CN109734914B - Phosphorus-containing organic silicon resin and preparation method thereof - Google Patents
Phosphorus-containing organic silicon resin and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a phosphorus-containing organic silicon resin and a preparation method thereof, wherein the preparation method comprises the following steps: under the action of heating and acid catalyst, phosphate or phosphite ester and silane containing different alkoxy groups are hydrolyzed and polymerized to obtain phosphorus modified organic silicon resin with corresponding structure.
Description
Technical Field
The invention relates to the field of silicone resin synthesis, in particular to a phosphorus-containing organic silicon resin and a preparation method thereof.
Background
The organic silicon resin has important application in the fields of weather-proof, high temperature resistant, insulation, flame retardation, ultraviolet radiation resistant coatings and the like, the structural composition of the organic silicon resin is very important for the performance of the organic silicon resin, the requirements on the relevant performance of the organic silicon resin are higher and higher along with the continuous upgrading of the application requirements, and in order to improve the relevant performance of the organic silicon resin, other functional units are introduced into the structure of the organic silicon resin, which is the most common method.
In the published patent CN 101671568, the authors disclose a method for preparing a phosphorus-containing silicone resin flame retardant, in which a chlorinated phosphate precursor and a silicone resin are separately synthesized, and then the two are subjected to a condensation reaction of amino and P-Cl bond under the action of an acid-binding agent to form a phosphorus-containing silicone resin with a corresponding structure in the publication, wherein the silicone resin simultaneously contains phosphorus, nitrogen and silicon units with flame retardant effect, so as to exhibit a better synergistic flame retardant effect; a phosphorus-containing polysiloxane prepared by condensation of amino groups and P-Cl bonds is also disclosed in document CN 1631942.
In the invention patent CN 103224707, a preparation method of an interwoven compound of organic silicon resin and phosphoric acid polyol ester melamine is disclosed, in the method, firstly, phosphoric acid and polyol are subjected to esterification reaction to form phosphoric acid polyol ester, then unreacted phosphoric acid groups in phosphate ester and melamine are subjected to neutralization reaction to form salt, and silicon resin containing a curing catalyst is blended in the salt while the salt is formed, and is heated and cured to form a final interwoven compound, the interwoven compound shows better temperature resistance and flame retardant performance, in the interwoven compound in the publication, the organic silicon resin and the phosphoric acid polyol ester melamine are only interwoven together after being cured, and no chemical bond is formed between the organic silicon resin and the phosphoric acid polyol ester melamine.
Patent CN 106700078 discloses a method for preparing a one-dimensional polysiloxane compound with side chains containing phosphorus, nitrogen and silicon by using hydrogen-containing silicone oil as a precursor, introducing a silicon-containing side chain and a glycidyl ether structure containing an epoxy group through a hydrosilylation/vinyl addition reaction, reacting the epoxy group with an active phosphorus component under the action of triphenylphosphine or triethanolamine catalyst to form a P-C bond, and reacting in one step to obtain the one-dimensional polysiloxane compound with side chains containing phosphorus, nitrogen and silicon, wherein the compound also has a relatively good flame retardant effect.
The method for synthesizing the phosphorus-modified organic silicon compound needs to synthesize the organic silicon polymer firstly and then carry out 'post-modification', and is a 'top-down' method, the process is complicated when related products are prepared, and the modified organic silicon polymer material has high cost; in view of the technical deficiencies and drawbacks, the present invention provides a direct synthesis method from bottom to top, in which a suitable phosphorus-containing small molecule is directly polymerized with a silane related to the synthesis of an organic silicon resin under the action of a catalyst, and the method has a simple process and is easy to adjust the structure of the resin.
Disclosure of Invention
The invention aims to simplify the process for synthesizing the phosphorus-containing organic silicon resin and provides a preparation method of phosphorus-modified organic silicon resin.
The invention relates to a phosphorus-containing organic silicon resin, which has a structural general formula as follows:
(PO1.5)h(R1 3SiO0.5)i(R2 2SiO)j(R3SiO1.5)k(SiO2)l
or (OPO)1.5)h(R1 3SiO0.5)i(R2 2SiO)j(R3SiO1.5)k(SiO2)l。
Wherein each R1，R2，R3Is independently a saturated alkyl group of 1 to 10 carbon atoms, such as methyl, ethyl, propylAlkyl, butyl, cyclohexyl, etc., or aromatic hydrocarbon groups such as phenyl, benzyl, phenethyl, etc.; h is an integer greater than 0; j, k, l are independent integers not less than 0, and at least one is not 0; i is an integer greater than 0.
Specific examples of the phosphorus-containing silicone resin may be, but are not limited to:
(PO1.5)h(Me3SiO0.5)i(Me2SiO)j(MeSiO1.5)k(SiO2)l
(PO1.5)h(Me3SiO0.5)i(Me2SiO)j(MeSiO1.5)k
(PO1.5)h(Me3SiO0.5)i(Me2SiO)j(SiO2)l
(PO1.5)h(Me3SiO0.5)i(Me2SiO)j(MeSiO1.5)k(SiO2)l
(OPO1.5)h(Me3SiO0.5)i(Me2SiO)j(MeSiO1.5)k(SiO2)l
(OPO1.5)h(Me3SiO0.5)i(Me2SiO)j(MeSiO1.5)k
(OPO1.5)h(Me3SiO0.5)i(Me2SiO)j(SiO2)l
(OPO1.5)h(Me3SiO0.5)i(Me2SiO)j(MeSiO1.5)k(SiO2)l。
preferably, the mole fraction of phosphorus-containing units in the phosphorus-containing silicone resin is 0.1-8%, and more preferably 0.5-3%.
Preferably, the mole fraction of methyl groups in the phosphorus-containing silicone resin is 80-100%, and more preferably 95-100%.
The preparation method of the phosphorus-containing organic silicon resin comprises the following steps.
(1) Weighing 0-5.0 parts by mole of tetraalkoxysilane, 0-5.0 parts by mole of trialkoxysilane, 0-5.0 parts by mole of dialkoxysilane and 0.1-1.0 part by mole of phosphite ester or phosphate ester, uniformly mixing, and dissolving in ethanol to obtain a mixture 1.
(2) And placing the mixture 1 in a constant-pressure dropping funnel, dropping the mixture into a three-neck flask containing catalyst/water, setting the temperature to be 30-100 ℃, introducing nitrogen or argon into a reaction system when phosphite ester is used, and reacting for 1-4 hours to obtain a mixture 2.
(3) And (3) dripping 0.5-8.0 molar parts of monoalkoxysilane into the mixture 2, continuously reacting at 30-100 ℃ for 1-2 hours, adding an organic solvent insoluble with water into the mixed solution after reaction to extract corresponding resin, washing the organic solvent layer for three times by using a sodium bicarbonate solution, drying by using a drying agent, and then performing rotary evaporation to remove the organic solvent to obtain the target phosphorus-containing organic silicon resin.
The alkoxysilanes used above have the following general formula:
R4 xSi(OR5)4-x。
wherein R is4，R5Is independent saturated alkyl with 1-10 carbon atoms, such as methyl, ethyl, propyl, butyl, cyclohexyl, etc., or aromatic alkyl, such as phenyl, benzyl, phenethyl, etc., and x is a positive integer of 0-4.
Specific examples of tetraalkoxysilanes can be, but are not limited to:
Si(OMe)4
Si(OEt)4。
specific examples of trialkoxysilanes can be, but are not limited to:
MeSi(OMe)3
MeSi(OEt)3
EtSi(OMe)3
EtSi(OEt)3。
specific examples of dialkoxysilanes can be, but are not limited to:
Me2Si(OMe)2
Me2Si(OEt)2
Et2Si(OMe)2
Et2Si(OEt)2。
specific examples of monoalkoxysilanes can be, but are not limited to:
Me3Si(OMe)
Me3Si(OEt)
Et3Si(OMe)
Et3Si(OEt) 。
preferably, the molar fraction of methyl groups in the silane hydrocarbyl groups is 85 to 100%, more preferably 95 to 100%.
The phosphate esters used in the present invention have the general formula O = P (OR)7)3The phosphite has the formula P (OR)6)3Wherein R is6，R7Is independently saturated alkyl with 1-10 carbon atoms, such as methyl, ethyl, propyl, butyl, cyclohexyl, etc., or aromatic alkyl, such as phenyl, benzyl, phenethyl, etc.
Examples of phosphates or phosphites may be, but are not limited to:
O=P(OMe)3
O=P(OEt)3
P(OMe)3
P(OEt)3。
the catalyst used in the invention can be inorganic acid base or organic acid base, and comprises any one of hydrochloric acid, sulfuric acid, acetic acid, trifluoroacetic acid, trifluoromethanesulfonic acid, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide and concentrated ammonia water.
The organic solvent used in the invention comprises one or more of toluene, benzene, xylene, ethyl acetate, acetone, butanone, dichloromethane, chloroform and carbon tetrachloride.
The drying agent used in the invention is any one of calcium chloride, sodium sulfate and 4A molecular sieve.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments; all other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1.
Weighing 3.5 moles of methyl orthosilicate and 0.4 mole of triethyl phosphite or triethyl phosphate, uniformly mixing, dissolving in 100g of ethanol, placing in a constant-pressure dropping funnel, dropping the mixed solution into a three-neck flask containing 50mL of concentrated hydrochloric acid/50 mL of water, setting the temperature to be 70 ℃, dropping 2 moles of monomethoxysilane into the reaction mixture after reacting for 2 hours, continuing to react for 1 hour, adding 200mL of chloroform into the reacted mixed solution, separating a lower chloroform layer, washing three times (50 mL of 3) with saturated sodium bicarbonate solution, drying the washed chloroform solution with anhydrous calcium chloride, and performing rotary evaporation to remove a chloroform solvent to obtain a white solid, namely the phosphorus-containing organic silicon resin.
Example 2.
Weighing 0.5 mol of trimethoxy silane, 3.0 mol of dimethoxy silane and 0.7 mol of triethyl phosphite or triethyl phosphate, uniformly mixing, dissolving in 100g of ethanol, placing in a constant pressure dropping funnel, dropping the mixed solution into a three-neck flask containing 50mL of concentrated sulfuric acid/50 mL of water, setting the temperature at 80 ℃, after reacting for 3 hours, dropping 2 mol of monomethoxy silane into the reaction mixture, continuing to react for 1 hour, adding 200mL of chloroform into the mixed solution after the reaction, separating a lower chloroform layer, washing three times (50 mL of 3) with saturated sodium bicarbonate solution, drying the washed chloroform solution with anhydrous calcium chloride, and then performing rotary evaporation to remove chloroform solvent to obtain colorless oily matter, namely the phosphorus-containing organic silicon resin.
Example 3.
Weighing 0.2 mol of methyl orthosilicate, 0.3 mol of trimethoxy silane, 4 mol of dimethoxy silane and 0.5 mol of triethyl phosphite or triethyl phosphate, uniformly mixing, dissolving in 150g of ethanol, placing in a constant pressure dropping funnel, dropping the mixed solution into a three-neck flask containing 70mL of concentrated sulfuric acid/70 mL of water, setting the temperature at 80 ℃, after reacting for 3 hours, dropping 2 mol of monomethoxy silane into the reaction mixture, continuing to react for 1 hour, adding 300mL of chloroform into the mixed solution after the reaction, separating a lower chloroform layer, washing three times (70 mL of 3) with a saturated sodium bicarbonate solution, drying the washed chloroform solution with anhydrous calcium chloride, and then performing rotary evaporation to remove a chloroform-imitation solvent to obtain a colorless viscous oily substance, namely the phosphorus-containing organic silicon resin.
The synthesized phosphorus-containing organic silicon resin is structurally improved, and a phosphorus-containing unit is introduced, so that the introduction of the unit is expected to further improve the temperature resistance, flame retardance and other properties of the organic silicon resin.
Claims (6)
1. A preparation method of phosphorus-containing organic silicon resin is characterized by comprising the following steps:
(1) weighing 0-5.0 parts by mole of tetraalkoxysilane, 0-5.0 parts by mole of trialkoxysilane, 0-5.0 parts by mole of dialkoxysilane and 0.1-1.0 part by mole of phosphite ester or phosphate ester, uniformly mixing, dissolving in ethanol to obtain a mixture 1,
(2) placing the mixture 1 in a constant pressure dropping funnel, dropping the mixture into a three-neck flask containing catalyst/water, setting the temperature to be 30-100 ℃, introducing nitrogen or argon into a reaction system when phosphite ester is used, reacting for 1-4 hours to obtain a mixture 2,
(3) dripping 0.5-8.0 molar parts of monoalkoxysilane into the mixture 2, continuously reacting at 30-100 ℃ for 1-2 hours, adding an organic solvent insoluble with water into the mixed solution after reaction to extract corresponding resin, washing the organic solvent layer for three times by using a sodium bicarbonate solution, drying by using a drying agent, and then removing the organic solvent by rotary evaporation to obtain the target phosphorus-containing organic silicon resin;
the structural general formula of the prepared phosphorus-containing organic silicon resin is as follows:
(PO1.5)h(R1 3SiO0.5)i(R2 2SiO)j(R3SiO1.5)k(SiO2)l
or (OPO)1.5)h(R1 3SiO0.5)i(R2 2SiO)j(R3SiO1.5)k(SiO2)l
Wherein each R1，R2，R3Is independent saturated alkyl or aromatic alkyl with 1-10 carbon atoms; h is an integer greater than 0; j, k, l are independent integers not less than 0, and at least one is not 0; i is an integer greater than 0; the molar fraction of phosphorus-containing units is 0.1-8%.
2. The method for producing the phosphorus-containing silicone resin according to claim 1, characterized in that: the tetraalkoxysilane, trialkoxysilane, dialkoxysilane and monoalkoxysilane have the following general formulas:
R4 xSi(OR5)4-x
wherein R is4，R5Is independent saturated alkyl or aromatic alkyl with 1-10 carbon atoms, and x is a positive integer of 0-4.
3. The method for producing the phosphorus-containing silicone resin according to claim 1, characterized in that: the phosphite ester has the general formula P (OR)6)3The phosphate ester has the general formula O = P (OR)7)3Wherein R is6，R7Is an independent saturated alkyl or aromatic alkyl with 1-10 carbon atoms.
4. The method for producing the phosphorus-containing silicone resin according to claim 1, characterized in that: the catalyst is any one of hydrochloric acid, sulfuric acid, acetic acid, trifluoroacetic acid, trifluoromethanesulfonic acid, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide and concentrated ammonia water.
5. The method for producing the phosphorus-containing silicone resin according to claim 1, characterized in that: the organic solvent is at least one of toluene, benzene, xylene, ethyl acetate, acetone, butanone, dichloromethane, chloroform and carbon tetrachloride.
6. The method for producing the phosphorus-containing silicone resin according to claim 1, characterized in that: the drying agent is any one of calcium chloride, sodium sulfate and a 4A molecular sieve.
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| CN114031779B (en) * | 2021-11-01 | 2023-02-28 | 兰州瑞朴科技有限公司 | Phosphorus-containing ladder-shaped polysiloxane, preparation method thereof and application of phosphorus-containing ladder-shaped polysiloxane as flame-retardant synergist |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1875053A (en) * | 2003-11-06 | 2006-12-06 | 电化学工业有限公司（国际） | Method for the production of organosiloxanes modified by a phosponic acid ester |
| US7700711B2 (en) * | 2007-03-02 | 2010-04-20 | Chung Shan Institute Of Science And Technology, Armaments Bureau, M.N.D. | Manufacturing method of ladder-like phosphorous-containing polysilsesquioxanes nanocomposite material |
| CN101935399A (en) * | 2010-07-28 | 2011-01-05 | 杭州师范大学 | Method for preparing phosphorus-containing organosilicon flame retardant |
| CN102079758A (en) * | 2009-11-30 | 2011-06-01 | 中国中化股份有限公司 | Preparation method of phosphorus-silicon compound |
| CN102886069A (en) * | 2012-09-24 | 2013-01-23 | 华南理工大学 | Method for preparing sol-gel bioglass-high polymer hybrid material |
| CN103080192A (en) * | 2010-05-20 | 2013-05-01 | 道康宁公司 | Polymer compositions containing alkoxysilanes |
| EP2593497A1 (en) * | 2010-05-20 | 2013-05-22 | Dow Corning Corporation | Silicone resins and their use in polymer compositions |
| CN103946276A (en) * | 2011-11-17 | 2014-07-23 | 道康宁公司 | Silicone resins |
| CN108794751A (en) * | 2017-04-28 | 2018-11-13 | 中蓝晨光化工研究设计院有限公司 | One kind resin fire retardant of structural silicone containing phosphonitrile and preparation method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2593496A1 (en) * | 2010-05-20 | 2013-05-22 | Dow Corning Corporation | Polymer compositions containing alkoxysilanes |
-
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- 2019-01-15 CN CN201910033623.1A patent/CN109734914B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1875053A (en) * | 2003-11-06 | 2006-12-06 | 电化学工业有限公司（国际） | Method for the production of organosiloxanes modified by a phosponic acid ester |
| US7700711B2 (en) * | 2007-03-02 | 2010-04-20 | Chung Shan Institute Of Science And Technology, Armaments Bureau, M.N.D. | Manufacturing method of ladder-like phosphorous-containing polysilsesquioxanes nanocomposite material |
| CN102079758A (en) * | 2009-11-30 | 2011-06-01 | 中国中化股份有限公司 | Preparation method of phosphorus-silicon compound |
| CN103080192A (en) * | 2010-05-20 | 2013-05-01 | 道康宁公司 | Polymer compositions containing alkoxysilanes |
| EP2593497A1 (en) * | 2010-05-20 | 2013-05-22 | Dow Corning Corporation | Silicone resins and their use in polymer compositions |
| CN101935399A (en) * | 2010-07-28 | 2011-01-05 | 杭州师范大学 | Method for preparing phosphorus-containing organosilicon flame retardant |
| CN103946276A (en) * | 2011-11-17 | 2014-07-23 | 道康宁公司 | Silicone resins |
| CN102886069A (en) * | 2012-09-24 | 2013-01-23 | 华南理工大学 | Method for preparing sol-gel bioglass-high polymer hybrid material |
| CN108794751A (en) * | 2017-04-28 | 2018-11-13 | 中蓝晨光化工研究设计院有限公司 | One kind resin fire retardant of structural silicone containing phosphonitrile and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| Hydrolysis-condensation reactions of diethylphosphato-ethyltriethoxysilane involved in organic-inorganic talc-like hybrid synthesis: liquid and solid-state NMR investigations;A. Garnier et al;《RSC Advances》;20160801(第6期);第312-321页 * |
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