CN112812272A - Preparation method of organic silicon modified epoxy acrylate, organic silicon modified epoxy acrylate resin composition and cured product - Google Patents
Preparation method of organic silicon modified epoxy acrylate, organic silicon modified epoxy acrylate resin composition and cured product Download PDFInfo
- Publication number
- CN112812272A CN112812272A CN202110171536.XA CN202110171536A CN112812272A CN 112812272 A CN112812272 A CN 112812272A CN 202110171536 A CN202110171536 A CN 202110171536A CN 112812272 A CN112812272 A CN 112812272A
- Authority
- CN
- China
- Prior art keywords
- epoxy acrylate
- modified epoxy
- organic silicon
- preparation
- reaction
- 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.)
- Pending
Links
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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/14—Polycondensates modified by chemical after-treatment
- C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
- C08G59/1438—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing oxygen
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
- C09D163/10—Epoxy resins modified by unsaturated compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Emergency Medicine (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Silicon Polymers (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
The invention provides a preparation method of organic silicon modified epoxy acrylate, an organic silicon modified epoxy acrylate resin composition and a cured product. The preparation method comprises the following steps: the epoxy acrylate and the silane modifier are subjected to substitution reaction under the catalysis of organic tin to obtain the organic silicon modified epoxy acrylate, wherein the silane modifier is any one of phenyl trialkoxysilanes. The organosilicon modified epoxy acrylate is utilized, and resin is not modified through copolycondensation reaction, so that the organosilicon and the epoxy acrylate can be connected at a lower reaction temperature to obtain the organosilicon modified epoxy acrylate. And the modification is carried out under the catalysis of organic tin, so that higher reaction efficiency is ensured. The organic silicon modified epoxy acrylate resin is prepared through polymerization, and can be used as a photosensitive material to realize 3D printing. And has the advantages of good thermal stability, weather resistance, oxidation resistance and good low-temperature characteristics due to the Si-O bond.
Description
Technical Field
The invention relates to the field of photosensitive resin, in particular to a preparation method of organic silicon modified epoxy acrylate, an organic silicon modified epoxy acrylate resin composition and a cured product.
Background
The three-dimensional rapid forming 3D printing technology using photosensitive resin as a raw material has the advantages of low cost, high precision, rapid forming and the like, and is widely applied to various fields. However, the photosensitive resin material suitable for the photosensitive resin material is high in price and is monopolized by some large foreign companies, and related research and development in China are late, so that few enterprises capable of producing and developing 3D printing photosensitive resin with excellent performance are provided. The prior photosensitive resin mainly adopts epoxy resin materials, resists high temperature of about 55 ℃, and cannot meet the use conditions of high-temperature places. Epoxy acrylic resin is the most common material for 3D printing, has the advantages of low price, good performance and the like, but can not meet the use condition in a high-temperature environment, and the toughness of the material is also deficient, so the epoxy acrylic resin can be used after being modified.
The main chain of the epoxy acrylic resin is composed of saturated C-C bonds, and the side chain is-COOH with polarity. Many researches at home and abroad show that the organosilicon modified epoxy acrylic resin post-material has better heat resistance, curing rate and the like. From the aspect of molecular structure, the organic silicon polymer contains Si-O bonds, and the bond energy (450KJ/mol) is far larger than the C-C bond energy (345KJ/mol) in an acrylic acid molecular chain, so that the organic silicon polymer has the advantages of good thermal stability, weather resistance, oxidation resistance, good low-temperature property and the like. The epoxy acrylic resin modified by the epoxy acrylic resin can reduce the internal stress among material molecules and can also improve the high temperature resistance and toughness of the material. Because the structural difference between the organic silicon and the resin is huge, the compatibility is poor, and the physical blending is difficult to achieve a good modification effect. The general organosilicon modified epoxy acrylate is prepared by adopting a chemical method from a material with-OH or-OC2H5The organosilicon intermediate and epoxy acrylic resin containing-OH are subjected to copolycondensation reaction in an ester solvent, and the copolycondensation reaction can be realized at a high temperature of over 150 ℃ for a long time, so that the energy consumption is high and the modification degree is insufficient.
Disclosure of Invention
The invention mainly aims to provide a preparation method of organic silicon modified epoxy acrylate, an organic silicon modified epoxy acrylate resin composition and a cured product, so as to solve the problem of high energy consumption of copolymer modification in the prior art.
In order to achieve the above object, according to one aspect of the present invention, there is provided a method for preparing a silicone-modified epoxy acrylate, the method comprising: the epoxy acrylate and the silane modifier are subjected to substitution reaction under the catalysis of organic tin to obtain the organic silicon modified epoxy acrylate, wherein the silane modifier is any one of phenyl trialkoxysilanes.
Further, the silane modifier is phenyl triethoxysilane, the epoxy acrylate and the silane modifier are subjected to substitution reaction at 50-100 ℃, and the preferable molar ratio of the epoxy acrylate to the silane modifier is 2: 1-3: 1.
further, the organic tin is selected from one or more of dibutyltin dilaurate, dithiol alkyl tin and dialkyl tin dimaleate, and the molar ratio of the epoxy acrylate to the organic tin is 100: 0.5 to 2.
The substitution reaction is carried out in a solvent, the molar ratio of the epoxy acrylate to the solvent is 2-3: 45, the solvent is a polar solvent, and the solvent is preferably any one selected from xylene, toluene and propyl ether.
Further, the preparation method comprises the following steps: dispersing epoxy acrylate and organic tin in a solvent to form a dispersion liquid; adding a silane modifier to the dispersion under stirring and heating conditions to perform a substitution reaction, wherein the stirring speed is 100-400 rpm, the heating target temperature is 50-100 ℃, and the phenyltrialkoxysilane is preferably added to the dispersion at a speed of 30-40 s/d.
According to another aspect of the invention, an organosilicon modified epoxy acrylate resin composition is provided, which comprises a prepolymer, an acrylic monomer, an initiator and a cross-linking agent, wherein the prepolymer is the organosilicon modified epoxy acrylate obtained by any one of the preparation methods.
Further, the composition comprises, by weight, 50-75 parts of a prepolymer, 30-50 parts of an acrylic monomer and 2-3 parts of an initiator.
Further, the acrylate monomer is selected from any one or more of tripropylene glycol diacrylate, trimethylolpropane triacrylate, 1, 6-hexanediol diacrylate and beta-hydroxyethyl methacrylate.
Further, the initiator is selected from any one or more of 2-hydroxy-2-methyl-1-phenyl-1-acetone, 1-hydroxycyclohexyl phenyl ketone, benzophenone/tertiary amine system and 2-hydroxy-2-methyl propiophenone.
According to another aspect of the present invention, there is provided a cured product of a silicone-modified epoxy acrylate resin, which is obtained by photocuring a polymer obtained by polymerization of any one of the above-mentioned compositions as a raw material, preferably at a polymerization temperature of 30 to 70 ℃.
By applying the technical scheme of the invention, the organosilicon modified epoxy acrylate is utilized to modify the monomer, but not modify the resin through copolycondensation reaction, so that the organosilicon and the epoxy acrylate can be connected at a lower reaction temperature to obtain the organosilicon modified epoxy acrylate. And the modification is carried out under the catalysis of organic tin, so that higher reaction efficiency is ensured. The organic silicon modified epoxy acrylate resin can be used as a photosensitive material to realize 3D printing, and has Si-O bonds, so that the organic silicon modified epoxy acrylate resin has the advantages of good thermal stability, weather resistance, oxidation resistance and good low-temperature characteristics.
Detailed Description
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present invention will be described in detail with reference to examples.
As analyzed in the background of the present application, the copolycondensation reaction of the prior art generally requires a long time to be carried out at a high temperature of 150 ℃ or more, resulting in high energy consumption and insufficient modification degree. In order to solve the problem, the application provides a preparation method of organic silicon modified epoxy acrylate, an organic silicon modified epoxy acrylate resin composition and a cured product.
In one exemplary embodiment of the present application, there is provided a method of preparing a silicone-modified epoxy acrylate, the method comprising: the epoxy acrylate and the silane modifier are subjected to substitution reaction under the catalysis of organic tin to obtain the organic silicon modified epoxy acrylate, wherein the silane modifier is any one of phenyl trialkoxysilanes.
Since the organosilicon modified epoxy acrylate is used for modifying the monomer, but not for modifying the resin through copolycondensation reaction, the organosilicon and the epoxy acrylate can be connected at a lower reaction temperature to obtain the organosilicon modified epoxy acrylate. And the modification is carried out under the catalysis of organic tin, so that higher reaction efficiency is ensured. The organic silicon modified epoxy acrylate resin can be used as a photosensitive material to realize 3D printing, and has Si-O bonds, so that the organic silicon modified epoxy acrylate resin has the advantages of good thermal stability, weather resistance, oxidation resistance and good low-temperature characteristics.
The silane modifier is, for example, phenyltriethoxysilane. In order to further control the energy consumption of the preparation method and improve the reaction efficiency as much as possible, the epoxy acrylate and the silane modifier are preferably subjected to a substitution reaction at 50-100 ℃. In addition, in order to improve the raw material utilization rate, the molar ratio of the epoxy acrylate to the silane modifier is preferably 2: 1-3: 1.
the organotin used to catalyze the above reaction can be any organotin catalyst which is conventional at present, preferably, the organotin is any one or more selected from dibutyltin dilaurate, alkyltin dithiolate, dialkyltin dimaleate, and the molar ratio of epoxy acrylate to organotin is 100: 0.5-2, so as to avoid introducing excessive catalyst to cause catalyst waste.
In order to improve the contact uniformity of the reaction materials, the preparation method is preferably carried out in a homogeneous system, preferably, the substitution reaction is carried out in a solvent, the molar ratio of the epoxy acrylate to the solvent is 2-3: 45, the solvent is a polar solvent, and the solvent is preferably any one selected from xylene, toluene and propyl ether. The above solvents have high solubility to the respective reaction materials.
In some embodiments, the above preparation method comprises: dispersing epoxy acrylate and organic tin in a solvent to form a dispersion liquid; under the conditions of stirring and heating, adding a silane modifier into the dispersion liquid to perform substitution reaction, wherein the stirring speed is 100-400 rpm, and the heating target temperature is 50-100 ℃. In the above embodiment, the epoxy acrylate and the organotin are first dispersed in the solvent to form a homogeneous solution system, and then the silane modifier is added thereto under stirring and heating conditions, so that on one hand, the utilization rate of the silane modifier is improved, and on the other hand, the uniformity of the reaction is ensured. In order to further control the reaction progress and improve the raw material utilization rate, it is preferable that the phenyltrialkoxysilane is added to the dispersion at a rate of 30 to 40 seconds per droplet. In the scale-up production, the addition rate of phenyltrialkoxysilane can be controlled with reference to the above rate, and the addition by flow can be performed as converted into a volume amount even if the manner of dropping is not employed due to the expansion of the amount of the raw material.
In another exemplary embodiment of the present application, a silicone-modified epoxy acrylate resin composition is provided, which includes a prepolymer, an acrylic monomer, an initiator, and a cross-linking agent, where the prepolymer is the silicone-modified epoxy acrylate obtained by any one of the above-mentioned preparation methods. The components in the composition are all common components for resin synthesis, and the organic silicon modified epoxy acrylate prepared by the method is used as a prepolymer, so that the high temperature caused by the need of separately introducing silane in a copolycondensation reaction like the copolycondensation reaction mentioned in the background art can be avoided during the further polymerization to form the resin, and the energy consumption for resin preparation is reduced.
In some embodiments of the present invention, in order to obtain a resin with better mechanical properties, the composition preferably comprises 50 to 75 parts by weight of prepolymer, 30 to 50 parts by weight of acrylic monomer and 2 to 3 parts by weight of initiator. Preferably, the acrylate monomer is selected from any one or more of tripropylene glycol diacrylate (TPGDA), trimethylolpropane triacrylate (TMPTA), 1, 6-hexanediol diacrylate, and beta-hydroxyethyl methacrylate. The initiator is selected from any one or more of 2-hydroxy-2-methyl-1-phenyl-1-acetone, 1-hydroxycyclohexyl phenyl ketone (184), benzophenone/tertiary amine system and 2-hydroxy-2-methyl propiophenone.
In another exemplary embodiment of the present application, there is provided a cured product of a silicone-modified epoxy acrylate resin obtained by photocuring a polymer obtained by polymerization of the composition as a raw material, preferably at a polymerization temperature of 30 to 70 ℃. The polymer obtained by polymerizing the above-mentioned composition may be polymerized at a low temperature and then cured by light to form a cured product.
When applied to 3D printing, the cross-linking is achieved by 3D printing technology molding and then by photo-curing, which may employ commonly used uv curing.
The light curing time can be determined according to the polymer composition and the product requirements, and is controlled to be 10-200 s, for example.
The advantageous effects of the present application will be further described below with reference to examples and comparative examples.
Preparation of organosilicon modified epoxy acrylate
Examples 1 to 1
Adding dimethylbenzene into a round-bottom flask, then adding epoxy acrylate to completely dissolve the epoxy acrylate, then adding dibutyltin dilaurate into a pipette to be used as a catalyst (the molar ratio of the catalyst to the epoxy acrylate is 2: 100), building an experimental device, starting automatic stirring, wherein the stirring speed is 230rpm, the stirring reaction time is 4 hours, controlling the reaction temperature to be 70 ℃, slowly dripping phenyltriethoxysilane (the molar ratio of the epoxy acrylate, the phenyltriethoxysilane and the dimethylbenzene is 3: 1: 45) into the flask by using a constant-pressure dropping funnel at a speed of 40 seconds per drop, observing that the solution in the flask is yellow after the reaction is finished, and then carrying out reduced-pressure distillation on the solution to obtain a thick yellow liquid, namely the target product, namely the organic silicon modified epoxy acrylate.
Examples 1 to 2
Adding dimethylbenzene into a round-bottom flask, then adding epoxy acrylate to completely dissolve the epoxy acrylate, then adding dibutyltin dilaurate into a pipette to be used as a catalyst (the molar ratio of the catalyst to the epoxy acrylate is 2: 100), building an experimental device, starting automatic stirring, wherein the stirring speed is 210rpm, the stirring reaction time is 3 hours, controlling the reaction temperature to be 75 ℃, slowly dripping phenyltriethoxysilane (the molar ratio of the epoxy acrylate, the phenyltriethoxysilane and the dimethylbenzene is 3: 1: 45) into the flask by using a constant-pressure dropping funnel at the speed of 35 seconds per drop, observing that the solution in the flask is yellow after the reaction is finished, and then carrying out reduced-pressure distillation on the solution to obtain thick yellow liquid, namely the target product, namely the organic silicon modified epoxy acrylate.
Examples 1 to 3
Adding dimethylbenzene into a round-bottom flask, then adding epoxy acrylate to completely dissolve the epoxy acrylate, then adding dibutyltin dilaurate into a pipette to be used as a catalyst (the molar ratio of the catalyst to the epoxy acrylate is 2: 100), building an experimental device, starting automatic stirring, wherein the stirring speed is 200rpm, the stirring reaction time is 3 hours, controlling the reaction temperature to be 100 ℃, slowly dripping phenyltriethoxysilane (the molar ratio of the epoxy acrylate, the phenyltriethoxysilane and the dimethylbenzene is 3: 1: 45) into the round-bottom flask at the speed of 40 seconds per drop by using a constant-pressure dropping funnel, after the reaction is finished, observing that the solution in the round-bottom flask is yellow, and then carrying out reduced-pressure distillation on the solution to obtain a thick yellow liquid, namely the target product, namely the organic silicon modified epoxy acrylate.
Examples 1 to 4
Adding dimethylbenzene into a round-bottom flask, then adding epoxy acrylate to completely dissolve the epoxy acrylate, then adding dibutyltin dilaurate into a pipette to be used as a catalyst (the molar ratio of the catalyst to the epoxy acrylate is 2: 100), building an experimental device, starting automatic stirring, wherein the stirring speed is 100rpm, the stirring reaction time is 4 hours, controlling the reaction temperature to be 50 ℃, slowly dripping phenyltriethoxysilane (the molar ratio of the epoxy acrylate, the phenyltriethoxysilane and the dimethylbenzene is 3: 1: 45) into the flask by using a constant-pressure dropping funnel at a speed of 40 seconds per drop, observing that the solution in the flask is yellow after the reaction is finished, and then carrying out reduced-pressure distillation on the solution to obtain thick yellow liquid, namely the target product, namely the organic silicon modified epoxy acrylate.
Examples 1 to 5
Adding dimethylbenzene into a round-bottom flask, then adding epoxy acrylate to completely dissolve the epoxy acrylate, then adding dibutyltin dilaurate into a pipette to be used as a catalyst (the molar ratio of the catalyst to the epoxy acrylate is 2: 100), building an experimental device, starting automatic stirring, wherein the stirring speed is 300rpm, the stirring reaction time is 4 hours, controlling the reaction temperature to be 70 ℃, slowly dripping phenyltriethoxysilane (the molar ratio of the epoxy acrylate to the phenyltriethoxysilane dimethylbenzene is 2: 1: 45) into the flask by using a constant-pressure dropping funnel at the speed of 40 seconds per drop, after the reaction is finished, observing that the solution in the flask is yellow, and then carrying out reduced-pressure distillation on the solution to obtain a thick yellow liquid, namely the target product, namely the organic silicon modified epoxy acrylate.
Examples 1 to 6
Adding dimethylbenzene into a round-bottom flask, then adding epoxy acrylate to completely dissolve the epoxy acrylate, then adding dibutyltin dilaurate into a pipette to be used as a catalyst (the molar ratio of the catalyst to the epoxy acrylate is 0.5: 100), building an experimental device, starting automatic stirring, wherein the stirring speed is 240rpm, the stirring reaction time is 6 hours, controlling the reaction temperature to be 70 ℃, slowly dripping phenyltriethoxysilane (the molar ratio of the epoxy acrylate, the phenyltriethoxysilane and the dimethylbenzene is 3: 1: 45) into the reaction by using a constant-pressure dropping funnel at a speed of 40 seconds per drop, observing that the solution in the flask is yellow after the reaction is finished, and then carrying out reduced-pressure distillation on the solution to obtain a thick yellow liquid, namely the target product, namely the organic silicon modified epoxy acrylate.
Examples 1 to 7
Adding dimethylbenzene into a round-bottom flask, then adding epoxy acrylate to completely dissolve the epoxy acrylate, then adding dibutyltin dilaurate into a pipette to be used as a catalyst (the molar ratio of the catalyst to the epoxy acrylate is 2: 100), building an experimental device, starting automatic stirring, wherein the stirring speed is 240rpm, the stirring reaction time is 3 hours, controlling the reaction temperature to be 70 ℃, slowly dripping phenyltriethoxysilane (the molar ratio of the epoxy acrylate, the phenyltriethoxysilane and the dimethylbenzene is 3: 1: 45) into the round-bottom flask at the speed of 30 seconds per drop by using a constant-pressure dropping funnel, after the reaction is finished, observing that the solution in the round-bottom flask is yellow, and then carrying out reduced-pressure distillation on the solution to obtain a thick yellow liquid, namely the target product, namely the organic silicon modified epoxy acrylate.
Preparation of ultraviolet light cured organosilicon modified epoxy acrylic resin
Example 2-1
The silicone-modified epoxy acrylic resin of example 1-1, tripropylene glycol diacrylate (TPGDA), trimethylolpropane triacrylate (TMPTA), 2-hydroxy-2-methyl-1-phenyl-1-propanone (HMPP, 1173), 1-hydroxycyclohexyl phenyl ketone (184) were added to a light-tight, closed reaction vessel in a mass ratio of 50: 20: 30: 2: 1, controlling the reaction temperature at 50 ℃, the stirring speed at 240rpm, and the stirring reaction time at 1 h. And after the reaction is finished, taking out the prepared modified epoxy acrylic resin solution, storing in a dark place, and defoaming.
Preparing a cleaned and dried glass plate and a film scraping rod, pouring a proper amount of modified epoxy acrylic resin solution on the glass plate, quickly spreading the solution by using the glass rod, and curing the solution in an ultraviolet curing box for 10 seconds to obtain the cured modified epoxy acrylic resin material.
Examples 2 to 2
The silicone-modified epoxy acrylic resin of example 1-2, tripropylene glycol diacrylate (TPGDA), trimethylolpropane triacrylate (TMPTA), 2-hydroxy-2-methyl-1-phenyl-1-propanone (HMPP, 1173), 1-hydroxycyclohexyl phenyl ketone (184) were added to a light-tight closed reaction vessel in a mass ratio of 60: 20: 20: 2: 1, controlling the reaction temperature at 50 ℃, the stirring speed at 240rpm, and the stirring reaction time at 2 h. And after the reaction is finished, taking out the prepared modified epoxy acrylic resin solution, storing in a dark place, and defoaming.
Preparing a cleaned and dried glass plate and a film scraping rod, pouring a proper amount of modified epoxy acrylic resin solution on the glass plate, quickly spreading the solution by using the glass rod, and curing the solution in an ultraviolet curing box for 10 seconds to obtain the cured modified epoxy acrylic resin material.
Examples 2 to 3
The organosilicon modified epoxy acrylic resin, tripropylene glycol diacrylate (TPGDA), trimethylolpropane triacrylate (TMPTA), 2-hydroxy-2-methyl-1-phenyl-1-propanone (HMPP, 1173) and 1-hydroxycyclohexyl phenyl ketone (184) in example 1-2 are added into a lightproof closed reaction kettle, and the mass ratio is 60: 30: 10: 2: 1, controlling the reaction temperature to be 45 ℃, the stirring speed to be 240rpm, and the stirring reaction time to be 1 h. And after the reaction is finished, taking out the prepared modified epoxy acrylic resin solution, storing in a dark place, and defoaming.
Preparing a cleaned and dried glass plate and a film scraping rod, pouring a proper amount of modified epoxy acrylic resin solution on the glass plate, quickly spreading the solution by using the glass rod, and curing the solution in an ultraviolet curing box for 10 seconds to obtain the cured modified epoxy acrylic resin material.
Examples 2 to 4
The silicone-modified epoxy acrylic resin of example 1-1, tripropylene glycol diacrylate (TPGDA), trimethylolpropane triacrylate (TMPTA), 2-hydroxy-2-methyl-1-phenyl-1-propanone (HMPP, 1173), 1-hydroxycyclohexyl phenyl ketone (184) were added in a light-tight closed reaction vessel in a mass ratio of 70: 20: 10: 2: 1, controlling the reaction temperature at 50 ℃, the stirring speed at 240rpm, and the stirring reaction time at 0.5 h. And after the reaction is finished, taking out the prepared modified epoxy acrylic resin solution, storing in a dark place, and defoaming.
Preparing a cleaned and dried glass plate and a film scraping rod, pouring a proper amount of modified epoxy acrylic resin solution on the glass plate, quickly spreading the solution by using the glass rod, and curing the solution in an ultraviolet curing box for 10 seconds to obtain the cured modified epoxy acrylic resin material.
Examples 2 to 5
The silicone-modified epoxy acrylic resin of examples 1 to 3, tripropylene glycol diacrylate (TPGDA), trimethylolpropane triacrylate (TMPTA), 2-hydroxy-2-methyl-1-phenyl-1-propanone (HMPP, 1173), 1-hydroxycyclohexyl phenyl ketone (184) were added in a light-tight, closed reaction vessel in a mass ratio of 50: 20: 30: 2: 1, controlling the reaction temperature at 50 ℃, the stirring speed at 240rpm, and the stirring reaction time at 1 h. And after the reaction is finished, taking out the prepared modified epoxy acrylic resin solution, storing in a dark place, and defoaming.
Preparing a cleaned and dried glass plate and a film scraping rod, pouring a proper amount of modified epoxy acrylic resin solution on the glass plate, quickly spreading the solution by using the glass rod, and curing the solution in an ultraviolet curing box for 10 seconds to obtain the cured modified epoxy acrylic resin material.
Examples 2 to 6
The difference from examples 2 to 5 is that the silicone-modified epoxy acrylic resins of examples 1 to 3 were replaced with the silicone-modified epoxy acrylic resins of examples 1 to 4. The reaction temperature was controlled at 50 ℃, the stirring speed was 240rpm, and the stirring reaction time was 4 hours. And after the reaction is finished, taking out the prepared modified epoxy acrylic resin solution, storing in a dark place, and defoaming.
Preparing a cleaned and dried glass plate and a film scraping rod, pouring a proper amount of modified epoxy acrylic resin solution on the glass plate, quickly spreading the solution by using the glass rod, and curing the solution in an ultraviolet curing box for 25 seconds to obtain the cured modified epoxy acrylic resin material.
Examples 2 to 7
The difference from examples 2 to 5 is that the silicone-modified epoxy acrylic resin of examples 1 to 3 was replaced with the silicone-modified epoxy acrylic resin of examples 1 to 5. The reaction temperature was controlled at 50 ℃, the stirring speed was 240rpm, and the stirring reaction time was 1 h. And after the reaction is finished, taking out the prepared modified epoxy acrylic resin solution, storing in a dark place, and defoaming.
Preparing a cleaned and dried glass plate and a film scraping rod, pouring a proper amount of modified epoxy acrylic resin solution on the glass plate, quickly spreading the solution by using the glass rod, and curing the solution in an ultraviolet curing box for 10 seconds to obtain the cured modified epoxy acrylic resin material.
Examples 2 to 8
The difference from examples 2 to 5 is that the silicone-modified epoxy acrylic resins of examples 1 to 3 were replaced with the silicone-modified epoxy acrylic resins of examples 1 to 6. The reaction temperature was controlled at 50 ℃, the stirring speed was 240rpm, and the stirring reaction time was 3 hours. And after the reaction is finished, taking out the prepared modified epoxy acrylic resin solution, storing in a dark place, and defoaming.
Preparing a cleaned and dried glass plate and a film scraping rod, pouring a proper amount of modified epoxy acrylic resin solution on the glass plate, quickly spreading the solution by using the glass rod, and curing the solution in an ultraviolet curing box for 40 seconds to obtain the cured modified epoxy acrylic resin material.
Examples 2 to 9
The difference from examples 2 to 5 is that the silicone-modified epoxy acrylic resins of examples 1 to 3 were replaced with the silicone-modified epoxy acrylic resins of examples 1 to 7. The reaction temperature was controlled at 50 ℃, the stirring speed was 240rpm, and the stirring reaction time was 1.5 h. And after the reaction is finished, taking out the prepared modified epoxy acrylic resin solution, storing in a dark place, and defoaming.
Preparing a cleaned and dried glass plate and a film scraping rod, pouring a proper amount of modified epoxy acrylic resin solution on the glass plate, quickly spreading the solution by using the glass rod, and curing the solution in an ultraviolet curing box for 10 seconds to obtain the cured modified epoxy acrylic resin material.
Examples 2 to 10
The silicone-modified epoxy acrylic resin of example 1-1, tripropylene glycol diacrylate (TPGDA), trimethylolpropane triacrylate (TMPTA), 2-hydroxy-2-methyl-1-phenyl-1-propanone (HMPP, 1173), 1-hydroxycyclohexyl phenyl ketone (184) were added to a light-tight, closed reaction vessel in a mass ratio of 50: 20: 30: 2: 1, controlling the reaction temperature to be 30 ℃, the stirring speed to be 230rpm, and the stirring reaction time to be 2 h. And after the reaction is finished, taking out the prepared modified epoxy acrylic resin solution, storing in a dark place, and defoaming.
Preparing a cleaned and dried glass plate and a film scraping rod, pouring a proper amount of modified epoxy acrylic resin solution on the glass plate, quickly spreading the solution by using the glass rod, and curing the solution in an ultraviolet curing box for 50 seconds to obtain the cured modified epoxy acrylic resin material.
Examples 2 to 11
The silicone-modified epoxy acrylic resin of example 1-1, tripropylene glycol diacrylate (TPGDA), trimethylolpropane triacrylate (TMPTA), 2-hydroxy-2-methyl-1-phenyl-1-propanone (HMPP, 1173), 1-hydroxycyclohexyl phenyl ketone (184) were added to a light-tight, closed reaction vessel in a mass ratio of 50: 20: 30: 2: 1, controlling the reaction temperature at 70 ℃, the stirring speed at 230rpm, and the stirring reaction time at 20 min. And after the reaction is finished, taking out the prepared modified epoxy acrylic resin solution, storing in a dark place, and defoaming.
Preparing a cleaned and dried glass plate and a film scraping rod, pouring a proper amount of modified epoxy acrylic resin solution on the glass plate, quickly spreading the solution by using the glass rod, and curing the solution in an ultraviolet curing box for 100 seconds to obtain the cured modified epoxy acrylic resin material.
Examples 2 to 12
The silicone-modified epoxy acrylic resin of example 1-1, tripropylene glycol diacrylate (TPGDA), trimethylolpropane triacrylate (TMPTA), 2-hydroxy-2-methyl-1-phenyl-1-propanone (HMPP, 1173), 1-hydroxycyclohexyl phenyl ketone (184) were added in a light-tight closed reaction vessel in a mass ratio of 75: 20: 30: 2: 1, controlling the reaction temperature at 50 ℃, the stirring speed at 220rpm, and the stirring reaction time at 1 h. And after the reaction is finished, taking out the prepared modified epoxy acrylic resin solution, storing in a dark place, and defoaming.
Preparing a cleaned and dried glass plate and a film scraping rod, pouring a proper amount of modified epoxy acrylic resin solution on the glass plate, quickly spreading the solution by using the glass rod, and curing the solution in an ultraviolet curing box for 10 seconds to obtain the cured modified epoxy acrylic resin material.
Examples 2 to 13
The silicone-modified epoxy acrylic resin of example 1-1, tripropylene glycol diacrylate (TPGDA), trimethylolpropane triacrylate (TMPTA), 2-hydroxy-2-methyl-1-phenyl-1-propanone (HMPP, 1173), 1-hydroxycyclohexyl phenyl ketone (184) were added to a light-tight, closed reaction vessel in a mass ratio of 40: 30: 30: 2: 1, controlling the reaction temperature at 70 ℃, the stirring speed at 240rpm, and the stirring reaction time at 2 h. And after the reaction is finished, taking out the prepared modified epoxy acrylic resin solution, storing in a dark place, and defoaming.
Preparing a cleaned and dried glass plate and a film scraping rod, pouring a proper amount of modified epoxy acrylic resin solution on the glass plate, quickly spreading the solution by using the glass rod, and curing the solution in an ultraviolet curing box for 10 seconds to obtain the cured modified epoxy acrylic resin material.
From the above description, it can be seen that the above-described embodiments of the present invention achieve the following technical effects:
since the organosilicon modified epoxy acrylate is used for modifying the monomer, but not for modifying the resin through copolycondensation reaction, the organosilicon and the epoxy acrylate can be connected at a lower reaction temperature to obtain the organosilicon modified epoxy acrylate. And the modification is carried out under the catalysis of organic tin, so that higher reaction efficiency is ensured. The organic silicon modified epoxy acrylate resin can be used as a photosensitive material to realize 3D printing, and has Si-O bonds, so that the organic silicon modified epoxy acrylate resin has the advantages of good thermal stability, weather resistance, oxidation resistance and good low-temperature characteristics.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A preparation method of organosilicon modified epoxy acrylate is characterized by comprising the following steps:
the epoxy acrylate and a silane modifier are subjected to substitution reaction under the catalysis of organic tin to obtain the organic silicon modified epoxy acrylate, wherein the silane modifier is any one of phenyl trialkoxysilanes.
2. The preparation method according to claim 1, wherein the silane modifier is phenyl triethoxysilane, the epoxy acrylate and the silane modifier are subjected to substitution reaction at 50-100 ℃, and preferably the molar ratio of the epoxy acrylate to the silane modifier is 2: 1-3: 1.
3. the preparation method according to claim 1, wherein the organotin is selected from any one or more of dibutyltin dilaurate, alkyltin dithiolate and dialkyltin dimaleate, and the molar ratio of the epoxy acrylate to the organotin is 100: 0.5 to 2.
4. The preparation method according to claim 1, wherein the substitution reaction is carried out in a solvent, the molar ratio of the epoxy acrylate to the solvent is 2-3: 45, the solvent is a polar solvent, and the solvent is preferably any one selected from xylene, toluene and propyl ether.
5. The method of manufacturing according to claim 4, comprising:
dispersing the epoxy acrylate and the organotin in the solvent to form a dispersion;
adding the silane modifier to the dispersion under stirring and heating conditions to perform the substitution reaction, wherein the stirring speed is 100-400 rpm, the heating target temperature is 50-100 ℃, and the phenyltrialkoxysilane is preferably added to the dispersion at a speed of 30-40 s/d.
6. An organic silicon modified epoxy acrylate resin composition comprises a prepolymer, an acrylic monomer, an initiator and a cross-linking agent, and is characterized in that the prepolymer is the organic silicon modified epoxy acrylate obtained by the preparation method of any one of claims 1 to 5.
7. The composition of claim 6, wherein the composition comprises 50 to 75 parts by weight of a prepolymer, 30 to 50 parts by weight of an acrylic monomer, and 2 to 3 parts by weight of an initiator.
8. The composition according to claim 6 or 7, wherein the acrylate monomer is selected from any one or more of tripropylene glycol diacrylate, trimethylolpropane triacrylate, 1, 6-hexanediol diacrylate, beta-hydroxyethyl methacrylate.
9. Composition according to claim 6 or 7, characterized in that the initiator is selected from any one or more of 2-hydroxy-2-methyl-1-phenyl-1-propanone, 1-hydroxycyclohexyl phenyl ketone, benzophenone/tertiary amine system, 2-hydroxy-2-methyl propiophenone.
10. A cured product of an organosilicon-modified epoxy acrylate resin, which is obtained by photocuring a polymer obtained by polymerization of the composition according to any one of claims 6 to 9 as a raw material, preferably at a polymerization temperature of 30 to 70 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110171536.XA CN112812272A (en) | 2021-02-08 | 2021-02-08 | Preparation method of organic silicon modified epoxy acrylate, organic silicon modified epoxy acrylate resin composition and cured product |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110171536.XA CN112812272A (en) | 2021-02-08 | 2021-02-08 | Preparation method of organic silicon modified epoxy acrylate, organic silicon modified epoxy acrylate resin composition and cured product |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112812272A true CN112812272A (en) | 2021-05-18 |
Family
ID=75863756
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110171536.XA Pending CN112812272A (en) | 2021-02-08 | 2021-02-08 | Preparation method of organic silicon modified epoxy acrylate, organic silicon modified epoxy acrylate resin composition and cured product |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112812272A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114249878A (en) * | 2022-01-19 | 2022-03-29 | 深圳市丽冠卓宏科技有限公司 | Resin for high-temperature-resistant low-yellowing UV (ultraviolet) ink and preparation method and application thereof |
-
2021
- 2021-02-08 CN CN202110171536.XA patent/CN112812272A/en active Pending
Non-Patent Citations (1)
| Title |
|---|
| 李垒等: "紫外光固化有机硅改性环氧丙烯酸酯树脂的制备及性能", 《山东化工》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114249878A (en) * | 2022-01-19 | 2022-03-29 | 深圳市丽冠卓宏科技有限公司 | Resin for high-temperature-resistant low-yellowing UV (ultraviolet) ink and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1754915B (en) | Silicone resin composition and molded product thereof | |
| CN102220062B (en) | Aqueous UV curing coating and preparation method thereof | |
| CN101875710B (en) | Siloxane-group light-initiated polyacrylic ester/silicon dioxide nanometer material and preparation method thereof | |
| CN103031105A (en) | Ultraviolet curing liquid optical clear adhesive and preparation method thereof | |
| CN103608396A (en) | Resin compositions | |
| CN109608589A (en) | A kind of 3D printing dual cure resin material and preparation method thereof | |
| CN104910344A (en) | Preparation method of rapid UV-cured fluorine-containing hydrophobic polyurethane elastic coating layer | |
| CN112080241B (en) | Photo-curing adhesive and preparation method and application thereof | |
| CN110183665B (en) | Preparation method and application of MTQ resin containing sulfydryl | |
| JPH02289611A (en) | Photo-setting resin composition | |
| CN106634761A (en) | Ultraviolet-light curing composition and master pattern preparation method | |
| CN106029721A (en) | Polymerizable composition containing reactive silsesquioxane compound | |
| CN101831176B (en) | Solidification composition of aryl mercaptan-olefinic unsaturated double-bond polyether sulfone | |
| CN106672895A (en) | Preparation method of patterning of azo based supramolecular polymer | |
| CN103717630B (en) | Resin combination | |
| CN112812272A (en) | Preparation method of organic silicon modified epoxy acrylate, organic silicon modified epoxy acrylate resin composition and cured product | |
| CN104693408B (en) | Organic fluoride modified polyurethane photocuring prepolymer and preparation method and its ultraviolet light cured film being made | |
| CN109370508A (en) | A kind of radiation-curable black shading Adhesive composition | |
| CN113004783A (en) | Ultraviolet-curing polyurethane acrylate coating and preparation method thereof | |
| CN110028639B (en) | Photosensitive Zr-B-Si-C ceramic precursor and in-situ preparation method thereof | |
| CN113429876B (en) | Water-based UV paint and preparation method thereof | |
| CN112457455B (en) | Preparation method of fluorocarbon resin, fluorocarbon resin and application | |
| CN112159593B (en) | Application of epoxy group porous polythioether microspheres as epoxy structural adhesive toughening agent | |
| CN108264618A (en) | A kind of shape memory polymer networks formation system of light and heat two-stage reaction and preparation method thereof | |
| CN113755077A (en) | Hydrophobic anti-fouling ultraviolet curing coating and preparation method thereof |
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 | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20210518 |
|
| RJ01 | Rejection of invention patent application after publication |