CN113999396B - Preparation method of epoxy modified polysiloxane photosensitive polymer - Google Patents
Preparation method of epoxy modified polysiloxane photosensitive polymer Download PDFInfo
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- CN113999396B CN113999396B CN202111272352.9A CN202111272352A CN113999396B CN 113999396 B CN113999396 B CN 113999396B CN 202111272352 A CN202111272352 A CN 202111272352A CN 113999396 B CN113999396 B CN 113999396B
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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
- C08G77/42—Block-or graft-polymers containing polysiloxane sequences
- C08G77/44—Block-or graft-polymers containing polysiloxane sequences containing only polysiloxane sequences
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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
- C08G77/38—Polysiloxanes modified by chemical after-treatment
Abstract
The invention relates to a preparation method of a polysiloxane photosensitive polymer, in particular to a preparation method of an epoxy modified polysiloxane photosensitive polymer. The preparation method comprises the following steps: firstly, long-chain alkanol and a platinum catalyst are used for coordination complexing, so that the catalyst efficiency of the platinum catalyst is enhanced; in the presence of the catalyst and a nitrogen atmosphere, the low molecular weight polysiloxane diluted by the solvent and the epoxy monomer are subjected to hydrosilylation reaction to synthesize the epoxy modified polysiloxane photosensitive prepolymer with high conversion rate; under the alkaline condition, the photosensitive prepolymer and polysiloxane ring body are subjected to chain extension reaction at high temperature to obtain the high molecular weight epoxy modified polysiloxane photosensitive polymer. The method has simple process and high epoxy conversion rate, and solves the problem of local crosslinking caused by the residual silicon hydrogen.
Description
Technical Field
The invention relates to a preparation method of a polysiloxane photosensitive polymer, in particular to a preparation method of an epoxy modified polysiloxane photosensitive polymer.
Background
The structural particularity of the organic silicon polymer endows the organic silicon polymer with a plurality of excellent performances, such as high and low temperature resistance, aging resistance, corrosion resistance and the like, so that the organic silicon polymer is widely applied to a plurality of aspects, such as aerospace, transportation, electronic and electric products, chemical industry, medical treatment and health, daily life and the like. The epoxy modified polysiloxane photosensitive prepolymer is one of ultraviolet curing materials, has the characteristics of strong cohesiveness, no oxygen inhibition and low shrinkage, and has wide application prospects in the fields of release, photocuring molding, fabric treatment and the like.
Because the compatibility of the long polysiloxane chain and the epoxy active monomer is poor, the current epoxy modified polysiloxane preparation method is to modify the organic silicon end sealing agent by epoxy first and then seal the end in the synthesis process of the polysiloxane chain. The reaction of the epoxy active monomer directly with the polysiloxane chain segment mostly has residual silicon hydrogen, and the reaction cannot be completed. The residual silicon-hydrogen bond reacts with water in the presence of a catalyst to generate a local cross-linking substance, and the transparency and the quality of the product are influenced.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a preparation method of an epoxy modified polysiloxane photosensitive polymer, which solves the problems of insufficient addition, low conversion rate and local cross-linking in the existing epoxy modified polysiloxane process.
The preparation method of the epoxy modified polysiloxane photosensitive polymer comprises the following steps:
1) Activation of the platinum catalyst:
mixing chloroplatinic acid hexahydrate and long-chain alkanol, stirring and heating, heating to 60-70 ℃, removing by-products (ethers and aldehydes generated by oxidizing the long-chain alkanol) under the vacuum condition while stirring, and reacting for 35-50 hours;
after the reaction is finished, cooling to room temperature and pressure, adding an alkane reagent, purifying and filtering, and removing the alkane reagent to obtain a coordination complex product of long-chain alkanol and platinum, namely the activated platinum catalyst;
2) Preparation of photosensitive prepolymer:
adding the activated platinum catalyst, the activated epoxy active body, hydrogen-containing polysiloxane and a solvent into a reaction container, and stirring and reacting for 3-5 hours under the atmosphere of nitrogen at the reaction temperature of 60-90 ℃;
after the reaction is finished, cooling to room temperature, adding activated carbon, stirring for 1-2 hours, filtering, collecting filtrate, and removing the solvent to obtain the low-chain epoxy modified polysiloxane photosensitive prepolymer;
3) Preparation of photopolymer:
adding the low-chain epoxy modified polysiloxane photosensitive prepolymer, polysiloxane ring bodies and tetramethylammonium hydroxide into a reaction bottle, heating to 90-120 ℃, and reacting for 4-8 hours;
after the reaction is finished, heating to 130-150 ℃ for reaction for 2-4 hours to obtain the epoxy modified polysiloxane photosensitive polymer with high molecular weight.
In the step 1), the long-chain alkanol is one or more of pentanol, hexanol, heptanol, octanol or derivatives thereof, and n-octanol is preferred.
In the step 1), the molar ratio of the long-chain alkanol to the chloroplatinic acid hexahydrate is 5.
In the step 1), the vacuum degree under the vacuum condition is 0.01-0.03MPa.
In the step 1), the alkane reagent is n-hexane.
In the step 1), the by-products are aldehydes and ether derivatives generated by the long-chain alkanol in the presence of platinum.
In the step 2), the epoxy active body is one or more of the following structures;
in step 2), the hydrogenpolysiloxane is H (CH)3)2SiO1/2Chain end capping, (CH)3)2SiO linked to H (CH)3) Copolymer silicone oil of SiO chain or Containing H (CH)3)2SiO1/2End-capping of the chain, (CH)3)2Silicon oil containing SiO chain or (CH)3)SiO3/2、SiO2Linking with H (CH)3)2SiO1/2The chain end-capped silicone resin, and the hydrogenpolysiloxane has the number of the chain joints of more than or equal to 1 and less than or equal to 30.
In the step 2), the molar ratio of the epoxy active body to the hydrogen-containing polysiloxane is 1-2.
In the step 2), the solvent is one or a mixture of more of toluene, xylene, DMF or DMSO, and toluene is preferred.
In the step 3), the concentration of the tetramethylammonium hydroxide is 100-500ppm, the polysiloxane ring bodies are DMC and D4, and the adding amount is adjusted according to the required chain number.
Preferably, the preparation method of the epoxy modified polysiloxane photosensitive polymer comprises the following steps:
1) Activation of the platinum catalyst:
adding chloroplatinic acid hexahydrate and long-chain alkanol into a flask, mixing, stirring and heating, removing by-products (ethers and aldehydes generated by oxidation of the long-chain alkanol) under stirring at a certain vacuum degree after the temperature is raised to 60-70 ℃, and reacting for 35-50 hours;
after the reaction is finished, cooling to room temperature and pressure, adding n-hexane for purification and filtration, then heating to 50-60 ℃, and distilling under reduced pressure to remove the n-hexane, thereby obtaining a coordination complex product of long-chain alkanol and platinum, namely the activated platinum catalyst;
2) Preparation of photosensitive prepolymer:
adding the weighed activated platinum catalyst, the epoxy active body, the hydrogen-containing polysiloxane and the solvent into a flask, and stirring and reacting for 3-5 hours in the nitrogen atmosphere at the reaction temperature of 60-90 ℃;
after the reaction is finished, cooling to room temperature, adding activated carbon, stirring for 1-2 hours, heating the filtered filtrate to 70 ℃, and distilling under reduced pressure to remove the solvent to obtain the low-chain epoxy modified polysiloxane photosensitive prepolymer;
3) Preparation of photopolymer:
adding the low-chain epoxy modified polysiloxane photosensitive prepolymer, polysiloxane ring bodies and tetramethylammonium hydroxide into a reaction bottle, heating to 90-120 ℃, and reacting for 4-8 hours;
after the reaction is finished, heating to 130-150 ℃ for reaction for 2-4 hours to obtain the epoxy modified polysiloxane photosensitive polymer.
Compared with the prior art, the invention has the beneficial effects that:
the invention adopts long-chain alkanol to carry out coordination and complexation on the platinum catalyst, thereby increasing the compatibility of the catalyst and the epoxy monomer and improving the conversion efficiency. In addition, a synthesis mode of low-chain polymerization and chain extension is adopted, the process is simple, the problem of residual silicon hydrogen in the synthesis process of hydrogen-containing polysiloxane and epoxy active body is solved, and the product quality is improved.
Drawings
FIG. 1 is an IR spectrum of example 1 of the present invention;
FIG. 2 is a nuclear magnetic spectrum of example 1 of the present invention.
Detailed Description
The present invention is further illustrated by, but is not limited to, the following examples.
Catalyst preparation example 1
2.58g of chloroplatinic acid hexahydrate and 4.56g of n-octanol (molar ratio: 1. Adding 20g of n-hexane, stirring uniformly, and filtering to obtain a brownish red filtrate. The temperature is raised to 60 ℃, and the normal hexane is removed by reduced pressure distillation, thus obtaining 5.14g of octanol activated platinum catalyst.
Example 1
62g of 4-vinyl-1-cyclohexene-1, 2-epoxy, 93g of hydrogen-terminated polysiloxane having a molecular weight of 532 and a hydrogen content of 0.37%, 60g of toluene and 2ppm of the catalyst of preparation example 1 were charged into a 500ml flask equipped with a stirrer, reflux condenser, thermometer and nitrogen gas tube, the temperature was raised to 90 ℃ and the reaction was carried out for 5 hours, whereupon 2100cm of infrared ray detection was carried out-1Stopping the reaction after no characteristic peak of silicon hydrogen exists. And cooling to room temperature, adding activated carbon, stirring for 1.5 hours, filtering, collecting filtrate, and distilling at 70 ℃ under reduced pressure to remove toluene to obtain the low-chain epoxy modified polysiloxane photosensitive prepolymer. Through nuclear magnetic detection, no silicon-hydrogen bond residue exists near the chemical shift of 4.5, and all the residues participate in the reaction.
34.15g of the prepared low epoxy modified polysiloxane photosensitive prepolymer, 265.85g of octamethylcyclotetrasiloxane and 7.5g of tetramethylammonium hydroxide base gum (base content: 1.8%) were put into a 500ml flask, heated to 90 ℃ and reacted for 4 hours. Then the temperature is raised to 140 ℃ for reaction for 2h. Removing low molecules at 120 ℃ under reduced pressure to obtain the polysiloxane photosensitive polymer with the molecular weight of 9603.
Example 2
To a 500ml flask equipped with a stirrer, reflux condenser, thermometer, and nitrogen gas tube62g of 4-vinyl-1-cyclohexene-1, 2-epoxy, 44g of side chain hydrogenpolysiloxane (molecular weight 1800, hydrogen content 0.75%), 70g of toluene and 2ppm of the catalyst from preparation example 1 were added to a flask, the temperature was raised to 70 ℃ and after 3 hours of reaction, 2100cm of infrared detection was carried out-1Stopping the reaction after no silicon hydrogen characteristic peak exists. And cooling to room temperature, adding activated carbon, stirring for 1 hour, filtering, collecting filtrate, and distilling at 70 ℃ under reduced pressure to remove toluene to obtain the low-chain epoxy modified polysiloxane photosensitive prepolymer. Through nuclear magnetic detection, silicon-hydrogen bond residue does not exist near the chemical shift of 4.5, and all the silicon-hydrogen bond residue participates in the reaction.
35g of the prepared low epoxy modified polysiloxane photosensitive prepolymer, 265g of octamethylcyclotetrasiloxane and 2.5g of tetramethylammonium hydroxide alkali gel (alkali content is 1.8%) are added into a 500ml flask, and the temperature is raised to 110 ℃ for reaction for 7h. Then the temperature is raised to 130 ℃ for reaction for 3h. Removing low molecules at 120 ℃ under reduced pressure to obtain the polysiloxane photosensitive polymer with the molecular weight of 9200.
Example 3
A500-ml flask equipped with a stirrer, reflux condenser, thermometer and nitrogen gas tube was charged with 57g of allyl glycidyl ether, 44g of side chain hydrogenpolysiloxane (molecular weight 510, hydrogen content 0.75%), 50g of toluene and 2ppm of the catalyst of preparation example 1, heated to 80 ℃ for 4 hours, reacted for 2100cm by infrared detection-1Stopping the reaction after no silicon hydrogen characteristic peak exists. Cooling to room temperature, adding activated carbon, stirring for 2 hours, filtering, collecting filtrate, and distilling under reduced pressure at 70 ℃ to remove toluene to obtain the low-chain epoxy modified polysiloxane photosensitive prepolymer. Through nuclear magnetic detection, no silicon-hydrogen bond residue exists near the chemical shift of 4.5, and all the residues participate in the reaction.
35g of the prepared low epoxy modified polysiloxane photosensitive prepolymer, 265g of octamethylcyclotetrasiloxane and 5g of tetramethylammonium hydroxide alkali gel (alkali content is 1.8%) are added into a 500ml flask, the temperature is raised to 100 ℃, and the reaction is carried out for 8h. Then the temperature is raised to 150 ℃ for reaction for 4h. Removing low molecules at 120 deg.C under reduced pressure to obtain polysiloxane photopolymer with molecular weight of 9310.
Example 4
Into a 500ml flask equipped with a stirrer, reflux condenser, thermometer, nitrogen gas tube were charged 49g of 1, 2-epoxy-5-hexene, 44g of a side-chain hydrogenpolysiloxane (molecular weight 510, hydrogen content 0.75%), 50g of xylene, 2ppm of the catalyst from preparation example 1, heating to 60 deg.C, reacting for 4h, and detecting with infrared radiation at 2100cm-1Stopping the reaction after no silicon hydrogen characteristic peak exists. Cooling to room temperature, adding activated carbon, stirring for 1.5 hours, filtering, collecting filtrate, and distilling at 70 ℃ under reduced pressure to remove xylene to obtain the low-chain epoxy modified polysiloxane photosensitive prepolymer. Through nuclear magnetic detection, silicon-hydrogen bond residue does not exist near the chemical shift of 4.5, and all the silicon-hydrogen bond residue participates in the reaction.
35g of the prepared low epoxy modified polysiloxane photosensitive prepolymer, 265g of octamethylcyclotetrasiloxane and 5g of tetramethylammonium hydroxide alkali gum (alkali content is 1.8%) are added into a 500ml flask, and the temperature is raised to 120 ℃ for reaction for 5 hours. Then the temperature is raised to 140 ℃ for reaction for 2h. Removing low molecules at 120 ℃ under reduced pressure to obtain the polysiloxane photopolymer with the molecular weight of 8635.
Comparative example 1
62g of 4-vinyl-1-cyclohexene-1, 2-epoxy, 44g of side chain hydrogen-containing polysiloxane (molecular weight 510, hydrogen content 0.75%), 70g of toluene and 2ppm of Karstedt's catalyst were put into a 500ml flask equipped with a stirrer, reflux condenser, thermometer and nitrogen line, and the reaction was stopped after 5 hours of reaction at 90 ℃. And cooling to room temperature, adding activated carbon, stirring for 1.5 hours, filtering, collecting filtrate, and distilling at 70 ℃ under reduced pressure to remove toluene to obtain the low-chain epoxy modified polysiloxane photosensitive prepolymer. The reaction conversion rate was 73% and the unreacted silicon-hydrogen bonds were not completely involved in the reaction by nuclear magnetic detection.
Comparative example 2
62g of 4-vinyl-1-cyclohexene-1, 2-epoxy, 95g of side chain hydrogenpolysiloxane (molecular weight: 8900, hydrogen content: 0.35%), 100g of toluene and 2ppm of the catalyst of preparation example 1 were charged into a 500ml flask equipped with a stirrer, reflux condenser, thermometer and nitrogen gas tube, and the reaction was stopped after the temperature was raised to 80 ℃ and the reaction was carried out for 5 hours. Cooling to room temperature, adding active carbon, stirring for 1.5 hours, filtering, collecting filtrate, and distilling at 70 ℃ under reduced pressure to remove toluene to obtain the epoxy modified long-chain polysiloxane. Through nuclear magnetic detection, the reaction conversion rate is 52 percent, and the unreacted silicon hydrogen bonds are not completely involved in the reaction.
Comparative example 3
62g of 4-vinyl-1-cyclohexene-1, 2-epoxy, 44g of side chain hydrogenpolysiloxane (molecular weight 2300, hydrogen content 0.75%), 100g of toluene and 2ppm of the catalyst in preparation example 1 were charged into a 500ml flask equipped with a stirrer, reflux condenser, thermometer and nitrogen gas tube, and the reaction was stopped after the temperature was raised to 90 ℃ and the reaction was carried out for 5 hours. Cooling to room temperature, adding activated carbon, stirring for 1.5 hours, filtering, collecting filtrate, and distilling at 70 ℃ under reduced pressure to remove toluene to obtain the low-chain epoxy modified polysiloxane photosensitive prepolymer. Through nuclear magnetic detection, the reaction conversion rate of the silicon-hydrogen bond containing unreacted silicon-hydrogen bond is 86%, and the silicon-hydrogen bond does not completely participate in the reaction.
Claims (6)
1. A preparation method of an epoxy modified polysiloxane photosensitive polymer is characterized by comprising the following steps: the method comprises the following steps:
1) Activation of the platinum catalyst:
mixing, stirring and heating chloroplatinic acid hexahydrate and long-chain alkanol, heating to 60-70 ℃, removing by-products under the vacuum condition while stirring, and reacting for 35-50 hours;
after the reaction is finished, cooling to room temperature and pressure, adding an alkane reagent, purifying and filtering, and removing the alkane reagent to obtain a coordination complex product of long-chain alkanol and platinum, namely an activated platinum catalyst;
2) Preparation of photosensitive prepolymer:
adding the activated platinum catalyst, the activated epoxy active body, hydrogen-containing polysiloxane and a solvent into a reaction container, and stirring and reacting for 3-5 hours under the atmosphere of nitrogen at the reaction temperature of 60-90 ℃;
after the reaction is finished, cooling to room temperature, adding activated carbon, stirring for 1-2 hours, filtering, collecting filtrate, and removing the solvent to obtain the low-chain epoxy modified polysiloxane photosensitive prepolymer;
3) Preparation of photopolymer:
adding the low-chain epoxy modified polysiloxane photosensitive prepolymer, polysiloxane ring bodies and tetramethylammonium hydroxide into a reaction bottle, heating to 90-120 ℃, and reacting for 4-8 hours;
after the reaction is finished, heating to 130-150 ℃ for reaction for 2-4 hours to obtain epoxy modified polysiloxane photosensitive polymer;
in the step 1), the long-chain alkanol is one or more of pentanol, hexanol, heptanol or octanol;
in the step 2), the epoxy active body is one or more of the following structures;
in step 2), the hydrogenpolysiloxane is H (CH)3)2SiO1/2Chain end capping, (CH)3)2SiO linked to H (CH)3) Copolymer silicone oil of SiO chain or Containing H (CH)3)2SiO1/2Chain end capping, (CH)3)2Silicon oil containing SiO chain or (CH)3)SiO3/2、SiO2Linking to H (CH)3)2SiO1/2The chain-terminated silicone resin, and the hydrogenpolysiloxane has the number of chains of more than or equal to 1 and less than or equal to 30;
in the step 3), the polysiloxane ring body is DMC and D4.
2. The method of preparing an epoxy-modified polysiloxane photopolymer according to claim 1, wherein: in the step 1), the molar ratio of the long-chain alkanol to the chloroplatinic acid hexahydrate is 5.
3. The method of preparing an epoxy-modified polysiloxane photopolymer according to claim 1, wherein: in the step 1), the vacuum degree under the vacuum condition is 0.01-0.03MPa.
4. The method of preparing an epoxy-modified polysiloxane photopolymer according to claim 1, wherein: in the step 2), the molar ratio of the epoxy active body to the hydrogen-containing polysiloxane is 1-2.
5. The method of preparing an epoxy-modified polysiloxane photopolymer according to claim 1, wherein: in the step 2), the solvent is one or a mixture of more of toluene, xylene, DMF or DMSO.
6. The method of preparing an epoxy-modified polysiloxane photopolymer according to claim 1, wherein: in the step 3), the concentration of the tetramethylammonium hydroxide is 100-500ppm.
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