CN106750318B - Polysiloxane acrylate containing tertiary amine structure and preparation method and application thereof - Google Patents
Polysiloxane acrylate containing tertiary amine structure and preparation method and application thereof Download PDFInfo
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- CN106750318B CN106750318B CN201611122108.3A CN201611122108A CN106750318B CN 106750318 B CN106750318 B CN 106750318B CN 201611122108 A CN201611122108 A CN 201611122108A CN 106750318 B CN106750318 B CN 106750318B
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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
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- C08G77/38—Polysiloxanes modified by chemical after-treatment
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- C08G77/04—Polysiloxanes
- C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
- C08G77/26—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen nitrogen-containing groups
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- 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
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/102—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds
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- 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
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
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- C09D183/06—Polysiloxanes containing silicon bound to oxygen-containing groups
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/04—Polysiloxanes
- C09D183/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen
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Abstract
The invention provides a novel polysiloxane acrylate oligomer with weather resistance and containing a tertiary amine group structure, which can be cured by L ED light, and is prepared by taking amino-terminated polysiloxane of formula I as a raw material, reacting the amino-terminated polysiloxane with one or two monofunctional acrylate or methacrylate, and then reacting the amino-terminated polysiloxane with one or two bifunctional acrylate or methacrylate;
Description
Technical Field
The invention relates to an amino-containing polysiloxane acrylate photocuring oligomer for L ED photocuring, and a preparation method and application thereof.
Background
The market share of the photocuring technology in the traditional industries such as coatings, printing ink, adhesives and the like is getting larger and larger by virtue of the characteristics of high efficiency, environmental protection and energy conservation, in recent years, with the development of L ED light sources, the photocuring technology also adopts L ED as a radiation light source more and more, although L ED light sources have the advantages of long service life, low energy consumption, flexible design, no ozone and the like, the current photocuring technology can be matched with few formulas, mainly because the existing L ED light sources mainly comprise 365nm, 385nm, 395nm and 405nm long-wavelength light sources, wherein 395nm and 405nm are the most mature light sources.
O2The stable state of (a) is a triplet state, with two unpaired electrons having the same spin direction. Therefore, it competes with the polymerization reaction of the radical to consume the radical. Since most of the photo-curing processes are carried out in an air environment and the main applications are materials with an extremely large surface/volume ratio such as paints and inks, O2The polymerization inhibition effect which is not negligible for the free radical polymerization reaction of the photo-curing material often causes the condition that the bottom layer of the coating is cured and the surface is not cured and sticky. Oxygen inhibition can ultimately lead to the appearance of a large number of oxidative structures such as hydroxyl, carbonyl, peroxy and the like on the surface of the coating, thereby affecting the long-term stability of the coating and possibly even the properties such as hardness, glossiness, scratch resistance and the like of the cured paint film.
There are many methods for inhibiting oxygen polymerization, and one of them is added with amine auxiliary agents, such as EDB, EHA, active amine P115, P116, etc. which are currently marketed auxiliary initiators. The synthesis and photocuring performance of tertiary amine type urethane acrylate (chapter of horse, etc., 17-20) in polyurethane industry [ J ],2010, Vol.25(6):17-20) uses trimethylolpropane triacrylate and diethanol amine as raw materials, and then synthesizes tertiary amine type acrylate through Michael addition reaction, thereby playing the role of anti-oxygen polymerization inhibition to a certain extent in the photocuring process; pottery et al (pottery et al, synthesis and application of hyperbranched oligomers in UV inkjet inks, master paper, 2007) designed tertiary amine structures when hyperbranched oligomers were made, but their tertiary amine structures were all embedded inside the hyperbranched structures, and their tertiary amines basically did not play their due roles due to steric hindrance.
For example, EDB and EHA which are most widely applied at present have molecular weight below 300 daltons and smaller molecular weight, belong to small molecular amine auxiliaries, and the compounds and fragments thereof generated in the light guiding process have the tendency of migration and volatilization, so that the application of the compounds in certain fields is limited.
Disclosure of Invention
The invention aims to overcome the defects of the existing amine auxiliary agent and provide a novel amino-containing polysiloxane acrylate oligomer for L ED photocuring, which has better performance, has a large amount of tertiary amine structures and siloxane structures, can improve the anti-oxidation polymerization inhibition effect of a photocuring formula under a L ED light source to a great extent and promote the surface drying performance of a coating.
The invention provides an amino-containing polysiloxane acrylate oligomer for L ED photocuring, which is characterized in that:
the end-capped amine polysiloxane is prepared by taking the end-capped amine polysiloxane of the formula I as a raw material, reacting with one or two monofunctional acrylate or methacrylate, and then reacting with one or two difunctional acrylate or methacrylate,
wherein:
r is selected from C1-C5 alkyl;
a is selected from- (CH)2)yNH2；
y is selected from an integer from 1 to 6;
x is an integer from 1 to 3;
n is selected from integers from 1 to 100, preferably from 1 to 50.
The monofunctional acrylate or methacrylate is selected from 4-tert-butyl cyclohexyl acrylate; dicyclopentenyl acrylate; dicyclopentenyl ethoxylated acrylate; 2-phenoxyethyl acrylate; ethoxylated phenoxy acrylate; 3,3, 5-trimethylcyclohexyl acrylate; o-phenylphenoxyethyl acrylate; 2- (p-cumyl-phenoxy) -ethyl acrylate; ethoxyethoxyethyl acrylate; cyclotrimethylolpropane formal acrylate; tetrahydrofurfuryl acrylate; 2-octahydro-1, 3-dioxo-isoindoline methacrylate; lauric acid acrylate; 4-Mohr ethoxylated nonylphenol acrylate; stearic acid acrylate; isodecyl acrylate; C8-C10 alkyl acrylate; isodecyl methacrylate; 2-phenoxyethyl methacrylate; isotridecyl methacrylate; isobornyl acrylate; benzyl acrylate; isobornyl methacrylate; one or more of benzyl methacrylate.
The difunctional acrylate or methacrylate is selected from 3-hydroxy-2, 2-dimethylpropyl-3-hydroxy-2, 2-dimethylpropyl diacrylate; 1, 9-nonanediol diacrylate; 1, 6-hexanediol diacrylate; ethoxylated 1, 6-hexanediol diacrylate; dipropylene glycol diacrylate; tripropylene glycol diacrylate; polyethylene glycol (200) diacrylate; polyethylene glycol (400) diacrylate; polyethylene glycol (600) diacrylate; 1, 4-butanediol diacrylate; neopentyl glycol diacrylate; propylene oxide neopentyl glycol diacrylate; ethoxylated bisphenol a diacrylate; 2-methyl-1, 3-propanediol diacrylate; ethylene glycol dimethacrylate; triethylene glycol dimethacrylate; one or more of diethylene glycol dimethacrylate.
In analyzing the oligomer of the present invention, the numbers represented by n in the above formula are not necessarily integers, and in fact, they cannot all take integers, because the starting material of the compound of the present invention may be a mixture of several or several tens of compounds in which the number n is different. According to the invention, this will be satisfactory as long as the average value of each of these numbers is as defined above.
The preparation method of the amino-containing polysiloxane acrylate oligomer for L ED photocuring comprises the following steps:
1) adding the end-capped amine polysiloxane with the structure of the formula I into a reaction kettle, and then adding one or two monofunctional acrylate or methacrylate;
2) maintaining the reaction kettle at 40-60 deg.C, stirring for 30min, heating to 70-150 deg.C for heat preservation reaction, infrared monitoring reaction, and detecting double bond (1645 cm)-1) Stopping the reaction when the reaction is disappeared, and cooling to 40-60 ℃;
3) adding one or two bifunctional acrylates or methacrylates and a polymerization inhibitor into the reaction kettle;
4) maintaining the reaction kettle at 40-60 deg.C, stirring for 30min, heating to 70-150 deg.C, infrared monitoring reaction, and infrared detecting-NH (3300 cm)-1) Stopping the reaction when the reaction is disappeared, and cooling to room temperature to obtain the corresponding amino-containing polysiloxane acrylate oligomer.
The preparation method provided by the invention is characterized in that the monofunctional acrylate or methacrylate in the step 1) is selected from 4-tert-butyl cyclohexyl acrylate; dicyclopentenyl acrylate; dicyclopentenyl ethoxylated acrylate; 2-phenoxyethyl acrylate; ethoxylated phenoxy acrylate; 3,3, 5-trimethylcyclohexyl acrylate; o-phenylphenoxyethyl acrylate; 2- (p-cumyl-phenoxy) -ethyl acrylate; ethoxyethoxyethyl acrylate; cyclotrimethylolpropane formal acrylate; tetrahydrofurfuryl acrylate; 2-octahydro-1, 3-dioxo-isoindoline methacrylate; lauric acid acrylate; 4-Mohr ethoxylated nonylphenol acrylate; stearic acid acrylate; isodecyl acrylate; C8-C10 alkyl acrylate; isodecyl methacrylate; 2-phenoxyethyl methacrylate; isotridecyl methacrylate; isobornyl acrylate; benzyl acrylate; isobornyl methacrylate; one or more of benzyl methacrylate.
The preparation method provided by the invention is characterized in that in the step 3), bifunctional acrylate or methacrylate is selected from 3-hydroxy-2, 2-dimethylpropyl-3-hydroxy-2, 2-dimethylpropyl diacrylate; 1, 9-nonanediol diacrylate; 1, 6-hexanediol diacrylate; ethoxylated 1, 6-hexanediol diacrylate; dipropylene glycol diacrylate; tripropylene glycol diacrylate; polyethylene glycol (200) diacrylate; polyethylene glycol (400) diacrylate; polyethylene glycol (600) diacrylate; 1, 4-butanediol diacrylate; neopentyl glycol diacrylate; propylene oxide neopentyl glycol diacrylate; ethoxylated bisphenol a diacrylate; 2-methyl-1, 3-propanediol diacrylate; ethylene glycol dimethacrylate; triethylene glycol dimethacrylate; one or more of diethylene glycol dimethacrylate.
The preparation method provided by the invention is characterized in that the polymerization inhibitor in the step 1) is selected from one or more of 1, 4-hydroquinone, p-benzoquinone, methyl hydroquinone, p-hydroxyanisole, 2-tert-butyl hydroquinone and 2, 5-di-tert-butyl hydroquinone; the amount is selected from 0.1% to 0.5% of the amount of the blocked amine polysiloxane material.
The preparation method is characterized in that the amount ratio of the blocked amine polysiloxane and the monofunctional acrylate or methacrylate in the step 1) is selected from 1 (2.0-2.2), and if two monofunctional acrylates or methacrylates are used, the amount ratio of the sum of the two monofunctional acrylates or methacrylates and the amount ratio of the blocked amine polysiloxane is selected from 2.0-2.2) to 1.
The preparation method is characterized in that the amount of the difunctional acrylate or methacrylate in the step 3) is selected from the ratio of the amount of the substances of the end-capped amine polysiloxane and the difunctional acrylate or methacrylate to 1 (2.0-2.2), and if two difunctional acrylates or methacrylates are used, the ratio of the sum of the amounts of the substances and the amount of the substances of the end-capped amine polysiloxane is selected from (2.0-2.2) to 1.
The preparation method provided by the invention can be purchased in the market and can also be prepared, and the preparation method is disclosed in a plurality of documents, such as CN 100508942; wang navigation, etc., synthesis and characterization of amino-terminated polysiloxane, Chinese adhesive [ J ], Vol.23(10), 2014: 545-548; duckweed et al, synthesis and performance comparison of several aminosilicones with different end groups, science and engineering of high molecular materials [ J ], vol.26(11), 2010: 24-27; huanglianxian, etc., synthesis and performance of amino-terminated polyether modified silicone oil, printing and dyeing assistant [ J ], Vol.30(5), 2003: 23-27.
The preparation method of the amino-containing polysiloxane acrylate oligomer provided by the invention almost has no generation of three wastes through a Michael addition method, the whole production process is clean and energy-saving, the operation is simple, the reaction condition is mild, high temperature and high pressure are not needed, and the environment-friendly production is really realized.
The present invention provides a photopolymerizable system comprising:
(a) at least one compound containing an ethylenically unsaturated double bond and
(b) at least one amino-containing silicone acrylate oligomer provided by the invention and
(c) photoinitiator
The compound containing an ethylenically unsaturated double bond may contain one or more double bonds. They may be of low molecular weight (monomeric) or relatively high molecular weight (oligomeric). Examples of monomers containing double bonds are alkyl or hydroxyalkyl acrylates or methacrylates, for example methyl, ethyl, butyl, 2-ethylhexyl-or 2-hydroxyethyl acrylate, isobornyl acrylate, or methyl or ethyl methacrylate; a silicone acrylate; acrylamide, methacrylamide, N-substituted (meth) acrylamides; vinyl esters such as vinyl acetate, vinyl ethers such as isobutyl vinyl ether, styrene, alkyl-and halostyrenes, N-vinylpyrrolidone, vinyl chloride or 1, 1-dichloroethylene.
Monomers containing two or more double bonds, such as ethylene glycol, propylene glycol, neopentyl glycol, the diacrylates of 1, 6-hexanediol and bisphenol A, 4,4' -bis (2-acryloyloxyethoxy) diphenylpropane, trimethylolpropane triacrylate, pentaerythritol triacrylate or tetraacrylate, vinyl acrylate, divinylbenzene, divinyl succinate, diallyl phthalate, triallyl phosphate, triallyl isocyanurate and tris (2-acryloylethyl) isocyanurate.
The photoinitiator is a combination of a cracking type free radical photoinitiator and a hydrogen abstraction type photoinitiator or is used independently, and the cracking type photoinitiator is as follows: 2-hydroxy-2-methyl-1-phenyl-1-propanone (JRcure 1103), 1-hydroxycyclohexyl phenyl methanone (JRcure1104), 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl ] -1-propanone (JRcure 1113), Esacure KIP150, Irgacure 127, 2, 2-dimethoxy-2-phenylacetophenone (JRcure 1065), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone (JRcure 1112), 2- (4-benzyl) -2-dimethylamino-1- (4-morpholinophenyl) butanone (JRcure 1112), 2-methyl-1- (4-methylthiophenyl) -2-morpholino-1-propanone (JRcure 1107), one or more combinations of methyl benzoylformate (JRcure 1055), 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide (JRcure 1108), ethyl 2,4, 6-trimethylbenzoylphenylphosphonate (JRcure 1110), phenylbis (2,4, 6-trimethylbenzoyl) phosphine oxide, 2, 2-diethoxyacetophenone; the hydrogen abstraction photoinitiator was: 2-isopropylthioxanthone (JRcure 1105), 2, 4-diethylthioxanthone (JRcure 1106), benzophenone (JRcure 1020), 4-methylbenzophenone (JRcure 1024), 4-chlorobenzophenone (JRcure 1046), 4-phenyltolidine (JRcure 1059), methyl 2-benzoylbenzoate (JRcure 1056), 4,4' -bis (diethylamino) benzophenone (JRcure 1022).
The photopolymerization system can generate a cured product with the performance of paint, varnish, enamel, paint, pigment or ink after photopolymerization, in particular printing ink.
Detailed Description
The invention will be further illustrated by the following non-limiting examples.
Example 1: preparation of end-capped amino polysiloxane by using octamethylcyclotetrasiloxane as monomer and 1, 3-bis (3-aminopropyl) -1,1,3, 3-tetramethyldisiloxane as end-capping agent
Under nitrogen atmosphere, adding octamethylcyclotetrasiloxane, an end-capping agent 1, 3-bis (3-aminopropyl) -1,1,3, 3-tetramethyldisiloxane, a catalyst tetramethylammonium hydroxide and dimethyl sulfoxide (DMSO) into a reaction vessel in an amount of n (octamethylcyclotetrasiloxane): n (capping agent): n (tetramethylammonium hydroxide) is 1.2:1.0:1.5, the amount of DMSO is 0.5 percent of the total mass of the octamethylcyclotetrasiloxane and the end-capping reagent, the temperature is kept at 90 ℃ for reaction for 3 hours, and after the reaction is finished, the temperature is raised to 140 ℃ for reaction for 1 hour; then, low molecular weight substances and unreacted raw materials were distilled off under reduced pressure to obtain a colorless transparent blocked aminopolysiloxane.
Example 2: preparation of amino-containing polysiloxane acrylate oligomer 1
To a reaction vessel were added the terminal aminosilicone prepared in example 1 and 2-phenoxyethyl acrylate in an amount of n (terminal aminosilicone): n (2-phenoxyethyl acrylate) ═ 1: 2; heating, keeping the temperature at 40 deg.C, stirring for 30min, heating to 70 deg.C, and reacting while keeping the temperature until the double bond (1645 cm) is detected by infrared-1) Stopping the reaction when the reaction is disappeared, and cooling to 40 ℃; adding 1, 6-hexanediol diacrylate (n-terminal aminosiloxane): n (1, 6-hexanediol diacrylate): 1: 2) into the reaction system, adding p-hydroxyanisole in an amount of 0.2% of the amount of the terminal aminosiloxane, stirring at 40 deg.C for 30min, heating to 70 deg.C, and maintaining the temperature for reaction until infrared detection of-NH (3300 cm)-1) Stopping the reaction when the reaction is disappeared, and cooling to room temperature to obtain the corresponding amino-containing polysiloxane acrylate oligomer 1.
Example 3: preparation of amino-containing polysiloxane acrylate oligomer 2
To a reaction vessel were added the terminal aminosiloxane prepared in example 1, 2-phenoxyethyl acrylate and tetrahydrofurfuryl acrylate, in amounts n (terminal aminosiloxane): n (2-phenoxyethyl acrylate): n (tetrahydrofurfuryl acrylate) ═ 1:1: 1; heating, keeping the temperature at 40 deg.C, stirring for 30min, heating to 70 deg.C, and reacting while keeping the temperature until the double bond (1645 cm) is detected by infrared-1) Stopping the reaction when the reaction is disappeared, and cooling to 40 ℃; adding 1, 6-hexanediol diacrylate (n-terminal aminosiloxane): n (1, 6-hexanediol diacrylate): 1: 2) into the reaction system, adding p-hydroxyanisole in an amount of 0.2% of the amount of the terminal aminosiloxane, stirring at 40 deg.C for 30min, heating to 70 deg.C, and maintaining the temperature for reaction until infrared detection of-NH (3300 cm)-1) Stopping the reaction when the reaction is disappeared, and cooling to room temperature to obtain the corresponding amino-containing polysiloxane acrylate oligomer 2.
Example 4: preparation of amino-containing polysiloxane acrylate oligomer 3
To a reaction vessel were added the terminal aminosiloxane prepared in example 1, 2-phenoxyethyl acrylate and tetrahydrofurfuryl acrylate, in amounts n (terminal aminosiloxane): n (2-phenoxyethyl acrylate): n (tetrahydrofurfuryl acrylate) ═ 1:1: 1; heating, keeping the temperature at 40 deg.C, stirring for 30min, heating to 70 deg.C, and reacting while keeping the temperature until the double bond (1645 cm) is detected by infrared-1) Stopping the reaction when the reaction is disappeared, and cooling to 40 ℃; adding 1, 6-hexanediol diacrylate and neopentyl glycol diacrylate to the reaction system in an amount of n (amino terminated siloxane): n (1, 6-hexanediol diacrylate): n (neopentyl glycol diacrylate) is 1:1:1, p-hydroxyanisole with the amount of 0.2% of that of the terminal aminosiloxane substance is added, the mixture is kept at 40 ℃ and stirred for 30min, then the temperature is raised to 70 ℃, and the reaction is kept until-NH (3300 cm) is detected by infrared ray-1) Stopping the reaction when the reaction is disappeared, and cooling to room temperature to obtain the corresponding amino-containing polysiloxane acrylate oligomer 3.
Example 5: evaluation of photocuring Properties
Photo initiation rate
The photocurable compositions were prepared according to the formulation of Table 1, resin 1 of this patent was selected for group A, resin 1 of this patent was selected for group B, and epoxy acrylate resin (without amine) was used for group C for comparison.A 22 μm wire bar coater was used to apply the formulated photocurable compositions to glass slides.the coated samples were mounted on a belt and transported under a 395nm L ED light source.
Table 1: formula of photocuring system
| Composition of | The mixture ratio is A% | The mixture ratio is B% | The mixture ratio is C% | The mixture ratio is D% | The mixture ratio is E% |
| Oligomer 1 | 40 | -- | -- | 43 | -- |
| Oligomer 2 | -- | 40 | -- | -- | 43 |
| Bisphenol A epoxy acrylate | -- | -- | 40 | -- | -- |
| Trimethylolpropane triacrylate | 25 | 25 | 25 | 25 | 25 |
| Neopentyl glycol diacrylate | 28.5 | 28.5 | 28.5 | 28.5 | 28.5 |
| Antifoaming agent (BYK-067A) | 0.4 | 0.4 | 0.4 | 0.4 | 0.4 |
| Wetting agent (BYK-377) | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 |
| Flatting agent (BYK-UV 3530) | 0.6 | 0.6 | 0.6 | 0.6 | 0.6 |
| ITX | 2 | 2 | 2 | 2 | 2 |
| EDB | 3 | 3 | 3 | -- | -- |
The evaluation results are shown in table 2:
table 2: evaluation results
| Curing speed m/min | Xenon lamp aging | |
| Group A | 90 | No obvious aging phenomenon after 80 hours |
| Group B | 92 | No obvious aging phenomenon after 80 hours |
| Group C | 65 | After 50 hours, the phenomena of yellowing and embrittlement are obvious |
| Group D | 89 | No obvious aging phenomenon after 80 hours |
| Group E | 88 | No obvious aging phenomenon after 80 hours |
From the results in Table 2, it can be seen that the synthetic resin of this patent has a good curing speed under L ED light source, and the cured coating has a good aging resistance.
Claims (5)
1. A preparation method of polysiloxane acrylate oligomer containing a tertiary amine structure and capable of being cured by L ED light is characterized in that:
the amino polysiloxane is prepared by taking amino-terminated polysiloxane of formula I as a raw material, reacting with one or two monofunctional group (methyl) acrylates, and then reacting with one or two bifunctional group (methyl) acrylates;
wherein:
r is selected from C1-C5 alkyl;
a is selected from- (CH)2)yNH2；
y is selected from an integer from 1 to 6;
x is an integer from 1 to 3;
n is an integer from 1 to 100;
the detailed preparation method comprises the following steps:
1) adding amino-terminated polysiloxane with a structure shown in the formula I into a reaction kettle, and then adding one or two monofunctional group (methyl) acrylate;
2) maintaining the reaction kettle at 40-60 deg.C, stirring for 30min, heating to 70-150 deg.C for heat preservation reaction, infrared monitoring reaction, and detecting double bond (1645 cm)-1) Stopping the reaction when the reaction is disappeared, and cooling to 40-60 ℃;
3) adding one or two bifunctional (methyl) acrylate and polymerization inhibitor into the reaction kettle;
4) maintaining the reaction kettle at 40-60 deg.C, stirring for 30min, heating to 70-150 deg.C, infrared monitoring reaction, and infrared detecting-NH (330)0cm-1) Stopping the reaction when the reaction disappears, and cooling to room temperature to obtain the corresponding polysiloxane acrylate oligomer with the tertiary amine structure;
wherein in step 1) the ratio of the amount of the substance of the amino-terminated polysiloxane to the amount of the monofunctional (meth) acrylate is selected from 1 (2.0 to 2.2), and if two monofunctional (meth) acrylates are used, the ratio of the sum of the amounts of the substances to the amount of the amino-terminated polysiloxane substance is selected from 2.0 to 2.2: 1;
in step 3), the amount of difunctional (meth) acrylate is selected from the ratio of the amount of the amino-terminated polysiloxane to the amount of difunctional (meth) acrylate 1 (2.0-2.2), and if two difunctional (meth) acrylates are used, the ratio of the sum of the amounts of these difunctional (meth) acrylates to the amount of the amino-terminated polysiloxane is selected from the ratio of (2.0-2.2): 1.
2. The method for preparing a polysiloxane acrylate oligomer containing a tertiary amine structure according to claim 1, wherein the monofunctional (meth) acrylate in step 1) is selected from 4-t-butylcyclohexyl acrylate; dicyclopentenyl acrylate; dicyclopentenyl ethoxylated acrylate; 2-phenoxyethyl acrylate; ethoxylated phenoxy acrylate; 3,3, 5-trimethylcyclohexyl acrylate; o-phenylphenoxyethyl acrylate; 2- (p-cumyl-phenoxy) -ethyl acrylate; ethoxyethoxyethyl acrylate; cyclotrimethylolpropane formal acrylate; tetrahydrofurfuryl acrylate; lauric acid acrylate; 4-Mohr ethoxylated nonylphenol acrylate; stearic acid acrylate; isodecyl acrylate; C8-C10 alkyl acrylate; isodecyl methacrylate; 2-phenoxyethyl methacrylate; isotridecyl methacrylate; isobornyl acrylate; benzyl acrylate; isobornyl methacrylate; one or more of benzyl methacrylate.
3. The method for preparing a polysiloxane acrylate oligomer containing a tertiary amine structure according to claim 1, wherein the difunctional (meth) acrylate in step 3) is selected from the group consisting of 3-hydroxy-2, 2-dimethylpropyl-3-hydroxy-2, 2-dimethylpropyl diacrylate; 1, 9-nonanediol diacrylate; 1, 6-hexanediol diacrylate; ethoxylated 1, 6-hexanediol diacrylate; dipropylene glycol diacrylate; tripropylene glycol diacrylate; polyethylene glycol (200) diacrylate; polyethylene glycol (400) diacrylate; polyethylene glycol (600) diacrylate; 1, 4-butanediol diacrylate; neopentyl glycol diacrylate; propylene oxide neopentyl glycol diacrylate; ethoxylated bisphenol a diacrylate; 2-methyl-1, 3-propanediol diacrylate; ethylene glycol dimethacrylate; triethylene glycol dimethacrylate; one or more of diethylene glycol dimethacrylate.
4. The method of claim 1, wherein the polymerization inhibitor in step 3) is selected from one or more of 1, 4-hydroquinone, p-benzoquinone, methyl hydroquinone, p-hydroxyanisole, 2-tert-butylhydroquinone, and 2, 5-di-tert-butylhydroquinone; the amount is selected from 0.1% to 0.5% of the amount of amino terminated polysiloxane material.
5. A photopolymerizable system comprising:
(a) at least one compound containing an ethylenically unsaturated double bond and
(b) at least one polysiloxane acrylate oligomer containing a tertiary amine structure prepared as described in claim 1 and
(c) a photoinitiator.
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| CN108484915A (en) * | 2018-04-27 | 2018-09-04 | 常州大学 | A kind of ultraviolet light（UV）Cure the preparation method of the polymethyl siloxane of end acrylate structural |
| CN108841235B (en) * | 2018-06-05 | 2021-12-10 | 深圳市容大感光科技股份有限公司 | Composition for resisting oxygen resistance and improving surface curing degree of photo-curing ink and application |
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