CN102443172A - Polysiloxane polymer and preparation method thereof - Google Patents
Polysiloxane polymer and preparation method thereof Download PDFInfo
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- CN102443172A CN102443172A CN2011102204692A CN201110220469A CN102443172A CN 102443172 A CN102443172 A CN 102443172A CN 2011102204692 A CN2011102204692 A CN 2011102204692A CN 201110220469 A CN201110220469 A CN 201110220469A CN 102443172 A CN102443172 A CN 102443172A
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Abstract
The invention provides a polysiloxane polymer and a preparation method thereof. The polysiloxane polymer is shown in formula (I). The preparation method of the polymer comprises the following step: carrying out ring-opening polymerization reaction on methyl hydrogen cyclosiloxane and methyl vinyl cyclosiloxane, or methyl hydrogen cyclosiloxane, methyl vinyl cyclosiloxane and monomer A in the presence of organic silicon blocking agent and cationic polymerization initiator, thus obtaining the polysiloxane polymer, wherein the monomer A is dimethyl cyclosiloxane, methyl phenyl cyclosiloxane or R'-substituted methyl hydrogen cyclosiloxane; R' is methyl, phenyl, CH2CH2Ph, CH2CH2CN, CH2CH2CO2CH3, CH2CH2CO2C4H9, CH2CH(CH3)CO2CH3 or CH2CH2OR''; and R'' is C1-20 alkyl, cycloalkyl, ether or alcohol.
Description
Technical field
The present invention relates to a kind of polysiloxane polymer and preparation method thereof, belong to high temperature resistant thermosetting resin and preparation field thereof.
Background technology
Presoma pyrolysis conversion method prepares ceramic technology (PDC) owing to can prepare the material with ceramic performance with the processing and forming technology near organic resin; Have excellent practicality and designability and enjoy attention, become the research focus of current ceramic fiber and ceramic matric composite preparation field.Presoma pyrolysis conversion method prepares stupalith, and a primary step is to design to synthesize to have the precursor polymer of excellent processability and high ceramic yield, then its pyrolysis is obtained stupalith.Adopt siloxicon (Si-C-O) pottery of presoma ZGK 5 preparation to have good performances such as high temperature resistant, anti-oxidant, corrosion-resistant, low density, simultaneously and the Si-C-N, particularly SiC ceramic phase ratio of precursor process preparation, have outstanding advantage cheaply.Conventional linear polysiloxane, like general methyl-silicone oil and Zylox, can not be because high temperature is prone to into the ring degraded as the Si-C-O ceramic forerunner.Though the silicone resin that some are commercial; Like methyl silicon resin, vinyl polysiloxane (methyl silicon resin that contains the part vinyl), phenyl polysiloxane, have more branching three dimensional structure and crosslinkable groups, in theory can be as the Si-C-O ceramic forerunner; But has the silicone resin of higher ceramic yield owing to have higher branching and three dimensional structure; Be solid often under the room temperature, or need certain solvent and could guarantee certain shelf lives, in some applications inconvenience.With ethylene methacrylic radical siloxane ring body and methyl hydrogen siloxane ring body (like the raw material of 3M company preparation " black glass "), containing hydrogen silicone oil and ethylene methacrylic radical siloxane ring body (like Chinese patent CN101074159A); Or vinyl silicone oil with contain methyl hydrogen siloxane ring body mixing crosslinking curing, pyrolysis prepares the Si-C-O pottery; Can partly overcome above-mentioned deficiency; But the volatility that small molecules brought of its more amount and environment are harmful to problem, and mixture rheology characteristic has also limited the use of some aspects.International monopoly WO 2008/036662 A2 discloses and has a kind ofly contained Si-H, Si-Ph or Si-CH=CH through chlorosilane monomer hydrolysis preparation
2Multipolymer, be a kind of good Si-C-O ceramics polymer presoma, can become simultaneously the fire resistant resin material of high glass transition temperature through the preparation of control pyrolysis temperature.But owing to adopt the preparation of hydrolytie polycondensation method, be prone to cause microgel and some branched structures in the reaction process, can increase product viscosity and reduce stability in storage, be difficult for simultaneously removing the very deleterious Cl of many application (like microelectronics Packaging)
-Ion.
Summary of the invention
The purpose of this invention is to provide a kind of polysiloxane polymer and preparation method thereof.
Polysiloxane polymer provided by the invention is suc as formula shown in (I),
Wherein, R is Wasserstoffatoms, vinyl, hydroxyl or methyl; R ' is methyl, phenyl, CH
2CH
2Ph, CH
2CH
2CN, CH
2CH
2CO
2CH
3, CH
2CH
2CO
2C
4H
9, CH
2CH (CH
3) CO
2CH
3Or CH
2CH
2OR ", R " be C
1-20Alkyl, naphthenic base, ether or alcohol; X+y+z=1, x are the number between the 0.1-0.9, and y is the number between the 0.1-0.9, and z is the number between the 0-0.5; N is the number between the 40-1500.
In the above-mentioned polysiloxane polymer, x, y and z specifically can be 0.8,0.2 and 0,0.55,0.45 and 0,0.67,0.33 and 0,0.45,0.38 and 0.17,0.5,0.5 and 0,0.38,0.62 and 0,0.29,0.71 and 0.2,0.8 and 0,0.4,0.4 and 0.2 or 0.44,0.37 and 0.19 respectively; N specifically can be 100,107,118,125,200,293,303,357,368,400,558,1100 or 1111.
In the above-mentioned polysiloxane polymer, said R can be Wasserstoffatoms or vinyl; R ' can be methyl, phenyl, CH
2CH
2CN, CH
2CH
2CO
2C
4H
9, CH
2CH (CH
3) CO
2CH
3Or CH
2CH
2OR ", R " can be C
1-6Naphthenic base, C
1-6Alcohol or C
1-6Ether.
The present invention also provides the preparation method of above-mentioned polysiloxane polymer; Comprise the steps: methyl hydrogen siloxane ring body and ethylene methacrylic radical siloxane ring body, or methyl hydrogen siloxane ring body, ethylene methacrylic radical siloxane ring body and monomer A are carried out ring-opening polymerization and are promptly got said polysiloxane polymer under the condition that organosilicon end capping agent and cationic polymerization initiators exist; Said monomer A can be dimethyl siloxane ring body, methylphenyl siloxane ring body or by the substituted methyl hydrogen siloxane ring body of R ', wherein R ' can be methyl, phenyl, CH
2CH
2Ph, CH
2CH
2CN, CH
2CH
2CO
2CH
3, CH
2CH
2CO
2C
4H
9, CH
2CH (CH
3) CO
2CH
3Or CH
2CH
2OR ", R " be C
1-20Alkyl, naphthenic base, ether or alcohol.
Among the above-mentioned preparation method, said can be by the substituted methyl hydrogen siloxane ring body of R ' by excessive methyl hydrogen cyclotetrasiloxane (D
4 H) or methyl hydrogen mixed methylcyclosiloxane (ring three, ring four are main) carry out the addition reaction of silicon with hydrogen preparation with vinylbenzene, vinyl cyanide, methyl acrylate, Bing Xisuandingzhi, TEB 3K, cyclohexyl vinyl ether, 4-hydroxy butyl vinyl ether, 2-chloroethyl vinyl ether, Diethylene Glycol mono vinyl ether, IVE, ethylene glycol monoallyl ether etc., wherein can make Wasserstoffatoms on its ring body silicon have 25～50% to be replaced through the control feed ratio by R '.
Among the above-mentioned preparation method, said organosilicon end capping agent can be tetramethyl divinyl disiloxane, tetramethyl disiloxane or SWS-F 221.
Among the above-mentioned preparation method, said cationic polymerization initiators can be the vitriol oil, trifluoromethane sulfonic acid, fluorocarboxylic acid, acidic white earth, phosphonitrilic chloride and oligopolymer thereof, and the polymerization degree of said oligopolymer can be 3-11.
Among the above-mentioned preparation method, the temperature of said ring-opening polymerization can be 0 ℃-80 ℃, specifically can be 25 ℃, 50 ℃, 55 ℃, 60 ℃, 65 ℃ or 75 ℃; The time of said ring-opening polymerization can be 3 hours-10 hours, specifically can be 3 hours, 4 hours, 5 hours, 8 hours or 10 hours.
Among the above-mentioned preparation method, the mol ratio of methyl hydrogen siloxane ring body and ethylene methacrylic radical siloxane ring body can be (1-9): (9-1), monomer A and methyl hydrogen siloxane ring body can be (0-0.5) with the molfraction ratio of the summation of ethylene methacrylic radical siloxane ring body: 1; Said organosilicon end capping agent can be 1 with the molfraction ratio of total amount of substance of methyl hydrogen siloxane ring body, ethylene methacrylic radical siloxane ring body and monomer A: (20-500); Said cationic polymerization initiators accounts for the 0.05%-5% of the total mass of methyl hydrogen siloxane ring body, ethylene methacrylic radical siloxane ring body and monomer A.
Among the above-mentioned preparation method, the mol ratio of methyl hydrogen siloxane ring body and ethylene methacrylic radical siloxane ring body specifically can be 1: 1,1: 1.2,1: 1.6,1: 2.5,1: 4,1.2: 1,2: 1,2.33: 1 or 3: 1; The molfraction of monomer A and methyl hydrogen siloxane ring body and the summation of ethylene methacrylic radical siloxane ring body than specifically can be 0.11: 1,0.2: 1,0.3: 1 or 0.5: 1; The molfraction of said organosilicon end capping agent and total amount of substance of methyl hydrogen siloxane ring body, ethylene methacrylic radical siloxane ring body and monomer A than specifically can be 1: 100,0.5: 100,0.2: 100,0.56: 100,0.36: 100,0.18: 100,1.6: 100,0.54: 100,0.66: 100,1.4: 100,1: 50,1.7: 100 or 1: 53.3; Said cationic polymerization initiators account for methyl hydrogen siloxane ring body, ethylene methacrylic radical siloxane ring body and monomer A total mass 0.06%, 0.1%, 0.11%, 0.12%, 0.15%, 0.2%, 0.3%, 1.34%, 3% or 3.8%.
The be hydrolyzed method of polycondensation of preparation method provided by the invention and the monomeric mixture of corresponding chlorosilane is compared; Reaction is simple, few, the favorable reproducibility of side reaction; The product of said method preparation has LV, high ceramic yield and high storage stability; And can under relatively mild condition, be cured moulding; And prepare fire resistant resin and Si-C-O stupalith through further high-temperature heat treatment and pyrolysis, can be used as the matrix resin of advanced resin base or ceramic matric composite, and the important raw and processed materials of porous material and coating.
Description of drawings
Fig. 1 is the thermogravimetric curve of the polysiloxane polymer of embodiment 4,6,8 and 9 preparations.
Fig. 2 is the polysiloxane polymer of embodiment 1 preparation
1H-NMR.
Fig. 3 is the polysiloxane polymer of embodiment 4 preparation
1H-NMR.
Fig. 4 is the polysiloxane polymer of embodiment 8 preparation
1H-NMR.
Embodiment
Employed experimental technique is ordinary method like no specified otherwise among the following embodiment.
Used material, reagent etc. like no specified otherwise, all can obtain from commercial sources among the following embodiment.
The preparation of embodiment 1, polysiloxane polymer
In the there-necked flask of 250mL; (in this reaction system, the mol ratio of methyl hydrogen siloxane ring body and methyl ethylene cyclotetrasiloxane is 1: 4 to add monomer methyl hydrogen siloxane ring body 96.2g, methyl ethylene cyclotetrasiloxane 34.5g and end-capping reagent tetramethyl divinyl disiloxane 1.87g; The mol ratio of the amount of substance that the monomeric unit of end-capping reagent unit tetramethyl divinyl disiloxane and methyl hydrogen siloxane ring body and methyl ethylene cyclotetrasiloxane is total is 1: 100); Under the magnetic agitation, add 0.39g CF
3SO
3H (its account for methyl hydrogen siloxane ring body and methyl ethylene cyclotetrasiloxane siloxanyl monomers total mass 0.3%) and 0.015g deionized water; After 3 hours viscosity of 65 ℃ of following stirring reactions of oil bath does not have considerable change; After feeding the capacity ammonia, remove low-boiling-point substance in 140-150 ℃ of following vacuum decompression; After the G3 sand core funnel filters, obtain 115g colourless transparent liquid (productive rate 86%), shown in (I), wherein, x is 0.8, and y is 0.2, and z is 0, and R is vinyl (Vi), and n is 200, and viscosity is 40 centipoises.Through the GPC molecular-weight determination, its M
n=4905, M
w=8380, M
p=8749.This polymkeric substance
1H nuclear magnetic resonance spectrum such as Fig. 2, the Si-H/Si-CH=CH that it is actual
2Lower than theoretical value, be 3.3.
The preparation of embodiment 2, polysiloxane polymer
In the there-necked flask of 1000mL; Add 451g methyl hydrogen siloxane ring body; (in this reaction system, the mol ratio of methyl hydrogen siloxane ring body and methyl ethylene cyclotetrasiloxane is 3: 1 for 215g methyl ethylene cyclotetrasiloxane and 4.66g end-capping reagent tetramethyl divinyl disiloxane; The mol ratio of total amount of substance of end-capping reagent tetramethyl divinyl disiloxane and methyl hydrogen siloxane ring body and methyl ethylene cyclotetrasiloxane is 0.5: 100); Magnetic stirs down, adds 0.78g CF
3SO
3H (its account for methyl hydrogen siloxane ring body and methyl ethylene cyclotetrasiloxane the siloxanyl monomers total mass 0.1%), 65 ℃ of following stirring reactions of oil bath 4 hours, feed the capacity ammonia after, remove low-boiling-point substance in 140-150 ℃ of following vacuum decompression; After the G3 sand core funnel filters, obtain 143g colourless transparent liquid (productive rate 89%), shown in (I), wherein, x is 0.75, and y is 0.25, and z is 0, and R is vinyl (Vi), and n is 400, and viscosity is 110 centipoises.
The preparation of embodiment 3, polysiloxane polymer
In the there-necked flask of 1000mL; Add 361g methyl hydrogen siloxane ring body; (in this reaction system, the mol ratio of methyl hydrogen siloxane ring body and methyl ethylene cyclotetrasiloxane is 1.2: 1 for 433g methyl ethylene cyclotetrasiloxane and 1.87g end-capping reagent tetramethyl divinyl disiloxane; The mol ratio of total amount of substance of end-capping reagent tetramethyl divinyl disiloxane and methyl hydrogen siloxane ring body and methyl ethylene cyclotetrasiloxane is 0.2: 100); Magnetic stirs down, adds 0.86g CF
3SO
3H (its account for methyl hydrogen siloxane ring body and methyl ethylene cyclotetrasiloxane the siloxanyl monomers total mass 0.11%) and 0.086 deionized water, 65 ℃ of following stirring reactions of oil bath 4 hours, feed the capacity ammonia after, remove low-boiling-point substance in 140-150 ℃ of following vacuum decompression; After the G3 sand core funnel filters, obtain 590g colourless transparent liquid (productive rate 75%), shown in (I), wherein; X is 0.55, and y is 0.45, and z is 0; R is Vi, and n is 1100, and viscosity is 150 centipoises.
The preparation of embodiment 4, polysiloxane polymer
In the there-necked flask of 250mL; Add 90.2g methyl hydrogen siloxane ring body; 64.6g (in this reaction system, the mol ratio of methyl hydrogen siloxane ring body and methyl ethylene cyclotetrasiloxane is 2: 1 for methyl ethylene cyclotetrasiloxane and 1.05g end-capping reagent tetramethyl divinyl disiloxane; The mol ratio of total amount of substance of end-capping reagent tetramethyl divinyl disiloxane and methyl hydrogen siloxane ring body and methyl ethylene cyclotetrasiloxane is 0.56: 100); Magnetic stirs down, adds 0.23g CF
3SO
3H (its account for methyl hydrogen siloxane ring body and methyl ethylene cyclotetrasiloxane the siloxanyl monomers total mass 0.15%), 65 ℃ of following stirring reactions of oil bath 4 hours, feed the capacity ammonia after, remove low-boiling-point substance in 140-150 ℃ of following vacuum decompression; After the G3 sand core funnel filters, obtain 143g colourless transparent liquid (productive rate 89%), shown in (I), wherein; X is 0.67, and y is 0.33, and z is 0; R is Vi, and n is 357, and viscosity is 80 centipoises.Through the GPC molecular-weight determination, its M
n=4989, M
w=8552, M
p=8357; This polymkeric substance
1H nuclear magnetic resonance spectrum such as Fig. 3, the Si-H/Si-CH=CH that it is actual
2Lower slightly than theoretical value, be 1.9.Under the catalyst-free condition, the TGA ceramic yield of this clean polymkeric substance is 75%.
The preparation of embodiment 5, polysiloxane polymer
In the there-necked flask of 1000mL; Add 361g methyl hydrogen siloxane ring body; (in this reaction system, the mol ratio of methyl hydrogen siloxane ring body and methyl ethylene cyclotetrasiloxane is 1.2: 1 for 433g methyl ethylene cyclotetrasiloxane and 4.02g end-capping reagent tetramethyl divinyl disiloxane; The mol ratio of total amount of substance of end-capping reagent tetramethyl divinyl disiloxane and methyl hydrogen siloxane ring body and methyl ethylene cyclotetrasiloxane is 0.36: 100); Magnetic stirs down, adds 0.86g CF
3SO
3H (its account for methyl hydrogen siloxane ring body and methyl ethylene cyclotetrasiloxane the siloxanyl monomers total mass 0.1%) and 0.086 deionized water, 65 ℃ of following stirring reactions of oil bath 4 hours, feed the capacity ammonia after, remove low-boiling-point substance in 140-150 ℃ of following vacuum decompression; After the G3 sand core funnel filters, obtain 590g colourless transparent liquid (productive rate 75%), shown in (I), wherein; X is 0.55, and y is 0.45, and z is 0, and R is Vi; N is 558, and viscosity is 60 centipoises, through the GPC molecular-weight determination, and its M
n=1889, M
w=3552, M
p=4221.
The preparation of embodiment 6, polysiloxane polymer
In the there-necked flask of 1000mL; Add 361g methyl hydrogen siloxane ring body; (in this reaction system, the mol ratio of methyl hydrogen siloxane ring body and methyl ethylene cyclotetrasiloxane is 1.2: 1 for 433g methyl ethylene cyclotetrasiloxane and 1.34g end-capping reagent tetramethyl disiloxane; The mol ratio of total amount of substance of end-capping reagent tetramethyl disiloxane and methyl hydrogen siloxane ring body and methyl ethylene cyclotetrasiloxane is 0.18: 100); Magnetic stirs down, adds 0.86gCF
3SO
3H (its account for methyl hydrogen siloxane ring body and methyl ethylene cyclotetrasiloxane the siloxanyl monomers total mass 0.1%), 65 ℃ of following stirring reactions of oil bath 4 hours, feed the capacity ammonia after, remove low-boiling-point substance in 140-150 ℃ of following vacuum decompression; After the G3 sand core funnel filters, obtain 550g colourless transparent liquid (productive rate 70%), shown in (I), wherein; X is 0.55, and y is 0.45, and z is 0; N is 1111, and R is H, and viscosity is 130 centipoises.
The preparation of embodiment 7, polysiloxane polymer
In the there-necked flask of 2000mL; Add 720g methyl hydrogen siloxane ring body; 862g methyl ethylene cyclotetrasiloxane; (in this reaction system, the mol ratio of methyl hydrogen siloxane ring body and methyl ethylene cyclotetrasiloxane is 1.2: 1, and the mol ratio of the summation of octamethylcyclotetrasiloxane and methyl hydrogen siloxane ring body and methyl ethylene cyclotetrasiloxane is 0.11: 1 for 185g octamethylcyclotetrasiloxane and 13.4g end-capping reagent tetramethyl divinyl disiloxane; The mol ratio of total amount of substance of tetramethyl divinyl disiloxane and methyl hydrogen siloxane ring body, methyl ethylene cyclotetrasiloxane and octamethylcyclotetrasiloxane is 0.54: 100); Magnetic stirs down; Add the 29ml vitriol oil (its account for methyl hydrogen siloxane ring body, methyl ethylene cyclotetrasiloxane and octamethylcyclotetrasiloxane the siloxanyl monomers total mass 3%), stirring reaction added the 25ml deionized water after 5 hours under the room temperature; After stirring half a hour, leave standstill; After the layering, tell the upper strata, and slowly add anhydrous Na
2CO
3110g continues to stir more than the 3h.Filter through the G3 sand core funnel, 140-150 ℃ of following vacuum decompression removed low-boiling-point substance, obtains 1250g (productive rate 70%) colourless transparent liquid, shown in (I); Wherein, x is 0.45, and y is 0.38, and z is 0.17; N is 368, and R is a vinyl, and R ' is a methyl, and viscosity is 50 centipoises.
The preparation of embodiment 8, polysiloxane polymer
In the there-necked flask of 250mL; Add 60.1g methyl hydrogen siloxane ring body; 86.2g (in this reaction system, the mol ratio of methyl hydrogen siloxane ring body and methyl ethylene cyclotetrasiloxane is 1: 1 for methyl ethylene cyclotetrasiloxane and 1.87g end-capping reagent tetramethyl divinyl disiloxane; The mol ratio of total amount of substance of end-capping reagent tetramethyl divinyl disiloxane and methyl hydrogen siloxane ring body and methyl ethylene cyclotetrasiloxane is 1: 100); Magnetic stirs down, add the 3ml vitriol oil (its account for methyl hydrogen siloxane ring body and methyl ethylene cyclotetrasiloxane the siloxanyl monomers total mass 3.8%), stirring reaction is after 5 hours under the room temperature; Add the 2.5ml deionized water; After stirring half a hour, leave standstill, after the layering; Tell the upper strata, and slowly add anhydrous Na
2CO
310.6g, continue to stir more than the 3h; Filter through the G3 sand core funnel, 140-150 ℃ of following vacuum decompression removed low-boiling-point substance, obtains 105g (productive rate 70%) colourless transparent liquid, and shown in (I), wherein, x is 0.5, and y is 0.5, and z is 0, and n is 200, and R is a vinyl, and viscosity is 110 centipoises; Through GPC molecular-weight determination, M
n=4952, M
w=9012, M
p=15877; This polymkeric substance
1H nuclear magnetic resonance spectrum such as Fig. 4, the Si-H/Si-CH=CH that it is actual
2Lower than theoretical value, be 0.9; When it is liquid and 180 ℃ of thermogravimetric curve such as Fig. 1 that solidify down behind the 1h, the thermal weight loss temperature of cured product is higher than 500 ℃, and ceramic yield can reach 85%.
The preparation of embodiment 9, polysiloxane polymer
In the there-necked flask of 1000mL; Add 240.5g methyl hydrogen siloxane ring body; 413.6g (in this reaction system, the mol ratio of methyl hydrogen siloxane ring body and methyl ethylene cyclotetrasiloxane is 1: 1.2 for methyl ethylene cyclotetrasiloxane and 4.03g end-capping reagent tetramethyl disiloxane; The mol ratio of total amount of substance of end-capping reagent tetramethyl disiloxane and methyl hydrogen siloxane ring body and methyl ethylene cyclotetrasiloxane is 0.54: 100); Magnetic stirs down, adds 0.86gCF
3SO
3H (its account for methyl hydrogen siloxane ring body and methyl ethylene cyclotetrasiloxane the siloxanyl monomers total mass 0.2%), 65 ℃ of following stirring reactions of oil bath 8 hours, feed the capacity ammonia after, remove low-boiling-point substance in 140-150 ℃ of following vacuum decompression; After the G3 sand core funnel filters, obtain 564g colourless transparent liquid (productive rate 85.6%), shown in (I), wherein; X is 0.45, and y is 0.55, and z is 0; N is 293, and R is a vinyl, and viscosity at ambient temperature is 390 centipoises.
The preparation of embodiment 10, polysiloxane polymer
In the there-necked flask of 1000mL; Add 210.5g methyl hydrogen siloxane ring body; 483.5g (in this reaction system, the mol ratio of methyl hydrogen siloxane ring body and methyl ethylene cyclotetrasiloxane is 1: 1.6 for methyl ethylene cyclotetrasiloxane and 4.03g end-capping reagent tetramethyl disiloxane; The mol ratio of total amount of substance of end-capping reagent tetramethyl disiloxane and methyl hydrogen siloxane ring body and methyl ethylene cyclotetrasiloxane is 0.66: 100); Magnetic stirs down, adds 0.86gCF
3SO
3H (its account for methyl hydrogen siloxane ring body and methyl ethylene cyclotetrasiloxane total mass 0.12%), 65 ℃ of following stirring reactions of oil bath 8 hours, feed the capacity ammonia after, remove low-boiling-point substance in 140-150 ℃ of following vacuum decompression.After the G3 sand core funnel filters, obtain 563g colourless transparent liquid (productive rate 81%), shown in (I), wherein, x is 0.38, and y is 0.62, and z is 0, and n is 303, and R is a Wasserstoffatoms, and viscosity at ambient temperature is 500 centipoises.
The preparation of embodiment 11, polysiloxane polymer
In the there-necked flask of 1000mL; Add 120.3g methyl hydrogen siloxane ring body; 430.8g (in this reaction system, the mol ratio of methyl hydrogen siloxane ring body and methyl ethylene cyclotetrasiloxane is 1: 2.5 for methyl ethylene cyclotetrasiloxane and 6.7g end-capping reagent tetramethyl disiloxane; The mol ratio of total amount of substance of end-capping reagent tetramethyl disiloxane ring body and methyl ethylene cyclotetrasiloxane is 1.4: 100); Magnetic stirs down, adds 0.55g CF
3SO
3H (its account for methyl hydrogen siloxane ring body and methyl ethylene cyclotetrasiloxane the siloxanyl monomers total mass 0.1%), 55 ℃ of following stirring reactions of oil bath 10 hours, feed the capacity ammonia after, remove low-boiling-point substance in 140-150 ℃ of following vacuum decompression.After the G3 sand core funnel filters, obtain 483g colourless transparent liquid (productive rate 86%), shown in (I), wherein, x is 0.29, and y is 0.71, and z is 0, and n is 140, and R is a Wasserstoffatoms, and viscosity is 200 centipoises.
The preparation of embodiment 12, polysiloxane polymer
In the there-necked flask of 1000mL; Add 120.3g methyl hydrogen siloxane ring body; 689.3g (in this reaction system, the mol ratio of methyl hydrogen siloxane ring body and methyl ethylene cyclotetrasiloxane is 1: 4 for methyl ethylene cyclotetrasiloxane and 6.7g end-capping reagent tetramethyl disiloxane; The mol ratio of total amount of substance of end-capping reagent tetramethyl disiloxane ring body and methyl ethylene cyclotetrasiloxane is 1: 100); Magnetic stirs down, adds 1.0g CF
3SO
3H (its account for methyl hydrogen siloxane ring body and methyl ethylene cyclotetrasiloxane the siloxanyl monomers total mass 0.12%), 55 ℃ of following stirring reactions of oil bath 10 hours, feed the capacity ammonia after, remove low-boiling-point substance in 140-150 ℃ of following vacuum decompression; After the G3 sand core funnel filters, obtain 661g colourless transparent liquid (productive rate 81%), shown in (I), wherein; X is 0.2, and y is 0.8, and z is 0; N is 200, and R is a Wasserstoffatoms, and viscosity is 300 centipoises.
The preparation of embodiment 13, polysiloxane polymer
In the there-necked flask of 1000mL; Add 120.3g methyl hydrogen siloxane ring body; 136.0g aminomethyl phenyl cyclotrisiloxane; 172.3g (in this reaction system, the mol ratio of methyl hydrogen siloxane ring body and aminomethyl phenyl cyclotrisiloxane is 1: 1, and the mol ratio of the summation of methyl ethylene cyclotetrasiloxane and methyl hydrogen siloxane ring body and aminomethyl phenyl cyclotrisiloxane is 0.2: 1 for methyl ethylene cyclotetrasiloxane and 6.7g end-capping reagent tetramethyl disiloxane; The mol ratio of total amount of substance of end-capping reagent tetramethyl disiloxane and methyl hydrogen siloxane ring body, aminomethyl phenyl cyclotrisiloxane and methyl ethylene cyclotetrasiloxane is 2: 100); Magnetic stirs down, adds 0.5g CF
3SO
3H (its account for methyl hydrogen siloxane ring body, aminomethyl phenyl cyclotrisiloxane and methyl ethylene cyclotetrasiloxane the siloxanyl monomers total mass 0.12%), 75 ℃ of following stirring reactions of oil bath 10 hours, feed the capacity ammonia after, remove low-boiling-point substance in 140-150 ℃ of following vacuum decompression; After the G3 sand core funnel filters, obtain 321g colourless transparent liquid (productive rate 75%), shown in (I), wherein; X is 0.4, and y is 0.4, and z is 0.2, and n is 100; R is a Wasserstoffatoms, and R ' is a phenyl, and viscosity is 340 centipoises.
The preparation of embodiment 14, polysiloxane polymer
In the there-necked flask of 1000mL, (in this product, the methyl hydrogen siloxane ring body is 120g, by CH through the product after the addition of silicon hydrogen to add 180g methyl hydrogen siloxane ring body and 100g TEB 3K
2CH (CH
3) CO
2CH
3Substituted methyl hydrogen siloxane ring body cell mesh is 160g), 172.3g methyl ethylene cyclotetrasiloxane and 6.7g end-capping reagent tetramethyl disiloxane (in this reaction system, the methyl hydrogen siloxane ring body with by CH
2CH (CH
3) CO
2CH
3The mol ratio of substituted methyl hydrogen siloxane ring body is 1: 1, methyl ethylene cyclotetrasiloxane and methyl hydrogen siloxane ring body and by CH
2CH (CH
3) CO
2CH
3The mol ratio of the summation of substituted methyl hydrogen siloxane ring body is 0.2: 1; End-capping reagent tetramethyl disiloxane and methyl hydrogen siloxane ring body, methyl ethylene cyclotetrasiloxane and by CH
2CH (CH
3) CO
2CH
3The mol ratio of total amount of substance of substituted methyl hydrogen siloxane ring body is 1.7: 100); Magnetic stirs down, adds 0.45g CF
3SO
3(it accounts for methyl hydrogen siloxane ring body, methyl ethylene cyclotetrasiloxane and by CH to H
2CH (CH
3) CO
2CH
3The total mass of substituted methyl hydrogen siloxane ring body siloxanyl monomers 0.1%), 55 ℃ of following stirring reactions of oil bath 10 hours, feed the capacity ammonia after, remove low-boiling-point substance in 140-150 ℃ of following vacuum decompression; After the G3 sand core funnel filters, obtain 390g colourless transparent liquid (productive rate 85%), shown in (I), wherein; X is 0.4, and y is 0.4, and z is 0.2, and n is 118; R is a Wasserstoffatoms, and R ' is the TEB 3K base, and viscosity is 250 centipoises.
The preparation of embodiment 15, polysiloxane polymer
In the there-necked flask of 1000mL; Add 180g methyl hydrogen siloxane ring body and 132g Diethylene Glycol mono vinyl ether and pass through product after the addition of silicon hydrogen (in this product; The methyl hydrogen siloxane ring body is 120g; By the substituted methyl hydrogen siloxane ring body of Diethylene Glycol mono vinyl ether is 60g); 172.3g (in this reaction system, the mol ratio of methyl hydrogen siloxane ring body and substituted methyl hydrogen siloxane ring body is 2: 1, and the mol ratio of the summation of methyl ethylene cyclotetrasiloxane and methyl hydrogen siloxane ring body and substituted methyl hydrogen siloxane ring body is 0.3: 1 for methyl ethylene cyclotetrasiloxane and 6.7g end-capping reagent tetramethyl disiloxane; The mol ratio of total amount of substance of tetramethyl disiloxane and methyl hydrogen siloxane ring body, methyl ethylene cyclotetrasiloxane and substituted methyl hydrogen siloxane ring body is 1.7: 100); Magnetic stirs down, adds 0.5g CF
3SO
3H (its account for methyl hydrogen siloxane ring body, methyl ethylene cyclotetrasiloxane and substituted methyl hydrogen siloxane ring body the siloxanyl monomers total mass 0.1%), 50 ℃ of following stirring reactions of oil bath 10 hours, feed the capacity ammonia after, remove low-boiling-point substance in 140-150 ℃ of following vacuum decompression; After the G3 sand core funnel filters, obtain 432g colourless transparent liquid (productive rate 88%), shown in (I), wherein; X is 0.4, and y is 0.4, and z is 0.2; N is 118, and R is a Wasserstoffatoms, and R ' is-CH
2CH
2-OCH
2CH
2-CH
2CH
2-OH, viscosity is 220 centipoises.
The preparation of embodiment 16, polysiloxane polymer
In the there-necked flask of 1000mL, (in this product, the methyl hydrogen siloxane ring body is 140g, by CH through the product after the addition of silicon hydrogen to add 200g methyl hydrogen siloxane ring body and 53g vinyl cyanide
2CH
2The substituted methyl hydrogen siloxane of CN unit is 113g), 172.3g methyl ethylene cyclotetrasiloxane and 9.3g tetramethyl divinyl disiloxane (in this reaction system, the methyl hydrogen siloxane ring body with by CH
2The mol ratio of the substituted methyl hydrogen siloxane ring body of=CHCN 2.33: 1, methyl ethylene cyclotetrasiloxane and methyl hydrogen siloxane ring body and by CH
2The mol ratio of the summation of the substituted methyl hydrogen siloxane ring body of=CHCN is 0.5: 1; Tetramethyl divinyl disiloxane and methyl hydrogen siloxane ring body, methyl ethylene cyclotetrasiloxane and by CH
2CH
2The mol ratio of total amount of substance of the substituted methyl hydrogen siloxane ring body of CN is 1.6: 100); Magnetic stirs down, adds 0.25g CF
3SO
3(it accounts for methyl hydrogen siloxane ring body, methyl ethylene cyclotetrasiloxane and by CH to H
2CH
2The siloxanyl monomers total mass of the substituted methyl hydrogen siloxane ring body of CN 0.06%), 60 ℃ of following stirring reactions of oil bath 12 hours, feed the capacity ammonia after, remove low-boiling-point substance in 140-150 ℃ of following vacuum decompression; After the G3 sand core funnel filters, obtain 374g colourless transparent liquid (productive rate 86%), shown in (I), wherein; X is 0.44, and y is 0.37, and z is 0.19; N is 125, and R is a vinyl, and R ' is-CH
2CH
2CN, viscosity is 280 centipoises.
The preparation of embodiment 17, polysiloxane polymer
In the there-necked flask of 1000mL; (wherein the methyl hydrogen siloxane ring body accounts for 140g to add 200g methyl hydrogen siloxane ring body and the 128g Bing Xisuandingzhi product after through the addition of silicon hydrogen; By the substituted methyl hydrogen siloxane ring body of methyl Bing Xisuandingzhi base unit is 188g); 172.3g methyl ethylene cyclotetrasiloxane and 6.7g tetramethyl disiloxane (in this reaction system, the methyl hydrogen siloxane ring body be 2.33: 1, methyl vinyl siloxane unit and methyl hydrogen siloxane ring body by the unitary mol ratio of the substituted siloxanes ring body of methyl Bing Xisuandingzhi base and be 0.5: 1 by the mol ratio of the unitary summation of the substituted siloxanes ring body of methyl Bing Xisuandingzhi base; Tetramethyl disiloxane and methyl hydrogen siloxane ring body, methyl ethylene cyclotetrasiloxane and by CH
2=CHCO
2C
4H
9The mol ratio of the unitary total amount of substance of substituted methyl hydrogen siloxane ring body is 1.6: 100); Magnetic stirs down, adds 0.5g CF
3SO
3H (its account for methyl hydrogen siloxane ring body, methyl ethylene cyclotetrasiloxane and by the siloxanyl monomers total mass of the substituted methyl hydrogen siloxane ring body of methyl Bing Xisuandingzhi base 0.1%), 60 ℃ of following stirring reactions of oil bath 10 hours, feed the capacity ammonia after; Remove low-boiling-point substance in 140-150 ℃ of following vacuum decompression, after the G3 sand core funnel filters, obtain 420g colourless transparent liquid (productive rate 83%); Shown in (I), wherein, x is 0.44; Y is 0.37, and z is 0.19, and n is 125; R is a Wasserstoffatoms, and R ' is-CH
2CHCO
2C
4H
9, viscosity is 240 centipoises.
The preparation of embodiment 18, polysiloxane polymer
In the there-necked flask of 1000mL, (in this mix products, the methyl hydrogen siloxane ring body is 140g, by CH through the product after the addition of silicon hydrogen to add 200g methyl hydrogen siloxane ring body and 126g cyclohexyl vinyl ether
2CH
2OC
6H
11Substituted methyl hydrogen siloxane ring body unit is 60g), 172.3g methyl ethylene cyclotetrasiloxane and 6.7g end-capping reagent tetramethyl disiloxane (in this reaction system, the methyl hydrogen siloxane ring body with by CH
2CH
2OC
6H
11The unitary mol ratio of substituted methyl hydrogen siloxane ring body is 2.33: 1, methyl ethylene cyclotetrasiloxane and methyl hydrogen siloxane ring body and by CH
2CH
2OC
6H
11The mol ratio of the unitary summation of substituted methyl hydrogen siloxane ring body 0.5: 1; End-capping reagent tetramethyl disiloxane and methyl hydrogen siloxane ring body, by CH
2CH
2OC
6H
111: 53.3 of the summation of substituted methyl hydrogen siloxane ring body unit and methyl ethylene cyclotetrasiloxane; Magnetic stirs down, adds 0.5g CF
3SO
3(it accounts for methyl hydrogen siloxane ring body, methyl ethylene cyclotetrasiloxane and by CH to H
2CH
2OC
6H
11The unitary siloxanyl monomers total mass of substituted methyl hydrogen siloxane ring body 1.34%), 60 ℃ of following stirring reactions of oil bath 10 hours, feed the capacity ammonia after, remove low-boiling-point substance in 140-150 ℃ of following vacuum decompression; After the G3 sand core funnel filters, obtain 440g colourless transparent liquid (productive rate 87%), shown in (I), wherein; X is 0.44, and y is 0.37, and z is 0.19; N is 107, and R is a Wasserstoffatoms, and R ' is-CH
2CH
2OC
6H
11, viscosity is 260 centipoises.
Claims (7)
1. polysiloxane polymer shown in the formula (I),
Wherein, R is Wasserstoffatoms, vinyl, hydroxyl or methyl; R ' is methyl, phenyl, CH
2CH
2Ph, CH
2CH
2CN, CH
2CH
2CO
2CH
3, CH
2CH
2CO
2C
4H
9, CH
2CH (CH
3) CO
2CH
3Or CH
2CH
2OR ", R " be C
1-20Alkyl, naphthenic base, ether or alcohol; X+y+z=1, x are the number between the 0.1-0.9, and y is the number between the 0.1-0.9, and z is the number between the 0-0.5; N is the number between the 40-1500.
2. polysiloxane polymer according to claim 1 is characterized in that: said R is Wasserstoffatoms or vinyl; R ' is methyl, phenyl, CH
2CH
2CN, CH
2CH
2CO
2C
4H
9, CH
2CH (CH
3) CO
2CH
3Or CH
2CH
2OR ", R wherein " be C
1-6Naphthenic base, C
1-6Alcohol or C
1-6Ether.
3. the preparation method of claim 1 or 2 said polysiloxane polymers; Comprise the steps: methyl hydrogen siloxane ring body and ethylene methacrylic radical siloxane ring body, or methyl hydrogen siloxane ring body, ethylene methacrylic radical siloxane ring body and monomer A are carried out ring-opening polymerization and are promptly got said polysiloxane polymer under the condition that organosilicon end capping agent and cationic polymerization initiators exist; Said monomer A is dimethyl siloxane ring body, methylphenyl siloxane ring body or by the substituted methyl hydrogen siloxane ring body of R ', wherein, R ' is methyl, phenyl, CH
2CH
2Ph, CH
2CH
2CN, CH
2CH
2CO
2CH
3, CH
2CH
2CO
2C
4H
9, CH
2CH (CH
3) CO
2CH
3Or CH
2CH
2OR ", R " be C
1-20Alkyl, naphthenic base, ether or alcohol.
4. method according to claim 3 is characterized in that: said organosilicon end capping agent is tetramethyl divinyl disiloxane, tetramethyl disiloxane or SWS-F 221.
5. according to claim 3 or 4 described methods, it is characterized in that: said cationic polymerization initiators is the vitriol oil, trifluoromethane sulfonic acid, fluorocarboxylic acid, acidic white earth or phosphonitrilic chloride and oligopolymer thereof, and the polymerization degree of said oligopolymer is 3-11.
6. according to arbitrary described method among the claim 3-5, it is characterized in that: the temperature of said ring-opening polymerization is 0 ℃-80 ℃; The time of said ring-opening polymerization is 3 hours-10 hours.
7. according to arbitrary described method among the claim 3-6; It is characterized in that: the molfraction of methyl hydrogen siloxane ring body, ethylene methacrylic radical siloxane ring body is than being (1-9): (9-1), said monomer A is (0-0.5) with the molfraction ratio of the summation of methyl hydrogen siloxane ring body and ethylene methacrylic radical siloxane ring body: 1; Said organosilicon end capping agent is 1 with the molfraction ratio of total amount of substance of methyl hydrogen siloxane ring body, ethylene methacrylic radical siloxane ring body and monomer A: (20-500); Said cationic polymerization initiators accounts for the 0.05%-5% of the total mass of methyl hydrogen siloxane ring body, ethylene methacrylic radical siloxane ring body and monomer A.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102703023A (en) * | 2012-06-05 | 2012-10-03 | 烟台德邦先进硅材料有限公司 | Adhesive and compounding method thereof |
| CN104672455A (en) * | 2013-11-29 | 2015-06-03 | 浙江新安化工集团股份有限公司 | Preparation method of methylphenyl hydrogen-containing silicone oil |
| CN105367798A (en) * | 2015-11-27 | 2016-03-02 | 广州市银讯光电科技有限公司 | Organosilicone basic adhesive for LED chip packaging and preparation method for organosilicone basic adhesive |
| CN108239285A (en) * | 2018-01-25 | 2018-07-03 | 广东优聚实业有限公司 | A kind of low phenyl-vinyl silicon oil and preparation method thereof |
| CN109796955A (en) * | 2019-01-30 | 2019-05-24 | 中国石油大学(华东) | A kind of preparation method of trapezoidal branch modified siloxane polymer supercritical carbon dioxide thickener |
| CN113024810A (en) * | 2021-03-23 | 2021-06-25 | 南昌大学 | Single-component self-crosslinkable fluorosilicone release agent and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5275980A (en) * | 1990-12-14 | 1994-01-04 | Union Carbide Chemicals & Plastics | Self-curing ceramicizable polysiloxanes |
-
2011
- 2011-08-02 CN CN 201110220469 patent/CN102443172B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5275980A (en) * | 1990-12-14 | 1994-01-04 | Union Carbide Chemicals & Plastics | Self-curing ceramicizable polysiloxanes |
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| CN102703023A (en) * | 2012-06-05 | 2012-10-03 | 烟台德邦先进硅材料有限公司 | Adhesive and compounding method thereof |
| CN102703023B (en) * | 2012-06-05 | 2013-07-31 | 烟台德邦先进硅材料有限公司 | Adhesive and compounding method thereof |
| CN104672455A (en) * | 2013-11-29 | 2015-06-03 | 浙江新安化工集团股份有限公司 | Preparation method of methylphenyl hydrogen-containing silicone oil |
| CN105367798A (en) * | 2015-11-27 | 2016-03-02 | 广州市银讯光电科技有限公司 | Organosilicone basic adhesive for LED chip packaging and preparation method for organosilicone basic adhesive |
| CN108239285A (en) * | 2018-01-25 | 2018-07-03 | 广东优聚实业有限公司 | A kind of low phenyl-vinyl silicon oil and preparation method thereof |
| CN109796955A (en) * | 2019-01-30 | 2019-05-24 | 中国石油大学(华东) | A kind of preparation method of trapezoidal branch modified siloxane polymer supercritical carbon dioxide thickener |
| CN109796955B (en) * | 2019-01-30 | 2020-12-25 | 中国石油大学(华东) | Preparation method of trapezoidal branched chain modified siloxane polymer supercritical carbon dioxide thickener |
| CN113024810A (en) * | 2021-03-23 | 2021-06-25 | 南昌大学 | Single-component self-crosslinkable fluorosilicone release agent and preparation method thereof |
| CN115572390A (en) * | 2022-09-09 | 2023-01-06 | 新纳奇材料科技江苏有限公司 | Preparation method of phosphonitrile chloride catalyst and application of phosphonitrile chloride catalyst in preparation of vinyl-terminated polydimethylsiloxane |
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