CN101210074A - Method for producing alpha, omega-dihydroxy polydimethyl siloxane - Google Patents
Method for producing alpha, omega-dihydroxy polydimethyl siloxane Download PDFInfo
- Publication number
- CN101210074A CN101210074A CNA200710304027XA CN200710304027A CN101210074A CN 101210074 A CN101210074 A CN 101210074A CN A200710304027X A CNA200710304027X A CN A200710304027XA CN 200710304027 A CN200710304027 A CN 200710304027A CN 101210074 A CN101210074 A CN 101210074A
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- China
- Prior art keywords
- omega
- alpha
- polydimethyl siloxane
- der
- dihydroxy polydimethyl
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- 235000013870 dimethyl polysiloxane Nutrition 0.000 title claims description 21
- 239000004205 dimethyl polysiloxane Substances 0.000 title claims description 21
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 title claims description 21
- 238000004519 manufacturing process Methods 0.000 title description 18
- 238000000034 method Methods 0.000 claims abstract description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 12
- 239000003054 catalyst Substances 0.000 claims abstract description 6
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 6
- HMMGMWAXVFQUOA-UHFFFAOYSA-N octamethylcyclotetrasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 HMMGMWAXVFQUOA-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims description 26
- 239000007788 liquid Substances 0.000 claims description 12
- 238000005507 spraying Methods 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 9
- 229920000642 polymer Polymers 0.000 abstract description 8
- 238000006731 degradation reaction Methods 0.000 abstract description 7
- 230000015556 catabolic process Effects 0.000 abstract description 5
- 238000007334 copolymerization reaction Methods 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 abstract 1
- 238000000926 separation method Methods 0.000 abstract 1
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 6
- 230000018044 dehydration Effects 0.000 description 5
- 238000006297 dehydration reaction Methods 0.000 description 5
- 229920001296 polysiloxane Polymers 0.000 description 5
- 238000010792 warming Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000012667 polymer degradation Methods 0.000 description 2
- 229920002379 silicone rubber Polymers 0.000 description 2
- 238000000889 atomisation Methods 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
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- Silicon Polymers (AREA)
Abstract
The invention relates to a method for preparing Alpha and Omega-dihydroxy dimethylsiloxane and is characterized in that: copolymerization occurs between octamethylcy clotetrasiloxane or dimethyl cyclosiloxane and an alkaline catalyst; when the polymerization reaches to a certain degree, atomized water is sprayed on the surface of high viscosity high polymer to lead to degradation reaction, and after low-boiling-point compound separation process is carried out for 2 to 3 hours, the Alpha and Omega-dihydroxy dimethylsiloxane is obtained. The degradation method is characterized by being capable of leading molecular weight of the prepared Alpha and Omega-dihydroxy dimethylsiloxane to be distributed uniformly and high yield, etc.
Description
Technical field
The present invention relates to a kind of method of producing rubber, specifically, relate to a kind of production α, the method for alpha, omega-dihydroxy polydimethyl siloxane.
Background technology
α, alpha, omega-dihydroxy polydimethyl siloxane are mainly used in and produce condensed type silicon rubber, and its molecular weight size, molecular weight distribution will directly have influence on the performance of the condensed type silicon rubber of being produced.Using octamethylcyclotetrasiloxane (D
4) or dimethyl cyclosiloxane (DMC) production α, in the process of alpha, omega-dihydroxy polydimethyl siloxane, degradation technique plays a decisive role to molecular weight size and distribution.
Traditional mode of production α, the degradation technique of alpha, omega-dihydroxy polydimethyl siloxane: D
4Or DMC and copolymerization such as basic catalyst such as KOH; After the polymerization degree for the treatment of polymkeric substance reached to a certain degree, the stopped reaction still stirred, promptly disposable in reactor the manual liquid water that adds capacity, start then and stir; Behind the 30min, reaction kettle for vacuumizing heats up and removes low-boiling-point substance promptly.
This degradation technique adopts the liquid water of disposable adding capacity, because water just can not full and uniformly be distributed in the polymeric superpolymer, the polymer degradation degree varies causes, and causes resulting α, alpha, omega-dihydroxy polydimethyl siloxane molecular weight distribution broad; And after removing low-boiling-point substance under 170 ℃ of vacuum tightness 0.098Mpa, yield only is 80%～83%.
At the drawback of above technology, domestic have degradation water be heated into steam just directly feed then in polymeric superpolymer inside its technology of degrading, but this method needs vapour pipe is stretched into high viscosity superpolymer inside, vapour pipe easily stops up; And steam feeding amount is difficult for metering, causes the α that produces, alpha, omega-dihydroxy polydimethyl siloxane molecular weight size and distribute wayward, unstable product quality.
Summary of the invention
The purpose of this invention is to provide a kind of molecular weight of product size and the production α more even, high yield that distributes, the method for alpha, omega-dihydroxy polydimethyl siloxane.
In order to realize purpose of the present invention, a kind of production α of the present invention, the method for alpha, omega-dihydroxy polydimethyl siloxane is:
D
4Or DMC and basic catalyst generation copolyreaction, treat that the polymerization degree reaches to a certain degree after, the surface that atomized water is sprayed on polymer product makes it degraded, takes off low-boiling-point substance 2～3h promptly.
Concrete method is: octamethylcyclotetrasiloxane or dimethyl cyclosiloxane and basic catalyst generation copolyreaction, after treating that the polymerization degree reaches 500000～550000Mpas, atomized water all is sprayed on the surface of high viscosity superpolymer product in 8～15s, make it to take place DeR, take off low-boiling-point substance 2～3h.
Described atomized water is 0.1～0.2% of described octamethylcyclotetrasiloxane or a dimethyl cyclosiloxane weight.
Described atomized water is with liquid water gained after the spraying gun atomizing.
Described copolyreaction is at 110～150 ℃, negative pressure 0.03～0.05Mpa, 10～30min.
Described DeR is reacted 3～5min under stirring, preferably 3min.
Carry out under the condition that the described vacuum tightness that removes low-boiling-point substance is 0.090～0.096Mpa.
Described basic catalyst is this area catalyzer commonly used, as KOH, Tetramethylammonium hydroxide.
Production α of the present invention, the whole process of alpha, omega-dihydroxy polydimethyl siloxane all needs to stir, and mixing speed is not had special requirement, can be located at 80r/min.
Described reactor preferably inwall upper end is provided with the vertical response still of liquid water spraying gun.
Adopt a kind of production α of the present invention, the method of alpha, omega-dihydroxy polydimethyl siloxane, since atomized water can be more effective and wide as far as possible be distributed in the high viscosity Polymer Surface, and impel its degraded, solved the problem of liquid water, and made the α that molecular weight is too big or too little the polymer degradation inequality, alpha, omega-dihydroxy polydimethyl siloxane reduces, thereby obviously reduce low-boiling-point substance, improve yield, make ultimate yield reach 87%～90%.
Production α of the present invention, the method of alpha, omega-dihydroxy polydimethyl siloxane is sprayed on atomization water after the polymerisate surface makes it DeR, only need to continue to stir 3～5min, just can reach the purpose that makes the even degraded of high viscosity high polymers, shortened the reaction times.
Adopt the vertical response still,, stop up the situation generation that spraying gun portals thereby stopped polymerization process medium-high viscosity superpolymer product because spraying gun is installed on the inwall upper end of vertical response still.Thereby save production cost, enhance productivity.
Embodiment
Can further be expressly understood the present invention by specific embodiments of the invention given below, but following embodiment not a limitation of the invention.
Embodiment 1
The production method of room temperature vulcanized silicone rubber-107 (RTV-107)
With 300kg D
4Add to 500L vertical response still, open and stir, 170 ℃ of dehydration 1h, add the 0.09kg Tetramethylammonium hydroxide 110 ℃, vacuumize catalyzed polymerization 20min under-0.03Mpa, when treating that superpolymer viscosity reaches 530000Mpas, the vacuum valve of off-response still, the 300g liquid water is sprayed on Polymer Surface makes it degraded after the spraying gun atomizing in 8s, after continuing to stir 5min, be warming up to 170 ℃ rapidly and vacuumize 0.090Mpa, keep 2h, stop to stir, promptly get 267kg RTV-107 (α, alpha, omega-dihydroxy polydimethyl siloxane).
The product RTV-107 theoretical yield of present embodiment is 90%, actual recovery 89%.
Embodiment 2
The production method of room temperature vulcanized silicone rubber-107 (RTV-107)
With 300kg D
4Add to 500L vertical response still, open and stir, 170 ℃ of dehydration 1h, add the 0.11kg Tetramethylammonium hydroxide at 110 ℃, vacuumize catalyzed polymerization 15min under-0.04Mpa, when treating that superpolymer viscosity reaches 500000Mpas, the vacuum valve of off-response still, the 300g liquid water is sprayed on Polymer Surface makes it degraded after the spraying gun atomizing in 10s, after continuing to stir 3min, be warming up to 170 ℃ rapidly and vacuumize 0.093Mpa, keep 2h, stop to stir and promptly get 265kg RTV-107 (α, alpha, omega-dihydroxy polydimethyl siloxane), its theoretical yield is 90%, and actual recovery is 88%.
Embodiment 3
Except that degraded continues to stir the 30min, other condition gets the about 268kg of RTV-107 with embodiment 2, and yield 89% is very nearly the same with 88% yield that stirs 3min.
Take all factors into consideration factors such as yield, energy consumption, continue to stir 3min and have higher economic benefit.
Embodiment 4
The production method of room temperature vulcanized silicone rubber-133 (RTV-133).
With 300kg D
4Add to 500L vertical response still, open and stir, 170 ℃ of dehydration 1h, add 0.04kg KOH at 150 ℃, vacuumize catalyzed polymerization 20min under-0.05Mpa, when treating that superpolymer viscosity reaches 550000Mpas, the vacuum valve of off-response still is sprayed on Polymer Surface with the 350g liquid water and makes it degraded in 15s after the spraying gun atomizing, after continuing to stir 3min, add in an amount of white carbon black and KOH, be warming up to 170 ℃ rapidly and vacuumize 0.096Mpa, keep 2h, stop to stir, promptly get 272kg RTV-133 (α, alpha, omega-dihydroxy polydimethyl siloxane), its theoretical yield is 92%, and reality is yield 90%.
Embodiment 5
The production method of room temperature vulcanized silicone rubber-133 (RTV-133).
300kg DMC is added to 500L vertical response still, open and stir, stirring velocity is 80r/min, 170 ℃ of dehydration 1h, add 0.04kg KOH at 130 ℃, vacuumize catalyzed polymerization 25min under-0.05Mpa, when treating that superpolymer viscosity reaches 540000Mpas, the vacuum valve of off-response still, the 600g liquid water is sprayed on Polymer Surface makes it degraded after the spraying gun atomizing in 15s, after continuing to stir 4min, add in an amount of white carbon black and KOH, be warming up to 170 ℃ rapidly and vacuumize 0.096Mpa, keep 2h, stop to stir, promptly get 272kgRTV-133 (α, alpha, omega-dihydroxy polydimethyl siloxane), its theoretical yield is 91%, and actual recovery is 90%.
What embodiments of the invention adopted is the vertical response still that the inwall upper end is provided with the liquid water spraying gun.
Comparative Examples 1
Traditional technology is produced room temperature vulcanized silicone rubber-133 (RTV-133).
300kg D4 is added to 500L vertical response still, open and stir, 170 ℃ of dehydration 1h add KOH at 150 ℃ of following catalyzed polymerization 30min.When treating that superpolymer viscosity reaches 550000Mpas, the vacuum valve of off-response still.Open the reactor hand hole, the 850g liquid water is added in the reactor, close hand hole, after continuing to stir 30min, add in an amount of white carbon black and KOH, be warming up to 170 ℃ rapidly and vacuumize 0.095Mpa, keep 2h, stop to stir, promptly get 242kg RTV-133 (α, alpha, omega-dihydroxy polydimethyl siloxane), its yield is 80%.
Relatively can find with embodiment 4, adopt production method of the present invention can significantly improve product yield.
Comparative Examples 2
Other condition is with Comparative Examples 1, and the time that will add the continuation stirring of water degraded back is reduced to 5min, gets RTV-133 (α, alpha, omega-dihydroxy polydimethyl siloxane) 228kg, yield 76%.As seen in conventional production methods, take all factors into consideration the weight of yield, energy consumption etc., degraded back churning time 30min should not shorten.
Therefore, compare with traditional production method, when method of the present invention can shorten degradation reaction Between, and significantly improve the yield of product.
Claims (10)
1. produce α for one kind, the method of alpha, omega-dihydroxy polydimethyl siloxane, it is characterized in that, described method is: octamethylcyclotetrasiloxane or dimethyl cyclosiloxane and basic catalyst generation copolyreaction, after treating that the polymerization degree reaches to a certain degree, atomized water is sprayed on the polymerisate surface makes it to take place DeR, take off low-boiling-point substance 2～3h.
2. the method for claim 1 is characterized in that, described atomized water is 0.1～0.2% of described octamethylcyclotetrasiloxane or a dimethyl cyclosiloxane weight.
3. method as claimed in claim 1 or 2 is characterized in that, the described polymerization degree is 500000～550000Mpas.
4. as the arbitrary described method of claim 1-3, it is characterized in that described atomized water all is sprayed on the product surface in 8～15s.
5. as the arbitrary described method of claim 1-4, it is characterized in that, described copolyreaction 110～150 ℃ ,-0.03～-0.05Mpa, carry out 10～30min.
6. as the arbitrary described method of claim 1-5, it is characterized in that, stir 3～5min after the DeR.
7. method as claimed in claim 6 is characterized in that, stirs 3min after the described DeR.
8. as the arbitrary described method of claim 1～7, it is characterized in that the described low-boiling-point substance that takes off is to carry out under 0.090～0.096Mpa in vacuum tightness.
9. as the arbitrary described method of claim 1～8, it is characterized in that described DeR is carried out in the vertical response still.
10. method as claimed in claim 9 is characterized in that, described vertical response still inwall upper end is provided with the liquid water spraying gun.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN200710304027XA CN101210074B (en) | 2007-12-24 | 2007-12-24 | Method for producing alpha, omega-dihydroxy polydimethyl siloxane |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200710304027XA CN101210074B (en) | 2007-12-24 | 2007-12-24 | Method for producing alpha, omega-dihydroxy polydimethyl siloxane |
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| CN101210074A true CN101210074A (en) | 2008-07-02 |
| CN101210074B CN101210074B (en) | 2010-11-10 |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102093561A (en) * | 2010-12-27 | 2011-06-15 | 蓝星化工新材料股份有限公司江西星火有机硅厂 | High-efficiency catalyst used for preparing high ring 107 glue and preparation method thereof |
| CN102675644A (en) * | 2012-05-22 | 2012-09-19 | 山东东岳有机硅材料有限公司 | Preparation method of medium/high-viscosity alpha,omega-dihydroxypolydimethylsiloxane |
| CN103917856A (en) * | 2011-09-06 | 2014-07-09 | 霍尼韦尔国际公司 | Rigid structural and low back face signature ballistic ud/articles and method of making |
| CN104140529A (en) * | 2014-07-10 | 2014-11-12 | 何少云 | Preparation method of high-viscosity silicone oil |
| CN104562775A (en) * | 2014-07-03 | 2015-04-29 | 东莞市良展有机硅科技有限公司 | Condensed type printing silica gel, preparation method and application |
| CN105111470A (en) * | 2015-08-13 | 2015-12-02 | 四川大学 | Reversible covalent crosslinking polysiloxane elastomer, preparation method therefor and application thereof |
| CN112831049A (en) * | 2021-03-09 | 2021-05-25 | 浙江新安化工集团股份有限公司 | Preparation method of alpha, omega-dihydroxy polydimethylsiloxane |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100348646C (en) * | 2005-04-29 | 2007-11-14 | 中国石油天然气股份有限公司 | Method for catalytic synthesis of alpha, omega-dihydroxy polydimethylsiloxane |
-
2007
- 2007-12-24 CN CN200710304027XA patent/CN101210074B/en not_active Expired - Fee Related
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102093561A (en) * | 2010-12-27 | 2011-06-15 | 蓝星化工新材料股份有限公司江西星火有机硅厂 | High-efficiency catalyst used for preparing high ring 107 glue and preparation method thereof |
| CN102093561B (en) * | 2010-12-27 | 2013-05-29 | 蓝星化工新材料股份有限公司江西星火有机硅厂 | High-efficiency catalyst used for preparing high ring 107 glue and preparation method thereof |
| CN103917856A (en) * | 2011-09-06 | 2014-07-09 | 霍尼韦尔国际公司 | Rigid structural and low back face signature ballistic ud/articles and method of making |
| CN103917856B (en) * | 2011-09-06 | 2017-04-26 | 霍尼韦尔国际公司 | Rigid structural and low back face signature ballistic ud/articles and method of making |
| CN102675644A (en) * | 2012-05-22 | 2012-09-19 | 山东东岳有机硅材料有限公司 | Preparation method of medium/high-viscosity alpha,omega-dihydroxypolydimethylsiloxane |
| CN104562775A (en) * | 2014-07-03 | 2015-04-29 | 东莞市良展有机硅科技有限公司 | Condensed type printing silica gel, preparation method and application |
| CN104140529A (en) * | 2014-07-10 | 2014-11-12 | 何少云 | Preparation method of high-viscosity silicone oil |
| CN105111470A (en) * | 2015-08-13 | 2015-12-02 | 四川大学 | Reversible covalent crosslinking polysiloxane elastomer, preparation method therefor and application thereof |
| CN105111470B (en) * | 2015-08-13 | 2017-12-01 | 四川大学 | A kind of THERMALLY REVERSIBLE COVALENT silicone elastomer and preparation method and application |
| CN112831049A (en) * | 2021-03-09 | 2021-05-25 | 浙江新安化工集团股份有限公司 | Preparation method of alpha, omega-dihydroxy polydimethylsiloxane |
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| CN101210074B (en) | 2010-11-10 |
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