CN111333843A - Preparation method of alkoxy-terminated polysiloxane - Google Patents

Preparation method of alkoxy-terminated polysiloxane Download PDF

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Publication number
CN111333843A
CN111333843A CN202010247664.3A CN202010247664A CN111333843A CN 111333843 A CN111333843 A CN 111333843A CN 202010247664 A CN202010247664 A CN 202010247664A CN 111333843 A CN111333843 A CN 111333843A
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polysiloxane
terminated
alkoxy
molecular weight
weight regulator
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CN111333843B (en
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何业明
刘勇
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Orange Sky New Materials Guangzhou Co ltd
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Orange Sky New Materials Guangzhou Co ltd
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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
    • C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
    • C08G77/18—Polysiloxanes containing silicon bound to oxygen-containing groups to alkoxy or aryloxy groups
    • 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
    • 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
    • C08G77/80—Siloxanes having aromatic substituents, e.g. phenyl side groups

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Silicon Polymers (AREA)

Abstract

The invention discloses a preparation method of alkoxy-terminated polysiloxane, which comprises the following steps: (1) adding a hydrocarbyl-terminated linear polysiloxane with the viscosity of 100,000-300,000mPa.s and a dimeric siloxane terminating agent into a reactor according to a certain proportion, wherein the main chain silicon of the hydrocarbyl-terminated linear polysiloxane has two side groups, and the side groups are alkyl or phenyl; (2) stirring and mixing the raw materials in the step (1), heating to a certain temperature, and adding a molecular weight regulator for reacting for a certain time; (3) and (3) reacting the crude product for a certain time at a certain temperature and under a certain vacuum degree, and decomposing the residual molecular weight regulator to obtain the alkoxy end-capped polysiloxane. The alkoxy-terminated polysiloxane prepared by the method has the advantages of low silicon hydroxyl value, less impurities, safe and efficient reaction, simple steps and no waste discharge in the process.

Description

Preparation method of alkoxy-terminated polysiloxane
The technical field is as follows:
the invention relates to the field of synthesis of organic silicon polymers, and particularly relates to a preparation method of alkoxy-terminated polysiloxane.
Background art:
with the development of industrial technology, the varieties of adhesives such as low-odor, environment-friendly and corrosion-free room-temperature curing organosilicon sealant and pouring sealant increasingly become hot spots of industrial research and development, and the development of the organosilicon adhesives needs high-quality alkoxy-terminated polysiloxane as a raw material.
The preparation method of the alkoxy-terminated polysiloxane in the prior art mainly comprises two methods, namely, one method is to prepare the alkoxy-terminated polysiloxane by using chlorosilane such as dimethyldichlorosilane and the like as raw materials through alcoholysis, hydrolysis, neutralization and filtration, and the other method is to prepare the alkoxy-terminated polysiloxane by using α omega-dihydroxy polydimethyl as raw materials, using ammonium salt, carboxylic acid, organic amine or alkali as catalysts, using excessive micromolecular alkoxy silane such as trimethoxy silane, tetramethoxy silane or vinyl trimethoxy silane as an end-capping agent, capping, neutralizing, distilling and the like.
The invention content is as follows:
the invention provides a preparation method of alkoxy-terminated polysiloxane aiming at the defects of the method. The method comprises the following steps of selecting easily obtained commercial hydrocarbyl-terminated linear polysiloxane which has the viscosity of 100,000-300,000mPa.s and does not contain silicon hydroxyl as an initial raw material, wherein the main chain silicon of the hydrocarbyl-terminated linear polysiloxane is provided with two side groups, the side groups are alkyl or phenyl, and the side groups and the end groups do not contain hydroxyl, so that halogen and silicon hydroxyl introduced by the raw materials are completely avoided; the dimeric siloxane is selected as the end-capping reagent, has a chemical structure similar to that of the finished alkoxy end-capping polysiloxane, and after the end-capping is finished, the residual end-capping reagent does not need to be removed by a distillation process with operation risk and can be remained to be a part of the finished product; the raw materials are subjected to molecular weight regulation and end-capping reaction under the action of heat by an alkaline molecular weight regulator to obtain an alkoxy end-capped polysiloxane product with target viscosity; the selected molecular weight regulator can be heated and decomposed after the reaction is finished, so that the complicated operations such as neutralization, filtration and the like are avoided. The alkoxy-terminated polysiloxane prepared by the method can realize the characteristics of low silicon hydroxyl value, less impurities, safe and efficient reaction, simple steps, no waste discharge and the like.
The technical scheme provided by the invention comprises the following steps:
(1) adding a hydrocarbyl-terminated linear polysiloxane with the viscosity of 100,000-300,000mPa.s and a dimeric siloxane terminating agent into a reactor according to a certain proportion, wherein the hydrocarbyl-terminated linear polysiloxane main chain silicon has two side groups, the side groups are alkyl or phenyl, and the side groups and the end groups do not contain hydroxyl;
(2) stirring and mixing the raw materials in the step (1), heating to a certain temperature, adding an alkaline molecular weight regulator, and reacting for a certain time;
(3) and (3) reacting the crude product obtained by the reaction in the step (2) for a certain time at a certain temperature and under a certain vacuum degree, and decomposing the residual molecular weight regulator to obtain the alkoxy end-capped polysiloxane with the viscosity smaller than that of the raw material alkyl end-capped polysiloxane.
The preferable hydrocarbyl-terminated linear polysiloxane of step (1) is α, omega-dimethyl polydimethylsiloxane having the formula (CH)3)3Si[OSi(CH3)2]nOSi(CH3)3Or α, omega-divinylpolydimethylsiloxanes of the formula (CH)2＝CH2)(CH3)2Si[OSi(CH3)2]nOSi(CH3)2(CH2＝CH2)。
The preferred dimeric siloxane end-capping agent of step (1) is 1,1,3, 3-tetramethyl-1, 3-bis (2-trimethoxysilylethylene) disiloxane having the formula (CH)3O)3SiCH2CH2Si(CH3)2OSi(CH3)2CH2CH2Si(OCH3)3Or 1,1,3, 3-tetramethyl-1, 3-bis (2-triethoxysilylethylene) disiloxane, of formula (CH)3CH2O)3SiCH2CH2Si(CH3)2OSi(CH3)2CH2CH2Si(OCH2CH3)3。
Preferably, the molecular weight regulator in step (2) is one of anhydrous tetramethylammonium hydroxide, anhydrous tetraethylammonium hydroxide and anhydrous tetrapropylammonium hydroxide.
The mass ratio of the alkyl-terminated linear polysiloxane to the end-capping agent in the reaction is 100 (5-15), and the amount of the molecular weight regulator is 20-150ppm of the mass of the alkyl-terminated linear polysiloxane.
Preferably, the raw materials in the step (2) are stirred and mixed, the temperature is increased to 80-110 ℃, and then a molecular weight regulator is added for reaction for 1-2.5 h;
preferably, in the step (3), the crude product is reacted for 1-3h at the temperature of 130-180 ℃ and the vacuum degree of-0.03 to-0.06 MPa, and the residual molecular weight regulator is decomposed.
The specific implementation mode is as follows:
the present invention will be further described with reference to the following specific examples, but the present invention is not limited thereto.
Example 1
Adding 100 parts by mass of hydrocarbyl-terminated linear polysiloxane (the main chain silicon has two side groups, the side groups are alkyl or phenyl, and the side groups and the end groups do not contain hydroxyl) with the viscosity of 100,000mPa.s and 15 parts by mass of dimeric siloxane end-capping reagent into a reactor with heating and stirring functions, fully and uniformly stirring, heating to 90 ℃, adding 100ppm of anhydrous tetramethylammonium hydroxide calculated according to the mass of the hydrocarbyl-terminated linear polysiloxane, reacting for 2.5 hours at constant temperature, vacuumizing to-0.06 MPa, heating to 130 ℃, and continuing to react for 2 hours to obtain colorless and transparent liquid, namely alkoxy-terminated polysiloxane with the viscosity of 22,000 mPa.s.
Example 2
Adding 100 parts by mass of hydrocarbyl-terminated linear polysiloxane (the main chain silicon has two side groups, the side groups are alkyl or phenyl, and the side groups and the end groups do not contain hydroxyl) with the viscosity of 200,000mPa.s and 15 parts by mass of dimeric siloxane end-capping reagent into a reactor with heating and stirring functions, fully and uniformly stirring, heating to 90 ℃, adding 50ppm of anhydrous tetramethylammonium hydroxide calculated according to the mass of the hydrocarbyl-terminated linear polysiloxane, reacting for 2.5 hours at constant temperature, vacuumizing to-0.06 MPa, heating to 130 ℃, and continuing to react for 2 hours to obtain colorless and transparent viscous liquid, namely alkoxy-terminated polysiloxane with the viscosity of 62,500 mPa.s.
Example 3
Adding 100 parts by mass of hydrocarbyl-terminated linear polysiloxane (the main chain silicon has two side groups, the side groups are alkyl or phenyl, and the side groups and the end groups do not contain hydroxyl) with the viscosity of 300,000mPa.s and 15 parts by mass of dimeric siloxane end-capping reagent into a reactor with heating and stirring functions, fully and uniformly stirring, heating to 90 ℃, adding 50ppm of anhydrous tetramethylammonium hydroxide calculated according to the mass of the hydrocarbyl-terminated linear polysiloxane, reacting for 2.5 hours at constant temperature, vacuumizing to-0.06 MPa, heating to 130 ℃, and continuing to react for 2 hours to obtain colorless and transparent viscous liquid, namely alkoxy-terminated polysiloxane with the viscosity of 99,500 mPa.s.
Example 4
Adding 100 parts by mass of α, omega-dimethyl polydimethylsiloxane with the viscosity of 150,000mPa.s and 5 parts by mass of 1,1,3, 3-tetramethyl-1, 3-di (2-triethoxysilylethylene) disiloxane into a reactor with heating and stirring functions, fully and uniformly stirring, heating to 80 ℃, adding 20ppm of anhydrous tetrapropylammonium hydroxide calculated according to the mass of α, omega-dimethyl polydimethylsiloxane, reacting for 1 hour at constant temperature, vacuumizing to-0.03 MPa, heating to 150 ℃, and continuing to react for 3 hours to obtain colorless and transparent viscous liquid, namely alkoxy-terminated polydimethylsiloxane with the viscosity of 48,800 mPa.s.
Example 5
Adding 100 parts by mass of α, omega-divinyl polydimethylsiloxane with the viscosity of 250,000mPa.s and 10 parts by mass of 1,1,3, 3-tetramethyl-1, 3-bis (2-trimethoxysilylethylene) disiloxane into a reactor with heating and stirring functions, fully stirring uniformly, heating to 110 ℃, adding 150ppm of anhydrous tetraethylammonium hydroxide calculated according to the mass of α, omega-dimethyl polydimethylsiloxane, reacting at constant temperature for 2 hours, vacuumizing to-0.06 MPa, heating to 180 ℃, and continuing to react for 1 hour to obtain colorless and transparent viscous liquid, namely alkoxy-terminated polydimethylsiloxane with the viscosity of 87,800 mPa.s.

Claims (7)

1. A method of preparing an alkoxy-terminated polysiloxane, comprising the steps of:
(1) adding a hydrocarbyl-terminated linear polysiloxane with the viscosity of 100,000-300,000mPa.s and a dimeric siloxane terminating agent into a reactor according to a certain proportion, wherein the main chain silicon of the hydrocarbyl-terminated linear polysiloxane has two side groups, and the side groups are alkyl or phenyl;
(2) stirring and mixing the raw materials in the step (1), heating to a certain temperature, adding an alkaline molecular weight regulator, and reacting for a certain time;
(3) and (3) reacting the crude product obtained by the reaction in the step (2) for a certain time at a certain temperature and under a certain vacuum degree, and decomposing the residual molecular weight regulator to obtain the alkoxy end-capped polysiloxane with the viscosity smaller than that of the raw material alkyl end-capped linear polysiloxane.
2. The method of claim 1, wherein the linear alkyl-terminated polysiloxane of step (1) is α omega-dimethylpolysiloxane of the formula (CH)3)3Si[OSi(CH3)2]nOSi(CH3)3Or α, omega-divinylpolydimethylsiloxanes of the formula (CH)2＝CH2)(CH3)2Si[OSi(CH3)2]nOSi(CH3)2(CH2＝CH2)。
3. The method of producing an alkoxy-terminated polysiloxane according to claim 1, wherein: the dimeric siloxane end-capping agent in the step (1) is 1,1,3, 3-tetramethyl-1, 3-bis (2-trimethoxysilylethylene) disiloxane, and the molecular formula of the dimeric siloxane end-capping agent is (CH)3O)3SiCH2CH2Si(CH3)2OSi(CH3)2CH2CH2Si(OCH3)3Or 1,1,3, 3-tetramethyl-1, 3-bis (2-triethoxysilylidene)Ethyl) disiloxane of formula (CH)3CH2O)3SiCH2CH2Si(CH3)2OSi(CH3)2CH2CH2Si(OCH2CH3)3。
4. The method of producing an alkoxy-terminated polysiloxane according to claim 1, wherein: the molecular weight regulator in the step (2) is one of anhydrous tetramethylammonium hydroxide, anhydrous tetraethylammonium hydroxide and anhydrous tetrapropylammonium hydroxide.
5. The method of producing an alkoxy-terminated polysiloxane according to claim 1, wherein: the mass ratio of the alkyl-terminated linear polysiloxane to the end-capping agent is 100 (5-15), and the amount of the molecular weight regulator is 20-150ppm of the mass of the alkyl-terminated linear polysiloxane.
6. The method of producing an alkoxy-terminated polysiloxane according to claim 1, wherein: and (3) stirring and mixing the raw materials in the step (2), heating to 80-110 ℃, adding a molecular weight regulator, and reacting for 1-2.5 h.
7. The method of producing an alkoxy-terminated polysiloxane according to claim 1, wherein: and (3) decomposing the residual molecular weight regulator by reacting the crude product for 1-3h at the temperature of 130-.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115505126A (en) * 2022-07-08 2022-12-23 橙天新材料(广州)有限公司 Preparation method of beta-siloxane-terminated polydimethylsiloxane

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB792470A (en) * 1953-12-14 1958-03-26 Union Carbide Corp Alkoxy-terminated siloxane polymers
CN101646717A (en) * 2006-12-28 2010-02-10 道康宁东丽株式会社 Catalyst for dealcoholization condensation reaction and method for producing organopolysiloxane using the same
CN106519246A (en) * 2016-11-21 2017-03-22 成都硅宝科技股份有限公司 Polyalkyloxy-terminated polysiloxane and preparation method thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB792470A (en) * 1953-12-14 1958-03-26 Union Carbide Corp Alkoxy-terminated siloxane polymers
CN101646717A (en) * 2006-12-28 2010-02-10 道康宁东丽株式会社 Catalyst for dealcoholization condensation reaction and method for producing organopolysiloxane using the same
CN106519246A (en) * 2016-11-21 2017-03-22 成都硅宝科技股份有限公司 Polyalkyloxy-terminated polysiloxane and preparation method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
周菊兴: "《合成树脂与塑料工艺》", 31 August 2000, 化学工业出版社 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115505126A (en) * 2022-07-08 2022-12-23 橙天新材料(广州)有限公司 Preparation method of beta-siloxane-terminated polydimethylsiloxane
CN115505126B (en) * 2022-07-08 2023-06-06 橙天新材料(广州)有限公司 Preparation method of beta-end siloxane-based polydimethylsiloxane

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