CN104774334A - Preparation method for silicon-titanium polymer capable of being used as additive - Google Patents
Preparation method for silicon-titanium polymer capable of being used as additive Download PDFInfo
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- CN104774334A CN104774334A CN201510100853.7A CN201510100853A CN104774334A CN 104774334 A CN104774334 A CN 104774334A CN 201510100853 A CN201510100853 A CN 201510100853A CN 104774334 A CN104774334 A CN 104774334A
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Abstract
The invention provides a preparation method for a silicon-titanium polymer capable of being used as an additive. According to the method, hydroxyl terminated polysiloxane and titanium chloride are used as raw materials, and two-step condensation is carried out so as to prepare the silicon-titanium polymer. The method has the following advantages: the raw materials are cheap and easily available; and the prepared polymer has no corrosivity on metal. The silicon-titanium polymer can be applied in the field of bonding materials; and when used as an additive for an adhesive, the silicon-titanium polymer has good compatibility and can improve heat resistance and bonding performance of the adhesive.
Description
Technical field
The present invention relates to a kind of preparation method of silicon titanium polymer, it can be used as additive and uses, and can improve sizing agent thermotolerance and adhesiveproperties, preparation method is two step method of condensing, is obtained by hydroxy-terminated polysiloxane and titanium chloride condensation polymerization.
Background technology
Organic-inorganic hybrid material is the one " matrix material " of crossing over organic materials and inorganic materials boundary, and this hybrid material can have both the advantage of organism and inorganics.Research containing the organic-inorganic hybrid material of this class formation of Si-O-M was just never interrupted, and covered the reaction of Determination of multiple metal elements and non-metallic element.As far back as the fifties in last century, Andrianov etc. are just studied metallic silicoorganic compound and polymkeric substance, and content relates to aluminium, titanium, boron, tin, and germanium and non-metallic element phosphorus, started the beginning of containing metal organosilicon polymer.After this, due to the needs of thermotolerance, more scholars have carried out the research of polytitanosiloxane.
Silicon titanium polymer refers to the organic-inorganic hybrid polymer containing Si-O-Ti structure.Si-O-Ti key is more common in inorganic materials, main application has unorganic glass, molecular sieve etc., and be not very comprehensive at elemento-organic polymer and the research all of organic-inorganic hybrid material field, but because of its high thermal resistance had, it is with a wide range of applications.
Hydrolytic condensation method is taked in the synthetic method major part reaction of polytitanosiloxane.The chemical process of hydrolytic condensation method (sol-gel method) is first by stock dispersion in a solvent, then reactive monomer is generated through hydrolysis reaction, reactive monomer is polymerized, start to become colloidal sol, and then generate the gel with certain space structure, prepare nanoparticle and required material through super-dry and thermal treatment.
Synthesizing silicon titanium polymer by sol-gel process is select the silane oxide of band active function groups and metal oxide to carry out cohydrolysis, polycondensation.As far back as the eighties, Philipp and the Schmide Acrylic Acid Monomer of Germany obtains the contact lenses glass of specific function with the silane oxide and titanium alcoxyl of being with functional group, the nineties France Clement etc. by the molecular designing of alkoxide precursor, the metal alkoxide selecting network to be formed makes the connectivity of inorganic network increase, and improves modulus and the intensity of material.
But, organoalkoxysilane and titanic acid ester cohydrolysis is made to need to make catalyzer with protonic acid owing to using sol-gol method, thus carry out there will be the phenomenon of erode metallic surfaces when metallic surface is bonding, therefore need the silicon titanium polymer probing into the bonding use of metallic substance preferably.
Summary of the invention
The invention discloses a kind of application two step condensation methods and prepare the method for silicon titanium polymer. the method for raw material, adopts two step condensation reactions with hydroxyl polysiloxane and titanium chloride:
The first step, the preparation of terminal hydroxy group silicon titanium oligopolymer, titanium chloride and hydroxy-terminated polysiloxane react, and add to receive agent and make it generate precipitate with the hydrogenchloride generated in reaction, and impel reaction forward to carry out, products therefrom is terminal hydroxy group silicon titanium oligopolymer, and operation steps is as follows,
By hydroxy-terminated polysiloxane and to receive agent be 1:(0.6-2 with mol ratio) be dissolved in organic solvent, above-mentioned joined solution is placed in there-necked flask magnetic agitation; Be dissolved in by titanium chloride in organic solvent same as described above, constant pressure funnel drips; The titanium chloride added and hydroxy-terminated polysiloxane mol ratio are 1:(2-5), temperature of reaction 0-45 DEG C, drip terminate rear continuations reaction 1-5h after stopped reaction, with filter paper filtering fall reaction generation white precipitate powder; Gained filtrate is placed in separating funnel and carries out distilled water washing, until cl content is zero; Organic phase after washing adds anhydrous Na
2sO
4dry 10 hours, filter paper filtering removed sodium sulfate; Afterwards dried solution Rotary Evaporators is carried out revolving steaming, remove solvent, obtain the terminal hydroxy group silicon titanium oligopolymer of thickness; Products therefrom is evacuated to constant weight in vacuum drying oven.
Second step, the terminal hydroxy group silicon titanium oligopolymer that the first step is obtained carries out high temperature polycondensation, and experimental procedure is as follows;
The silicon titanium oligopolymer of synthesis is put into there-necked flask and carries out mass polymerization, temperature of reaction 100-230 DEG C, reaction inflated with nitrogen, makes the moisture of generation discharge with nitrogen gas stream, reaction 5-15 hour, obtained viscoelastic solid.
Further, hydroxy-terminated polysiloxane is one or more in hydroxyl-terminated injecting two methyl siloxane, terminal hydroxy group Polymethyl methacrylate, and described titanium chloride is titanous chloride or titanium tetrachloride.
Further, in the first step process, organic solvent is benzene, toluene or tetrahydrofuran (THF).
Further, in the first step, reception agent used is DMA, N, N-Diethyl Aniline, N-ethylaniline or N-methyldiphenylamine.
The present invention's application material adhesive field, the additive that can be used as sizing agent uses the resistance toheat and adhesiveproperties that improve sizing agent.
Resol PF2176 is mixed with the ethyl acetate solution of 45%, add the silicon titanium polymer prepared by aforesaid method of different number (mass fraction), before using, sizing agent is stirred evenly, by the sizing agent scraper for preparing or plastic plate at 45# steel surface coating, ensure that solvent can volatilize as much as possible simultaneously, control thickness 0.2mm, 80 DEG C of 30min dry solvent simultaneously.After solvent evaporates, 45# steel is overlapped, gives certain pressure, make it fit tightly, continue to be warmed up to 150, solidification 5h, the mensuration (rigid material is to rigid material) according to GBT7124-2008 tackiness agent tensile shear strength carries out tensile shear strength test, N
2carry out thermogravimetic analysis (TGA) with the speed of 10 DEG C/min under condition and carry out thermotolerance test.
Embodiment
For making the object, technical solutions and advantages of the present invention clearly, below in conjunction with embodiment, the present invention is explained in detail, but does not limit practical range of the present invention.
Embodiment 1
The first step, the preparation of terminal hydroxy group silicon titanium oligopolymer, titanous chloride and hydroxyl-terminated injecting two methyl siloxane react: be hydroxyl-terminated injecting two methyl siloxane and the N of 400 by molecular weight, it is that 1:0.6 is dissolved in toluene with mol ratio that accelerine receives agent, and above-mentioned joined solution is placed in there-necked flask magnetic agitation; Titanous chloride and hydroxyl-terminated injecting two methyl siloxane mol ratio are 1:2, are dissolved in by titanous chloride in toluene, and constant pressure funnel drips; Temperature of reaction 0 DEG C, drip terminate rear continuations reaction 5h after stopped reaction, with filter paper filtering fall reaction generation white precipitate powder; Gained filtrate is placed in separating funnel and carries out distilled water washing, until cl content is zero; Organic phase after washing is added anhydrous Na
2sO
4dry 10 hours, filter paper filtering removed sodium sulfate; Dried solution Rotary Evaporators is carried out revolving steaming, removes solvent, obtain the terminal hydroxy group silicon titanium oligopolymer of thickness; Products therefrom is evacuated to constant weight in vacuum drying oven.
Second step, the terminal hydroxy group silicon titanium oligopolymer that the first step is obtained carries out high temperature polycondensation, and experimental procedure is as follows;
The silicon titanium oligopolymer of synthesis is put into there-necked flask and carries out mass polymerization, temperature of reaction 120 DEG C, reaction inflated with nitrogen, makes the moisture of generation discharge with nitrogen gas stream, reacts 15 hours, obtained viscoelastic solid.
Product infrared spectra (IR) test result is: 925cm
-1(Si-O-Ti), 3200cm
-1(-OH), 1000-1100cm
-1(Si-O-Si)
Embodiment 2
The first step, the preparation of terminal hydroxy group silicon titanium oligopolymer, titanous chloride and hydroxyl-terminated injecting two methyl siloxane react: be hydroxyl-terminated injecting two methyl siloxane and the N of 10000 by molecular weight, it is that 1:1 is dissolved in benzene with mol ratio that N-Diethyl Aniline receives agent, and above-mentioned joined solution is placed in there-necked flask magnetic agitation; Titanous chloride and hydroxyl-terminated injecting two methyl siloxane mol ratio are 1:3, are dissolved in by titanous chloride in benzene, and constant pressure funnel drips; Temperature of reaction 25 DEG C, drip terminate rear continuations reaction 3h after stopped reaction, with filter paper filtering fall reaction generation white precipitate powder; Gained filtrate is placed in separating funnel and carries out distilled water washing, until cl content is zero; Organic phase after washing is added anhydrous Na
2sO
4dry 10 hours, filter paper filtering removed sodium sulfate; Dried solution Rotary Evaporators is carried out revolving steaming, removes solvent, obtain the terminal hydroxy group silicon titanium oligopolymer of thickness; Products therefrom is evacuated to constant weight in vacuum drying oven.
Second step, the terminal hydroxy group silicon titanium oligopolymer that the first step is obtained carries out high temperature polycondensation, and experimental procedure is as follows;
The silicon titanium oligopolymer of synthesis is put into there-necked flask and carries out mass polymerization, temperature of reaction 180 DEG C, reaction inflated with nitrogen, makes the moisture of generation discharge with nitrogen gas stream, reacts 5 hours, obtained viscoelastic solid.
Product infrared spectra (IR) test result is: 925cm
-1(Si-O-Ti), 3200cm
-1(-OH), 1000-1100cm
-1(Si-O-Si)
Embodiment 3
The first step, the preparation of terminal hydroxy group silicon titanium oligopolymer, titanium tetrachloride and terminal hydroxy group Polymethyl methacrylate react: by molecular weight be 18000 terminal hydroxy group Polymethyl methacrylate and N-ethylaniline to receive agent be that 1:2 is dissolved in tetrahydrofuran (THF) with mol ratio, above-mentioned joined solution is placed in there-necked flask magnetic agitation; Titanium tetrachloride and terminal hydroxy group Polymethyl methacrylate mol ratio are 1:5, are dissolved in by titanium chloride in tetrahydrofuran (THF), and constant pressure funnel drips; Temperature of reaction 25 DEG C, drip terminate rear continuations reaction 3h after stopped reaction, with filter paper filtering fall reaction generation white precipitate powder; Gained filtrate is placed in separating funnel and carries out distilled water washing, until cl content is zero; Organic phase after washing is added anhydrous Na
2sO
4dry 10 hours, filter paper filtering removed sodium sulfate; Dried solution Rotary Evaporators is carried out revolving steaming, removes solvent, obtain the terminal hydroxy group silicon titanium oligopolymer of thickness; Products therefrom is evacuated to constant weight in vacuum drying oven.
Second step, the terminal hydroxy group silicon titanium oligopolymer that the first step is obtained carries out high temperature polycondensation, and experimental procedure is as follows;
The silicon titanium oligopolymer of synthesis is put into there-necked flask and carries out mass polymerization, temperature of reaction 180 DEG C, reaction inflated with nitrogen, makes the moisture of generation discharge with nitrogen gas stream, reacts 5 hours, obtained viscoelastic solid.
Product infrared spectra (IR) test result is: 925cm
-1(Si-O-Ti), 3200cm
-1(-OH), 1000-1100cm
-1(Si-O-Si), 1600cm
-1(C=C)
Embodiment 4
The first step, the preparation of terminal hydroxy group silicon titanium oligopolymer, the reaction of titanium tetrachloride and hydroxyl-terminated injecting two methyl siloxane and terminal hydroxy group Polymethyl methacrylate: be the hydroxyl-terminated injecting two methyl siloxane of 10000 by molecular weight, molecular weight be 1000 terminal hydroxy group Polymethyl methacrylate and N-methyldiphenylamine to receive agent three take mol ratio as 1:1:2, above-mentioned joined solution is placed in there-necked flask magnetic agitation; Titanium tetrachloride and the total mol ratio of hydroxy-terminated polysiloxane are 1:3, are dissolved in by titanium tetrachloride in benzene, and constant pressure funnel drips; Temperature of reaction 45 DEG C, drip terminate rear continuations reaction 3h after stopped reaction, with filter paper filtering fall reaction generation white precipitate powder; Gained filtrate is placed in separating funnel and carries out distilled water washing, until cl content is zero; Organic phase after washing is added anhydrous Na
2sO
4dry 10 hours, filter paper filtering removed sodium sulfate; Dried solution Rotary Evaporators is carried out revolving steaming, removes solvent, obtain the terminal hydroxy group silicon titanium oligopolymer of thickness; Products therefrom is evacuated to constant weight in vacuum drying oven.
Second step, the terminal hydroxy group silicon titanium oligopolymer that the first step is obtained carries out high temperature polycondensation, and experimental procedure is as follows;
The silicon titanium oligopolymer of synthesis is put into there-necked flask and carries out mass polymerization, temperature of reaction 230 DEG C, reaction inflated with nitrogen, makes the moisture of generation discharge with nitrogen gas stream, reacts 7 hours, obtained viscoelastic solid.
Product infrared spectra (IR) test result is: 925cm
-1(Si-O-Ti), 3200cm
-1(-OH), 1000-1100cm
-1(Si-O-Si), 1600cm
-1(C=C)
Embodiment 5
The first step, the preparation of terminal hydroxy group silicon titanium oligopolymer, titanium tetrachloride and hydroxyl-terminated injecting two methyl siloxane react: by molecular weight be 10000 hydroxyl-terminated injecting two methyl siloxane and N-methyldiphenylamine to receive agent be that 1:2 is dissolved in benzene with mol ratio, above-mentioned joined solution is placed in there-necked flask magnetic agitation; Titanium tetrachloride and hydroxyl-terminated injecting two methyl siloxane mol ratio are 1:4, are dissolved in by titanium tetrachloride in benzene, and constant pressure funnel drips; Temperature of reaction 45 DEG C, drip terminate rear continuations reaction 3h after stopped reaction, with filter paper filtering fall reaction generation white precipitate powder; Gained filtrate is placed in separating funnel and carries out distilled water washing, until cl content is zero; Organic phase after washing is added anhydrous Na
2sO
4dry 10 hours, filter paper filtering removed sodium sulfate; Dried solution Rotary Evaporators is carried out revolving steaming, removes solvent, obtain the terminal hydroxy group silicon titanium oligopolymer of thickness; Products therefrom is evacuated to constant weight in vacuum drying oven.
Second step, the terminal hydroxy group silicon titanium oligopolymer that the first step is obtained carries out high temperature polycondensation, and experimental procedure is as follows;
The silicon titanium oligopolymer of synthesis is put into there-necked flask and carries out mass polymerization, temperature of reaction 150 DEG C, reaction inflated with nitrogen, makes the moisture of generation discharge with nitrogen gas stream, reacts 10 hours, obtained viscoelastic solid.
Product infrared spectra (IR) test result is: 925cm
-1(Si-O-Ti), 3200cm
-1(-OH), 1000-1100cm
-1(Si-O-Si)
Embodiment 6
The first step, the preparation of terminal hydroxy group silicon titanium oligopolymer, titanium tetrachloride and hydroxyl-terminated injecting two methyl siloxane react: by molecular weight be 700 hydroxyl-terminated injecting two methyl siloxane and N-methyldiphenylamine to receive agent be that 1:2 is dissolved in benzene with mol ratio, above-mentioned joined solution is placed in there-necked flask magnetic agitation; Titanium tetrachloride and hydroxyl-terminated injecting two methyl siloxane mol ratio are 1:4, are dissolved in by titanium tetrachloride in benzene, and constant pressure funnel drips; Temperature of reaction 35 DEG C, drip terminate rear continuations reaction 3h after stopped reaction, with filter paper filtering fall reaction generation white precipitate powder; Gained filtrate is placed in separating funnel and carries out distilled water washing, until cl content is zero; Organic phase after washing is added anhydrous Na
2sO
4dry 10 hours, filter paper filtering removed sodium sulfate; Dried solution Rotary Evaporators is carried out revolving steaming, removes solvent, obtain the terminal hydroxy group silicon titanium oligopolymer of thickness; Products therefrom is evacuated to constant weight in vacuum drying oven.
Second step, the terminal hydroxy group silicon titanium oligopolymer that the first step is obtained carries out high temperature polycondensation, and experimental procedure is as follows;
The silicon titanium oligopolymer of synthesis is put into there-necked flask and carries out mass polymerization, temperature of reaction 200 DEG C, reaction inflated with nitrogen, makes the moisture of generation discharge with nitrogen gas stream, reacts 10 hours, obtained viscoelastic solid.
Product infrared spectra (IR) test result is: 925cm
-1(Si-O-Ti), 3200cm
-1(-OH), 1000-1100cm
-1(Si-O-Si)
Above examples of implementation are added in sizing agent when being used for metal sticking, improve resistance to elevated temperatures and the adhesiveproperties of sizing agent.
Embodiment 7
Resol PF2176 is mixed with the ethyl acetate solution of 45%, add the silicon titanium polymer prepared by embodiment 1 of 5 parts (mass fractions), before using, sizing agent is stirred evenly, by the sizing agent scraper for preparing or plastic plate at 45# steel surface coating, ensure that solvent can volatilize as much as possible simultaneously, control thickness about 0.2mm, 80 DEG C of 30min dry solvent simultaneously.After solvent evaporates, 45# steel is overlapped, give certain pressure, make it fit tightly, continue to be warmed up to 150, solidification 5h, tensile shear strength test is carried out according to GBT7124-2008 (mensuration (rigid material is to rigid material) of tackiness agent tensile shear strength), carry out thermogravimetic analysis (TGA) with the speed of 10 DEG C/min under N2 condition and carry out thermotolerance test, compared to the resol PF2176 not adding silicon titanium polymer, add the phenolic aldehyde sizing agent solidification back draft shearing resistance after silicon titanium polymer and bring up to 4.8MPa from 4MPa, the carbon yield of 950 DEG C is increased to 66.4% from 64.6%, glue-line compactness is better.
Embodiment 8
Resol PF2176 is mixed with the ethyl acetate solution of 45%, add the silicon titanium polymer prepared by embodiment 2 of 15 parts (mass fractions), before using, sizing agent is stirred evenly, by the sizing agent scraper for preparing or plastic plate at 45# steel surface coating, ensure that solvent can volatilize as much as possible simultaneously, control thickness about 0.2mm, 80 DEG C of 30min dry solvent simultaneously.After solvent evaporates, 45# steel is overlapped, give certain pressure, make it fit tightly, continue to be warmed up to 150, solidification 5h, tensile shear strength test is carried out according to GBT7124-2008 (mensuration (rigid material is to rigid material) of tackiness agent tensile shear strength), carry out thermogravimetic analysis (TGA) with the speed of 10 DEG C/min under N2 condition and carry out thermotolerance test, compared to the resol PF2176 not adding silicon titanium polymer, add the phenolic aldehyde sizing agent solidification back draft shearing resistance after silicon titanium polymer and bring up to 6MPa from 4MPa, the carbon yield of 950 DEG C is increased to 68.4% from 64.6%, glue-line compactness is better.
Embodiment 9
Resol PF2176 is mixed with the ethyl acetate solution of 45%, add the silicon titanium polymer prepared by embodiment 3 of 25 parts (mass fractions), before using, sizing agent is stirred evenly, by the sizing agent scraper for preparing or plastic plate at 45# steel surface coating, ensure that solvent can volatilize as much as possible simultaneously, control thickness about 0.2mm, 80 DEG C of 30min dry solvent simultaneously.After solvent evaporates, 45# steel is overlapped, give certain pressure, make it fit tightly, continue to be warmed up to 150, solidification 5h, tensile shear strength test is carried out according to GBT7124-2008 (mensuration (rigid material is to rigid material) of tackiness agent tensile shear strength), carry out thermogravimetic analysis (TGA) with the speed of 10 DEG C/min under N2 condition and carry out thermotolerance test, compared to the resol PF2176 not adding silicon titanium polymer, add the phenolic aldehyde sizing agent solidification back draft shearing resistance after silicon titanium polymer and bring up to 6.5MPa from 4MPa, the carbon yield of 950 DEG C is increased to 70.4% from 64.6%, glue-line compactness is better.
Embodiment 10
Resol PF2176 is mixed with the ethyl acetate solution of 45%, add the silicon titanium polymer prepared by embodiment 4 of 7 parts (mass fractions), before using, sizing agent is stirred evenly, by the sizing agent scraper for preparing or plastic plate at 45# steel surface coating, ensure that solvent can volatilize as much as possible simultaneously, control thickness about 0.2mm, 80 DEG C of 30min dry solvent simultaneously.After solvent evaporates, 45# steel is overlapped, give certain pressure, make it fit tightly, continue to be warmed up to 150, solidification 5h, tensile shear strength test is carried out according to GBT7124-2008 (mensuration (rigid material is to rigid material) of tackiness agent tensile shear strength), carry out thermogravimetic analysis (TGA) with the speed of 10 DEG C/min under N2 condition and carry out thermotolerance test, compared to the resol PF2176 not adding silicon titanium polymer, add the phenolic aldehyde sizing agent solidification back draft shearing resistance after silicon titanium polymer and bring up to 5.3MPa from 4MPa, the carbon yield of 950 DEG C is increased to 66.9% from 64.6%, glue-line compactness is better.
Embodiment 11
Resol PF2176 is mixed with the ethyl acetate solution of 45%, add the silicon titanium polymer prepared by embodiment 5 of 10 parts (mass fractions), before using, sizing agent is stirred evenly, by the sizing agent scraper for preparing or plastic plate at 45# steel surface coating, ensure that solvent can volatilize as much as possible simultaneously, control thickness about 0.2mm, 80 DEG C of 30min dry solvent simultaneously.After solvent evaporates, 45# steel is overlapped, give certain pressure, make it fit tightly, continue to be warmed up to 150, solidification 5h, tensile shear strength test is carried out according to GBT7124-2008 (mensuration (rigid material is to rigid material) of tackiness agent tensile shear strength), carry out thermogravimetic analysis (TGA) with the speed of 10 DEG C/min under N2 condition and carry out thermotolerance test, compared to the resol PF2176 not adding silicon titanium polymer, add the phenolic aldehyde sizing agent solidification back draft shearing resistance after silicon titanium polymer and bring up to 6MPa from 4MPa, the carbon yield of 950 DEG C is increased to 68% from 64.6%, glue-line compactness is better.
Embodiment 12
Resol PF2176 is mixed with the ethyl acetate solution of 45%, add the silicon titanium polymer prepared by embodiment 6 of 23 parts (mass fractions), before using, sizing agent is stirred evenly, by the sizing agent scraper for preparing or plastic plate at 45# steel surface coating, ensure that solvent can volatilize as much as possible simultaneously, control thickness about 0.2mm, 80 DEG C of 30min dry solvent simultaneously.After solvent evaporates, 45# steel is overlapped, give certain pressure, make it fit tightly, continue to be warmed up to 150, solidification 5h, tensile shear strength test is carried out according to GBT7124-2008 (mensuration (rigid material is to rigid material) of tackiness agent tensile shear strength), carry out thermogravimetic analysis (TGA) with the speed of 10 DEG C/min under N2 condition and carry out thermotolerance test, compared to the resol PF2176 not adding silicon titanium polymer, add the phenolic aldehyde sizing agent solidification back draft shearing resistance after silicon titanium polymer and bring up to 6.9MPa from 4MPa, the carbon yield of 950 DEG C is increased to 70.3% from 64.6%, glue-line compactness is better.
Claims (4)
1. a preparation method for silicon titanium polymer, is characterized in that, described method comprises two-step reaction:
The first step, the preparation of terminal hydroxy group silicon titanium oligopolymer, concrete operation step is as follows: by hydroxy-terminated polysiloxane and to receive agent be 1:(0.6-2 with mol ratio) be dissolved in organic solvent, above-mentioned joined solution is placed in there-necked flask magnetic agitation; Be dissolved in by titanium chloride in organic solvent same as described above, constant pressure funnel drips; The titanium chloride added and hydroxy-terminated polysiloxane mol ratio are 1:(2-5), temperature of reaction 0-45 DEG C, drip terminate rear continuations reaction 1-5h after stopped reaction, with filter paper filtering fall reaction generation white precipitate powder; Gained filtrate is placed in separating funnel and carries out distilled water washing, until cl content is zero; Organic phase after washing adds anhydrous Na
2sO
4dry 10 hours, filter paper filtering removed sodium sulfate; Afterwards dried solution Rotary Evaporators is carried out revolving steaming, remove solvent, obtain the terminal hydroxy group silicon titanium oligopolymer of thickness; Products therefrom is evacuated to constant weight;
Second step, the terminal hydroxy group silicon titanium oligopolymer that the first step is obtained carries out high temperature polycondensation, and experimental procedure is as follows;
The terminal hydroxy group silicon titanium oligopolymer of synthesis is put into there-necked flask and carries out mass polymerization, temperature of reaction 120-230 DEG C, reaction inflated with nitrogen, makes the moisture of generation discharge with nitrogen gas stream, and reaction 5-15 hour, obtains viscoelastic solid.
2. the method for claim 1, is characterized in that: hydroxy-terminated polysiloxane is one or more in hydroxyl-terminated injecting two methyl siloxane, terminal hydroxy group Polymethyl methacrylate, and described titanium chloride is titanous chloride or titanium tetrachloride.
3. method as claimed in claim 1, is characterized in that: in the first step process, organic solvent is benzene, toluene or tetrahydrofuran (THF).
4. method as claimed in claim 1, is characterized in that: in the first step, reception agent used is DMA, N, N-Diethyl Aniline, N-ethylaniline or N-methyldiphenylamine.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105238325A (en) * | 2015-11-14 | 2016-01-13 | 华文蔚 | High-temperature-water-resistant saturated anti-abrasion macromolecular cementing compound and preparation method |
| CN108546410A (en) * | 2018-03-31 | 2018-09-18 | 长春物恒新技术有限公司 | A kind of high-temperature resistant single-component RTV fluorocarbon silicone rubber |
| CN108841178A (en) * | 2018-05-04 | 2018-11-20 | 长春物恒新技术有限公司 | A kind of preparation method of room temperature vulcanization high-temperature resistant one-component fluorine silicone rubber |
| CN111040177A (en) * | 2019-12-25 | 2020-04-21 | 大连海事大学 | Silicon-titanium oligomer containing bifunctional group and preparation method thereof |
| CN111116213A (en) * | 2019-02-21 | 2020-05-08 | 张家港市恒乐阳方高温材料有限公司 | Dry refractory material |
| CN114806691A (en) * | 2022-05-25 | 2022-07-29 | 中国科学院兰州化学物理研究所 | Room-temperature curing dry film lubricant and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030195321A1 (en) * | 2002-04-10 | 2003-10-16 | Congji Zha | Metal alkoxide polymers |
| CN103265703A (en) * | 2013-05-06 | 2013-08-28 | 北京化工大学 | High refractive index titanium hybrid silicon resin and preparation method thereof |
| CN103408763A (en) * | 2013-04-08 | 2013-11-27 | 北京化工大学 | Method for preparing silicon-titanium polymers |
-
2015
- 2015-03-08 CN CN201510100853.7A patent/CN104774334B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030195321A1 (en) * | 2002-04-10 | 2003-10-16 | Congji Zha | Metal alkoxide polymers |
| CN103408763A (en) * | 2013-04-08 | 2013-11-27 | 北京化工大学 | Method for preparing silicon-titanium polymers |
| CN103265703A (en) * | 2013-05-06 | 2013-08-28 | 北京化工大学 | High refractive index titanium hybrid silicon resin and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 刘辰等: "聚钛硅氧烷的合成与表征", 《材料导报》 * |
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| CN105238325A (en) * | 2015-11-14 | 2016-01-13 | 华文蔚 | High-temperature-water-resistant saturated anti-abrasion macromolecular cementing compound and preparation method |
| CN108546410A (en) * | 2018-03-31 | 2018-09-18 | 长春物恒新技术有限公司 | A kind of high-temperature resistant single-component RTV fluorocarbon silicone rubber |
| CN108841178A (en) * | 2018-05-04 | 2018-11-20 | 长春物恒新技术有限公司 | A kind of preparation method of room temperature vulcanization high-temperature resistant one-component fluorine silicone rubber |
| CN111116213A (en) * | 2019-02-21 | 2020-05-08 | 张家港市恒乐阳方高温材料有限公司 | Dry refractory material |
| CN111040177A (en) * | 2019-12-25 | 2020-04-21 | 大连海事大学 | Silicon-titanium oligomer containing bifunctional group and preparation method thereof |
| CN114806691A (en) * | 2022-05-25 | 2022-07-29 | 中国科学院兰州化学物理研究所 | Room-temperature curing dry film lubricant and preparation method and application thereof |
| CN114806691B (en) * | 2022-05-25 | 2023-04-14 | 中国科学院兰州化学物理研究所 | Room temperature curing dry film lubricant and preparation method and application thereof |
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