CN101875710A - Siloxane-group light-initiated polyacrylic ester/silicon dioxide nanometer material and preparation method thereof - Google Patents
Siloxane-group light-initiated polyacrylic ester/silicon dioxide nanometer material and preparation method thereof Download PDFInfo
- Publication number
- CN101875710A CN101875710A CN 201010215732 CN201010215732A CN101875710A CN 101875710 A CN101875710 A CN 101875710A CN 201010215732 CN201010215732 CN 201010215732 CN 201010215732 A CN201010215732 A CN 201010215732A CN 101875710 A CN101875710 A CN 101875710A
- Authority
- CN
- China
- Prior art keywords
- light trigger
- silicon dioxide
- acrylic ester
- acrylate
- preparation
- 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.)
- Granted
Links
Images
Abstract
The invention discloses a siloxane group contained bifunctional light initiator initiated polymerized ultraviolet light cured acrylic ester/silicon dioxide nanometer hybrid material and a preparation method thereof. The preparation method is characterized by comprising the following steps of: firstly, preparing a light initiator with a sulfhydryl group by adopting sulfhydryl carboxylic acid and a hydroxyl functional light initiator; then reacting the light initiator with a silane coupling agent to obtain a siloxane group contained bifunctional light initiator; and mixing the bifunctional light initiator with an acrylic ester monomer, an acrylic ester low polymer and a tetraethyl orthosilicate prepolymer to prepare an ultraviolet light curable acrylic ester/silicon dioxide nanometer hybrid coating of the invention. The ultraviolet light cured acrylic ester/silicon dioxide nanometer hybrid material obtained through the irradiation of a medium-pressure mercury lamp for the hybrid coating has good physical and mechanical performance and heat resisting property and wide industrial application prospect. The preparation method of the invention has simple and easy operation and can obtain an organic-inorganic nanometer hybrid coating with excellent dispersibility and better two-phase compatibility.
Description
Technical field
The invention belongs to ultraviolet curing acrylic ester/silicon dioxide nano-hybrid material technical field, be specifically related to ultraviolet curing acrylic ester/silicon dioxide nano-hybrid material with the difunctionality light trigger initiated polymerization that contains siloxanes and preparation method thereof.
Background technology
In recent years, the coating UV-curing technology is because characteristics such as its curing speed is fast, less contamination, less energy-consumption, cured product excellent performance are considered to a kind of eco-friendly green technology.As the important component of photo-cured coating, acrylate resin has been widely used in coating, printing ink and adhesive formula.And light trigger (photoinitiator is that can decision formula system origoester acrylate and monomer in the illumination process be transformed into the solid-state key that forms cross-linked structure by liquid state rapidly PI).The basic role characteristics of light trigger are: initiator molecule absorbs behind certain luminous energy promptly from the ground state transition to excited state, generation can the initiating methacrylates oligopolymer and the biologically active fragment of monomer polymerization, and these fragments can be free radical, positively charged ion, negatively charged ion or ion free radical.Yet the small molecules light trigger has run into a series of problem when using.For example, the initiator molecule or its photolytic product that remain in the solidified coating can move at a slow speed to the surface, and this will cause toxicity problem, also can make the xanthochromia aggravation of filming; In addition, the photolysis debris relative molecular mass of most of small molecules light triggers is lower, and volatility is higher, can produce certain peculiar smell, influences environment.Solution to the problems described above is with small molecules light trigger macromoleization, increases the molecular weight of its photolytic product; Or residual light trigger and photolysis debris be fixed in the crosslinking structure, reduce even eliminate their migration and volatilization with this.
Organic-inorganic hybrid material is a kind of finely dispersed heterogeneous material.Compare with single organic polymer, organic-inorganic hybrid material has remarkable advantages at aspects such as optical transparence, adjustable specific refractory power, mechanical property, heat resistance, wear resisting propertys.The preparation of organic-inorganic hybrid material is generally based on sol-gel method.This method can be in room temperature or is allowed under a little more than the mild conditions of room temperature to introduce organic molecule, oligopolymer or superpolymer and the final organic-inorganic hybrid material with fine structure of obtaining, be convenient to select plural components, satisfy the purpose of optimizing, widening material property.U.S.'s " sol-gel science and technology magazine " (Journal of Sol-Gel Science and Technology 33,9-13,2005) reported that a kind of elder generation carries out the trimethoxy vinyl silanes radical polymerization of thermal initiation, again the trimethoxy silicon group is carried out acid catalyzed hydrolytic condensation, finally obtain the method for organic inorganic hybridization mould material, yet this heat cured system power consumption again consuming time, be unfavorable for realizing industrialization, so the organic-inorganic hybrid material of ultraviolet light polymerization has become the focus of research.According to U.S.'s " organic coating progress " magazine (Progress in Organic Coatings 51,312-320,2004) introduce, by with positive tetraethyl orthosilicate (Tetraethyl orthosilicate, TEOS) obtain prepolymer with coupling agent 3-(methacryloxypropyl) propyl trimethoxy silicane cohydrolysis, mix with acrylate monomer and origoester acrylate again, after ultraviolet light polymerization has obtained ultraviolet curing acrylic ester/silicon dioxide nano-hybrid material, used coupling agent has promoted organic phase and inorganic combination mutually, make the final mechanical property of materials and thermal characteristics be improved, but in this ultraviolet light polymerization system and unresolved or improve the migration problem of small molecules light trigger.
Summary of the invention
The objective of the invention is to propose a kind of ultraviolet curing acrylic ester/silicon dioxide nano-hybrid material with the difunctionality light trigger initiated polymerization that contains siloxanes and preparation method thereof, to overcome the above-mentioned defective of prior art.
Preparation method with ultraviolet curing acrylic ester/silicon dioxide nano-hybrid material of containing siloxanes difunctionality light trigger initiated polymerization of the present invention, comprise: adopt the positive tetraethyl orthosilicate (Tetraethylorthosilicate of Prepared by Sol Gel Method earlier, TEOS) prepolymer: will be by weight 20～60% positive tetraethyl orthosilicate, 0.05～0.15% hydrochloric acid and join in the ethanol by the water of 1～4 times of the molar weight of positive tetraethyl orthosilicate, be the condensation 2～5 hours that is hydrolyzed under the condition of 200～500rpm in room temperature and stirring velocity, obtain positive tetraethyl orthosilicate prepolymer; It is characterized in that:
In the light trigger mol ratio of mercaptan carboxylic acid and hydroxy-functional is that 1.05: 1～1.15: 1 and reactant total concn are in the solution of 0.4～0.9g/mL, press 0.1～1% of reactant weight and add esterifying catalyst 1, under inert atmosphere, 110～130 ℃ condition, refluxed 12～24 hours, obtain to have the light trigger of sulfydryl; Described esterifying catalyst 1 is 4-Dimethylamino pyridine tosilate, methylsulphonic acid, tosic acid, Phenylsulfonic acid, hydrochloric acid or phosphoric acid;
Be that 1: 1, reactant total concn are in the solution of 1～2g/mL toward the mol ratio that contains the light trigger of being with sulfydryl and silane coupling agent again, press 0.1～1% of reactant weight and add basic catalyst 2, under inert atmosphere, room temperature condition, reacted 12～36 hours, remove and desolvate, promptly get the difunctionality light trigger that contains siloxanes; Described basic catalyst 2 is tertiary amine, alkaline carbonate, alkali metal hydrocarbonate or alkoxide, comprises triethylamine, yellow soda ash, salt of wormwood, sodium bicarbonate, saleratus or sodium ethylate;
Then, again by weight with 50～80% origoester acrylate, 10～40% acrylate monomer and 2～10% the difunctionality light trigger that contains siloxane groups, mix with 2～10% positive tetraethyl orthosilicate prepolymer, continue stirring and ultrasonic, promptly get the acrylate/silicon dioxide nano-hybrid coating of uV curable to transparent and homogeneous.
During use; place the 10-20cm lamp apart from the place acrylate/silicon dioxide nano-hybrid coating of the above-mentioned uV curable for preparing; under nitrogen protection; the medium pressure mercury lamp illumination of adopting 1000-3000W power is after 40～120 seconds; cured film was heated 1～3 hour in 60～80 ℃ of baking ovens, promptly obtain ultraviolet light irradiation solidified acrylate/nanometer silicon dioxide composite material.
It is HS-(CH that described mercaptan carboxylic acid is selected from the chemical structure skeleton symbol
2)
nThe compound of one end band sulfydryl the other end band carboxylic acid of the long-chain of-COOH, n=1 wherein, 2,3,5,10 or 15.
The light trigger of described hydroxy-functional is cracking type free radical ultraviolet initiator or hydrogen-abstraction free radical ultraviolet initiator, comprise 2-hydroxyl-4 '-(2-hydroxy ethoxy)-2-methyl isophthalic acid-phenyl-acetone-1,1-hydroxyl-cyclohexyl benzophenone, Alpha-hydroxy benzoin methylether, 2-hydroxy-2-methyl-1-phenyl-acetone-1,2-hydroxy-2-methyl-1-p-isopropyl phenyl-acetone-1 or 4-dihydroxy benaophenonel, their structural formula can be expressed as respectively:
2-hydroxyl-4 '-(2-hydroxy ethoxy)-2-methyl isophthalic acid-phenyl-acetone-1 1-hydroxyl-cyclohexyl benzophenone
Alpha-hydroxy benzoin methylether 2-hydroxy-2-methyl-1-phenyl-acetone-1
2-hydroxy-2-methyl-1-p-isopropyl phenyl-acetone-1 4-dihydroxy benaophenonel.
Described silane coupling agent is γ-glycidyl ether oxygen propyl trimethoxy silicane or γ-methacryloxypropyl trimethoxy silane, and their structural formula can be expressed as respectively:
γ-glycidyl ether oxygen propyl trimethoxy silicane γ-methacryloxypropyl trimethoxy silane.
Described solvent is toluene, benzene, dimethylbenzene, oil of mirbane, chlorobenzene, dichlorobenzene, N, N-N,N-DIMETHYLACETAMIDE, N, dinethylformamide, methylene dichloride, trichloromethane, hexanaphthene, ethanol, ethyl acetate, butylacetate, methyl ethyl ketone, methyl iso-butyl ketone (MIBK) or tetrahydrofuran (THF).
Described origoester acrylate is urethane acrylate oligomer, epoxy acrylate oligomer, polyester acrylic ester oligomer or origoester acrylate.
Described acrylate monomer is simple function group acrylate monomer, bifunctional acrylate's monomer, trifunctional group acrylate's monomer or multi-functional acrylate's monomer.
UV curable acrylate/silicon dioxide nano-hybrid the coating of employing method for preparing of the present invention is characterized in that consisting of by weight: 50～80% origoester acrylate, 10～40% acrylate monomer, 2～10% the difunctionality light trigger that contains siloxane groups and 2～10% positive tetraethyl orthosilicate prepolymer.
Compared with prior art, the preparation of ultraviolet curing acrylic ester/silicon dioxide nano-hybrid material of the present invention combines the advantage of UV-curing technology, and preparation condition is simple, and is environmentally friendly, is easier to industrial application;
Employing method for preparing of the present invention contain siloxanes difunctionality light trigger, because the one end has the light trigger group, the other end has siloxane groups, photopolymerization reaction that can initiating methacrylates, and owing to form silica network after the siloxane groups hydrolytic condensation, residual initiator molecule and photolysis debris can be fixed therein, greatly reduce mobility, help solving toxicity and smell problem; In addition, this contain siloxanes difunctionality light trigger the light trigger group can with the organic component reaction bonded, siloxane groups can with inorganic positive tetraethyl orthosilicate prepolymer cohydrolysis condensation, so when utilizing this to contain siloxanes difunctionality light trigger and cause uV curable acrylate/silicon dioxide nano-hybrid coating, need not to add again in addition coupling agent, this difunctionality light trigger in fact just is equivalent to a coupling agent molecule, organic phase is engaged with molecular linkage with inorganic, promoted the biphase consistency widely, thereby the physical and mechanical properties and the thermotolerance of the ultraviolet curing acrylic ester/silicon dioxide nano-hybrid material that finally obtains are improved a lot.
Description of drawings
Fig. 1 is the visible light transmissivity graphic representation of ultraviolet curing acrylic ester/silicon dioxide nano composite material;
Fig. 2 is the stereoscan photograph of ultraviolet curing acrylic ester/silicon dioxide nano composite material.
Embodiment
Embodiment 1:
The positive tetraethyl orthosilicate (TEOS) of 20.8g (0.1mol), 5.4g (0.3mol) water and 0.05g hydrochloric acid are joined in the 23.75g ethanol, making this mixture is the condensation 4 hours that is hydrolyzed under the 300rpm condition in room temperature and stirring velocity, promptly gets positive tetraethyl orthosilicate prepolymer;
(Ciba company produces to add 0.20mol 2-hydroxyl-4 '-(2-hydroxy ethoxy)-2-methyl isophthalic acid-phenyl-acetone-1 in the 250mL there-necked flask, ProductName Irgacure 2959), 0.22mol Thiovanic acid, 150mL toluene and press 0.5% 4-Dimethylamino pyridine tosilate of Irgacure2959 weight, refluxed 12 hours down at 120 ℃, obtain having the light trigger 0.184mol of sulfydryl; Said process can adopt reaction formula to be expressed as:
Get light trigger, 0.184mol γ-glycidyl ether oxygen propyl trimethoxy silicane (Chinese Academy of Sciences that 0.184mol has sulfydryl again, ProductName KH560), 60mL methylene dichloride and join in the there-necked flask of 150mL by 0.5% triethylamine of KH560 weight, reaction is 15 hours under the condition of nitrogen protection, room temperature, remove and desolvate, just obtain containing the difunctionality light trigger A 0.183mol of siloxanes; Said process can adopt reaction formula to be expressed as:
Difunctionality light trigger A with the above-mentioned preparation of 7g; the positive tetraethyl orthosilicate prepolymer of 3g; 80g urethane acrylate (ProductName EB270; the special company of U.S.'s cyanogen produces) and 10g 1; 6-hexanediyl ester (ProductName HDDA; Changxing, Taiwan chemical company produces) mixing stirring and ultrasonic to transparent and homogeneous; getting its sample places the 10cm lamp apart from the place; under nitrogen protection; with medium pressure mercury lamp F300S-6 (Fusion UV Systems; USA) illumination is after 80 seconds; cured film was heated 2 hours in 80 ℃ of baking ovens, promptly obtain ultraviolet curing acrylic ester/nanometer silicon dioxide composite material.
Adopt the omnipotent stretching testing machine in Tianjin, island to measure tensile strength of material, the result shows: the tensile strength of this ultraviolet curing acrylic ester/nanometer silicon dioxide composite material has improved 110% than pure acrylic acid ester material.
Adopt Tianjin, island thermogravimetric analyzer to measure material cured film thermostability, the result shows: the heat decomposition temperature of this matrix material has improved 21 ℃ than ultraviolet curing acrylic ester material.
Adopt the pencil hardness of the QBY type pencil hardness tester of Tianjin instrument plant manufacturing according to GB GB/T6739-1996 mensuration ultraviolet curing acrylic ester/nanometer silicon dioxide composite material, the result shows: the pencil hardness of this composite material solidification film A1 has been increased to 6H from the 2H of pure acrylic acid ester material.
Fig. 1 is the visible light transmissivity graphic representation of ultraviolet curing acrylic ester/silicon dioxide nano composite material of preparing in the present embodiment.Light transmission rate curve a from figure as seen, its visible light transmissivity of ultraviolet curing acrylic ester/silicon dioxide nano composite material for preparing in the present embodiment has surpassed 90%, hence one can see that, and this hybrid material transparency is excellent.
Fig. 2 is the stereoscan photograph of ultraviolet curing acrylic ester/silicon dioxide nano composite material of preparing in the present embodiment.From photo, can see, the inorganic silicon dioxide particle that forms by sol-gel process is evenly distributed in the organic medium, and organic phase and inorganic interphase interface are fuzzy, illustrate because the coupled action of difunctionality light trigger, two alternate consistencies have obtained improving well, and this extremely helps the raising of ultraviolet curing acrylic ester/silicon dioxide nano composite material performance.
Embodiment 2:
The positive tetraethyl orthosilicate (TEOS) of 10.4g (0.05mol), 1.8g (0.1mol) water, 0.075g hydrochloric acid are joined in the 37.73g ethanol, making this mixture is the condensation 2 hours that is hydrolyzed under the condition of 500rpm in room temperature and stirring velocity, promptly obtains the prepolymer of positive tetraethyl orthosilicate;
(Ciba company produces to add 0.20mol1-hydroxyl-cyclohexyl benzophenone in the 250mL there-necked flask, ProductName Irgacure184), 0.21mol2-thiohydracrylic acid, 110mL toluene and press 0.3% methylsulphonic acid of Irgacure 184 weight, refluxed 20 hours at 125 ℃, obtain having the light trigger 0.182mol of sulfydryl;
Get light trigger that 0.182mol has sulfydryl, 0.182mol γ-glycidyl ether oxygen propyl trimethoxy silicane, 75mL methylene dichloride again and join in the 150mL there-necked flask by 0.3% yellow soda ash of γ-glycidyl ether oxygen propyl trimethoxy silicane weight; reaction is 24 hours under the condition of nitrogen protection, room temperature; remove and desolvate, obtain containing the difunctionality photoinitiator b 0.182mol. of siloxanes
With the positive tetraethyl orthosilicate prepolymer of difunctionality photoinitiator b, the 2g of the above-mentioned preparation of 5g, 53g urethane acrylate (ProductName EB8402; the production of the special company of U.S.'s cyanogen), 30g 1; 6-hexanediyl ester, 10g tripropylene glycol dipropyl enol ester mix stirring and ultrasonic to transparent and homogeneous; getting its sample places the 10cm lamp apart from the place; under nitrogen protection; with medium pressure mercury lamp F300S-6 (Fusion UV Systems; USA) illumination is after 90 seconds; cured film was heated 2 hours in 80 ℃ of baking ovens, promptly obtain ultraviolet curing acrylic ester/nanometer silicon dioxide composite material.
Mode same in employing and embodiment 1 detects as can be known: the transparency of this ultraviolet curing acrylic ester/silicon dioxide nano composite material is good; Its tensile strength has improved 95% than ultraviolet curing acrylic ester material; Its heat decomposition temperature has improved 16 ℃ than pure acrylic acid ester material; Its pencil hardness has been increased to 5H from the 2H of pure acrylic acid ester material.
Embodiment 3:
The positive tetraethyl orthosilicate (TEOS) of 15g (0.072mol), 1.29g (0.072mol) water, 0.04g hydrochloric acid are joined in the 33.67g ethanol, making this mixture is the condensation 5 hours that is hydrolyzed under the condition of 400rpm in room temperature and stirring velocity, promptly obtains positive tetraethyl orthosilicate prepolymer;
In the 250mL there-necked flask, add 0.20mol Alpha-hydroxy benzoin methylether, 0.23mol 2-sulfydryl butyric acid, 170mL p-Xylol and press 0.8% tosic acid of Alpha-hydroxy benzoin methylether weight, refluxed 24 hours at 130 ℃, obtain the light trigger that 0.18mol has sulfydryl;
Get the γ-methacryloxypropyl trimethoxy silane, 55mL methylene dichloride of the light trigger that has sulfydryl, the 0.18mol of 0.18mol again and join in the 150mL there-necked flask by 0.8% salt of wormwood of γ-methacryloxypropyl trimethoxy silane weight; reaction is 24 hours under the condition of nitrogen protection, room temperature; remove and desolvate, obtain the difunctionality light trigger C that 0.18mol contains siloxanes.
The positive tetraethyl orthosilicate prepolymer of difunctionality light trigger C, 7g, 65g polyester acrylate (ProductName EB800 with the above-mentioned preparation of 3g; the production of the special company of U.S.'s cyanogen), 25g 1; the 6-hexanediyl ester mixes stirring and ultrasonic to transparent and homogeneous; getting its sample places the 10cm lamp apart from the place; under nitrogen protection; with medium pressure mercury lamp F300S-6 (Fusion UVSystems; USA) illumination is after 60 seconds; cured film heating in 80 ℃ of baking ovens 2 hours, is promptly obtained ultraviolet curing acrylic ester/nanometer silicon dioxide composite material.
Mode same in employing and embodiment 1 detects as can be known: the transparency of this ultraviolet curing acrylic ester/silicon dioxide nano composite material cured film is good; Its tensile strength has improved 85% than ultraviolet curing acrylic ester material; Its heat decomposition temperature has improved 18 ℃ than pure acrylic acid ester material; Its pencil hardness has been increased to 5H from the 2H of pure acrylic acid ester material.
Embodiment 4:
The positive tetraethyl orthosilicate (TEOS) of 30g (0.144mol), 10.368g (0.576mol) water, 0.025g hydrochloric acid are joined in the 9.6g ethanol, making this mixture is the condensation 5 hours that is hydrolyzed under the condition of 200rpm in room temperature and stirring velocity, promptly obtains positive tetraethyl orthosilicate prepolymer;
(Ciba company produces to add 0.20mol 2-hydroxy-2-methyl-1-phenyl-acetone-1 in the 250mL there-necked flask, ProductName Darocur 1173), the toluene of 0.214mol 4-mercaptohexanoic acid, 110mL and press 1% Phenylsulfonic acid of Darocur 1173 weight, refluxed 24 hours at 110 ℃, obtain having the light trigger 0.185mol of sulfydryl;
Get light trigger that 0.185mol has sulfydryl, 0.185mol γ-methacryloxypropyl trimethoxy silane, 55mL methylene dichloride again and join in the 150mL there-necked flask by 1% triethylamine of γ-methacryloxypropyl trimethoxy silane weight; reaction is 28 hours under the condition of nitrogen protection, room temperature; remove and desolvate, obtain containing the difunctionality light trigger D 0.185mol. of siloxanes
The positive tetraethyl orthosilicate prepolymer of difunctionality light trigger D, 10g, 50g urethane acrylate (ProductName EB215 with the above-mentioned preparation of 10g; the production of the special company of U.S.'s cyanogen), 30g 1; the 6-hexanediyl ester mixes stirring and ultrasonic to transparent and homogeneous; getting its sample places the 10cm lamp apart from the place; under nitrogen protection; with medium pressure mercury lamp F300S-6 (FusionUV Systems; USA) illumination is after 90 seconds; cured film heating in 80 ℃ of baking ovens 2 hours, is obtained ultraviolet curing acrylic ester/nanometer silicon dioxide composite material.
Mode same in employing and embodiment 1 detects as can be known: the transparency of this ultraviolet curing acrylic ester/silicon dioxide nano composite material is good; Its tensile strength has improved 70% than pure acrylic acid ester material; Its heat decomposition temperature has improved 14 ℃ than pure acrylic acid ester material; Its pencil hardness has been increased to 4H from the 2H of ultraviolet curing acrylic ester material.
Embodiment 5:
The hydrochloric acid of the positive tetraethyl orthosilicate (TEOS) of 14.56g (0.07mol), 3.15g (0.175mol) water, 0.06g is joined in the 32.23g ethanol, making this mixture is under the condition of 350rpm in room temperature and stirring velocity, the condensation 3 hours that is hydrolyzed promptly obtains positive tetraethyl orthosilicate prepolymer.
(Ciba company produces to add 0.20mol 2-hydroxy-2-methyl-1-p-isopropyl phenyl-acetone-1 in the 250mL there-necked flask, ProductName Darocur 1116), 0.224mol 11-sulfydryl undeeanoic acid, 100mL toluene and press 0.1% methylsulphonic acid of Darocur 1116 weight, refluxed 20 hours at 120 ℃, obtain having the light trigger 0.181mol of sulfydryl;
Get light trigger that 0.181mol has sulfydryl, 0.181mol γ-glycidyl ether oxygen propyl trimethoxy silicane, 115mL ethanol again and join in the there-necked flask of 150mL by 0.1% sodium ethylate of γ-glycidyl ether oxygen propyl trimethoxy silicane weight; reaction is 36 hours under the condition of nitrogen protection, room temperature; remove and desolvate, just obtain containing the difunctionality light trigger E 0.181mol. of siloxanes
The positive tetraethyl orthosilicate prepolymer of difunctionality light trigger E, 5g, 60g epoxy acrylate (ProductName EB600 with the above-mentioned preparation of 2g; the production of the special company of U.S.'s cyanogen), 33g 1; the 6-hexanediyl ester mixes stirring and ultrasonic to transparent and homogeneous; getting its sample places the 10cm lamp apart from the place; under nitrogen protection; with medium pressure mercury lamp F300S-6 (Fusion UV Systems; USA) illumination is after 70 seconds; cured film was heated 2 hours in 80 ℃ of baking ovens, promptly obtain ultraviolet curing acrylic ester/nanometer silicon dioxide composite material.
Mode same in employing and embodiment 1 detects as can be known: the transparency of this ultraviolet curing acrylic ester/silicon dioxide nano composite material is good; Its tensile strength has improved 60% than pure acrylic acid ester material; Its heat decomposition temperature has improved 12 ℃ than pure acrylic acid ester material; Its pencil hardness has been increased to 4H from the 2H of ultraviolet curing acrylic ester material.
Claims (9)
1. preparation method with ultraviolet curing acrylic ester/silicon dioxide nano-hybrid material of containing siloxanes difunctionality light trigger initiated polymerization, comprise the prepolymer that adopts earlier the positive tetraethyl orthosilicate of Prepared by Sol Gel Method: will join in the ethanol by weight 20～60% positive tetraethyl orthosilicate, 0.05～0.15% hydrochloric acid with by the water of 1～4 times of the molar weight of positive tetraethyl orthosilicate, be the condensation 2～5 hours that is hydrolyzed under the condition of 200～500rpm in room temperature and stirring velocity, obtain positive tetraethyl orthosilicate prepolymer; It is characterized in that:
In the light trigger mol ratio of mercaptan carboxylic acid and hydroxy-functional is that 1.05: 1～1.15: 1 and reactant total concn are in the solution of 0.40～0.9g/mL, press 0.1～1% of reactant weight and add esterifying catalyst 1, under inert atmosphere, 110～130 ℃ condition, refluxed 12～24 hours, obtain to have the light trigger of sulfydryl; Described esterifying catalyst 1 is 4-Dimethylamino pyridine tosilate, methylsulphonic acid, tosic acid, Phenylsulfonic acid, hydrochloric acid or phosphoric acid;
Be that 1: 1, reactant total concn are in the solution of 1～2g/mL toward the mol ratio that contains the light trigger of being with sulfydryl and silane coupling agent again, press 0.1～1% of reactant weight and add basic catalyst 2, under inert atmosphere, room temperature condition, reacted 12～36 hours, remove and desolvate, promptly get the difunctionality light trigger that contains siloxanes; Described basic catalyst 2 is tertiary amine, alkaline carbonate, alkali metal hydrocarbonate or alkoxide, comprises triethylamine, yellow soda ash, salt of wormwood, sodium bicarbonate, saleratus or sodium ethylate;
Then, again by weight with 50～80% origoester acrylate, 10～40% acrylate monomer and 2～10% the difunctionality light trigger that contains siloxane groups, mix with 2～10% positive tetraethyl orthosilicate prepolymer, continue stirring and ultrasonic, promptly get the acrylate/silicon dioxide nano-hybrid coating of uV curable to transparent and homogeneous.
2. according to claim 1 with the preparation method of ultraviolet curing acrylic ester/silicon dioxide nano-hybrid material of containing siloxanes difunctionality light trigger initiated polymerization, be characterised in that it is HS-(CH that described mercaptan carboxylic acid is selected from the chemical structure skeleton symbol
2)
nThe compound of one end band sulfydryl the other end band carboxylic acid of the long-chain of-COOH, n=1 wherein, 2,3,5,10 or 15.
3. according to claim 1 with the preparation method of ultraviolet curing acrylic ester/silicon dioxide nano-hybrid material of containing siloxanes difunctionality light trigger initiated polymerization, the light trigger that is characterised in that described hydroxy-functional is cracking type free radical ultraviolet initiator or hydrogen-abstraction free radical ultraviolet initiator.
4. according to claim 1 with the preparation method of ultraviolet curing acrylic ester/silicon dioxide nano-hybrid material of containing siloxanes difunctionality light trigger initiated polymerization, the light trigger that is characterised in that described hydroxy-functional is 2-hydroxyl-4 '-(2-hydroxy ethoxy)-2-methyl isophthalic acid-phenyl-acetone-1,1-hydroxyl-cyclohexyl benzophenone, Alpha-hydroxy benzoin methylether, 2-hydroxy-2-methyl-1-phenyl-acetone-1,2-hydroxy-2-methyl-1-p-isopropyl phenyl-acetone-1 or 4-dihydroxy benaophenonel.
5. according to claim 1 with the preparation method of ultraviolet curing acrylic ester/silicon dioxide nano-hybrid material of containing siloxanes difunctionality light trigger initiated polymerization, be characterised in that described silane coupling agent is γ-glycidyl ether oxygen propyl trimethoxy silicane or γ-methacryloxypropyl trimethoxy silane.
6. according to claim 1 with the preparation method of ultraviolet curing acrylic ester/silicon dioxide nano-hybrid material of containing siloxanes difunctionality light trigger initiated polymerization, be characterised in that described solvent is toluene, benzene, dimethylbenzene, oil of mirbane, chlorobenzene, dichlorobenzene, N, N-N,N-DIMETHYLACETAMIDE, N, dinethylformamide, methylene dichloride, trichloromethane, hexanaphthene, ethanol, ethyl acetate, butylacetate, methyl ethyl ketone, methyl iso-butyl ketone (MIBK) or tetrahydrofuran (THF).
7. according to claim 1 with the preparation method of ultraviolet curing acrylic ester/silicon dioxide nano-hybrid material of containing siloxanes difunctionality light trigger initiated polymerization, be characterised in that described origoester acrylate is urethane acrylate oligomer, epoxy acrylate oligomer, polyester acrylic ester oligomer or origoester acrylate.
8. according to claim 1 with the preparation method of ultraviolet curing acrylic ester/silicon dioxide nano-hybrid material of containing siloxanes difunctionality light trigger initiated polymerization, be characterised in that described acrylate monomer is simple function group acrylate monomer, bifunctional acrylate's monomer, trifunctional group acrylate's monomer or multi-functional acrylate's monomer.
9. uV curable acrylate/silicon dioxide nano-hybrid coating that adopts the preparation of the described method of claim 1 is characterized in that consisting of by weight: 50～80% origoester acrylate, 10～40% acrylate monomer, 2～10% the difunctionality light trigger that contains siloxane groups and 2～10% positive tetraethyl orthosilicate prepolymer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010102157324A CN101875710B (en) | 2010-06-30 | 2010-06-30 | Siloxane-group light-initiated polyacrylic ester/silicon dioxide nanometer material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010102157324A CN101875710B (en) | 2010-06-30 | 2010-06-30 | Siloxane-group light-initiated polyacrylic ester/silicon dioxide nanometer material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101875710A true CN101875710A (en) | 2010-11-03 |
| CN101875710B CN101875710B (en) | 2012-05-23 |
Family
ID=43018399
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2010102157324A Active CN101875710B (en) | 2010-06-30 | 2010-06-30 | Siloxane-group light-initiated polyacrylic ester/silicon dioxide nanometer material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101875710B (en) |
Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102558970A (en) * | 2011-12-16 | 2012-07-11 | 江南大学 | Method for preparing low-viscosity ultraviolet (UV) coating color paste by sol dilution |
| CN102775831A (en) * | 2012-07-31 | 2012-11-14 | 华南理工大学 | Method for curing and grafting amphoteric ion gel coat on external surface on material surface by ultraviolet |
| CN103130831A (en) * | 2011-12-01 | 2013-06-05 | 深圳市有为化学技术有限公司 | Acyl phosphine oxygen compound containing sulfydryl substituent group and photoinitiator containing compound |
| CN104513607A (en) * | 2014-12-24 | 2015-04-15 | 浙江佑谦特种材料有限公司 | Photo-cured wear-resistant anti-fogging coating, and construction method thereof |
| CN105111419A (en) * | 2015-10-12 | 2015-12-02 | 天津凯华绝缘材料股份有限公司 | High-flexibility polyester curing agent containing nano SiO2 material and synthesis method of polyester curing agent |
| CN106456454A (en) * | 2014-06-13 | 2017-02-22 | 斯特拉斯堡大学 | Disintegratable core/shell silica particles for encapsulating and releasing bioactive macromolecules |
| CN106634102A (en) * | 2016-12-29 | 2017-05-10 | 佛山市高明绿化纳新材料有限公司 | Graphite phase carbon nitride/graphene oxide heterojunction-epoxy acrylate composite material as well as preparation method and application thereof |
| CN106986973A (en) * | 2017-03-30 | 2017-07-28 | 同济大学 | SiO2Nanoparticle surface graft-polymer light trigger, preparation method and applications |
| CN108913023A (en) * | 2018-06-13 | 2018-11-30 | 北京化工大学 | A kind of preparation method of ultraviolet curing acrylic ester polysiloxanes clear coat |
| CN109770905A (en) * | 2019-03-12 | 2019-05-21 | 长兴县人民医院 | A kind of offline Exhaled nitric oxide detection device |
| CN111278924A (en) * | 2017-10-31 | 2020-06-12 | 信越化学工业株式会社 | Organopolysiloxane composition, organosilicon compound, and method for producing same |
| CN113060939A (en) * | 2021-03-15 | 2021-07-02 | 蓝思科技股份有限公司 | Method for forming frosting by dry etching substrate, frosting substrate and application |
| CN113552348A (en) * | 2021-07-28 | 2021-10-26 | 四川省医学科学院·四川省人民医院 | Nanoparticle solution for detecting SARS-CoV-2 coronavirus S protein, preparation method, kit and application |
| CN110452417B (en) * | 2019-07-08 | 2022-02-22 | 广东工业大学 | Modified nano SiO2 and photocuring composite elastomer material |
| CN114736549A (en) * | 2022-03-23 | 2022-07-12 | 武汉长盈鑫科技有限公司 | FRP (fiber reinforced Plastic) coating resin composition suitable for UV-LED (ultraviolet-light emitting diode) curing and preparation method thereof |
| CN116646547A (en) * | 2023-05-26 | 2023-08-25 | 上海氢晨新能源科技有限公司 | Resin mixture for preparing graphite bipolar plate and preparation method and application thereof |
| CN116646547B (en) * | 2023-05-26 | 2024-04-26 | 上海氢晨新能源科技有限公司 | Resin mixture for preparing graphite bipolar plate and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101255219A (en) * | 2008-03-21 | 2008-09-03 | 常州华钛化学股份有限公司 | Ultraviolet curing acrylic ester/modified montmorillonite nano composite material and preparation thereof |
| CN101497749A (en) * | 2009-03-06 | 2009-08-05 | 浙江池禾化工有限公司 | Surface modified nano silicon dioxide and acrylic resin coating containing the same |
-
2010
- 2010-06-30 CN CN2010102157324A patent/CN101875710B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101255219A (en) * | 2008-03-21 | 2008-09-03 | 常州华钛化学股份有限公司 | Ultraviolet curing acrylic ester/modified montmorillonite nano composite material and preparation thereof |
| CN101497749A (en) * | 2009-03-06 | 2009-08-05 | 浙江池禾化工有限公司 | Surface modified nano silicon dioxide and acrylic resin coating containing the same |
Non-Patent Citations (3)
| Title |
|---|
| 《Progress in Organic Coatings》 20041231 M.E.L.Wouters，et al. Transparent UV curable antistatic hybrid coatings on polycarbonate prepared by the sol-gel method 312-320 第51卷, 2 * |
| 《高校化学工程学报》 20080430 蔡星等 硅烷偶联剂对光固化PUA/SiO2杂化涂料的改性研究 361-364 第22卷, 第2期 2 * |
| 《高等学校化学学报》 20020228 童昕等 利用聚合物乳液合成聚甲基丙烯酸甲酯/二氧化硅纳米杂化材料 306-309 第23卷, 第2期 2 * |
Cited By (23)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103130831A (en) * | 2011-12-01 | 2013-06-05 | 深圳市有为化学技术有限公司 | Acyl phosphine oxygen compound containing sulfydryl substituent group and photoinitiator containing compound |
| CN102558970B (en) * | 2011-12-16 | 2014-04-09 | 江南大学 | Method for preparing low-viscosity ultraviolet (UV) coating color paste by sol dilution |
| CN102558970A (en) * | 2011-12-16 | 2012-07-11 | 江南大学 | Method for preparing low-viscosity ultraviolet (UV) coating color paste by sol dilution |
| CN102775831A (en) * | 2012-07-31 | 2012-11-14 | 华南理工大学 | Method for curing and grafting amphoteric ion gel coat on external surface on material surface by ultraviolet |
| CN102775831B (en) * | 2012-07-31 | 2014-11-12 | 华南理工大学 | Method for curing and grafting amphoteric ion gel coat on external surface on material surface by ultraviolet |
| CN106456454A (en) * | 2014-06-13 | 2017-02-22 | 斯特拉斯堡大学 | Disintegratable core/shell silica particles for encapsulating and releasing bioactive macromolecules |
| CN106456454B (en) * | 2014-06-13 | 2021-02-02 | 斯特拉斯堡大学 | Disintegrable core/shell silica particles for encapsulating and releasing biologically active macromolecules |
| CN104513607A (en) * | 2014-12-24 | 2015-04-15 | 浙江佑谦特种材料有限公司 | Photo-cured wear-resistant anti-fogging coating, and construction method thereof |
| CN104513607B (en) * | 2014-12-24 | 2016-09-28 | 浙江佑谦特种材料有限公司 | A kind of wear-resisting anti-fog coating of photocuring and construction method thereof |
| CN105111419B (en) * | 2015-10-12 | 2017-05-10 | 天津凯华绝缘材料股份有限公司 | High-flexibility polyester curing agent containing nano SiO2 material and synthesis method of polyester curing agent |
| CN105111419A (en) * | 2015-10-12 | 2015-12-02 | 天津凯华绝缘材料股份有限公司 | High-flexibility polyester curing agent containing nano SiO2 material and synthesis method of polyester curing agent |
| CN106634102A (en) * | 2016-12-29 | 2017-05-10 | 佛山市高明绿化纳新材料有限公司 | Graphite phase carbon nitride/graphene oxide heterojunction-epoxy acrylate composite material as well as preparation method and application thereof |
| CN106986973A (en) * | 2017-03-30 | 2017-07-28 | 同济大学 | SiO2Nanoparticle surface graft-polymer light trigger, preparation method and applications |
| CN111278924A (en) * | 2017-10-31 | 2020-06-12 | 信越化学工业株式会社 | Organopolysiloxane composition, organosilicon compound, and method for producing same |
| CN108913023A (en) * | 2018-06-13 | 2018-11-30 | 北京化工大学 | A kind of preparation method of ultraviolet curing acrylic ester polysiloxanes clear coat |
| CN109770905A (en) * | 2019-03-12 | 2019-05-21 | 长兴县人民医院 | A kind of offline Exhaled nitric oxide detection device |
| CN110452417B (en) * | 2019-07-08 | 2022-02-22 | 广东工业大学 | Modified nano SiO2 and photocuring composite elastomer material |
| CN113060939A (en) * | 2021-03-15 | 2021-07-02 | 蓝思科技股份有限公司 | Method for forming frosting by dry etching substrate, frosting substrate and application |
| CN113552348A (en) * | 2021-07-28 | 2021-10-26 | 四川省医学科学院·四川省人民医院 | Nanoparticle solution for detecting SARS-CoV-2 coronavirus S protein, preparation method, kit and application |
| CN114736549A (en) * | 2022-03-23 | 2022-07-12 | 武汉长盈鑫科技有限公司 | FRP (fiber reinforced Plastic) coating resin composition suitable for UV-LED (ultraviolet-light emitting diode) curing and preparation method thereof |
| CN114736549B (en) * | 2022-03-23 | 2022-09-30 | 武汉长盈鑫科技有限公司 | FRP (fiber reinforced plastic) coating resin composition suitable for UV-LED (ultraviolet-light emitting diode) curing and preparation method thereof |
| CN116646547A (en) * | 2023-05-26 | 2023-08-25 | 上海氢晨新能源科技有限公司 | Resin mixture for preparing graphite bipolar plate and preparation method and application thereof |
| CN116646547B (en) * | 2023-05-26 | 2024-04-26 | 上海氢晨新能源科技有限公司 | Resin mixture for preparing graphite bipolar plate and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101875710B (en) | 2012-05-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101875710B (en) | Siloxane-group light-initiated polyacrylic ester/silicon dioxide nanometer material and preparation method thereof | |
| CN101531839B (en) | Silicon- and fluorine-containing epoxy (meth) acrylate UV-curing composite coating and preparation method thereof | |
| CN101775143B (en) | Ultraviolet light-curing compound paint containing fluorine-containing polysiloxane and preparation method thereof | |
| Sangermano et al. | Cationic UV‐curing: Technology and applications | |
| CN101555386B (en) | Epoxy organosilicone ultraviolet curing coating modified by (methyl) acrylic acid and preparation method thereof | |
| CN103936996B (en) | Synthesis of photo-cured fluorosilicone polymer and preparation method of photo-cured fluorosilicone polymer coating | |
| CN1754915A (en) | Silicone resin composition and molded product thereof | |
| CN108659471A (en) | A kind of light-cured resin and preparation method thereof that polyfunctionality POSS is modified | |
| CN102070981A (en) | Ultraviolet curing paint and preparation method and application thereof | |
| CN103360540B (en) | Organic-silicon-modified fluorine-containing (methyl) acrylic resin of a kind of long side chain | |
| JP4398500B2 (en) | Resin composition and optical member | |
| CN104788725B (en) | A kind of light stabilizer for having ultraviolet screener and absorption function concurrently and preparation method thereof | |
| TW200940604A (en) | Organosilicon compounds which have oxetanyl groups, and a method for the production and curable compositions of the same | |
| CN106062042B (en) | Silsesquioxane composite polymer and method for producing same | |
| CN102731788A (en) | Organosilicone hybrid and organosilicone composite paint and preparations thereof | |
| CN101864204A (en) | Dedicated high-performance primer of ultraviolet-curing vacuum coating for reflector of automobile lamps | |
| CN104761994A (en) | Preparation method of photocuring organic silicon modified epoxy resin paint film | |
| CN106029747B (en) | Silsesquioxane composite polymer and method for producing same | |
| CN108384406A (en) | A kind of graphene oxide UV is coating material solidified and preparation method thereof | |
| CN114292485A (en) | Antibacterial adhesion-resistant hydrophobic anti-reflection material and preparation method and application thereof | |
| CN106753217B (en) | A kind of preparation method of novel heat cure liquid silastic | |
| CN108264640A (en) | For the preparation method of the molding UV photo-curable silicone resins of direct write | |
| TW201540749A (en) | Silsesquioxane composite polymer and method for manufacturing thereof | |
| CN106632875A (en) | Inorganic nanoparticle-modified fluorinated acrylate hydrophobic emulsion and preparation method thereof | |
| CN101935457A (en) | Method for manufacturing high-refractive index TiO2/organic silicon hybrid coating |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CP03 | Change of name, title or address |
Address after: 519050 Guangdong province Zhuhai City Road nine Petrochemical Gaolan Port Economic Zone No. 307 Patentee after: Changxin special materials (Zhuhai) Co., Ltd. Address before: 519050 Guangdong province Zhuhai Gaolan Port Industrial Zone Petrochemical Zone Bi Yang Road Patentee before: Eternal Chemical Material (Zhuhai) Co., Ltd. |
|
| CP03 | Change of name, title or address |