CN1470539A - Improved hydroxy acrylic acid resin - Google Patents
Improved hydroxy acrylic acid resin Download PDFInfo
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- CN1470539A CN1470539A CNA031319718A CN03131971A CN1470539A CN 1470539 A CN1470539 A CN 1470539A CN A031319718 A CNA031319718 A CN A031319718A CN 03131971 A CN03131971 A CN 03131971A CN 1470539 A CN1470539 A CN 1470539A
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- acrylic resin
- hydroxylated acrylic
- monomer
- resin
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Abstract
The present invention relates to an improved acrolactic resin, in particular it is an acrolactic resin with excellent solvent resistance and oil resistance. It is characterized by that in its copolymerization reaction there are 3-10 wt% of acrylonitrile and/or 5-12 wt% of methyl acrylate, 3-10 wt% of isobutyl methacrylate and/or 1.5-8 wt.% of cyclohexyl methacrylate functional monomer, so that the improved acrolactic resin has srong oil resistance (for example it can resist 0# diesel oil and 90# gasoline, etc.) and strong solvent resistance (for example it can resist butyl alcohol and butyl acetate, etc).
Description
Technical field
The present invention relates to a kind of Hydroxylated acrylic resin of improvement, especially a kind of anti-solvent, the Hydroxylated acrylic resin that oil-proofness is good.
Background technology
Hydroxylated acrylic resin is methacrylic acid monomer, Acrylic Acid Monomer and vinylbenzene, by the initiator high molecular polymer that polyreaction obtains in solvent (having a kind of hydroxyl monomer that is in the comonomer at least).Yet common Hydroxylated acrylic resin itself, preservative property are general, and especially oil resistant, solvent resistance are relatively poor, can not satisfy high oil resistant, anti-solvent service requirements.People are for improving some characteristic of Hydroxylated acrylic resin coating, usually adopt the cold assembly mode of physical mixed, promptly carry out modification, as Chinese patent 94119145.1 disclosed a kind of Weather-resisting liquid porcelains that titanium dioxide, anti-settling agent, solvent and urethane resin etc. are formed that in Hydroxylated acrylic resin, add by adding some properties-correcting agent; Chinese patent 01130021.3 disclosed Weather-resisting powder coating is the tosic acid that adds the sealing of tetramethoxymethylglycoluril, dimethyl ethanol in Hydroxylated acrylic resin, acrylate type flow agent, mineral filler, pigment, st-yrax etc.; The disclosed nano uvioresistant polyurethane paint of Chinese patent 01128269.X is to add nano material in Hydroxylated acrylic resin, or the like.Yet this by the non-response type modification of cold assembly physical mixed, effect is obvious not as response type, can not reach desirable preferable effect, and the cold assembly composition price that has is higher, causes product cost bigger, is difficult to reach industrial application.
Summary of the invention
The objective of the invention is to overcome the deficiency of above-mentioned prior art, provide a kind of, anti-solvent, the Hydroxylated acrylic resin that oil-proofness is good by modification by copolymerization.
The object of the invention realizes that main the improvement is: introduce vinyl cyanide and/or methyl acrylate and Propenoic acid, 2-methyl, isobutyl ester and/or cyclohexyl methacrylate in the polymerization process of Hydroxylated acrylic resin simultaneously, the Hydroxylated acrylic resin that copolymerization is obtained promptly has good anti-solvent and oil-proofness.Specifically, Hydroxylated acrylic resin of the present invention, comprise methacrylic acid monomer, Acrylic Acid Monomer and vinylbenzene, initiator, solvent copolyreaction, has a kind of hydroxyl monomer that is in the described comonomer at least, it is characterized in that in the said copolyreaction also having 3-10% vinyl cyanide and/or 5-12% methyl acrylate, the Propenoic acid, 2-methyl, isobutyl ester of 3-10% and/or the 1.5-8% cyclohexyl methacrylate function monomer of (weight, down with).
Comonomer of the present invention can adopt common Hydroxylated acrylic resin comonomer, as some kinds of methyl methacrylate, butyl methacrylate, methacrylic acid, vinylformic acid, Hydroxyethyl acrylate, Propylene glycol monoacrylate, butyl acrylates etc., concrete monomer is selected and can be used service requirementss such as required second-order transition temperature, molecular weight, resin outward appearance, acid number, hydroxyl value by resin, selects corresponding hard monomer and soft monomer.The hydroxyl monomer can be methacrylic acid hydroxyl monomer and/or vinylformic acid carboxylic monomer, and a kind of being preferably selected vinylformic acid carboxylic monomer such as Hydroxyethyl acrylate for use, and its price is relatively cheap, helps reducing cost.Initiator can adopt BPO, DCP, TBPB, Diisopropyl azodicarboxylate etc. with usually copolymerization is similar, but the present invention is comparatively desirable with BPO (dibenzoyl peroxide) especially through test, relative low price not only, and also technology is controlled easily.Solvent can adopt common copolymerization solvent, but the present invention is comparatively desirable with dimethylbenzene and N-BUTYL ACETATE mixed solvent, this double solvents in the present invention, temperature of reaction, solvency power, composition paint drying rate, the flow levelings of paint film etc. are all good than other solvents.Vinyl cyanide and methyl acrylate function monomer are introduced in copolymerization of the present invention, mainly be the oil-proofness that improves copolymer resins, can add wherein a kind ofly, also can two kinds add together, vinyl cyanide of the present invention is comparatively desirable to add 3-10%, and methyl acrylate is comparatively desirable to add 5-12%.Add-on is low excessively, and the modification of multipolymer oil resistant is not outstanding; Add-on is too high, can influence other monomer add-on, influences the over-all properties of multipolymer.Propenoic acid, 2-methyl, isobutyl ester and cyclohexyl methacrylate function monomer are introduced, and mainly are the solvent resistances that improves copolymer resins, can add wherein a kind ofly, also can two kinds add simultaneously.Add-on is low excessively, and multipolymer is anti-solvent modified not outstanding; Add-on is too high, can influence other monomer add-on, influences the over-all properties of multipolymer.Therefore the present invention is comparatively appropriate with above-mentioned add-on.The adding of function monomer is especially to make up whole adding effect optimums.For guaranteeing that polymkeric substance has better comprehensive performance, used monomer better adopts high-purity monomer.
Be better oil-proofness and the solvent resistance that improves Hydroxylated acrylic resin, polymer resin molecular weight of the present invention with more conventional resin bigger for well, its resin viscosity is comparatively suitable with 35-80 second (form viscosity), big molecular weight can make oil resistant and solvent resistance better.The hydroxyl value of polymer resin of the present invention is also higher for well with more conventional resin, when being made into paint like this with the degree of crosslinking of solidifying agent just greatly, can form bigger reticulated structure, big degree of crosslinking solvent resistance and oil-proofness are better.For well, hydroxyl percentage ratio is low excessively with 2.4-3 (100% resin) for the hydroxyl percentage ratio of polymer resin of the present invention, and degree of crosslinking is little, influences performance; Hydroxyl percentage ratio is too high, and the solidifying agent dosage is too much, also can influence other performances, does not reach more satisfactory effect, is worthless.The second-order transition temperature of polymer resin of the present invention (Tg ℃), comparatively appropriate with 9.8-15, second-order transition temperature is too high, easily causes the paint film embrittlement, poor impact resistance; Second-order transition temperature is low excessively, and coating surface hardness is not good enough.
Hydroxylated acrylic resin copolymerization process of the present invention and common Hydroxylated acrylic resin copolymerization are similar, do not have difference especially.
Copolymerization Hydroxylated acrylic resin of the present invention, owing to add vinyl cyanide and/or methyl acrylate and Propenoic acid, 2-methyl, isobutyl ester and/or cyclohexyl methacrylate function monomer, the Hydroxylated acrylic resin itself that copolymerization is obtained has very strong oil resistant (as 0# diesel oil, 90# gasoline etc.) property and anti-solvent (as butanols, N-BUTYL ACETATE etc.) property, the more conventional resin of oil resistant and solvent resistance can improve 4-8 doubly at least, can satisfy some oil resistant, anti-solvent particular requirement.The present invention passes through modification by copolymerization, the modification of colder assembly physical mixed, and not only better effects if, and price is low, and technology is simple, can finish with copolymerization, need not technological process separately, greatly reduces production cost.Hydroxylated acrylic resin of the present invention, outward appearance is light yellow transparent liquid; Solid content: 60-70%; Viscosity: 35～80 seconds (Ge Shi, 25 ℃); Acid value :≤10mgKOH/g; Hydroxyl %:2.4-3 (100% resin); Second-order transition temperature (Tg ℃): 9.8-15.
Hydroxylated acrylic resin of the present invention and polyurethane curing agent (aromatic series) are pieced together usefulness, can be made into the acroleic acid polyurethane antifouling paste, this lacquer have under the normal temperature do soon, hardness is high, gloss of film good, the excellent decoration effect is arranged, particularly You Yi water-fast, anti-solvent, oil resistance can have been done higher oil resistant, the use of solvent-proof antifouling paste.
Below in conjunction with several embodiments, further specify the present invention, but the concrete prescription of embodiment not the qualification to technical solution of the present invention.
Embodiment
Embodiment: material proportion is seen attached list
Hydroxylated acrylic resin polymerization of the present invention, earlier solvent is added in stainless steel or the enamel reaction still, stirring is warming up to reflux state, drip mix monomer (dripping in 2.5-3 hour) then, be incubated 2-4 hour, add initiator 1-4 time, be incubated 2～3 hours, control in carrying out and detect, till regulation and control are extremely qualified, cooling, filtration, packing.
The present invention is according to concrete service requirements, and its general used Acrylic Acid Monomer, methacrylic acid monomer, vinylbenzene, initiator, solvent can suitably be adjusted and selection according to the copolymer resins technical requirements.
Be convenient and describe, the said copolymerization of the present invention be polymerized to synonym.
Hydroxylated acrylic resin Example formulations table
| The formula material title | Prescription | Comparative example | ||||
| One | Two | Three | Four | Five | ||
| Methyl acrylate | ????6 | ????4 | ????4 | ????11 | ||
| Acrylic acid hydroxy-ethyl acrylate acrylonitrile styrene-acrylonitrile copolymer acid butyl ester Isooctyl acrylate monomer isobutyl methacrylate cyclohexyl methacrylate methyl methacrylate | ????0.7 ????11.8 ????4 ????25.3 ????5 ????11.7 ????2 | ????0.7 ????11.8 ????3 ????25.3 ????5 ????11.7 ????4 ????3.5 | ????0.7 ????11.8 ????10 ????24.0 ????5 ????11.7 ????7 ????7 | ????0.7 ????11.8 ????25.3 ????5 ????11.7 ????10 ????3.5 | ????0.7 ????11.8 ????8 ????23.0 ????4 ????9.7 ????5 | ????0.7 ????11.7 ????26.5 ????18.8 ????5.2 |
| BPO | ????1.6 | ????1.6 | ????1.6 | ????1.6 | ????1.6 | ????1.6 |
| The xylylene diacetate butyl ester | ????20.5 ????11.4 | ????18.0 ????11.4 | ????10.1 ????11.1 | ????15 ????11.4 | ????14.0 ????11.2 | ????25.5 ????10 |
| Corrosion-resistant fate (intact) 0# diesel oil 100# gasoline propyl carbinol N-BUTYL ACETATE | ????72 ????72 ????72 ????72 | ????90 ????90 ????90 ????90 | ????76 ????76 ????76 ????76 | ????70 ????70 ????70 ????70 | ????74 ????74 ????74 ????74 | ????15 ????15 ????15 ????15 |
Annotate: the erosion resistance fate is made into the observed data of white anticorrosive lacquer for the embodiment resin.
Integrity is judged: with the no variable color of antifouling paste light, still be white in color, and complete nothing comes off, bubbling, corrosion swelling phenomenon.
By embodiment and comparative example as can be known: introduce the acrylate functional monomer and make hydroxy acryl acid resin, and polyurethane curing agent (aromatic series) is made anti-corrosive paint, its oil resistant and solvent resistance are very outstanding, and the antifouling paste that the hydroxy acryl acid resin of not introducing functional monomer is made, oil resistant and solvent resistance are general.
Four kinds of function monomers are introduced simultaneously, its effect optimum.
Claims (8)
1, a kind of Hydroxylated acrylic resin, comprise methacrylic acid monomer, Acrylic Acid Monomer and vinylbenzene, initiator, solvent copolyreaction, has a kind of hydroxyl monomer that is in the described comonomer at least, it is characterized in that also having in the said copolyreaction vinyl cyanide and/or 5-12% methyl acrylate, the Propenoic acid, 2-methyl, isobutyl ester of 3-10% and/or the 1.5-8% cyclohexyl methacrylate function monomer of 3-10% (weight).
2,, it is characterized in that said initiator is BPO according to the described Hydroxylated acrylic resin of claim 1.
3,, it is characterized in that said solvent is dimethylbenzene and N-BUTYL ACETATE according to the described Hydroxylated acrylic resin of claim 1.
4,, it is characterized in that said copolymer resins viscosity is 35-80 second (form viscosity) according to the described Hydroxylated acrylic resin of claim 1.
5, according to the described Hydroxylated acrylic resin of claim 1, the hydroxyl percentage ratio that it is characterized in that said copolymer resins is 2.4-3 (100% resin).
6, according to the described Hydroxylated acrylic resin of claim 1, the second-order transition temperature that it is characterized in that said copolymer resins is 9.8-15 ℃.
7,, it is characterized in that said function monomer is vinyl cyanide and methyl acrylate and Propenoic acid, 2-methyl, isobutyl ester and cyclohexyl methacrylate according to claim 1,2,3,4,5 or 6 described Hydroxylated acrylic resins.
8,, it is characterized in that said comonomer is a high-purity monomer according to the described Hydroxylated acrylic resin of claim 7.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB031319718A CN1239537C (en) | 2003-06-19 | 2003-06-19 | Improved hydroxy acrylic acid resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB031319718A CN1239537C (en) | 2003-06-19 | 2003-06-19 | Improved hydroxy acrylic acid resin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1470539A true CN1470539A (en) | 2004-01-28 |
| CN1239537C CN1239537C (en) | 2006-02-01 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB031319718A Expired - Fee Related CN1239537C (en) | 2003-06-19 | 2003-06-19 | Improved hydroxy acrylic acid resin |
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| Country | Link |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105504140A (en) * | 2016-01-08 | 2016-04-20 | 广东邦固化学科技有限公司 | Synthetic method of high-hydroxyl-value acrylic resin |
| CN107236077A (en) * | 2017-07-17 | 2017-10-10 | 江苏三木化工股份有限公司 | The preparation method of the high rigidity acrylic resin of resistance to gasoline |
-
2003
- 2003-06-19 CN CNB031319718A patent/CN1239537C/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105504140A (en) * | 2016-01-08 | 2016-04-20 | 广东邦固化学科技有限公司 | Synthetic method of high-hydroxyl-value acrylic resin |
| CN107236077A (en) * | 2017-07-17 | 2017-10-10 | 江苏三木化工股份有限公司 | The preparation method of the high rigidity acrylic resin of resistance to gasoline |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1239537C (en) | 2006-02-01 |
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