CN1166722C - Fluorosilicic phenylene copolymer and its prepn process - Google Patents
Fluorosilicic phenylene copolymer and its prepn process Download PDFInfo
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- CN1166722C CN1166722C CNB011267720A CN01126772A CN1166722C CN 1166722 C CN1166722 C CN 1166722C CN B011267720 A CNB011267720 A CN B011267720A CN 01126772 A CN01126772 A CN 01126772A CN 1166722 C CN1166722 C CN 1166722C
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Abstract
The present invention relates to a copolymer containing phenylene fluorine silicon and a preparation method. The structure formula of the copolymer is the right formula, wherein Me represents CH3-; Rf represents CF3 CH2 CH2-; the content of phenylene chain links m/(m+3n) is from 10 to 95 %; the viscosity is from 20 to 500 Pa. s25 DEG C; the highest number-average molecular weight is 600, 000. The copolymer is prepared by anion ring opening, polycondensation and balance reactions of a pair of (3, 3, 3-trifluorine propyl methyl oxhydryl silicon-based) phenylene monomers and a 3, 3, 3-trifluorine propyl methyl cyclotrisiloxane monomer under the catalysis action of alkli. Compared with the prior art, the product of the present invention has the advantages of wide range of use temperature, high temperature resistance of fuel oil, chemical reagent resistance, radiation resistance, solidification at the room temperature, etc. Meanwhile, the method of the present invention has the advantages of low cost and good environmental protection effect.
Description
Technical field
The present invention relates to a kind of fluorine silicon penylene multipolymer and preparation method thereof, relate in particular to a kind of fluorine silicon penylene multipolymer of holding hydroxyl and preparation method thereof.
Background technology
As everyone knows, silicon rubber and other organic synthesis rubber phase ratio have characteristics such as good thermotolerance, winter hardiness, weathering resistance, electric property, compression deformability, rebound resilience, release property, heat conductivity, nontoxicity.And the structure of fluorine silicon based elastomers is to introduce fluoro-alkyl on the silica side chain on the general silicon rubber skeleton, thereby makes its numerous characteristics that not only kept silicon rubber, and, also make it have excellent oil resistant and chemical reagent resistance.
The existing so far about 50 years history of fluorine silicon based elastomers development, along with current development of high-tech, it largely is restricted in application facet.As: the high temperature grade of original trifluoropropyl siloxane fuel oil resistance is 180 ℃, and the temperature resistant grade that is applied to fuel tanker and integral fuel cell seal gum requires to reach 230 ℃.
Summary of the invention
Purpose of the present invention is exactly that a kind of have wide use temperature scope, high temperature resistant oil fuel, chemical reagent resistance, radioprotective, solidified fluorine silicon penylene multipolymer and preparation method thereof at room temperature are provided in order to overcome the defective that above-mentioned prior art exists.
Purpose of the present invention can be achieved through the following technical solutions: a kind of fluorine silicon penylene multipolymer is characterized in that having the compound of following structural formula:
Wherein, Me represents CH
3-, R
fRepresent CF
3CH
2CH
2-, penylene chain link content m/ (m+3n)=10～95%, 25 ℃ of viscosity 20～500Pa.s, number-average molecular weight is up to 600,000.
Described penylene chain link content m/ (m+3n)=40～45%.
25 ℃ of described viscosity 100～400Pa.s.
Described number-average molecular weight is 3～50,000.
A kind of preparation method of fluorine silicon penylene multipolymer of following structural formula
Wherein, Me represents CH
3-, R
fRepresent CF
3CH
2CH
2-, m/ (m+3n)=10～95%, viscosity 20～500Pa.s25 ℃, number-average molecular weight is up to 600,000, it is characterized in that, and it is that its structural formula is as follows by right-two (3,3,3-trifluoro propyl methyl hydroxyl is silica-based) penylene monomer:
In the formula, Me represents CH
3-, R
fRepresent CF
3CH
2CH
2-, with 3,3,3-trifluoro propyl methyl cyclotrisiloxane monomer, structural formula is as follows:
In the formula, Me represents CH
3-, R
fRepresent CF
3CH
2CH
2-, under base catalysis, make through negatively charged ion open loop, polycondensation, balanced reaction.
Right-two (3,3,3-trifluoro propyl methyl hydroxyl is silica-based) monomeric preparation method of penylene of described following structural formula carries out in two steps
In the formula, Me represents CH
3-, R
fRepresent CF
3CH
2CH
2-, the first step, right-two (3,3,3-trifluoro propyl methyl ethoxy is silica-based) benzene synthetic, structural formula is as follows:
The synthetic of said structure formula is as solvent with tetrahydrofuran (THF), in reactor, make Grignard reagent in advance, low temperature stirs equilibration reaction down then, then improve temperature of reaction, equilibration reaction once more, when removing the tetrahydrochysene furan food in one's mouth, keeping 3～5% (weight) tetrahydrochysene furan feeds, when the content of gas chromatograph tracking extractive reaction thing in sherwood oil is lower than 0.5%, remove sherwood oil with simple distillation, make a pair of (3,3,3-trifluoro propyl methyl ethoxy is silica-based) penylene monomer through rectification under vacuum again; Second step, at first the penylene monomer that the above-mentioned the first step is obtained is made sodium alkoxide, low temperature is added drop-wise in the reactor that fills Glacial acetic acid, deionized water and methylene dichloride hydrolyzation system then, fully stir balance, add saturated aqueous solution of sodium bicarbonate again, make it slightly meta-alkalescence of pH value, standing demix, with the organic layer washed with de-ionized water, until being neutral fully, use the petroleum ether precipitation hydrolysate at last, promptly get white powder consolidate the shape polymerization-grade to a pair of (3,3,3-trifluoro propyl methyl hydroxyl is silica-based) the penylene monomer.
Provided by the present invention right-two (3,3,3-trifluoro propyl methyl hydroxyl is silica-based) penylene monomers (hereinafter to be referred as dihydroxy penylene monomer), its structural formula is as follows:
Above-mentioned dihydroxy penylene monomer is the principal monomer of the hydroxy-end capped liquid fluorine silicon of the present invention penylene multipolymer.
Prepare dihydroxy penylene monomer in the past, adopt 3,3,3-trifluoro propyl dimethyl dichlorosilane (DMCS) and paradibromobenzene are made solvent with ether, make by the grignard reaction method right-two (3,3,3-trifluoro propyl methyl hydroxyl is silica-based) benzene again in alkalescence hydrolysis make following formula dihydroxy penylene monomer.This preparation method is owing to adopt 3,3, the mole ratio of 3-trifluoro propyl dichlorosilane and paradibromobenzene is 6: 1, so when purification and aftertreatment, not only there is a large amount of HCl smog to release, and can not get the high dihydroxyl penylene monomer of purity, and in monomer also residual 0.07% chlorine element and paradibromobenzene, so the monomer sealing is placed and is easily become redness.Thereby influenced the stability of rubber when solidifying.Simultaneously a large amount of HCl are severe corrosion equipment, and cause the pollution of environment.In addition, this reaction has selected ether as solvent, owing to be subjected to the restriction in season, and higher so dangerous also bigger as summer temperature.Have, recrystallization has adopted the bigger benzene of toxicity to make solvent again again, and the time of separating out is grown (2～5 days), has so not only polluted environment, and human body is also worked the mischief.Even the chloro penylene also can only reach 90% with rectification and purification, thereby be difficult to reach high purity 99%, the polymerization-grade monomer that will obtain through hydrolysis must be by above-mentioned recrystallization method, thus grignard reaction yield low 30～38%), cost is relatively also expensive.In addition, former technology adopts the solvent of methyl alcohol as hydrolysis reaction, and because of methyl alcohol toxicity is bigger, poor stability is used KH again
2PO
4/ H
2When the O system is hydrolyzed, because KH
2PO
4Solubleness in water less (90 ℃, 83.5g, 25 ℃, 33g/100ml), so hydrolysis 0.1mol's right-two (3,3,3-trifluoro propyl methyl hydroxyl is silica-based) required 1500mLKH of benzene
2PO
4/ H
2O because the volume of reaction system is bigger, causes very big difficulty to (amplifications) production high-volume.
The present invention provides high yield of grignard reaction (50～60%) and the monomeric preparation method of highly purified dihydroxy penylene for solving the problem of above-mentioned existence.The present invention is right-and two (3,3,3-trifluoro propyl methyl hydroxyl is silica-based) penylene monomer is to make by typical grignard reaction method.This reaction also is an of paramount importance single step reaction in the whole comonomer synthesis step, and the height of product yield directly influences the cost of hydroxy-end capped fluorine-containing liquid copolymer.The present invention adopts 3,3,3-trifluoro propyl diethoxy silane replaces 3,3,3-trifluoro propyl dimethyl dichlorosilane (DMCS), (THF) makes solvent with tetrahydrofuran (THF), low temperature drips 3,3, the method for 3-trifluoro propyl methyldiethoxysilane, product yield not only can reach (50～60%), and the existence of no chlorine element and paradibromobenzene in the dihydroxy penylene monomer by analysis.In the former technology, when reaction finished extraction, product was rolled into hard bulk together with magnesium salts, had only it is pulverized again to make with petroleum ether extraction.Treatment process of the present invention, promptly when removing tetrahydrofuran (THF), keep certain amount of solvent in reaction system, treat that temperature is low to moderate below the solvent boiling point, slowly dripping sherwood oil magnesium salts this moment again separates out with finely powdered fully, and then add the extraction of bulk petroleum ether, and the recyclable use repeatedly of sherwood oil, adopt gas chromatograph to follow the tracks of extraction results.
The invention provides and adopt acetolysis system (HAC/H
2O), since the solubleness of HAC in water greater than KH
2PO
4, right-two (3,3,3-trifluoro propyl methyl hydroxyl is silica-based) benzene of hydrolysis 0.1mol only needs 175mol, thereby makes the volume of hydrolysis reaction system be far smaller than above-mentioned KH
2PO
4/ H
2The volume of O hydrolyzation system, and help high-volume (amplification) production.
The present invention relates to second monomer of structural formula II, promptly 3,3,3 trifluoro propyl methyl cyclotrisiloxane, can be according to hydroxy-end capped liquid fluorine silicon rubber in the demand of using, as to the not harsh field of oil-proofness the time, can select to use not fluorine-containing hexamethyl cyclosiloxane and octamethylcyclotetrasiloxane with right-two (3,3,3-trifluoro propyl methyl hydroxyl is silica-based) copolymerization of benzene monomer.Also reduced simultaneously the cost of interpolymer.
The present invention has also done selection to alkaline catalysts, thinks that hydroxy-end capped liquid fluorine silicon rubber is consistent with general organo-silicone rubber polymerization rule, and promptly along with catalyzer alkalescence is strong more, polymerization velocity is fast more, and progressive law is:
LiOH＜NaOH＜KOH＜(CH
3)
4OH
The present invention selects for use the most weak LiOH of alkalescence as catalyzer, and this catalyzer can make polyreaction relatively gentleer, and polymerization viscosity is easy to control.
Also to the monomeric optimum mole ratio of dihydroxyl penylene: m/ (m+3n)=40～45% in the hydroxy-end capped liquid fluorine silicon penylene multipolymer of structural formula II I, the molecular weight of polymkeric substance is 3～50,000 in the present invention, and viscosity is that 100～400Pa.s has done development.But above-mentioned molar ratio range does not limit, and promptly m/ (m+3n)=10～95% can regulate arbitrarily according to the requirement of use properties, improves the second-order transition temperature of the heat-resistant stability or the reduction multipolymer of multipolymer.
Embodiment
Below in conjunction with embodiment the present invention is described in further detail.In an embodiment, used chemical unless otherwise indicated is the commodity that market can be buied.The analytical and testing instrument that the embodiment of the invention adopted has: 102G gas chromatograph (Shanghai analytical instrument factory), FTS-40 infrared spectrometer, FX-100NMR nuclear magnetic resonance analyser, the 150G-GPC of Walers company (U.S.), PE company's T QS-2 type thermal weight loss tester (U.S.), the hot analysis tester of DuPont1090 (U.S.), NOJ-79 type rotor viscosity apparatus.
Embodiment:
The preparation method of the fluorine silicon penylene multipolymer of the following structural formula of the present invention
Wherein, Me represents CH
3-, R
fRepresent CF
3CH
2CH
2-, m/ (m+3n)=40～45%, viscosity 100～400Pa.s25 ℃, number-average molecular weight is up to 3～50,000, comprises following processing step:
The first step
3,3,3-trifluoro propyl methyldiethoxysilane synthetic, structural formula is as follows:
With having 1000 milliliters of there-necked flasks of the reinforced bottle of balance, prolong, nitrogen bubble device, use nitrogen (drying was handled) in advance with above-mentioned reaction unit drying treatment.Add 3,3 then in there-necked flask, 3-trifluoro propyl dimethyl dichlorosilane (DMCS) 633 grams (3.0mol) add dehydrated alcohol 290 grams (6.3mol) in the reinforced bottle of balance.The question response system temperature slowly dripped dehydrated alcohol about 1 hour under nitrogen bubble in the time of 5～30 ℃, drip balance 2 hours.
Then temperature of reactor is brought up to 45～65 ℃, reequilibrate 1 hour, underpressure distillation goes out ethanol and low-boiling-point substance, gets product 509 grams, and through gas chromatographic analysis, purity is 90%, and yield is 82%.
In addition, the vapor pipe with this reaction unit inserts the HCl gas that aqueous sodium hydroxide solution neutralization (absorption) is discharged.
Second step
Synthesizing of right-two (3,3,3-trifluoro propyl methyl ethoxy is silica-based) benzene, structural formula is as follows:
In having 5000 milliliters of there-necked flasks of agitator, thermometer, reflux condensing tube and balance feeding device, use nitrogen (drying processing) with the reaction unit drying.Add magnesium chips 120 grams (18mol) then through the vacuum drying oven drying treatment, the tetrahydrofuran (THF) (THF) that adds 240 milliliters during room temperature, make the magnesium chips surface moistening fully under stirring, drip 30～50 milliliters of paradibromobenzene/THF solution of preparation (/ 1080 milliliters of 576 grams) in advance then.This reaction is started.This reaction very easily starts, and sharply rises in case start the back temperature, a large amount of backflow occur until tetrahydrofuran (THF).And then slowly drip paradibromobenzene/THF solution, and keep the tetrahydrofuran (THF) reflux temperature.For Grignard reagent is fully formed, drip back balance 1～4 hour under this temperature, at this moment, the liquid in the reactor is thickness gradually, and the tetrahydrofuran (THF) that need add 1250 milliliters is again diluted.Reequilibrate 1～2 hour.Temperature of reactor is reduced to 0～20 ℃ then, slowly drip then by embodiment 1 make 3,3,3-trifluoro propyl methyldiethoxysilane 1200 grams.The reinforced balance 1～2 hour of finishing kept temperature of reactor the tetrahydrofuran (THF) reflux temperature 1～3 hour again.When removing tetrahydrofuran solvent, make the non-caking purpose of magnesium salts in order to reach, leave the tetrahydrofuran (THF) of 3～5% weight (gas chromatographic analysis), so that extraction process is operated easily, when the question response actuator temperature is reduced to below 50 ℃, with 3000 milliliters sherwood oils (SILVER REAGENT RC, b.p:90～120 ℃) extractive reaction thing, and follow the tracks of with gas chromatograph and to be lower than till 0.5% until extractive reaction thing content in sherwood oil.Again extraction solution is removed sherwood oil with simple distillation, remaining still liquid gets 789 grams with underpressure distillation, through stratographic analysis, content is right-two (3,3,3-trifluoro propyl methyl ethoxy is silica-based) benzene crude monomer of 78%, after rectification under vacuum makes 653 grams, through stratographic analysis, content is 99.3%, and ultimate yield is 64%.
Above-mentioned tetrahydrochysene furan is fed solvent and is that water content is below the 30ppm after the sodium Metal 99.5 dehydration.In addition, the recyclable extraction solvent of doing repeatedly of sherwood oil uses.
The 3rd step
Right-two (3,3,3-trifluoro propyl methyl hydroxyl is silica-based) monomeric preparation of penylene, structural formula is as follows:
This preparation method carries out in two steps.At first with right-two (3 of second step of present embodiment gained, 3,3-trifluoro propyl methyl ethoxy is silica-based) benzene makes sodium alkoxide, be hydrolyzed again, promptly in 1000 milliliters of there-necked flasks that have agitator, thermometer, the reinforced bottle of balance, add 40 gram sodium hydroxide (1mol) earlier, stir the deionized water that adds 40 milliliters down, treat that sodium hydroxide dissolves the back fully and drips 175 milliliters of dehydrated alcohols (3mol), dropwised balance 20～60 minutes.Drip then by second step prepared right-two (3 of present embodiment, 3,3-trifluoro propyl methyl ethoxy is silica-based) benzene 223 grams (0.5mol), dripped back balance 1～3 hour, then add dissolved 40 gram (1mol) sodium hydroxide and 200 ml deionized water solution in advance again, make it fully stir balance 20～60 minutes.
In having 2000 milliliters of there-necked flasks of the reinforced bottle of whipping appts, thermometer, balance, another adds 125 milliliters Glacial acetic acid, 750 ml deionized water and 400 milliliters methylene dichloride then, temperature of reaction is remained between 2～10 ℃, stir and slowly drip above-mentioned ready-formed sodium alkoxide down.When to be dripped, fully stirring and balance are 1～2 hour, then add a spot of saturated aqueous solution of sodium bicarbonate again, make it slightly meta-alkalescence of pH value.Restir 20～60 minutes, standing demix, and with lower floor's organic solution washed with de-ionized water, after deionized water is neutrality, wash again three times.Hydrolysate is placed in 1000 milliliters of glass beakers,, left standstill under the room temperature 5～10 hours, use suction method elimination solvent then, obtain the monomer of the solid shape of white powder with the petroleum ether precipitation of this product cumulative volume 1/3rd.Again this monomer is placed the vacuum drying oven drying, obtain right-two (3,3,3-trifluoro propyl methyl hydroxyl is silica-based) penylene monomer 218.5 grams of polymerization-grade, yield is 98%.
The 4th step
The preparation of catalyzer lithium glue, structural formula is as follows:
Take into account lithium hydroxide and 60 grams 3 that add 0.78 gram (0.03mol) in 150 milliliters the pyriform there-necked flask of nitrogen bubble conduit having condenser, temperature, 3,3-trifluoro propyl methyl cyclotrisiloxane (0.13mol), decompression is (10mmHg) down, temperature is controlled at 60 ℃ under the nitrogen bubble, mixed dehydration, liquid in the question response bottle is complete when transparent, temperature is risen to 100 ℃ of balances 30 minutes, normal pressure continues logical nitrogen down and heats up gradually then, and the beginning polymerization slightly vacuumizes in the time of 140-160 ℃, this moment, viscosity increased gradually, until required viscosity.Be 0.8% through surveying lithium content, viscosity is 50Pa.s.
The 5th step
The preparation of hydroxy-end capped liquid fluorine silicon penylene multipolymer, structural formula is as follows:
In 2000 milliliters the there-necked flask that has agitator, thermometer, nitrogen bubble conduit, the reinforced bottle of balance and condensing reflux pipe, add right-two (3 of 400 grams (40.1mol), 3,3-trifluoro propyl methyl hydroxyl is silica-based) penylene monomer and adding 722 grams 3 in the reinforced bottle of balance, 3,3-trifluoro propyl methyl cyclotrisiloxane.Stir bubbling then and heat the reinforced bottle of balance with infrared lamp, temperature is controlled at 80 ℃, be controlled at 110 ℃ with oil bath heating there-necked flask temperature, vacuum tightness is 700mmHg, dewatered respectively 2 hours, then with 3,3,3-trifluoro propyl methyl cyclotrisiloxane is put into there-necked flask by the reinforced bottle of balance, remix dehydration 1 hour.Then add lithium glue 9.6 grams (63.4ppm), activate, rise poly-when slowly being warming up to 127 ℃ again as catalyzer.And then slightly vacuumize, this moment, viscosity was cumulative, and vacuum degree control is at 700mmHg during to 165 ℃, and viscosimetric is 150Pa.S after 2 hours.Cooling then, balance is 30 minutes under the normal pressure, gets polymkeric substance 1023.7 grams, and viscosity is that 170Pa.s, yield are 91.3%.
Claims (7)
1. fluorine silicon penylene multipolymer is characterized in that having the compound of following structural formula:
Wherein, Me represents CH
3-, R
fRepresent CF
3CH
2CH
2-, penylene chain link content m/ (m+3n)=10～95%, 25 ℃ of viscosity 20～500Pa.s, number-average molecular weight is 3～50,000.
2. a kind of fluorine silicon penylene multipolymer according to claim 1 is characterized in that described penylene chain link content m/ (m+3n)=40～45%.
3. a kind of fluorine silicon penylene multipolymer according to claim 1 is characterized in that 25 ℃ of described viscosity 100～400Pa.s.
4. the preparation method of the fluorine silicon penylene multipolymer of a following structural formula
Wherein, Me represents CH
3-, R
fRepresent CF
3CH
2CH
2-, m/ (m+3n)=10～95%, viscosity 20～500Pa.s25 ℃, number-average molecular weight is 3～50,000, it is characterized in that, it is that its structural formula is as follows by right-two (3,3,3-trifluoro propyl methyl hydroxyl is silica-based) penylene monomer:
In the formula, Me represents CH
3-, R
fRepresent CF
3CH
2CH
2-, with 3,3,3-trifluoro propyl methyl cyclotrisiloxane monomer, structural formula is as follows:
In the formula, Me represents CH
3-, R
fRepresent CF
3CH
2CH
2-, under base catalysis, make through negatively charged ion open loop, polycondensation, balanced reaction.
5. the preparation method of the fluorine silicon penylene multipolymer as structural formula (III) according to claim 4 is characterized in that the employed alkali of described base catalysis technology is selected from LiOH, NaOH, KOH, (CH
3)
4A kind of among the OH.
6. the preparation method of the fluorine silicon penylene multipolymer as structural formula (III) according to claim 5 is characterized in that the employed alkali of described base catalysis technology is LiOH.
7. the preparation method of the fluorine silicon penylene multipolymer as structural formula (III) according to claim 4 is characterized in that right-two (3,3,3-trifluoro propyl methyl hydroxyl is silica-based) monomeric preparation method of penylene of described following structural formula carries out in two steps
In the formula, Me represents CH
3-, R
fRepresent CF
3CH
2CH
2-, the first step, right-two (3,3,3-trifluoro propyl methyl ethoxy is silica-based) benzene synthetic, structural formula is as follows:
The synthetic of said structure formula is as solvent with tetrahydrofuran (THF), in reactor, make Grignard reagent in advance, low temperature stirs equilibration reaction down then, then improve temperature of reaction, equilibration reaction once more, when removing tetrahydrofuran (THF), keep 3～5% (weight) tetrahydrofuran (THF), when the content of gas chromatograph tracking extractive reaction thing in sherwood oil is lower than 0.5%, remove sherwood oil with simple distillation, make right-two (3,3,3-trifluoro propyl methyl ethoxy is silica-based) penylene monomer again through rectification under vacuum; Second step, at first the penylene monomer that the above-mentioned the first step is obtained is made sodium alkoxide, low temperature is added drop-wise in the reactor that fills Glacial acetic acid, deionized water and methylene dichloride hydrolyzation system then, fully stir balance, add saturated aqueous solution of sodium bicarbonate again, make it slightly meta-alkalescence of pH value, standing demix, with the organic layer washed with de-ionized water, until being neutral fully, use the petroleum ether precipitation hydrolysate at last, promptly get right-two (3 of the solid shape polymerization-grade of white powder, 3,3-trifluoro propyl methyl hydroxyl is silica-based) the penylene monomer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011267720A CN1166722C (en) | 2001-09-17 | 2001-09-17 | Fluorosilicic phenylene copolymer and its prepn process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011267720A CN1166722C (en) | 2001-09-17 | 2001-09-17 | Fluorosilicic phenylene copolymer and its prepn process |
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|---|---|
| CN1337417A CN1337417A (en) | 2002-02-27 |
| CN1166722C true CN1166722C (en) | 2004-09-15 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1302048C (en) * | 2005-06-13 | 2007-02-28 | 上海三爱富新材料股份有限公司 | Fluorine-silicon compounded rubber stock and method for making same |
| US7943697B2 (en) * | 2005-07-11 | 2011-05-17 | Saint-Gobain Performance Plastics Corporation | Radiation resistant silicone formulations and medical devices formed of same |
| JP7004010B2 (en) * | 2018-01-22 | 2022-01-21 | 信越化学工業株式会社 | A coating agent composition, a surface treatment agent containing the composition, and an article surface-treated with the surface treatment agent. |
| WO2020137277A1 (en) * | 2018-12-28 | 2020-07-02 | 信越化学工業株式会社 | Surface treated optical member |
| CN113801625B (en) * | 2021-10-27 | 2023-01-13 | 中国航发北京航空材料研究院 | Hybrid polythioether sealant |
| CN115975201A (en) * | 2022-12-22 | 2023-04-18 | 常州大学 | Hydroxy fluorosilicone oil with main chain containing phenylene ether structure and preparation method thereof |
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2001
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Address after: Room 801, 560 Xujiahui Road, Huangpu District, Shanghai 200025 Patentee after: Shanghai Huayi sanaifu New Material Co., Ltd Address before: 200025 Xujiahui Road, Shanghai, room 560, No. 1301, room Patentee before: SHANGHAI 3F NEW MATERIAL TECHNOLOGY Co.,Ltd. |
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Granted publication date: 20040915 |
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