CN111763321A - Preparation method of propyl silane oligomer product - Google Patents
Preparation method of propyl silane oligomer product Download PDFInfo
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- CN111763321A CN111763321A CN202010735213.4A CN202010735213A CN111763321A CN 111763321 A CN111763321 A CN 111763321A CN 202010735213 A CN202010735213 A CN 202010735213A CN 111763321 A CN111763321 A CN 111763321A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/045—Polysiloxanes containing less than 25 silicon atoms
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/06—Preparatory processes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/06—Preparatory processes
- C08G77/08—Preparatory processes characterised by the catalysts used
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/32—Post-polymerisation treatment
- C08G77/34—Purification
Abstract
The invention relates to a preparation method of propyl silane oligomer products, belonging to the technical field of fine chemical engineering. The invention takes propyl alkoxy silane crude product (pH = 7) and tap water as raw materials, concentrated hydrochloric acid as catalyst, trisodium trithiocyanate as metal trapping agent, alcohol as solvent, and adopts hydrolysis and condensation process to synthesize propyl silane oligomer product, because of using the trisodium trithiocyanate metal trapping agent, can well remove metal ions which are dissolved by the propyl trichlorosilane and corrode a storage tank and a conveying pipeline, compared with the synthesis method for synthesizing the propyl silane oligomer product by hydrolyzing the propyl alkoxy silane product, the propyl alkoxy silane does not need a distillation process and does not produce a byproduct of propyl alkoxy silane heavy components, so the synthesis method of the patent is economic and environment-friendly, in addition, the synthesized propyl silane oligomer product has low cost and low price, can be comprehensively popularized to the field of building waterproof materials, and solves the problems of inventory and environmental protection brought by propyl alkoxy silane.
Description
Technical Field
The invention relates to a preparation method of propyl silane oligomer products, belonging to the technical field of fine chemical engineering.
Background
In recent years, silane monomolecular derivative oligomers have the characteristics of low VOC, strong bonding, high boiling point, low volatility, high crosslinking, low dosage, yellowing resistance, good water resistance and the like, and are widely used in the fields of coatings, adhesives, sealants, plastics, powder, metals, water resistance and the like, so the research on the silane derivative oligomerization technology is widely concerned at home and abroad, functional siloxane oligomers (also called silane oligomers) are functional organic silicon polymers with low viscosity, few chain segments and high functionality formed by hydrolysis/condensation of one or more than two silane coupling agents, modified organic polymers of the functional siloxane oligomers have excellent compatibility and molecular controllability, the heat resistance, impact resistance, bonding, lubrication, flame retardance, pollution resistance, wear resistance, solvent resistance, air permeability and the like of polymer materials can be obviously improved, for example, aminoalkyl block copolymer oligomeric siloxanes not only show excellent wettability to material interfaces, and can form chemical bonds with the interface of materials difficult to be adhered, which have strong weather resistance and moisture resistance, wherein amino groups provide chemical fields capable of reacting with active matrix polymers, and alkyl groups impart excellent hydrophobicity, so that it is widely used in paints, adhesives, sealants and the like to improve the adhesion and wettability with inorganic surfaces, plastic surfaces.
At present, organosilicone waterproofing agents are widely researched and applied to building waterproofing materials, alkyl silicate organosilicone waterproofing agents such as methyl sodium silicate, ethyl sodium silicate and phenyl sodium silicate which are widely used in the market can be condensed into a waterproofing membrane under the action of water and CO2, the waterproofing membrane surrounds particles of concrete, so that the base material is hydrophobic, free access of water vapor is not hindered, the air permeability of the base material is ensured, the impermeability and the durability are improved, other performances of the base material cannot be improved, the silicate is a water-soluble polymer with low molecular weight, the silicate can run off along with the washing of rainwater, and the hydrophobicity can lose within months or two years. On the other hand, in industrial production, the production of by-products of 20% by mass of the product is accompanied, and the demand is rapidly increasing with the expansion of the application field thereof, thereby leading to the occurrence of a large amount of by-products, the main components of which are tetraalkoxysilane and propylalkoxysilane, which can be sold, and the propylalkoxysilane which is small in the market and cannot be completely sold.
Disclosure of Invention
The invention aims to: the preparation method of the propyl silane oligomer product is economic and environment-friendly, and the synthesized product can be comprehensively popularized to the field of building waterproof materials and can realize industrial production.
The technical scheme of the invention is as follows:
a process for the preparation of a propyl silane oligomer product, comprising the steps of:
1) the method comprises the following steps of adding a crude propyl alkoxysilane (pH = 7), trisodium trithiocyanate and a solvent into a four-neck flask connected with a reflux condenser (connected with a cooling circulating water device) and a thermometer, and adding tap water, the solvent and a hydrochloric acid catalyst into a constant-pressure dropping funnel connected with the four-neck flask, wherein the mass ratio of the trisodium trithiocyanate to the crude propyl alkoxysilane is 0.5-1%: 1, the molar ratio of tap water to the crude propyl alkoxysilane is 0.8: 1, the ratio of the crude propyl alkoxy silane to the solvent in the four-neck flask is 3.0: 1, the mass ratio of tap water to solvent in the constant-pressure funnel is 1: 1, the hydrochloric acid catalyst is 0.05 to 0.1 percent of crude propyl alkoxy silane,
2) after the material preparation is finished, opening a magnetic stirrer, starting a constant-temperature heating device, slowly and uniformly dropping a mixture material in a constant-pressure dropping funnel into a four-neck flask to perform hydrolysis reaction and hydroxyl condensation reaction after the temperature of a kettle reaches 60 ℃, and controlling the temperature of the kettle to be 60-70 ℃ in the hydrolysis reaction process;
3) after the dropwise addition of the mixed materials is finished, controlling the temperature of the kettle to be 60-70 ℃, and carrying out an aging reaction for 2 hours to ensure that the tap water reacts completely;
4) after the reaction is finished, gradually heating the four-neck flask to raise the temperature, and evaporating the solvent in the four-neck flask until the solvent is distilled;
5) after the solvent distillation is finished, reducing the temperature of a kettle of the four-mouth flask to 50-60 ℃, then adding a proper amount of decolorant into the flask to decolor and adsorb, heating the four-mouth flask gradually to decolor and adsorb, wherein the decoloring and adsorbing time is 5 hours,
6) and after the decoloring and adsorption processes are finished, cooling the kettle in the four-neck flask to room temperature, and filtering to obtain a colorless and transparent propyl silane oligomer product.
The reaction equation of the present invention is as follows:
5C3H7Si(OR)3+ 4H2O → RO[C3H7Si(OR)O]5R+ 8ROH
in the formula, R is a hydrocarbyl group such as methyl, ethyl, isopropyl and the like.
In order to verify the influence of the whole process of catalyst and decoloration and adsorption on the product quality, the inventor carries out a comparative test, and the result is as follows:
table 1: influence of catalyst feed ratio on the product:
table 2: the kettle temperature in the whole decoloring and adsorption process is controlled to be 110-120 ℃, and the influence of the decoloring kettle temperature on the product quality is as follows:
the invention has the following effects:
the invention takes propyl alkoxy silane crude product (pH = 7) and tap water as raw materials, concentrated hydrochloric acid as catalyst, trisodium trithiocyanate as metal trapping agent, alcohol as solvent, and adopts hydrolysis and condensation process to synthesize propyl silane oligomer product, because of using the trisodium trithiocyanate metal trapping agent, can well remove metal ions which are dissolved by the propyl trichlorosilane and corrode a storage tank and a conveying pipeline, compared with the synthesis method for synthesizing the propyl silane oligomer product by hydrolyzing the propyl alkoxy silane product, the propyl alkoxy silane does not need a distillation process and does not produce a byproduct of propyl alkoxy silane heavy components, so the synthesis method of the patent is economic and environment-friendly, in addition, the synthesized propyl silane oligomer product has low cost and low price, can be comprehensively popularized to the field of building waterproof materials, and solves the problems of inventory and environmental protection brought by propyl alkoxy silane.
Detailed Description
Example 1
820g of crude propyltrimethoxysilane (pH = 7), 5g of trithiocyanuric acid trisodium salt and 273g of methanol are put into a four-neck flask connected with a reflux condenser (connected with a cooling circulating water device) and a thermometer, 72g of tap water, 72g of methanol and 0.5g of hydrochloric acid catalyst are put into a constant-pressure dropping funnel connected with the four-neck flask, after the materials are prepared, a magnetic stirrer is opened, a constant-temperature heating device is started, after the temperature of a kettle reaches 60 ℃, a mixture in the constant-pressure dropping funnel is slowly and uniformly dropped into the four-neck flask for hydrolysis reaction and hydroxyl condensation reaction, the temperature of the kettle is controlled to be 60-70 ℃ in the hydrolysis reaction process, after the dropping of the mixture is finished, the temperature of the kettle is controlled to be 60-70 ℃ for aging reaction for 2 hours, the tap water is ensured to be reacted completely, after the reaction is finished, the four-neck flask is gradually heated to evaporate the methanol in the, until the methanol distillation is finished; after the methanol distillation is finished, reducing the temperature of a kettle of a four-neck flask to 50-60 ℃, then adding a proper amount of decolorant into the flask to decolor and adsorb, heating the four-neck flask gradually to decolor and adsorb, wherein the time for decoloring and adsorbing is 5h, the temperature of the kettle in the whole process of decoloring and adsorbing is controlled to be 110-120 ℃, after the decoloring and adsorbing process is finished, reducing the temperature of the kettle in the four-neck flask to room temperature, and then filtering to obtain a colorless and transparent propyl silane oligomer product, wherein the chromaticity (Pt-Co) of the product is 10, the free chlorine of the product is 18ppm, and the molar yield of the product is 99.4%.
Example 2
820g of crude propyltrimethoxysilane (pH = 7), 8g of trithiocyanuric acid trisodium salt and 273g of methanol are put into a four-neck flask connected with a reflux condenser (connected with a cooling circulating water device) and a thermometer, 72g of tap water, 72g of methanol and 0.5g of hydrochloric acid catalyst are put into a constant-pressure dropping funnel connected with the four-neck flask, after the materials are prepared, a magnetic stirrer is opened, a constant-temperature heating device is started, after the temperature of the kettle reaches 60 ℃, mixture materials in the constant-pressure dropping funnel are slowly and uniformly dropped into the four-neck flask for hydrolysis reaction and hydroxyl condensation reaction, the temperature of the kettle is controlled to be 60-70 ℃ in the hydrolysis reaction process, after the dropping of the mixture materials is finished, the temperature of the kettle is controlled to be 60-70 ℃ for aging reaction for 2 hours, the tap water is ensured to be reacted completely, after the reaction is finished, the four-neck flask is gradually heated to evaporate the methanol in, until the methanol distillation is finished; after the methanol distillation is finished, reducing the temperature of a kettle of a four-neck flask to 50-60 ℃, then adding a proper amount of decolorant into the flask to decolor and adsorb, heating the four-neck flask gradually to heat and decolor and adsorb, wherein the time for decoloring and adsorbing is 5h, the temperature of the kettle in the whole process of decoloring and adsorbing is controlled to be 110-120 ℃, after the decoloring and adsorbing process is finished, reducing the temperature of the kettle in the four-neck flask to room temperature, and then filtering to obtain a colorless and transparent propyl silane oligomer product, wherein the chromaticity (Pt-Co) of the product is 10, the free chlorine of the product is 3ppm, and the molar yield of the product is 99.2%.
Example 3
1030g of crude propyltriethoxysilane (pH = 7), 10g of trithiocyanuric acid trisodium salt and 343g of ethanol are put into a four-neck flask connected with a reflux condenser (connected with a cooling circulating water device) and a thermometer, 72g of tap water, 72g of ethanol and 0.6g of hydrochloric acid catalyst are put into a constant-pressure dropping funnel connected with the four-neck flask, after the materials are prepared, a magnetic stirrer is opened, a constant-temperature heating device is started, after the temperature of a kettle reaches 60 ℃, a mixture material in the constant-pressure dropping funnel is slowly and uniformly dropped into the four-neck flask for hydrolysis reaction and hydroxyl condensation reaction, the temperature of the kettle is controlled to be 60-70 ℃ in the hydrolysis reaction process, after the dropping of the mixture material is finished, the temperature of the kettle is controlled to be 60-70 ℃ for aging reaction for 2 hours, the tap water is ensured to be reacted completely, after the reaction is finished, the four-neck flask is gradually heated, the ethanol in the, until the ethanol is distilled; after the ethanol distillation is finished, reducing the temperature of a kettle of a four-neck flask to 50-60 ℃, then adding a proper amount of decolorant into the flask to decolor and adsorb, heating the four-neck flask gradually to heat and decolor and adsorb, wherein the time for decoloring and adsorbing is 5h, the temperature of the kettle in the whole process of decoloring and adsorbing is controlled to be 110-120 ℃, after the decoloring and adsorbing process is finished, reducing the temperature of the kettle in the four-neck flask to room temperature, and then filtering to obtain a colorless and transparent propyl silane oligomer product, wherein the chromaticity (Pt-Co) of the product is 10, the free chlorine of the product is 5ppm, and the molar yield of the product is 99.6%.
Example 4
1240g of a crude product of propyltriisopropoxysilane (pH = 7), 12g of trithiocyanuric acid trisodium salt and 413g of isopropanol are added into a four-neck flask connected with a reflux condenser and a thermometer, 72g of tap water, 72g of isopropanol and 0.9g of a hydrochloric acid catalyst are added into a constant-pressure dropping funnel connected with the four-neck flask, after the materials are prepared, a magnetic stirrer is opened, a constant-temperature heating device is started, after the temperature of a kettle reaches 60 ℃, a mixture material in the constant-pressure dropping funnel is slowly and uniformly dropped into the four-neck flask for hydrolysis reaction and hydroxyl condensation reaction, the temperature of the kettle is controlled to be 60-70 ℃ in the hydrolysis reaction process, after the dropping of the mixture material is finished, the temperature of the kettle is controlled to be 60-70 ℃, an aging reaction is carried out for 2 hours, the tap water is ensured to be completely reacted, after the reaction is finished, the four-neck flask is gradually heated, the isopropanol in the four-neck flask, until the isopropanol is distilled; after the isopropanol is distilled, the temperature of a kettle of a four-neck flask is reduced to 50-60 ℃, then an appropriate amount of decolorant is added into the flask for decoloration and adsorption, then the four-neck flask is gradually heated to raise the temperature for decoloration and adsorption, the time for decoloration and adsorption is 5h, the temperature of the kettle in the whole process of decoloration and adsorption is controlled to be 110-120 ℃, after the decoloration and adsorption process is completed, the temperature of the kettle in the four-neck flask is reduced to room temperature, and then filtration is carried out to obtain a colorless and transparent propyl silane oligomer product, wherein the chromaticity (Pt-Co) of the product is 10, the free chlorine of the product is 2ppm, and the molar yield of the product is 99.5%.
Claims (1)
1. A process for the preparation of a propyl silane oligomer product, comprising the steps of:
1) the method comprises the following steps of adding a crude propyl alkoxysilane (pH = 7), trisodium trithiocyanate and a solvent into a four-neck flask connected with a reflux condenser (connected with a cooling circulating water device) and a thermometer, and adding tap water, the solvent and a hydrochloric acid catalyst into a constant-pressure dropping funnel connected with the four-neck flask, wherein the mass ratio of the trisodium trithiocyanate to the crude propyl alkoxysilane is 0.5-1%: 1, the molar ratio of tap water to the crude propyl alkoxysilane is 0.8: 1, the ratio of the crude propyl alkoxy silane to the solvent in the four-neck flask is 3.0: 1, the mass ratio of tap water to solvent in the constant-pressure funnel is 1: 1, the hydrochloric acid catalyst is 0.05-0.1% of a crude product of propyl alkoxy silane;
2) after the material preparation is finished, opening a magnetic stirrer, starting a constant-temperature heating device, slowly and uniformly dropping a mixture material in a constant-pressure dropping funnel into a four-neck flask to perform hydrolysis reaction and hydroxyl condensation reaction after the temperature of a kettle reaches 60 ℃, and controlling the temperature of the kettle to be 60-70 ℃ in the hydrolysis reaction process;
3) after the dropwise addition of the mixed materials is finished, controlling the temperature of the kettle to be 60-70 ℃, and carrying out an aging reaction for 2 hours to ensure that the tap water reacts completely;
4) after the reaction is finished, gradually heating the four-neck flask to raise the temperature, and evaporating the solvent in the four-neck flask until the solvent is distilled;
5) after the solvent distillation is finished, reducing the temperature of a kettle of the four-mouth flask to 50-60 ℃, then adding a proper amount of decolorant into the flask to decolor and adsorb, gradually heating the four-mouth flask to decolor and adsorb, wherein the decoloring and adsorbing time is 5 hours, and the temperature of the kettle in the whole process of decoloring and adsorbing is controlled to be 110-120 ℃;
6) and after the decoloring and adsorption processes are finished, cooling the kettle in the four-neck flask to room temperature, and filtering to obtain a colorless and transparent propyl silane oligomer product.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6069259A (en) * | 1998-02-06 | 2000-05-30 | Rensselaer Polytechnic Institute | Multifunctional polymerizible alkoxy siloxane oligomers |
| CN102580668A (en) * | 2012-02-17 | 2012-07-18 | 四川银邦硅业有限公司 | Alkoxy silane high-boiling residue decoloring agent and decoloring method |
| CN102634028A (en) * | 2012-04-08 | 2012-08-15 | 荆州市江汉精细化工有限公司 | Method for preparing modified tetraethoxysilane by use of waste in production of 3-chloropropyltrichlorosilane |
-
2020
- 2020-07-28 CN CN202010735213.4A patent/CN111763321A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6069259A (en) * | 1998-02-06 | 2000-05-30 | Rensselaer Polytechnic Institute | Multifunctional polymerizible alkoxy siloxane oligomers |
| CN102580668A (en) * | 2012-02-17 | 2012-07-18 | 四川银邦硅业有限公司 | Alkoxy silane high-boiling residue decoloring agent and decoloring method |
| CN102634028A (en) * | 2012-04-08 | 2012-08-15 | 荆州市江汉精细化工有限公司 | Method for preparing modified tetraethoxysilane by use of waste in production of 3-chloropropyltrichlorosilane |
Non-Patent Citations (1)
| Title |
|---|
| 杨建高: ""三聚硫氰酸三钠盐的应用及研究进展"", 《化工中间体》 * |
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