CN100509890C - Organosilicon epoxide acrylate water dispersion, preparation method and application thereof - Google Patents
Organosilicon epoxide acrylate water dispersion, preparation method and application thereof Download PDFInfo
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- CN100509890C CN100509890C CNB2006100375008A CN200610037500A CN100509890C CN 100509890 C CN100509890 C CN 100509890C CN B2006100375008 A CNB2006100375008 A CN B2006100375008A CN 200610037500 A CN200610037500 A CN 200610037500A CN 100509890 C CN100509890 C CN 100509890C
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Abstract
The invention discloses a organosilicon acroleic acid epoxide fat water dispersion, which is characterized by the following: the raw materials of preparing and forming are epoxide resin, fatty acid, unsaturated acid anhydride, acroleic acid monomer, silane couple connecting agent, neutralizing agent, accelerant, trigger, reducer, deionized water and so on; the product can be used as indoor temperature dry type paint pitch and as roasting type paint pitch, the paint of preparing can be used mainly to melt anti-rust.
Description
Technical field
The present invention relates to the Water-borne modification of epoxy resins technology, particularly a kind of organosilicon epoxide acrylate water dispersion and preparation method thereof.
Background technology
Resins, epoxy has non-corrosibility, chemical-resistant and solvent resistance, especially alkali resistance good and with characteristics such as metal sticking power height, be widely used at aspects such as military project, civilian, industrial maintenances.But traditional Resins, epoxy only is dissolved in aromatic hydrocarbons, ketone and alcohol organic solvent, and not only price is more expensive but also have a volatility, and human body and environment are worked the mischief and pollute, and has also wasted resource.Therefore, Water-borne modification of epoxy resins research becomes one of important research direction.The method of Resins, epoxy Water-borne modification is mainly and comprises: (1) is emulsion process directly: methods such as employing mechanical process grind Resins, epoxy, add emulsifier solution then, by mechanical stirring particle are scattered in the water again.The product stability of this method preparation is relatively poor.(2) conversion method: in the mixture of response type water-base epoxy emulsifying agent and Resins, epoxy, add water, polymkeric substance bag water state is transformed into the state of water packet aggregation thing; What existing market was mainly sold is the product of this method preparation, as Anquamine 777 waterborne curing agents of U.S. AirProduct and Chemicals company release and the epoxy emulsion EPI-REZResin 3520-W-55 of Rpp company.The product that this method is produced is a two-component coating, and Resins, epoxy and solidifying agent there are differences on solubility parameter during application, can cause paint film property bad, has the construction restricted problem of working life simultaneously.(3) self-emulsification: surfactant is incorporated in the Resins, epoxy molecule, makes its possess hydrophilic property, thereby can in water, disperse.The typical products of this method preparation is the epoxy acrylic hybrid dispersions, and it had both had the advantage of Resins, epoxy, had the advantage of acrylic resin again; The disclosed a kind of water-base epoxy of Chinese invention patent CN1164706C/acrylic-amino resin emulsion and water-thinned baking paint thereof for example; HIT also releases a kind of water-base epoxy/acrylic coating, be with unsaturated acid and Resins, epoxy one end addition, obtain the epoxy/acrylic acid resin with the copolymerization of esters of acrylic acid mix monomer again, through neutralization, add emulsifying water and obtain the epoxy/acrylic acid emulsion, be used to prepare water-thinned baking paint.This emulsion shortcoming is to contain more pure ethers solubility promoter, and VOC is higher, and latex film generally needs the baking that heats up when still having the aqueous industrial coating of deficiency and product preparation to solidify aspect water tolerance and erosion resistance, be difficult to realize room temperature crosslinking curing.At present, the existing higher coat metal substrates use rosin productss of over-all properties that are used for such as U.S. cyanogen spy (Cytec Industries), Japanese DIC company are sold in China, but such rosin products price is comparatively expensive, applies being subjected to certain restriction.
Summary of the invention
The objective of the invention is to overcome the shortcoming that exists in the prior art, a kind of preparation method of organosilicon epoxide acrylate water dispersion is provided.
Another object of the present invention is to provide a kind of organosilicon epoxide acrylate water dispersion that is obtained by method for preparing; But this water dispersion room temperature crosslinking curing also can further solidify by baking and improve performance.
A further object of the present invention is to provide the application of above-mentioned organosilicon epoxide acrylate water dispersion.
The synthesizing formula of organosilicon epoxide acrylate water dispersion provided by the invention is as follows:
Parts by weight of raw materials
Resins, epoxy 30～50
Lipid acid 15～20
Unsaturated acid anhydride 5～10
Acrylic monomer 30～40
Silane coupling agent 3～8
Neutralizing agent 2～6
Catalyzer 0.02～0.06
Initiator 0.3～0.8
Reductive agent 0.2～0.5
Deionized water 120～230
Described Resins, epoxy is bisphenol A type epoxy resin, can be that the trade mark commonly used is one or more among E44, E20 and the E12, and the optimum amount scope is 35～45 weight parts.
Described lipid acid can be dehydrated castor oleic acid, eleostearic acid, linolenic acid, chooses wherein one or more, and the optimum amount scope is 16～18 weight parts.
Described unsaturated acid anhydride can be MALEIC ANHYDRIDE, FUMARIC ACID TECH GRADE, tetrahydrophthalic anhydride, chooses wherein one or more, and the optimum amount scope is 6～9 weight parts.
Described acrylic monomer can be one or more the mixture in vinylformic acid, methacrylic acid, butyl acrylate, methyl methacrylate, butyl methacrylate, the Isooctyl acrylate monomer, and its optimum amount scope is 25～35 weight parts.
Described silane coupling agent is that functional group is the siloxanes of vinyl, specifically can be in vinyltrimethoxy silane, vinyltriethoxysilane, vinyl silane triisopropoxide, vinyl three (2-methoxy ethoxy) silane, the γ-methacryloxypropyl trimethoxy silane one or more, the optimum amount scope be 4～6 weight parts.
Described neutralizing agent is triethylamine, N, one or more in N-dihydroxymethyl thanomin, 2-amino-2-methyl-1-propyl alcohol, and the optimum amount scope is 3～5 weight parts.
Described catalyzer is a kind of of lithium hydroxide, plumbous oxide, and optimum amount is 0.03～0.05 weight part.
Described initiator is one or both in benzoyl peroxide, Diisopropyl azodicarboxylate, the tertbutyl peroxide, and the optimum amount scope is 0.4～0.6 weight part.
Described reductive agent be in sodium metabisulphite, the sodium formaldehyde sulphoxylate one or both, the optimum amount scope is 0.3～0.5 weight part.
Described deionized water optimum amount scope is 150～200 weight parts, requires its specific conductivity≤20 μ s/cm.
Preparation method's concrete steps of above-mentioned organosilicon epoxide acrylate water dispersion are as follows:
(1) in reactor, add the lipid acid of formula ratio, when stirring and being warming up to 110～130 ℃, stop to stir, add the Resins, epoxy and the catalyzer of formula ratio, start stirring, continue to be warming up to 200～240 ℃; Esterification is carried out in insulation, reaches 6～10mgKOH/g until acid number, and viscosity (25 ℃ of form pipes) when reaching 8～10s, finish by esterification;
When (2) reducing temperature of reaction to 160～180 ℃, stop to stir, add the unsaturated acid anhydride of formula ratio, start stirring, be warming up to 230～250 ℃ with the speed of 2～4 ℃/min, insulation reaction is 0.5～1 hour then;
(3) be cooled to 100～120 ℃, begin to drip acrylic monomer, silane coupling agent and initiator that the premix of formula ratio gets togather, 2～3 hours dropping time, continued insulation reaction then 3～5 hours, and, added the reductive agent of formula ratio when system viscosity (form pipe) when reaching 10～12s, continue reaction 0.5～1 hour, when monomer conversion 〉=95%, temperature is reduced to 80～80 ℃, graft polymerization reaction is finished;
(4) in another reactor, add the neutralizing agent and the deionized water of formula ratio, stir and be warming up to 50～60 ℃, slowly join in the resin of above-mentioned preparation, stirred 0.5～1 hour, and promptly got solid content and be 35～50% drying at room temperature type organosilicon epoxide acrylate water dispersion.
The organosilicon epoxide acrylate water dispersion that the present invention makes both can be used as drying at room temperature type coating resin, also can be used as the baking-type coating resin, and coating prepared therefrom is mainly used in metal rust preventing.
Action principle of the present invention is: the synthetic technology route of this organosilicon epoxide acrylate water dispersion is as follows---Resins, epoxy and lipid acid generation esterification are prepared epoxy ester; The two keys of lipid acid that add then on unsaturated acid anhydride and the above-mentioned epoxy ester carry out addition reaction, obtain the epoxy ester that side chain contains the anhydride functional group on the α position of the unsaturated double-bond of unsaturated acid anhydride addition fatty acid chain in epoxy ester; Again itself and acrylic acid or the like mix monomer, silane coupling agent are carried out free radicals copolymerization reaction; Unsaturated double-bond in acrylic acid or the like mix monomer and the silane coupling agent is under the effect of initiator, catalyzer, carry out 1 with the conjugated double bond of lipid acid in the epoxy ester that contains acid anhydrides, 4 or 1,2 addition copolymerizations, and then add reductive agent and further improve the copolyreaction transformation efficiency, obtain the organosilicon acrylic acid epoxy ester multipolymer.Multipolymer is neutralized and add deionized water with neutralizing agent and carry out self-emulsifying and obtain drying at room temperature type organosilicon epoxide acrylate water dispersion.
The present invention compared with prior art has following advantage and effect: vinyl silicane coupling agent is grafted on the side chain of acrylic acid epoxy ester copolymer in the building-up process of (1) organosilicon epoxide acrylate water dispersion, the acrylic acid epoxy ester copolymer sheet surface tension that contains siloxanes group is lower, minimum for reaching the system surface energy, the low surface energy component will migrate to high surface energy component outside gradually, thereby form the siloxanes segment at water dispersion glued membrane surface enrichment, the glued membrane of acquisition has lower surface tension; (2) in the polymkeric substance because of hydrolysis produces activity-Si (OH) group, its can and the inner or surperficial active group condensation of polymkeric substance form cubic network (-Si-O-Si-) crosslinking structure, produce more cross-linking set, help forming the self-vulcanizing glued membrane; In addition, in the polymkeric substance-Si-O-Si-key has hydrophobic performance, thus make the polymer molecule interchain be difficult to be permeated and produce swelling by water molecules; Strengthen the density on the top layer of filming, hinder water molecules effectively and enter polymeric film; (3) organosilicon epoxide acrylate water dispersion for preparing has Resins, epoxy physical strength height, the good characteristics of antiseptic property, have good, the ornamental high characteristics of acrylic resin weather resistance again, introduce organosilicon and help to realize the self-crosslinking function, and absorbed organosilyl good adhesion, resistance toheat and chemical resistance etc.; (4) in the process of synthesizing organo-silicon epoxide acrylate water dispersion, graft copolymerization is to finish in solvent phase, polymerization need not to add emulsifying agent, can in glued membrane, not form surfactant and assemble the pore form, all have significant improvement at corrosion-resistant, antiblocking, levelling, aspect of performance such as water-fast.Polymerization reaction late stage has adopted the redox initiator that appends, and has further improved monomeric transformation efficiency, has reduced the content of free monomer, and (VOC) is lower for organic volatile content.
Embodiment
The invention will be further described below in conjunction with embodiment, but the present invention claimed scope be not limited to the scope of embodiment statement.
What following table 1 was listed is the formulation Example and the Comparative Examples of organosilicon epoxide acrylate water dispersion, and table 2 is performance index of the organosilicon epoxide acrylate water dispersion of correspondence table 1.
The preparation method of organosilicon epoxide acrylate water dispersion is in the table 1:
(1) in reactor, add the lipid acid of formula ratio, when stirring and being warming up to 110～130 ℃, stop to stir, add the Resins, epoxy and the catalyzer of formula ratio, start stirring, continue to be warming up to 200～240 ℃; Esterification is carried out in insulation, reaches 6～10mgKOH/g until acid number, and viscosity (25 ℃ of form pipes) when reaching 8～10s, finish by esterification;
When (2) reducing temperature of reaction to 160～180 ℃, stop to stir, add the unsaturated acid anhydride of formula ratio, start stirring, be warming up to 230～250 ℃ with the speed of 2 ℃/min, insulation reaction is 0.5～1 hour then;
(3) be cooled to 100～120 ℃, begin to drip acrylic monomer, silane coupling agent and initiator that the premix of formula ratio gets togather, 2～3 hours dropping time, continued insulation reaction then 3～5 hours, and, added the reductive agent of formula ratio when system viscosity (form pipe) when reaching 10～12s, continue reaction 0.5～1 hour, when monomer conversion 〉=95%, temperature is reduced to 80～80 ℃, graft polymerization reaction is finished;
(4) in another reactor, add the neutralizing agent and the deionized water of formula ratio, stir and be warming up to 50～60 ℃, slowly join in the resin of above-mentioned preparation, stirred 0.5～1 hour, and promptly got solid content and be 35～50% organosilicon epoxide acrylate water dispersion.
Table 1 organosilicon epoxide acrylate water dispersion synthesizing formula
Table 2 organosilicon epoxide acrylate water dispersion and glue film performance index thereof
The foregoing description is a preferred implementation of the present invention; but embodiments of the present invention are not restricted to the described embodiments; other any do not deviate from change, the modification done under spirit of the present invention and the principle, substitutes, combination, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (10)
1, a kind of organosilicon epoxide acrylate water dispersion is characterized in that by following prescription synthetic:
Parts by weight of raw materials
Resins, epoxy 30～50
Lipid acid 15～20
Unsaturated acid anhydride 5～10
Acrylic monomer 30～40
Silane coupling agent 3～8
Neutralizing agent 2～6
Catalyzer 0.02～0.06
Initiator 0.3～0.8
Reductive agent 0.2～0.5
Deionized water 120～230
Described neutralizing agent is triethylamine, N, one or more in N-dihydroxymethyl thanomin, 2-amino-2-methyl-1-propyl alcohol; Described catalyzer is lithium hydroxide or plumbous oxide; Described initiator is one or both in benzoyl peroxide, Diisopropyl azodicarboxylate, the tertbutyl peroxide; Described reductive agent be in sodium metabisulphite, the sodium formaldehyde sulphoxylate one or both.
2, organosilicon epoxide acrylate water dispersion according to claim 1 is characterized in that: described Resins, epoxy is bisphenol A type epoxy resin, and its amount ranges is 35～45 weight parts.
3, organosilicon epoxide acrylate water dispersion according to claim 1 is characterized in that: described lipid acid is one or both or three kinds in dehydrated castor oleic acid, eleostearic acid, the linolenic acid, and its amount ranges is 16～18 weight parts.
4, organosilicon epoxide acrylate water dispersion according to claim 1 is characterized in that: described unsaturated acid anhydride is one or both or three kinds in MALEIC ANHYDRIDE, FUMARIC ACID TECH GRADE, the tetrahydrophthalic anhydride, and its amount ranges is 6～9 weight parts.
5, organosilicon epoxide acrylate water dispersion according to claim 1, it is characterized in that: described acrylic monomer is one or more the mixture in vinylformic acid, methacrylic acid, butyl acrylate, methyl methacrylate, butyl methacrylate, the Isooctyl acrylate monomer, and its amount ranges is 30～35 weight parts.
6, organosilicon epoxide acrylate water dispersion according to claim 1, it is characterized in that: described silane coupling agent is one or more in vinyltrimethoxy silane, vinyltriethoxysilane, vinyl silane triisopropoxide, vinyl tris silane, the γ-methacryloxypropyl trimethoxy silane, and its amount ranges is 4～6 weight parts.
7, organosilicon epoxide acrylate water dispersion according to claim 1 is characterized in that: described neutralizing agent amount ranges is 3～5 weight parts.
8, organosilicon epoxide acrylate water dispersion according to claim 1 is characterized in that: described catalyst levels is 0.03～0.05 weight part; Described initiator amount scope is 0.4～0.6 weight part; Described reductive agent amount ranges is 0.3～0.5 weight part; The amount ranges of described deionized water is 150～200 weight parts, its specific conductivity≤20 μ s/cm.
9,, it is characterized in that preparation process is as follows according to the preparation method of each described organosilicon epoxide acrylate water dispersion of claim 1～8:
(1) in reactor, add the lipid acid of formula ratio, when stirring and being warming up to 110～130 ℃, stop to stir, add the Resins, epoxy and the catalyzer of formula ratio, start stirring, continue to be warming up to 200～240 ℃; Esterification is carried out in insulation, reaches 6～10mgKOH/g until acid number, and when viscosity reached 8～10s, esterification was finished;
When (2) reducing temperature of reaction to 160～180 ℃, stop to stir, add the unsaturated acid anhydride of formula ratio, start stirring, be warming up to 230～250 ℃ with the speed of 2～4 ℃/min, insulation reaction is 0.5～1 hour then;
(3) be cooled to 100～120 ℃, begin to drip acrylic monomer, silane coupling agent and initiator that the premix of formula ratio gets togather, 2～3 hours dropping time, continue insulation reaction then 3～5 hours, and when the system viscosity reaches 10～12s, added the reductive agent of formula ratio, continue reaction 0.5～1 hour, when monomer conversion 〉=95%, temperature is reduced to 80～80 ℃, graft polymerization reaction is finished;
(4) in another reactor, add the neutralizing agent and the deionized water of formula ratio, stir and be warming up to 50～60 ℃, slowly join in the resin of above-mentioned preparation, stirred 0.5～1 hour, and promptly got solid content and be 35～50% drying at room temperature type organosilicon epoxide acrylate water dispersion.
10, according to the application of each described organosilicon epoxide acrylate water dispersion of claim 1～8, it is characterized in that: as drying at room temperature type coating resin, or as the baking-type coating resin.
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