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CN-121975127-A - Bridging active MQ silicone resin modified silicone oil stripping force regulator and preparation method and application thereof

CN121975127ACN 121975127 ACN121975127 ACN 121975127ACN-121975127-A

Abstract

The invention belongs to the field of organosilicon release agents, and discloses a bridging active MQ silicone resin modified silicone oil release force regulator, and a preparation method and application thereof. Firstly, carrying out self-condensation and co-condensation on conventional low-molecular-weight vinyl MQ silicon resin in a trace alkali and solvent medium to respectively obtain a silicon vinyl bridging MQ silicon resin solution with medium molecular weight, then adding double-end active silicone oil with the molar number of the MQ silicon resin vinyl of 0.9-1.1 times, catalyzing by platinum, and finally removing the solvent to obtain the bridging active MQ silicon resin modified silicone oil. The modified silicone oil or the composite modified active silicone oil doped with the ethylene glycol diallyl ether bridged end-hydrosilyl polydimethylsiloxane is used in an addition type vinyl silicone oil release agent, can adjust and increase the release force of a release coating, has relatively stable release force before and after aging, and has wide application prospect in a wide range from middle release to heavy release.

Inventors

  • HUANG YUEWEN
  • QIU DAN
  • Peng Quanqin
  • WANG BIN
  • HU JIWEN
  • HUANG ZHENZHU

Assignees

  • 国科广化精细化工孵化器(南雄)有限公司
  • 中科院广州化学有限公司
  • 国科广化(南雄)新材料研究院有限公司
  • 国科广化韶关新材料研究院

Dates

Publication Date
20260505
Application Date
20260213

Claims (10)

  1. 1. A bridging active MQ silicone resin modified silicone oil stripping force regulator is characterized in that the stripping force regulator has a structural general formula Gr ( CH2-CH2 M)( CH3 M)QOQ(M CH3 ) or Gr ( CH2-CH2 M)( CH3 M)QOQ(M CH3 ) (M CH2-CH2 ) Gr; o in the general formula is a bridged oxygen atom, and the structural expression of the end group Gr is as follows: ; wherein n is 19 to 135; CH2-CH2 The structural expression of M or M CH2-CH2 is: ; The structural expression of M CH3 or CH3 M is: ; the structural expression of Q is: 。
  2. 2. The preparation method of the bridged active MQ silicone resin modified silicone oil stripping force regulator according to claim 1 is characterized by comprising the following operation steps of taking low-molecular-weight vinyl MQ silicone resin VMQ1 solid as a raw material or taking low-molecular-weight vinyl MQ silicone resin VMQ2 solid and methyl MQ silicone resin solid as raw materials, preparing a medium-molecular-weight bridged vinyl MQ silicone resin solution in an inert hydrocarbon solvent under the heating and catalytic action, then adding the solution with active silicone oil through platinum catalysis, and removing the solvent under reduced pressure to obtain the bridged active MQ silicone resin modified silicone oil stripping force regulator; The low molecular weight vinyl MQ silicon resin VMQ1 solid is MQ silicon resin with M/Q mole ratio of 0.65-0.95, vinyl content of less than 0.05mol/100g and number average molecular weight of 1500-4000; The low-molecular-weight vinyl MQ silicon resin VMQ2 solid is MQ silicon resin with M/Q mole ratio of 0.65-0.95, vinyl content of less than 0.11mol/100g and number average molecular weight of 1500-4000; The medium molecular weight bridged vinyl MQ silicone resin has a structural general formula ( CH2=CH M)( CH3 M)QOQ(M CH3 ) or ( CH2=CH M)( CH3 M)QOQ(M CH3 ) (M CH=CH2 ); O in the general formula is a bridged oxygen atom, and the structural expression of CH2=CH M or M CH=CH2 is as follows: ; The structural expression of M CH3 or CH3 M is: ; the structural expression of Q is: ; The active silicone oil is double-end silicon hydrogen-based silicone oil.
  3. 3. The preparation method of the bridging active MQ silicone resin modified silicone oil stripping force regulator as claimed in claim 2, wherein the medium molecular weight bridging vinyl MQ silicone resin is a silicon vinyl-containing bridging vinyl MQ silicone resin solid with a number average molecular weight of 3000-8000, and the average vinyl content is 0.0125-0.066 mol/100g.
  4. 4. The preparation method of the bridged active MQ silicone resin modified silicone oil peeling force regulator as recited in claim 1, which is characterized by comprising the following steps: Step A 1 : A 11 , dissolving low molecular weight vinyl MQ silicon resin VMQ1 solid in an inert hydrocarbon solvent to prepare 50-75wt% solution, adding a strong alkali solution to obtain a reaction system, wherein the concentration of the strong alkali in the reaction system is 40-150 ppm, heating the reaction system to the oil temperature of 110-160 ℃ in an oil bath for reaction for 3-6 hours, distilling off low boiling point alcohols and water in the reaction process, and cooling to obtain a medium molecular weight bridged vinyl MQ silicon resin solution taking O as a bridge; Or A 12 , dissolving low-molecular-weight vinyl MQ silicon resin VMQ2 solid and methyl MQ silicon resin solid in an inert hydrocarbon solvent to prepare 50-75wt% solution, adding a strong alkali solution to obtain a reaction system, wherein the concentration of strong alkali in the reaction system is 40-150 ppm, heating the reaction system to the oil temperature of 110-160 ℃ in an oil bath for reaction for 3-6 h, distilling to remove low-boiling-point alcohols and water in the reaction process, and cooling to obtain a medium-molecular-weight bridging vinyl MQ silicon resin solution taking O as a bridge; step A 2 : And C, adding long-chain C8-C12 alkyl carboxylic acid with the equivalent number of alkali being 0.5-1.5 times into the medium molecular weight bridged vinyl MQ silicone resin solution prepared in the step A 1 at room temperature, or introducing carbon dioxide to neutralize for 10-30 minutes, then sequentially adding a platinum catalyst and double-end silicon hydrogen-based silicone oil, reacting for 0.5-1 h at room temperature, heating an oil bath to the temperature of 50-60 ℃ for reacting for 1-2h, then raising the temperature of 80 ℃ for reacting for 1-2h, cooling to obtain a stripping force regulator solution, and finally distilling the stripping force regulator solution under reduced pressure at the temperature of 50 ℃ to remove the solvent to obtain the solvent-free bridged active MQ silicone resin modified silicone oil stripping force regulator.
  5. 5. The method for preparing the bridged active MQ silicone resin modified silicone oil peel force regulator as recited in claim 4, wherein the method is characterized in that: the inert hydrocarbon solvents in the step A 1 are toluene, xylene or isoparaffin, the strong alkali solutions are aqueous solutions or alcohol solutions of potassium hydroxide, sodium hydroxide and lithium hydroxide, and the concentration of the strong alkali solutions is 0.5-5wt%; The low molecular weight vinyl MQ silicon resin VMQ1 solid in the step A 11 is MQ silicon resin with M/Q mole ratio of 0.65-0.95, vinyl content of less than 0.05mol/100g and number average molecular weight of 1500-4000; The low-molecular-weight vinyl MQ silicon resin VMQ2 solid in the step A 12 is MQ silicon resin with the molar ratio of M/Q of 0.65-0.95, the vinyl content of less than 0.11mol/100g and the number average molecular weight of 1500-4000, the raw material methyl MQ silicon resin solid is MQ silicon resin with the molar ratio of M/Q of 0.65-0.95 and the number average molecular weight of 2000-4000, and the mass ratio of the low-molecular-weight vinyl MQ silicon resin VMQ2 solid to the methyl MQ silicon resin solid is 0.5-1:1; The platinum catalyst in the step A 2 is Karstedt catalyst diluted by inert organic solvent, wherein the concentration of platinum is 1000ppm, the inert organic solvent is toluene, xylene, ethyl acetate or alkane, the double-end hydrosilyl silicone oil is double-end hydrosilyl polydimethylsiloxane with the molecular weight of 1500-8000, and the molar dosage of the double-end hydrosilyl polydimethylsiloxane is 0.9-1.1 times of the molar number of vinyl in the medium-molecular-weight bridged vinyl MQ silicone resin solution.
  6. 6. The stripping force regulator mixture of the bridged active MQ silicone resin modified silicone oil is characterized by comprising the stripping force regulator of claim 1 and diallyl ether modified hydrogen-terminated silicone oil with a structure shown in the following formula (1), wherein the mass percentage of the stripping force regulator mixture is 80-99% and 1-20% respectively; ; (1) Wherein m=10 to 50, x=1 to 10, r= H, CH 2 CH 2 Si(OCH 3 ) 3 or CH 2 CH 2 Si(OCH 2 CH 3 ) 3 .
  7. 7. The bridged active MQ silicone resin modified silicone oil peel force modifier mixture as set forth in claim 6, wherein the silyl terminated diallyl ether modified silyl terminated silicone oil of the structure of formula (1) is prepared by the steps of: Uniformly mixing 1 mol part of ethylene glycol diallyl ether or polyethylene glycol diallyl ether and 1.5-2 mol parts of double-end silicon hydride silicone oil with an inert hydrocarbon solvent at room temperature to obtain a mixture, wherein the amount of the inert hydrocarbon solvent is less than 30% of the total mass of the mixture, adding a platinum catalyst, heating to an oil temperature of 50 ℃ for reaction for 1h in an oil bath, heating to 80 ℃ for reaction for 2h, heating to 110 ℃ for reaction for 2h, adding vinyl trialkoxysilane which is 0-0.2 times of the mol number of the double-end silicon hydride silicone oil, reacting for 0-1 h at the oil temperature of 110 ℃, cooling, and then distilling under reduced pressure to remove the solvent at the oil temperature of less than 50 ℃ to obtain the double-end silicon hydride modified diallyl ether silicone oil; the double-end hydrosilyl silicone oil is double-end hydrosilyl polydimethylsiloxane with a molecular weight of 1500-8000; the inert hydrocarbon solvent is toluene, xylene or isoparaffin; the vinyl trialkoxysilane is vinyl trimethoxy silane or vinyl triethoxy silane.
  8. 8. The bridging active MQ silicone resin modified silicone oil stripping force regulator as set forth in claim 7, wherein the platinum catalyst is Karstedt catalyst diluted by inert organic solvent, wherein the concentration of platinum is 2-10 ppm, and the inert organic solvent is toluene, xylene, ethyl acetate or alkane.
  9. 9. Use of a bridging-active MQ silicone resin-modified silicone oil peel force modifier according to claim 1 in an addition-type silicone release agent.
  10. 10. Use of a bridged active MQ silicone resin modified silicone oil peel force modifier mixture in accordance with claim 6 in an addition type silicone release agent.

Description

Bridging active MQ silicone resin modified silicone oil stripping force regulator and preparation method and application thereof Technical Field The invention belongs to the field of organosilicon release agents, and particularly relates to a bridging active MQ silicone resin modified silicone oil release force regulator, and a preparation method and application thereof. Background The solvent-free addition type organic silicon release agent has the characteristics of environmental protection, good transparency, high and low temperature resistance, adjustable release force and the like, and the release film prepared by coating and thermally curing paper, PET and other films has wide application. The release force regulator regulates the release force of the organosilicon release agent through the regulator so as to adapt to the application requirements of release force of different protective films. The stripping force regulator can be divided into a light stripping regulator and a heavy stripping regulator, but the poor stability of the conventional regulator often leads to obvious climbing of the release agent after the release force of the release agent is aged, and the compatibility of the pure vinyl MQ silicone resin with the main agent of the addition type vinyl silicone oil is improved by a solvent, so that the release force of the cured protective film after aging can be obviously reduced, and the application is obviously limited. Chinese patent publication No. CN101003631a discloses a solvent-free silicone composition for release paper, which is obtained by subjecting MQ silicone resin and vinyl-containing VF oil to condensation rearrangement reaction under the action of base catalyst. Disclosure of Invention In order to overcome the defects and shortcomings in the prior art, the primary purpose of the invention is to provide a bridging active MQ silicone resin modified silicone oil stripping force regulator. The invention further aims to provide a preparation method of the bridged active MQ silicone resin modified silicone oil stripping force regulator, which is based on the polyorganosiloxane containing terminal hydrogen groups or terminal vinyl groups, which is prepared by reacting the bridged active MQ silicone resin with silicone oil and is prepared by an addition method, and the regulator which does not need a solvent, has good compatibility, remarkably enhanced stripping strength and stable stripping performance before and after aging can be obtained when the regulator is applied to the stripping force regulator in an addition type organosilicon release agent. It is a further object of the present invention to provide the use of the bridging active MQ silicone resin modified silicone oil peel force modifier described above. The aim of the invention is achieved by the following technical scheme: A bridging active MQ silicone resin modified silicone oil stripping force regulator has a structural general formula Gr (CH2-CH2M)(CH3M)QOQ(MCH3) or Gr (CH2-CH2M)(CH3M)QOQ(MCH3) (MCH2-CH2) Gr; o in the general formula is a bridged oxygen atom, and the structural expression of the end group Gr is as follows: wherein n is 19 to 135; CH2-CH2 The structural expression of M or M CH2-CH2 is: ; The structural expression of M CH3 or CH3 M is: ; the structural expression of Q is: 。 The preparation method of the bridged active MQ silicone resin modified silicone oil stripping force regulator comprises the following steps of taking low-molecular-weight vinyl MQ silicone resin VMQ1 solid as a raw material or taking low-molecular-weight vinyl MQ silicone resin VMQ2 solid and methyl MQ silicone resin solid as raw materials, preparing a medium-molecular-weight bridged vinyl MQ silicone resin solution in an inert hydrocarbon solvent under the heating and catalytic action, then adding the solution with active silicone oil through platinum catalysis, and removing the solvent under reduced pressure to obtain the bridged active MQ silicone resin modified silicone oil stripping force regulator; The low molecular weight vinyl MQ silicon resin VMQ1 solid is MQ silicon resin with M/Q mole ratio of 0.65-0.95, vinyl content of less than 0.05mol/100g and number average molecular weight of 1500-4000; The low-molecular-weight vinyl MQ silicon resin VMQ2 solid is MQ silicon resin with M/Q mole ratio of 0.65-0.95, vinyl content of less than 0.11mol/100g and number average molecular weight of 1500-4000; The medium molecular weight bridged vinyl MQ silicone resin has a structural general formula (CH2=CHM)(CH3M)QOQ(MCH3) or (CH2=CHM)(CH3M)QOQ(MCH3) (MCH=CH2); O in the general formula is a bridged oxygen atom, and the structural expression of CH2=CH M or M CH=CH2 chain links is as follows: ; The structural expression of the M CH3 or CH3 M chain link is: ; The structural expression of the Q chain link is as follows: ; The active silicone oil is double-end silicon hydrogen-based silicone oil. The medium molecular weight bridged vinyl MQ