CN104774334B - A kind of preparation method of the silicon titanium polymer used as additive - Google Patents
A kind of preparation method of the silicon titanium polymer used as additive Download PDFInfo
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- CN104774334B CN104774334B CN201510100853.7A CN201510100853A CN104774334B CN 104774334 B CN104774334 B CN 104774334B CN 201510100853 A CN201510100853 A CN 201510100853A CN 104774334 B CN104774334 B CN 104774334B
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Abstract
The invention provides a kind of preparation method of the silicon titanium polymer used as additive, this method is using hydroxy-terminated polysiloxane and titanium chloride as raw material, the method being condensed using two steps obtains silicon titanium polymer, this method has raw material cheap and easy to get, polymer does not have corrosive advantage to metal, present invention can apply to adhesives field, the additive as adhesive has good compatibility when using, and can improve the heat resistance and adhesive property of adhesive.
Description
Technical field
The present invention relates to a kind of preparation method of silicon titanium polymer, and it can be used as additive, and it is resistance to can to improve adhesive
Hot and adhesive property, preparation method are two step method of condensing, are made by hydroxy-terminated polysiloxane and titanium chloride condensation polymerization.
Background technology
Organic-inorganic hybrid material is across one kind " composite " of organic material and inorganic material boundary, this hydridization
Material can have both the advantages of organic matter and inorganic matter.The research of the organic-inorganic hybrid material of this class formation containing Si-O-M just from
It was not interrupted, and covered the reaction of Determination of multiple metal elements and nonmetalloid.Early in the fifties in last century, Andrianov etc. is just
Organo-silicon compound containing metal and polymer are studied, content is related to aluminium, titanium, boron, tin, germanium and nonmetalloid
Phosphorus, the beginning of the polymer containing silicon organo-metallic is started.Hereafter, due to the needs of heat resistance, more scholars have carried out poly- titanium silicon
The research of oxygen alkane.
Silicon titanium polymer refers to the organic-inorganic hybrid polymer containing Si-O-Ti structures.Si-O-Ti keys are in inorganic material
Relatively common, main application has unorganic glass, molecular sieve etc., and in elemento-organic polymer and organic-inorganic hybrid material field
Research all is not very comprehensive, but because of the heat-resisting quantity that it has it is with a wide range of applications.
Largely hydrolytic condensation method is taken in reaction to the synthetic method of polytitanosiloxane.Hydrolytic condensation method (sol-gel process)
Chemical process be first by stock dispersion in a solvent, then by hydrolysis generate activated monomer, activated monomer carry out
Polymerization, start to turn into colloidal sol, and then generate the gel with certain space structure, nanoparticle is prepared by dry and heat treatment
Sub and required material.
It is to select silane oxide and metal oxide with active function groups to synthesize silicon titanium polymer by sol-gel process
Carry out cohydrolysis, polycondensation.Early in the eighties, German Philipp and the Schmide same silane with functional group of acrylic monomers
Oxide and titanium alcoxyl are made the contact lenses glass for having specific function, and the nineties, the Clement etc. of France passed through alkoxide
The MOLECULE DESIGN of thing precursor, the metal alkoxide formed from network increase the connectivity of inorganic network, improve material
The modulus and intensity of material.
But due to making alkoxy silane and titanate esters cohydrolysis need to be urged with Bronsted acid using sol-gol methods
Agent, thus carry out the phenomenon that corrosion metal surface occurs during the bonding of metal surface, it is therefore desirable to probe into metal material preferably
The silicon titanium polymer that material bonding uses.
The content of the invention
The invention discloses a kind of two step condensation methods of application to prepare method this method of silicon titanium polymer with the poly- silica of hydroxyl
Alkane and titanium chloride are raw material, using two step condensation reactions：
The first step, the preparation of terminal hydroxy group silicon titanium oligomer, titanium chloride react with hydroxy-terminated polysiloxane, add and connect in reaction
Receiving agent makes the hydrogen chloride of itself and generation generate precipitation, promotes reaction forward to carry out, and products therefrom is terminal hydroxy group silicon titanium oligomer, behaviour
It is as follows to make step,
By hydroxy-terminated polysiloxane and agent is received using mol ratio as 1：(0.6-2) is dissolved in organic solvent, is matched somebody with somebody above-mentioned
Solution is placed in there-necked flask magnetic agitation；Titanium chloride is dissolved in organic solvent same as described above, constant pressure funnel is added dropwise；Institute
The titanium chloride of addition is 1 with hydroxy-terminated polysiloxane mol ratio：(2-5), 0-45 DEG C of reaction temperature, continue to react after completion of dropwise addition
Stop reaction after 1-5h, the white precipitate powder of reaction generation is filtered out with filter paper；Gained filtrate is placed in separatory funnel
Row distilled water is washed, until chlorinity is zero；Organic after washing is added to anhydrous Na2SO4Dry 10 hours, filter paper, which is crossed, to be filtered out
Fall sodium sulphate；Dried solution is rotated with Rotary Evaporators afterwards, solvent is removed, it is low to obtain sticky terminal hydroxy group silicon titanium
Polymers；Products therefrom is evacuated to constant weight in vacuum drying chamber.
Second step, terminal hydroxy group silicon titanium oligomer made from the first step is subjected to high temperature polycondensation, experimental procedure is as follows；
The silicon titanium oligomer of synthesis is put into there-necked flask and carries out polymerisation in bulk, 100-230 DEG C of reaction temperature, reacts nitrogen charging
Gas, caused moisture is discharged with nitrogen stream, react 5-15 hours, viscoelastic solid is made.
Further, hydroxy-terminated polysiloxane is hydroxyl-terminated injecting two methyl siloxane, terminal hydroxy group Polymethyl methacrylate
In one or more, the titanium chloride is titanium trichloride or titanium tetrachloride.
Further, organic solvent is benzene, toluene or tetrahydrofuran during the first step.
Further, in the first step it is used reception agent be DMA, N, N- diethylanilines, N-ethylaniline or
N- methyldiphenylamines.
Application material of the present invention is bonded field, can be used as the additive of adhesive raising adhesive heat resistance and
Adhesive property.
Phenolic resin PF2176 is configured to 45% ethyl acetate solution, add different numbers (mass fraction) by upper
The silicon titanium polymer of method preparation is stated, is stirred evenly adhesive using preceding, by the adhesive scraper or plastic plate that prepare in 45#
Steel surface gluing, while ensure that solvent can volatilize as far as possible, thickness 0.2mm is controlled, while 80 DEG C of 30min dry solvent.Treat
After solvent volatilization, 45# steel is overlapped, gives certain pressure, is brought into close contact it, continued to be warming up to 150, solidify 5h, according to
Measure (rigid material is to rigid material) the progress tensile shear strength test of GBT7124-2008 adhesive tensile shear strengths,
N2Under the conditions of thermogravimetic analysis (TGA) carried out with 10 DEG C/min speed carry out heat resistance test.
Embodiment
To make the object, technical solutions and advantages of the present invention clearer, below in conjunction with embodiment to this hair
It is bright to be explained in detail, but the practical range of the present invention is not limited.
Embodiment 1
The first step, the preparation of terminal hydroxy group silicon titanium oligomer, titanium trichloride react with hydroxyl-terminated injecting two methyl siloxane：It will divide
Son amount is 400 hydroxyl-terminated injecting two methyl siloxane and N, and accelerine reception agent is using mol ratio as 1：0.6 is dissolved in toluene
In, above-mentioned matched somebody with somebody solution is placed in there-necked flask magnetic agitation；Titanium trichloride and hydroxyl-terminated injecting two methyl siloxane mol ratio are 1：
2, titanium trichloride is dissolved in toluene, constant pressure funnel is added dropwise；0 DEG C of reaction temperature, continue to stop after reacting 5h after completion of dropwise addition
Only react, the white precipitate powder of reaction generation is filtered out with filter paper；Gained filtrate is placed in separatory funnel and carries out distilled water
Washing, until chlorinity is zero；Organic after washing is added to anhydrous Na2SO4Dry 10 hours, filter paper is removed by filtration sulfuric acid
Sodium；Dried solution is rotated with Rotary Evaporators, solvent is removed, obtains sticky terminal hydroxy group silicon titanium oligomer；Gained
Product is evacuated to constant weight in vacuum drying chamber.
Second step, terminal hydroxy group silicon titanium oligomer made from the first step is subjected to high temperature polycondensation, experimental procedure is as follows；
The silicon titanium oligomer of synthesis is put into there-necked flask and carries out polymerisation in bulk, 120 DEG C of reaction temperature, reacts inflated with nitrogen,
Moisture caused by making is discharged with nitrogen stream, is reacted 15 hours, and viscoelastic solid is made.
Product infrared spectrum (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 oligomer, titanium trichloride react with hydroxyl-terminated injecting two methyl siloxane：It will divide
The hydroxyl-terminated injecting two methyl siloxane and N, N- diethylaniline that son amount is 10000 receive agent using mol ratio as 1：1 is dissolved in benzene,
Above-mentioned matched somebody with somebody solution is placed in there-necked flask magnetic agitation；Titanium trichloride and hydroxyl-terminated injecting two methyl siloxane mol ratio are 1：3, will
Titanium trichloride is dissolved in benzene, and constant pressure funnel is added dropwise；25 DEG C of reaction temperature, continue to stop instead after reacting 3h after completion of dropwise addition
Should, the white precipitate powder for reacting generation is filtered out with filter paper；Gained filtrate is placed in progress distilled water washing in separatory funnel,
Until chlorinity is zero；Organic after washing is added to anhydrous Na2SO4Dry 10 hours, filter paper is removed by filtration sodium sulphate；Will
Dried solution is rotated with Rotary Evaporators, is removed solvent, is obtained sticky terminal hydroxy group silicon titanium oligomer；Products therefrom exists
Constant weight is evacuated in vacuum drying chamber.
Second step, terminal hydroxy group silicon titanium oligomer made from the first step is subjected to high temperature polycondensation, experimental procedure is as follows；
The silicon titanium oligomer of synthesis is put into there-necked flask and carries out polymerisation in bulk, 180 DEG C of reaction temperature, reacts inflated with nitrogen,
Moisture caused by making is discharged with nitrogen stream, is reacted 5 hours, and viscoelastic solid is made.
Product infrared spectrum (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 oligomer, titanium tetrachloride react with terminal hydroxy group Polymethyl methacrylate：
The terminal hydroxy group Polymethyl methacrylate and N-ethylaniline that are 18000 by molecular weight receive agent using mol ratio as 1：2 are dissolved in
In tetrahydrofuran, above-mentioned matched somebody with somebody solution is placed in there-necked flask magnetic agitation；Titanium tetrachloride and the poly- methyl ethylene silica of terminal hydroxy group
Alkane mol ratio is 1：5, titanium chloride is dissolved in tetrahydrofuran, constant pressure funnel is added dropwise；25 DEG C of reaction temperature, after completion of dropwise addition
Continue to stop reaction after reacting 3h, the white precipitate powder of reaction generation is filtered out with filter paper；Gained filtrate is placed in liquid separation leakage
Distilled water washing is carried out in bucket, until chlorinity is zero；Organic after washing is added to anhydrous Na2SO4Dry 10 hours, filter
Paper is removed by filtration sodium sulphate；Dried solution is rotated with Rotary Evaporators, solvent is removed, obtains sticky terminal hydroxy group silicon
Titanium oligomer；Products therefrom is evacuated to constant weight in vacuum drying chamber.
Second step, terminal hydroxy group silicon titanium oligomer made from the first step is subjected to high temperature polycondensation, experimental procedure is as follows；
The silicon titanium oligomer of synthesis is put into there-necked flask and carries out polymerisation in bulk, 180 DEG C of reaction temperature, reacts inflated with nitrogen,
Moisture caused by making is discharged with nitrogen stream, is reacted 5 hours, and viscoelastic solid is made.
Product infrared spectrum (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 oligomer, titanium tetrachloride and hydroxyl-terminated injecting two methyl siloxane and terminal hydroxy group
The reaction of Polymethyl methacrylate：It is 1000 by hydroxyl-terminated injecting two methyl siloxane that molecular weight is 10000, molecular weight
Terminal hydroxy group Polymethyl methacrylate and N- methyldiphenylamines receive agent three using mol ratio as 1：1：2, will be above-mentioned matched somebody with somebody molten
Liquid is placed in there-necked flask magnetic agitation；Titanium tetrachloride and the total mol ratio of hydroxy-terminated polysiloxane are 1：3, titanium tetrachloride is dissolved in benzene
In, constant pressure funnel is added dropwise；45 DEG C of reaction temperature, continue to stop reaction after reacting 3h after completion of dropwise addition, filtered out with filter paper
React the white precipitate powder of generation；Gained filtrate is placed in progress distilled water washing in separatory funnel, until chlorinity is zero；
Organic after washing is added to anhydrous Na2SO4Dry 10 hours, filter paper is removed by filtration sodium sulphate；Dried solution is revolved
Turn evaporimeter to be rotated, remove solvent, obtain sticky terminal hydroxy group silicon titanium oligomer；Products therefrom is taken out very in vacuum drying chamber
It is empty to constant weight.
Second step, terminal hydroxy group silicon titanium oligomer made from the first step is subjected to high temperature polycondensation, experimental procedure is as follows；
The silicon titanium oligomer of synthesis is put into there-necked flask and carries out polymerisation in bulk, 230 DEG C of reaction temperature, reacts inflated with nitrogen,
Moisture caused by making is discharged with nitrogen stream, is reacted 7 hours, and viscoelastic solid is made.
Product infrared spectrum (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 oligomer, titanium tetrachloride react with hydroxyl-terminated injecting two methyl siloxane：It will divide
The hydroxyl-terminated injecting two methyl siloxane and N- methyldiphenylamines that son amount is 10000 receive agent using mol ratio as 1：2 are dissolved in benzene, will
Above-mentioned matched somebody with somebody solution is placed in there-necked flask magnetic agitation；Titanium tetrachloride and hydroxyl-terminated injecting two methyl siloxane mol ratio are 1：4, by four
Titanium chloride is dissolved in benzene, and constant pressure funnel is added dropwise；45 DEG C of reaction temperature, continue to stop reaction after reacting 3h after completion of dropwise addition,
The white precipitate powder of reaction generation is filtered out with filter paper；Gained filtrate is placed in progress distilled water washing in separatory funnel, directly
It is zero to chlorinity；Organic after washing is added to anhydrous Na2SO4Dry 10 hours, filter paper is removed by filtration sodium sulphate；Will be dry
Solution after dry is rotated with Rotary Evaporators, is removed solvent, is obtained sticky terminal hydroxy group silicon titanium oligomer；Products therefrom is true
Constant weight is evacuated in empty drying box.
Second step, terminal hydroxy group silicon titanium oligomer made from the first step is subjected to high temperature polycondensation, experimental procedure is as follows；
The silicon titanium oligomer of synthesis is put into there-necked flask and carries out polymerisation in bulk, 150 DEG C of reaction temperature, reacts inflated with nitrogen,
Moisture caused by making is discharged with nitrogen stream, is reacted 10 hours, and viscoelastic solid is made.
Product infrared spectrum (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 oligomer, titanium tetrachloride react with hydroxyl-terminated injecting two methyl siloxane：It will divide
The hydroxyl-terminated injecting two methyl siloxane and N- methyldiphenylamines that son amount is 700 receive agent using mol ratio as 1：2 are dissolved in benzene, will be upper
State matched somebody with somebody solution and be placed in there-necked flask magnetic agitation；Titanium tetrachloride and hydroxyl-terminated injecting two methyl siloxane mol ratio are 1：4, by tetrachloro
Change titanium to be dissolved in benzene, constant pressure funnel is added dropwise；35 DEG C of reaction temperature, continue to stop reaction after reacting 3h after completion of dropwise addition, use
Filter paper filters out the white precipitate powder of reaction generation；Gained filtrate is placed in progress distilled water washing in separatory funnel, until
Chlorinity is zero；Organic after washing is added to anhydrous Na2SO4Dry 10 hours, filter paper is removed by filtration sodium sulphate；By drying
Solution afterwards is rotated with Rotary Evaporators, is removed solvent, is obtained sticky terminal hydroxy group silicon titanium oligomer；Products therefrom is in vacuum
Constant weight is evacuated in drying box.
Second step, terminal hydroxy group silicon titanium oligomer made from the first step is subjected to high temperature polycondensation, experimental procedure is as follows；
The silicon titanium oligomer of synthesis is put into there-necked flask and carries out polymerisation in bulk, 200 DEG C of reaction temperature, reacts inflated with nitrogen,
Moisture caused by making is discharged with nitrogen stream, is reacted 10 hours, and viscoelastic solid is made.
Product infrared spectrum (IR) test result is:925cm-1(Si-O-Ti), 3200cm-1(-OH),1000-1100cm-1
(Si-O-Si)
Above embodiment is used for addition during metal adhesive and in adhesive, improves the resistance to elevated temperatures and bonding of adhesive
Performance.
Embodiment 7
Phenolic resin PF2176 is configured to 45% ethyl acetate solution, add 5 parts (mass fraction) by embodiment 1
The silicon titanium polymer of preparation, is stirred evenly adhesive using preceding, by the adhesive scraper prepared or plastic plate in 45# steel surfaces
Gluing, while ensure that solvent can volatilize as far as possible, control thickness 0.2mm or so, while 80 DEG C of 30min dry solvent.Treat molten
After agent volatilization, 45# steel is overlapped, gives certain pressure, is brought into close contact it, continued to be warming up to 150, solidify 5h, according to
GBT7124-2008 (measure (rigid material is to rigid material) of adhesive tensile shear strength) carries out tensile shear strength survey
Thermogravimetic analysis (TGA) is carried out with 10 DEG C/min speed under the conditions of examination, N2 and carries out heat resistance test, is polymerize compared to silicon titanium is added without
The phenolic resin PF2176 of thing, add the solidification of the phenolic aldehyde adhesive after silicon titanium polymer post-tensioning shear strength and brought up to from 4MPa
4.8MPa, 950 DEG C of carbon yield increase to 66.4% from 64.6%, and glue-line compactness is more preferable.
Embodiment 8
Phenolic resin PF2176 is configured to 45% ethyl acetate solution, add 15 parts (mass fraction) by embodiment
The 2 silicon titanium polymers prepared, are stirred evenly adhesive using preceding, by the adhesive scraper prepared or plastic plate in 45# steel tables
Face gluing, while ensure that solvent can volatilize as far as possible, control thickness 0.2mm or so, while 80 DEG C of 30min dry solvent.Treat
After solvent volatilization, 45# steel is overlapped, gives certain pressure, is brought into close contact it, continued to be warming up to 150, solidify 5h, according to
GBT7124-2008 (measure (rigid material is to rigid material) of adhesive tensile shear strength) carries out tensile shear strength survey
Thermogravimetic analysis (TGA) is carried out with 10 DEG C/min speed under the conditions of examination, N2 and carries out heat resistance test, is polymerize compared to silicon titanium is added without
The phenolic resin PF2176 of thing, add the solidification of the phenolic aldehyde adhesive after silicon titanium polymer post-tensioning shear strength and brought up to from 4MPa
6MPa, 950 DEG C of carbon yield increase to 68.4% from 64.6%, and glue-line compactness is more preferable.
Embodiment 9
Phenolic resin PF2176 is configured to 45% ethyl acetate solution, add 25 parts (mass fraction) by embodiment
The 3 silicon titanium polymers prepared, are stirred evenly adhesive using preceding, by the adhesive scraper prepared or plastic plate in 45# steel tables
Face gluing, while ensure that solvent can volatilize as far as possible, control thickness 0.2mm or so, while 80 DEG C of 30min dry solvent.Treat
After solvent volatilization, 45# steel is overlapped, gives certain pressure, is brought into close contact it, continued to be warming up to 150, solidify 5h, according to
GBT7124-2008 (measure (rigid material is to rigid material) of adhesive tensile shear strength) carries out tensile shear strength survey
Thermogravimetic analysis (TGA) is carried out with 10 DEG C/min speed under the conditions of examination, N2 and carries out heat resistance test, is polymerize compared to silicon titanium is added without
The phenolic resin PF2176 of thing, add the solidification of the phenolic aldehyde adhesive after silicon titanium polymer post-tensioning shear strength and brought up to from 4MPa
6.5MPa, 950 DEG C of carbon yield increase to 70.4% from 64.6%, and glue-line compactness is more preferable.
Embodiment 10
Phenolic resin PF2176 is configured to 45% ethyl acetate solution, add 7 parts (mass fraction) by embodiment 4
The silicon titanium polymer of preparation, is stirred evenly adhesive using preceding, by the adhesive scraper prepared or plastic plate in 45# steel surfaces
Gluing, while ensure that solvent can volatilize as far as possible, control thickness 0.2mm or so, while 80 DEG C of 30min dry solvent.Treat molten
After agent volatilization, 45# steel is overlapped, gives certain pressure, is brought into close contact it, continued to be warming up to 150, solidify 5h, according to
GBT7124-2008 (measure (rigid material is to rigid material) of adhesive tensile shear strength) carries out tensile shear strength survey
Thermogravimetic analysis (TGA) is carried out with 10 DEG C/min speed under the conditions of examination, N2 and carries out heat resistance test, is polymerize compared to silicon titanium is added without
The phenolic resin PF2176 of thing, add the solidification of the phenolic aldehyde adhesive after silicon titanium polymer post-tensioning shear strength and brought up to from 4MPa
5.3MPa, 950 DEG C of carbon yield increase to 66.9% from 64.6%, and glue-line compactness is more preferable.
Embodiment 11
Phenolic resin PF2176 is configured to 45% ethyl acetate solution, add 10 parts (mass fraction) by embodiment
The 5 silicon titanium polymers prepared, are stirred evenly adhesive using preceding, by the adhesive scraper prepared or plastic plate in 45# steel tables
Face gluing, while ensure that solvent can volatilize as far as possible, control thickness 0.2mm or so, while 80 DEG C of 30min dry solvent.Treat
After solvent volatilization, 45# steel is overlapped, gives certain pressure, is brought into close contact it, continued to be warming up to 150, solidify 5h, according to
GBT7124-2008 (measure (rigid material is to rigid material) of adhesive tensile shear strength) carries out tensile shear strength survey
Thermogravimetic analysis (TGA) is carried out with 10 DEG C/min speed under the conditions of examination, N2 and carries out heat resistance test, is polymerize compared to silicon titanium is added without
The phenolic resin PF2176 of thing, add the solidification of the phenolic aldehyde adhesive after silicon titanium polymer post-tensioning shear strength and brought up to from 4MPa
6MPa, 950 DEG C of carbon yield increase to 68% from 64.6%, and glue-line compactness is more preferable.
Embodiment 12
Phenolic resin PF2176 is configured to 45% ethyl acetate solution, add 23 parts (mass fraction) by embodiment
The 6 silicon titanium polymers prepared, are stirred evenly adhesive using preceding, by the adhesive scraper prepared or plastic plate in 45# steel tables
Face gluing, while ensure that solvent can volatilize as far as possible, control thickness 0.2mm or so, while 80 DEG C of 30min dry solvent.Treat
After solvent volatilization, 45# steel is overlapped, gives certain pressure, is brought into close contact it, continued to be warming up to 150, solidify 5h, according to
GBT7124-2008 (measure (rigid material is to rigid material) of adhesive tensile shear strength) carries out tensile shear strength survey
Thermogravimetic analysis (TGA) is carried out with 10 DEG C/min speed under the conditions of examination, N2 and carries out heat resistance test, is polymerize compared to silicon titanium is added without
The phenolic resin PF2176 of thing, add the solidification of the phenolic aldehyde adhesive after silicon titanium polymer post-tensioning shear strength and brought up to from 4MPa
6.9MPa, 950 DEG C of carbon yield increase to 70.3% from 64.6%, and glue-line compactness is more preferable.
Claims (3)
- A kind of 1. preparation method of silicon titanium polymer, it is characterised in that, methods described includes two-step reaction:The first step, the preparation of terminal hydroxy group silicon titanium oligomer, concrete operation step are as follows：By hydroxy-terminated polysiloxane and receive agent with Mol ratio is 1：(0.6-2) is dissolved in organic solvent, and above-mentioned matched somebody with somebody solution is placed in into there-necked flask magnetic agitation；Titanium chloride is dissolved in In organic solvent same as described above, constant pressure funnel is added dropwise；The titanium chloride added and hydroxy-terminated polysiloxane mol ratio For 1：(2-5), 0-45 DEG C of reaction temperature, continue to stop reaction after reacting 1-5h after completion of dropwise addition, reaction life is filtered out with filter paper Into white precipitate powder；Gained filtrate is placed in progress distilled water washing in separatory funnel, until chlorinity is zero；After washing Organic be added to anhydrous Na2SO4Dry 10 hours, filter paper is removed by filtration sodium sulphate；Dried solution is steamed with rotation afterwards Hair instrument is rotated, and is removed solvent, is obtained sticky terminal hydroxy group silicon titanium oligomer；Products therefrom is evacuated to constant weight；Second step, terminal hydroxy group silicon titanium oligomer made from the first step is subjected to high temperature polycondensation, experimental procedure is as follows；The terminal hydroxy group silicon titanium oligomer of synthesis is put into there-necked flask and carries out polymerisation in bulk, 120-230 DEG C of reaction temperature, reaction is filled Nitrogen, caused moisture is discharged with nitrogen stream, react 5-15 hours, obtain viscoelastic solid；Hydroxy-terminated polysiloxane is hydroxyl-terminated injecting two methyl siloxane, one kind in terminal hydroxy group Polymethyl methacrylate or several Kind, the titanium chloride is titanium trichloride or titanium tetrachloride.
- 2. method as claimed in claim 1, it is characterised in that:Organic solvent is benzene, toluene or tetrahydrochysene during the first step Furans.
- 3. method as claimed in claim 1, it is characterised in that:Reception agent used is N in the first step, accelerine, N, N- diethylaniline, N-ethylaniline or N- methyldiphenylamines.
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| 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 |
| 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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| Title |
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| 聚钛硅氧烷的合成与表征;刘辰等;《材料导报》;20131130;232-233,247 * |
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