CN104045831B - A kind of siloxanes abutting ladder poly-siloxane and preparation method thereof - Google Patents
A kind of siloxanes abutting ladder poly-siloxane and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to siloxanes as abutment, the main chain siloxanes abutting ladder poly-siloxane as siloxanes and preparation method thereof.The present invention is with RSiX3、R’SiX3Carry out first step condensation reaction with α, ω silicon diol, form intermediate；Further carry out second step condensation reaction with intermediate, then carry out the siloxanes abutting ladder poly-siloxane that separating-purifying obtains having following structure.This siloxanes abutting ladder poly-siloxane taken into account ladder polymer and the high temperature tolerance of polysiloxanes, high intensity and with general organic macromolecule high-compatibility, abutment, side base, end group and the change of the degree of polymerization can be passed through, regulate the combination properties such as its air-tightness, caking property, refractivity.
Description
Technical field
The present invention relates to trapezoidal organosilicon polymer, particularly to siloxanes as abutment, main chain is as silica
Siloxanes abutting ladder poly-siloxane of alkane and preparation method thereof.
Background technology
Organosilicon polymer practical on general industry, as silicone oil and silicone rubber etc. be main chain be the poly-of strand
Siloxanes macromolecule, it has the prominent advantages that excellent heat-resisting quantity compared with general organic polymer for they
(temperature resistant grade is up to more than 200 DEG C), lower temperature resistance (can less than less than-100 DEG C), radiation hardness, weather-proof
Property and breathability etc..And " trapezoidal organosilicon polymer " is main chain is the polysiloxanes macromolecule of double-strand
(R-LPS), they to have more excellent heat-resisting quantity compared with general strand polysiloxanes macromolecule (resistance to
Temperature grade up to more than 300 DEG C), radiation hardness, weatherability, high intensity, high-air-tightness, relatively high-adhesion
With good filming etc..Typically according to the difference of its abutment structure, oxygen abutment-trapezoidal poly-sesquialter can be divided into
Siloxanes (R-LPSQ, R are side base)；Organic abutment-ladder polysiloxane (O-LPRS, O are abutment,
R is side base) and siloxanes abutment-ladder polysiloxane (S-LPRS, S are abutment, and R is side base).
Owing to ladder polysiloxane (R-LPS) has many excellent performances, the most extremely concern of people.
As far back as nineteen sixty former Soviet Union K.A.Andrianov et.al (Izu.Akad.Nauk.S S S R, Otdel
Khim.Nauk, 1958,1004) once attempted synthesis benzene abutting ladder poly-siloxane (Ph-LPMS), fail
Success, only obtains random oligomer.The same year, U.S. J.F.Brown et.al(J.Am.Chem.Soc.1960,
82,6194) report employing " balance thermal polycondensation " method and synthesize the ladder with high-fire resistance and high intensity
Shape polyphenylsilsesquioxane (Ph-LPSQ).Cause the biggest sensation the most in the world, and occur in that
Relate to article and the patent of the ladder-like polysiloxane (R-LPSQ, R are side base) of not homonymy base in a large number.
As United States Patent (USP) US3017386 discloses a kind of poly-silsesquioxane of phenyl solvable, that have trapezium structure
Alkane and preparation method thereof.United States Patent (USP) 5081202, United States Patent (USP) 6153689 and Japan Patent 200159892
Etc. also disclosing that, with trichlorosilane synthesis, there is the ladder-like polysiloxane of not homonymy base.
Condensation reaction is to prepare the method that organic siloxane polymer is conventional, general condensation reaction include dehydration,
De-HCl, dealcoholization etc..If in the condensation course of siloxanes, uncontrolled to reaction condition, many
The silane monomer of functional group can form the random or structure of crosslinking.Thanking to " the supermolecule structure that duckweed et al. is write
Build regulation and control Polymer Synthesizing introduction " (Xie Ping, Zhang Rongben, Cao Xinyu Chemical Industry Press, 2009 years
December, ISBN 978-7-122-05947-5) reported under comparatively gentle reaction condition, silane and
Hydrolyzate can form trapezoidal superstructure by the interaction between group, between silane and solvent,
The most again by condensation, the polysiloxanes with trapezium structure can be formed, and raw material kind can be passed through
Class, solvent, catalyst, reaction temperature, response time, charging sequence etc. are to the molecular weight of product and knot
Structure is adjusted, but be not related to the present invention with siloxanes as abutment, the main chain siloxane bridge as siloxanes
Base ladder polysiloxane.
The Zhang Rongben seminar of Institute of Chemistry, Academia Sinica uses the method that supermolecule constructs regulation and control polymerization
Be prepared for a series of organosilicon ladderlike polymer, CN1105677, PCT/CN2008/072588,
WO2010/034161 A1 discloses and includes that the highly-ordered ladder-like of the side chains such as phenyl, methyl, vinyl gathers
Silsesquioxane (R-LPSQ, R represent side base).They are special in Chinese patent CN 1280995, the U.S.
Profit US6423772B1 discloses a kind of ladder polysiloxane containing organic abutment and preparation method thereof, and
At J.Am.Chem.Soc.2002,124,10482, Angew.Chem.Int.Ed.2006,45,3112 and
Multiple organic abutting ladder poly-siloxane reported in the documents such as Chem.Commun.2009,4079
(O-LPRS) preparation and sign.Additionally, these ladder polysiloxanes can provide through further modification
Many new function materials.Zhang Rongben seminar discloses a kind of trapezoidal poly-with heliosensitivity at CN1255527
Siloxanes is liquid crystal orientating membrane of base material and preparation method thereof, and it is with the trapezoidal poly-organic sesquialter silicon of heliosensitivity
Oxygen alkane is base material, by solution rotating film and 180 DEG C of heat treatments, at glass substrate and ITO conductive surface layer
On define polymer solid membrane, after rubbed directional process, then with long wave ultraviolet light carry out appropriateness illumination
Processing, available tilt angle is the high stability liquid crystal alignment layer of 8～10 °.Zhang Rongben seminar exists
CN1284514 discloses a kind of tubular high polymer being made up of organic abutting ladder poly-siloxane and preparation thereof
Method, discloses a kind of tubular high polymer being made up of organic abutting ladder poly-siloxane at CN1284513
Complex and preparation method thereof.Size and chemically compatible difference according to tubular high polymer can select
Property the matched guest molecule of ground embedding, thus form multiple supramolecular complex, and at molecule device
Part, the catalysis of molecular recognition, separation and the field such as novel optical material and novel electricity material have extensively
General application prospect.
It is known that the performance of ladder polysiloxane depends on its molecular size range, aggregated structure, bridge
Base, side base and the Nomenclature Composition and Structure of Complexes of end group, wherein the structure of abutment is particularly important.Trapezoidal poly-silsesquioxane
Alkane (R-LPSQ)；Organic abutment-ladder polysiloxane (O-LPRS) and siloxanes abutment-trapezoidal poly-silicon
Oxygen alkane (S-LPRS) has different performances.Ladder-like polysiloxane excellent heat resistance, its vitrification
Temperature may be up to more than 180 DEG C.But owing to trapezoidal double-strand flexibility can be made with oxygen atom to reduce for abutment,
Polymer fragility is higher, particularly general ladder-like polysiloxane and organic macromolecule poor compatibility,
It is difficult to dissolve each other, for being used for improving organic macromolecule performance and bringing difficulty；And the poly-silicon of organic abutting ladder poly
Oxygen alkane (as penylene abutment or phenylate support abutment etc.) pliability is higher, with general general organic macromolecule
The compatibility is good, and to improving, organic macromolecule performance is highly beneficial, but its thermostability is slightly poorer than trapezoidal poly-
Silsesquioxane.Industrial expansion has high-fire resistance, high-air-tightness in the urgent need to one, refractivity can
Adjust, have and the solubility ladder polysiloxane of general organic polymer excellent compatibility simultaneously.This
Bright described with siloxanes as abutment, the main chain ladder polysiloxane as siloxanes can meet above industry and send out
The exhibition requirement to solubility ladder polysiloxane.
Summary of the invention
It is an object of the invention to provide a kind of can overcome ladder-like polysiloxane fragility with siloxanes be
Abutment, main chain are the solubility siloxanes abutting ladder poly-siloxane of siloxanes, and this solubility silica
Alkane abutting ladder poly-siloxane has high-flexibility energy, cold-hot performance, high-air-tightness, high intensity, good
Good optical property and processing characteristics etc..
The a further object of the present invention be to provide a kind of with siloxanes as abutment, the main chain solubility as siloxanes
The preparation method of siloxanes abutting ladder poly-siloxane.
The present invention with siloxanes as abutment, the main chain solubility poly-silicon of siloxanes abutting ladder poly as siloxanes
Oxygen alkane has a following formula (I) structure:
Described R, R ', A, A ' it is independently selected from hydrogen, methyl (Me), ethyl, isopropyl, isobutyl
Base, vinyl (Vi), pi-allyl (ally), phenyl (Ph), glycydoxy, methyl
Acryloxypropyl, acryloxypropyl, aminopropyl, 3-(2-aminoethyl)-aminopropyl, chloropropyl,
One in the groups such as mercapto propyl group, chlorophenyl, phenylol, benzyl alcohol base.
Z, Z ' separately selected from hydrogen, methyl (Me), ethyl, isopropyl, isobutyl group, alkyl silicon
One in base etc..
Described alkyl silyl is selected from-Si (Me)3、-Si(Ph)3、-SiH(Me)2、-SiVi(Me)2、-SiH(Ph)2、
-SiVi(Ph)2、-Si-ally(Me)2、-Si-ally(Ph)2、-Si-acryl(Me)2、-Si-acryl(Ph)2In Deng
A kind of；Wherein Me is methyl；Ph is phenyl；Vi is vinyl；Ally is pi-allyl；Acryl is first
Base acryloxypropyl.
M is the integer of 1-5.
N is the integer of 1-1000.
The present invention with siloxanes as abutment, the main chain solubility poly-silicon of siloxanes abutting ladder poly as siloxanes
Oxygen alkane is prepared by condensation reaction, wherein with RSiX3、R’SiX3With α, ω-silicon diol
(HO(AA’SiO)mH) carry out first step condensation reaction, form intermediate；Further carry out with intermediate
Second step condensation reaction, then carries out separating-purifying；Its preparation method comprises the following steps:
(1) in the reactor, RSiX is added3、R’SiX3And organic solvent, wherein RSiX3With R ' SiX3
Mol ratio be 1:0～1:1, add α, ω-silicon diol and catalyst；Wherein (RSiX3+R’SiX3) total
Molal quantity and α, the mol ratio of the molal quantity of ω-silicon diol is 1.8:1 to 20:1, and the consumption of catalyst is
0.0001 to 10 times of α, ω-silicon diol molal quantity；Then react 30 minutes at-10 DEG C to 150 DEG C
To 10 hours, through filtering and/or distillation and concentration, obtain midbody solution；
(2) in the midbody solution that step (1) obtains, add water and catalyst, or add alcohol and urge
Agent, the water wherein added or the amount of alcohol are the α added in step (1), the molal quantity of ω-silicon diol
0～10 times, the consumption of catalyst by step (1) is added the 0.0001 of α, ω-silicon diol molal quantity
To 10 times；React 30 minutes to 10 hours at 0 DEG C to 150 DEG C；Add end-capping reagent and catalyst,
React 30 minutes to 10 hours；Added by during wherein the consumption of end-capping reagent and catalyst is respectively step (1)
0～10 times of the molal quantity of the α entered, ω-silicon diol；Reaction gained mixture is separated by filtration, purification etc.
Process, obtain the siloxanes abutting ladder poly-siloxane of above-mentioned formula (I) structure；Its productivity is 68～95%.
Described adds water and catalyst in the midbody solution that step (1) obtains, or adds alcohol and urge
Agent；Preferably when the concentration of the midbody solution that step (1) obtains not is 10～60wt%, pass through
Distillation and concentration or with organic solvent, the midbody solution that step (1) obtains to be deployed into concentration be 10～60wt%
Midbody solution after add water and catalyst, or add alcohol and catalyst.
Described adds water and catalyst in the midbody solution that step (1) obtains, or adds alcohol and urge
Agent；Under conditions of 0 DEG C to 150 DEG C, preferably add water and catalyst, or add alcohol and catalyst.
Described RSiX3And R ' SiX3In R, R ' be independently selected from hydrogen, methyl (Me), second
Base, isopropyl, isobutyl group, vinyl (Vi), pi-allyl (ally), phenyl (Ph), (+)-2,3-Epoxy-1-propanol
Ether epoxide propyl group, methacryloxypropyl, acryloxypropyl, aminopropyl, 3-(2-aminoethyl)-
One in the groups such as aminopropyl, chloropropyl, mercapto propyl group, chlorophenyl, phenylol, benzyl alcohol base；X
One in OH, Cl, methoxyl group, ethyoxyl, isopropoxy, isobutoxy etc. can be independently selected from
Kind.
Described α, ω-silicon diol has following molecular formula: HO (AA ' SiO)mH, wherein A, A ' respectively
Independent selected from hydrogen, methyl (Me), ethyl, isopropyl, isobutyl group, vinyl (Vi), pi-allyl
(ally), phenyl (Ph), glycydoxy, methacryloxypropyl, acryloyl-oxy
Base propyl group, aminopropyl, 3-(2-aminoethyl)-aminopropyl, chloropropyl, mercapto propyl group, chlorophenyl, phenylol,
One in the groups such as benzyl alcohol base；M is the integer of 1-5.
Described end-capping reagent is selected from XSi (Me)3、XSi(Ph)3、XSiH(Me)2、XSiVi(Me)2、
XSi-ally(Me)2、XSiH(Ph)2、XSiVi(Ph)2、XSi-ally(Ph)2、XSi-acryl(Ph)2、
H(Me)2Si-O-Si(Me)2H、H(Ph)2Si-O-Si(Ph)2H、Vi(Me)2Si-O-Si(Me)2Vi、
Vi(Ph)2Si-O-Si(Ph)2One or more in Vi etc.；X can be independently selected from OH, Cl, methoxy
One or more in base, ethyoxyl, isopropoxy, isobutoxy etc.；Wherein Me is methyl, Ph
For phenyl, Vi is vinyl, and ally is pi-allyl, and acryl is methacryloxypropyl.
Described catalyst be selected from acid, metal, the oxide of metal, the hydroxide of metal or they
Hydrate, transistion metal compound, organic amine, one or more in ion exchange resin etc..
One or more in hydrochloric acid, sulphuric acid, nitric acid, sulfonic acid, formic acid, acetic acid etc. of described acid.
One or more in lithium, sodium, potassium, calcium, magnesium, barium of described metal.
One or more in calcium oxide, magnesium oxide, Barium monoxide etc. of the oxide of described metal.
The hydroxide of described metal selected from Lithium hydrate, sodium hydroxide, potassium hydroxide, calcium hydroxide,
One or more in magnesium hydroxide, barium hydroxide etc..
Described transistion metal compound is selected from dibutyl tin dilaurate ester, dioctyl tin cinnamic acid stannum
One or more in ester, dialkyl group diaryltin, butyl titanate, tetraethyl titanate etc..
Described organic amine is selected from Tetramethylammonium hydroxide, TBAH, triethylamine, pyridine etc.
In one or more.
Described ion exchange resin is handed over selected from the quaternary ammonium type ion that styrene divinylbenzene copolymer is matrix
Change resin, styrene divinylbenzene copolymer is the sulfonic acid ion exchange resin of matrix, styrene diethyl
Alkene benzene copolymer be the carboxylic acid type ion exchange resin of matrix, polyacrylic acid be that the carboxylic acid type ion of matrix is handed over
Change one or more in resin etc..
Described organic solvent is selected from: toluene, dimethylbenzene, methanol, ethanol, hexane, acetone, butanone,
Oxolane, Ketohexamethylene, dimethylformamide (DMF), dimethyl acetylamide (DMA), dimethyl sulfoxide
(DMSO), one or more in dioxane, ether, petroleum ether, acetonitrile etc..
The present invention with siloxanes as abutment, the main chain solubility poly-silicon of siloxanes abutting ladder poly as siloxanes
Oxygen alkane taken into account ladder polymer and the high temperature tolerance of polysiloxanes, high intensity and with general organic polymer
High-compatibility, have good molten in oxolane (THF), toluene, chloroform, DMF equal solvent
Xie Xing, proves its composition structure by tests such as FTIR, further through VPO(vapour-pressure osmometer) etc.
Its mean molecule quantity can be recorded, calculate its average n value.The present invention with siloxanes as abutment, main chain
For the XRD spectra of solubility siloxanes abutting ladder poly-siloxane of siloxanes at the model that 2 θ are 1～40 °
At least occurring 2 obvious peaks in enclosing, its peak value is corresponding to the molecule of siloxanes abutting ladder poly-siloxane
The shot-range ordered structure of chain.
Owing to the main chain of solubility siloxanes abutting ladder poly-siloxane and the abutment of the present invention are all Si-O keys
Being connected, making solubility siloxanes abutting ladder poly-siloxane material have high-flexibility can be with cold-hot performance；
Wherein A, A ' is the side base of abutment, R, R ' it is the side base of main chain, Z is end group, and these side bases are organic
Group, provides good for solubility siloxanes abutting ladder poly-siloxane material with general organic polymer again
The good compatibility.The solubility siloxanes abutting ladder poly-siloxane of this molecular structure can pass through abutment,
The change of side base, end group and the degree of polymerization etc., regulates the combination properties such as its air-tightness, caking property, refractivity；
Material high-air-tightness, high intensity, good optical property (refractive index=1.42～1.65) and processing can be given
Performance etc..
The abutment of solubility siloxanes abutting ladder poly-siloxane, side base and the selection of end group of the present invention and
Combination can make the above-mentioned performance of solubility siloxanes abutting ladder poly-siloxane material be adjusted flexibly, to adapt to
Various different application demands, can be widely used for improving general organic polymer, especially for organic painting
Expect the improvement of the performances such as high molecular heatproof, radiation hardness and weather-resistant；And high-power light emitting can be improved
Diode (LED) packaging plastic and the thermostability of organic pressure-sensitive gel, index of refraction, caking property, air-tightness and
Mechanical property, such as: intensity, modulus, hardness etc..Additionally, this kind of siloxanes abutting ladder poly-siloxane
Itself can be widely used for optics and weather-resistant coating and multiple protective coating etc..
Accompanying drawing explanation
Fig. 1. the FTIR spectrogram of the embodiment of the present invention 1 products therefrom.
Fig. 2. the embodiment of the present invention 1 products therefrom29Si-NMR spectrogram.
Fig. 3. the XRD spectra of the embodiment of the present invention 1 products therefrom.
Detailed description of the invention
Embodiment 1
Siloxanes abutting ladder poly-siloxane is prepared by phenyl trichlorosilane, Diphenylsilanediol.
(1) under dry nitrogen protection, in the many necks bottle being mounted with condensing tube and Dropping funnel, insert
50.8 grams of (0.24 mole) phenyl trichlorosilanes, toluene 150 grams, oxolanes 150 grams, stirring is all
Even；At-10 DEG C, 26.0 grams of (0.12 mole) Diphenylsilanediols are dividedly in some parts many necks bottle
In, it is simultaneously added dropwise the triethylamine of 26 grams (0.26 moles)；After dripping, progressively it is warming up to 60 DEG C instead
Answer 1 hour；After stopped reaction, solution is filtered, collect clear liquid, obtain midbody solution；To obtain
Midbody solution obtain, by distillation and concentration, the midbody solution that concentration is about 30wt%；
(2) at temperature is 0 DEG C, the concentration obtained to step (1) is about in the midbody solution of 30wt%
Drip 2.88 grams of (0.16 mole) water and 40.5 grams of (0.4 mole) triethylamines, after dripping,
React 1.5 hours at 25 DEG C～40 DEG C；Add end-capping reagent vinyldimethylchlorosilane 6.4 gram (0.053
Mole) and triethylamine 11.2 grams (0.11 mole), it is warming up to after continuing reaction at 40 DEG C 7 hours
120 DEG C distill out oxolane and water；Then reaction gained mixture is filtered separation, collect clear liquid, water
Being washed till neutrality, concentration, drying under reduced pressure purify, and obtain the siloxanes abutment ladder of aforementioned formula (I) structure
Shape polysiloxanes, wherein R=R '=phenyl, A=A '=phenyl, Z=H, Z '=SiMe2Vi, Me=methyl,
Vi=vinyl, m=1.The productivity of gained siloxanes abutting ladder poly-siloxane is 87%.
Gained siloxanes abutting ladder poly-siloxane dissolves in toluene, FTIR as shown in Figure 1,29Si-NMR
As shown in Figure 2, XRD spectra is as shown in Figure 3；By VPO(vapour-pressure osmometer) test analysis its
Molecular weight, the meansigma methods obtaining n is 8.It is prepared as with solution film formation the thin film of 0.1 millimeter,
The transmitance of visible light wave range is higher than 93%, and refractive index is 1.59.
Embodiment 2
By phenyl trichlorosilane, vinyl trichlorosilane and HO (MePhSiO)5H prepares siloxanes abutment
Ladder polysiloxane.
(1) under dry nitrogen protection, in the many necks bottle being mounted with condensing tube and Dropping funnel, put
Enter 31.7 grams of (0.15 mole) phenyl trichlorosilanes, 24.2 grams of (0.15 mole) vinyl trichlorosilanes
With toluene 500 grams, stir；By 83.9 grams of HO (MePhSiO) at-10 DEG C5H(0.12 mole)
It is dividedly in some parts in many necks bottle, is simultaneously added dropwise the triethylamine of 60.7 grams (0.6 moles)；After dripping, by
Step is warming up to 60 DEG C and reacts 3 hours；After stopped reaction, solution is filtered, collect clear liquid, obtain centre
Liquid solution；
(2) at temperature is 25 DEG C, (0.5 rubs to drip 9 grams in the midbody solution that step (1) obtains
You) water and 60.7 grams of (0.6 mole) triethylamines (molecular weight 101.19), after dripping, at 60 DEG C
React 2 hours；Add end-capping reagent vinyldimethylchlorosilane 49 grams (0.053 mole) and triethylamine
24.3 grams (0.11 mole), continues reaction 2 hours at 60 DEG C；Then will reaction gained mixture mistake
Filter separates, and collects clear liquid, is washed to neutrality, and concentration, drying under reduced pressure purify, and obtain aforementioned formula (I)
The siloxanes abutting ladder poly-siloxane of structure, wherein R=Ph, R '=Vi, A=Me, A '=Ph, Z=Z '=
SiViMe2, m=5, n=2, Ph are phenyl, and Me is methyl, and Vi is vinyl.Gained siloxane bridge
The productivity of base ladder polysiloxane is 91%.
From FTIR spectrogram, at 1070cm-1, 1120cm-1, 1430cm-1, 1600cm-1, 2940
cm-1And 3380cm-1Absworption peak occurs.By1H-NMR spectrum understands, at 7.3ppm, 5.3ppm, 0.6ppm
With 0.14ppm, peak occurs.Product dissolves in dimethylbenzene, and with solution film formation, it is prepared as 0.1 millimeter
Thin film, in the transmitance of visible light wave range higher than 95%, refractive index is 1.53.
Embodiment 3
By methyl trichlorosilane, 3-acryloxy trichlorosilane and HO (MePhSiO)3H prepares silica
Alkane abutting ladder poly-siloxane.
(1) under dry nitrogen protection, in the many necks bottle being mounted with condensing tube and Dropping funnel, put
Enter 17.9 grams of (0.06 mole) methyl trichlorosilanes and 29.7 grams of (0.18 mole) 3-acryloxies
Trichlorosilane, Ketohexamethylene 300 grams, stirs；By 51.2 grams of HO (MePhSiO) at 30 DEG C3H
(0.12 mole) is dividedly in some parts in many necks bottle, is simultaneously added dropwise the triethylamine of 60.7 grams (0.6 moles)；
After dripping, progressively it is warming up to 60 DEG C and reacts 5 hours；After stopped reaction, solution is filtered, collect clear
Liquid, obtains midbody solution；The midbody solution obtained is obtained by adding toluene after distillation and concentration
Concentration is about the midbody solution of 30wt%；
(2) at temperature is 25 DEG C, the concentration obtained to step (1) is about the midbody solution of 30wt%
Middle dropping 21.6 grams (1.2 moles) water and 0.18 gram of (0.002 mole) triethylamine, after dripping,
React 4 hours at 60 DEG C～150 DEG C；Then reaction gained mixture is filtered separation, collect clear liquid, water
Be washed till neutrality, with anhydrous sodium sulfate be dried, filter, drying under reduced pressure purifies, and obtains aforementioned formula (I)
The siloxanes abutting ladder poly-siloxane of structure, wherein R=Me, R '=3-acryloxy, A=Me,
A '=Ph, end group Z=Z '=H, Me are methyl, and Ph is phenyl, and the meansigma methods of m=3, n is 950.
The productivity of gained siloxanes abutting ladder poly-siloxane is 94%.
From XRD spectra, having obvious peak to occur in the position that 2 θ are 5.5 ° and 19.5 °, product is solvable
In dimethylbenzene, it is prepared as with solution film formation the thin film of 0.1 millimeter, passing through at visible light wave range
Rate is higher than 90%, and refractive index is 1.47.From FTIR spectrogram, at 740cm-1, 1070cm-1, 1120
cm-1, 1430cm-1, 1590cm-1, 1,720cm-1, 2940cm-1And 3340cm-1Absworption peak occurs.
Embodiment 4
Siloxanes abutting ladder poly-siloxane is prepared by chloropropyl trichloro-silane, Diphenylsilanediol.
(1) under dry nitrogen protection, in the many necks bottle being mounted with condensing tube and Dropping funnel, insert
0.22 mole of chloropropyl trichloro-silane and toluene 100 milliliters, 100 milliliters of acetone, stir；At 25 DEG C
The lower triethylamine by 0.12 mole of Diphenylsilanediol and 0.24 mole joins in many necks bottle；Dropping
After complete, progressively it be warming up to 60 DEG C and react 2 hours；After stopped reaction, solution is filtered, collects clear liquid,
Obtain midbody solution；
(2) at temperature is 25 DEG C, in the midbody solution that step (1) obtains, 0.18 mole of water is added,
And drip the triethylamine of 0.36 mole, then react 4 hours at 40 DEG C～60 DEG C；Then institute will be reacted
Obtain mixture and filter separation, collect clear liquid, be washed to neutrality, be dried with anhydrous sodium sulfate, filter, subtract
Press dry dry purification, obtain the siloxanes abutting ladder poly-siloxane of aforementioned formula (I) structure, wherein
R=R '=chloropropyl, A=A '=phenyl, Z=Z '=H；The meansigma methods of m=1, n is 120.Gained silica
The productivity of alkane abutting ladder poly-siloxane is 87%.
From FTIR spectrogram, at 1070cm-1, 1120cm-1, 1310cm-1, 2940cm-1With 3300
cm-1Absworption peak occurs.From XRD spectra, obvious peak is had to go out in the position that 2 θ are 8.1 ° and 19.5 °
Existing.
Embodiment 5
The siloxanes abutting ladder poly-siloxane of Z=Z '=H that embodiment 4 is prepared and 1,1,3,3-
Tetramethyl disiloxane reacts further and obtains Z=Z '=SiHMe2Siloxanes abutting ladder poly-siloxane.
Siloxanes abutting ladder poly-siloxane 88.6g embodiment 4 prepared is dissolved in 60 milliliters of first
In benzene and 20 milliliters of butanone, add water, the 1 of 0.03 mole, 1,3,3-tetramethyl two silica of 0.06 mole
Alkane and HCl 0.005 mole, react 2 hours at temperature is 25～80 DEG C；Decompression is distilled and is dried
Purify, obtain the siloxanes abutting ladder poly-siloxane of aforementioned formula (I) structure, wherein R=R '=
Chloropropyl, side base the A=A '=phenyl of siloxanes abutment, end group Z=Z '=SiHMe2, wherein Me is
Methyl；The meansigma methods of m=1, n is 120.The productivity of gained siloxanes abutting ladder poly-siloxane is 74%.
By FTIR spectrogram compared with the FTIR spectrogram of embodiment 4 product, at 1260cm-1With
2240cm-1New absworption peak occurs, is attributed to the absworption peak of Si-Me and Si-H, XRD spectra base respectively
This does not change.
Embodiment 6
The poly-silica of siloxanes abutting ladder poly is prepared by phenyltrimethoxysila,e, Diphenylsilanediol
Alkane.
(1) in the many necks bottle being mounted with condensing tube and Dropping funnel, 40 grams of (0.2 mole) phenyl are inserted
Trimethoxy silane, 80 grams of acetone, 20 grams of methanol and 100 grams of toluene, stir；At 25～60 DEG C
The lower Ba (OH) by 0.004 mole2H2O and 21.6 grams of (0.1 mole) Diphenylsilanediols add
In many necks bottle；After adding, reaction 2 hours at a reflux temperature；Then acetone and methanol, mistake are steamed
Filter, collects solution, obtains midbody solution；
(2) at temperature is 40～80 DEG C, in the midbody solution that step (1) obtains, 18 gram (1 is added
Mole) water, 20 grams of oxolanes and the sulphuric acid of 0.001 mole, at 40 DEG C～80 DEG C, then react 3
Hour, then heat to 120 DEG C and react 1 hour；It is cooled to room temperature, filters, collect clear liquid, washing
To neutral, drying under reduced pressure purifies, and obtains the poly-silica of siloxanes abutting ladder poly of aforementioned formula (I) structure
Alkane, wherein R=R '=phenyl, A=A '=phenyl, Z=H, Z '=H, the meansigma methods of m=1, n is
85.The productivity of gained siloxanes abutting ladder poly-siloxane is 95%.
From FTIR spectrogram, at 1069cm-1, 1128cm-1, 1261cm-1, 1428cm-1, 2841cm-1,
2940cm-1And 3381cm-1Absworption peak occurs.From XRD spectra, it it is 7.1 ° and 20.1 ° at 2 θ
Position have obvious peak to occur.
Embodiment 7
By vinyltrimethoxy silane, aminopropyl trimethoxysilane, Diphenylsilanediol system
Standby siloxanes abutting ladder poly-siloxane.
(1) vinyltrimethoxy silane 22.2 grams and aminopropyl trimethoxysilane in the reactor, are inserted
33.2 grams and Diphenylsilanediol 32.5 grams, and add methanol: dimethylbenzene: the mass ratio of acetone is
The mixed solvent of 1:5:1 15 grams, stirs；By Ba (OH)2·8H2O 9.5 grams joins in reactor；
After adding, react 10 hours at 60 DEG C；Then steam acetone and methanol, filter, collect solution,
Obtain midbody solution；Toluene and butanone (toluene: the matter of butanone is added in the midbody solution obtained
Amount than be 1:1) mixed liquor, obtain the midbody solution that concentration is 60wt%；
(2) in the midbody solution that concentration is 60wt% that step (1) obtains add 5.4 grams of water,
Ba(OH)2·8H2O 0.19 gram, after adding, reacts 4 hours at 100 DEG C；Add triphenyl ethyoxyl
1.83 grams of silane, reacts 2 hours at 150 DEG C；Then reaction gained mixture is filtered separation, receive
Collection clear liquid, drying under reduced pressure purifies, and obtains the poly-silica of siloxanes abutting ladder poly of aforementioned formula (I) structure
Alkane, wherein R=vinyl, R '=aminopropyl, A=A '=phenyl, Z=Z '=SiPh3, Ph is phenyl, m=1,
The meansigma methods of n is 75.The productivity of gained siloxanes abutting ladder poly-siloxane is 90%.
From XRD spectra, obvious peak is had to occur in the position that 2 θ are 7.6 ° and 19.4 °.By FTIR
Spectrogram understands, at 1072cm-1, 1130cm-1, 1428cm-1, 1595cm-1, 3020cm-1With 3370
cm-1Absworption peak occurs.
Embodiment 8
Siloxane bridge is prepared by (3-glycidylpropyl) trimethoxy silane and Diphenylsilanediol
Base ladder polysiloxane.
(1) 56.7 grams of (0.24 mole) (3-glycidylpropyl) trimethoxies in the reactor, are inserted
Silane, 26 grams of (0.12 mole) Diphenylsilanediols, 50 grams of toluene and 10 grams of methanol, stirring
Uniformly；By 0.04 gram of (0.0006 mole) Ca (OH)2Join in reactor；After adding, at 60～80 DEG C
Lower reaction 4 hours；Then steam methanol, filter, collect solution, obtain midbody solution；To obtaining
Midbody solution in add 100 grams of toluene and 100 grams of oxolanes；
(2) midbody solution obtained after step (1) adds toluene and oxolane adds water 14.4
Gram (0.8 mole) and CaO 0.34 gram (0.006 mole), after adding, react 2 at a reflux temperature
Hour；Oxolane is steamed, then reaction 2 hours at 120 DEG C；Will reaction gained mixture filtration point
From, collect clear liquid, drying under reduced pressure purifies, and obtains the siloxanes abutting ladder poly of aforementioned formula (I) structure
Polysiloxanes, wherein R=R '=3-glycidylpropyl, A=A '=phenyl, Z=Z '=methoxyl group, m=1,
The meansigma methods of n is 450.The productivity of gained siloxanes abutting ladder poly-siloxane is 87%.
From XRD spectra, obvious peak is had to occur in the position that 2 θ are 7.9 ° and 18.5 °.By FTIR
Spectrogram understands, at 1072cm-1, 1130cm-1, 1428cm-1, 1595cm-1, 2841cm-1And 3040cm-1
Absworption peak occurs.
Embodiment 9
Siloxanes is prepared by trimethoxy silane, MTMS and Diphenylsilanediol
Abutting ladder poly-siloxane.
(1) trimethoxy silane 18.3 grams (0.15 mole), methyl trimethoxy epoxide in the reactor, are inserted
17.7 grams of silane (0.13 mole), Diphenylsilanediol 26 grams (0.12 mole), add benzene second
Alkene divinylbenzene copolymer is 0.15 gram of the carboxylic acid type ion exchange resin of matrix；After adding, at 150 DEG C
Lower reaction 30 minutes；Stopped reaction, adds 50 grams of toluene and 50 grams of oxolane diluent liquid, filter,
Collect solution, obtain midbody solution；
(2) in the midbody solution that step (1) obtains, 3.6 grams of water (0.2 mole) and styrene are added
Divinylbenzene copolymer is the sulfonic acid ion exchange resin 0.15 gram of matrix, after adding, anti-at 65 DEG C
Answer 3 hours, after reaction terminates, reaction gained mixture is filtered separation, collects clear liquid, drying under reduced pressure
Purify, obtain the siloxanes abutting ladder poly-siloxane of aforementioned formula (I) structure, wherein R=H, R '=
Methyl, A=A '=phenyl, Z=Z '=methoxyl group, the meansigma methods of m=1, n is 50.Gained siloxane bridge
The productivity of base ladder polysiloxane is 82%.
From XRD spectra, obvious peak is had to occur in the position that 2 θ are 9.9 ° and 18.5 °.By FTIR
Spectrogram understands, at 830cm-1, 1100cm-1, 1030cm-1, 1260cm-1,1580cm-1,2240cm-1,
2840cm-1And 3040cm-1Absworption peak occurs.
Embodiment 10
The poly-silica of siloxanes abutting ladder poly is prepared with MTMS and Diphenylsilanediol
Alkane.
(1) MTMS 98 grams (0.72 mole), dimethyl dihydroxy in the reactor, are inserted
Base silane 11 grams (0.12 mole), dimethylbenzene and each 20 grams of dioxane, add tetra-n-butyl titanate
0.02 gram；After adding, react 2 hours at 100 DEG C；Then by the MTMS of excess
(boiling point 102 DEG C) steams, and obtains midbody solution；
(2) in the midbody solution that step (1) obtains, toluene 20 grams, oxolane 20 grams and water are added
4.3 grams (0.24 mole), after adding, at 80 DEG C, stirring reaction 1 hour, adds tetra-n-butyl titanate
0.02 gram, react 1 hour；Steam the methanol of oxolane and generation, after reaction terminates, institute will be reacted
Obtaining mixture and filter separation, collect clear liquid, drying under reduced pressure purifies, and obtains aforementioned formula (I) structure
Siloxanes abutting ladder poly-siloxane, wherein R=R '=methyl, A=A '=methyl, Z=Z '=methoxyl group,
The meansigma methods of m=1, n is about 600.The productivity of gained siloxanes abutting ladder poly-siloxane is 71%.
From XRD spectra, obvious peak is had to occur in the position that 2 θ are 9.4 ° and 19.5 °.By FTIR
Spectrogram understands, at 780cm-1, 850cm-1, 1120cm-1, 1070cm-1, 1265cm-1,2840cm-1
And 3010cm-1Absworption peak occurs.
Claims (9)
1. a siloxanes abutting ladder poly-siloxane, is characterized in that: described siloxanes abutting ladder poly-siloxane has with following formula (I) structure:
Wherein: described R, R ', A, A ' it is independently selected from hydrogen, methyl, ethyl, isopropyl, isobutyl group, vinyl, pi-allyl, phenyl, glycydoxy, methacryloxypropyl, acryloxypropyl, aminopropyl, 3-(2-aminoethyl)-aminopropyl, chloropropyl, the one in mercapto propyl group, chlorophenyl, phenylol, benzyl alcohol base group；
Z, Z ' separately it is selected from the one in hydrogen, methyl, ethyl, isopropyl, isobutyl group, alkyl silyl；
M is the integer of 1-5；
N is the integer of 1-1000.
Siloxanes abutting ladder poly-siloxane the most according to claim 1, is characterized in that: described alkyl silyl is selected from-Si (Me)3、-Si(Ph)3、-SiH(Me)2、-SiVi(Me)2、-SiH(Ph)2、-SiVi(Ph)2、-Si-ally(Me)2、-Si-ally(Ph)2、-Si-acryl(Me)2、-Si-acryl(Ph)2In one；Wherein Me is methyl；Ph is phenyl；Vi is vinyl；Ally is pi-allyl；Acryl is methacryloxypropyl.
3. a preparation method for siloxanes abutting ladder poly-siloxane according to claim 1 and 2, is characterized in that, described preparation method comprises the following steps:
(1) in the reactor, RSiX is added3、R’SiX3And organic solvent, wherein RSiX3With R ' SiX3Mol ratio be 1:0～1:1, add α, ω-silicon diol and catalyst；Wherein (RSiX3+R’SiX3) and α, the mol ratio of ω-silicon diol is 1.8:1 to 20:1, and the consumption of catalyst is α, 0.0001 to 10 times of ω-silicon diol molal quantity；Then react 30 minutes to 10 hours at-10 DEG C to 150 DEG C, through filtering and/or distillation and concentration, obtain midbody solution；
(2) in the midbody solution that step (1) obtains, water and catalyst are added, or add alcohol and catalyst, the water wherein added or the amount of alcohol are the α added in step (1), 0～10 times of the molal quantity of ω-silicon diol, the consumption of catalyst is added in step (1) 0.0001 to 10 times of α, ω-silicon diol molal quantity；React 30 minutes to 10 hours at 0 DEG C to 150 DEG C；Add end-capping reagent and catalyst, react 30 minutes to 10 hours；The α that wherein consumption of end-capping reagent and catalyst is added in being respectively step (1), 0～10 times of the molal quantity of ω-silicon diol；Reaction gained mixture is separated by filtration, purifies, obtains the siloxanes abutting ladder poly-siloxane of formula (I) structure in claim 1；
Described RSiX3And R ' SiX3In R, R ' be independently selected from the one in hydrogen, methyl, ethyl, isopropyl, isobutyl group, vinyl, pi-allyl, phenyl, glycydoxy, methacryloxypropyl, acryloxypropyl, aminopropyl, 3-(2-aminoethyl)-aminopropyl, chloropropyl, mercapto propyl group, chlorophenyl, phenylol, benzyl alcohol base；X is independently selected from the one in OH, Cl, methoxyl group, ethyoxyl, isopropoxy, isobutoxy；
Described end-capping reagent is selected from XSi (Me)3、XSi(Ph)3、XSiH(Me)2、XSiVi(Me)2、XSi-ally(Me)2、XSiH(Ph)2、XSiVi(Ph)2、XSi-ally(Ph)2、XSi-acryl(Ph)2、H(Me)2Si-O-Si(Me)2H、H(Ph)2Si-O-Si(Ph)2H、Vi(Me)2Si-O-Si(Me)2Vi、Vi(Ph)2Si-O-Si(Ph)2One or more in Vi；X is independently selected from one or more in OH, Cl, methoxyl group, ethyoxyl, isopropoxy, isobutoxy；Wherein Me is methyl, and Ph is phenyl, and Vi is vinyl, and ally is pi-allyl, and acryl is methacryloxypropyl.
Preparation method the most according to claim 3, it is characterized in that: described adds water and catalyst in the midbody solution that step (1) obtains, or add alcohol and catalyst, it is when the concentration of the midbody solution that step (1) obtains not is 10～60wt%, by distillation and concentration or add water and catalyst after the midbody solution that step (1) obtains being deployed into the midbody solution that concentration is 10～60wt% with organic solvent, or add alcohol and catalyst.
5. according to the preparation method described in claim 3 or 4, it is characterized in that: described adds water and catalyst in the midbody solution that step (1) obtains, or add alcohol and catalyst, it is under conditions of 0 DEG C to 150 DEG C, add water and catalyst, or adds alcohol and catalyst.
Preparation method the most according to claim 3, is characterized in that: described α, ω-silicon diol has following molecular formula: HO (AA ' SiO)mH, wherein A, A ' is independently selected from hydrogen, methyl, ethyl, isopropyl, isobutyl group, vinyl, pi-allyl, phenyl, glycydoxy, methacryloxypropyl, acryloxypropyl, aminopropyl, 3-(2-aminoethyl)-aminopropyl, chloropropyl, the one in mercapto propyl group, chlorophenyl, phenylol, benzyl alcohol base group；M is the integer of 1-5.
Preparation method the most according to claim 3, is characterized in that: one or more in acid, metal, the oxide of metal, the hydroxide of metal or its hydrate, transistion metal compound, organic amine, ion exchange resin, dibutyl tin dilaurate ester, dioctyl tin cinnamic acid stannum ester, dialkyl group diaryltin of described catalyst.
Preparation method the most according to claim 7, is characterized in that: one or more in hydrochloric acid, sulphuric acid, nitric acid, sulfonic acid, formic acid, acetic acid of described acid；
One or more in lithium, sodium, potassium, calcium, magnesium, barium of described metal；
One or more in calcium oxide, magnesium oxide, Barium monoxide of the oxide of described metal；
One or more in Lithium hydrate, sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium hydroxide, barium hydroxide of the hydroxide of described metal；
One or more in butyl titanate, tetraethyl titanate of described transistion metal compound；
One or more in Tetramethylammonium hydroxide, TBAH, triethylamine, pyridine of described organic amine；
Described ion exchange resin selected from styrene divinylbenzene copolymer be the quarternary ammoniumion exchange resin of matrix, styrene divinylbenzene copolymer be the sulfonic acid ion exchange resin of matrix, styrene divinylbenzene copolymer be the carboxylic acid type ion exchange resin of matrix, polyacrylic acid be one or more in the carboxylic acid type ion exchange resin of matrix.
Preparation method the most according to claim 3, is characterized in that: described organic solvent is selected from: one or more in toluene, dimethylbenzene, methanol, ethanol, hexane, acetone, butanone, oxolane, Ketohexamethylene, dimethylformamide, dimethyl acetylamide, dimethyl sulfoxide, dioxane, ether, petroleum ether, acetonitrile.
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| CN104893310A (en) * | 2015-06-29 | 2015-09-09 | 山东东岳有机硅材料有限公司 | Polysilsesquioxane-contained liquid silicone rubber for LED packaging and preparation method of polysilsesquioxane-contained liquid silicone rubber |
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| CN107400239B (en) * | 2016-05-19 | 2019-07-16 | 中国科学院化学研究所 | A kind of trapezoidal/cage type polysiloxanes and its preparation method and application from sealing end |
| CN107880267B (en) * | 2017-11-17 | 2021-02-05 | 长兴（中国）投资有限公司 | Siloxane-bridged-group trapezoidal polysiloxane blocked by siloxane-bridged silane and preparation method thereof |
| CN108003348B (en) * | 2017-12-15 | 2021-02-23 | 长兴（中国）投资有限公司 | Siloxane bridged ladder-shaped polysiloxane, preparation method and application thereof |
| CN109957110B (en) * | 2017-12-25 | 2022-01-04 | 北京科化新材料科技有限公司 | Trapezoidal organic silicon polymer, preparation method and application thereof, and LED packaging adhesive |
| CN108129664A (en) * | 2017-12-25 | 2018-06-08 | 无锡创彩光学材料有限公司 | Organic siloxane modified Kapton of trapezium structure containing amino and preparation method thereof |
| CN109096758A (en) * | 2018-08-21 | 2018-12-28 | 无锡创彩光学材料有限公司 | A kind of low dielectric coefficient polyimide film and preparation method thereof |
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