control polymerization with end capping reaction and obtain the siloxane bridge of formula (1) structure Base silane blocks ladder polysiloxane.
Preferably, the preparation side of the siloxanes abutting ladder poly-siloxane of the siloxane bridge base silane end-blocking of present embodiment Method its comprise the steps of：By structural formula (2), (3) and (4) silane (i.e. I-shaped siloxane bridge radical siloxane monomer of tetrafunctional With the I-shaped siloxane bridge base silane end-capping reagent of difunctionality) cohydrolysis in the presence of solvent, catalyst, water, it is weak by supermolecule Key interaction (including the interaction such as π-π superpositions, electron donor and acceptor, electrostatic, hydrophilic and hydrophobic and hydrogen bond) forms ladder The siloxanes abutting ladder poly that the polymerization of shape superstructure regulation and control hydrolysate and end capping reaction obtain siloxane bridge base silane end-blocking gathers Siloxanes.The preparation method comprises the following steps：
Into reactor structural formula (2) (3) and (4) silane, solvent, water and catalysis are added in a manner of dropwise addition or " treating different things alike " Agent is hydrolyzed and condensation reaction, and intermittently or continually property vacuumizes reaction, and reaction products therefrom is handled by separating-purifying etc., The siloxanes abutting ladder poly-siloxane of the siloxane bridge base silane end-blocking of above-mentioned formula (1) structure is obtained, its yield is 70%- 100%.
The I-shaped monomer of described tetrafunctional is represented by structural formula (2)：
Wherein,
m、R1、R2、A1、A2Implication it is each identical with foregoing definition；
X is selected from OH, halogen, C1-25Alkoxy or C1-25One kind in acyloxy；
The described I-shaped monomer of two functions is represented by structural formula (3)：
Wherein,
m、R3、R4、R5、R6、A3、A4Implication it is each identical with foregoing definition；
X is selected from OH, halogen, C1-25Alkoxy or C1-25One kind in acyloxy；
The described I-shaped monomer of two functions is represented by structural formula (4)：
Wherein,
m、R7、R8、R9、R10、A5、A6Implication it is each identical with foregoing definition；
X is selected from OH, halogen, C1-25Alkoxy or C1-25One kind in acyloxy；
The above-mentioned I-shaped monomer of tetrafunctional (2) is preferably by trifunctional silane coupler-RSiX3(R=R1,R2；X=halogen Element, C1-25Alkoxy, C1-25Acyloxy etc.；Such as MTMS, phenyltrimethoxysila,e, vinyl trimethoxy Silane, methacrylic acid propyl trimethoxy silicane, 3- glycidoxy-propyltrimethoxy silanes and 3- aminopropyl trimethoxies Silane etc.) with silicon diol (such as diphenyl silanediol, di-t-butyl silicon diol etc.) be condensed in the presence of a catalyst (including dealcoholysis, Dehydration, dehydrohalogenation, depickling or de-ester reaction) prepare.
The above-mentioned I-shaped silane end-cappers of two functions (3) and (4) are preferably by difunctional silane coupling agent-R ' R " SiX2 (R ' R "=R3With R5Combination, R4With R6Combination or R7With R9Combination, R8With R10Combination；X=halogens, alkoxy, acyloxy etc.) with Silicon diol (A3A4Si(OH)2,A5A6Si(OH)2, instantiation such as diphenyl silanediol, aminomethyl phenyl silicon diol, di-t-butyl silicon Glycol etc.) (including dealcoholysis, dehydration, dehydrohalogenation, depickling or de-ester reaction) preparation is condensed in the presence of a catalyst.The R3- R10、A3、A4、A5、A6Respectively as it was previously stated, the R3、R5It may be the same or different, the R4、R6It may be the same or different, the R7、R9 It may be the same or different, the R8、R10It may be the same or different, the A3、A4It may be the same or different, the A5、A6Can be identical or not Together, the R3With R5Combination, R4With R6Combination may be the same or different, the R7With R9Combination, R8With R10Combination may be the same or different.
Preferably, the R in described formula (1), formula (2), formula (3) and formula (4)1、R2、R3、R4、R5、R6、R7、R8、R9、 R10、A1、A2、A3、A4、A5、A6It is respectively and independently selected from hydrogen, hydroxyl, substituted or unsubstituted straight chain, the side chain that carbon number is 1-25 Or one kind in cyclic alkyl, alkenyl, aryl, as methyl, ethyl, propyl group, isopropyl, butyl, isobutyl group, the tert-butyl group, hexyl, Cyclohexyl, octyl group, positive decyl, dodecyl, n-hexadecyl, n-octadecane base, n-docosane base, vinyl, allyl Base, phenyl, aminomethyl phenyl, chlorophenyl, to ethenylphenyl, 3- (oxygen of 2,3- epoxies third) propyl group, 2- (3,4- 7-oxa-bicyclo[4.1.0s Base) ethyl, acryloxypropyl, 3- methacryloxypropyls, mercapto propyl group, aminopropyl, 3- (2- aminoethyls)-ammonia third Base, 4- amino -3,3- dimethylbutyls, N- normal-butyl -3- aminopropyls, 2- cyano ethyls, 3- cyanopropyls, 3,3,3- trifluoropropyls Base, 1H, 1H, 2H, 2H- perfluoro capryls, 1H, 1H, 2H, in 2H- perfluoro decyls, chloropropyl, urea propyl group, methoxyl group, ethyoxyl It is a kind of.
Described reaction temperature is not particularly limited, and is usually -50 DEG C to 150 DEG C, is, for example, -45 DEG C -100 DEG C.Wherein Hydrolysis and setting-up point are -50 DEG C to 50 DEG C；End capping reaction temperature early stage is -50 DEG C to 50 DEG C, and the later stage is complete for end-blocking Reaction temperature can rise to 100 DEG C.
The described reaction time is not particularly limited, usually 30 minutes to 120 hours, for example, -80 hours 1 hour.
The amount that water is added into described structural formula (2) silane is not particularly limited, and the molal quantity of usual water is structural formula (2) 0.001-50 times of molal quantity, for example, 0.01-30 times.
The amount that structural formula (3) or (4) silane is added into described structural formula (2) silane is not particularly limited, generally knot Structure formula (3) or the respective molal quantity of (4) silane are 0.001-20 times of structural formula (2) silane molal quantity, for example, 0.01-10 Times.
The amount that catalyst is added into described structural formula (2) silane is not particularly limited, the molal quantity of usual catalyst It is 0-10 times of the molal quantity of structural formula (2) silane, for example, 0.01-5 times.
The amount that solvent is added into described structural formula (2) silane is not particularly limited, and the weight of usual solvents is structure The 1-1000%, for example, 2-500% of total weight of formula (2) (3) (4).
Preferably, described dropwise addition or " one pot synthesis " add after structural formula (3) and (4) silane persistently or are connected on -50 DEG C to vacuumizing reaction -120 hours 0 minute, such as -72 hours 1 minute at 150 DEG C.
Described organic solvent is preferably selected from：Alkanes are (such as：N-hexane, hexamethylene etc.), alkane substitute class (such as：Three Chloromethanes, tetrachloroethanes etc.), alcohols (such as：Methanol, ethanol etc.), ethers (such as：Diethylene glycol dimethyl ether, tetrahydrofuran, 1,4- Dioxane etc.), ketone (such as：Acetone, cyclohexanone etc.), esters (such as：Ethyl acetate etc.), acid amides (such as dimethyl acetamide Deng), nitrile (such as：Acetonitrile etc.), pyrrolidinone compounds (such as 1-METHYLPYRROLIDONE (NMP)), sulfoxide type (such as dimethyl sulfoxide (DMSO) (DMSO) one or more in etc.).Tetrafunctional end group polymer and the Silante terminated agent molecule of double functionary-enterprise's fonts in course of reaction Supermolecule weak bond synergy to each other is significantly affected by solvent polarity, thus need to select to have appropriate polarity and it is weak mutually The reaction dissolvent of the group of effect is so as to obtaining compound with regular structure, the complete ladder polymer of end-blocking, preferably described organic solvent For selected from：N-hexane, hexamethylene, dichloroethanes, chloroform, tetrachloroethanes, methanol, ethanol, isopropanol, ethylene glycol list first Ether, diethylene glycol dimethyl ether, tetrahydrofuran, 1,4- dioxane, acetone, cyclohexanone, methylisobutylketone, ethyl acetate, N, N- One in dimethylformamide, DMAC N,N' dimethyl acetamide, acetonitrile, 1-METHYLPYRROLIDONE (NMP), dimethyl sulfoxide (DMSO) (DMSO) Kind is several.
Described catalyst be preferably selected from acid, oxide and hydroxide, ammonia or amine, transistion metal compound, from One or more in sub-exchange resin, in order to obtain compound with regular structure, the preferably complete ladder polymer of end-blocking, amine and oxygen Compound and hydroxide species catalyst.In addition to preparation structure formula (2) (3) and the optional silane coupler of (4) silane are upper State and be condensed in the presence of catalyst.
Described acid catalyst is preferably selected from inorganic acids (such as：Hydrochloric acid, sulfuric acid etc.), organic acid (such as：Formic acid, vinegar Acid etc.) one or more；
Described oxide is preferably selected from metal oxide (such as：Calcium oxide, magnesia etc.) one or more；
Described hydroxide is preferably selected from TMAH, tetrabutylammonium hydroxide phosphorus, lithium hydroxide, hydroxide One or more in sodium, potassium hydroxide, cesium hydroxide, calcium hydroxide, magnesium hydroxide, barium hydroxide；
Described transistion metal compound is preferably selected from organic tin (such as：Dibutyl tin dilaurate, the vinegar of dibutyl two Sour tin etc.), titanate ester (such as：Butyl titanate etc.) in one or more；
Described ammonia or amine is preferably selected from ammonia, n-butylamine, tert-butylamine, dimethylamine, diethylamine, diisopropylamine, second Diamines, TMAH, the carbon -7- alkene of 1,8- diazabicyclos [5.4.0] 11,1,5- diazabicyclos [4.3.0] -5- Nonene, triethylamine, pyridine, the one or more of triethanolamine；
Described ion exchange resin is preferably selected from the quaternary ammonium type ion that styrene divinylbenzene copolymer is matrix and handed over Change resin, styrene divinylbenzene copolymer is the sulfonic acid ion exchange resin of matrix, styrene divinylbenzene copolymer is Carboxylic acid type ion exchange resin, the polyacrylic acid of matrix are the one or more in the carboxylic acid type ion exchange resin of matrix.
The siloxanes abutting ladder poly-siloxane of the siloxane bridge base silane end-blocking of the present invention is according to molecular size range, end group The different outward appearances of side base abutment can have a fabulous light transmittance from colourless transparent liquid to solid, excellent temperature tolerance and flexible Property.There is good dissolving in tetrahydrofuran, 1,4- dioxane, toluene, 1-METHYLPYRROLIDONE, acetone, DMA equal solvents Property by nucleus magnetic hydrogen spectrum, nuclear-magnetism silicon spectrum, infrared spectrum, show the tests such as heat scan calorimeter (DSC) prove its form structure, again Its average degree of polymerization can be calculated by nuclear-magnetism silicon spectrum, vapour pressure osmometry (VPO) etc., by testing the viscosity under high-temperature fusion Value can then reflect the viscosity B coefficent that degree of polymerization difference is brought from another angle.
Glass transition temperature (Tg) by showing that heat scan calorimeter (DSC) is measured, DSC test condition is 20 DEG C/min from the highest temperature for needing the lowest temperature rise tested to be tested to needs, lowest temperature then is quickly cooled to from the highest temperature, then Second of heating detection is carried out with 10 DEG C/min.
Index of refraction is measured by abbe's refractometer, and the test condition of index of refraction is under 298K constant temperature, is applied Film is measured.
Sample is carried out the melting suitable rotating speed of reselection by high temperature modification cone and plate viscometer and surveyed by viscosity at high temperature It is fixed.
Heat decomposition temperature is measured by thermogravimetric analyzer (TGA), and TGA test condition is under air atmosphere, 20 DEG C/ Minute is warming up to 900 DEG C from 30 DEG C；Either, under nitrogen atmosphere, 20 DEG C/min are warming up to 600 DEG C from 30 DEG C, then in air gas Under atmosphere, 20 DEG C/min from 600 DEG C are warming up to 900 DEG C.
Embodiment is exemplified below this present embodiment is described in detail.But the invention is not restricted to these examples Son.
For simplicity, I-shaped Silante terminated siloxane bridge based polysiloxane is abbreviated as R ' R "-I-R-SLPS below, its In：R is polysiloxanes R-SLPS side base.I- represents I-shaped Silante terminated meaning；R ' R " represent two of I-shaped silane End group.
Embodiment 1：Ph2- I-Ph-SLPS is synthesized
Siloxanes abutment silicon is prepared by phenyltrimethoxysila,e, dimethoxydiphenylsilane and diphenyl silanediol Alkane endcapped siloxanes abutting ladder poly-siloxane.
By 39.6 grams of phenyltrimethoxysila,es (0.20mol), 21.6 grams of diphenyl silicon two under dry nitrogen protection 15 grams of alcohol (0.01mol) and ethyl acetate are placed in three mouthfuls of burnings equipped with mechanical agitation, constant pressure funnel and reflux condenser In bottle, it is stirred at room temperature uniformly, 0.02 gram of triethanolamine is added at 0 DEG C, reaction obtains intermediate 1 in 8 hours；Have simultaneously at another Dry nitrogen is protected, and 41.9 gram two is added in the three-necked flask equipped with mechanical agitation, constant pressure funnel and reflux condenser Phenyidimethoxysilane (0.17mol), 10 grams of ethyl acetate, 18.6 grams of diphenyl silanediols (0.09mol) stir, 0.04 gram of triethanolamine is added at 0 DEG C, reacts 10 hours, obtains intermediate 2, intermediate 2 is all added in intermediate 1, added Enter water 12.6 grams (0.70mol), reacted 5 hours at -10 DEG C, be warming up to 0 DEG C and continue reaction 10 hours；Then gained is mixed Thing is neutralized with hydrochloric acid, and adds 50mL toluene, and washing separation is concentrated under reduced pressure, and obtains the siloxane bridge base silane end-blocking of formula (1) structure Siloxanes abutting ladder poly-siloxane, wherein R1-R10For phenyl, A1-A6For phenyl, m=1, n=14, gained yield is 95%.
The siloxane bridge base silane endcapped siloxanes abutting ladder poly-siloxane of gained is water white transparency solid, polymerization degree n Average value be 14, index of refraction be 1.59 (25 DEG C), and glass transition temperature is 48.51 DEG C, 230 DEG C, glutinous under 800rpm rotating speeds Spend for 133 pools (poise).The thermal oxidation of resistance to air is respectively：Its hydroxy-end capped ladder polymer 4HO-blocked Ph-SLPS It is non-discolouring and be not crosslinked in 400 DEG C × 15h；And corresponding monofunctional silanes (such as diphenylmethylsilane base) endcapped siloxanes abutment Ladder polysiloxane MePh2SiO-I-blocked Ph-SLPS are not crosslinked non-discolouring in 400 DEG C × 15h.And corresponding diphenyl silicon The Silante terminated siloxanes abutting ladder poly-siloxane Ph of oxygen alkane abutment2- I-Ph-SLPS shows more best performance in 400 DEG C × 24h It is not crosslinked non-discolouring.1H NMR(400MHz,CDCl3,298K):δ7.14-7.53ppm；29Si NMR(80MHz,CDCl3, 298K):δ-79.16,-43.46ppm。
Embodiment 2：PhMe-I-Ph-SLPS is synthesized
Siloxanes abutment is prepared by phenyltrimethoxysila,e, aminomethyl phenyl dimethoxysilane and diphenyl silanediol Silante terminated siloxanes abutting ladder poly-siloxane.
By 39.6 grams of phenyltrimethoxysila,es (0.20mol), 21.6 grams of diphenyl silicon two under dry nitrogen protection Alcohol (0.10mol) and 10 grams of DMAC N,N' dimethyl acetamides are placed in equipped with mechanical agitation, constant pressure funnel and reflux condenser Three-necked flask in, be stirred at room temperature uniformly, at -5 DEG C add 0.10 gram of liquefied ammonia, reaction 12 hours intermediate 1；Simultaneously another One has in dry three-necked flask of the nitrogen protection equipped with mechanical agitation, constant pressure funnel and reflux condenser and adds 3.65 Gram aminomethyl phenyl dimethoxysilane (0.02mol), 10 grams of DMAC N,N' dimethyl acetamides, 2.16 grams of diphenyl silanediols (0.01mol) is stirred, and 0.02 gram of liquefied ammonia is added at 0 DEG C, is reacted 18 hours, is obtained intermediate 2, and intermediate 2 is all added Enter into intermediate 1, add water 9.00 grams (0.50mol), reacted 15 hours at 0 DEG C；Then by gained mixture hydrochloric acid Neutralize, add 20mL toluene, washing separation is concentrated under reduced pressure, and obtains the siloxane bridge base silane endcapped siloxanes bridge of formula (1) structure Base ladder polysiloxane, wherein R1=R2=R3=R4=R7=R8For phenyl, R5=R6=R9=R10For methyl, A1-A6For benzene Base, m=1, n=80, gained yield are 92%.
The siloxane bridge base silane endcapped siloxanes abutting ladder poly-siloxane of gained is water white transparency solid, polymerization degree n Average value be 80, index of refraction be 1.57 (25 DEG C), and glass transition temperature is 39.45 DEG C, 230 DEG C, viscosity under 50rpm rotating speeds For 2430 pools (poise).The thermal oxidation of resistance to air is respectively：Its hydroxy-end capped ladder polymer 4HO-blocked Ph-SLPS It is non-discolouring and be not crosslinked in 400 DEG C × 15h；And corresponding monofunctional silanes (such as diphenylmethylsilane base) endcapped siloxanes abutment Ladder polysiloxane MePh2SiO-I-blocked Ph-SLPS are not crosslinked non-discolouring in 400 DEG C × 15h.And corresponding aminomethyl phenyl Siloxane bridge base silane endcapped siloxanes abutting ladder poly-siloxane PhMe-I-Ph-SLPS show more best performance 400 DEG C × 20h is not crosslinked non-discolouring.1H NMR(400MHz,CDCl3,298K):δ-0.06-0.11,7.14-7.53ppm；29Si NMR (80MHz,CDCl3,298K):δ-80.02,-43.96,-27.23ppm。
Embodiment 3：Ph2- I-Me-SLPS is synthesized
Siloxanes abutment silicon is prepared by MTMS, dimethoxydiphenylsilane and diphenyl silanediol Alkane endcapped siloxanes abutting ladder poly-siloxane.
By 27.2 grams of MTMSs (0.20mol), 21.6 grams of diphenyl silicon two under dry nitrogen protection Alcohol (0.10mol) and 20 grams of chloroforms are placed in three mouthfuls of burnings equipped with mechanical agitation, constant pressure funnel and reflux condenser In bottle, it is stirred at room temperature uniformly, 0.08 gram of tetrabutylammonium hydroxide phosphine is added at -10 DEG C, reaction obtains intermediate 1 in 8 hours；Exist simultaneously Another, which has in dry three-necked flask of the nitrogen protection equipped with mechanical agitation, constant pressure funnel and reflux condenser, adds 48.9 grams of dimethoxydiphenylsilanes (0.20mol), 40 grams of chloroforms, 21.6 grams of diphenyl silanediols (0.10mol) are stirred Mix uniformly, add 0.3 gram of tetrabutylammonium hydroxide phosphine at 5 DEG C, react 24 hours, obtain intermediate 2, intermediate 2 is all added Into intermediate 1, water 10.8 grams (0.60mol) is added, is reacted 15 hours at 5 DEG C；Then by gained mixture hydrochloric acid With, add 60mL toluene, washing separation be concentrated under reduced pressure, obtain the siloxane bridge base silane endcapped siloxanes abutment of formula (1) structure Ladder polysiloxane, wherein R1=R2For methyl, R3-R10For phenyl, A1-A6It is for phenyl, m=1, n=12, gained yield 96%.
The siloxane bridge base silane endcapped siloxanes abutting ladder poly-siloxane water white transparency solid of gained, polymerization degree n Average value is 12, and index of refraction is 1.55 (25 DEG C), and glass transition temperature is 34.31 DEG C, 230 DEG C, viscosity under 100rpm rotating speeds For 973 pools (Poise).The thermal oxidation of resistance to air is respectively：Its hydroxy-end capped ladder polymer 4HO-blocked Me-SLPS exists 300 DEG C × 15h is non-discolouring and is not crosslinked；And corresponding monofunctional silanes (such as diphenylmethylsilane base) endcapped siloxanes abutment ladder Shape polysiloxanes MePh2SiO-I-blocked Me-SLPS are not crosslinked non-discolouring in 300 DEG C × 15h.And corresponding diphenyl silica The Silante terminated siloxanes abutting ladder poly-siloxane Ph of alkane abutment2- I-Me-SLPS shows more best performance in 300 DEG C × 24h not It is crosslinked non-discolouring.1H NMR(400MHz,CDCl3,298K):δ-0.06-0.12,7.14-7.53ppm；29Si NMR(80MHz, CDCl3,298K):δ-65.28,-43.35ppm。
Embodiment 4：PhMe-I-Me-SLPS is synthesized
Siloxanes abutment is prepared by MTMS, aminomethyl phenyl dimethoxysilane and diphenyl silanediol Silante terminated siloxanes abutting ladder poly-siloxane.
By 27.2 grams of MTMSs (0.20mol), 21.6 grams of diphenyl silicon two under dry nitrogen protection Alcohol (0.10mol) and 20 grams of N,N-dimethylformamides are placed in equipped with mechanical agitation, constant pressure funnel and reflux condenser Three-necked flask in, be stirred at room temperature uniformly, at -10 DEG C add 0.10 gram of monoethanolamine, reaction 8 hours intermediate 1；Exist simultaneously Another, which has in dry three-necked flask of the nitrogen protection equipped with mechanical agitation, constant pressure funnel and reflux condenser, adds 0.81 gram of aminomethyl phenyl dimethoxysilane (0.0044mol), 2 grams of N,N-dimethylformamides, 0.476 gram of diphenyl silanediol (0.0022mol) is stirred, and 0.02 gram of monoethanolamine is added at 0 DEG C, is reacted 18 hours, is obtained intermediate 2, and intermediate 2 is complete Portion is added in intermediate 1, adds water 7.2 grams (0.40mol), is reacted at -5 DEG C and is vacuumized within 5 hours reaction 12 hours again；So Gained mixture is neutralized with hydrochloric acid afterwards, adds 40mL toluene, washing separation is concentrated under reduced pressure, and obtains the siloxanes of formula (1) structure The Silante terminated siloxanes abutting ladder poly-siloxane of abutment, wherein R1=R2=R5=R6=R9=R10For methyl, R3=R4=R7 =R8For phenyl, A1-A6For phenyl, m=1, n=80, gained yield is 94%.
The siloxane bridge base silane endcapped siloxanes abutting ladder poly-siloxane water white transparency solid of gained, polymerization degree n Average value is 80, and index of refraction is 1.54 (25 DEG C), and glass transition temperature is 28.51 DEG C, 230 DEG C, viscosity is under 50rpm rotating speeds 365 pools (Poise).The thermal oxidation of resistance to air is respectively：Its hydroxy-end capped ladder polymer 4HO-blocked Me-SLPS exists 300 DEG C × 15h is non-discolouring and is not crosslinked；And corresponding monofunctional silanes (such as dimethylphenylsilaneand base) endcapped siloxanes abutment ladder Shape polysiloxanes Me2PhSiO-I-blocked Me-SLPS are not crosslinked non-discolouring in 300 DEG C × 15h.And corresponding aminomethyl phenyl silicon The Silante terminated siloxanes abutting ladder poly-siloxane PhMe-I-Me-SLPS of oxygen alkane abutment show more best performance 300 DEG C × 24h is not crosslinked non-discolouring.1H NMR(400MHz,CDCl3,298K):δ-0.06-0.12,7.14-7.53ppm；29Si NMR (80MHz,CDCl3,298K):δ-64.32,-43.02,-28.73ppm。
Embodiment 5：MeEpoxy-I-Ph-SLPS is synthesized
Pass through phenyltrimethoxysila,e, 3- (oxygen of (2,3)-epoxy third) hydroxypropyl methyl diethoxy silanes and diphenyl silicon Glycol prepares siloxane bridge base silane endcapped siloxanes abutting ladder poly-siloxane.
By 39.7 grams of phenyltrimethoxysila,es (0.20mol), 21.6 grams of diphenyl silicon two under dry nitrogen protection Alcohol (0.10mol) and 10 grams of acetone are placed in the three-necked flask equipped with mechanical agitation, constant pressure funnel and reflux condenser, It is stirred at room temperature uniformly, the ammoniacal liquor that 0.3 gram of styrene divinylbenzene copolymer is matrix is added at 0 DEG C, during reaction obtains for 15 hours Mesosome 1；There is dry nitrogen to protect three mouthfuls equipped with mechanical agitation, constant pressure funnel and reflux condenser at another simultaneously 23.6 grams of 3- (oxygen of (2,3)-epoxy third) hydroxypropyl methyl diethoxy silanes (0.10mol), 20 grams of acetone, 10.8 are added in flask Gram diphenyl silanediol (0.05mol) is stirred, and 0.60 gram of ammoniacal liquor is added at 10 DEG C, is reacted 20 hours, is obtained intermediate 2, Intermediate 2 is all added in intermediate 1, water 27.0 grams (1.50mol) is added, is reacted 20 hours at 0 DEG C；Then by institute Obtain mixture to be neutralized with hydrochloric acid, add 40ml toluene, washing separation is concentrated under reduced pressure, and obtains the siloxanes abutment silicon of formula (1) structure Alkane terminated silane abutting ladder poly-siloxane, wherein R1=R2For phenyl, R3=R4=R7=R8For methyl, R5=R6=R9=R10 For 3- (oxygen of (2,3)-epoxy third) propyl group, A1-A6For phenyl, m=1, n=34, gained yield is 92%.
The siloxane bridge base silane endcapped siloxanes abutting ladder poly-siloxane water white transparency solid of gained, polymerization degree n Average value is 34, and index of refraction is 1.56 (25 DEG C), and glass transition temperature is 40.28 DEG C.TGA measures 5% heat decomposition temperature 400℃.230 DEG C, viscosity is 8550 pools (Poise) under 30rpm rotating speeds.1H NMR(400MHz,CDCl3,298K):δ-0.06- 0.12,0.21-0.44,1.41-1.73,2.52-3.64,7.02-7.53ppm；29Si NMR(80MHz,CDCl3,298K):δ- 78.6,-45.16,-17.87ppm。
Embodiment 6：MeVi-I-Ph-SLPS is synthesized
Silane abutment is prepared by phenyltrimethoxysila,e, methylvinyldimethoxysilane and diphenyl silanediol Silante terminated siloxanes abutting ladder poly-siloxane.
By 39.7 grams of phenyltrimethoxysila,es (0.20mol), 21.6 grams of diphenyl silicon two under dry nitrogen protection 30 grams of alcohol (0.10mol) and diethylene glycol dimethyl ether are placed in equipped with mechanical agitation, constant pressure funnel and reflux condenser In three-necked flask, it is stirred at room temperature uniformly, 0.30 gram 1 of the addition at -20 DEG C, the carbon -7- alkene of 8- diazabicyclos [5.4.0] 11, Reaction obtains intermediate 1 in 5 hours；There is dry nitrogen protection equipped with mechanical agitation, constant pressure funnel at another simultaneously and return 8.8 grams of methylvinyldimethoxysilanes (0.067mol), 40 grams of diethylene glycols two are added in the three-necked flask of flow condenser Methyl ether, 7.2 grams of diphenyl silanediols (0.033mol) are stirred, and 0.30 gram of 1,8- diazabicyclo is added at -20 DEG C [5.4.0] 11 carbon -7- alkene, react 12 hours, obtain intermediate 2, intermediate 2 is all added in intermediate 1, adds water 33.6 grams (1.86mol), reacted 15 hours at 0 DEG C；Then gained mixture is neutralized with hydrochloric acid, adds the washing of 50mL toluene Separation is concentrated under reduced pressure, and obtains the siloxane bridge base silane endcapped siloxanes abutting ladder poly-siloxane of formula (1) structure, wherein R3= R4=R7=R8For vinyl, R1=R2For phenyl, R5=R6=R9=R10For methyl, A1-A6For phenyl, m=1, n=6, gained Yield is 83%.
The siloxane bridge base silane endcapped siloxanes abutting ladder poly-siloxane water white transparency soft solid of gained, polymerization degree n Average value be 6, index of refraction is 1.57 (25 DEG C).Glass transition temperature is 28.83 DEG C, contrast product dimethyl vinyl envelope Hold phenyl homopolymer 0.47 DEG C.TGA measures 5% heat decomposition temperature as 390 DEG C, contrasts product dimethyl ethenyl blocking phenyl 5% heat decomposition temperature of homopolymer is 330 DEG C.230 DEG C, viscosity is 1973 pools (Poise) under 100rpm rotating speeds.1H NMR (400MHz,CDCl3,298K):δ-0.06-0.13,5.51-6.02,7.01-7.56ppm；29Si NMR(80MHz,CDCl3, 298K):δ-78.27,-44.75,-32.76ppm。
Embodiment 7：MeVi-I-Me-SLPS is synthesized
Siloxane bridge is prepared by MTMS, methylvinyldimethoxysilane and diphenyl silanediol Base silane endcapped siloxanes abutting ladder poly-siloxane.
By 27.2 grams of MTMSs (0.20mol), 21.6 grams of diphenyl silicon two under dry nitrogen protection 20 grams of alcohol (0.10mol) and hexamethylene are placed in the three-necked flask equipped with mechanical agitation, constant pressure funnel and reflux condenser In, it is stirred at room temperature uniformly, 0.40 gram of 1,5- diazabicyclos [4.3.0] -5- nonene is added at -10 DEG C, during reaction obtains for 8 hours Mesosome 1；There is dry nitrogen to protect three mouthfuls equipped with mechanical agitation, constant pressure funnel and reflux condenser at another simultaneously 21.9 grams of methylvinyldimethoxysilanes (0.17mol), 30 grams of dioxane, 18 grams of diphenyl silanediols are added in flask (0.083mol) is stirred, and 0.40 gram of 1,5- diazabicyclos [4.3.0] -5- nonene is added at 0 DEG C, is reacted 18 hours, Intermediate 2 is obtained, intermediate 2 is all added in intermediate 1, water 18 grams (1.0mol) is added, adds 20 grams of diethylene glycols two Methyl ether reacts 15 hours at 0 DEG C；Then gained mixture is neutralized with hydrochloric acid, adds 35mL toluene, washing separation decompression is dense Contracting, obtains the siloxane bridge base silane endcapped siloxanes abutting ladder poly-siloxane of formula (1) structure, wherein R1=R2=R3=R4 =R7=R8For methyl, R5=R6=R9=R10For vinyl, A1-A6For phenyl, m=1, n=12, gained yield is 97%.
The siloxane bridge base silane endcapped siloxanes abutting ladder poly-siloxane water white transparency solid of gained, polymerization degree n Average value is 12, and index of refraction is 1.53 (25 DEG C), and glass transition temperature is 47.51 DEG C.230 DEG C, viscosity under 100rpm rotating speeds For 718 pools (Poise).1H NMR(400MHz,CDCl3,298K):δ-0.06-0.11,5.51-6.02,7.02-7.53ppm；29SiNMR(80MHz,CDCl3,298K):δ-65.12,-44.47,-31.87ppm。
Embodiment 8：MeEpoxy-I-Vi-SLPS is synthesized
Pass through vinyltrimethoxy silane, 3- (oxygen of (2,3)-epoxy third) hydroxypropyl methyl diethoxy silanes and diphenyl Silicon diol prepares siloxane bridge base silane endcapped siloxanes abutting ladder poly-siloxane.
By 29.7 grams of vinyltrimethoxy silanes (0.20mol), 21.6 grams of diphenyl silicon under dry nitrogen protection Glycol (0.10mol) and 5 grams of DMFs are placed in equipped with mechanical agitation, constant pressure funnel and reflux condenser Three-necked flask in, be stirred at room temperature uniformly, at 5 DEG C add 2 grams of diethanol amine, reaction 16 hours intermediate 1；Simultaneously another One has in dry three-necked flask of the nitrogen protection equipped with mechanical agitation, constant pressure funnel and reflux condenser and adds 4.97 Gram 3- (oxygen of (2,3)-epoxy third) hydroxypropyl methyl diethoxy silane (0.02mol), 10 grams of DMFs, 2.2 grams Diphenyl silanediol (0.01mol) is stirred, and 0.40 gram of diethanol amine is added at 10 DEG C, is reacted 18 hours, is obtained intermediate 2, intermediate 2 is all added in intermediate 1, water 9 grams (0.50mol) is added, 5 grams of DMFs is added, 5 Reaction 15 hours is vacuumized at DEG C；Then gained mixture is neutralized with formic acid, adds 40mL toluene, washing separation decompression is dense Contracting, obtains the siloxane bridge base silane endcapped siloxanes abutting ladder poly-siloxane of formula (1) structure, wherein R1=R2For vinyl, R3=R4=R7=R8For methyl, R5=R6=R9=R10For 3- (oxygen of (2,3)-epoxy third) propyl group, A1-A6For phenyl, m=1, n= 15, gained yield is 77%.
The siloxane bridge radical siloxane endcapped siloxanes abutting ladder poly-siloxane of gained is water white transparency solid, the degree of polymerization N average value is 15, and index of refraction is 1.55 (25 DEG C), and glass transition temperature is 34.66 DEG C.230 DEG C, stick under 50rpm rotating speeds Spend for 3701 pools (Poise).1H NMR(400MHz,CDCl3,298K):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,CDCl3,298K):δ-79.46,-44.87,- 17.94ppm。
Embodiment 9：MeAcryl-I-Me-SLPS is synthesized
Pass through MTMS, 3- methacryloyloxypropyl methyls dimethoxysilane and diphenyl silicon two Alcohol prepares siloxane bridge base silane endcapped siloxanes abutting ladder poly-siloxane.
By 27.2 grams of MTMSs (0.20mol), 21.6 grams of diphenyl silicon two under dry nitrogen protection 25 grams of alcohol (0.10mol) and dioxane are placed in three mouthfuls of burnings equipped with mechanical agitation, constant pressure funnel and reflux condenser In bottle, it is stirred at room temperature uniformly, 0.20 gram of monoethanolamine is added at -30 DEG C, reaction obtains intermediate 1 in 16 hours；Simultaneously at another Have in dry three-necked flask of the nitrogen protection equipped with mechanical agitation, constant pressure funnel and reflux condenser and add 3.9 grams of 3- Methacryloyloxypropyl methyl dimethoxysilane (0.017mol), 10 grams of dioxane, 1.8 grams of diphenyl silanediols (0.0083mol) is stirred, and 0.04 gram of monoethanolamine is added at -20 DEG C, is reacted 18 hours, intermediate 2 is obtained, at -20 DEG C Water 12.6 grams (0.70mol) is added into intermediate 1, intermediate 2 is added dropwise in the mixed liquor of intermediate 1 and water, it is small to be added dropwise 3 When finish continue reaction 10 hours；Then gained mixture is neutralized with formic acid, adds 50mL toluene, washing separation decompression is dense Contracting, obtains the siloxane bridge base silane endcapped siloxanes abutting ladder poly-siloxane of formula (1) structure, wherein R1=R2=R3=R4 =R7=R8For methyl, R5=R6=R9=R10For 3- methacryloxypropyls, A1-A6For phenyl, m=1, n=120, institute It is 87% to obtain yield.
The siloxane bridge radical siloxane terminated silane abutting ladder poly-siloxane of gained is water white transparency thick liquid, polymerization The average value for spending n is 120, and index of refraction is 1.53 (25 DEG C), and glass transition temperature is 10.32 DEG C.230 DEG C, under 30rpm rotating speeds Viscosity is 9490 pools (Poise).1H NMR(400MHz,CDCl3,298K):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,CDCl3,298K):δ-65.02,- 45.15,-17.94ppm。
Embodiment 10：Me2- I-Ph/Acryl-SLPS is synthesized
Pass through 3- (methacryloxypropyl) propyl trimethoxy silicane, phenyltrimethoxysila,e, dimethylformamide dimethyl epoxide Silane and diphenyl silanediol prepare siloxane bridge base silane endcapped siloxanes abutting ladder poly-siloxane.
By 19.8 grams of phenyltrimethoxysila,es (0.10mol), 24.8 grams of 3- (metering systems under dry nitrogen protection Acyl-oxygen) propyl trimethoxy silicane (0.10mol), 21.6 grams of diphenyl silanediols (0.10mol) and 40 grams of diethylene glycols two Methyl ether is placed in the three-necked flask equipped with mechanical agitation, constant pressure funnel and reflux condenser, is stirred at room temperature uniformly, -20 0.20 gram of TMAH is added at DEG C, reaction obtains intermediate 1 in 14 hours；There is dry nitrogen protection at another simultaneously 0.15 gram of dimethyldimethoxysil,ne is added in three-necked flask equipped with mechanical agitation, constant pressure funnel and reflux condenser (0.0012mol), 5 grams of diethylene glycol dimethyl ethers, 0.14 gram of diphenyl silanediol (0.00062mol) stir, at -20 DEG C 0.02 gram of tetramethyl oxyammonia of lower addition, is reacted 18 hours, obtains intermediate 2, and intermediate 2 is all added in intermediate 1, Water 9 grams (0.50mol) is added, is reacted 5 hours at -20 DEG C；Then gained mixture is neutralized with hydrochloric acid, adds 80mL first Benzene, washing separation are concentrated under reduced pressure, and obtain the siloxane bridge base silane endcapped siloxanes abutting ladder poly-siloxane of formula (1) structure, Wherein R1For 3- (methacryloxypropyl) propyl group, R2For phenyl, R3=R4=R7=R8=R5=R6=R9=R10For methyl, A1-A6 For phenyl, m=1, n=300, gained yield is 87%.
The siloxane bridge base silane endcapped siloxanes abutting ladder poly-siloxane of gained is water white transparency thick liquid, polymerization The average value for spending n is 300, and index of refraction is 1.53 (25 DEG C), and glass transition temperature is -12.34 DEG C.230 DEG C, 100rpm rotating speeds Lower viscosity is 61.62 pools (Poise).1H NMR(400MHz,CDCl3,298K):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,CDCl3,298K):δ-79.22,- 64.85,-45.21,-18.02ppm。
Embodiment 11：Ph2- I-Vi/Epoxy-SLPS is synthesized
Pass through 3- (oxygen of (2,3)-epoxy third) propyl trimethoxy silicane, vinyltrimethoxy silane, diphenyl diformazan TMOS and diphenyl silanediol prepare siloxane bridge base silane endcapped siloxanes abutting ladder poly-siloxane.
Under dry nitrogen protection by 14.82 grams of phenyltrimethoxysila,es (0.10mol), 23.6 grams of 3- ((2,3)- The oxygen of epoxy third) propyl trimethoxy silicane (0.10mol), 21.6 grams of diphenyl silanediols (0.10mol) and 10 grams of tetrahydrochysene furans Mutter and be placed in the three-necked flask equipped with mechanical agitation, constant pressure funnel and reflux condenser, be stirred at room temperature uniformly, at 0 DEG C 0.70 gram of DBN is added, reaction obtains intermediate 1 in 10 hours；There is dry nitrogen protection equipped with mechanical agitation, perseverance at another simultaneously Press added in the three-necked flask of dropping funel and reflux condenser 0.92 gram of dimethoxydiphenylsilane (0.0038mol), 2 grams Chloroform, 0.40 gram of diphenyl silanediol (0.0019mol) are stirred, and it is small that 0.02 gram of DBN reaction 18 is added at 0 DEG C When, intermediate 2 is obtained, intermediate 2 is all added in intermediate 1, water 8 grams (0.44mol) is added, reacts 15 at -10 DEG C Hour；Then gained mixture is neutralized with hydrochloric acid, adds 30mL toluene, washing separation is concentrated under reduced pressure, and obtains formula (1) structure Siloxane bridge base silane endcapped siloxanes abutting ladder poly-siloxane, wherein R1For 3- (oxygen of (2,3)-epoxy third) propyl group, R2For second Alkenyl, R3=R4=R7=R8=R5=R6=R9=R10For phenyl, A1-A6For phenyl, m=1, n=90, gained yield is 80%.
The siloxane bridge base silane terminated silane abutting ladder poly-siloxane water white transparency thick liquid of gained, polymerization degree n Average value be 90, index of refraction be 1.55 (25 DEG C), and glass transition temperature is -3.4 DEG C.230 DEG C, viscosity under 100rpm rotating speeds For 94.54 pools (Poise).1H NMR(400MHz,CDCl3,298K):δ-0.04-0.13,0.20-0.41,1.40-1.73, 2.52-3.64,7.02-7.53ppm；29Si NMR(80MHz,CDCl3,298K):δ-78.72,-64.18,-45.28ppm。
Embodiment 12：MePh-I-AE/AP-SLPS
Pass through N- (2- aminoethyls) -3- aminopropyl trimethoxysilanes, aminomethyl phenyl dimethoxysilane and HO (Ph2SiO)2H prepares siloxane bridge base silane endcapped siloxanes abutting ladder poly-siloxane.
Under dry nitrogen protection by 44.5 grams of N- (2- aminoethyls) -3- aminopropyl trimethoxysilanes (0.20mol), 41.4 grams of HO (Ph2SiO)2H (0.10mol) and 40 grams of tetrahydrofurans are placed in equipped with mechanical agitation, constant pressure funnel and backflow In the three-necked flask of condenser, it is stirred at room temperature uniformly, 0.20 gram of pyridine is added at 0 DEG C, reaction obtains intermediate 1 in 6 hours；Simultaneously Have at another in dry three-necked flask of the nitrogen protection equipped with mechanical agitation, constant pressure funnel and reflux condenser and add 11.5 grams of aminomethyl phenyl dimethoxysilanes (0.063mol), 20 grams of tetrahydrofurans, 12.9 grams of HO (Ph2SiO)2H(0.031mol) Stir, 0.20 gram of triethanolamine is added at 0 DEG C, react 13 hours, obtain intermediate 2, during intermediate 2 is all added to In mesosome 1, water 9 grams (0.50mol) is added, is reacted 15 hours at -10 DEG C；Then gained mixture is neutralized with hydrochloric acid, added Enter 40mL toluene, washing separation is concentrated under reduced pressure, and the siloxane bridge base silane endcapped siloxanes abutting ladder poly for obtaining formula (1) structure gathers Siloxanes, wherein R1=R2For N- (2- aminoethyls) -3- aminopropyls, R3=R4=R7=R8For methyl, R5=R6=R9=R10For benzene Base, A1-A6For phenyl, m=2, n=320, gained yield is 86%.
The siloxane bridge base silane endcapped siloxanes abutting ladder poly-siloxane water white transparency thick liquid of gained, the degree of polymerization N average value is 320, and index of refraction is 1.53 (25 DEG C), and glass transition temperature is -37.3 DEG C.230 DEG C, under 100rpm rotating speeds Viscosity is 32.65 pools (Poise).1H NMR(400MHz,CDCl3,298K):δ-0.04-0.13,1.15-1.22,2.52- 2.58,3.70-3.85,7.02-7.53ppm；29Si NMR(80MHz,CDCl3,298K):δ-64.67,-44.81,- 28.65ppm。
Embodiment 13：MeEpoxy-I-Pr-SLPS is synthesized
Pass through propyl trimethoxy silicane, 3- (oxygen of (2,3)-epoxy third) hydroxypropyl methyl diethoxy silane, dimethyl two Methoxy silane and diphenyl silanediol prepare siloxane bridge base silane endcapped siloxanes abutting ladder poly-siloxane.
By 32.9 grams of propyl trimethoxy silicanes (0.20mol), 21.6 grams of diphenyl silicon two under dry nitrogen protection Alcohol (0.10mol) and 10 grams of dioxane are placed in three mouthfuls of burnings equipped with mechanical agitation, constant pressure funnel and reflux condenser In bottle, it is stirred at room temperature uniformly, 0.20 gram of triethylamine is added at -5 DEG C, reaction obtains intermediate 1 in 12 hours；Have simultaneously at another 3.3 grams of 3- are added in dry three-necked flask of the nitrogen protection equipped with mechanical agitation, constant pressure funnel and reflux condenser (oxygen of (2,3)-epoxy third) hydroxypropyl methyl diethoxy silane (0.013mol), 1.6 grams of dimethyldimethoxysil,nes (0.013mol) and 2.9 grams of diphenyl silanediols (0.013mol), 10 grams of dioxane are stirred, and 0.2 is added at -5 DEG C Gram triethylamine, react 16 hours, obtain intermediate 2, intermediate 2 is all added in intermediate 1, adds 12.6 grams of water (0.70mol), reacted 10 hours at 0 DEG C；Then gained mixture is neutralized with hydrochloric acid, adds 30mL toluene, washing separation It is concentrated under reduced pressure, obtains the siloxane bridge base silane endcapped siloxanes abutting ladder poly-siloxane of formula (1) structure, wherein R1=R2For Propyl group, R3=R4=R5=R7=R8=R9For methyl, R6=R10For 3- (oxygen of (2,3)-epoxy third) propyl group, A1-A6For phenyl, m= 1, n=75, gained yield is 89%.
The siloxane bridge base silane endcapped siloxanes abutting ladder poly-siloxane of gained is water white transparency solid, polymerization degree n Average value be 75, index of refraction be 1.53 (25 DEG C), and glass transition temperature is 27.54 DEG C.230 DEG C, viscosity under 30rpm rotating speeds For 8490 pools (Poise).1H NMR(400MHz,CDCl3,298K):δ-0.04-0.13,0.19-0.41,1.42-1.74, 2.52-3.64,7.01-7.57ppm；29Si NMR(80MHz,CDCl3,298K):δ-64.85,-45.24,-18.32ppm。
Embodiment 14：Ph2- I-Me-SLBuS is synthesized
Siloxanes abutment is prepared by MTMS, dimethoxydiphenylsilane and diisobutyl silicon diol Silante terminated siloxanes abutting ladder poly-siloxane.
By 27.2 grams of MTMSs (0.20mol), 17.6 grams of diisobutyl silicon under dry nitrogen protection Glycol (0.10mol) and 20 grams of chloroforms are placed in three mouthfuls equipped with mechanical agitation, constant pressure funnel and reflux condenser In flask, it is stirred at room temperature uniformly, 0.08 gram of liquefied ammonia is added at -20 DEG C, reaction obtains intermediate 1 in 6 hours；Have simultaneously at another 48.9 grams of hexichol are added in dry three-necked flask of the nitrogen protection equipped with mechanical agitation, constant pressure funnel and reflux condenser Base dimethoxysilane (0.20mol), 40 grams of chloroforms, 17.6 grams of diisobutyl silicon diols (0.10mol) stir, 0.30 gram of liquefied ammonia is added at 0 DEG C, reacts 20 hours, obtains intermediate 2, intermediate 2 is all added in intermediate 1, adds water 10.8 grams (0.60mol), reacted 10 hours at 0 DEG C；Then gained mixture is neutralized with hydrochloric acid, adds 40mL toluene, water Wash separation to be concentrated under reduced pressure, obtain the siloxane bridge base silane endcapped siloxanes abutting ladder poly-siloxane of formula (1) structure, wherein R1 =R2For methyl, R3-R10For phenyl, A1-A6For isobutyl group, m=1, n=12, gained yield is 94%.
The siloxane bridge base silane endcapped siloxanes abutting ladder poly-siloxane water white transparency solid of gained, polymerization degree n Average value is 12, index of refraction 1.52, and glass transition temperature is 14.82 DEG C, 210 DEG C, viscosity is 345 pools under 100rpm rotating speeds (Poise)。1H NMR(400MHz,CDCl3,298K):δ-0.06-0.12,0.89-1.02,1.52-1.71,7.12- 7.51ppm；29SiNMR(80MHz,CDCl3,298K):δ-63.28,-44.23,-21.25ppm。
Embodiment 15：Me2- I-Me-SLPrS is synthesized
Siloxanes abutment silicon is prepared by MTMS, dimethyldimethoxysil,ne and dipropyl silicon diol Alkane endcapped siloxanes abutting ladder poly-siloxane.
By 27.2 grams of MTMSs (0.20mol), 14.8 grams of dipropyl silicon two under dry nitrogen protection Alcohol (0.10mol) and 15 grams of N,N-dimethylformamides are placed in equipped with mechanical agitation, constant pressure funnel and reflux condenser Three-necked flask in, be stirred at room temperature uniformly, at -10 DEG C add 0.10 gram of DBU, reaction 10 hours intermediate 1；Simultaneously another One has in dry three-necked flask of the nitrogen protection equipped with mechanical agitation, constant pressure funnel and reflux condenser and adds 0.53 Gram 3,5-dimethylphenyl dimethoxysilane (0.0044mol), 2 grams of N,N-dimethylformamides, 0.33 gram of dipropyl silicon diol (0.0022mol) is stirred, and 0.02 gram of DBU is added at 0 DEG C, is reacted 20 hours, is obtained intermediate 2, and intermediate 2 is all added Enter into intermediate 1, add water 7.2 grams (0.40mol), then gained mixture is neutralized with hydrochloric acid, add 40mL toluene, water Wash separation to be concentrated under reduced pressure, obtain the siloxane bridge base silane endcapped siloxanes abutting ladder poly-siloxane of formula (1) structure, wherein R1-R10For methyl, A1-A6For propyl group, m=1, n=450, gained yield is 92%.
The siloxane bridge base silane endcapped siloxanes abutting ladder poly-siloxane water white transparency solid of gained, polymerization degree n Average value is 450, and index of refraction is 1.52 (25 DEG C), and glass transition temperature is 13.51 DEG C, 210 DEG C, viscosity under 50rpm rotating speeds For 134 pools (Poise).1H NMR(400MHz,CDCl3,298K):δ-0.06-0.11ppm；29Si NMR(80MHz,CDCl3, 298K):δ-56.43,-21.73ppm。
The present application is described in detail above with reference to specific embodiment and embodiment, but for ability , can be to above-mentioned embodiment in the range of the essence and purport feature of the present application is not departed from for field technique personnel Various changes, amendment, replacement etc. are carried out with embodiment to implement.As change, correct, replace obtained from embodiment it is also equal In the protection domain of the present application.

Claims (10)

  1. A kind of 1. siloxanes abutting ladder poly-siloxane of siloxane bridge base silane end-blocking, it is characterised in that the siloxane bridge Base ladder polysiloxane has with molecular structure shown in following formula (1)：
    Wherein：
    M is 1-10 integer,
    N is 1-1000 integer,
    A1、A2、A3、A4、A5、A6Separately it is selected from hydrogen, substituted or unsubstituted straight chain, side chain or ring-type C1-25Alkyl, substitution Or unsubstituted straight chain, side chain or ring-type C2-25Alkenyl, substituted or unsubstituted C5-25Aryl,
    R1、R2、R3、R4、R5、R6、R7、R8、R9、R10Separately selected from hydrogen, hydroxyl, substituted or unsubstituted straight chain, side chain or Ring-type C1-25Alkyl, substituted or unsubstituted straight chain, side chain or ring-type C2-25Alkenyl, substituted or unsubstituted C5-25Aryl, substitution Or unsubstituted straight chain, side chain or ring-type C1-25Alkoxy, substituted or unsubstituted C5-25Aryloxy group,
    When above-mentioned group has substituent, the substituent is selected from following at least one：Straight chain, side chain or ring-type C1-25Alkyl, straight chain, the C of side chain or ring-type2-25Alkenyl, C5-25Aryl, containing former selected from oxygen atom, sulphur atom, nitrogen-atoms and phosphorus Group, the halogen atom of at least one atom in son,
    Can have in each comfortable chain of abovementioned alkyl, alkoxy, alkenyl, aryl, aryloxy group or in ring it is at least one be selected from by O, S, the hetero atom in the group that P, N are formed is as chain constituting atom or ring atom.
  2. 2. the siloxanes abutting ladder poly-siloxane of siloxane bridge base silane end-blocking according to claim 1, its feature exist In,
    The group of at least one atom containing in oxygen atom, sulphur atom, nitrogen-atoms and phosphorus atoms is selected from hydroxyl, ring Oxygen propoxyl group, C5-25Epoxy cycloalkyl, acryloxy, C1-25Alkyl-substituted acryloxy, sulfydryl, amino, amino-straight The C of chain, side chain or ring-type1-25Alkyl, C6-25Arylamino, cyano group, urea groups, phosphino-.
  3. 3. the siloxanes abutting ladder poly-siloxane of siloxane bridge base silane end-blocking according to claim 1, its feature exist In the R1、R2、R3、R4、R5、R6、R7、R8、R9、R10、A1、A2、A3、A4、A5、A6Separately selected from hydrogen, hydroxyl, methyl, Ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, the tert-butyl group, n-hexyl, cyclohexyl, n-octyl, positive decyl, n-dodecane It is base, n-hexadecyl, n-octadecane base, n-docosane base, vinyl, pi-allyl, phenyl, aminomethyl phenyl, chlorophenyl, right Ethenylphenyl, 3- (2,3- glycidoxies) propyl group, 2- (3,4- epoxycyclohexyls) ethyl, acryloxypropyl, 3- first Base acryloxypropyl, mercapto propyl group, aminopropyl, 3- (2- aminoethyls)-aminopropyl, 4- amino -3,3- dimethylbutyls, N- are just Butyl -3- aminopropyls, 2- cyano ethyls, 3- cyanopropyls, 3,3,3- trifluoro propyls, 1H, 1H, 2H, 2H- perfluoro capryls, 1H, One kind in 1H, 2H, 2H- perfluoro decyl, chloropropyl, urea propyl group, methoxyl group, ethyoxyl.
  4. A kind of 4. preparation of the siloxanes abutting ladder poly-siloxane of siloxane bridge base silane end-blocking according to claim 1 Method, it is characterised in that the I-shaped siloxane bridge radical siloxane monomer of tetrafunctional and the I-shaped siloxane bridge base silane of difunctionality End-capping reagent cohydrolysis, acted synergistically by supermolecule weak bond to be formed trapezoidal superstructure come regulate and control polymerization with end capping reaction and obtain formula (1) the siloxanes abutting ladder poly-siloxane of the siloxane bridge base silane end-blocking of structure.
  5. 5. the siloxanes abutting ladder poly-siloxane preparation method of siloxane bridge base silane end-blocking according to claim 4, It is characterized in that comprise the steps of：
    The silane of structural formula (2), (3) and (4) is added in the reactor, and organic solvent, water and catalyst are hydrolyzed and be condensed Reaction, at the same it is sustainable or discontinuously vacuumize, remove condensation by-product；Products therefrom separating-purifying will be reacted afterwards, be obtained The siloxanes abutting ladder poly-siloxane of the siloxane bridge base silane end-blocking of above-mentioned formula (1) structure,
    The I-shaped monomer structure formula (2) of described tetrafunctional represents
    Wherein,
    m、R1、R2、A1、A2Implication it is each identical with the implication in claim 1；
    X is selected from OH, halogen, C1-25Alkoxy or C1-25One kind in acyloxy；
    The I-shaped silane end-cappers structural formula (3) of two functions represents
    Wherein,
    m、R3、R4、R5、R6、A3、A4Implication it is each identical with the implication in claim 1；
    X is selected from OH, halogen, C1-25Alkoxy or C1-25One kind in acyloxy；
    The I-shaped silane end-cappers structural formula (4) of two functions represents
    Wherein,
    m、R7、R8、R9、R10、A5、A6Implication it is each identical with the implication in claim 1；
    X is selected from OH, halogen, C1-25Alkoxy or C1-25One kind in acyloxy.
  6. 6. the siloxanes abutting ladder poly-siloxane preparation method of siloxane bridge base silane end-blocking according to claim 5, Characterized in that,
    The I-shaped monomer of tetrafunctional of the formula (2) is condensed in the presence of a catalyst with silicon diol by trifunctional silane coupler Prepare,
    The trifunctional silane coupler is by formula-RSiX3Represent,
    In formula, R=R1,R2；X=halogens, C1-25Alkoxy, C1-25Acyloxy.
  7. 7. the siloxanes abutting ladder poly-siloxane preparation method of siloxane bridge base silane end-blocking according to claim 5, Characterized in that,
    The I-shaped silane end-cappers of two functions of the formula (3) by difunctional silane coupling agent and silicon diol in the presence of a catalyst It is prepared by condensation,
    The difunctional silane coupling agent is by formula R ' R " SiX2Represent,
    In formula, R ', R "=R3With R5Combination, R4With R6Combination；X=halogens, C1-25Alkoxy, C1-25Acyloxy；
    The I-shaped silane end-cappers of two functions of the formula (4) by difunctional silane coupling agent and silicon diol in the presence of a catalyst It is prepared by condensation,
    The difunctional silane coupling agent is by formula R ' R " SiX2Represent,
    In formula, R ', R "=R7With R9Combination, R8With R10Combination；X=halogens, C1-25Alkoxy, C1-25Acyloxy.
  8. 8. the siloxanes abutting ladder poly-siloxane preparation method of siloxane bridge base silane end-blocking according to claim 5, It is characterized in that described reaction temperature is -50 DEG C to 150 DEG C；The hydrolysis and setting-up point are -50 DEG C to 50 DEG C；Envelope It is -50 DEG C to 50 DEG C to hold reaction temperature early stage, and the later stage can rise to 100 DEG C to block complete reaction temperature.
  9. 9. the siloxanes abutting ladder poly-siloxane preparation method of siloxane bridge base silane end-blocking according to claim 5, its Be characterised by, the organic solvent be selected from：Alkanes, alkane substitute class, alcohols, ethers, ketone, esters, amide-type, nitrile One or more in class, pyrrolidinone compounds, sulfoxide type.
  10. 10. the siloxanes abutting ladder poly-siloxane preparation method of siloxane bridge base silane end-blocking according to claim 5, its It is characterised by,
    The catalyst is selected from acid, oxide and hydroxide, ammonia or amine, transistion metal compound, ion exchange resin In one or more.
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WO2019096188A1 (en) * 2017-11-17 2019-05-23 长兴（中国）投资有限公司 Siloxane bridged trapezoidal polysiloxane terminated with siloxane bridged silane and preparation method therefor
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CN112341625A (en) * 2020-11-27 2021-02-09 广州天赐高新材料股份有限公司 High-temperature-resistant high-compatibility trapezoidal silicone resin and preparation method and application thereof
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CN112480862B (en) * 2020-11-27 2022-07-12 广州天赐高新材料股份有限公司 Trapezoidal silicone resin reinforced organic silicon pressure-sensitive adhesive and preparation method thereof
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CN116082639A (en) * 2022-12-19 2023-05-09 广州一新科技有限公司 Trapezoidal polysilsesquioxane containing two active functional groups and preparation method thereof

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