CN105693758A - Preparation method of trimerization isocyan urea acid ester silane - Google Patents
Preparation method of trimerization isocyan urea acid ester silane Download PDFInfo
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- CN105693758A CN105693758A CN201610144249.9A CN201610144249A CN105693758A CN 105693758 A CN105693758 A CN 105693758A CN 201610144249 A CN201610144249 A CN 201610144249A CN 105693758 A CN105693758 A CN 105693758A
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- trimerization
- chloroalkylalkoxylsilane
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- silane
- naocn
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
- C07F7/1872—Preparation; Treatments not provided for in C07F7/20
- C07F7/1892—Preparation; Treatments not provided for in C07F7/20 by reactions not provided for in C07F7/1876 - C07F7/1888
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
Abstract
The invention relates to a synthesis method of trimerization isocyan urea acid ester silane and belongs to the technical field of organic chemistry. According to the method, sodium cyanate and chlorine hydrocarbon alkoxy silane serve as raw materials, a condensation polymerization reaction is conducted under the action of a phase transfer catalyst and a polycondensation promotion agent, after chlorine alkyl silane is converted, filtrate is filtered, generated sodium chloride salt is filtered, the trimerization isocyan urea acid ester silane is obtained, and the general formula is [RX(RO)3-XSi(CH2)nNCO]3. The method is simple in operation, no solvent is needed, product purity is high, and the method is suitable for industrial production.
Description
Technical field
The present invention relates to the synthetic method of a kind of trimerization isocyanurate silane, belong to technical field of organic chemistry。
Background technology
The famous scientist's Huffman of Germany is found that three NCOs react and can generate isocyanide arteries and veins acid esters。Three poly-isocyanurates are owing to there being stable isocyanuric acid ester heterocycle structure in molecule, thus volatility is low, toxicity is little, storage stability is good, compared with biuret, there is more excellent weatherability, thermostability, light stability, viscosity is low, Article Stiffness Determination is high, is therefore widely used in polyurethane material。
Chinese patent CN101805366 " preparation method of three (the silica-based propyl group of 3-trimethoxy) isocyanuric acid ester " is with 3-NCO propyl trimethoxy silicane for monomer, polycondensation reaction is carried out under catalysts and solvents existence condition, filtrate concentration after being filtered by reactant obtains three (the silica-based propyl group of 3-trimethoxy) isocyanuric acid ester crude product, obtains sterling then through post processing。The catalyst that the method adopts is sodium acetate, Feldalat NM etc., and the solvent of employing is DMF, N, N-diethylformamide etc., and reaction temperature, at 80-250 DEG C, adopts molecular distillation to be easily separated purification。Technology path is as follows:
But the raw material 3-NCO propyl trimethoxy silicane that the method uses is expensive, and adopts the method for molecular distillation to be easily separated purification and also make industrial volume production be difficult to carry out。
US Patent No. 2006013093 " preparation method of silicyl isocyanuric acid fat " provides a kind of method preparing silylisocyanurate, the method is using carboxylic acid ammonium, alkali metal carboxylate or alkaline earth metal carboxylation as Cracking catalyst, silyl-carbamate is made to be cracked into isocyanates, then proceed to be polymerized under the catalytic action of carboxylate, form silylisocyanurate。Technology path is as follows:
The catalyst that this reaction is commonly used is lithium formate, sodium formate etc., and reaction temperature is 160-250 DEG C。Due to higher reaction temperature, side reaction is more serious, and the trimer extent of reaction is aggravated, and polymer increases, and the different final products viscosity that causes increases, and owing to system is in alkalescence, trimer easily turns yellow, and has a strong impact on the application performance of product。
Summary of the invention
It is an object of the invention to: provide a kind of without solvent, the preparation method of the trimerization isocyanurate silane being suitable to industrialized production simple to operate。
The technical scheme is that
A kind of preparation method of trimerization isocyanurate silane；It is characterized in that: it comprises the following steps:
1), equipped with mechanical agitation, thermometer, spherical condensation tube reactor in add Sodium cyanate (NaOCN), γ-chloroalkylalkoxylsilane, the short poly-agent of quaternary ammonium salt catalyst and tertiary amine salt；
2), by reactor it is positioned in heat collecting type constant temperature blender with magnetic force, opens mechanical agitation, and to arrange oil temperature be 130 DEG C；
3), when reacting liquid temperature rises to 130 DEG C, due to Sodium cyanate (NaOCN) and γ-chloroalkylalkoxylsilane exothermic heat of reaction, temperature of charge can rise to 135 DEG C, now keeps reaction temperature at 130-140 DEG C, reacts 4h；
4), sample by gas chromatographic detection γ-chloroalkylalkoxylsilane content after reaction 4h, after γ-chloroalkylalkoxylsilane content deteriorates to less than 1%, cooling, it is cooled to after under 50 DEG C until material, filter, to filter the sodium chloride salt of generation, obtain three (3-trimethoxy propyl group is silica-based) isocyanuric acid ester crude product；
5) low boil, by crude product is evaporated off under negative pressure, and vapo(u)rizing temperature controls at 80-90 DEG C, and distillation vacuum cannot be less than 0.98MPa, distills 2h, obtains three (3-trimethoxy propyl group is silica-based) isocyanuric acid ester finished product。
The mol ratio of described Sodium cyanate (NaOCN) and γ-chloroalkylalkoxylsilane is (1-1.2): 1。
Sodium cyanate (NaOCN) is anhydrous Sodium cyanate (NaOCN) or the Sodium cyanate (NaOCN) after dehydration, it is desirable to moisture is less than 0.1%。
Described γ-chloroalkylalkoxylsilane is any one in r-chloropropyl trimethoxyl silane, chloropropyl triethoxysilane, chloropropyl three positive propoxy silane, chloropropylmethyldimethoxysilane, chloropropyl diethoxy silane。
Described quaternary ammonium salt catalyst is any one in tetrabutyl ammonium bromide, tetraethylammonium bromide, 4-propyl bromide, 4 bromide, Tetramethylammonium hydroxide, benzyltriethylammoinium chloride；Preferentially select tetrabutyl ammonium bromide；
The described 1-2% that quaternary ammonium salt catalyst charge is γ-chloroalkylalkoxylsilane quality。
The short poly-agent of described tertiary amine salt is triethylamine, and triethylamine addition is the 0.5-1% of γ-chloroalkylalkoxylsilane quality
The formula of the compound trimerization isocyanurate silane of present invention synthesis is [RX(RO)3-XSi(CH2)nNCO]3。
X=0,1,2,3,
N=1,2,3,4,5,6 ... 12,
R is alkane, to be carbon atom the be alkane of 1-12 or the cycloalkane that carbon atom is 5-8。
Chemical equation of the present invention is as follows:
The invention has the advantages that:
By the present invention in that the phase transfer catalyst with suitable carrys out the carrying out of catalytic reaction, namely the organoalkoxysilanes such as Sodium cyanate (NaOCN) and r-chloropropyl trimethoxyl silane can be reacted under solvent-free existence condition, avoid employing nitrogen, nitrogen dimethylformamide, nitrogen, the use of the high boiling solvents such as nitrogen diethyl acetamide, meets the requirement of green economy environmental protection。Simultaneously by substantial amounts of experiment screening, it has been found that add a small amount of tertiary amine in the reaction and can significantly improve the selectivity of reaction, generate highly purified isocyanuric acid ester silane product。Short poly-agent selects lower boiling tertiary amines material, after having reacted, is evaporated off at low temperatures so that it is do not end up in product, so can improve the stability that product is deposited, it is to avoid product turns yellow or viscosity increases, and impacts without to the application performance in product later stage。
Detailed description of the invention
Embodiment 1:
Equipped with churned mechanically, thermometer, spherical condensation tube 1000ml four-hole boiling flask in add 150g Sodium cyanate (NaOCN), 400g r-chloropropyl trimethoxyl silane, 4g tetrabutyl ammonium bromide, 2g triethylamine。Four-hole boiling flask is positioned in heat collecting type constant temperature blender with magnetic force, open mechanical agitation, and to arrange oil temperature be 130 DEG C, when reacting liquid temperature rises to 130 DEG C, due to Sodium cyanate (NaOCN) and r-chloropropyl trimethoxyl silane exothermic heat of reaction, temperature of charge can rise to 135 DEG C, now keeps reaction temperature at 130-140 DEG C, reacts 4h。Then sample by gas chromatographic detection r-chloropropyl trimethoxyl silane content, after r-chloropropyl trimethoxyl silane content deteriorates to less than 1%, cooling, it is cooled to after under 50 DEG C until material, filter, filter the sodium chloride salt of generation, obtain three (3-trimethoxy propyl group is silica-based) isocyanuric acid ester crude product。Crude product is evaporated off low boiling under negative pressure, and vapo(u)rizing temperature controls at 80-90 DEG C, and distillation vacuum cannot be less than 0.98MPa, and namely distillation 2h obtains three (3-trimethoxy propyl group is silica-based) isocyanuric acid ester finished product。Adopting liquid chromatographic detection, its content is 98.9%。
Embodiment 2:
Equipped with churned mechanically, thermometer, spherical condensation tube 1000ml four-hole boiling flask in add 150g Sodium cyanate (NaOCN), 480g chloropropyl triethoxysilane, 5g tetrabutyl ammonium bromide, 1g triethylamine。Four-hole boiling flask is positioned in heat collecting type constant temperature blender with magnetic force, open mechanical agitation, and to arrange oil temperature be 130 DEG C, when reacting liquid temperature rises to 130 DEG C, due to Sodium cyanate (NaOCN) and chloropropyl triethoxysilane exothermic heat of reaction, temperature of charge can rise to 135 DEG C, now keeps reaction temperature at 130-140 DEG C, reacts 4h。Then sample by gas chromatographic detection chloropropyl triethoxysilane content, after chloropropyl triethoxysilane content deteriorates to less than 1%, cooling, it is cooled to after under 50 DEG C until material, filter, filter the sodium chloride salt of generation, obtain three (3-triethoxy propyl group is silica-based) isocyanuric acid ester crude product。Crude product is evaporated off low boiling under negative pressure, and vapo(u)rizing temperature controls at 80-90 DEG C, and distillation vacuum cannot be less than 0.98MPa, and namely distillation 2h obtains three (3-triethoxy propyl group is silica-based) isocyanuric acid ester product。Adopting liquid chromatographic detection, its content is 98.3%。
Embodiment 3:
Equipped with churned mechanically, thermometer, spherical condensation tube 1000ml four-hole boiling flask in add 150g Sodium cyanate (NaOCN), 364g chloropropylmethyldimethoxysilane, 4g tetrabutyl ammonium bromide, 1g triethylamine。Four-hole boiling flask is positioned in heat collecting type constant temperature blender with magnetic force, open mechanical agitation, and to arrange oil temperature be 130 DEG C, when reacting liquid temperature rises to 130 DEG C, due to Sodium cyanate (NaOCN) and chloropropylmethyldimethoxysilane exothermic heat of reaction, temperature of charge can rise to 135 DEG C, now keeps reaction temperature at 130-140 DEG C, reacts 4h。Then sample by gas chromatographic detection chloropropylmethyldimethoxysilane content, after chloropropylmethyldimethoxysilane content deteriorates to less than 1%, cooling, it is cooled to after under 50 DEG C until material, filter, filter the sodium chloride salt of generation, obtain three (3-methyl dimethoxy oxygen base propyl group is silica-based) isocyanuric acid ester crude product。Then crude product is evaporated off low boiling under negative pressure, and vapo(u)rizing temperature controls at 80-90 DEG C, and distillation vacuum cannot be less than 0.98MPa, and distillation 2h obtains, three (3-methyl dimethoxy oxygen base propyl group is silica-based) isocyanuric acid ester finished product。Adopting liquid chromatographic detection, its content is 97.2%。
Embodiment 4:
Equipped with churned mechanically, thermometer, spherical condensation tube 1000ml four-hole boiling flask in add 150g Sodium cyanate (NaOCN), 420g chloropropyl diethoxy silane, 4g tetrabutyl ammonium bromide, 1g triethylamine。Four-hole boiling flask is positioned in heat collecting type constant temperature blender with magnetic force, open mechanical agitation, and to arrange oil temperature be 130 DEG C, when reacting liquid temperature rises to 130 DEG C, due to Sodium cyanate (NaOCN) and chloropropyl diethoxy silane exothermic heat of reaction, temperature of charge can rise to 135 DEG C, now keeps reaction temperature at 130-140 DEG C, reacts 4h。Then sample by gas chromatographic detection chloropropyl diethoxy silane content, after chloropropyl diethoxy silane content deteriorates to less than 1%, cooling, it is cooled to after under 50 DEG C until material, filter, filter the sodium chloride salt of generation, three (3-methyl diethoxy propyl group is silica-based) isocyanuric acid ester crude product。Crude product is evaporated off low boiling under negative pressure, and vapo(u)rizing temperature controls at 80-90 DEG C, and distillation vacuum cannot be less than 0.98MPa, and distillation 2h obtains, three (3-methyl diethoxy propyl group is silica-based) isocyanuric acid ester finished product。Adopting liquid chromatographic detection, its content is 98.7%。
Embodiment 5:
Equipped with churned mechanically, thermometer, spherical condensation tube 1000ml four-hole boiling flask in add 150g Sodium cyanate (NaOCN), 564g chloropropyl three positive propoxy silane, 6g tetrabutyl ammonium bromide, 2g triethylamine。Four-hole boiling flask is positioned in heat collecting type constant temperature blender with magnetic force, open mechanical agitation, and to arrange oil temperature be 130 DEG C, when reacting liquid temperature rises to 130 DEG C, now due to Sodium cyanate (NaOCN) and chloropropyl three positive propoxy silane reaction heat release, temperature of charge can rise to 135 DEG C, now keeps reaction temperature at 130-140 DEG C, reacts 4h。Then sample by gas chromatographic detection chloropropyl three positive propoxy silane contents, after chloropropyl three positive propoxy silane contents deteriorates to less than 1%, cooling, it is cooled to after under 50 DEG C until material, filter, filter the sodium chloride salt of generation, obtain three (3-positive propoxy propyl group is silica-based) isocyanuric acid ester crude product。Then crude product is evaporated off low boiling under negative pressure, and vapo(u)rizing temperature controls at 80-90 DEG C, and distillation vacuum cannot be less than 0.98MPa, and namely distillation 2h obtains three (3-positive propoxy propyl group is silica-based) isocyanuric acid ester product。Adopting liquid chromatographic detection, its content is 96.5%。
Claims (7)
1. the preparation method of a trimerization isocyanurate silane；It is characterized in that: it comprises the following steps:
1), equipped with mechanical agitation, thermometer, spherical condensation tube reactor in add Sodium cyanate (NaOCN), γ-chloroalkylalkoxylsilane, the short poly-agent of quaternary ammonium salt catalyst and tertiary amine salt；
2), by reactor it is positioned in heat collecting type constant temperature blender with magnetic force, opens mechanical agitation, and to arrange oil temperature be 130 DEG C；
3), when reacting liquid temperature rises to 130 DEG C, Sodium cyanate (NaOCN) and γ-chloroalkylalkoxylsilane exothermic heat of reaction, temperature of charge can rise to 135 DEG C, now keeps reaction temperature at 130-140 DEG C, reacts 4h；
4), sample by gas chromatographic detection γ-chloroalkylalkoxylsilane content after reaction 4h, after γ-chloroalkylalkoxylsilane content deteriorates to less than 1%, cooling, it is cooled to after under 50 DEG C until material, filter, to filter the sodium chloride salt of generation, obtain three (3-trimethoxy propyl group is silica-based) isocyanuric acid ester crude product；
5) low boil, by crude product is evaporated off under negative pressure, and vapo(u)rizing temperature controls at 80-90 DEG C, and distillation vacuum cannot be less than 0.98MPa, and distillation 2h obtains, three (3-trimethoxy propyl group is silica-based) isocyanuric acid ester finished product。
2. the preparation method of a kind of trimerization isocyanurate silane according to claim 1；It is characterized in that: the mol ratio of described Sodium cyanate (NaOCN) and γ-chloroalkylalkoxylsilane is (1-1.2): 1。
3. the preparation method of a kind of trimerization isocyanurate silane according to claim 1；It is characterized in that: described Sodium cyanate (NaOCN) is anhydrous Sodium cyanate (NaOCN) or the Sodium cyanate (NaOCN) after dehydration, it is desirable to moisture is less than 0.1%。
4. the preparation method of a kind of trimerization isocyanurate silane according to claim 1；It is characterized in that: described γ-chloroalkylalkoxylsilane is any one in r-chloropropyl trimethoxyl silane, chloropropyl triethoxysilane, chloropropyl three positive propoxy silane, chloropropylmethyldimethoxysilane, chloropropyl diethoxy silane。
5. the preparation method of a kind of trimerization isocyanurate silane according to claim 1；It is characterized in that: described quaternary ammonium salt catalyst is any one in tetrabutyl ammonium bromide, tetraethylammonium bromide, 4-propyl bromide, 4 bromide, Tetramethylammonium hydroxide, benzyltriethylammoinium chloride；Preferentially select tetrabutyl ammonium bromide。
6. the preparation method of a kind of trimerization isocyanurate silane according to claim 5；It is characterized in that: the described 1-2% that quaternary ammonium salt catalyst charge is γ-chloroalkylalkoxylsilane quality。
7. the preparation method of a kind of trimerization isocyanurate silane according to claim 1；It is characterized in that: the short poly-agent of described tertiary amine salt is triethylamine, and triethylamine addition is the 0.5-1% of γ-chloroalkylalkoxylsilane quality。
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| CN201610144249.9A CN105693758A (en) | 2016-03-15 | 2016-03-15 | Preparation method of trimerization isocyan urea acid ester silane |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113292591A (en) * | 2021-06-23 | 2021-08-24 | 唐山三孚新材料有限公司 | Synthesis method and application of 1, 3-bis (isocyanatoalkyl) -1,1,3, 3-tetramethyldisiloxane |
| CN115403609A (en) * | 2022-05-09 | 2022-11-29 | 江苏瑞洋安泰新材料科技有限公司 | Preparation method of tris [3- (trimethoxysilyl) propyl ] isocyanurate |
Citations (4)
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| US3821218A (en) * | 1967-09-20 | 1974-06-28 | Gen Electric | Nitrogen-containing organosilicon materials |
| US4196289A (en) * | 1978-03-31 | 1980-04-01 | Nippon Kasei Chemical Co., Ltd. | Process for producing triallyl isocyanurate |
| US5905150A (en) * | 1997-08-27 | 1999-05-18 | General Electric Company | Process for preparing organosilanes |
| CN101133069A (en) * | 2005-03-03 | 2008-02-27 | 瓦克化学股份公司 | Method for producing alkoxysilyl methyl isocyanurates |
-
2016
- 2016-03-15 CN CN201610144249.9A patent/CN105693758A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3821218A (en) * | 1967-09-20 | 1974-06-28 | Gen Electric | Nitrogen-containing organosilicon materials |
| US4196289A (en) * | 1978-03-31 | 1980-04-01 | Nippon Kasei Chemical Co., Ltd. | Process for producing triallyl isocyanurate |
| US5905150A (en) * | 1997-08-27 | 1999-05-18 | General Electric Company | Process for preparing organosilanes |
| CN101133069A (en) * | 2005-03-03 | 2008-02-27 | 瓦克化学股份公司 | Method for producing alkoxysilyl methyl isocyanurates |
Non-Patent Citations (1)
| Title |
|---|
| 朱玲: "三烯丙基异氰尿酸酯的合成研究", 《中国石油大学（华东）硕士学位论文》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113292591A (en) * | 2021-06-23 | 2021-08-24 | 唐山三孚新材料有限公司 | Synthesis method and application of 1, 3-bis (isocyanatoalkyl) -1,1,3, 3-tetramethyldisiloxane |
| CN115403609A (en) * | 2022-05-09 | 2022-11-29 | 江苏瑞洋安泰新材料科技有限公司 | Preparation method of tris [3- (trimethoxysilyl) propyl ] isocyanurate |
| CN115403609B (en) * | 2022-05-09 | 2023-11-03 | 江苏瑞洋安泰新材料科技有限公司 | Preparation method of tris [3- (trimethoxysilyl) propyl ] isocyanurate |
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