CN108264640B - Preparation method of UV (ultraviolet) light-cured organic silicon resin for direct-writing forming - Google Patents

Preparation method of UV (ultraviolet) light-cured organic silicon resin for direct-writing forming Download PDF

Info

Publication number
CN108264640B
CN108264640B CN201810139310.XA CN201810139310A CN108264640B CN 108264640 B CN108264640 B CN 108264640B CN 201810139310 A CN201810139310 A CN 201810139310A CN 108264640 B CN108264640 B CN 108264640B
Authority
CN
China
Prior art keywords
poss
organic silicon
acrylate
direct
silicon resin
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201810139310.XA
Other languages
Chinese (zh)
Other versions
CN108264640A (en
Inventor
李婧
张帅
陈素芬
彭倩玉
李洁
刘梅芳
尹强
李波
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Laser Fusion Research Center China Academy of Engineering Physics
Original Assignee
Laser Fusion Research Center China Academy of Engineering Physics
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Laser Fusion Research Center China Academy of Engineering Physics filed Critical Laser Fusion Research Center China Academy of Engineering Physics
Priority to CN201810139310.XA priority Critical patent/CN108264640B/en
Publication of CN108264640A publication Critical patent/CN108264640A/en
Application granted granted Critical
Publication of CN108264640B publication Critical patent/CN108264640B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/045—Polysiloxanes containing less than 25 silicon atoms
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y70/00—Materials specially adapted for additive manufacturing
    • 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
    • C08G77/14—Polysiloxanes containing silicon bound to oxygen-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
    • C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
    • C08G77/16—Polysiloxanes containing silicon bound to oxygen-containing groups to hydroxyl 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
    • C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Silicon Polymers (AREA)

Abstract

The invention discloses a preparation method of UV (ultraviolet) light-cured organic silicon resin for direct-writing forming, which comprises the following steps: (1) preparing a siloxane solution by adopting reactants of hydroxyl-terminated siloxane, alkoxy silane acrylate and the like; (2) preparing an acrylate modified POSS intermediate by adopting reactants such as epoxy modified POSS, hydroxyl acrylate and the like; (3) preparing POSS modified organic silicon resin by adopting the prepared POSS intermediate modified by acrylic ester and siloxane solution; (4) adding a photoinitiator into the POSS modified organic silicon resin, carrying out ultrasonic oscillation, and removing the solvent under reduced pressure after the photoinitiator is completely dissolved and dispersed to the whole system to obtain the UV photocuring organic silicon resin for direct-writing forming. The preparation method of the rapid UV light-cured organic silicon resin for direct-write forming provided by the invention has the advantages of simple process, environmental friendliness, rapid forming and curing and the like, can meet the requirements of direct-write forming, and provides a new idea for modification of the UV light-cured organic silicon resin.

Description

Preparation method of UV (ultraviolet) light-cured organic silicon resin for direct-writing forming
Technical Field
The invention relates to the technical field of light-cured materials, in particular to a preparation method of UV light-cured organic silicon resin for direct-write molding.
Background
The direct-writing forming is an additive manufacturing mode which extrudes the slurry according to a pre-designed structure and a forming path and superposes the slurry layer by layer until the forming of the whole three-dimensional structure is completed. The technology has the advantages of high manufacturing efficiency, low cost, wide material application range, simple post-treatment and the like. The slurry for direct-write forming is mainly formed in a thermal curing or light curing mode, wherein ultraviolet light (UV) is used for initiating a high polymer material to generate polymerization crosslinking, so that a solid material can be formed instantly, and a thermal curing reaction process with high energy consumption and long reaction time can be replaced.
The organic silicon resin is an important organic polymer material, has excellent weather resistance, high and low temperature resistance, corrosion resistance and yellowing resistance, and can greatly improve the curing efficiency by introducing photosensitive groups into the organic silicon resin. The silicone resin capable of being rapidly cured by UV light combines the advantages of the light-cured resin and the silicone material, and can be directly used for direct-write molding. However, the most reported silicone resins at present are acrylate-based polysiloxane prepolymers, and because the compatibility of the silicone resins and other resins is poor, phase separation is easy to occur when acrylate groups are introduced, so that the introduction of reaction end groups is greatly limited; in addition, acrylate-based silicone resins are susceptible to oxygen resistance during ultraviolet curing, thereby affecting the curing reaction speed, curing precision and resin performance of the silicone resin.
In view of the situation, the organic silicon resin containing oligomeric silsesquioxane (POSS) is prepared by the invention, because the three-dimensional size of the POSS is generally 1-3 nm and the structure size is small, the POSS is easily combined with other organic and inorganic materials by a modification, grafting or physical blending method, so that the material performance is improved on the molecular level, and a new material with obviously improved various performances is obtained. Therefore, POSS is introduced into the organic silicon resin as an additive, based on the principle of similar compatibility, excellent dispersion performance can be obtained, and POSS can be uniformly connected into the organic silicon resin through chemical reaction bonding, so that the mechanical property and the intermolecular binding force of the organic silicon resin are enhanced, rapid UV photocuring can be realized, and a new thought is provided for modification of the UV photocuring organic silicon resin.
Disclosure of Invention
An object of the present invention is to solve at least the above problems and/or disadvantages and to provide at least the advantages described hereinafter.
The invention provides UV (ultraviolet) photocuring organic silicon resin for direct-writing forming, which is POSS modified organic silicon resin obtained by hydrolysis reaction of hydroxyl-terminated siloxane, alkoxy silane acrylate, epoxy modified POSS and hydroxyl acrylate, wherein the POSS is obtained by hydrolysis modification of the hydroxyl acrylate.
Before use, the organic silicon resin and the photoinitiator are uniformly mixed to obtain the rapid UV photocuring organic silicon resin for direct-writing forming.
To achieve these objects and other advantages in accordance with the present invention, there is provided a method for preparing a UV light-curable silicone resin for direct write molding, comprising the steps of:
step one, dissolving hydroxyl-terminated siloxane and alkoxy silane acrylate in an anhydrous solvent I, stirring until the hydroxyl-terminated siloxane and alkoxy silane acrylate are completely dissolved, adding concentrated hydrochloric acid and deionized water, and introducing N2Protecting, stirring and hydrolyzing at the temperature of 10-30 ℃ and at the speed of 50-100 rpm, and reacting for 8-16 h to obtain a siloxane solution;
step two, dissolving the epoxy modified POSS and the hydroxyl acrylic ester in an anhydrous solvent II, stirring until the epoxy modified POSS and the hydroxyl acrylic ester are completely dissolved, adding a catalyst and a polymerization inhibitor, and introducing N2Protecting, heating in an oil bath at 90-110 ℃, stirring at 50-100 rpm, and reacting for 4-8 h to obtain an acrylate modified POSS intermediate;
step three, dropwise adding the POSS intermediate modified by the acrylic ester prepared in the step two into a siloxane solution, stirring and hydrolyzing at the temperature of 10-30 ℃ and at the rpm of 50-100 for 2-3 h, then heating to the temperature of 45-55 ℃, and carrying out reduced pressure distillation for 1-2 h to obtain POSS modified organic silicon resin;
and step four, adding a photoinitiator into the POSS modified organic silicon resin prepared in the step three, carrying out ultrasonic oscillation for 0.5-1h, and removing the solvent under reduced pressure after the photoinitiator is completely dissolved and dispersed to the whole system to prepare the UV photocuring organic silicon resin for direct writing forming.
Preferably, in step one, the hydroxyl terminated siloxane is [ (CH3)0.96(OR)0.04SiO1.5]nWherein the crosslinking end group OR is hydroxyl-OH and alkoxy-OC2H5(ii) a The alkoxysilane acrylate is methacryloxypropyltrimethylsilane.
Preferably, the anhydrous solvent I and the anhydrous solvent II are one or more of tetrahydrofuran, 1, 4-dioxane and ethylene glycol dimethyl ether.
Preferably, in the first step, the mass ratio of the hydroxyl-terminated siloxane to the alkoxy silane acrylate is 4:1, and the anhydrous solvent I is adopted to prepare a solution of 0.5-1 g/m L according to the mass ratio, and the molar weight of the concentrated hydrochloric acid and the deionized water is 1-2% and 100% of that of the alkoxy silane acrylate respectively.
Preferably, in the second step, the epoxy modified POSS is glycidyl ether methyl silsesquioxane; the hydroxyl acrylate is one or more of hydroxypropyl acrylate, hydroxyethyl methacrylate and pentaerythritol triacrylate; the catalyst is one or more of N, N-dimethylbenzylamine, triphenylphosphine and tetramethylammonium bromide; the polymerization inhibitor is one or more of hydroquinone, hydroquinone and p-methoxyphenol.
Preferably, in the second step, the mass ratio of the epoxy modified POSS to the hydroxyl acrylate is 1: 1-2, the anhydrous solvent II is added to ensure that the solution concentration of the epoxy modified POSS is 0.05-0.1 g/m L, the dosage of the catalyst is 2% of the mass of the hydroxyl acrylate, and the dosage of the polymerization inhibitor is 0.1% of the mass of the hydroxyl acrylate.
Preferably, in the third step, the mass of the siloxane and the POSS intermediate modified by the acrylate in the siloxane solution is 50-100: 1.
Preferably, in the fourth step, the photoinitiator is one or more of α -hydroxycyclohexyl benzophenone, benzoin dimethyl ether and 2- (4-methylmercaptobenzoyl) -2-morpholinyl propane, and the dosage of the photoinitiator is 3% of the mass of the POSS modified organic silicon resin.
Preferably, in the fourth step, the frequency of ultrasonic oscillation is 30-45 KHz, the ultrasonic wave adopts intermittent irradiation, and the intermittent time during the intermittent irradiation is 15-20 s/5-10 s; the viscosity of the obtained UV light-cured organic silicon resin for direct-writing forming is 840-1080 Pas.
The invention at least comprises the following beneficial effects:
(1) compared with the prior art, the rapid UV light-cured organic silicon resin for direct-writing forming is prepared by introducing POSS into an organic silicon polyacrylic acid prepolymer by a chemical bonding method, has the advantages of POSS, acrylate group and organic silicon, improves the mechanical property of an organic silicon material on the molecular level, can rapidly realize curing under UV light, and overcomes the defects of low chemical compatibility and low curing speed of the traditional acrylate organic silicon resin;
(2) the preparation method of the rapid UV light-cured organic silicon resin for direct-write forming provided by the invention has the advantages of simple process, environmental friendliness, rapid forming and curing and the like, can meet the requirements of direct-write forming, and provides a new idea for modification of the UV light-cured organic silicon resin.
Additional advantages, objects, and features of the invention will be set forth in part in the description which follows and in part will become apparent to those having ordinary skill in the art upon examination of the following or may be learned from practice of the invention.
Description of the drawings:
FIG. 1 is a graph showing the viscosity properties of the silicone resin obtained in example 1;
FIG. 2 is a photomicrograph of a sample obtained by using the rapid UV light-curing silicone resin paste obtained in example 2 for direct-write molding;
FIG. 3 is a chemical reaction scheme of the step one reaction of the present invention;
FIG. 4 shows the chemical reaction scheme of the step two reaction of the present invention;
FIG. 5 shows the chemical reaction scheme of the step three reaction of the present invention;
fig. 6 is a reaction formula of UV curing reaction of the UV light-curable silicone resin for direct write molding according to the present invention.
The specific implementation mode is as follows:
the present invention is further described in detail below with reference to the attached drawings so that those skilled in the art can implement the invention by referring to the description text.
It will be understood that terms such as "having," "including," and "comprising," as used herein, do not preclude the presence or addition of one or more other elements or groups thereof.
Step one, 20g of hydroxyl terminated siloxane resin, 5g of methacryloxypropyltrimethylsilane (20.1mmol) were dissolved in 25m L Tetrahydrofuran (THF), stirred at 50rpm until completely dissolved, 143. mu. L concentrated hydrochloric acid (0.2mmol) and 362. mu. L deionized water (20.1mmol) were added, and N was passed through2Protecting, stirring and hydrolyzing at 10 ℃, and reacting for 16h to obtain a siloxane solution;
step two, adding 1g of glycidyl ether methyl silsesquioxane (POSS) and 1g of pentaerythritol triacrylate (PETA) into 20m L THF, stirring at 50rpm until complete dissolution, adding 20mg of N, N-dimethylbenzylamine and 1mg of hydroquinone, and introducing N2Protecting, heating in oil bath at 90 ℃, and reacting for 8h to obtain an acrylate modified POSS intermediate;
step three, dropwise adding the acrylate modified POSS intermediate (0.1g) prepared in the step two of 1m L into the siloxane solution (containing 5g of reaction product siloxane) obtained in the step one of 5m L, stirring and hydrolyzing at 10 ℃ and 50rpm for 2h, then heating to 50 ℃, and distilling under reduced pressure for 2h to obtain POSS modified organic silicon resin;
and step four, adding 0.15g of α -hydroxycyclohexyl benzophenone serving as a photoinitiator into the POSS modified organic silicon resin prepared in the step three, ultrasonically oscillating for 1h, and removing a THF solvent under reduced pressure after the photoinitiator is completely dissolved and dispersed to the whole system to prepare the rapid UV photocuring organic silicon resin for photocuring direct writing.
The silicone resin prepared in inventive example 1 was tested using a (rotational viscometer) to a viscosity of 1080Pas @25 ℃; the UV light-cured organic silicon resin for direct-write forming prepared by the embodiment of the invention is transferred into a needle cylinder for direct-write, is centrifuged by a high-speed centrifuge (8000rpm) to remove air bubbles, is extruded on a clean glass substrate, is cured by an ultraviolet lamp, and has the wavelength of 365nm and workThe rate is 200mW/cm2And exposing for 1s to obtain cured silicone resin dots.
Example 2:
step one, 20g of hydroxyl-terminated siloxane resin and 5g of methacryloxypropyltrimethylsilane (20.1mmol) are dissolved in 50m L1, 4-dioxane, stirred until the materials are completely dissolved, 286 mu L concentrated hydrochloric acid (0.4mmol) and 362 mu L deionized water (20.1mmol) are added, and N is introduced2Protecting, stirring and hydrolyzing at 20 ℃, and reacting for 12h to obtain a siloxane solution;
step two, dissolving 1g of glycidyl ether methyl silsesquioxane (POSS) and 1g of hydroxypropyl acrylate in 20m L1, 4-dioxane, adding 20mg of N, N-dimethylbenzylamine and 1mg of hydroquinone, and introducing N2Protecting, heating in oil bath at 100 ℃, and reacting for 6h to obtain an acrylate modified POSS intermediate;
step three, dropwise adding the acrylate modified POSS intermediate 2(0.1g) prepared in the step two of 1m L into the siloxane solution (containing 5g of reaction product siloxane) obtained in the step one of 5m L, stirring and hydrolyzing at 10 ℃ for 2h, then heating to 45 ℃, and distilling under reduced pressure for 2h to obtain POSS modified organic silicon resin;
and step four, adding 0.15g of α -hydroxycyclohexyl benzophenone serving as a photoinitiator into the POSS modified organic silicon resin prepared in the step three, ultrasonically oscillating for 1h, and removing the 1, 4-dioxane solvent under reduced pressure after the photoinitiator is completely dissolved and dispersed into the whole system to prepare the rapid UV photocuring direct-writing organic silicon resin.
The silicone resin prepared in the examples of the present invention was tested using a (rotational viscometer) and had a viscosity of 960Pas @25 ℃; the UV light-cured silicone resin for direct-write molding prepared in the example of the present invention was transferred to a syringe for direct-write, centrifuged at 8000rpm to remove air bubbles, extruded on a clean glass substrate, cured with an ultraviolet lamp at 365nm with a power of 200mW/cm2And exposing for 1s to obtain the cured organic silicon resin.
Example 3:
step one, dissolving 20g of alkoxy-terminated siloxane resin and 5g of methacryloxypropyltrimethylsilane (20.1mmol) in 25m L1, 4-dioxane, stirring at 70rpm until the materials are completely dissolved, adding 286 mu L of concentrated hydrochloric acid (0.2mmol) and 362 mu L of deionized water (20.1mmol), introducing N2 for protection, stirring at 20 ℃ for hydrolysis, and reacting for 12 hours to obtain a siloxane solution;
step two, adding 1g of glycidyl ether methyl silsesquioxane (POSS) and 1g of hydroxyethyl methacrylate into 20m L1, 4-dioxane, stirring at 90rpm until the mixture is completely dissolved, adding 20mg of triphenylphosphine and 1mg of p-phenylenediamine, and introducing N2Protecting, heating in oil bath at 100 ℃, and reacting for 6h to obtain an acrylate modified POSS intermediate;
step three, dropwise adding the acrylate modified POSS intermediate (0.1g) prepared in the step two of 1m L into the siloxane solution (containing 10g of reaction product siloxane) obtained in the step one of 10m L, stirring and hydrolyzing at 10 ℃ and 70rpm for 2h, then heating to 50 ℃, and distilling under reduced pressure for 2h to obtain POSS modified organic silicon resin;
and step four, adding 0.3g of benzoin dimethyl ether serving as a photoinitiator into the POSS modified organic silicon resin prepared in the step three, ultrasonically oscillating for 1h, and removing the 1, 4-dioxane solvent under reduced pressure after the photoinitiator is completely dissolved and dispersed to the whole system to prepare the rapid UV photocuring organic silicon resin for photocuring direct writing.
The silicone resin prepared in the examples of the present invention was tested using a (rotational viscometer) and had a viscosity of 870Pas @25 ℃; the UV light-cured silicone resin for direct-write molding prepared in the example of the present invention was transferred to a syringe for direct-write, centrifuged at 8000rpm to remove air bubbles, extruded on a clean glass substrate, cured with an ultraviolet lamp at 365nm with a power of 200mW/cm2And exposing for 1s to obtain cured silicone resin dots.
Example 4:
step one, 20g of hydroxyl-terminated siloxane resin and 5g of methacryloxypropyltrimethylsilane (20.1mmol) are dissolved in 50m L ethylene glycol dimethyl ether, stirred at 70rpm until the materials are completely dissolved, 286 mu L of concentrated hydrochloric acid (0.4mmol) and 362 mu L of deionized water (20.1mmol) are added, and N is introduced2Protecting, stirring and hydrolyzing at 10 ℃, and reacting for 16h to obtain a siloxane solution;
step two, adding 0.5g of glycidyl ether methyl silsesquioxane (POSS) and 1g of pentaerythritol triacrylate into 5m L ethylene glycol dimethyl ether, stirring at 60rpm until the mixture is completely dissolved, adding 20mg of tetramethylammonium bromide and 1mg of p-methoxyphenol, and introducing N2Protecting, heating in oil bath at 100 ℃, and reacting for 6h to obtain an acrylate modified POSS intermediate;
step three, dropwise adding the acrylate modified POSS intermediate (0.3g) prepared in the step two of 1m L into the siloxane solution (containing 10g of reaction product siloxane) obtained in the step one of 30m L, stirring and hydrolyzing at 10 ℃ and 80rpm for 2h, then heating to 55 ℃, and distilling under reduced pressure for 2h to obtain POSS modified organic silicon resin;
and step four, adding 0.3g of photoinitiator into the POSS modified organic silicon resin prepared in the step three, ultrasonically oscillating for 1h, and removing the 1, 4-dioxane solvent under reduced pressure after the photoinitiator is completely dissolved and dispersed into the whole system to prepare the rapid UV photocuring organic silicon resin for photocuring direct writing.
The silicone resin prepared in the examples of the present invention was tested using a rotational viscometer, and had a viscosity of 1020Pas @25 ℃; the UV light-cured silicone resin for direct-write molding prepared in the example of the invention was transferred to a needle cylinder for direct-write, centrifuged by a high-speed centrifuge (8000rpm) to remove air bubbles, extruded on a clean glass substrate, cured with an ultraviolet lamp at a wavelength of 365nm and a power of 200mW/cm2And exposing for 1s to obtain cured silicone resin dots.
Example 5:
step one, 20g of hydroxyl terminated siloxane resin, 5g of methacryloxypropyltrimethylsilane (20.1mmol) were dissolved in 50m L Tetrahydrofuran (THF), stirred at 100rpm until completely dissolved, 143. mu. L concentrated hydrochloric acid (0.4mmol) and 362. mu. L deionized water (20.1mmol) were added, and N was passed through2Protecting, stirring and hydrolyzing at 30 ℃, and reacting for 16h to obtain a siloxane solution 1;
step two, 1g of glycidolEther methyl silsesquioxane (POSS) and 1g pentaerythritol triacrylate (PETA) were added to 10m L THF, stirred at 80rpm until completely dissolved, then 20mg N, N-dimethylbenzylamine and 1mg hydroquinone were added, and N was bubbled through2Protecting, heating in oil bath at 90 ℃, and reacting for 4h to obtain an acrylate modified POSS intermediate;
step three, dropwise adding the acrylate modified POSS intermediate (0.1g) prepared in the step two of 0.5m L into the siloxane solution (containing 5g of reaction product siloxane) obtained in the step one of 10m L, stirring and hydrolyzing at 30 ℃ and 60rpm for 2h, then heating to 45 ℃, and distilling under reduced pressure for 2h to obtain POSS modified organic silicon resin;
and step four, adding 0.15g of photoinitiator into the POSS modified organic silicon resin prepared in the step three, ultrasonically oscillating for 1h, and removing the THF solvent under reduced pressure after the photoinitiator is completely dissolved and dispersed into the whole system to prepare the rapid UV photocuring organic silicon resin for photocuring direct writing.
The silicone resin prepared in the examples of the present invention was tested using a (rotational viscometer) and had a viscosity of 910Pas @25 ℃; the UV light-cured silicone resin for direct-write molding prepared in the example of the present invention was transferred to a syringe for direct-write, centrifuged at 8000rpm to remove air bubbles, extruded on a clean glass substrate, cured with an ultraviolet lamp at 365nm with a power of 200mW/cm2And exposing for 1s to obtain cured silicone resin dots.
Example 6:
step one, 20g of hydroxyl-terminated siloxane resin and 5g of methacryloxypropyltrimethylsilane (20.1mmol) were dissolved in 50m L tetrahydrofuran, stirred at 80rpm until completely dissolved, 143. mu. L of concentrated hydrochloric acid (0.4mmol) and 362. mu. L of deionized water (20.1mmol) were added, and N was introduced2Protecting, stirring and hydrolyzing at 30 ℃, and reacting for 16h to obtain a siloxane solution;
step two, adding 1g of glycidyl ether methyl silsesquioxane (POSS) and 1g of pentaerythritol triacrylate into 20m L tetrahydrofuran, stirring at 100rpm until the mixture is completely dissolved, adding 20mg of triphenylphosphine and 1mg of hydroquinone,introduction of N2Protecting, heating in oil bath at 90 ℃, and reacting for 6h to obtain an acrylate modified POSS intermediate;
step three, dropwise adding the acrylate modified POSS intermediate 2(0.1g) prepared in the step two of 1m L into the siloxane solution (containing 10g of reaction product siloxane) obtained in the step one of 20m L, stirring and hydrolyzing at 30 ℃ and 100rpm for 2h, then heating to 50 ℃, and distilling under reduced pressure for 2h to obtain POSS modified organic silicon resin;
and step four, adding 0.3g of α -hydroxycyclohexyl benzophenone serving as a photoinitiator into the POSS modified organic silicon resin prepared in the step three, ultrasonically oscillating for 1h, and removing the tetrahydrofuran solvent under reduced pressure after the photoinitiator is completely dissolved and dispersed into the whole system to prepare the rapid UV photocuring organic silicon resin for photocuring direct writing.
The silicone resin prepared in the examples of the present invention was tested using a (rotational viscometer) and had a viscosity of 840Pas @25 ℃; the UV light-cured silicone resin for direct-write molding prepared in the example of the present invention was transferred to a syringe for direct-write, centrifuged at 8000rpm to remove air bubbles, extruded on a clean glass substrate, cured with an ultraviolet lamp at 365nm with a power of 200mW/cm2And exposing for 1s to obtain cured silicone resin dots.
Example 7:
step one, dissolving 20g of alkoxy-terminated siloxane resin and 5g of methacryloxypropyltrimethylsilane (20.1mmol) in 50m L ethylene glycol dimethyl ether, stirring at 50rpm until the materials are completely dissolved, adding 143 mu L concentrated hydrochloric acid (0.4mmol) and 362 mu L deionized water (20.1mmol), and introducing N2Protecting, stirring and hydrolyzing at 30 ℃, and reacting for 16h to obtain a siloxane solution;
step two, adding 1g of glycidyl ether methyl silsesquioxane (POSS) and 1g of hydroxyethyl methacrylate into 20m L ethylene glycol dimethyl ether, stirring at 50rpm until the mixture is completely dissolved, adding 20mg of tetramethylammonium bromide and 1mg of p-methoxyphenol, and introducing N2Protecting, heating in oil bath at 90 ℃, and reacting for 6h to obtain an acrylate modified POSS intermediate;
step three, dropwise adding the acrylate modified POSS intermediate (0.1g) prepared in the step two of 1m L into the siloxane solution (containing 10g of reaction product siloxane) obtained in the step one of 20m L, stirring and hydrolyzing at 30 ℃ and 50rpm for 2h, then heating to 55 ℃, and distilling under reduced pressure for 2h to obtain POSS modified organic silicon resin;
and step four, adding 0.3g of benzoin dimethyl ether serving as a photoinitiator into the POSS modified organic silicon resin prepared in the step three, ultrasonically oscillating for 1h, and removing the ethylene glycol dimethyl ether solvent under reduced pressure after the photoinitiator is completely dissolved and dispersed to the whole system to prepare the rapid UV photocuring organic silicon resin for photocuring direct writing.
The silicone resin prepared in the examples of the present invention was tested using a (rotational viscometer) viscosity of 860Pas @25 ℃; the UV light-cured silicone resin for direct-write molding prepared in the embodiment of the invention is transferred into a needle cylinder for direct-write molding, is centrifuged by a high-speed centrifuge (8000rpm) to remove air bubbles, is extruded on a clean glass substrate, is cured by an ultraviolet lamp with the wavelength of 365nm and the power of 200mW/cm2 for 1s, and then cured silicone resin dots are obtained.
While embodiments of the invention have been described above, it is not limited to the applications set forth in the description and the embodiments, which are fully applicable in various fields of endeavor to which the invention pertains, and further modifications may readily be made by those skilled in the art, it being understood that the invention is not limited to the details shown and described herein without departing from the general concept defined by the appended claims and their equivalents.

Claims (5)

1. A preparation method of UV light-cured organic silicon resin for direct-write molding is characterized by comprising the following steps:
step one, dissolving hydroxyl-terminated siloxane and alkoxy silane acrylate in an anhydrous solvent I, stirring until the hydroxyl-terminated siloxane and alkoxy silane acrylate are completely dissolved, adding concentrated hydrochloric acid and deionized water, and introducing N2Protecting, stirring and hydrolyzing at the temperature of 10-30 ℃ and at the speed of 50-100 rpm, and reacting for 8-16 h to obtain a siloxane solution;
step two, modifying POSS by epoxy,Dissolving hydroxyl acrylic ester in anhydrous solvent II, stirring to dissolve completely, adding catalyst and polymerization inhibitor, introducing N2Protecting, heating in an oil bath at 90-110 ℃, stirring at 50-100 rpm, and reacting for 4-8 h to obtain an acrylate modified POSS intermediate;
step three, dropwise adding the POSS intermediate modified by the acrylic ester prepared in the step two into a siloxane solution, stirring and hydrolyzing at the temperature of 10-30 ℃ and at the rpm of 50-100 for 2-3 h, then heating to the temperature of 45-55 ℃, and carrying out reduced pressure distillation for 1-2 h to obtain POSS modified organic silicon resin;
step four, adding a photoinitiator into the POSS modified organic silicon resin prepared in the step three, carrying out ultrasonic oscillation for 0.5-1h, and removing the solvent under reduced pressure after the photoinitiator is completely dissolved and dispersed to the whole system to prepare the UV photocuring organic silicon resin for direct writing forming;
in the first step, the hydroxyl-terminated siloxane is [ (CH3)0.96(OR)0.04SiO1.5]nWherein the crosslinking end group OR is hydroxyl-OH and alkoxy-OC2H5(ii) a The alkoxy silane acrylate is methacryloxypropyl trimethoxy silane;
in the first step, the mass ratio of hydroxyl-terminated siloxane to alkoxy silane acrylate is 4:1, an anhydrous solvent I is adopted to prepare a solution of 0.5-1 g/m L according to the mass ratio, and the molar weight of concentrated hydrochloric acid and deionized water is 1-2% and 100% of that of alkoxy silane acrylate respectively;
in the second step, the epoxy modified POSS is glycidyl ether methyl silsesquioxane; the hydroxyl acrylate is one or more of hydroxypropyl acrylate, hydroxyethyl methacrylate and pentaerythritol triacrylate; the catalyst is one or more of N, N-dimethylbenzylamine, triphenylphosphine and tetramethylammonium bromide; the polymerization inhibitor is one or more of hydroquinone, hydroquinone and p-methoxyphenol;
in the second step, the mass ratio of the epoxy modified POSS to the hydroxyl acrylate is 1: 1-2, the solution concentration of the epoxy modified POSS is 0.05-0.1 g/m L due to the added anhydrous solvent II, the dosage of the catalyst is 2% of the mass of the hydroxyl acrylate, and the dosage of the polymerization inhibitor is 0.1% of the mass of the hydroxyl acrylate.
2. The method for preparing the UV light-curable silicone resin for direct write molding according to claim 1, wherein the anhydrous solvent I and the anhydrous solvent II are both one or more of tetrahydrofuran, 1, 4-dioxane, and ethylene glycol dimethyl ether.
3. The method for preparing the UV light-cured silicone resin for direct-write forming according to claim 1, wherein in the third step, the mass ratio of siloxane in the siloxane solution to the acrylate-modified POSS intermediate is 50-100: 1.
4. The method for preparing the UV light-curable silicone resin for direct write forming according to claim 1, wherein in the fourth step, the photoinitiator is one or more of α -hydroxycyclohexyl benzophenone, benzoin dimethyl ether and 2-methyl-1- (4-methylthiophenyl) -2-morpholinyl-1-propanone, and the dosage of the photoinitiator is 3% of the mass of the POSS modified silicone resin.
5. The method for preparing the UV light-curable silicone resin for direct write molding according to claim 1, wherein in the fourth step, the frequency of ultrasonic oscillation is 30 to 45kHz, the ultrasonic wave is intermittent irradiation, and the irradiation time/intermittent time during intermittent irradiation is 15 to 20s/5 to 10 s; the viscosity of the obtained UV light-cured organic silicon resin for direct-writing forming is 840-1080 Pa & s.
CN201810139310.XA 2018-02-11 2018-02-11 Preparation method of UV (ultraviolet) light-cured organic silicon resin for direct-writing forming Active CN108264640B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201810139310.XA CN108264640B (en) 2018-02-11 2018-02-11 Preparation method of UV (ultraviolet) light-cured organic silicon resin for direct-writing forming

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201810139310.XA CN108264640B (en) 2018-02-11 2018-02-11 Preparation method of UV (ultraviolet) light-cured organic silicon resin for direct-writing forming

Publications (2)

Publication Number Publication Date
CN108264640A CN108264640A (en) 2018-07-10
CN108264640B true CN108264640B (en) 2020-07-21

Family

ID=62774162

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201810139310.XA Active CN108264640B (en) 2018-02-11 2018-02-11 Preparation method of UV (ultraviolet) light-cured organic silicon resin for direct-writing forming

Country Status (1)

Country Link
CN (1) CN108264640B (en)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109384931B (en) * 2018-08-23 2021-04-23 杭州师范大学 Preparation method and application of photosensitive silicone resin containing polyurethane bridged polysilsesquioxane
CN110408070B (en) * 2019-07-31 2022-03-01 中国工程物理研究院激光聚变研究中心 High-threshold-value scratch-resistant high-transmittance fundamental-frequency laser film and preparation method thereof
CN111362702B (en) * 2020-03-17 2022-05-17 中国工程物理研究院激光聚变研究中心 Preparation method of SiOC radar type wave-absorbing material
TWI747655B (en) 2020-12-09 2021-11-21 財團法人工業技術研究院 Organic-inorganic hybrid resin, coating material, and composite structure

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101024751A (en) * 2007-03-09 2007-08-29 厦门大学 Coating material containing POSS acrylate copolymer and preparing method
CN102186861A (en) * 2008-10-15 2011-09-14 关西涂料株式会社 Silsesquioxane compound having polymerizable functional group
CN102241866A (en) * 2011-06-02 2011-11-16 苏州大学 Transparent acrylic acid silicone resin nano composite material and preparation method thereof
JP2015218288A (en) * 2014-05-20 2015-12-07 三菱レイヨン株式会社 Curable composition, cured product, and laminate

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101024751A (en) * 2007-03-09 2007-08-29 厦门大学 Coating material containing POSS acrylate copolymer and preparing method
CN102186861A (en) * 2008-10-15 2011-09-14 关西涂料株式会社 Silsesquioxane compound having polymerizable functional group
CN102241866A (en) * 2011-06-02 2011-11-16 苏州大学 Transparent acrylic acid silicone resin nano composite material and preparation method thereof
JP2015218288A (en) * 2014-05-20 2015-12-07 三菱レイヨン株式会社 Curable composition, cured product, and laminate

Also Published As

Publication number Publication date
CN108264640A (en) 2018-07-10

Similar Documents

Publication Publication Date Title
CN108264640B (en) Preparation method of UV (ultraviolet) light-cured organic silicon resin for direct-writing forming
CN104559196B (en) Colorless and transparent light-cured 3D printing material
EP3196229B1 (en) Branched polyorganosiloxanes and related curable compositions, methods, uses and devices
KR101194153B1 (en) Polyorganosiloxane and curable composition containing same
CN104610696B (en) Organic silicon composition for UV curing
KR960031510A (en) Preparation of organically modified radiation-curable siloxane resin
CN1754915A (en) Silicone resin composition and molded product thereof
CN1747985A (en) Silicon compound containing epoxy group and thermosetting resin composition
CN102471585A (en) Silicon-containing curable composition and cured product thereof
CN1961026A (en) Active energy ray-curable organopolysiloxane resin composition, optical transmission component, and manufacturing method thereof
CN1417259A (en) Organosilicon resin composition and molded organosilicon resin body
CN101555386A (en) Epoxy organosilicone ultraviolet curing coating modified by (methyl) acrylic acid and preparation method thereof
CN112080241B (en) Photo-curing adhesive and preparation method and application thereof
CN1064055C (en) Epoxy acrylates
JP3976778B2 (en) Oxetane compound and curable composition containing the same
JPH06128354A (en) One-pack ultraviolet-curing epoxy silicone composition
JPH0629382B2 (en) UV curable hard coating agent
JP2023521261A (en) Silicone composition and cured product thereof
KR20140007800A (en) Photosensitive resin composition
WO2019205802A1 (en) Method for preparing ultraviolet (uv) curing polymethylsiloxane containing acrylate structure
JP2009270027A (en) Photosensitive resin composition and method for producing base material with resin layer using the same
JP2012180462A (en) Curable resin composition, cured product thereof, and various articles derived from the same
JP2008518050A (en) Coating composition containing a carbinol functional silicone resin or an anhydride functional silicone resin
JPH02294314A (en) Ultraviolet-curing phenyl-containing acrylamide composition
CN110183664B (en) Preparation method and application of ultraviolet-curing methacrylate-containing silicone oil

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant