CN103694478B - A kind of synthetic method of polysiloxane - Google Patents
A kind of synthetic method of polysiloxane Download PDFInfo
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- CN103694478B CN103694478B CN201310667318.0A CN201310667318A CN103694478B CN 103694478 B CN103694478 B CN 103694478B CN 201310667318 A CN201310667318 A CN 201310667318A CN 103694478 B CN103694478 B CN 103694478B
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Abstract
The invention discloses a kind of synthetic method of polysiloxane, it comprises the following steps and processing condition: add at least one siloxanes in the reactor, the organic aluminium compound of siloxanes total mass 0.0001% ~ 5% is added as catalyzer after stirring, the water of 0.0001 ~ 10.0 times for adding alkoxyl group amount of substance in siloxanes is instilled after stirring and evenly mixing, drip after post-heating carries out back flow reaction, continue heating and under normal pressure, steam the alcohols of reaction generation and unnecessary water, when material temperature rises to more than 100 DEG C, residual alcohols is sloughed in underpressure distillation, water and low-boiling-point substance, obtain.Environmental protection of the present invention, decreases pollution, reduces cost, and technical process is shortened greatly, improves production efficiency, and the silicone product storge quality of production is stablized.
Description
[technical field]
The present invention relates to a kind of synthetic method of polysiloxane, belong to organic polymer material technical field.
[background technology]
Polysiloxane is a class with the silica silicon key repeated for main chain, the polymkeric substance of direct connection organic group on Siliciumatom, and its general structure is expressed as follows:
[R
nSiO
(4-n)/2]
m
In formula, R is organic group, as methyl, phenyl etc.; N is the organic group number that Siliciumatom connects, and scope is 1 ~ 3; M is the polymerization degree, and scope is m >=2.R in polysiloxane mostly is methyl and phenyl, because the siloxanyl monomers raw material of methyl and phenyl is cheaply easy to get, and versatility is good.
The complicated structure of polysiloxane, according to the difference of synthesis material monomer, can contain simple function chain link simultaneously, difunctionality chain link, tri functional chain, four pipe energy chain links, its composition and ratio can regulate as required, thus obtain various dissimilar polysiloxane.
Polysiloxane-based material has weathering resistance, temperature tolerance, electric property, water tolerance, the feature of the excellent performances such as winter hardiness, and at electronic material, automobile, machinery, articles for daily use, the fields such as medical treatment have application widely.
The synthesis of polysiloxane, at present both at home and abroad disclosed technology mainly contains two kinds: one is that the hydrolysis-condensation reaction of chlorosilane produces siloxanes, its advantage is that raw chlorsilane is with low cost, technology maturation, but a large amount of hydrogenchloride can be produced in hydrolyzing chlorosilane process, also need to consume a large amount of organic solvents, product need be washed to neutrality, consume a large amount of water, and produce acid waste water, bring the problem such as equipment corrosion and environmental pollution thus; Two is utilize siloxanes hydrolytic condensation under strong acid or strong base catalyst to produce polysiloxane, its advantage is that process stabilizing is easy to control, also hydrogenchloride is not produced, a large amount of acid waste water can not be produced, but still exist and need with an organic solvent, acid base catalysator needs washing neutralization to remove, and consumes great lot of water resources, the shortcoming that technique is complicated.
In sum, all there is more problem in the synthesis technique of current polysiloxane, finds new polysiloxane synthesis technique, decreasing pollution and consumption, and shorten operation, tool is of great significance.
Aluminum ion has empty sp track, and having very strong cohesiveness and receive electronic capability, is a class strong lewis acid, and for hydrolysis reaction, hydroxyl condensation, esterification etc. have stronger katalysis, therefore may be used for the hydrolytic condensation synthesis polysiloxane of catalyze siloxane.Residually after aluminum ion catalyzed reaction be unfavorable for the storage ability of polysiloxane in the product, the organic coordination compound of aluminium then can maintain stability at normal temperatures and not reduce the activity under comparatively high temps, also can strengthen the consistency of aluminium in organic phase.
Have in patent CN102532488A, CN1837284A, CN85102717A using aluminium organic coordination compound as silicone hydroxyl, the catalyzer of silane oxygen groups and other radical reaction.But there are no aluminium organic coordination compound being used for synthesis polysiloxane pertinent literature and patent.
[summary of the invention]
The object of the invention is the defect overcoming existing polysiloxane synthetic technology, provide a kind of without the need to solvent, without the need to washing, the synthetic method not producing the polysiloxane of waste water and waste liquid.
The object of the invention is to be achieved through the following technical solutions:
A kind of synthetic method of polysiloxane, it is characterized in that comprising the following steps and processing condition: add at least one siloxanes in the reactor, the organic aluminium compound of siloxanes total mass 0.0001% ~ 5% is added as catalyzer after stirring, the water of 0.0001 ~ 10.0 times for adding alkoxyl group amount of substance in siloxanes is instilled after stirring and evenly mixing, drip after post-heating carries out back flow reaction, continue heating and under normal pressure, steam the alcohols of reaction generation and unnecessary water, when material temperature rises to more than 100 DEG C, residual alcohols is sloughed in underpressure distillation, water and low-boiling-point substance, obtain polysiloxane.
Siloxanes in the present invention has following general structure:
R
1 aSi(OR
2)
bO
[(4-a-b)/2]
In formula
R
1represent same or different replacement or unsubstituted monovalent hydrocarbon,
R
2represent the monovalent hydrocarbon that carbon atom is less than 4,
A, b meet 0≤a≤3,1≤b≤4,0<a+b≤4.
R wherein
1be selected from methyl, ethyl, propyl group, butyl, phenyl, vinyl, 2-allyl group, γ-(2,3-epoxy third oxygen) propyl group, 3-chloropropyl, 3-aminopropyl, 3-methacryloxypropyl one or several.
R wherein
2be selected from methyl, ethyl, propyl group, one or more in butyl.
In monoalkoxysilane monomer in the present invention, dialkoxy silicane monomer, trialkoxy silane monomer, tetraalkoxysilane monomer and respectively corresponding oligomer thereof or mixing oligomer one or several,
Organic aluminium compound in the present invention to be selected from praseodynium aluminium, methyl aceto acetate aluminum-diisopropoxide, tri ethylacetoacetate aluminium, Acetacetic acid alkyl ester aluminum-diisopropoxide, diacetyl acetate ethyl ester single acetyl acetone aluminium one or several, preferred praseodynium aluminium.
The consumption of organic aluminium compound of the present invention is preferably 0.001% ~ 5% of siloxanes total mass, then is preferably 0.005% ~ 0.1%, is more preferably 0.005% ~ 0.05%.
In the present invention's reaction, the amount of substance of water is 0.0001 ~ 10.0 times of the total amount of substance of alkoxyl group in raw material siloxanes, be preferably 0.01 ~ 1.5 times of the total amount of substance of alkoxyl group in raw material siloxanes, be more preferably 0.1 ~ 1.0 times of the total amount of substance of alkoxyl group in raw material siloxanes.
Back flow reaction temperature of the present invention is the reflux temperature 70 DEG C of reaction system, and reflux time is 0.5 ~ 6h.
The vacuum tightness that residual alcohols, water and low-boiling-point substance are sloughed in underpressure distillation of the present invention is-0.075 ~-0.096MPa, and temperature is 100 DEG C ~ 250 DEG C, and the time of underpressure distillation is 1 ~ 2h.
The present invention compared with prior art, has the following advantages:
1. adopt siloxanes as raw material, do not produce hydrogenchloride, do not produce acid waste water, can not etching apparatus contaminate environment.
2. in production process completely not with an organic solvent, reduce production cost, decreasing pollution.
3. decrease this technique of washing in production process, saved water resources, decreased sewage discharge.
4. technical process is shortened greatly, improves production efficiency.
5. the highly versatile of synthetic method, can synthesize various types of polysiloxane according to demand.
6. the silicone product storge quality produced is stablized.
[embodiment]
Below in conjunction with specific embodiment, the invention will be further described:
Add phenyltrimethoxysila,e 49.6g (0.25mol), dimethoxydiphenylsilane 122.2g (0.5mol), dimethyldimethoxysil,ne 180.3g (1.5mol) in embodiment 1:1L there-necked flask, after stirring, add the aluminium acetylacetonate toluene solution 1.76g that massfraction is 10%; After stirring and evenly mixing, drip 64.1g (3.57mol) water in 5min, after dripping water, stirring at normal temperature is hydrolyzed 1h, is heated to 70 DEG C of back flow reaction 4h; React rear continuation heating, and under normal pressure, steam the methyl alcohol of reaction generation and unnecessary water, underpressure distillation is changed into when material temperature rises to more than 100 DEG C, be at 110 DEG C ~ 120 DEG C, maintain 1.5h under the vacuum condition of-0.075MPa to slough residual methanol, water and low-boiling-point substance in vacuum tightness, obtain polysiloxane.
The polysiloxane that embodiment 1 obtains is water white transparency, viscosity 230mPas.Fourier infrared spectrograph is utilized to analyze sample, at 1000cm
-1~ 1130cm
-1there is strong absorption peak in scope, be the characteristic peak of silica silicon key, prove to obtain polysiloxane.By sample constant temperature 48h at 70 DEG C, constant temperature 48h at 100 DEG C, test its viscosity respectively, viscosity is unchanged, illustrates that its storage endurance is functional.
Add phenyltrimethoxysila,e 89.2g (0.45mol), dimethoxydiphenylsilane 110.0g (0.45mol), dimethyldimethoxysil,ne 108.2g (0.90mol) in embodiment 2:1L there-necked flask, stir after add the aluminium acetylacetonate toluene solution 1.54g that massfraction is 10%; After stirring and evenly mixing, drip 54.7g (3.04mol) water in 5min, after dripping water, stirring at normal temperature is hydrolyzed 1h, is then warming up to 70 DEG C of back flow reaction 4h; React rear continuation heating, and under normal pressure, steam the methyl alcohol of reaction generation and unnecessary water, underpressure distillation is changed into when material temperature rises to more than 100 DEG C, be at 110 DEG C ~ 120 DEG C, maintain 1.5h under the vacuum condition of-0.075MPa to slough residual methanol, water and low-boiling-point substance in vacuum tightness, obtain polysiloxane 194g.
The polysiloxane that embodiment 2 obtains is water white liquid, viscosity 3100mPas.Fourier infrared spectrograph is utilized to analyze sample, at 1000cm
-1~ 1130cm
-1there is strong absorption peak in scope, be the characteristic peak of silica silicon key, prove to obtain polysiloxane.By sample constant temperature 48h at 70 DEG C, constant temperature 48h at 100 DEG C, test its viscosity respectively, viscosity is unchanged, illustrates that its storage endurance is functional.
Add phenyltrimethoxysila,e 89.2g (0.45mol), dimethoxydiphenylsilane 110.0g (0.45mol), dimethyldimethoxysil,ne 108.2g (0.90mol) in embodiment 3:1L there-necked flask, stir after add the aluminium acetylacetonate toluene solution 0.15g that massfraction is 10%; After stirring and evenly mixing, in 5min, drip 54.7g (3.04mol) water; After dripping water, stirring at normal temperature is hydrolyzed 1h, then 70 DEG C of back flow reaction 4h are warming up to, react rear continuation heating, and under normal pressure, steam the methyl alcohol of reaction generation and unnecessary water, underpressure distillation is changed into when material temperature rises to more than 80 DEG C, be at 80 DEG C ~ 90 DEG C, maintain 1.5h under the vacuum condition of-0.075MPa to slough residual methanol, water and low-boiling-point substance in vacuum tightness, obtain polysiloxane.
The polysiloxane that embodiment 3 obtains is water white liquid, viscosity 570mPas.Fourier infrared spectrograph is utilized to analyze sample, at 1000cm
-1~ 1130cm
-1there is strong absorption peak in scope, be the characteristic peak of silica silicon key, prove to obtain polysiloxane.By sample constant temperature 48h at 70 DEG C, constant temperature 48h at 100 DEG C, test its viscosity respectively, viscosity is unchanged, illustrates that its storage endurance is functional.
Add phenyltrimethoxysila,e 79.3g (0.40mol), methyltrimethoxy silane 136.2g (1.0mol), dimethoxydiphenylsilane 97.7g (0.40mol) in embodiment 4:1L there-necked flask, stir after add the aluminium acetylacetonate toluene solution 0.16g that massfraction is 10%; After stirring and evenly mixing, 67.5g (3.75mol) water is dripped in 5min, after dripping water, stirring at normal temperature is hydrolyzed 1h, then 70 DEG C of back flow reaction 4h are warming up to, react rear continuation heating, and under normal pressure, steamed the methyl alcohol of reaction generation and unnecessary water, when material temperature rises to more than 80 DEG C, change underpressure distillation into, be at 80 DEG C ~ 90 DEG C, maintain 1.5h under the vacuum condition of-0.075MPa to slough residual methanol, water and low-boiling-point substance in vacuum tightness, obtain polysiloxane.
The polysiloxane that embodiment 4 obtains is water white liquid, viscosity 136000mPas.Fourier infrared spectrograph is utilized to analyze sample, at 1000cm
-1~ 1130cm
-1there is strong absorption peak in scope, be the characteristic peak of silica silicon key, prove to obtain polysiloxane.By sample constant temperature 48h at 70 DEG C, constant temperature 48h at 100 DEG C, test its viscosity respectively, viscosity is unchanged, illustrates that its storage endurance is functional.
Add phenyltrimethoxysila,e 19.8g (0.10mol), methyltrimethoxy silane 40.8g (0.30mol), dimethoxydiphenylsilane 146.6g (0.60mol), methyltrimethoxy silane 96.2g (0.80mol) in embodiment 5:1L there-necked flask, stir after add the aluminium acetylacetonate toluene solution 0.30g that massfraction is 10%; After stirring and evenly mixing, in 5min, drip 54.0g (3.0mol) water; After dripping water, stirring at normal temperature is hydrolyzed 1h, then 70 DEG C of back flow reaction 4h are warming up to, react rear continuation heating, and under normal pressure, steam the methyl alcohol of reaction generation and unnecessary water, underpressure distillation is changed into when material temperature rises to more than 80 DEG C, be at 80 DEG C ~ 90 DEG C, maintain 1.5h under the vacuum condition of-0.075MPa to slough residual methanol, water and low-boiling-point substance in vacuum tightness, obtain polysiloxane.
The polysiloxane that embodiment 5 obtains is water white liquid, viscosity 387mPas.Fourier infrared spectrograph is utilized to analyze sample, at 1000cm
-1~ 1130cm
-1there is strong absorption peak in scope, be the characteristic peak of silica silicon key, prove to obtain polysiloxane.By sample constant temperature 48h at 70 DEG C, constant temperature 48h at 100 DEG C, test its viscosity respectively, viscosity is unchanged, illustrates that its storage endurance is functional.
Claims (8)
1. the synthetic method of a polysiloxane, it is characterized in that comprising the following steps and processing condition: add at least one siloxanes in the reactor, the organic aluminium compound of siloxanes total mass 0.0001% ~ 5% is added as catalyzer after stirring, the water of 0.0001 ~ 10.0 times for adding alkoxyl group amount of substance in siloxanes is instilled after stirring and evenly mixing, drip after post-heating carries out back flow reaction, continue heating and under normal pressure, steam the alcohols of reaction generation and unnecessary water, when material temperature rises to more than 100 DEG C, residual alcohols is sloughed in underpressure distillation, water and low-boiling-point substance, obtain polysiloxane.
2. the synthetic method of a kind of polysiloxane according to claim 1, is characterized in that described siloxanes has following general structure:
R
1 aSi(OR
2)
bO
[(4-a-b)/2]，
In formula
R
1represent same or different replacement or unsubstituted monovalent hydrocarbon,
R
2represent the monovalent hydrocarbon that carbonatoms is less than 4,
A, b meet 0≤a≤3,1≤b≤4,0<a+b≤4.
3. the synthetic method of a kind of polysiloxane according to claim 2, is characterized in that described R
1be selected from methyl, ethyl, propyl group, butyl, phenyl, vinyl, 2-allyl group, γ-(2,3-epoxy third oxygen) propyl group, 3-chloropropyl, 3-aminopropyl, 3-methacryloxypropyl one or several.
4. the synthetic method of a kind of polysiloxane according to claim 2, is characterized in that described R
2be selected from methyl, ethyl, one or several in propyl group.
5. the synthetic method of a kind of polysiloxane according to claim 1, it is characterized in that described siloxanes be in monoalkoxysilane monomer, dialkoxy silicane monomer, trialkoxy silane monomer, tetraalkoxysilane monomer and respectively corresponding oligomer thereof or mixing oligomer one or several.
6. the synthetic method of a kind of polysiloxane according to claim 1, is characterized in that described organic aluminium compound to be selected from praseodynium aluminium, methyl aceto acetate aluminum-diisopropoxide, tri ethylacetoacetate aluminium, diacetyl acetate ethyl ester single acetyl acetone aluminium one or several.
7. the synthetic method of a kind of polysiloxane according to claim 1, it is characterized in that described back flow reaction temperature is the reflux temperature of reaction system, reflux time is 0.5 ~ 6h.
8. the synthetic method of a kind of polysiloxane according to claim 1, it is characterized in that the vacuum tightness that residual alcohols, water and low-boiling-point substance are sloughed in described underpressure distillation is-0.075 ~-0.096MPa, temperature is 100 DEG C ~ 250 DEG C, and the time of underpressure distillation is 1 ~ 2h.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1837284A (en) * | 2005-03-22 | 2006-09-27 | 信越化学工业株式会社 | Epoxy-organosilicon mixed resin composition and method for preparing same, and light-emitting semiconductor device |
| CN1955209A (en) * | 2005-10-27 | 2007-05-02 | 信越化学工业株式会社 | Method of producing high molecular weight organopolysiloxane, compositon comprising the high molecular weight organopolysiloxane, and optical semiconductor device sealed with cured product thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1837284A (en) * | 2005-03-22 | 2006-09-27 | 信越化学工业株式会社 | Epoxy-organosilicon mixed resin composition and method for preparing same, and light-emitting semiconductor device |
| CN1955209A (en) * | 2005-10-27 | 2007-05-02 | 信越化学工业株式会社 | Method of producing high molecular weight organopolysiloxane, compositon comprising the high molecular weight organopolysiloxane, and optical semiconductor device sealed with cured product thereof |
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Address after: 528400 Zhongshan Torch Development Zone, Jiangxi, along the road No. two, No. 1, Guangdong Patentee after: Guangdong poly Polytron Technologies Inc Address before: 528400 Guangdong Guangdong polymerization silicone material Co., Ltd. Zhongshan Torch Development Zone Patentee before: Guangdong Juhe Organic Silicon Material Co., Ltd. |
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Address after: 528400 No. 20 Jiexin Road, Shazai Industrial Park, Zhongshan Citizen Town, Guangdong Province Patentee after: Aiken silicone material (Zhongshan) Co.,Ltd. Address before: 528400 No. 20 Jiexin Road, Shazai Industrial Park, Zhongshan Citizen Town, Guangdong Province Patentee before: Zhongshan City Poly chemical materials Co.,Ltd. |