CN104045831A - Siloxane bridged ladderlike polysiloxane and preparation method thereof - Google Patents
Siloxane bridged ladderlike polysiloxane and preparation method thereof Download PDFInfo
- Publication number
- CN104045831A CN104045831A CN201310081054.0A CN201310081054A CN104045831A CN 104045831 A CN104045831 A CN 104045831A CN 201310081054 A CN201310081054 A CN 201310081054A CN 104045831 A CN104045831 A CN 104045831A
- Authority
- CN
- China
- Prior art keywords
- catalyzer
- group
- polysiloxane
- add
- abutment
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Abstract
The invention relates to siloxane bridged ladderlike polysiloxane with siloxane as the bridge base and the main chain and a preparation method thereof. The method includes: subjecting RSiX3, R'SiX3 and alpha, omega-silandiol to first step condensation reaction so as to form an intermediate; and then further subjecting the intermediate to second step condensation reaction, and then carrying out separation and purification to obtain the siloxane bridged ladderlike polysiloxane with the following structure. The siloxane bridged ladderlike polysiloxane gives consideration to the high temperature resistance, high strength and high compatibility of a ladderlike polymer and polysiloxane with general organic macromolecules, and by changing the bridge base, the side group, the terminal group and degree of polymerization, the air tightness, adhesion, refraction and other comprehensive performance of the siloxane bridged ladderlike polysiloxane can be regulated. (formula I).
Description
Technical field
The present invention relates to trapezoidal organosilicon polymer, particularly taking siloxanes as abutment, main chain is siloxanes abutment ladder polysiloxane of siloxanes and preparation method thereof.
Background technology
The organosilicon polymer of practicality on general industry, if silicone oil and silicon rubber etc. are that main chain is the polysiloxane polymer of strand, their its outstanding advantages compared with general organic polymer are good high thermal resistance (temperature resistant grade can reach more than 200 DEG C), lower temperature resistance (can be following lower than-100 DEG C), radiation hardness, weathering resistance and highly air-permeable etc.Be double-stranded polysiloxane polymer (R-LPS) and " trapezoidal organosilicon polymer " is main chain, they have better high thermal resistance (temperature resistant grade can reach more than 300 DEG C), radiation hardness, weathering resistance, high strength, high-air-tightness compared with general strand polysiloxane polymer, compared with high-adhesion and good filming etc.Generally, according to the difference of its abutment structure, can be divided into oxo bridge base-ladder-like polysiloxane (R-LPSQ, R is side group); Organic abutment-ladder polysiloxane (O-LPRS, O is abutment, R is side group) and siloxanes abutment-ladder polysiloxane (S-LPRS, S is abutment, R is side group).Because ladder polysiloxane (R-LPS) has the performance of many excellences, therefore extremely people's concern always.
As far back as nineteen sixty USSR (Union of Soviet Socialist Republics) K.A.Andrianov et.al (Izu.Akad.Nauk.S S S R, Otdel Khim.Nauk, 1958,1004) the synthetic benzene abutting ladder poly-siloxane (Ph-LPMS) of once trial, fail, only obtain random oligopolymer.The same year, U.S. J.F.Brown et.al(J.Am.Chem.Soc.1960,82,6194) report that employing " balance thermal polycondensation " method synthesized and have high heat resistance and high-intensity trapezoid polyphenylsilsesquioxane (Ph-LPSQ).Cause in the world immediately very large sensation, and occurred relating in a large number article and the patent of the ladder-like polysiloxane (R-LPSQ, R is side group) of different side groups.As US Patent No. 3017386 disclose a kind of soluble, there is phenyl sesquisiloxane of ladder structure and preparation method thereof.United States Patent (USP) 5081202, United States Patent (USP) 6153689 and Japanese Patent 200159892 etc. also disclose with the synthetic ladder-like polysiloxane with different side groups of trichlorosilane.
Condensation reaction is to prepare the method that organosiloxane polymer is conventional, and general condensation reaction comprises dehydration, de-HCl, dealcoholization etc.If in the condensation course of siloxanes, reaction conditions is not added to control, multi-functional silane monomer can form random or crosslinked structure." supramolecule is constructed regulation and control Polymer Synthesizing the introduction " (Xie Ping writing people such as Xie Ping, Zhang Rongben, Cao Xinyu Chemical Industry Press, in December, 2009, ISBN 978-7-122-05947-5) report under comparatively gentle reaction conditions, silane and hydrolysate thereof can be by between groups, interaction between silane and solvent, form trapezoidal superstructure, and then by condensation, can form the polysiloxane with ladder structure, and can pass through raw material type, solvent, catalyzer, temperature of reaction, reaction times, molecular weight and the structure to product such as order of addition(of ingredients) regulates, but do not relate to of the present invention taking siloxanes as abutment, main chain is the siloxanes abutment ladder polysiloxane of siloxanes.
The method that the Zhang Rongben seminar of Institute of Chemistry, Academia Sinica adopts supramolecule to construct regulation and control polymerization has been prepared a series of organosilicon ladderlike polymer, the highly-ordered ladder-like polysilsesquioxane (R-LPSQ, R represents side group) of side chains such as comprising phenyl, methyl, vinyl is disclosed in CN1105677, PCT/CN2008/072588, WO2010/034161 A1.They disclose a kind of ladder polysiloxane containing organic abutment and preparation method thereof in Chinese patent CN 1280995, US Patent No. 6423772B1, and at J.Am.Chem.Soc.2002,124,10482, Angew.Chem.Int.Ed.2006,45,3112 and Chem.Commun.2009, in 4079 documents such as grade, report the Preparation and characterization of multiple organic abutting ladder poly-siloxane (O-LPRS).In addition, these ladder polysiloxanes can provide many new function materials through further modification.Zhang Rongben study group discloses a kind of liquid crystal orientating membrane taking photosensitivity ladder polysiloxane as base material and preparation method thereof at CN1255527, it is taking photosensitivity trapezoidal organic poly sesquisiloxane as base material, by solution rotating film and 180 DEG C of thermal treatments, on glass substrate and ITO conductive surface layer, form polymer solid membrane, after friction directional process, carry out appropriate photo-irradiation treatment with long wave ultraviolet light again, can obtain tilt angle and be the high stability liquid crystal alignment layer of 8～10 °.Zhang Rongben study group discloses a kind of tubular high polymer being made up of organic abutting ladder poly-siloxane and preparation method thereof at CN1284514, discloses a kind of tubular polymer compound being made up of organic abutting ladder poly-siloxane and preparation method thereof at CN1284513.According to the size of tubular high polymer and the chemically compatible difference guest molecule that optionally embedding matches with it, thereby form multiple supramolecular complex, and have wide practical use in fields such as catalysis, separation and novel optical material and the novel electricity materials of molecular device, molecular recognition.
We know, the performance of ladder polysiloxane depends on its molecular size range, the Nomenclature Composition and Structure of Complexes of aggregated structure, abutment, side group and end group, and wherein the structure of abutment is particularly important.Ladder-like polysiloxane (R-LPSQ); Organic abutment-ladder polysiloxane (O-LPRS) and siloxanes abutment-ladder polysiloxane (S-LPRS) have different performances.Ladder-like polysiloxane excellent heat resistance, its second-order transition temperature can be up to more than 180 DEG C.But owing to can make trapezoidal double-stranded flexibility reduce taking Sauerstoffatom as abutment, polymkeric substance fragility is higher, and particularly general ladder-like polysiloxane and organic macromolecule consistency are poor, are difficult to dissolve each other, and bring difficulty for being used for improving organic macromolecule performance; And organic abutting ladder poly-siloxane (as penylene abutment or phenylate support abutment etc.) snappiness is higher, good with general general organic macromolecule consistency, very favourable to improving organic macromolecule performance, but its thermotolerance is slightly poorer than ladder-like polysiloxane.Industrial expansion in the urgent need to a kind of have high heat resistance, high-air-tightness, refractivity is adjustable, have and the solubility ladder polysiloxane of general organic polymer excellent compatibility simultaneously.Of the present invention taking siloxanes as abutment, main chain can meet the requirement of above industrial development to solubility ladder polysiloxane as the ladder polysiloxane of siloxanes.
Summary of the invention
The object of this invention is to provide a kind of can overcome ladder-like polysiloxane fragility taking siloxanes as abutment, main chain is the solubility silica alkane 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 strength, good optical property and processing characteristics etc.
An also object of the present invention be to provide a kind of taking siloxanes as abutment, main chain is the preparation method of the solubility silica alkane abutting ladder poly-siloxane of siloxanes.
Of the present invention taking siloxanes as abutment, main chain has with following formula (I) structure as the solubility silica alkane abutting ladder poly-siloxane of siloxanes:
Described R, R ', A, A ' is independently selected from respectively hydrogen, methyl (Me), ethyl, sec.-propyl, isobutyl-, vinyl (Vi), allyl group (ally), phenyl (Ph), glycidyl ether oxygen base propyl group, methacryloxypropyl, acryloxy propyl group, aminopropyl, 3-(2-aminoethyl)-aminopropyl, chloropropyl, the one in the groups such as mercapto propyl group, chlorophenyl, phenylol, phenylcarbinol base.
Z, Z ' are respectively independently selected from the one in hydrogen, methyl (Me), ethyl, sec.-propyl, isobutyl-, alkyl silyl etc.
Be selected from-Si of described alkyl silyl (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)
2deng in one; Wherein Me is methyl; Ph is phenyl; Vi is vinyl; Ally is allyl group; Acryl is methacryloxypropyl.
M is the integer of 1-5.
N is the integer of 1-1000.
Of the present invention taking siloxanes as abutment, main chain prepares by condensation reaction as the solubility silica alkane abutting ladder poly-siloxane of siloxanes, wherein with RSiX
3, R ' SiX
3with α, ω-silicon diol (HO (AA ' SiO)
mh) carry out the first step condensation reaction, form intermediate; Further carry out second step condensation reaction with intermediate again, then carry out separating-purifying; Its preparation method comprises the following steps:
(1), in reactor, add RSiX
3, R ' SiX
3and organic solvent, wherein RSiX
3with R ' SiX
3mol ratio be 1:0～1:1, add α, ω-silicon diol and catalyzer; Wherein (RSiX
3+ R ' SiX
3) total mole number and α, the mol ratio of the mole number of ω-silicon diol is 1.8:1 to 20:1, the consumption of catalyzer is α, 0.0001 to 10 times of ω-silicon diol mole number; Then at-10 DEG C to 150 DEG C, react 30 minutes to 10 hours, after filtration and/or distillation and concentration, obtain midbody solution;
(2) in the midbody solution obtaining to step (1), add water and catalyzer, or add alcohol and catalyzer, the water that wherein added or the amount of alcohol are the α adding in step (1), 0～10 times of the mole number of ω-silicon diol, the α of the consumption of catalyzer for adding in step (1), 0.0001 to 10 times of ω-silicon diol mole number; At 0 DEG C to 150 DEG C, react 30 minutes to 10 hours; Add again end-capping reagent and catalyzer, react 30 minutes to 10 hours; Wherein the consumption of end-capping reagent and catalyzer is respectively the α adding in step (1), 0～10 times of the mole number of ω-silicon diol; By reaction gained mixture be separated by filtration, the processing such as purification, obtain the siloxanes abutment ladder polysiloxane of above-mentioned formula (I) structure; Its productive rate is 68～95%.
In the described midbody solution obtaining to step (1), add water and catalyzer, or add alcohol and catalyzer; When the concentration of the midbody solution preferably obtaining when step (1) is not 10～60wt%, after being deployed into by distillation and concentration or with the midbody solution that organic solvent obtains step (1) midbody solution that concentration is 10～60wt%, add again water and catalyzer, or add alcohol and catalyzer.
In the described midbody solution obtaining to step (1), add water and catalyzer, or add alcohol and catalyzer; Preferably under the condition of 0 DEG C to 150 DEG C, add water and catalyzer, or add alcohol and catalyzer.
Described RSiX
3and R ' SiX
3in R, R ' be independently selected from respectively the one in the groups such as hydrogen, methyl (Me), ethyl, sec.-propyl, isobutyl-, vinyl (Vi), allyl group (ally), phenyl (Ph), glycidyl ether oxygen base propyl group, methacryloxypropyl, acryloxy propyl group, aminopropyl, 3-(2-aminoethyl)-aminopropyl, chloropropyl, mercapto propyl group, chlorophenyl, phenylol, phenylcarbinol base; X can independently be selected from respectively the one in OH, Cl, methoxyl group, oxyethyl group, isopropoxy, isobutoxy etc.
Described α, ω-silicon diol has following molecular formula: HO (AA ' SiO)
mh, wherein A, A ' are independently selected from respectively hydrogen, methyl (Me), ethyl, sec.-propyl, isobutyl-, vinyl (Vi), allyl group (ally), phenyl (Ph), glycidyl ether oxygen base propyl group, methacryloxypropyl, acryloxy propyl group, aminopropyl, 3-(2-aminoethyl)-aminopropyl, chloropropyl, the one in the groups such as mercapto propyl group, chlorophenyl, phenylol, phenylcarbinol 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 independently be selected from respectively one or more in OH, Cl, methoxyl group, oxyethyl group, isopropoxy, isobutoxy etc.; Wherein Me is methyl, and Ph is phenyl, and Vi is vinyl, and ally is allyl group, and acryl is methacryloxypropyl.
Described catalyzer can be selected from one or more in the oxyhydroxide of oxide compound, metal of acid, metal, metal or their hydrate, transistion metal compound, organic amine, ion exchange resin etc.
Described acid is selected from one or more in hydrochloric acid, sulfuric acid, nitric acid, sulfonic acid, formic acid, acetic acid etc.
Described metal is selected from one or more in lithium, sodium, potassium, calcium, magnesium, barium.
The oxide compound of described metal is selected from one or more in calcium oxide, magnesium oxide, barium oxide etc.
The oxyhydroxide of described metal is selected from one or more in lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium hydroxide, hydrated barta etc.
Described transistion metal compound is selected from one or more in dibutyl tin dilaurate ester, dioctyl two tin laurate esters, dialkyl group diaryltin, butyl (tetra) titanate, titanium ethanolate etc.
Described organic amine is selected from one or more in Tetramethylammonium hydroxide, TBAH, triethylamine, pyridine etc.
Described ion exchange resin is selected from one or more in quarternary ammoniumion exchange resin that styrene divinylbenzene copolymer is matrix, sulfonic acid ion exchange resin that styrene divinylbenzene copolymer is matrix, carboxylic acid type ion exchange resin, the carboxylic acid type ion exchange resin that polyacrylic acid is matrix etc. that styrene divinylbenzene copolymer is matrix.
Described organic solvent is selected from: one or more in toluene, dimethylbenzene, methyl alcohol, ethanol, hexane, acetone, butanone, tetrahydrofuran (THF), pimelinketone, dimethyl formamide (DMF), N,N-DIMETHYLACETAMIDE (DMA), dimethyl sulfoxide (DMSO) (DMSO), dioxane, ether, sherwood oil, acetonitrile etc.
Of the present invention taking siloxanes as abutment, main chain as the solubility silica alkane abutting ladder poly-siloxane of siloxanes taken into account the high temperature tolerance, high strength of ladder polymer and polysiloxane and with general organic macromolecule high-compatibility, in tetrahydrofuran (THF) (THF), toluene, chloroform, DMF equal solvent, there is good solubility, prove its composition structure by tests such as FTIR, again by VPO(vapour-pressure osmometer) etc. can record its molecular-weight average, calculate its average n value.Of the present invention taking siloxanes as abutment, in the scope of 1～40 °, at least there are 2 obvious peaks at 2 θ as the XRD spectra of the solubility silica alkane abutting ladder poly-siloxane of siloxanes in main chain, its peak value is corresponding to the shot-range ordered structure of the molecular chain of siloxanes abutment ladder polysiloxane.
Because the main chain of solubility silica alkane abutting ladder poly-siloxane of the present invention is all that Si-O key is connected with abutment, make solubility silica alkane abutting ladder poly-siloxane material there is high-flexibility energy and cold-hot performance; The side group that wherein A, A ' they are abutment, the side group that R, R ' they are main chain, and Z is end group, and these side groups are organic group, again for solubility silica alkane abutting ladder poly-siloxane material and general organic polymer provide good consistency.The solubility silica alkane abutting ladder poly-siloxane of this molecular structure can pass through the change of abutment, side group, end group and the polymerization degree etc., regulates the over-all propertieies such as its resistance to air loss, cohesiveness, refractivity; Can give material high-air-tightness, high strength, good optical property (specific refractory power=1.42～1.65) and processing characteristics etc.
The selection of abutment, side group and the end group of solubility silica alkane abutting ladder poly-siloxane of the present invention and combination can make the above-mentioned performance of solubility silica alkane abutting ladder poly-siloxane material adjust flexibly, to adapt to various application demand, can be widely used in and improve general organic polymer, especially for the improvement of the performances such as the high molecular heatproof of organic coating, radiation hardness and weather-resistant; And can improve thermotolerance, refractive index, cohesiveness, resistance to air loss and the mechanical property of High Power LED (LED) packaging plastic and organic pressure-sensitive gel, and as: intensity, modulus, hardness etc.In addition, this class siloxanes abutment ?ladder polysiloxane itself can be widely used in optics and weather-resistant coating and kinds of protect coating etc.
Brief description of the drawings
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 therefrom
29si-NMR spectrogram.
Fig. 3. the XRD spectra of the embodiment of the present invention 1 products therefrom.
Embodiment
Embodiment 1
Prepare siloxanes abutment ladder polysiloxane by phenyl-trichloro-silicane, Diphenylsilanediol.
(1) under dry nitrogen protection, in many necks bottle that prolong and dropping funnel have been installed, insert 50.8 grams of (0.24 mole) phenyl-trichloro-silicanes, 150 grams of toluene, 150 grams of tetrahydrofuran (THF)s, stir; At-10 DEG C, 26.0 grams of (0.12 mole) Diphenylsilanediols are joined in many necks bottle in batches, drip the triethylamine of 26 grams (0.26 moles) simultaneously; After dripping, be progressively warming up to 60 DEG C of reactions 1 hour; After stopped reaction, by solution filter, collect clear liquid, obtain midbody solution; The midbody solution obtaining is obtained to the midbody solution that concentration is about 30wt% by distillation and concentration;
(2) be at 0 DEG C in temperature, the concentration obtaining to step (1) is about in the midbody solution of 30wt% and drips 2.88 grams of (0.16 mole) water and 40.5 grams of (0.4 mole) triethylamines, after dripping, at 25 DEG C～40 DEG C, reacts 1.5 hours; Add end-capping reagent vinyl-dimethyl base chlorosilane 6.4 grams of (0.053 mole) and 11.2 grams of triethylamines (0.11 mole), at 40 DEG C, continuation reaction is warming up to 120 DEG C after 7 hours and distills out tetrahydrofuran (THF) and water; Then will react gained mixture filtering separation, and collect clear liquid, and be washed to neutrality, concentrated, drying under reduced pressure is purified, and obtains the siloxanes abutment ladder polysiloxane of aforementioned formula (I) structure, wherein R=R '=phenyl, A=A '=phenyl, Z=H, Z '=SiMe
2vi, Me=methyl, Vi=vinyl, m=1.The productive rate of gained siloxanes abutment ladder polysiloxane is 87%.
Gained siloxanes abutment ladder polysiloxane dissolves in toluene, FTIR as shown in Figure 1,
29si-NMR as shown in Figure 2, XRD spectra as shown in Figure 3; By VPO(vapour-pressure osmometer) its molecular weight of test analysis, the mean value that obtains n is 8.Used solution film forming method to be prepared into the film of 0.1 millimeter, in the transmitance of visible light wave range, higher than 93%, specific refractory power is 1.59.
Embodiment 2
By phenyl-trichloro-silicane, vinyl trichloro silane and HO (MePhSiO)
5h prepares siloxanes abutment ladder polysiloxane.
(1) under dry nitrogen protection, in many necks bottle that prolong and dropping funnel have been installed, insert 500 grams of 31.7 grams of (0.15 mole) phenyl-trichloro-silicanes, 24.2 grams of (0.15 mole) vinyl trichloro silanes and toluene, stir; At-10 DEG C by 83.9 grams of HO (MePhSiO)
5h(0.12 mole) join in many necks bottle in batches, drip the triethylamine of 60.7 grams (0.6 moles) simultaneously; After dripping, be progressively warming up to 60 DEG C of reactions 3 hours; After stopped reaction, by solution filter, collect clear liquid, obtain midbody solution;
(2) be at 25 DEG C in temperature, in the midbody solution obtaining to step (1), drip 9 grams of (0.5 mole) 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 vinyl-dimethyl base chlorosilane 49 grams of (0.053 mole) and 24.3 grams of triethylamines (0.11 mole), at 60 DEG C, continue reaction 2 hours; Then will react gained mixture filtering separation, and collect clear liquid, and be washed to neutrality, concentrated, drying under reduced pressure is purified, and obtains the siloxanes abutment ladder polysiloxane of aforementioned formula (I) structure, wherein R=Ph, R '=Vi, A=Me, A '=Ph, Z=Z '=SiViMe
2, m=5, n=2, Ph is phenyl, and Me is methyl, and Vi is vinyl.The productive rate of gained siloxanes abutment ladder polysiloxane is 91%.
From FTIR spectrogram, at 1070cm
-1, 1120cm
-1, 1430cm
-1, 1600cm
-1, 2940cm
-1and 3380cm
-1there is absorption peak.By
1h-NMR spectrogram is known, at 7.3ppm, and 5.3ppm, there is peak in 0.6ppm and 0.14ppm.Product dissolves in dimethylbenzene, is used solution film forming method to be prepared into the film of 0.1 millimeter, and in the transmitance of visible light wave range, higher than 95%, specific refractory power is 1.53.
Embodiment 3
By METHYL TRICHLORO SILANE, 3-acryloxy trichlorosilane and HO (MePhSiO)
3h prepares siloxanes abutment ladder polysiloxane.
(1) under dry nitrogen protection, in many necks bottle that prolong and dropping funnel have been installed, insert 300 grams of 17.9 grams of (0.06 mole) METHYL TRICHLORO SILANE and 29.7 grams of (0.18 mole) 3-acryloxy trichlorosilanes, pimelinketone, stir; At 30 DEG C by 51.2 grams of HO (MePhSiO)
3h(0.12 mole) join in many necks bottle in batches, drip the triethylamine of 60.7 grams (0.6 moles) simultaneously; After dripping, be progressively warming up to 60 DEG C of reactions 5 hours; After stopped reaction, by solution filter, collect clear liquid, obtain midbody solution; Add again toluene to obtain the midbody solution that concentration is about 30wt% after by distillation and concentration the midbody solution obtaining;
(2) be at 25 DEG C in temperature, the concentration obtaining to step (1) is about in the midbody solution of 30wt% and drips 21.6 grams of (1.2 moles) water and 0.18 gram of (0.002 mole) triethylamine, after dripping, at 60 DEG C～150 DEG C, reacts 4 hours; Then will react gained mixture filtering separation, collect clear liquid, be washed to neutrality, purify with anhydrous sodium sulfate drying, filtration, drying under reduced pressure, obtain the siloxanes abutment ladder polysiloxane of aforementioned formula (I) structure, wherein R=Me, R '=3-acryloxy, A=Me, A '=Ph, end group Z=Z '=H, Me is methyl, Ph is phenyl, m=3, and the mean value of n is 950.The productive rate of gained siloxanes abutment ladder polysiloxane is 94%.
From XRD spectra, the position that is 5.5 ° and 19.5 ° at 2 θ has obvious peak to occur, product dissolves in dimethylbenzene, is used solution film forming method to be prepared into the film of 0.1 millimeter, and in the transmitance of visible light wave range, higher than 90%, specific refractory power is 1.47.From FTIR spectrogram, at 740cm
-1, 1070cm
-1, 1120cm
-1, 1430cm
-1, 1590cm
-1, 1,720cm
-1, 2940cm
-1and 3340cm
-1there is absorption peak.
Embodiment 4
Prepare siloxanes abutment ladder polysiloxane by chloropropyl trichloro-silane, Diphenylsilanediol.
(1) under dry nitrogen protection, in many necks bottle that prolong and dropping funnel have been installed, insert 100 milliliters of 0.22 mole of chloropropyl trichloro-silane and toluene, 100 milliliters, acetone, stir; At 25 DEG C, the triethylamine of 0.12 mole of Diphenylsilanediol and 0.24 mole is joined in many necks bottle; After dripping, be progressively warming up to 60 DEG C of reactions 2 hours; After stopped reaction, by solution filter, collect clear liquid, obtain midbody solution;
(2) be at 25 DEG C in temperature, in the midbody solution obtaining to step (1), add 0.18 mole, water, and drip the triethylamine of 0.36 mole, then at 40 DEG C～60 DEG C, react 4 hours; Then will react gained mixture filtering separation, collect clear liquid, be washed to neutrality, purify with anhydrous sodium sulfate drying, filtration, drying under reduced pressure, obtain the siloxanes abutment ladder polysiloxane of aforementioned formula (I) structure, wherein R=R '=chloropropyl, A=A '=phenyl, Z=Z '=H; M=1, the mean value of n is 120.The productive rate of gained siloxanes abutment ladder polysiloxane is 87%.
From FTIR spectrogram, at 1070cm
-1, 1120cm
-1, 1310cm
-1, 2940cm
-1and 3300cm
-1there is absorption peak.From XRD spectra, the position that is 8.1 ° and 19.5 ° at 2 θ has obvious peak to occur.
Embodiment 5
The siloxanes abutment ladder polysiloxane of Z=Z '=H that embodiment 4 is prepared and 1,1,3,3-tetramethyl disiloxane further reaction obtain Z=Z '=SiHMe
2siloxanes abutment ladder polysiloxane.
The siloxanes abutment ladder polysiloxane 88.6g that embodiment 4 is prepared is dissolved in 60 milliliters of toluene and 20 milliliters of butanone, add 0.06 mole water, 0.03 mole 1,1,3,0.005 mole of 3-tetramethyl disiloxane and HCl are at 25～80 DEG C, to react 2 hours in temperature; Underpressure distillation and be dried purification, obtains the siloxanes abutment ladder polysiloxane of aforementioned formula (I) structure, wherein R=R '=chloropropyl, side group the A=A '=phenyl of siloxanes abutment, end group Z=Z '=SiHMe
2, wherein Me is methyl; M=1, the mean value of n is 120.The productive rate of gained siloxanes abutment ladder polysiloxane is 74%.
Compared with the FTIR spectrogram of FTIR spectrogram and embodiment 4 products, at 1260cm
-1with at 2240cm
-1occur new absorption peak, be attributed to respectively the absorption peak of Si-Me and Si-H, XRD spectra does not change substantially.
Embodiment 6
Prepare siloxanes abutment ladder polysiloxane by phenyltrimethoxysila,e, Diphenylsilanediol.
(1) in many necks bottle that prolong and dropping funnel have been installed, insert 40 grams of (0.2 mole) phenyltrimethoxysila,e, 80 grams of acetone, 20 grams of methyl alcohol and 100 grams of toluene, stir; At 25～60 DEG C by the Ba of 0.004 mole (OH)
2h
2o and 21.6 grams of (0.1 mole) Diphenylsilanediols join in many necks bottle; After adding, under reflux temperature, react 2 hours; Then steam acetone and methyl alcohol, filter, collect solution, obtain midbody solution;
(2) be at 40～80 DEG C in temperature, in the midbody solution obtaining to step (1), add the sulfuric acid of 18 grams of (1 mole) water, 20 grams of tetrahydrofuran (THF)s and 0.001 mole, then at 40 DEG C～80 DEG C, react 3 hours, be then warming up to 120 DEG C of reactions 1 hour; Be cooled to room temperature, filter, collect clear liquid, be washed to neutrality, drying under reduced pressure is purified, and obtains the siloxanes abutment ladder polysiloxane of aforementioned formula (I) structure, wherein R=R '=phenyl, and A=A '=phenyl, Z=H, Z '=H, m=1, the mean value of n is 85.The productive rate of gained siloxanes abutment ladder polysiloxane is 95%.
From FTIR spectrogram, at 1069cm
-1, 1128cm
-1, 1261cm
-1, 1428cm
-1, 2841cm
-1, 2940cm
-1and 3381cm
-1there is absorption peak.From XRD spectra, the position that is 7.1 ° and 20.1 ° at 2 θ has obvious peak to occur.
Embodiment 7
Prepare siloxanes abutment ladder polysiloxane by vinyltrimethoxy silane, aminopropyl trimethoxysilane, Diphenylsilanediol.
(1) in reactor, insert 32.5 grams of 33.2 grams of 22.2 grams of vinyltrimethoxy silanes and aminopropyl trimethoxysilane and Diphenylsilanediols, and add methyl alcohol: dimethylbenzene: 15 grams of the mixed solvents that the mass ratio of acetone is 1:5:1, stir; By Ba (OH)
28H
29.5 grams of O join in reactor; After adding, at 60 DEG C, react 10 hours; Then steam acetone and methyl alcohol, filter, collect solution, obtain midbody solution; To the mixed solution that adds toluene and butanone (toluene: the mass ratio of butanone is 1:1) in the midbody solution obtaining, obtain the midbody solution that concentration is 60wt%;
(2) in the midbody solution that the concentration obtaining to step (1) is 60wt%, add 5.4 grams, water, Ba (OH)
28H
20.19 gram of O after adding, reacts 4 hours at 100 DEG C; Add 1.83 grams of triphenyl Ethoxysilanes, at 150 DEG C, react 2 hours; Then will react gained mixture filtering separation, and collect clear liquid, drying under reduced pressure is purified, and obtains the siloxanes abutment ladder polysiloxane of aforementioned formula (I) structure, wherein R=vinyl, R '=aminopropyl, A=A '=phenyl, Z=Z '=SiPh
3, Ph is phenyl, m=1, and the mean value of n is 75.The productive rate of gained siloxanes abutment ladder polysiloxane is 90%.
From XRD spectra, the position that is 7.6 ° and 19.4 ° at 2 θ has obvious peak to occur.From FTIR spectrogram, at 1072cm
-1, 1130cm
-1, 1428cm
-1, 1595cm
-1, 3020cm
-1and 3370cm
-1there is absorption peak.
Embodiment 8
Prepare siloxanes abutment ladder polysiloxane by (3-Racemic glycidol propyl group) Trimethoxy silane and Diphenylsilanediol.
(1) in reactor, insert 56.7 grams (0.24 moles) (3-Racemic glycidol propyl group) Trimethoxy silane, 26 grams of (0.12 mole) Diphenylsilanediols, 50 grams of toluene and 10 grams of methyl alcohol, stir; By 0.04 gram of (0.0006 mole) Ca (OH)
2join in reactor; After adding, at 60～80 DEG C, react 4 hours; Then steam methyl alcohol, filter, collect solution, obtain midbody solution; In the midbody solution obtaining, add 100 grams of toluene and 100 grams of tetrahydrofuran (THF)s;
(2) add in the midbody solution obtaining after toluene and tetrahydrofuran (THF) and add 14.4 grams, water (0.8 mole) and 0.34 gram of CaO (0.006 mole) to step (1), after adding, under reflux temperature, react 2 hours; Steam tetrahydrofuran (THF) at 120 DEG C, then react 2 hours; To react gained mixture filtering separation, and collect clear liquid, drying under reduced pressure is purified, obtain the siloxanes abutment ladder polysiloxane of aforementioned formula (I) structure, wherein R=R '=3-Racemic glycidol propyl group, A=A '=phenyl, Z=Z '=methoxyl group, m=1, the mean value of n is 450.The productive rate of gained siloxanes abutment ladder polysiloxane is 87%.
From XRD spectra, the position that is 7.9 ° and 18.5 ° at 2 θ has obvious peak to occur.From FTIR spectrogram, at 1072cm
-1, 1130cm
-1, 1428cm
-1, 1595cm
-1, 2841cm
-1and 3040cm
-1there is absorption peak.
Embodiment 9
Prepare siloxanes abutment ladder polysiloxane by Trimethoxy silane, methyltrimethoxy silane and Diphenylsilanediol.
(1) in reactor, insert 18.3 grams of Trimethoxy silanes (0.15 mole), methyltrimethoxy silane 17.7 grams of (0.13 mole), 26 grams of Diphenylsilanediols (0.12 mole), then to add styrene divinylbenzene copolymer be 0.15 gram, the carboxylic acid type ion exchange resin of matrix; After adding, at 150 DEG C, react 30 minutes; Stopped reaction, adds 50 grams of toluene and 50 grams of tetrahydrofuran (THF) diluted liquid, filters, collects solution, obtains midbody solution;
(2) in the midbody solution obtaining to step (1), add 0.15 gram of the sulfonic acid ion exchange resin that 3.6 grams, water (0.2 mole) and styrene divinylbenzene copolymer are matrix, after adding, at 65 DEG C, react 3 hours, after reaction finishes, to react gained mixture filtering separation, collect clear liquid, drying under reduced pressure is purified, obtain the siloxanes abutment ladder polysiloxane of aforementioned formula (I) structure, wherein R=H, R '=methyl, A=A '=phenyl, Z=Z '=methoxyl group, m=1, the mean value of n is 50.The productive rate of gained siloxanes abutment ladder polysiloxane is 82%.
From XRD spectra, the position that is 9.9 ° and 18.5 ° at 2 θ has obvious peak to occur.From FTIR spectrogram, at 830cm
-1, 1100cm
-1, 1030cm
-1, 1260cm
-1, 1580cm
-1, 2240cm
-1, 2840cm
-1and 3040cm
-1there is absorption peak.
Embodiment 10
Prepare siloxanes abutment ladder polysiloxane with methyltrimethoxy silane and Diphenylsilanediol.
(1), in reactor, insert each 20 grams of 98 grams of methyltrimethoxy silanes (0.72 mole), dimethyl dihydroxyl silane 11 grams of (0.12 mole), dimethylbenzene and dioxane, then add 0.02 gram of tetra-n-butyl titanate; After adding, at 100 DEG C, react 2 hours; Then excessive methyltrimethoxy silane (102 DEG C of boiling points) is steamed, obtain midbody solution;
(2) in the midbody solution obtaining to step (1), add 20 grams of toluene, 20 grams of tetrahydrofuran (THF)s and 4.3 grams, water (0.24 mole), after adding, stirring reaction 1 hour at 80 DEG C, adds 0.02 gram of tetra-n-butyl titanate, reacts 1 hour; Steam the methyl alcohol of tetrahydrofuran (THF) and generation, after reaction finishes, to react gained mixture filtering separation, and collect clear liquid, drying under reduced pressure is purified, obtain the siloxanes abutment ladder polysiloxane of aforementioned formula (I) structure, wherein R=R '=methyl, A=A '=methyl, Z=Z '=methoxyl group, m=1, the mean value of n is about 600.The productive rate of gained siloxanes abutment ladder polysiloxane is 71%.
From XRD spectra, the position that is 9.4 ° and 19.5 ° at 2 θ has obvious peak to occur.From FTIR spectrogram, at 780cm
-1, 850cm
-1, 1120cm
-1, 1070cm
-1, 1265cm
-1, 2840cm
-1and 3010cm
-1there is absorption peak.
Claims (9)
1. a siloxanes abutment ladder polysiloxane, is characterized in that: described siloxanes abutment ladder polysiloxane has with following formula (I) structure:
Wherein: described R, R ', A, A ' is independently selected from respectively hydrogen, methyl, ethyl, sec.-propyl, isobutyl-, vinyl, allyl group, phenyl, glycidyl ether oxygen base propyl group, methacryloxypropyl, acryloxy propyl group, aminopropyl, 3-(2-aminoethyl)-aminopropyl, chloropropyl, the one in mercapto propyl group, chlorophenyl, phenylol, phenylcarbinol base group;
Z, Z ' are respectively independently selected from the one in hydrogen, methyl, ethyl, sec.-propyl, isobutyl-, alkyl silyl;
M is the integer of 1-5;
N is the integer of 1-1000.
2. siloxanes abutment ladder polysiloxane according to claim 1, is characterized in that: be selected from-Si of described alkyl silyl (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 allyl group; Acryl is methacryloxypropyl;
3. a preparation method for siloxanes abutment ladder polysiloxane according to claim 1 and 2, is characterized in that, described preparation method comprises the following steps:
(1), in reactor, add RSiX
3, R ' SiX
3and organic solvent, wherein RSiX
3with R ' SiX
3mol ratio be 1:0～1:1, add α, ω-silicon diol and catalyzer; Wherein (RSiX
3+ R ' SiX
3) and α, the mol ratio of ω-silicon diol is 1.8:1 to 20:1, the consumption of catalyzer is α, 0.0001 to 10 times of ω-silicon diol mole number; Then at-10 DEG C to 150 DEG C, react 30 minutes to 10 hours, after filtration and/or distillation and concentration, obtain midbody solution;
(2) in the midbody solution obtaining to step (1), add water and catalyzer, or add alcohol and catalyzer, the water that wherein added or the amount of alcohol are the α adding in step (1), 0～10 times of the mole number of ω-silicon diol, the α of the consumption of catalyzer for adding in step (1), 0.0001 to 10 times of ω-silicon diol mole number; At 0 DEG C to 150 DEG C, react 30 minutes to 10 hours; Add again end-capping reagent and catalyzer, react 30 minutes to 10 hours; Wherein the consumption of end-capping reagent and catalyzer is respectively the α adding in step (1), 0～10 times of the mole number of ω-silicon diol; Reaction gained mixture is separated by filtration, is purified, obtain the siloxanes abutment ladder polysiloxane of claim 1 Chinese style (I) structure;
Described RSiX
3and R ' SiX
3in R, R ' be independently selected from respectively the one in hydrogen, methyl, ethyl, sec.-propyl, isobutyl-, vinyl, allyl group, phenyl, glycidyl ether oxygen base propyl group, methacryloxypropyl, acryloxy propyl group, aminopropyl, 3-(2-aminoethyl)-aminopropyl, chloropropyl, mercapto propyl group, chlorophenyl, phenylol, phenylcarbinol base; X is independently selected from respectively the one in OH, Cl, methoxyl group, oxyethyl group, 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 respectively one or more in OH, Cl, methoxyl group, oxyethyl group, isopropoxy, isobutoxy; Wherein Me is methyl, and Ph is phenyl, and Vi is vinyl, and ally is allyl group, and acryl is methacryloxypropyl.
4. preparation method according to claim 3, it is characterized in that: in the described midbody solution obtaining to step (1), add water and catalyzer, or add alcohol and catalyzer, that the concentration of the midbody solution that obtains when step (1) is while being not 10～60wt%, after being deployed into by distillation and concentration or with the midbody solution that organic solvent obtains step (1) midbody solution that concentration is 10～60wt%, add again water and catalyzer, or add alcohol and catalyzer.
5. according to the preparation method described in claim 3 or 4, it is characterized in that: in the described midbody solution obtaining to step (1), add water and catalyzer, or add alcohol and catalyzer, be under the condition of 0 DEG C to 150 DEG C, to add water and catalyzer, or add alcohol and catalyzer.
6. preparation method according to claim 3, is characterized in that: described α, ω-silicon diol has following molecular formula: HO (AA ' SiO)
mh, wherein A, A ' are independently selected from respectively hydrogen, methyl, ethyl, sec.-propyl, isobutyl-, vinyl, allyl group, phenyl, glycidyl ether oxygen base propyl group, methacryloxypropyl, acryloxy propyl group, aminopropyl, 3-(2-aminoethyl)-aminopropyl, chloropropyl, the one in mercapto propyl group, chlorophenyl, phenylol, phenylcarbinol base group; M is the integer of 1-5.
7. preparation method according to claim 3, is characterized in that: described catalyzer is selected from one or more in the oxyhydroxide of oxide compound, metal of acid, metal, metal or its hydrate, transistion metal compound, organic amine, ion exchange resin.
8. preparation method according to claim 7, is characterized in that: described acid is selected from one or more in hydrochloric acid, sulfuric acid, nitric acid, sulfonic acid, formic acid, acetic acid;
Described metal is selected from one or more in lithium, sodium, potassium, calcium, magnesium, barium;
The oxide compound of described metal is selected from one or more in calcium oxide, magnesium oxide, barium oxide;
The oxyhydroxide of described metal is selected from one or more in lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium hydroxide, hydrated barta;
Described transistion metal compound is selected from one or more in dibutyl tin dilaurate ester, dioctyl two tin laurate esters, dialkyl group diaryltin, butyl (tetra) titanate, titanium ethanolate;
Described organic amine is selected from one or more in Tetramethylammonium hydroxide, TBAH, triethylamine, pyridine;
Described ion exchange resin is selected from one or more in quarternary ammoniumion exchange resin that styrene divinylbenzene copolymer is matrix, sulfonic acid ion exchange resin that styrene divinylbenzene copolymer is matrix, carboxylic acid type ion exchange resin that styrene divinylbenzene copolymer is matrix, carboxylic acid type ion exchange resin that polyacrylic acid is matrix.
9. preparation method according to claim 3, is characterized in that: described organic solvent is selected from: one or more in toluene, dimethylbenzene, methyl alcohol, ethanol, hexane, acetone, butanone, tetrahydrofuran (THF), pimelinketone, dimethyl formamide, N,N-DIMETHYLACETAMIDE, dimethyl sulfoxide (DMSO), dioxane, ether, sherwood oil, acetonitrile.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310081054.0A CN104045831B (en) | 2013-03-14 | 2013-03-14 | A kind of siloxanes abutting ladder poly-siloxane and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310081054.0A CN104045831B (en) | 2013-03-14 | 2013-03-14 | A kind of siloxanes abutting ladder poly-siloxane and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104045831A true CN104045831A (en) | 2014-09-17 |
| CN104045831B CN104045831B (en) | 2016-12-28 |
Family
ID=51499254
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310081054.0A Active CN104045831B (en) | 2013-03-14 | 2013-03-14 | A kind of siloxanes abutting ladder poly-siloxane and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104045831B (en) |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN105315469A (en) * | 2015-09-30 | 2016-02-10 | 中国人民解放军国防科学技术大学 | Silicon-nitrile-based hybrid resin and synthesizing method thereof |
| CN107400238A (en) * | 2016-05-19 | 2017-11-28 | 中国科学院化学研究所 | A kind of multi-arm siloxanes abutting ladder poly-siloxane copolymer and its preparation method and application |
| CN107400239A (en) * | 2016-05-19 | 2017-11-28 | 中国科学院化学研究所 | A kind of trapezoidal/cage type polysiloxanes of end-blocking and its preparation method and application certainly |
| CN107880267A (en) * | 2017-11-17 | 2018-04-06 | 长兴（中国）投资有限公司 | Siloxanes abutting ladder poly-siloxane of siloxane bridge base silane end-blocking and preparation method thereof |
| CN108003348A (en) * | 2017-12-15 | 2018-05-08 | 长兴（中国）投资有限公司 | Siloxanes abutting ladder poly-siloxane, its preparation method and application |
| 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 |
| CN108299644A (en) * | 2013-12-09 | 2018-07-20 | 3M创新有限公司 | Curable silsesquioxane polymer, composition, product and method |
| 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 |
| CN109608641A (en) * | 2018-11-26 | 2019-04-12 | 江苏艾森半导体材料股份有限公司 | Fluorine-containing trapezoidal organic siliconresin for LED packaging plastic |
| CN109957110A (en) * | 2017-12-25 | 2019-07-02 | 北京科化新材料科技有限公司 | Trapezoidal organosilicon polymer and its preparation method and application and LED packaging plastic |
| CN111847464A (en) * | 2020-07-27 | 2020-10-30 | 湖北科技学院 | Radiation preparation method of nano silicon dioxide |
| 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 |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1280995A (en) * | 1999-07-16 | 2001-01-24 | 中国科学院化学研究所 | Trapezoidal polysiloxane containing organic bridge radical and its preparing process |
-
2013
- 2013-03-14 CN CN201310081054.0A patent/CN104045831B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1280995A (en) * | 1999-07-16 | 2001-01-24 | 中国科学院化学研究所 | Trapezoidal polysiloxane containing organic bridge radical and its preparing process |
Cited By (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108299644A (en) * | 2013-12-09 | 2018-07-20 | 3M创新有限公司 | Curable silsesquioxane polymer, composition, product and method |
| 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 |
| CN105315469B (en) * | 2015-09-30 | 2018-04-13 | 中国人民解放军国防科学技术大学 | Silicon substrate itrile group hybrid resin and its synthetic method |
| CN105315469A (en) * | 2015-09-30 | 2016-02-10 | 中国人民解放军国防科学技术大学 | Silicon-nitrile-based hybrid resin and synthesizing method thereof |
| CN107400238B (en) * | 2016-05-19 | 2020-05-26 | 中国科学院化学研究所 | Multi-arm siloxane bridged ladder-shaped polysiloxane copolymer and preparation method and application thereof |
| CN107400239A (en) * | 2016-05-19 | 2017-11-28 | 中国科学院化学研究所 | A kind of trapezoidal/cage type polysiloxanes of end-blocking and its preparation method and application certainly |
| CN107400238A (en) * | 2016-05-19 | 2017-11-28 | 中国科学院化学研究所 | A kind of multi-arm siloxanes abutting ladder poly-siloxane copolymer and its preparation method and application |
| 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 |
| CN107880267A (en) * | 2017-11-17 | 2018-04-06 | 长兴（中国）投资有限公司 | Siloxanes abutting ladder poly-siloxane of siloxane bridge base silane end-blocking and preparation method thereof |
| 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 |
| 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 |
| CN108003348A (en) * | 2017-12-15 | 2018-05-08 | 长兴（中国）投资有限公司 | Siloxanes abutting ladder poly-siloxane, its preparation method and application |
| WO2019114788A1 (en) * | 2017-12-15 | 2019-06-20 | 长兴（中国）投资有限公司 | Siloxane-bridged ladder polysiloxane, preparation method therefor, and use thereof |
| CN109957110A (en) * | 2017-12-25 | 2019-07-02 | 北京科化新材料科技有限公司 | Trapezoidal organosilicon polymer and its preparation method and application and LED packaging plastic |
| 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 |
| CN109608641A (en) * | 2018-11-26 | 2019-04-12 | 江苏艾森半导体材料股份有限公司 | Fluorine-containing trapezoidal organic siliconresin for LED packaging plastic |
| CN111847464A (en) * | 2020-07-27 | 2020-10-30 | 湖北科技学院 | Radiation preparation method of nano silicon dioxide |
| CN111847464B (en) * | 2020-07-27 | 2023-07-21 | 湖北科技学院 | Radiation preparation method of nano silicon dioxide |
| 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 |
| CN112341625B (en) * | 2020-11-27 | 2022-07-22 | 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104045831B (en) | 2016-12-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104045831A (en) | Siloxane bridged ladderlike polysiloxane and preparation method thereof | |
| CN1183183C (en) | Polyorganosilsesquioxane and process for preparing the same | |
| CN102181159B (en) | Polysilsesquioxane reinforced light emitting diode (LED) encapsulation organic silicon rubber and preparation method thereof | |
| CN107987278B (en) | Benzocyclobutene functionalized organic silicon resin and preparation method thereof | |
| CN102898649B (en) | Refractive index-adjustable MDT silicone resin and preparation method thereof | |
| CN105906810A (en) | Preparation method of organopolysiloxane resin | |
| CN108003348B (en) | Siloxane bridged ladder-shaped polysiloxane, preparation method and application thereof | |
| CN102898648B (en) | Chemical crosslinking-curable phenyl MDQ-type silicone resin and preparation method thereof | |
| CN101891893A (en) | Preparation method of phenyl-based hydrogen-based silicone resin for encapsulating LED | |
| CN103059306B (en) | High-refractive index transparent silicone resin and preparation method thereof | |
| CN103201317A (en) | Thermally stable compositions containing resin-linear organosiloxane block copolymers | |
| CN101880396A (en) | Preparation method of organic silicon rubber for encapsulating LED being convenient for vacuum defoamation | |
| WO2022105249A1 (en) | Methods for preparing silsesquioxane containing silicon-hydrogen bonds and corresponding polymer thereof | |
| CN111253575A (en) | Preparation method and application of high-refractive-index phenyl methyl amino silicone resin | |
| CN110156997A (en) | It is a kind of can moisture solidification organic silicon block copolymer and preparation method thereof | |
| KR101317776B1 (en) | Phenylpolysiloxane resin of core-shell structure | |
| CN110452386B (en) | Preparation and application of polyfunctional group POSS type organic silicon curing agent | |
| KR20130125224A (en) | Ladder-type thiol-based silsesquioxane polymer and method for preparing the same | |
| CN110229339B (en) | Phenyl vinyl siloxane resin, high-refractive-index LED packaging silicon resin composition and preparation method thereof | |
| Pohl et al. | Thermoplastic silsesquioxane hybrid polymers with a local ladder-type structure | |
| CN107400239B (en) | A kind of trapezoidal/cage type polysiloxanes and its preparation method and application from sealing end | |
| CN113321810B (en) | Q-type high-refraction phenyl vinyl silicone oil, and synthesis method and application thereof | |
| KR101474283B1 (en) | Hydrogen oligosiloxane resin and preparing method thereof | |
| CN101899156B (en) | Preparation method of multichain trapezoidal polyalkyl silsesquioxane | |
| CN107400238B (en) | Multi-arm siloxane bridged ladder-shaped polysiloxane copolymer and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20180323 Address after: 200233 Shanghai city Xuhui District No. 388 Tianlin Road Xinye building 12 room 1211 Patentee after: Changxin (China) Investment Co., Ltd. Address before: 100190 Haidian District, Zhongguancun, North Street, No. 1, No. 2, Beijing Patentee before: Institute of Chemistry, Chinese Academy of Sciences |