WO2017185737A1 - A method for preparing organopolysiloxane resins - Google Patents

A method for preparing organopolysiloxane resins Download PDF

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WO2017185737A1
WO2017185737A1 PCT/CN2016/107621 CN2016107621W WO2017185737A1 WO 2017185737 A1 WO2017185737 A1 WO 2017185737A1 CN 2016107621 W CN2016107621 W CN 2016107621W WO 2017185737 A1 WO2017185737 A1 WO 2017185737A1
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silane
acid
mentioned
organopolysiloxane resins
methyl
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PCT/CN2016/107621
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French (fr)
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Zhenhong Huang
Xianhui Chen
Jinshu WU
Huan JI
Runming LIU
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Guangdong Biomax Si&F New Material Co., Ltd.
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Application filed by Guangdong Biomax Si&F New Material Co., Ltd. filed Critical Guangdong Biomax Si&F New Material Co., Ltd.
Priority to US16/096,700 priority Critical patent/US10815339B2/en
Priority to EP16900242.5A priority patent/EP3448918B1/en
Publication of WO2017185737A1 publication Critical patent/WO2017185737A1/en

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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
    • C08G77/70—Siloxanes defined by use of the MDTQ nomenclature
    • 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
    • C08G77/04—Polysiloxanes
    • C08G77/06—Preparatory processes
    • C08G77/08—Preparatory processes characterised by the catalysts used
    • 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
    • C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
    • C08G77/28—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen sulfur-containing 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
    • C08G77/32—Post-polymerisation treatment
    • C08G77/34—Purification

Definitions

  • the present invention relates to the field of polymer synthesis, in particular, it relates to a method for preparing organopolysiloxane resins.
  • Organopolysiloxane is a new type of silicone polymer material, composed of Si-O-Si backbone and functional group connected on the silicon atom. It has characteristic like smoothness, high temperature resistance, hydrophobicity, insulation etc., and widely used in many fields as electricity, electronics, construction, industrial chemicals, personal care, medical and other accessories. It includes silicone oil, silicone rubber, silicone resin and modified derivative of the above three.
  • organopolysiloxane resin Structure of organopolysiloxane resin can be classified into four units: monofunctional unit (R 3 SiO 0.5 , referred to as M unit) , difunctional unit (R 2 SiO, referred to as D unit) , trifunctional unit (RSiO 1.5 , referred to as T unit) tetrafunctional units (SiO 2 , referred to as Q unit) . It is generally believed that organopolysiloxane containing T unit or Q unit is called organopolysiloxane resin.
  • Organopolysiloxane resin has a highly crosslinked structure which is cage-like, dendritic, branched or ladder.
  • R n SiO (4-n) /2 where, 0 ⁇ n ⁇ 4, R is the same or different organic group.
  • R n SiO (4-n) /2 where, 0 ⁇ n ⁇ 4, R is the same or different organic group.
  • R is the same or different organic group.
  • the typical structure of organopolysiloxane resin is shown below.
  • Organopolysiloxane resins may be transparent liquid, or powder solid. Because of their special structure, they have excellent heat resistance, low temperature resistance, film-forming property, flexibility, water resistance and adhesive effect, etc., are widely used in pressure-sensitive adhesive, liquid silicone rubber, LED encapsulating resin, anti-sticking isolation, mold release agent, waterproofing agent, personal care ingredient. At present, three main routes to prepare organopolysiloxane resins are presented as below.
  • organopolysiloxane resins are synthesized from chlorosilanes (eg, MeSiCl 3 , Me 2 SiCl 2 , MePhSiCl 2 , Ph 2 SiCl 2 , PhSiCl 3 ) , via hydrolysis, condensation, organic solvent extraction and then concentration. Performance of the resin depends on the type and proportion of the raw material silane, pH of the hydrolysis and condensation reaction, property and amount of solvent, catalysts characteristic and process conditions. At present, many organosilicone companies and research institutes have conducted a lot of research in chlorosilane hydrolysis and applied for patents.
  • chlorosilanes eg, MeSiCl 3 , Me 2 SiCl 2 , MePhSiCl 2 , Ph 2 SiCl 2 , PhSiCl 3
  • Sol-gel is commonly used method to synthesize MQ silicone resin. First acidified aqueous solution of sodium silicate, followed by acid catalyzed condensation reaction, and then adding monofunctional M units capped, and finally wash the product with water and obtain the MQ silicone resin. At present, lots of researches have been conducted in Sol-gel method to prepare MQ silicone resin.
  • silicates Since hydrochloric acid and sodium silicate react too quickly, people prefer to use alkyl silicate as raw material, i.e., silicates.
  • lots of researches in Silicate hydrolysis and condensation method have been reported. For example, Shenzhen City of New Asia New Materials Co., Ltd.
  • organopolysiloxane resin above three methods to prepare organopolysiloxane resin are all involved in hydrolysis and condensation route, which are with complex and long processing cycle, environmental unfriendly, easy gelation, low yield, poor reproducibility, high energy consumption and other shortcomings.
  • the present invention provides a method for preparing organopolysiloxane resins, including a solvent free, one-step process without adding in water, to reduce the disadvantages of the traditional methods for preparing organopolysiloxane resins as mentioned above.
  • a method for preparing organopolysiloxane resins as mentioned in claim 1 comprises the steps of below:
  • the alkoxysilane contains at least one of Q unit, D unit and T unit
  • the capping agent contains M unit.
  • the molar ratio of M unit and sum of Q unit, T units and D unit is 0 ⁇ 40: 1.
  • the alkoxysilane includes but not limited to methyl orthosilicate, ethyl orthosilicate, methyl polysilicate ester, ethyl polysilicate, methyl trimethoxysilane, methyl triethoxysilane, ethyl trimethoxysilane, ethyl triethoxysilane, trimethoxysilane, propyl triethoxy silane, cyclohexyl trimethoxysilane, cyclohexyl triethoxysilane, trimethoxysilane, triethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, allyl triethoxysilane, phenyl trimethoxysilane, phenyl triethoxysilane, dimethyl dimethoxy silane, dimethyl diethoxy silane, methyl ethyl dimethoxysilane,
  • the capping agent includes but not limited to 1, 1, 1, 3, 3, 3-hexamethyl disiloxane, 1, 1, 3, 3-tetramethyl disiloxane, 1, 1, 3, 3-tetramethyl-1, 3-divinyldisiloxane, 1, 1, 3, 3 tetramethyl 1, 3-diphenyl disiloxane, 1, 3-dimethyl-1, 1, 3, 3-tetraphenyldisiloxane, 1, 1, 1, 3, 3, 3, 5, 5, 7, 7, 7-decamethyltetrasiloxane, 1, 1, 3, 3, 3-pentamethyl disiloxane, 1, 1, 1, 3, 5, 5, 5 heptamethyltrisiloxane, one or several of the above.
  • capping agent is a silane containing a single chlorine/alkoxy groups, including but not limited to trimethylsilyl chloride, trimethyl methoxy silane, trimethyl ethoxy silane, dimethyl vinyl chlorosilane, vinyl dimethyl methoxysilane, vinyl dimethyl ethoxy silane, dimethylchlorosilane, one or several of the above silanes.
  • the acidic compound includes an acidic compound I containing carboxyl groups, wherein the molar ratio of carboxyl group and alkoxy group contained in alkoxy silane is 0.2 ⁇ 5: 1.
  • the acidic compound I includes but not limited to formic acid, acetic acid, propionic acid, butyric acid, valeric acid, oxalic acid, benzoic acid, C6 ⁇ C26 monocarboxylic acid, succinic acid, adipic acid, phthalic acid, one or several of the above.
  • the alkoxy groups include but not limited to methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy.
  • the alkoxy groups include but not limited to ethylene glycol monomethyl ether and ethylene glycol monoethyl ether.
  • the acidic compound herein comprises an acidic compound II, the amount of acidic compound II of the total raw materials is 0.1 ⁇ 5wt %.
  • the acidic compound II includes but not limited to one or a mixture of: sulfuric acid, hydrochloric acid, phosphoric acid, trifluoromethane sulfonic acid, p-toluenesulfonic acid, ferric chloride, aluminum chloride, zinc chloride, titanium tetrachloride, tin dichloride, solid super acid, acid clay, cation exchange resin.
  • the acidic compound comprises an acidic compound III, the amount of acidic compound III of the acidic compound II is 1 ⁇ 50wt%.
  • the compound III includes but is not limited to one or a mixture of: acetic anhydride, succinic anhydride, phthalic anhydride, phosphorus pentoxide, organic acid chloride.
  • step (2) requires a mixing of the raw material in 30 ⁇ 60mins.
  • Step (4) applies an aqueous solution of alkaline compound to adjust the reaction product to neutral
  • the alkaline compound include but not limited to one or a mixture of: sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, ethylene diamine, ethanolamines, triethylamine.
  • step (4) Furthermore, the purification process of the neutralized product of step (4) is as below:
  • the vacuum distillation is carried out at a temperature of 100 ⁇ 160 °C.
  • the structure of the resultant preparation organopolysiloxane resin can be anyone of the unit composition as below: MQ type, MT type, DT type, MDT type, MTQ type, DTQ type, MDTQ type, MD X M Type.
  • the present invention has the following advantages:
  • the starting material is prepared without adding in any extra organic solvent, so there is no large quantities of pollutants discharged;
  • the process takes one-step reaction, avoiding two-steps reaction including acid catalyzed hydrolysis and base catalyzed condensation, greatly shortens manufacturing time, and reduces labor intensity, thus facilitating the industrialization;
  • the one-step reaction requires a mild reaction condition, making it easy to control, avoids gelation frequently caused by rapid hydrolysis and condensation out of control, improves yield and repeatability of organopolysiloxane resin;
  • Organopolysiloxane resins prepared with the present invention method have wide applications in liquid silicone rubber, silicone pressure sensitive adhesive, LED encapsulating silicone rubber, lubricant and release agent additives and other personal care products.
  • Amount of reactants are shown in Table 1, the reaction conditions are listed in Table 2, the silane monomer and type I acidic compound were added to the reactor and stirred for 15 minutes, then acidic compound class II and class III acidic compound were added to the mixture, after stirring for 30 minutes, react for (reaction time) at the (reaction temperature) , the mixture was cooled down to room temperature, washed with aqueous sodium carbonate and separated, the upper layer was distillated under reduced pressure, to yield a polyorganosiloxane resin containing various functional groups, the results were shown in table 3 below.
  • 300g ethyl polysilicate, 100.44g hexamethyldisiloxane and 110.22g toluene were added into a 1L three-necked flask, stirred and added a mixture of 30g alcohol and 10.97g concentrated hydrochloric acid, stirred and added 220.44 g purified water by dropwise in about 65mins, then the mixture was heated to 72 °C and reacted for 3h.
  • the resultant was extracted by adding 110.22g toluene, separated. 22.04g 5wt%KOH aqueous solution was added to the organic layer and heated to 72 °C and reacted for 6h.
  • the resultant was neutralized, dried, filtrated and concentrated at 160 °C under reduced pressure to give 135.53g products, with yield 61.48%, volatile content 0.68%, M n 3370 g /mol.
  • 300g ethyl polysilicate, 100.44g hexamethyldisiloxane and 150.08g toluene were added into a 1L three-necked flask, stirred and added a mixture of 30g alcohol and 11.24g concentrated hydrochloric acid, stirred and added 126.36 g purified water by dropwise in about 68mins, then the mixture was heated to 72 °C and reacted for 3h. The resultant was extracted by adding 150.08g toluene, separated. 23.02g 5wt%KOH aqueous solution was added to the organic layer, heated to 72 °C and reacted for 6h. The resultant was neutralized, dried, filtrated and concentrated at 160 °Cunder reduced pressure to give 156.81g product, with yield 68.13%, volatile content 0.75%, M n 3022 g /mol.
  • 300g ethyl polysilicate, 129.6g hexamethyldisiloxane and 120g toluene were added into a 1L three-necked flask, stirred and added a mixture of 30g alcohol and 11.77g concentrated hydrochloric acid, stirred and added 129.6g purified water by dropwise in about 72mins, then the mixture was heated to 72 °C and reacted for 3h. The resultant was extracted by adding 129.6g toluene, separated. 24.96g 5wt%KOH aqueous solution was added to the organic layer and heated to 72 °C and reacted for 6h. The resultant was neutralized, dried, filtrated and concentrated at 160 °C under reduced pressure to give 135.53g products, with yield 83.00%, volatile content 0.78%, M n 2173 g /mol.
  • M n means number average molecular weight, in units of g/mol, is measured by GPC; testing condition of the volatile component is 150 °C ⁇ 3h.
  • the MQ resins prepared with the present invention method has a higher yield of resin, less volatile and larger average molecular weight, when compared with MQ resins prepared with the traditional method.
  • the MQ resin prepared with the present invention method namely MQ-1
  • MQ-1 has a 98.61%yield of resin, 0.12wt%volatile content, 4552 g/mol number average molecular weight
  • the MQ resin prepared with the traditional method namely, MQ-4
  • MQ-4 has a 61.48%yield of resin, 0.68 wt%volatile content, 3370 g/mol number average molecular weight.
  • the infrared spectra of MQ resin prepared respectively with the conventional methods and the present invention method has no significant difference in the characteristic absorption peak of Si-O-Si (1080cm -1 ) , Si-CH 3 (1260cm -1 ) , C-H (2960cm -1 ) .
  • the range of 3400 ⁇ 3700cm -1 absorption peak mainly reflects the residual of Si-OH group, and the residual of active Si-OH group would cause problems in shelf stability when applied in liquid silicone rubber and other products.
  • the MQ resin prepared with the present invention method has nearly none residual of Si-OH group, but the MQ resin prepared with the traditional method dose have a small residue of Si-OH group, which illustrates the advantage of the present invention method compared with the traditional method, on disposing residual of Si-OH group.
  • the present invention has great advantages, namely, solvent-free and environmental-friendly, one-step reaction and efficient process, high yield of MQ resin, low volatile content, having excellent performance in wide applications.

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Abstract

The present invention discloses a method for preparing organopolysiloxane resins, comprising the steps below: (1) use alkoxysilane, capping agent and an acidic compound as raw materials; (2) mix all the raw materials till uniform, herein capping agent, alkoxysilane and acidic compound have a mole ratio from 0 to 40: 1: 0.2 to 5; (3) polycondensation reaction occurs on temperature 40～150°C in 2～20h; (4) adjust the condensation product to neutral, and obtaining a product of organopolysiloxane resin after purification. Preparation of organopolysiloxane resins with the present invention method has benefits on less environmental pollution, low energy consumption, efficient productivity, high yield of silicone resin with excellent performance.

Description

A method for preparing organopolysiloxane resins TECHNICAL FIELD
The present invention relates to the field of polymer synthesis, in particular, it relates to a method for preparing organopolysiloxane resins.
Background technique
Organopolysiloxane is a new type of silicone polymer material, composed of Si-O-Si backbone and functional group connected on the silicon atom. It has characteristic like smoothness, high temperature resistance, hydrophobicity, insulation etc., and widely used in many fields as electricity, electronics, construction, industrial chemicals, personal care, medical and other accessories. It includes silicone oil, silicone rubber, silicone resin and modified derivative of the above three.
Structure of organopolysiloxane resin can be classified into four units: monofunctional unit (R3SiO0.5, referred to as M unit) , difunctional unit (R2SiO, referred to as D unit) , trifunctional unit (RSiO1.5, referred to as T unit) tetrafunctional units (SiO2, referred to as Q unit) . It is generally believed that organopolysiloxane containing T unit or Q unit is called organopolysiloxane resin.
Organopolysiloxane resin has a highly crosslinked structure which is cage-like, dendritic, branched or ladder. The general formula RnSiO (4-n) /2, where, 0≤n<4, R is the same or different organic group. In the crosslinking system, the typical structure of organopolysiloxane resin is shown below.
Figure PCTCN2016107621-appb-000001
Organopolysiloxane resins may be transparent liquid, or powder solid. Because of their special structure, they have excellent heat resistance, low temperature resistance, film-forming property, flexibility, water resistance and adhesive effect, etc., are widely used in pressure-sensitive adhesive, liquid silicone rubber, LED encapsulating resin, anti-sticking isolation, mold release agent, waterproofing agent, personal care ingredient. At present, three main routes to prepare organopolysiloxane resins are presented as below.
1 Chlorosilane hydrolysis
At the beginning, most organopolysiloxane resins are synthesized from chlorosilanes (eg, MeSiCl3, Me2SiCl2, MePhSiCl2, Ph2SiCl2, PhSiCl3) , via hydrolysis, condensation, organic solvent extraction and then concentration. Performance of the resin depends on the type and proportion of the raw material silane, pH of the hydrolysis and condensation reaction, property and amount of solvent,  catalysts characteristic and process conditions. At present, many organosilicone companies and research institutes have conducted a lot of research in chlorosilane hydrolysis and applied for patents. For example, the Institute of Petroleum Chemistry Heilongjiang Provincial Academy of Sciences filed a patent "one method for preparation of phenyl vinyl silicone resin " (Chinese invention patent, CN104151555A) , disclosing a method for preparing silicone resin, which conduct hydrolysis in toluene by control the feed of chlorosilane and the reaction temperature to reduce the reactivity difference between the raw materials, and further reflux condensation to obtain a resin with refractive index ≥1.50, light transmittance ≥90％, viscosity ≥7000mPa·s, silanol content ≤1000ppm； Luzhou North chemical industry Co., Ltd. applied a patent "liquid silicone resin and preparation method and application" (Chinese invention patent, CN104231271A) , disclosing condensation reaction of mixed monomer by dropwise addition of concentrated hydrochloric acid at a low temperature, to prepare silanol pre-polymer and purified liquid silicone resin.
2 Sodium silicate hydrolysis and condensation (Sol-Gel) method
Sol-gel is commonly used method to synthesize MQ silicone resin. First acidified aqueous solution of sodium silicate, followed by acid catalyzed condensation reaction, and then adding monofunctional M units capped, and finally wash the product with water and obtain the MQ silicone resin. At present, lots of researches have been conducted in Sol-gel method to prepare MQ silicone resin. For example, Bluestar Silicones French company filed a patent, "Synthetic routes to prepare MQ silicone resin " (Chinese invention patent, CN101460543A) , disclosing a method for preparing MQ silicone resin, which can better control the condensation reaction of sodium silicate to form a silicon dioxide hydrosol in an aqueous medium and in the presence of acid； Nanchang University filed a patent "A method for preparing MQ silicone resin" (Chinese invention patent, CN101899157A) , disclosing a method using tetrafunctional silicone monomer and a capping agent as raw materials, catalyzed by super acid solid, to prepare liquid or solid MQ silicone resin via hydrolysis and condensation.
3 Silicate hydrolysis and condensation method
Since hydrochloric acid and sodium silicate react too quickly, people prefer to use alkyl silicate as raw material, i.e., silicates. First, silicate hydrolyzes and turns into silicic acid under acid or base catalyst, then condensed, add monofunctional monomer to cap the resin. Lots of researches in Silicate hydrolysis and condensation method have been reported. For example, Shenzhen City of New Asia New Materials Co., Ltd. filed a patent "An environmentally friendly solvent-free method to prepare liquid silicone resin" (Chinese invention patent, CN1032412532A) , disclosing An environmentally friendly solvent-free method to prepare liquid silicone resin with an excess of a capping agent hexamethyldioxane as a solvent to hydrolyze under acid condition, and condensate under base condition； another patent applied by the Dow Corning Corporation "Method of preparing a silicone resin" (US patents, WO2007US13836 20070613) , disclosing a method using a alkoxy silane as raw material, acid hydrolysis condensation method to prepare a silicone resin.
Above three methods to prepare organopolysiloxane resin are all involved in hydrolysis and condensation route, which are with complex and long processing cycle, environmental unfriendly, easy gelation, low yield, poor reproducibility, high energy consumption and other shortcomings.
Invention Details
The present invention provides a method for preparing organopolysiloxane resins, including a solvent free, one-step process without adding in water, to reduce the disadvantages of the traditional methods for preparing organopolysiloxane resins as mentioned above.
A method for preparing organopolysiloxane resins as mentioned in claim 1 comprises the steps of below:
(1) Use alkoxy silane, capping agent and an acidic compound as raw materials；
(2) Mix all the raw materials till uniform, herein capping agent, alkoxy silane and acidic compound have a mole ratio from 0 to 40: 1: 0.2 to 5；
(3) Polycondensation reaction occurs on temperature 40～150 ℃ in 2～20h；
(4) Adjust the condensation product to neutral, and obtain a product of organopolysiloxane resin after purification.
In particular, the alkoxysilane contains at least one of Q unit, D unit and T unit, the capping agent contains M unit.
Preferably the molar ratio of M unit and sum of Q unit, T units and D unit is 0～40: 1.
Alternatively, the alkoxysilane includes but not limited to methyl orthosilicate, ethyl orthosilicate, methyl polysilicate ester, ethyl polysilicate, methyl trimethoxysilane, methyl triethoxysilane, ethyl trimethoxysilane, ethyl triethoxysilane, trimethoxysilane, propyl triethoxy silane, cyclohexyl trimethoxysilane, cyclohexyl triethoxysilane, trimethoxysilane, triethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, allyl triethoxysilane, phenyl trimethoxysilane, phenyl triethoxysilane, dimethyl dimethoxy silane, dimethyl diethoxy silane, methyl ethyl dimethoxysilane, methyl ethyl diethoxy silane, propyl methyl dimethoxy silane, propyl methyl diethoxy silane, methyl dimethoxy silane, methyl diethoxy silane, allyl methyl dimethoxy silane, allyl methyl diethoxy silane, diphenyl dimethoxy silane, diphenyl diethoxy silane, methyl phenyl dimethoxy silane, methyl phenyl diethoxy silane, acryloxy trimethoxy silane, acryloxy propyl triethoxy silane, methacryloxy propyl dimethoxysilane, methacryloxy propyl diethoxysilane, C4～C20 alkyl trimethoxysilane, C4～C20 alkyl triethoxy silane, γ-chloropropyl trimethoxy silane, γ-chloropropyl triethoxy silane, mercapto propyl trimethoxy silane, mercapto propyl triethoxy silane, one or several of the above silanes.
Further, the capping agent includes but not limited to 1, 1, 1, 3, 3, 3-hexamethyl disiloxane, 1, 1, 3, 3-tetramethyl disiloxane, 1, 1, 3, 3-tetramethyl-1, 3-divinyldisiloxane, 1, 1, 3, 3 tetramethyl 1, 3-diphenyl disiloxane, 1, 3-dimethyl-1, 1, 3, 3-tetraphenyldisiloxane, 1, 1, 1, 3, 3, 3, 5, 5, 7, 7, 7-decamethyltetrasiloxane, 1, 1, 3, 3, 3-pentamethyl disiloxane, 1, 1, 1, 3, 5, 5, 5 heptamethyltrisiloxane, one or several of the above.
Alternatively, the method for preparing organopolysiloxane resins as mentioned in claim 2, wherein capping agent is a silane containing a single chlorine/alkoxy groups, including but not limited to trimethylsilyl chloride, trimethyl methoxy silane, trimethyl ethoxy silane, dimethyl vinyl chlorosilane, vinyl dimethyl methoxysilane, vinyl dimethyl ethoxy silane, dimethylchlorosilane, one or several of the above silanes.
Furthermore, the acidic compound includes an acidic compound I containing carboxyl groups, wherein the molar ratio of carboxyl group and alkoxy group contained in alkoxy silane is 0.2～5: 1.
In particular, the acidic compound I includes but not limited to formic acid, acetic acid, propionic acid, butyric acid, valeric acid, oxalic acid, benzoic acid, C6～C26 monocarboxylic acid, succinic acid, adipic acid, phthalic acid, one or several of the above.
The alkoxy groups include but not limited to methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy. Alternatively, the alkoxy groups include but not limited to ethylene glycol monomethyl ether and ethylene glycol monoethyl ether.
Further, the acidic compound herein comprises an acidic compound II, the amount of acidic compound Ⅱ of the total raw materials is 0.1～5wt ％.
In particular, the acidic compound II includes but not limited to one or a mixture of: sulfuric acid, hydrochloric acid, phosphoric acid, trifluoromethane sulfonic acid, p-toluenesulfonic acid, ferric chloride, aluminum chloride, zinc chloride, titanium tetrachloride, tin dichloride, solid super acid, acid clay, cation exchange resin.
Further, the acidic compound comprises an acidic compound III, the amount of acidic compound III of the acidic compound II is 1 ～ 50wt％.
In particular, the compound III includes but is not limited to one or a mixture of: acetic anhydride, succinic anhydride, phthalic anhydride, phosphorus pentoxide, organic acid chloride.
Furthermore, step (2) requires a mixing of the raw material in 30～60mins.
Step (4) , applies an aqueous solution of alkaline compound to adjust the reaction product to neutral, the alkaline compound include but not limited to one or a mixture of: sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, ethylene diamine, ethanolamines, triethylamine.
Furthermore, the purification process of the neutralized product of step (4) is as below:
(4.1) Separate the oil phase, dry the oil phase out, filtrate, a mixture of organopolysiloxane resin and volatile components are obtained；
(4.2) Organopolysiloxane resin is obtained after separating the volatile components by vacuum distillation.
Preferably, the vacuum distillation is carried out at a temperature of 100～160 ℃.
The structure of the resultant preparation organopolysiloxane resin can be anyone of the unit composition as below: MQ type, MT type, DT type, MDT type, MTQ type, DTQ type, MDTQ type, MDXM Type.
Compared with the prior art, the present invention has the following advantages:
(1) The starting material is prepared without adding in any extra organic solvent, so there is no large quantities of pollutants discharged；
(2) The process applies condensation in combination of various functional units, decreases energy consumption largely when compared with acid catalyzed hydrolysis and base catalyzed condensation process.
(3) The process takes one-step reaction, avoiding two-steps reaction including acid catalyzed hydrolysis and base catalyzed condensation, greatly shortens manufacturing time, and reduces labor  intensity, thus facilitating the industrialization；
(4) The one-step reaction, requires a mild reaction condition, making it easy to control, avoids gelation frequently caused by rapid hydrolysis and condensation out of control, improves yield and repeatability of organopolysiloxane resin；
(5) Volatile by-products produced in the reaction are easy to separate and recycle by vacuum distillation consuming much lower energy, greatly reducing the volatile content of organopolysiloxane resin；
(6) Realize a yield of organopolysiloxane resin higher than 95％, with an average molecular weight from 2000g/mol to 8000g/mol, providing excellent film forming and reinforcing performance；
(7) The present invention method for preparing organopolysiloxane resins can be applied in preparing organopolysiloxane resins with various structure compositions. Organopolysiloxane resins prepared with the present invention method have wide applications in liquid silicone rubber, silicone pressure sensitive adhesive, LED encapsulating silicone rubber, lubricant and release agent additives and other personal care products.
Figure Description
Figure 1 Comparison of Infrared spectroscopy scan between the conventional method and the present invention method for preparing MQ resin (M/Q ＝ 0.65) .
Detailed description
Embodiments of the present invention are described in further detail.
The present invention may be further illustrated in the following example embodiment, but examples are not limiting the scope of the present invention.
Examples 1-21
Amount of reactants are shown in Table 1, the reaction conditions are listed in Table 2, the silane monomer and type I acidic compound were added to the reactor and stirred for 15 minutes, then acidic compound class II and class III acidic compound were added to the mixture, after stirring for 30 minutes, react for (reaction time) at the (reaction temperature) , the mixture was cooled down to room temperature, washed with aqueous sodium carbonate and separated, the upper layer was distillated under reduced pressure, to yield a polyorganosiloxane resin containing various functional groups, the results were shown in table 3 below.
Table 1: Formulation List of All Examples
Figure PCTCN2016107621-appb-000002
Table 1 Continued
Figure PCTCN2016107621-appb-000003
Table 1 Continued
Figure PCTCN2016107621-appb-000004
Table 1 Continued
Figure PCTCN2016107621-appb-000005
Table 2: Process Specification List of All Examples
Figure PCTCN2016107621-appb-000006
Table 3: Results of All Examples
Figure PCTCN2016107621-appb-000007
Comparative Example 1 (MQ-4)
300g ethyl polysilicate, 100.44g hexamethyldisiloxane and 110.22g toluene were added into a 1L three-necked flask, stirred and added a mixture of 30g alcohol and 10.97g concentrated hydrochloric acid, stirred and added 220.44 g purified water by dropwise in about 65mins, then the mixture was heated to 72 ℃ and reacted for 3h. The resultant was extracted by adding 110.22g toluene, separated. 22.04g 5wt％KOH aqueous solution was added to the organic layer and heated to 72 ℃ and reacted for 6h. The resultant was neutralized, dried, filtrated and concentrated at 160 ℃ under reduced pressure to give 135.53g products, with yield 61.48％, volatile content 0.68％, Mn 3370 g /mol.
Comparative Example 2 (MQ-5)
300g ethyl polysilicate, 100.44g hexamethyldisiloxane and 150.08g toluene were added into a 1L three-necked flask, stirred and added a mixture of 30g alcohol and 11.24g concentrated hydrochloric acid, stirred and added 126.36 g purified water by dropwise in about 68mins, then the mixture was heated to 72 ℃ and reacted for 3h. The resultant was extracted by adding 150.08g toluene, separated. 23.02g 5wt％KOH aqueous solution was added to the organic layer, heated to 72 ℃ and reacted for 6h. The resultant was neutralized, dried, filtrated and concentrated at 160 ℃under reduced pressure to give 156.81g product, with yield 68.13％, volatile content 0.75％, Mn  3022 g /mol.
Comparative Example 3 (MQ-6)
300g ethyl polysilicate, 129.6g hexamethyldisiloxane and 120g toluene were added into a 1L three-necked flask, stirred and added a mixture of 30g alcohol and 11.77g concentrated hydrochloric acid, stirred and added 129.6g purified water by dropwise in about 72mins, then the mixture was heated to 72 ℃ and reacted for 3h. The resultant was extracted by adding 129.6g toluene, separated. 24.96g 5wt％KOH aqueous solution was added to the organic layer and heated to 72 ℃ and reacted for 6h. The resultant was neutralized, dried, filtrated and concentrated at 160 ℃ under reduced pressure to give 135.53g products, with yield 83.00％, volatile content 0.78％, Mn 2173 g /mol.
Comparison of Technical Specification between the present invention method and the conventional method of synthesizing organopolysiloxane resin is shown in Table 4.
Table 4: Comparison of Technical Specification between the present invention method and the conventional method of synthesizing organopolysiloxane resins
Figure PCTCN2016107621-appb-000008
NOTE: Mn means number average molecular weight, in units of g/mol, is measured by GPC； testing condition of the volatile component is 150 ℃ × 3h.
From table 4 we can find that with the same M/Q ratio, the MQ resins prepared with the present invention method has a higher yield of resin, less volatile and larger average molecular weight, when compared with MQ resins prepared with the traditional method.
With the same M/Q ratio of 0.62, the MQ resin prepared with the present invention method, namely MQ-1, has a 98.61％yield of resin, 0.12wt％volatile content, 4552 g/mol number average molecular weight, meanwhile, the MQ resin prepared with the traditional method, namely, MQ-4, has a 61.48％yield of resin, 0.68 wt％volatile content, 3370 g/mol number average molecular weight.
Infrared spectroscopy of MQ resin prepared respectively with the conventional methods and the present invention method is shown in Figure 1.
From the Figure 1, it can be found: in a wavelength range of 500～3200cm-1, the infrared spectra of MQ resin prepared respectively with the conventional methods and the present invention method has no significant difference in the characteristic absorption peak of Si-O-Si (1080cm-1) ,  Si-CH3 (1260cm-1) , C-H (2960cm-1) . We know the range of 3400～3700cm-1 absorption peak mainly reflects the residual of Si-OH group, and the residual of active Si-OH group would cause problems in shelf stability when applied in liquid silicone rubber and other products.
Within this M/Q ratio range, the MQ resin prepared with the present invention method, has nearly none residual of Si-OH group, but the MQ resin prepared with the traditional method dose have a small residue of Si-OH group, which illustrates the advantage of the present invention method compared with the traditional method, on disposing residual of Si-OH group.
In summary, compared with the prior art, the present invention has great advantages, namely, solvent-free and environmental-friendly, one-step reaction and efficient process, high yield of MQ resin, low volatile content, having excellent performance in wide applications.
The embodiment of the present invention described above is just a preferred embodiment, it is not just limited to the above embodiment, any other change, like modifications, substitutions, combinations, simplification, made in the present invention does not depart from the spirit and principles, shall be equivalent replacement and included within the scope of the present invention.

Claims (19)

  1. A method for preparing organopolysiloxane resins, comprises the following steps:
    (1) Use alkoxysilane, capping agent and an acidic compound as raw materials；
    (2) Mix all the raw materials till uniform, herein capping agent, alkoxysilane and acidic compound have a mole ratio from 0 to 40: 1: 0.2 to 5；
    (3) Polycondensation reaction occurs on temperature 40～150 ℃ in 2～20h；
    (4) Adjust the condensation product to neutral, and obtain a product of organopolysiloxane resin after purification.
  2. The method for preparing organopolysiloxane resins as mentioned in claim 1, wherein the alkoxysilane contains at least one of Q unit, D unit and T unit, the capping agent contains M unit.
  3. The method for preparing organopolysiloxane resins as mentioned in claim 2, wherein the molar ratio of M unit and sum of Q unit, T unit and D unit is 0～40: 1.
  4. The method for preparing organopolysiloxane resins as mentioned in claim 2, wherein alkoxysilane includes but not limited to methyl orthosilicate, ethyl orthosilicate, methyl polysilicate ester, ethyl polysilicate, methyl trimethoxysilane, methyl triethoxysilane, ethyl trimethoxysilane, ethyl triethoxysilane, trimethoxysilane, propyl triethoxy silane, cyclohexyl trimethoxysilane, cyclohexyl triethoxysilane, trimethoxysilane, triethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, allyl triethoxysilane, phenyl trimethoxysilane, phenyl triethoxysilane, dimethyl dimethoxy silane, dimethyl diethoxy silane, methyl ethyl dimethoxysilane, methyl ethyl diethoxy silane, propyl methyl dimethoxy silane, propyl methyl diethoxy silane, methyl dimethoxy silane, methyl diethoxy silane, allyl methyl dimethoxy silane, allyl methyl diethoxy silane, diphenyl dimethoxy silane, diphenyl diethoxy silane, methyl phenyl dimethoxy silane, methyl phenyl diethoxy silane, acryloxy trimethoxy silane, acryloxy propyl triethoxy silane, methacryloxy propyl dimethoxysilane, methacryloxy propyl diethoxysilane, C4～C20 alkyl trimethoxysilane, C4～C20 alkyl triethoxy silane, γ-chloropropyl trimethoxy silane, γ-chloropropyl triethoxy silane, mercapto propyl trimethoxy silane, mercapto propyl triethoxy silane, one or several of the above silanes.
  5. The method for preparing organopolysiloxane resins as mentioned in claim 2, wherein capping agent includes but not limited to 1, 1, 1, 3, 3, 3-hexamethyl disiloxane, 1, 1, 3, 3-tetramethyl disiloxane, 1, 1, 3, 3-tetramethyl-1, 3-divinyldisiloxane, 1, 1, 3, 3 tetramethyl 1, 3-diphenyl disiloxane, 1, 3-dimethyl-1, 1, 3, 3-tetraphenyldisiloxane, 1, 1, 1, 3, 3, 3, 5, 5, 7, 7, 7-decamethyltetrasiloxane, 1, 1, 3, 3, 3-pentamethyl disiloxane, 1, 1, 1, 3, 5, 5, 5 heptamethyltrisiloxane, one or several of the above.
  6. The method for preparing organopolysiloxane resins as mentioned in claim 2, wherein capping agent is a silane containing a single chlorine/alkoxy groups, including but not limited to trimethylsilyl chloride, trimethyl methoxy silane, trimethyl ethoxy silane, dimethyl vinyl chlorosilane, vinyl dimethyl methoxysilane, vinyl dimethyl ethoxy silane, dimethylchlorosilane, one or several of the above silanes.
  7. The method for preparing organopolysiloxane resins as mentioned in claim 1, wherein acidic compound includes an acidic compoundⅠcontaining carboxyl groups, wherein the molar ratio of carboxyl group and alkoxy group contained in alkoxy silane is 0.2～5: 1.
  8. The method for preparing organopolysiloxane resins as mentioned in claim 7, wherein the acidic compound I includes but not limited to formic acid, acetic acid, propionic acid, butyric acid, valeric acid, oxalic acid, benzoic acid, C6～C26 monocarboxylic acid, succinic acid, adipic acid, phthalic acid, one or several of the above.
  9. The method for preparing organopolysiloxane resins as mentioned in claim 7, wherein alkoxy groups includes but not limited to methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy.
  10. The method for preparing organopolysiloxane resins as mentioned in claim 7, wherein alkoxy groups includes but not limited to ethylene glycol monomethyl ether and ethylene glycol monoethyl ether.
  11. The method for preparing organopolysiloxane resins as mentioned in claim 7, wherein: acidic compound herein further comprises an acidic compound II, the amount of acidic compound II of the total raw materials is 0.1～5wt ％.
  12. The method for preparing organopolysiloxane resins as mentioned in claim11, wherein: acidic compound II includes but not limited to one or a mixture of: sulfuric acid, hydrochloric acid, phosphoric acid, trifluoromethane sulfonic acid, p-toluenesulfonic acid, ferric chloride, aluminum chloride, zinc chloride, titanium tetrachloride, tin dichloride, solid super acid, acid clay, cation exchange resin.
  13. The method for preparing organopolysiloxane resins as mentioned in claim 7, wherein: the acidic compound further comprises an acidic compound III, the amount of acidic compound III of the acidic compound II is 1～50wt％.
  14. The method for preparing organopolysiloxane resins as mentioned in 13, wherein: the compound III includes but not limited to one or a mixture of: acetic anhydride, succinic anhydride, phthalic anhydride, phosphorus pentoxide, organic acid chloride.
  15. The method for preparing organopolysiloxane resins as mentioned in claim 1, wherein: step (2) requires a mixing of the raw material in 30～60mins.
  16. The method for preparing organopolysiloxane resins as mentioned in claim 1, wherein: step (4) , applies an aqueous solution of alkaline compound to adjust the reaction product to neutral, the alkaline compound includes but not limited to one or a mixture of: sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, ethylene diamine, ethanolamines, triethylamine.
  17. The method for preparing organopolysiloxane resins as mentioned in claim 1, wherein: the purification process of the neutralized product of step (4) is as below:
    (4.1) Separate the oil phase, dry the oil phase out, filtrate, a mixture of organopolysiloxane resin and volatile components are obtained；
    (4.2) Organopolysiloxane resin is obtained after separating the volatile components by vacuum distillation.
  18. The method for preparing organopolysiloxane resins as mentioned in claim 17, wherein: the vacuum distillation is carried out at a temperature of 100～160℃.
  19. The method for preparing organopolysiloxane resins as mentioned in claim 1, wherein: the structure of the resultant preparation organopolysiloxane resin can be anyone of the units composition as below: MQ type, MT type, DT type, MDT type, MTQ type, DTQ type, MDTQ type, MDXM Type.
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