CN101982512A - Silicone acrylate coating resin and preparation method thereof - Google Patents
Silicone acrylate coating resin and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the fields of coating, adhesive and functional material and in particular relates to silicone acrylate coating resin and a preparation method thereof. The preparation method comprises the following steps: copolymerizing acrylic monomer, acrylic monomer with epoxy groups and silane coupling agent with unsaturated bonds to obtain acrylic resin; then adding organosilicon resin to mixed evenly and obtain silicone acrylate resin, or adding silicone oil with double bonds in the polymerization of acrylic resin to directly obtain silicone acrylate resin; and mixing silicone acrylate resin with curing agent evenly to obtain the finished product, wherein the weight ratio of acrylic monomer to acrylic monomer with epoxy groups and silane coupling agent with unsaturated bonds is (75%-90%):(0%-15%):(5%-10%). The silicone acrylate resin obtained by the preparation method can be cured at the room temperature and have excellent aging resistance and paint film performances.
Description
Technical field
The invention belongs to coating, tackiness agent and field of functional materials, be specifically related to a kind of silicon-acrylic coatings resin and preparation method thereof.
Technical background
Organosilane monomer and polymkeric substance thereof have low surface tension, lower glass transition temperatures, good penetration rate and water-fast, heatproof, performance such as weather-proof, for the application of organosilicon in polymer material science plays an important role.But the molecular chain of silicon-type polymkeric substance is submissiveer, and intermolecular reactive force is less, so physical strength is lower, and is relatively poor with the adhesivity of other object.
Acrylic resin is the resin of being made by esters of acrylic acid and methyl acrylic ester and other olefinic type monomers copolymerization, by selecting different resin structures, different prescription, production technique and solvent composition for use, can synthesize the acrylic resin of dissimilar, different performance and different application occasion.Acrylic polymer has good weathering resistance, film-forming properties and cohesiveness, is widely used at aspects such as coating, tackiness agents.But there are shortcomings such as water tolerance, water vapour permeability and polluting proofing property difference.
At present, more to the research of silicone-modified polyacrylate resin, main direction of studying is to improve the over-all properties of resin, as weathering resistance, and solvent resistance, resistance to soiling etc.
The method that organosilicon modified crylic acid resin is commonly used has physical mixed method, chemic modified method.(1) physical mixed method physical mixed method claims cold spelling again, is a kind of simple and method that product property is greatly improved.But adopt the polysiloxane one acrylatcs systems less stable of physical blending preparation, and do not have chemical b ` more again, easily produce and be separated and the surface transport of polysiloxane because both structures and polarity differ.(2) chemic modified method is by chemical reaction, forms chemical bond between polysiloxane that polarity differs greatly and polyacrylic ester, can obviously improve consistency between the two.The acrylatcs systems of introducing siloxanes has the unexistent premium properties of polysiloxane one polyacrylic ester simple physical blend.But conventional chemic modified method, when containing a small amount of organosilicon in the modified poly ester, filming has good performance.And the organosilicon massfraction is when big, and the consistency of acrylic resin modified system can variation, and over-all properties descends.
Summary of the invention
The present invention adopts chemic modified method, on acrylate backbone, introduce siloxanes and epoxy construction, improve consistency and crosslinked ability, use can with the linking agent of water in air reaction, silicon-acrylic coatings resin that provides a kind of ageing resistance and every paint film good comprehensive properties ambient temperature curable and preparation method thereof is provided.
Silicon-acrylic coatings resin of the present invention is mixed with solidifying agent by organosilicon acrylic resin and obtains, wherein said organosilicon acrylic resin, comprise the organosilicon acrylic resin and two kinds of the organosilicon acrylic resins that contains silicone resin that contain silicone oil, wherein said solidifying agent is quadrol, γ-An Bingjisanyiyangjiguiwan, γ-aminopropyl methyl dimethoxysilane, γ-An Bingjisanjiayangjiguiwan or diethylamine etc.;
The wherein said organosilicon acrylic resin that contains silicone oil is to obtain organosilicon acrylic resin by acrylic ester monomer, the acrylic ester monomer that contains epoxide group, the silane coupling agent that contains unsaturated link(age) and double bond containing silicone oil copolymerization, presses the mass ratio reaction by following component and generates:
Acrylic ester monomer: 60～90 parts,
The acrylic ester monomer that contains epoxide group: 5～15 parts,
The silane coupling agent that contains unsaturated link(age): 5～10 parts,
Vinyl silicone oil: 2～30 parts.
After the wherein said organosilicon acrylic resin that contains silicone resin obtains acrylic resin by acrylic ester monomer and the silane coupling agent copolymerization that contains the acrylic ester monomer of epoxide group and contain unsaturated link(age) earlier, add silicone resin again and mix and obtain organosilicon acrylic resin, wherein acrylic resin is pressed the mass ratio reaction by following component and is generated:
Acrylic ester monomer: 75～90 parts,
The acrylic ester monomer that contains epoxide group: 0～15 part,
The silane coupling agent that contains unsaturated link(age): 5～10 parts.
Wherein the silicone resin of Jia Ruing accounts for 10%～50% of acrylic resin quality.
The preparation method of silicon-acrylic coatings resin of the present invention is divided into the preparation of organosilicon acrylic resin and two steps of preparation of coating resin, and concrete grammar is as follows:
The preparation method of wherein said organosilicon acrylic resin:
The wherein said preparation that contains the organosilicon acrylic resin of silicone oil:
(1) dimethylbenzene, isopropyl alcohol mixed solvent are joined in the reactor; The mixing quality ratio of the mixed solvent of wherein said dimethylbenzene and Virahol is (2～8): (8～2);
(2) acrylic ester monomer, the acrylic ester monomer that contains epoxide group, silane coupling agent and the initiator that contains the silicone oil of two keys and contain unsaturated link(age) are mixed, by mass percentage, acrylic ester monomer: the acrylic ester monomer that contains epoxide group: the silane coupling agent that contains unsaturated link(age): double bond containing silicone oil is (60～90): (5～15): (5～10): (2～30), and wherein initiator is 0.1%～10% of aforesaid propylene esters of gallic acid monomer and the acrylic ester monomer mix monomer total amount that contains epoxide group;
(3) with in the disposable adding step of 20% mixing solutions liquid (1) reactor in the step (2), 100～110 ℃, insulation 1h;
(4) 80% mixing solutions in the step (2) is added drop-wise in step (1) reactor, drips time 2h, drip insulation 3h, lower the temperature, obtain containing the organosilicon acrylic resin of silicone oil.
The wherein said preparation that contains the organosilicon acrylic resin of silicone resin:
(1) dimethylbenzene, isopropyl alcohol mixed solvent are joined in the reactor; The mixing quality ratio of the mixed solvent of wherein said dimethylbenzene and Virahol is (2～8): (8～2);
(2) acrylic ester monomer and the silane coupling agent and the initiator that contain the acrylic ester monomer of epoxide group and contain unsaturated link(age) are mixed; By mass percentage, acrylic ester monomer: the acrylic ester monomer that contains epoxide group: the silane coupling agent that contains unsaturated link(age) is (75～90): (0～15): (5～10), and wherein initiator is 0.1%～10% of acrylic ester monomer and the acrylic ester monomer mix monomer total amount that contains epoxide group;
(3) with in the disposable adding step of 20% mixing solutions liquid (1) reactor in the step (2), 100～110 ℃, insulation 1h;
(4) 80% mixing solutions in the step (2) is added drop-wise in step (1) reactor, drips time 2h, drip insulation 3h;
(5) cooling when temperature drops to 80 ℃, adds silicone resin, continues insulation, and reaction obtains organosilicon acrylic resin; Wherein the silicone resin add-on is 10%～50% of the resin quality that obtains of step (4).
Wherein said acrylate monomer is divided into hard monomer or soft monomer, and wherein hard monomer is a methyl methacrylate, vinyl acetate, n-BMA or Propenoic acid, 2-methyl, isobutyl ester; Wherein soft monomer can be methyl acrylate, ethyl propenoate, butyl acrylate or Isooctyl acrylate monomer etc.;
The wherein said acrylic ester monomer that contains epoxide group is one or several in glycidyl methacrylate, the methyl propenoic acid glycidyl ether etc.;
The wherein said silane coupling agent that contains unsaturated link(age) is γ-methacryloxypropyl trimethoxy silane, γ-vinyltriethoxysilane or γ-vinyltrimethoxy silane etc.
Wherein said initiator is peroxide initiator, Diisopropyl azodicarboxylate azo-initiator or redox radical initiators such as (AIBN) such as benzoyl peroxide.
Two, the preparation of coating resin
The above-mentioned organosilicon acrylic resin that obtains is mixed with solidifying agent, stir, can use; Solidifying agent wherein: contain the epoxide group acrylate monomer and be (1.5～1): 1 (mol ratio), also can add catalyzer and promote to solidify, catalyst levels is 0%～10% of a silicone resin quality; Wherein said solidifying agent is quadrol, γ-An Bingjisanyiyangjiguiwan, γ-aminopropyl methyl dimethoxysilane, γ-An Bingjisanjiayangjiguiwan or diethylamine etc.; Described catalyzer can be organotin, organic cobalt, organic lead, organic iron, dibutyl tin dilaurate or N, N, N ', N '-tetramethyl-guanidinesalt etc.
Wherein contain in the preparation of organosilicon acrylic resin of silicone resin, step (2) can not add the acrylic monomer (being that the acrylic ester monomer that contains epoxide group that adds in the step (2) is) that contains epoxide group at 0 o'clock, then the organosilicon acrylic resin that step (5) can be obtained mixes with linking agent, stir, can use, wherein dosage of crosslinking agent is 0%～15% of an organosilicon acrylic resin total mass; Described linking agent can be tetraethoxy, positive silicic acid propyl ester, butyl (tetra) titanate etc.
Wherein said vinyl silicone oil has following constitutional features:
In the formula, R is alkyl, aryl, and R ' is alkyl, aryl, hydrogen, carbon functional group or unsaturated double-bond, polyether chain etc.; N, m=0,1,2,3 Contents of ethylene: 1.0%～10% (molar content); Molecular weight is 300～300000.
Wherein said silicone resin have one of following constitutional features:
Silicone resin one:
In the formula, R is methyl or ethyl, and R ' is methyl or phenyl, n=20～40, phenyl/methyl (perhaps ethyl)=(0～1)/(1～0).
Silicone resin two:
In the formula, R is methyl or ethyl, n=10～20, m=10～20, phenyl/methyl (perhaps ethyl)=(0～1)/(1～0).
The present invention has the following advantages and beneficial effect: contain unsaturated link(age) in the silane coupling agent of unsaturated link(age) and can be used as active centre with acrylic ester copolymer, make after the reaction and have certain siloxanes segment in the acrylic resin main chain, the consistency of acrylic resin and silicone resin and silicone oil is improved greatly, has improved the over-all properties of organosilicon acrylic resin; Can introduce active epoxy group on the acrylic resin main chain,, form the organosilicon acrylic resin of the ambient temperature curable of isocyanate-free with solidifying agent generation chemical crosslink reaction; And the linking agent that adds, can with airborne water generation condensation reaction, produce the silica structure, strengthen paint film property, make modified resin can give full play of organosilyl characteristic, thereby make ageing resistance and every paint film property excellence of silicon-acrylic coatings resin.
Description of drawings
Shown in Figure 1 is to contain silicon-acrylic coatings resin and the common acrylic resin that the organosilicon acrylic resin of 10% silicone oil prepares to protect light rate change curve in time,
Shown in Figure 2 is to contain silicon-acrylic coatings resin and the common acrylic resin that the organosilicon acrylic resin of 30% silicone resin prepares to protect light rate change curve in time,
Shown in Figure 3 is to contain silicon-acrylic coatings resin and the commercially available fluorocarbon resin that the organosilicon acrylic resin of 30% silicone resin prepares to protect light rate change curve in time,
Annotate: protect the ageing-resistant performance that the light rate characterizes the silicon-acrylic coatings resin.Adopt Luv-2 ultraviolet accelerated weathering test punch-out equipment to carry out ultraviolet ageing, WGG-20/60 mirror image microcomputer glossmeter is measured glossiness, and protecting the light rate is to measure the calculation result of glossiness (60 °) behind the ultraviolet ageing certain hour, and concrete calculation formula is as follows:
Protect light rate=(certain hour is measured glossiness/original gloss) * 100%.
Embodiment
Each embodiment of following the present invention will divide two portions to further specify, i.e. the preparation of the preparation of organosilicon acrylic resin and coating.
Embodiment 1
One, the preparation of organosilicon acrylic resin (organosilicon acrylic resin that contains 10% silicone resin)
In the 500mL four-hole boiling flask, add 80g dimethylbenzene, the 20g Virahol; Take by weighing the 60g methyl methacrylate, the 20g butyl acrylate, the 10g glycidyl methacrylate, 10g γ-methacryloxypropyl trimethoxy silane is made into mix monomer, adds the 0.1g benzoyl peroxide, and stirring and dissolving is made into mixing solutions; In the disposable adding reactor of the above-mentioned mixing solutions of 20g, 100～110 ℃, under reflux state, be incubated 1h; Then that 80g is above-mentioned mixing solutions is added drop-wise in the reactor, drips time 2h, drips under reflux state and is incubated 3h; Cooling then when temperature drops to 80 ℃, adds 20g silicone resin one, continues insulation, obtains containing the organosilicon acrylic resin of 10% silicone resin.
Two, the preparation of coating resin
Add 15.56g solidifying agent γ-aminopropyl methyl dimethoxysilane in the organosilicon acrylic resin that obtains in the step 1, mixing and stirring obtains the silicon-acrylic coatings resin.And be made into paint film, and test its paint film property, every test performance the results are shown in Table 1.
Embodiment 2
One, the preparation of organosilicon acrylic resin (organosilicon acrylic resin that contains 20% silicone resin)
In the 500mL four-hole boiling flask, add 60g dimethylbenzene, the 40g Virahol; Take by weighing the 60g n-BMA, the 20g ethyl propenoate, the 15g glycidyl methacrylate, 5g γ-methacryloxypropyl trimethoxy silane is made into mix monomer, adds the 0.5g benzoyl peroxide, and stirring and dissolving is made into mixing solutions; In the disposable adding reactor of the above-mentioned mixing solutions of 20g, 100～110 ℃, under reflux state, be incubated 1h; Then that 80g is above-mentioned mixing solutions is added drop-wise in the reactor, drips time 2h, drips under reflux state and is incubated 3h; Cooling then when temperature drops to 80 ℃, adds 40g silicone resin one, continues insulation, obtains containing the organosilicon acrylic resin of 20% silicone resin.
One, the preparation of coating resin
Add 23.3g solidifying agent γ-aminopropyl methyl dimethoxysilane in the organosilicon acrylic resin that obtains in the step 1, mixing and stirring obtains the silicon-acrylic coatings resin.And be made into paint film, and test its paint film property, every test performance the results are shown in Table 1.
Embodiment 3
One, the preparation of organosilicon acrylic resin (organosilicon acrylic resin that contains 30% silicone resin)
In the 500mL four-hole boiling flask, add 50g dimethylbenzene, the 50g Virahol; Take by weighing the 50g methyl methacrylate, the 30g butyl acrylate, the 10g glycidyl methacrylate, 10g γ-methacryloxypropyl trimethoxy silane is made into mix monomer, adds the 0.2g benzoyl peroxide, and stirring and dissolving is made into mixing solutions; In the disposable adding reactor of the above-mentioned mixing solutions of 20g, 100～110 ℃, under reflux state, be incubated 1h; Then that 80g is above-mentioned mixing solutions is added drop-wise in the reactor, drips time 2h, drips under reflux state and is incubated 3h; Cooling then when temperature drops to 80 ℃, adds 60g silicone resin one, continues insulation, obtains containing the organosilicon acrylic resin of 30% silicone resin.
Two, the preparation of coating resin
Add 23.3g solidifying agent γ-An Bingjisanyiyangjiguiwan in the organosilicon acrylic resin that obtains in step 1, mixing and stirring obtains the silicon-acrylic coatings resin.And be made into paint film, and test its paint film property, every test performance the results are shown in Table 1.
Embodiment 4
One, the preparation of organosilicon acrylic resin (organosilicon acrylic resin that contains 30% silicone resin)
In the 500mL four-hole boiling flask, add 50g dimethylbenzene, the 50g Virahol; Take by weighing the 50g methyl methacrylate, the 30g butyl acrylate, the 10g glycidyl methacrylate, 10g γ-methacryloxypropyl trimethoxy silane is made into mix monomer, adds the 0.2g benzoyl peroxide, and stirring and dissolving is made into mixing solutions; In the disposable adding reactor of the above-mentioned mixing solutions of 20g, 100～110 ℃, under reflux state, be incubated 1h; Then that 80g is above-mentioned mixing solutions is added drop-wise in the reactor, drips time 2h, drips under reflux state and is incubated 3h; Cooling then when temperature drops to 80 ℃, adds 60g silicone resin one, continues insulation, obtains containing the organosilicon acrylic resin of 30% silicone resin.
Two, the preparation of coating resin (adding catalyst solidifies)
Add 23.3g solidifying agent γ-An Bingjisanyiyangjiguiwan in the organosilicon acrylic resin that in step 1, obtains, 0.4g catalyzer organotin, mixing and stirring obtains the silicon-acrylic coatings resin.And be made into paint film, test its paint film property, and ageing-resistant performance.Every test performance the results are shown in Table 1, Fig. 2 and Fig. 3.
Embodiment 5
One, the preparation of organosilicon acrylic resin (organosilicon acrylic resin that contains 50% silicone resin does not add the acrylic ester monomer that contains epoxide group, and the adding linking agent is crosslinked)
In the 500mL four-hole boiling flask, add 40g dimethylbenzene, the 60g Virahol; Take by weighing the 60g methyl methacrylate, the 30g butyl acrylate, 10g γ-methacryloxypropyl trimethoxy silane is made into mix monomer, adds the 0.5g benzoyl peroxide, and stirring and dissolving is made into mixing solutions; In the disposable adding reactor of the above-mentioned mixing solutions of 20g, 100～110 ℃, under reflux state, be incubated 1h; Then that 80g is above-mentioned mixing solutions is added drop-wise in the reactor, drips time 2h, drips under reflux state and is incubated 3h; Cooling then when temperature drops to 80 ℃, adds 100g silicone resin two, continues insulation, obtains containing the organosilicon acrylic resin of 50% silicone resin.
Two, the preparation of coating resin
Add 15g linking agent tetraethoxy in the organosilicon acrylic resin that obtains in step 1, mixing and stirring obtains the silicon-acrylic coatings resin.And be made into paint film, and test its paint film property, every test performance the results are shown in Table 1.
Embodiment 6
One, the preparation of organosilicon acrylic resin (organosilicon acrylic resin that contains 2% silicone oil)
In the 500mL four-hole boiling flask, add 60g dimethylbenzene, the 40g Virahol; Take by weighing the 60g methyl methacrylate, 18g butyl acrylate, 10g methyl propenoic acid glycidyl ether, 10g γ-methacryloxypropyl trimethoxy silane, 2g silicone oil is made into mix monomer, adds the 0.1g benzoyl peroxide, stirring and dissolving is made into mixing solutions; In the disposable adding reactor of the above-mentioned mixing solutions of 20g, 100～110 ℃, under reflux state, be incubated 1h; Then that 80g is above-mentioned mixing solutions is added drop-wise in the reactor, drips time 2h, drips under reflux state and is incubated 3h; Lower the temperature then, obtain containing the organosilicon acrylic resin of 2% silicone oil.
Two, the preparation of coating resin
Add 23.3g solidifying agent γ-An Bingjisanjiayangjiguiwan in the organosilicon acrylic resin that obtains in step 1, mixing and stirring obtains the silicon-acrylic coatings resin.And be made into paint film, and test its paint film property, every test performance the results are shown in Table 1.
Embodiment 7
One, the preparation of organosilicon acrylic resin (organosilicon acrylic resin that contains 5% silicone oil)
In the 500mL four-hole boiling flask, add 50g dimethylbenzene, the 50g Virahol; Take by weighing the 50g methyl methacrylate, 30g butyl acrylate, 10g glycidyl methacrylate, 10g γ-methacryloxypropyl trimethoxy silane, 5g silicone oil is made into mix monomer, adds the 0.2g benzoyl peroxide, stirring and dissolving is made into mixing solutions; In the disposable adding reactor of the above-mentioned mixing solutions of 20g, 100～110 ℃, under reflux state, be incubated 1h; Then that 80g is above-mentioned mixing solutions is added drop-wise in the reactor, drips time 2h, drips under reflux state and is incubated 3h; Lower the temperature then, obtain containing the organosilicon acrylic resin of 5% silicone oil.
Two, the preparation of coating resin
Add 23.3g solidifying agent γ-An Bingjisanyiyangjiguiwan in the organosilicon acrylic resin that step 1 obtains, mixing and stirring obtains the silicon-acrylic coatings resin.And be made into paint film, and test its paint film property, every test performance the results are shown in Table 1.
Embodiment 8
One, the preparation of organosilicon acrylic resin (organosilicon acrylic resin that contains 10% silicone oil)
In the 500mL four-hole boiling flask, add 40g dimethylbenzene, the 60g Virahol; Take by weighing the 50g Jia Jibingxisuanyizhi, 20g butyl acrylate, 10g methyl propenoic acid glycidyl ether, 10g γ-methacryloxypropyl trimethoxy silane, 10g silicone oil is made into mix monomer, adds the 0.5g benzoyl peroxide, stirring and dissolving is made into mixing solutions; In the disposable adding reactor of the above-mentioned mixing solutions of 20g, 100～110 ℃, under reflux state, be incubated 1h; Then that 80g is above-mentioned mixing solutions is added drop-wise in the reactor, drips time 2h, drips under reflux state and is incubated 3h; Lower the temperature then, obtain containing the organosilicon acrylic resin of 10% silicone oil.
Two, the preparation of coating resin
Add 23.3g solidifying agent γ-An Bingjisanyiyangjiguiwan in the organosilicon acrylic resin that step 1 obtains, mixing and stirring obtains the silicon-acrylic coatings resin.And be made into paint film, test its paint film property, and ageing-resistant performance.Every test performance the results are shown in Table 1.Annotate: the every common performance test methods of coating resin carries out with reference to following national standard method, sticking power wherein: measure according to GB1720-179288, pencil hardness: measure according to GB6739-86, impact strength: measure ageing-resistant performance: measure according to GB1732-791887 according to GB/T1865-88.
Table 1
Above-mentioned test as seen, the paint film over-all properties of organosilicon acrylic resin of the present invention is more excellent, and ageing-resistant performance is better than common acrylic resin, and near in addition be better than commercially available fluorocarbon resin.
The above-mentioned description to embodiment is can understand and apply the invention for ease of those skilled in the art.Those skilled in the art obviously can easily make various modifications to these embodiment, and needn't pass through performing creative labour being applied in the General Principle of this explanation among other embodiment.Therefore, the invention is not restricted to the embodiment here, those skilled in the art should be within protection scope of the present invention for the modification that the present invention makes according to announcement of the present invention.
Claims (7)
1. silicon-acrylic coatings resin, mix with solidifying agent by organosilicon acrylic resin and to obtain, wherein said organosilicon acrylic resin, for containing the organosilicon acrylic resin of silicone oil, wherein said solidifying agent is quadrol, γ-An Bingjisanyiyangjiguiwan, γ-aminopropyl methyl dimethoxysilane, γ-An Bingjisanjiayangjiguiwan or diethylamine; The wherein said organosilicon acrylic resin that contains silicone oil is to obtain organosilicon acrylic resin by acrylic ester monomer, the acrylic ester monomer that contains epoxide group, the silane coupling agent that contains unsaturated link(age) and double bond containing silicone oil copolymerization, presses the mass ratio reaction by following component and generates:
Acrylic ester monomer: 60～90 parts,
The acrylic ester monomer that contains epoxide group: 5～15 parts,
The silane coupling agent that contains unsaturated link(age): 5～10 parts,
Vinyl silicone oil: 2～30 parts.
2. silicon-acrylic coatings resin according to claim 1, it is characterized in that wherein said organosilicon acrylic resin is after the organosilicon acrylic resin that contains silicone resin earlier obtains acrylic resin by acrylic ester monomer and the silane coupling agent copolymerization that contains the acrylic ester monomer of epoxide group and contain unsaturated link(age), add silicone resin again and mix and obtain organosilicon acrylic resin, wherein acrylic resin is pressed the mass ratio reaction by following component and is generated:
Acrylic ester monomer: 75～90 parts,
The acrylic ester monomer that contains epoxide group: 0～15 part,
The silane coupling agent that contains unsaturated link(age): 5～10 parts.
Wherein the silicone resin of Jia Ruing accounts for 10%～50% of acrylic resin quality.
3. the preparation method of the described silicon-acrylic coatings resin of claim 1 is divided into the preparation of organosilicon acrylic resin and two steps of preparation of coating resin, and concrete grammar is as follows:
The preparation method of organosilicon acrylic resin:
The wherein said preparation that contains the organosilicon acrylic resin of silicone oil:
(1) dimethylbenzene, isopropyl alcohol mixed solvent are joined in the reactor; The mixing quality ratio of the mixed solvent of wherein said dimethylbenzene and Virahol is (2～8): (8～2);
(2) acrylic ester monomer, the acrylic ester monomer that contains epoxide group, silane coupling agent and the initiator that contains the silicone oil of two keys and contain unsaturated link(age) are mixed, by mass percentage, acrylic ester monomer: the acrylic ester monomer that contains epoxide group: the silane coupling agent that contains unsaturated link(age): double bond containing silicone oil is (60～90): (5～15): (5～10): (2～30), and wherein initiator is 0.1%～10% of aforesaid propylene esters of gallic acid monomer and the acrylic ester monomer mix monomer total mass that contains epoxide group;
(3) with in the disposable adding step of 20% mixing solutions liquid (1) reactor in the step (2), 100～110 ℃, insulation 1h;
(4) 80% mixing solutions in the step (2) is added drop-wise in step (1) reactor, drips time 2h, drip insulation 3h, lower the temperature, obtain containing the organosilicon acrylic resin of silicone oil;
Two, the preparation of coating resin
The above-mentioned organosilicon acrylic resin that obtains is mixed with solidifying agent, stir, can use; Solidifying agent wherein: the ratio that contains the epoxide group acrylate monomer is (1.5～1) with molar ratio computing: 1, and also can add catalyzer and promote to solidify, catalyst levels is 0%～10% of a silicone resin quality; Wherein said solidifying agent is quadrol, γ-An Bingjisanyiyangjiguiwan, γ-aminopropyl methyl dimethoxysilane, γ-An Bingjisanjiayangjiguiwan or diethylamine; Described catalyzer can be organotin, organic cobalt, organic lead, organic iron, dibutyl tin dilaurate or N, N, N ', a N ' tetramethyl-guanidinesalt.
4. the preparation method of the described silicon-acrylic coatings resin of claim 3 is characterized in that the preparation process of the wherein said organosilicon acrylic resin that contains silicone resin is as follows:
(1) dimethylbenzene, isopropyl alcohol mixed solvent are joined in the reactor; The mixing quality ratio of the mixed solvent of wherein said dimethylbenzene and Virahol is (2～8): (8～2);
(2) acrylic ester monomer and the silane coupling agent and the initiator that contain the acrylic ester monomer of epoxide group and contain unsaturated link(age) are mixed; By mass percentage, acrylic ester monomer: the acrylic ester monomer that contains epoxide group: the silane coupling agent that contains unsaturated link(age) is (75～90): (0～15): (5～10), and wherein initiator is 0.1%～10% of acrylic ester monomer and the acrylic ester monomer mix monomer total amount that contains epoxide group;
(3) with in the disposable adding step of 20% mixing solutions liquid (1) reactor in the step (2), 100～110 ℃, insulation 1h;
(4) 80% mixing solutions in the step (2) is added drop-wise in step (1) reactor, drips time 2h, drip insulation 3h;
(5) cooling when temperature drops to 80 ℃, adds silicone resin, continues insulation, and reaction obtains organosilicon acrylic resin; Wherein the silicone resin add-on is 10%～50% of the resin quality that obtains of step (4).
5. the preparation method of the described silicon-acrylic coatings resin of claim 4, it is characterized in that wherein containing in the preparation of organosilicon acrylic resin of silicone resin, step (2) can not add the acrylic monomer that contains epoxide group, be that the acrylic ester monomer that contains epoxide group that adds in the step (2) is 0 o'clock, then the organosilicon acrylic resin that step (5) can be obtained mixes with linking agent, stir, can use, wherein dosage of crosslinking agent is 0%～15% of an organosilicon acrylic resin total mass; Described linking agent can be tetraethoxy, positive silicic acid propyl ester or butyl (tetra) titanate.
6. claim 1 or 2 silicon-acrylic coatings resin is characterized in that wherein said acrylate monomer is divided into hard monomer or soft monomer, and wherein hard monomer is methyl methacrylate, vinyl acetate, n-BMA or Propenoic acid, 2-methyl, isobutyl ester; Wherein soft monomer can be methyl acrylate, ethyl propenoate, butyl acrylate or Isooctyl acrylate monomer; The wherein said acrylic ester monomer that contains epoxide group is one or several in glycidyl methacrylate, the methyl propenoic acid glycidyl ether etc.; The wherein said silane coupling agent that contains unsaturated link(age) is γ-methacryloxypropyl trimethoxy silane, γ-vinyltriethoxysilane or γ-vinyltrimethoxy silane; Wherein said initiator is peroxide initiator, Diisopropyl azodicarboxylate azo-initiator or redox radical initiators such as benzoyl peroxide; Wherein said vinyl silicone oil has following constitutional features:
In the formula, R is alkyl, aryl, and R ' is alkyl, aryl, hydrogen, carbon functional group or unsaturated double-bond, polyether chain; N, m=0,1,2,3 Vinyl molar content meter: 1.0%～10%; Molecular weight is 300～300000;
Wherein said silicone resin have one of following constitutional features:
Silicone resin one:
In the formula, R is methyl or ethyl, and R ' is methyl or phenyl, n=20～40, phenyl/methyl (perhaps ethyl)=(0～1)/(1～0);
Or silicone resin two:
In the formula, R is methyl or ethyl, n=10～20, m=10～20, phenyl/methyl (perhaps ethyl)=(0～1)/(1～0).
7. the preparation method of claim 3 or 4 silicon-acrylic coatings resin, it is characterized in that wherein said acrylate monomer is divided into hard monomer or soft monomer, wherein hard monomer is methyl methacrylate, vinyl acetate, n-BMA or Propenoic acid, 2-methyl, isobutyl ester; Wherein soft monomer can be methyl acrylate, ethyl propenoate, butyl acrylate or Isooctyl acrylate monomer; The wherein said acrylic ester monomer that contains epoxide group is one or several in glycidyl methacrylate, the methyl propenoic acid glycidyl ether etc.; The wherein said silane coupling agent that contains unsaturated link(age) is γ-methacryloxypropyl trimethoxy silane, γ-vinyltriethoxysilane or γ-vinyltrimethoxy silane; Wherein said initiator is azo-initiator or redox radical initiators such as peroxide initiator, Diisopropyl azodicarboxylate such as benzoyl peroxide; Wherein said vinyl silicone oil has following constitutional features:
In the formula, R is alkyl, aryl, and R ' is alkyl, aryl, hydrogen, carbon functional group or unsaturated double-bond, polyether chain etc.; N, m=0,1,2,3 Contents of ethylene: 1.0%～10% (molar content); Molecular weight is 300～300000;
Wherein said silicone resin have one of following constitutional features:
Silicone resin one:
In the formula, R is methyl or ethyl, and R ' is methyl or phenyl, n=20～40, phenyl/methyl (perhaps ethyl)=(0～1)/(1～0);
Or silicone resin two:
In the formula, R is methyl or ethyl, n=10～20, m=10～20, phenyl/methyl (perhaps ethyl)=(0～1)/(1～0).
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