CN100503622C - Organophosphorus ester preparation method - Google Patents
Organophosphorus ester preparation method Download PDFInfo
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- CN100503622C CN100503622C CNB2006100382302A CN200610038230A CN100503622C CN 100503622 C CN100503622 C CN 100503622C CN B2006100382302 A CNB2006100382302 A CN B2006100382302A CN 200610038230 A CN200610038230 A CN 200610038230A CN 100503622 C CN100503622 C CN 100503622C
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- organophosphorus ester
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Abstract
The invention provides a Method for preparation of organosilicon phosphate ester, using organo-silicone and phosphorus pentoxide as material. Among them, the organosiloxane would be low-viscosity polydimethyl siloxane, the proportioning of material is: organo-silicone 70-97. 8 mass shares, phosphorus pentoxide 2. 2-30 mass shares; controlled conditions: agitating velocity above 70 turn/min, controlling temperature 100-170 deg C, flow amount of nitrogen 2-3 ml/min. Applying organophosphorus ester of this invention as neutralizer in the production of methyl-vinyl-sil-licone which using potassium hydrate as catalyst, resolving the limitation which using tetramethyl ammonium hydroxide to catalyze, synthesize and high-temperature sulfur methyl-vinyl-sil-licone, causing structured easily, storage time shortly, postcure easily and becoming yellow easily of silicon rubber because the catalyzer hasing minor moisture and residual trimethylamine.
Description
Technical field
The present invention relates to vitochemical general method, be meant a kind of preparation method of organophosphorus ester especially.
Background technology
Still the synthetic technology that does not have organophosphorus ester in the existing actual production generally is to adopt the methyl cyclosiloxane to mix with phosphoric acid to make sour glue use, is mainly used in synthetic room temperature-vulcanized hydroxy-end capped polysiloxane.The alkali glue of the Tetramethylammonium hydroxide that the synthetic employing of present high temperature vulcanized methyl vinyl silicone rubber is traditional is made catalyzer, it also only is temporary catalyzer, this catalyzer at high temperature resolves into Trimethylamine 99 and methyl alcohol, and in the alkali glue of Tetramethylammonium hydroxide a spot of hydroxyl being arranged, the shortcoming of the high temperature vulcanized methyl vinyl silicone rubber of synthetic is easy structurizing and post cure xanthochromia.When the high temperature vulcanized methyl vinyl silicon kautschuk of silanol potassium catalysis ring-opening polymerization of potassium hydroxide is used in the current research exploitation, relate to the neutralization of silanol potassium, considering that the methyl cyclosiloxane mixes with phosphoric acid to make in the sour glue has moisture, easily form terminal hydroxy group and can cause high temperature vulcanized methyl vinyl silicone rubber recurring structureization, therefore press for a kind of properties of transparency that does not influence silicon rubber of exploitation, and the organophosphorus ester of fine blending is arranged with silicon rubber.
Summary of the invention
Technical problem to be solved by this invention can't provide the situation of synthetic organophosphorus ester when just being at exploitation with the high temperature vulcanized methyl vinyl silicon kautschuk of silanol potassium catalysis ring-opening polymerization of potassium hydroxide, a kind of employing organo-siloxane and Vanadium Pentoxide in FLAKES (P are provided
2O
5) mix, and under certain temperature and protection of nitrogen gas, react, mainly be used as the preparation method of the organophosphorus ester of potassium hydroxide catalysed synthesizing methyl vinylsiloxane rubber neutralizing agent.The preparation method of organophosphorus ester of the present invention is a raw material with organo-siloxane and Vanadium Pentoxide in FLAKES, wherein organo-siloxane is selected the polydimethylsiloxane of low-viscosity for use, proportioning raw materials: organo-siloxane 70～97.8 mass parts, Vanadium Pentoxide in FLAKES 2.2～30 mass parts; Control condition: stirring velocity is greater than 70 rev/mins, 100～170 ℃ of controlled temperature, nitrogen flow 2～3 ml/min.React to Vanadium Pentoxide in FLAKES all dissolve, the material bleach finishes 2～6 hours reaction times.Organo-siloxane also can be selected hexamethyldisiloxane for use.Reaction principle is as follows:
N=0～50. m=0～50 wherein
The starting material index that the present invention prepares the organophosphorus ester method is as follows:
(1) polydimethylsiloxane appearance transparent liquid, viscosity (centipoise) 5.0～50,
Density (g/ml) 0.830-0.920, purity (%) 99.5;
(2) hexamethyldisiloxane appearance transparent liquid, viscosity (centipoise) 0.412,
Boiling point (℃) 100～101, density (g/ml) 0.7619,
Purity (%) is greater than 95;
(3) Vanadium Pentoxide in FLAKES appearance white powder, purity (%) be greater than 98,
Iron level (%) is less than 0.01, and water-insoluble (%) is less than 0.02;
(4) the nitrogen dew point (℃)-75, purity (%) 99.9.
The organophosphorus ester of the inventive method preparation reaches following technical requirements:
The appearance colorless transparent liquid, viscosity (centipoise) 5～100, phosphorus content (%) 1～13.
When preparation during organophosphorus ester, earlier starting material organo-siloxane and Vanadium Pentoxide in FLAKES are metered into reaction unit by proportioning, start stirring, stirring velocity is controlled to be more than 70 rev/mins, feeds nitrogen simultaneously, progressively heat temperature raising to 100～170 ℃; React to Vanadium Pentoxide in FLAKES all dissolve, the material bleach finishes 2～6 hours reaction times.The organophosphorus ester of preparation mainly is used as the neutralizing acid glue of potassium hydroxide catalysed synthesizing methyl vinylsiloxane rubber.
Organophosphorus ester of the present invention is made the simultaneous test that the inferior silicon rubber of neutralizing agent synthetic silicon rubber and import sieve ground (model 751) and traditional catalyzer synthetic silicon rubber (model 110-2) are done equal conditions, result such as following table:
Three kinds of silicon rubber structured and sulfuration outward appearance contrasts
Advantage of the present invention just is because organo-siloxane is selected the polydimethylsiloxane and the hexamethyldisiloxane of low-viscosity for use, be applied to the production of potassium hydroxide catalysed synthesizing methyl vinylsiloxane rubber by organophosphorus ester as neutralizing agent with the Vanadium Pentoxide in FLAKES prepared in reaction, solved present domestic employing Tetramethylammonium hydroxide catalysis synthesizing high temperature sulfuration methyl vinyl silicone rubber, because of catalyzer has micro-moisture and residual Trimethylamine 99, cause the easy structurizing storage time of silicon rubber to shorten and the easy xanthochromic defective of post cure.Therefore the preparation method of organophosphorus ester of the present invention has the excellent popularization prospect.
Embodiment
Below be one embodiment of the present of invention, the actual use of the present invention is not limited to embodiment.
Embodiment 1 prepares the method for organophosphorus ester
Raw material (1) hexamethyldisiloxane Guilin Xinyaqiang Biochemical Co., Ltd. produces
Appearance transparent liquid, viscosity (centipoise) 0.412, purity (%) is greater than 95;
(2) production of worker company limited is foreignized by Vanadium Pentoxide in FLAKES Changzhou Wujin China
The appearance white powder, purity (%) is greater than 98%.
Proportioning raw materials: hexamethyldisiloxane 70 mass parts, Vanadium Pentoxide in FLAKES 30 mass parts.
Control condition: stirring velocity is more than 70 rev/mins, 100～125 ℃ of controlled temperature, nitrogen flow 2～3 ml/min.
In 2000 milliliters of there-necked flasks, add 525g hexamethyl siloxanes (MM) and 225g P
2O
5, start stirring, feed nitrogen, 100～125 ℃ of back flow reaction of electricity consumption heat temperature raising are until P
2O
5All dissolvings, the material bleach finishes, 3～4 hours time.
The organophosphorus ester of preparation reaches following technical requirements:
The appearance colorless transparent liquid, viscosity (centipoise) 5.2
P content is 12.95%.
The heavy 736.5g of product, yield about 98.2%.
Embodiment 2 prepares the method for organophosphorus ester
Raw material: (1) polydimethylsiloxane (commercial disignation 201 methyl-silicone oils)
Jiangsu Hongda Chemical New Material Co., Ltd produces
Appearance transparent liquid, viscosity (centipoise) 5.0, purity (%) 99.5;
(2) production of worker company limited is foreignized by Vanadium Pentoxide in FLAKES Changzhou Wujin China
The appearance white powder, purity (%) is greater than 98%.
Proportioning raw materials: polydimethylsiloxane 70 mass parts, Vanadium Pentoxide in FLAKES 30 mass parts.
Control condition: stirring velocity is more than 70 rev/mins, 155～170 ℃ of controlled temperature, nitrogen flow 2～3 ml/min.
The polydimethylsiloxane and the 225gP that in 2000 milliliters of there-necked flasks, add the 5255g low-viscosity
2O
5, start stirring, feed nitrogen, 155～170 ℃ of reactions of electricity consumption heat temperature raising are until P
2O
5All dissolvings, the material bleach finishes, 4～5 hours time.
The organophosphorus ester of preparation reaches following technical requirements:
The appearance colorless transparent liquid, viscosity (centipoise) 100
P content is 12.85%;
The heavy 738.7g of product, yield about 98.5%.
Embodiment 3 prepares the method for organophosphorus ester
Raw material: (1) polydimethylsiloxane (commercial disignation 201 methyl-silicone oils)
Jiangsu Hongda Chemical New Material Co., Ltd produces
Appearance transparent liquid, viscosity (centipoise) 50, purity (%) 99.5;
(2) production of worker company limited is foreignized by Vanadium Pentoxide in FLAKES Changzhou Wujin China
The appearance white powder, purity (%) is greater than 98%.
Proportioning raw materials: polydimethylsiloxane 97.8 mass parts, Vanadium Pentoxide in FLAKES 2.2 mass parts.
Control condition: stirring velocity is more than 70 rev/mins, 130～155 ℃ of controlled temperature, nitrogen flow 2～3 ml/min.
In 1500 milliliters of there-necked flasks, add 733.5g low-viscosity polydimethylsiloxane and 16.5gP
2O
5, start stirring, feed nitrogen, 130～155 ℃ of reactions of electricity consumption heat temperature raising are until P
2O
5All dissolvings, the material bleach finishes, 4～5 hours time.
The organophosphorus ester of preparation reaches following technical requirements:
The appearance colorless transparent liquid, viscosity (centipoise) 60
P content is 1.02%,
The heavy 734.6g of product, yield about 98%.
Claims (9)
1, a kind of preparation method of organophosphorus ester, it is characterized in that with organo-siloxane and Vanadium Pentoxide in FLAKES be raw material, wherein organo-siloxane is selected the polydimethylsiloxane of viscosity 5.0～50 centipoises for use, proportioning raw materials: organo-siloxane 70～97.8 mass parts, Vanadium Pentoxide in FLAKES 2.2～30 mass parts; Control condition: stirring velocity is greater than 70 rev/mins, 100～170 ℃ of controlled temperature, nitrogen flow 2～3 ml/min.
2, the preparation method of organophosphorus ester according to claim 1, it is characterized in that reacting to Vanadium Pentoxide in FLAKES all dissolve, the material bleach finishes 2～6 hours reaction times.
3, the preparation method of organophosphorus ester according to claim 1 and 2 is characterized in that raw material polydimethylsiloxane viscosity 5.0～50 centipoises, density 0.830-0.920g/ml, purity 99.5%; Vanadium Pentoxide in FLAKES purity is greater than 98%, and iron level is less than 0.01%, and water-insoluble is less than 0.02%.
4, the preparation method of organophosphorus ester according to claim 1 is characterized in that the organophosphorus ester for preparing is a colourless transparent liquid, viscosity 5～100 centipoises, phosphorus content 1～13%.
5, the preparation method of organophosphorus ester according to claim 1 is characterized in that proportioning raw materials polydimethylsiloxane 70 mass parts, Vanadium Pentoxide in FLAKES 30 mass parts; Control condition: 70 rev/mins of stirring velocitys, 155～170 ℃ of controlled temperature.
6, the preparation method of organophosphorus ester according to claim 1 is characterized in that proportioning raw materials polydimethylsiloxane 97.8 mass parts, Vanadium Pentoxide in FLAKES 2.2 mass parts; Control condition: stirring velocity is more than 70 rev/mins, 130～155 ℃ of controlled temperature.
7, a kind of preparation method of organophosphorus ester is characterized in that with organo-siloxane and Vanadium Pentoxide in FLAKES be raw material, and wherein the raw material organo-siloxane is selected hexamethyldisiloxane for use, proportioning raw materials hexamethyldisiloxane 70 mass parts, Vanadium Pentoxide in FLAKES 30 mass parts; Control condition: stirring velocity is more than 70 rev/mins, 100～125 ℃ of controlled temperature.
8, the preparation method of organophosphorus ester according to claim 7 is characterized in that the raw material hexamethyldisiloxane is a transparent liquid, viscosity 0.412 centipoise, and 100～101 ℃ of boiling points, density 0.7619g/ml, purity is greater than 95%; Vanadium Pentoxide in FLAKES purity is greater than 98%, and iron level is less than 0.01%, and water-insoluble is less than 0.02%.
9, the preparation method of organophosphorus ester according to claim 7 is characterized in that organophosphorus ester viscosity 5.2 centipoises that prepare, and phosphorus content is 12.95%, product yield 98.2%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100382302A CN100503622C (en) | 2006-02-09 | 2006-02-09 | Organophosphorus ester preparation method |
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| CNB2006100382302A CN100503622C (en) | 2006-02-09 | 2006-02-09 | Organophosphorus ester preparation method |
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| CN1807437A CN1807437A (en) | 2006-07-26 |
| CN100503622C true CN100503622C (en) | 2009-06-24 |
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102079758B (en) * | 2009-11-30 | 2013-09-11 | 中国中化股份有限公司 | Preparation method of phosphorus-silicon compound |
| CN103408587B (en) * | 2013-08-30 | 2016-04-20 | 湖北兴发化工集团股份有限公司 | A kind of preparation method of silica-based phosphoric acid ester |
| CN108892780B (en) * | 2018-05-31 | 2021-01-26 | 江苏邦杰防腐保温科技有限公司 | High-temperature-resistant organic silicon phosphate resin and preparation method thereof, and high-temperature-resistant coating and preparation method thereof |
| CN109503653B (en) * | 2018-12-25 | 2021-08-24 | 苏州祺添新材料有限公司 | Synthesis method of tri (trihydrocarbylsilyl) phosphate |
| CN111378135A (en) * | 2020-04-30 | 2020-07-07 | 新纳奇材料科技江苏有限公司 | Preparation method of low-viscosity alkoxy-terminated polydimethylsiloxane |
| CN115403611B (en) * | 2022-11-02 | 2023-01-31 | 江苏华盛锂电材料股份有限公司 | Preparation method of tris (trimethylsilyl) phosphate |
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Non-Patent Citations (2)
| Title |
|---|
| 聚醚/磷酸酯改性聚硅氧烷的合成. 王桂莲等.天津工业大学学报，第23卷第1期. 2004 |
| 聚醚/磷酸酯改性聚硅氧烷的合成. 王桂莲等.天津工业大学学报，第23卷第1期. 2004 * |
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Owner name: JIANGSU HONGDA NEW MATERIALS CO., LTD. Free format text: FORMER OWNER: JIANGSU HONGDA CHEMICAL NEW MATERIAL CO., LTD. Effective date: 20091016 |
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Effective date of registration: 20091016 Address after: Jiangsu province Yangzhong Mingzhu square Jiangsu Hongda new material Limited by Share Ltd Patentee after: Jiangsu Hongda New Material Co., Ltd. Address before: Jiangsu Yangzhong Mingzhu square Jiangsu Hongda Chemical new material Limited by Share Ltd Patentee before: Jiangsu Hongda Chemical New Material Co., Ltd. |
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