CN111116915A - Liquid methacrylic acid functionalized POSS (polyhedral oligomeric silsesquioxane), photocuring acrylic resin modified by liquid methacrylic acid functionalized POSS and preparation method of photocuring acrylic resin - Google Patents
Liquid methacrylic acid functionalized POSS (polyhedral oligomeric silsesquioxane), photocuring acrylic resin modified by liquid methacrylic acid functionalized POSS and preparation method of photocuring acrylic resin Download PDFInfo
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- CN111116915A CN111116915A CN201910418732.5A CN201910418732A CN111116915A CN 111116915 A CN111116915 A CN 111116915A CN 201910418732 A CN201910418732 A CN 201910418732A CN 111116915 A CN111116915 A CN 111116915A
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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
- C08G77/045—Polysiloxanes containing less than 25 silicon atoms
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/12—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes
- C08F283/124—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes on to polysiloxanes having carbon-to-carbon double bonds
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- 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
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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 the field of light-cured resin, in particular to liquid methacrylic acid functionalized POSS, light-cured acrylic resin modified by the liquid methacrylic acid functionalized POSS and a preparation method of the light-cured acrylic resin. Tetraethoxysilane is used as a raw material, cage octa poly (tetramethylammonium) silicate is obtained by hydrolysis under the catalysis of tetramethylammonium hydroxide, then the cage octa poly (dimethylsiloxy) silsesquioxane is synthesized by substitution reaction with dimethylchlorosilane, and liquid methacrylic acid functionalized POSS is prepared by hydrosilylation reaction of allyl methacrylate. The method disclosed by the invention has the advantages that the defects of poor compatibility of POSS and a base material and poor performance of a composite material in the prior art are overcome by introducing the light curing reaction into the acrylic resin, the thermodynamic performance of the acrylic resin can be greatly improved, the water absorption and curing shrinkage of the resin are reduced, the operation is simple, the raw materials are easy to obtain, and the control is easy, so that the method has great development advantages in the aspect of modifying the 3D printing photosensitive resin.
Description
Technical Field
The invention relates to the field of light-cured resin, in particular to liquid methacrylic acid functionalized POSS, light-cured acrylic resin modified by the liquid methacrylic acid functionalized POSS and a preparation method of the light-cured acrylic resin.
Background
3D printing is a novel technology which is widely concerned at present, and is expected to be widely applied to daily life production, and with the rapid development of the technology, the quality requirement of people on 3D printed products is higher and higher. In addition to further optimizing the performance of the printer, it is most important that researchers be able to produce photosensitive resins having the properties required for the target end product. In other words, the quality of the photosensitive resin directly affects the quality of the printed product, and determines the application prospect of the 3D printing technology.
At present, acrylic resin is one of the most commonly used photosensitive resins, but the resin system has obvious defects in the aspects of thermodynamic performance and the like: poor high temperature resistance, high water absorption, large curing shrinkage rate and the like. To solve the above problems, there are mainly two solutions: firstly, the components of the resin system and the formula of each component are adjusted to meet the requirements, and secondly, the filler is added into the resin system to improve the performance of each aspect of the resin system.
Compared with the common organic compound composed of C, H, O, the organic silicon product with Si-O as the main chain has the advantages of high and low temperature resistance, weather resistance, corrosion resistance, aging resistance, low surface tension, physiological inertia and the like. The introduction of organosilicon into photosensitive resin is undoubtedly a good method for improving performance, wherein polyhedral oligomeric silsesquioxane (POSS) has an inorganic-inorganic nano hybrid structure, so that toughness and excellent processing performance of organic polymer materials can be combined with oxidation resistance, high temperature resistance and excellent mechanical properties of inorganic materials, and the POSS has potential application values in the aspects of fillers, catalysts, biocompatible materials and the like.
However, the solid polyhedral oligomeric silsesquioxane has poor compatibility with a matrix material, and easily affects the performance of a composite material, so that the performance of the composite material is not affected after the solid polyhedral oligomeric silsesquioxane is modified, for example, a POSS modified waterborne nano transparent heat insulation coating with an authorization publication number of CN 102241937B and a preparation method thereof are provided, wherein a polyhedral oligomeric silsesquioxane modifier is added into the coating, and the side chain is extended by the free radical reaction between vinyl and acrylic acid monomers in the originally solid polyhedral oligomeric silsesquioxane, so that high compatibility is achieved. However, although the modification means has a certain effect, the relative content of POSS core in the molecule is greatly reduced due to the fact that the side chain is connected with a long chain segment, and the comprehensive performance of the modification means is not obviously improved.
Disclosure of Invention
The invention aims to overcome the defect of poor performance of the composite material caused by poor compatibility of POSS and base materials in the prior art.
Accordingly, a first object of the present invention is to provide a liquid methacrylic functionalized POSS capable of having excellent compatibility with a resin substrate and a method for preparing the same; a second object of the present invention is to modify photocurable acrylic resins by synthesized liquid methacrylic functionalized POSS.
In order to achieve the purpose, the invention is realized by the following technical scheme:
a liquid methacrylic functionalized POSS, said liquid methacrylic functionalized POSS having the formula shown in (I):
unlike conventional solid-state POSS, the methacrylic-functionalized POSS of the present invention is capable of existing in liquid form due to the flexible mer group attached to the side chain of the silicon atom in the cage-like structure molecule at the core. Thereby effectively improving the compatibility between the resin and the liquid resin. Meanwhile, the side chain contains a large number of acrylic groups, so that the photo-curing resin has good photosensitivity and can effectively participate in the curing reaction of the photo-curing resin in the presence of a photoinitiator. In addition, the chain link length of the side chain is shorter, so that the content of the core of the cage structure in the molecule is higher, and the higher the content of the core of the cage structure is under the condition of the same adding amount, the effect of improving the mechanical heat resistance can be correspondingly more obvious. Therefore, the liquid methacrylic acid functionalized POSS has good effects of mechanical enhancement and heat resistance improvement on the basis of higher compatibility with liquid resin.
In addition, the POSS used in the invention not only contains functional groups capable of reacting with acrylic resin, but also has better compatibility with resin matrix compared with solid powder POSS due to the liquid physical properties, and the performance of the final material is more excellent without introducing a solvent in the preparation process.
A method for preparing a liquid methacrylic functionalized POSS, said method comprising the steps of:
(1) tetraethyl orthosilicate is subjected to hydrolytic condensation under the catalysis of tetramethyl ammonium hydroxide pentahydrate to obtain cage octa-tetramethyl ammonium silicate, and then dimethylchlorosilane is added for substitution reaction to obtain cage octa-poly (dimethylsiloxy) silsesquioxane.
The synthesis reaction formula is as follows:
(2) and (2) carrying out hydrosilylation reaction on the cage octa-poly (dimethylsiloxy) silsesquioxane obtained in the step (1) and allyl methacrylate under the catalysis of a platinum catalyst to obtain the liquid methacrylic acid functionalized POSS.
The reaction formula of the synthetic process is as follows:
the existing preparation method of POSS is generally obtained by hydrolysis of trialkoxysilane, for example, vinyltrimethoxysilane forms octavinyl polysilsesquioxane under the action of potassium hydroxide, but the side chain group of the polysilsesquioxane can only change along with the change of the group on the trialkoxysilane, so that the modification and modification difficulty of the side chain group of the POSS after the POSS is prepared is larger. Also, such POSS is typically solid and typically less soluble, thus further increasing the difficulty of modification. In addition, because the traditional method is a one-step reaction between trialkoxysilane and alkali, another group in trialkoxysilane cannot contain a hydrosilation structure, otherwise, hydrosilation in molecules can firstly react with alkali to generate hydrogen, and POSS containing the hydrosilation structure cannot be finally formed.
The liquid methacrylic acid functionalized POSS adopts tetraethyl orthosilicate as a raw material, firstly, the tetraethyl orthosilicate is subjected to hydrolysis reaction under the catalytic action of tetramethylammonium hydroxide pentahydrate to obtain cage-shaped octatetramethylammonium silicate, then the cage-shaped octatetramethylammonium silicate is reacted with dimethylchlorosilane, and a silicon-chlorine structure in the dimethylchlorosilane is firstly reacted with the octatetramethylammonium silicate, so that dimethylsiloxy is grafted to silicon atoms at eight vertexes of the POSS, and thus the cage-shaped octapoly (dimethylsiloxy) silsesquioxane is formed. The modification difficulty is greatly reduced because the molecule of the POSS contains a hydrosilation structure with higher activity, and the liquid methacrylic acid functionalized POSS is finally obtained by performing addition condensation on the hydrosilation and allyl in allyl methacrylate through a hydrosilation addition reaction.
Preferably, the molar ratio of tetraethyl orthosilicate to tetramethylammonium hydroxide pentahydrate to dimethylchlorosilane in the step (1) is 1:1 to (3.5-5); in the step (2), the molar ratio of octa-poly (dimethylsiloxy) silsesquioxane to allyl methacrylate is 1: 8-10.
In the invention, the amount of tetramethylammonium hydroxide pentahydrate in the step (1) is equal to that of tetraethyl orthosilicate, so that the tetraethyl orthosilicate can be ensured to be completely reacted on the premise of keeping a faster reaction rate. The reason why the amount of the dimethylchlorosilane is larger than the theoretical addition amount is that the activity of the residual groups capable of reacting with the dimethylchlorosilane on the molecules of the caged octatetramethylammonium silicate is gradually reduced along with the continuous grafting of the dimethylsiloxy groups on the caged octatetramethylammonium silicate, and if the concentration of the dimethylchlorosilane is lower, the dimethylsiloxy groups cannot be completely grafted on the molecules of the caged octatetramethylammonium silicate, so that the improvement of the concentration of the dimethylchlorosilane is beneficial to the complete reaction of the reactive groups on the caged octatetramethylammonium silicate, and the grafting rate is improved.
Similarly, when the hydrosilylation reaction between octapoly (dimethylsiloxy) silsesquioxane and allyl methacrylate proceeds, the reactivity thereof also decreases, and thus, an appropriate increase in the amount of allyl methacrylate can effectively increase the reaction efficiency of octapoly (dimethylsiloxy) silsesquioxane.
A liquid methacrylic functionalized POSS modified photocurable acrylic resin, said photocurable acrylic resin comprising a liquid methacrylic functionalized POSS as described herein.
Because the liquid methacrylic acid functionalized POSS has the effects of high compatibility and good mechanical enhancement and heat resistance improvement, the liquid methacrylic acid functionalized POSS can effectively modify the defects of poor high temperature resistance, high water absorption and large curing shrinkage rate when added into the photocuring acrylic resin, so that the finally obtained photocuring acrylic resin has good heat resistance and mechanical property.
In addition, the liquid methacrylic acid functionalized POSS has more photosensitive groups, so the liquid methacrylic acid functionalized POSS has the advantages of high photoinitiation efficiency and good photocuring effect. Meanwhile, each photosensitive group can be respectively grafted with the acrylic resin matrix, so that a network structure taking liquid methacrylic acid functionalized POSS as a connection point can be finally formed, and the strength and the toughness of the composite material are greatly improved.
Preferably, the acrylic resin also comprises an acrylic resin matrix and a photoinitiator; according to the weight percentage, the acrylic resin matrix is 87-99%, the liquid methacrylic acid functionalized POSS is 0-12%, and the photoinitiator is 1%.
Preferably, the acrylic resin matrix is one or more of methyl acrylate, methyl methacrylate, ethyl methacrylate or n-butyl acrylate.
Preferably, the photoinitiator is one of 2-hydroxy-2-methyl-1-phenyl-1-propanone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-2- (4-morpholinyl) -1- [4- (methylthio) phenyl ] -1-propanone and 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl ] -1-propanone.
A method of making a liquid methacrylic functionalized POSS modified photocurable acrylic resin as described above comprising the steps of:
(S.1) mixing materials: blending and stirring liquid methacrylic acid functionalized POSS, a photoinitiator and an acrylic resin matrix uniformly, performing ultrasonic treatment, and removing bubbles to obtain uncured composite resin;
(S.2) ultraviolet light curing: and (4) pouring the composite resin obtained in the step (S.1) into a mold, and irradiating and curing the composite resin by using ultraviolet light at a certain temperature to obtain the POSS modified composite resin.
The preparation method of the cured acrylic resin is simple, and the uncured composite resin can be obtained only by fully mixing the liquid methacrylic acid functionalized POSS, the photoinitiator and the acrylic resin matrix uniformly and removing air bubbles. And then the resin product can be effectively cured by ultraviolet irradiation. Therefore, the ultraviolet curing three-dimensional printing method is suitable for large-scale popularization and application in the field of ultraviolet curing 3D printing.
Preferably, in the step (S.1), the ultrasonic power is 800-1800W, and the ultrasonic time is 10-50 min.
Preferably, in the step (S.2), the reaction temperature is 30-50 ℃, the ultraviolet light intensity is 20-60W, and the ultraviolet illumination time is 60-120 min.
Therefore, the invention has the following beneficial effects:
(1) the POSS used in the invention not only contains functional groups capable of reacting with acrylic resin, but also has better compatibility with resin matrix compared with solid powdery POSS due to the liquid physical properties, and the performance of the final material is more excellent without introducing a solvent in the preparation process.
(2) The liquid methacrylic acid functionalized POSS is simple to synthesize, has good effects of enhancing mechanics and improving heat resistance, and also has modification capability.
(3) The liquid methacrylic acid functionalized POSS is added into the photocuring acrylic resin, so that the defects of poor high temperature resistance, high water absorption and large curing shrinkage rate can be effectively modified, and the finally obtained photocuring acrylic resin has good heat resistance, low water absorption and curing shrinkage rate and good mechanical properties.
(4) The preparation method of the cured acrylic resin is simple, and is suitable for large-scale popularization and application in the field of ultraviolet curing 3D printing.
Drawings
FIG. 1 is a schematic representation of a liquid methacrylic functionalized POSS of the present invention1HNMR map.
FIG. 2 is a schematic representation of a liquid methacrylic functionalized POSS of the present invention29SiNMR diagram.
Detailed Description
The invention is further illustrated below with reference to examples, which are intended to aid understanding thereof.
All the raw materials of the present invention are commercially available, and the following examples are only for illustrating the technical scheme of the present invention more clearly, and therefore, are only examples, and the scope of the present invention is not limited thereby.
Example 1
A liquid methacrylic functionalized POSS, said liquid methacrylic functionalized POSS having the formula shown in (I):
example 2
A method for preparing a liquid methacrylic functionalized POSS, said method comprising the steps of:
(1) dissolving 6.25g of tetraethyl orthosilicate (0.03mol) and 5.43g of tetramethylammonium hydroxide pentahydrate (0.03mol) in 50ml of methanol, dropwise adding 0.54ml of distilled water (0.03mol) into the solution, carrying out hydrolytic condensation reaction at room temperature for 12h to obtain cage octa-tetramethylammonium silicate, and then dropwise adding a solution of 9.9g of dimethylchlorosilane (0.105mol) in 20ml of n-hexane into the solution to carry out substitution reaction to obtain cage octa-poly (dimethylsiloxy) silsesquioxane;
(2) then 1.016g of caged octapoly (dimethylsiloxy) silsesquioxane (0.01mol) and 10.08g of allyl methacrylate (0.08mol) were dissolved in 50ml of toluene and subjected to hydrosilylation reaction under the catalysis of a Karster catalyst containing platinum 2% at a concentration of 50ppm to obtain liquid methacrylic functionalized POSS.
FIGS. 1-2 are liquid methacrylic acid functionalized POSS of the invention1HNMR and29the SiNMR image has characteristic peaks consistent with the predicted result, and the synthesized POSS is consistent with theory.
Example 3
A method for preparing a liquid methacrylic functionalized POSS, said method comprising the steps of:
(1) dissolving 4.16g of tetraethyl orthosilicate (0.02mol) and 3.623g of tetramethylammonium hydroxide pentahydrate (0.02mol) in 50ml of isopropanol, dropwise adding 0.3.6ml of distilled water (0.02mol) into the isopropanol, performing reflux hydrolysis condensation reaction for 6 hours to obtain cage octa-poly (tetramethylammonium silicate), and then adding 9.46g of dimethylchlorosilane (0.1mol) into the cage octa (dimethylsiloxy) silsesquioxane for substitution reaction to obtain cage octa (dimethylsiloxy) silsesquioxane;
(2) then 1.016g of caged octapoly (dimethylsiloxy) silsesquioxane (0.01mol) and 12.6g of allyl methacrylate (0.1mol) were dissolved in 50ml of toluene and subjected to hydrosilylation reaction under the catalysis of 50ppm platinum-containing 2% Karster catalyst to obtain liquid methacrylic acid functionalized POSS.
Example 4
A method for preparing a liquid methacrylic functionalized POSS, said method comprising the steps of:
(1) dissolving 4.16g of tetraethyl orthosilicate (0.02mol) and 3.623g of tetramethylammonium hydroxide pentahydrate (0.02mol) in 50ml of isopropanol, dropwise adding 0.3.6ml of distilled water (0.02mol) into the isopropanol, performing reflux hydrolysis condensation reaction for 6 hours to obtain cage octa-poly (tetramethylammonium silicate), and then adding 7.57g of dimethylchlorosilane (0.08mol) into the cage octa (dimethylsiloxy) silsesquioxane for substitution reaction to obtain cage octa (dimethylsiloxy) silsesquioxane;
(2) then 1.016g of caged octapoly (dimethylsiloxy) silsesquioxane (0.01mol) and 8.5g of allyl methacrylate (0.09mol) were dissolved in 50ml of toluene and subjected to hydrosilylation reaction under the catalysis of 50ppm platinum-containing 2% Karster catalyst to obtain liquid methacrylic functionalized POSS.
Example 5
A preparation method of a liquid methacrylic acid functionalized POSS modified photo-cured acrylic resin comprises the steps of weighing 38.4g of methyl methacrylate, 0.4g of 2-hydroxy-2-methyl-1-phenyl-1-acetone and 1.2g of liquid methacrylic acid functionalized POSS, mixing and stirring uniformly, carrying out ultrasonic treatment at 800W for 20min, and removing bubbles to obtain the uncured composite resin.
And pouring the obtained composite resin into a mold, and irradiating the composite resin with 40W ultraviolet light for 120min at the temperature of 30 ℃ for curing to obtain the POSS modified composite resin.
Example 6
A preparation method of liquid methacrylic acid functionalized POSS modified photo-cured acrylic resin comprises the steps of weighing 38.4g of methyl methacrylate, 0.4g of 2-hydroxy-2-methyl-1-phenyl-1-acetone and 1.2g of liquid methacrylic acid functionalized POSS, mixing and stirring uniformly, carrying out ultrasonic treatment at 1000W for 10min, and removing bubbles to obtain uncured composite resin.
And pouring the obtained composite resin into a mold, and curing the composite resin at 30 ℃ by using 50W ultraviolet light for 80min to obtain the POSS modified composite resin.
Example 7
A preparation method of liquid methacrylic acid functionalized POSS modified photo-cured acrylic resin comprises the steps of weighing 40g of methyl acrylate, 0.4g of 1-hydroxycyclohexyl phenyl ketone and 2.4g of liquid methacrylic acid functionalized POSS, blending and stirring uniformly, carrying out 1800W ultrasonic treatment for 10min, and removing bubbles to obtain uncured composite resin.
And pouring the obtained composite resin into a mold, and irradiating the composite resin with 20W ultraviolet light for 120min at 35 ℃ for curing to obtain the POSS modified composite resin.
Example 8
A preparation method of liquid methacrylic acid functionalized POSS modified photo-cured acrylic resin comprises the steps of weighing 40g of methyl acrylate, 0.4g of 1-hydroxycyclohexyl phenyl ketone and 2.4g of liquid methacrylic acid functionalized POSS, blending and stirring uniformly, carrying out 1500W ultrasonic treatment for 30min, and removing bubbles to obtain uncured composite resin.
And pouring the obtained composite resin into a mold, and irradiating the composite resin with 60W ultraviolet light at 35 ℃ for 80min for curing to obtain the POSS modified composite resin.
Example 9
A preparation method of a liquid methacrylic acid functionalized POSS modified photo-curing acrylic resin comprises the steps of weighing 37.2g of ethyl methacrylate, 0.4g of 2-methyl-2- (4-morpholinyl) -1- [4- (methylthio) phenyl ] -1-acetone and 2.4g of liquid methacrylic acid functionalized POSS, blending and stirring uniformly, carrying out ultrasonic treatment at 1000W for 25min, and removing bubbles to obtain the uncured composite resin.
And pouring the obtained composite resin into a mold, and irradiating 80 with 45W ultraviolet light at 50 ℃ to obtain the POSS modified composite resin.
Example 10
A preparation method of a liquid methacrylic acid functionalized POSS modified photo-curing acrylic resin comprises the steps of weighing 36g of n-butyl acrylate, 0.4g of 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl ] -1-acetone and 3.6g of liquid methacrylic acid functionalized POSS, blending and stirring uniformly, carrying out 900W ultrasonic treatment for 40min, and removing bubbles to obtain the uncured composite resin.
And pouring the obtained composite resin into a mold, and irradiating the composite resin with 50W ultraviolet light for 60min at 50 ℃ for curing to obtain the POSS modified composite resin.
Example 11
A preparation method of a liquid methacrylic acid functionalized POSS modified photo-cured acrylic resin comprises the steps of weighing 36g of methyl methacrylate, 0.4g of 1-hydroxycyclohexyl phenyl ketone and 3.6g of liquid methacrylic acid functionalized POSS, mixing and stirring uniformly, carrying out 800W ultrasonic treatment for 50min, and removing bubbles to obtain the uncured composite resin.
And pouring the obtained composite resin into a mold, and irradiating 60W ultraviolet light for 60min at 50 ℃ for curing to obtain the POSS modified composite resin.
Example 12
A preparation method of liquid methacrylic acid functionalized POSS modified photo-cured acrylic resin comprises the steps of weighing 34.8g of ethyl methacrylate, 0.4g of 2-hydroxy-2-methyl-1-phenyl-1-acetone and 4.8g of liquid methacrylic acid functionalized POSS, mixing and stirring uniformly, carrying out 1500W ultrasonic treatment for 30min, and removing bubbles to obtain uncured composite resin.
And pouring the obtained composite resin into a mold, and irradiating the composite resin with 550W ultraviolet light for 100min at 50 ℃ for curing to obtain the POSS modified composite resin.
Example 13
A preparation method of a liquid methacrylic acid functionalized POSS modified photo-cured acrylic resin comprises the steps of weighing 34.8g of methyl methacrylate, 0.4g of 2-hydroxy-2-methyl-1-phenyl-1-acetone and 4.8g of liquid methacrylic acid functionalized POSS, blending and stirring uniformly, carrying out ultrasonic treatment at 1800W for 10min, and removing bubbles to obtain the uncured composite resin.
And pouring the obtained composite resin into a mold, and irradiating 60W ultraviolet light for 60min at 45 ℃ for curing to obtain the POSS modified composite resin.
The cured POSS modified composite resins obtained in examples 5-13 were tested, and the following methods were used to test the effects of the invention:
(1) the bending strength was measured by a three-point bending method, and a rectangular test specimen having dimensions of 80mm (length) x 10mm (width) x 4mm (thickness) was prepared according to the GB/T9341-2000 plastic bending property test method.
(2) Tensile Strength Using a high and low temperature tensile tester (AI-7000M), dumbbell-type test specimens were prepared, having dimensions of 80mm (length) × 12mm (end width) × 4mm (middle width) × 4mm (thickness).
(3) The impact strength was measured by a liquid crystal display impact tester (XJ-50Z), and the test specimen size was also 80mm (length) x 10mm (width) x 4mm (thickness).
(4) The curing volume shrinkage is calculated from the formula for liquid resin curing shrinkage (ShrinkageRatio, SR) in ISO 3521:1997, where ρ s represents the density of the cured resin and ρ l represents the density of the liquid resin:
the water absorption rate can be calculated by the following formula, the sample strip to be tested needs to be dried in an oven at 100 ℃ for about 5 hours in advance, and the moisture in the sample strip is ensured to be completely removed:
m0: mass before soaking
m1: mass after 10 days of soaking.
The following table shows the thermodynamic properties, water absorption and curing shrinkage of the liquid methacrylic POSS modified acrylic resin, and it can be seen from the table that the modified photosensitive resin obtained by the invention has better thermodynamic properties and lower water absorption and curing shrinkage.
Claims (10)
1. A liquid methacrylic functionalized POSS, wherein the liquid methacrylic functionalized POSS has a structural formula shown in formula (I):
2. a method of making a liquid methacrylic functionalized POSS as claimed in claim 1 comprising the steps of:
(1) tetraethyl orthosilicate is subjected to hydrolytic condensation under the catalysis of tetramethyl ammonium hydroxide pentahydrate to obtain cage octa-tetramethyl ammonium silicate, and then dimethylchlorosilane is added for substitution reaction to obtain cage octa-poly (dimethylsiloxy) silsesquioxane;
(2) and (2) carrying out hydrosilylation reaction on the cage octa-poly (dimethylsiloxy) silsesquioxane obtained in the step (1) and allyl methacrylate under the catalysis of a platinum catalyst to obtain the liquid methacrylic acid functionalized POSS.
3. The method for preparing liquid methacrylic acid functionalized POSS according to claim 2, wherein the molar ratio of tetraethyl orthosilicate, tetramethylammonium hydroxide pentahydrate and dimethylchlorosilane in the step (1) is 1: 3.5-5; in the step (2), the molar ratio of octa-poly (dimethylsiloxy) silsesquioxane to allyl methacrylate is 1: 8-10.
4. A liquid methacrylic functionalized POSS modified photocurable acrylic resin, wherein said photocurable acrylic resin comprises a liquid methacrylic functionalized POSS as recited in claim 1.
5. The liquid methacrylic functionalized POSS modified photocurable acrylic resin of claim 4 further comprising an acrylic resin matrix and a photoinitiator; according to the weight percentage, the acrylic resin matrix is 87-99%, the liquid methacrylic acid functionalized POSS is 0-12%, and the photoinitiator is 1%.
6. The liquid methacrylic functionalized POSS modified photocurable acrylic resin of claim 5 wherein the acrylic resin matrix is one or more of methyl acrylate, methyl methacrylate, ethyl methacrylate, or n-butyl acrylate.
7. The liquid methacrylic functionalized POSS modified photocurable acrylic resin of claim 5, wherein the photoinitiator is one of 2-hydroxy-2-methyl-1-phenyl-1-propanone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-2- (4-morpholinyl) -1- [4- (methylthio) phenyl ] -1-propanone, or 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl ] -1-propanone.
8. A method for preparing the liquid methacrylic functionalized POSS modified photocurable acrylic resin as claimed in any one of claims 4 to 7, wherein said method comprises the steps of:
(S.1) mixing materials: blending and stirring liquid methacrylic acid functionalized POSS, a photoinitiator and an acrylic resin matrix uniformly, performing ultrasonic treatment, and removing bubbles to obtain uncured composite resin;
(S.2) ultraviolet light curing: and (4) pouring the composite resin obtained in the step (S.1) into a mold, and irradiating and curing the composite resin by using ultraviolet light at a certain temperature to obtain the POSS modified composite resin.
9. The method for preparing the liquid methacrylic acid functionalized POSS modified photo-curable acrylic resin according to claim 8, wherein in the step (S.1), the ultrasonic power is 800-1800W, and the ultrasonic time is 10-50 min.
10. The method for preparing the liquid methacrylic acid functionalized POSS modified photo-curable acrylic resin according to claim 8, wherein in the step (S.2), the reaction temperature is 30-50 ℃, the ultraviolet light intensity is 20-60W, and the ultraviolet irradiation time is 60-120 min.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910418732.5A CN111116915B (en) | 2019-05-20 | 2019-05-20 | Liquid methacrylic acid functionalized POSS (polyhedral oligomeric silsesquioxane), photocuring acrylic resin modified by liquid methacrylic acid functionalized POSS and preparation method of photocuring acrylic resin |
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| CN201910418732.5A CN111116915B (en) | 2019-05-20 | 2019-05-20 | Liquid methacrylic acid functionalized POSS (polyhedral oligomeric silsesquioxane), photocuring acrylic resin modified by liquid methacrylic acid functionalized POSS and preparation method of photocuring acrylic resin |
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| Publication Number | Publication Date |
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| CN111116915A true CN111116915A (en) | 2020-05-08 |
| CN111116915B CN111116915B (en) | 2022-05-27 |
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Application publication date: 20200508 Assignee: Hangzhou Siyue New Material Technology Co.,Ltd. Assignor: Hangzhou Normal University Contract record no.: X2023980035547 Denomination of invention: A liquid methacrylic acid functionalized POSS and its modified photocurable acrylic resin and preparation method thereof Granted publication date: 20220527 License type: Common License Record date: 20230516 |
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