CN103709312B - A kind of can overcoating polyurethane coating by the preparation method of Hydroxylated acrylic resin - Google Patents
A kind of can overcoating polyurethane coating by the preparation method of Hydroxylated acrylic resin Download PDFInfo
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- CN103709312B CN103709312B CN201310688905.8A CN201310688905A CN103709312B CN 103709312 B CN103709312 B CN 103709312B CN 201310688905 A CN201310688905 A CN 201310688905A CN 103709312 B CN103709312 B CN 103709312B
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Abstract
The invention discloses a kind of can overcoating polyurethane coating by the preparation method of Hydroxylated acrylic resin, the method adopts two step discrete method copolymerization Hydroxylated acrylic resins, and in polymer segment, introduces a kind of monomer A CE with internal plasticization. This Hydroxylated acrylic resin is as the base-material of coating, be cured crosslinked with polyisocyanates, what make can have excellent weatherability, corrosion resistance by overcoating bicomponent polyurethane coating, good chemical proofing and good mechanical performance, this coating, as finish paint, has a large amount of application in heavy anti-corrosion paint.
Description
One, technical field
The present invention relates to a kind of synthetic method of acrylic resin, specifically, relate to a kind of special hydroxy acryl acid resinPreparation method, this resin uses polyisocyanates to solidify, being used for preparation can overcoating polyurethane coating.
Two, background technology
As everyone knows, aliphatic polyurethane coating is with its excellent weatherability, corrosion resistance, good chemical proofing and excellentGood mechanical performance is subject to numerous clients' favor, and still, this paint belongs to the crosslinked film forming of normal temperature cure, conventionally incomplete at filmApplication second paint before parching, makes two coating film close adhesion, if otherwise bottom is oversize hardening time, and paint film is too hard, two-layerBetween easily peel off decortication. Must could apply second paint with after sand paper hacking to the coating surface solidifying for a long time. As paint film officePortion destroys to be needed to repair, and painting can be covered to after hacking around in this part.
Nowadays,, along with the extensive application of long-acting anticorrosive paint system, steel construction rustless property improves greatly. In practical engineering applicationIn, often original anticorrosion priming coat is substantially intact after for many years, but the original gloss of finish paint, color and luster disappeared totally, to wholeThe visual appearance of building has brought discordant chapter. For retaining the new finishing coat of coated on intact priming paint, conventionally adoptSlight sandblast or carry out the processing such as surperficial hacking. Increase inter-coat adhesion by above-mentioned physical method, not only take a lot of work consuming time, reduceApplication work efficiency, also causes environmental pollution, and its effect is often not fully up to expectations, can not show a candle to the chemical bond between coating of the same race.Particularly bear for such as ship side outside plate, main deck, shell etc. the position that seawater wave spatters beating and often occur intermediate peeling, strippingFrom etc. disadvantage.
Therefore, in last century end, each main marine paint manufacturer of the world successively released can overcoating polyurethane finish (as world paintThe Interthan990 of the IP of company etc.), for shell and superstructure position, more fortunately solve the weight of high-weatherability finish paintPainting property problem. Along with the expansion of the market demand, recent year enterprise also developed similarly can overcoating polyurethane finish (as aboveS43-31, the BS52-12 of Jiangsu Lan Ling chemical company etc. of sea kairine Zao Qi factory) for shell and superstructure position. But stateWhat interior enterprise produced can overcoating polyurethane finish, is all by buying import resin mostly, for example A160 of Bayer company, fromThe very minority of main synthetic resin.
Domestic patent CN1778849 and CN101921537 are also the preparation about coating, do not relate to closing of resinBecome.
Three, summary of the invention
The present invention is intended to solve the less situation of home products on market, by the innovation of synthesis technique, to Hydroxylated acrylic resinCarry out segment MOLECULE DESIGN, make with cured with isocyanates after film there is certain internal plasticization, finish paint when recoat canSlight swelling original polyurethane coating film, thus make close adhesion between two coating films, ensure good ply adhesion.
The present invention is achieved in that to be that described Hydroxylated acrylic resin is prepared as follows:
(1) drip not mix monomer a and the initator of hydroxy acryl acid ester, through reacting a synthetic long-chain free radical;
(2) in the long-chain free radical generating, drip mix monomer b and the initator of hydroxy acryl acid ester, after reaction, obtain instituteStating can overcoating polyurethane coating Hydroxylated acrylic resin;
In the described mix monomer a of not hydroxy acryl acid ester and the mix monomer b of hydroxy acryl acid ester, all comprise a kind of specialDifferent monomer, this particular monomers is reacted and is formed with acrylic acid by tertiary carbonic acid glycidyl ester, is a kind of mixture, is called monomer A CE,Monomer A CE comprises following two kinds of primary structures:
Structural formula I:
Formula II:
Wherein, R1、R2For alkyl, R1In carbon number+R2In carbon number=7.
R described in structural formula I and formula II in the present invention1For CH3Time, R2For C6H13；R1For C2H5Time, R2For C5H11；R1For C3H7Time, R2For C4H9。
The mix monomer a of the not hydroxy acryl acid ester described in the present invention comprise (methyl) alkyl acrylate, monomer A CE,Unsaturated carboxylic acid and other vinyl monomer; The mix monomer b of described hydroxy acryl acid ester comprises (methyl) acrylic acid alkylEster, monomer A CE, (methyl) acrylic acid hydroxy alkyl ester, unsaturated carboxylic acid and other vinyl monomer; The described hydroxyl third of preparingThe raw material of olefin(e) acid resin forms by percentage to the quality, comprising:
(methyl) alkyl acrylate described in the present invention be selected from ethyl acrylate, n-butyl acrylate, isobutyl acrylate,Acrylic acid-2-ethyl caproite, acrylic acid stearyl, methyl methacrylate, EMA, methacrylic acid are justOne or more in butyl ester, isobutyl methacrylate, isobornyl methacrylate monomer; Described (methyl) propyleneAcid hydroxy alkyl ester is selected from hydroxy-ethyl acrylate, hydroxypropyl acrylate, acrylic acid hydroxy butyl ester, hydroxyethyl methacrylate, methyl-propOne or more in olefin(e) acid hydroxypropyl acrylate, methacrylic acid hydroxy butyl ester. Described unsaturated carboxylic acid is selected from acrylic acid, metering systemOne or more in acid; Other described vinyl monomer is selected from one or more in styrene, acrylonitrile.
Initator described in the present invention is selected from azodiisobutyronitrile, dibenzoyl peroxide, peroxidized t-butyl perbenzoate, mistakeOxidation-2 ethyl hexanoic acid the tert-butyl ester, peroxidating-2 ethyl hexanoic acid tert-pentyl ester, di-tert-butyl peroxide, two t-amyl peroxy thingsIn one or several.
Solvent described in the present invention is selected from dimethylbenzene, butyl acetate, Solvesso100,1-Methoxy-2-propyl acetate, second twoA kind of in alcohol monobutyl ether acetate or several.
Hydroxy acryl acid in the quality of the mix monomer a of hydroxy acryl acid ester and step (2) not in step of the present invention (1)The mass ratio of the mix monomer b of ester is 1:3～1:8.
Hydroxy acryl acid in the quality of the mix monomer a of hydroxy acryl acid ester and step (2) not in step of the present invention (1)The mass ratio of the mix monomer b of ester is preferably 1:4～1:6.
The reaction temperature of selecting in step of the present invention (1) and step (2) isThe decomposition temperature of 0.5～2h.
In step of the present invention (1), the time for adding of monomer and initator is 25～50 minutes, monomer and initator in step (2)Time for adding be 150～220 minutes.
What after reacting by step (1) and (2) in the present invention, obtain can have by overcoating polyurethane coating hydroxy acrylic acid treeThe solid acid number of 2～5mgKOH/g, the solid hydroxyl value of 66～88mgKOH/g.
Described in the present invention, can overcoating polyurethane coating by the preparation method's of Hydroxylated acrylic resin concrete steps be:
(A) in reactor, add solvent, pass into nitrogen, stir and be warming up to assigned temperature, start to drip mix monomer a, comprise (firstBase) mixture of alkyl acrylate, monomer A CE, unsaturated carboxylic acid and other vinyl monomer and initator, specifyingIn time, drip off a synthetic long-chain free radical;
(B) in the synthetic long-chain free radical of step (1), drip mix monomer b, comprise (methyl) alkyl acrylate, listThe mixture of body ACE, (methyl) acrylic acid hydroxy alkyl ester, unsaturated carboxylic acid and other vinyl monomer and initator, is referring toIn fixing time, drip off;
(C) after dropping finishes, at this temperature, be incubated 30min, add initator, keep temperature-resistant, continue insulation 2～4h;
(D) be cooled to 70～80 DEG C, be blended into solvent dilution, make water white hydroxyl polyacrylic resin.
The prepared hydroxy acryl acid resin of the present invention, compared with common hydroxy acryl acid resin, has following advantage:
The Hydroxylated acrylic resin synthetic method used that the present invention is synthetic, compared with traditional synthesis technique, has adopted two steps poly-The technique of closing, and introduced a kind of monomer A CE, has carried out Modification design to polymer segment, synthesized one have specialFunctional Hydroxylated acrylic resin, the two component polyurethane finish paint that uses Hydroxylated acrylic resin of the present invention to prepare, in applicationWhen second, can not cause layering between finish paint to come off because ply adhesion is poor. Even to solidify coating surface for a long time also withoutNeed sand papering, only need just can application second finish paint after removing surface dirt and dirt. And use resin of the present invention standbyTwo component polyurethane finish paint there are excellent weatherability, chemical-resistant and good resistance to anti-corrosive properties, and conventional polyurethanes be coated withThe feature that material has. Therefore, can use widely in corrosion-proof coating system as finish paint.
Detailed description of the invention
Further illustrate the present invention below in conjunction with embodiment, but protection scope of the present invention is in no way limited to these embodiment.
Embodiment 1:
770g tertiary carbonic acid glycidyl ester, 4g trisnonyl phenyl phosphite, 0.5g stannous octoate are joined in reactor, addHeat, to 90 DEG C, is incubated 30 minutes, is warming up to 105～110 DEG C, starts to drip 227g acrylic acid, 0.1g MEHQMixture, controls rate of addition even, about 1 hour, drips off. After dripping off, be incubated 2～3 hours, survey acid number. As tartaric acidValue higher than 5mgKOH/g, temperature is risen to 120 DEG C, until acid number lower than 5mgKOH/g after finish reaction, obtain product monomerACE。
Embodiment 2:
200g dimethylbenzene is joined in reactor, and logical nitrogen, stirs and is warming up to 126～132 DEG C, starts to drip 17.5g propyleneAcid butyl ester, 31.2g methyl methacrylate, the prepared monomer A CE of 10.5g embodiment 1,0.4g acrylic acid and 0.4g mistakeThe mixture of Oxybenzene t-butyl formate, control rate of addition even, about 40 minutes, mixture is dripped off, after dripping off immediatelyStart to drip 87.7g butyl acrylate, 156g methyl methacrylate, 37.6g hydroxy-ethyl acrylate, 53.5g embodiment 1The mixture of prepared monomer A CE, 2g acrylic acid and 2g peroxidized t-butyl perbenzoate, at the uniform velocity drips, and in 3 hours, dripsComplete, be incubated after 1 hour, add 1.2g peroxidized t-butyl perbenzoate, continue insulation 2～3 hours, be cooled to 80 DEG C, addEnter 200g dimethylbenzene and dilute,, dispersed with stirring obtains water white Hydroxylated acrylic resin. The parameter index of embodiment 1See the following form:
Table 1
| Solid hydroxyl value | 79mgKOH/g |
| Solid acid number | 4.8mgKOH/g |
| Solid content (gross data) | 50% |
| Viscosity | 877mPa·s-1 |
Embodiment 3:
200g dimethylbenzene is joined in reactor, and logical nitrogen, stirs and is warming up to 126～132 DEG C, starts to drip 18g acrylic acidButyl ester, 30g methyl methacrylate, the prepared monomer A CE of 10.5g embodiment 1,0.4g acrylic acid and 0.4g peroxidatingThe mixture of t-butyl perbenzoate, controls rate of addition even, about 40 minutes, mixture is dripped off, and after dripping off, starts immediatelyDrip 90g butyl acrylate, 150g methyl methacrylate, 42g hydroxypropyl acrylate, 53.5g embodiment 1 preparedThe mixture of monomer A CE, 2g acrylic acid and 2g peroxidized t-butyl perbenzoate, at the uniform velocity drips, and drips off insulation in 3 hoursAfter 1 hour, add 1.2g peroxidized t-butyl perbenzoate, continue insulation 2～3 hours, be cooled to 80 DEG C, add 200g bis-Toluene dilutes,, dispersed with stirring obtains water white Hydroxylated acrylic resin. The parameter index of embodiment 2 sees the following form:
Table 2
| Solid hydroxyl value | 79mgKOH/g |
| Solid acid number | 4.7mgKOH/g |
| Solid content (gross data) | 50% |
| Viscosity | 605mPa·s-1 |
Embodiment 4:
240g dimethylbenzene is joined in reactor, and logical nitrogen, stirs and is warming up to 126～132 DEG C, starts to drip 20.2g propyleneAcid butyl ester, 36g methyl methacrylate, the prepared monomer A CE of 12.8g embodiment 1,0.4g acrylic acid and 1.3g peroxideChange the mixture of t-butyl perbenzoate, control rate of addition even, about 50 minutes, mixture is dripped off, after dripping off, open immediatelyBegin to drip 101.3g butyl acrylate, 179.7g methyl methacrylate, 54g hydroxy-ethyl acrylate, 64g embodiment 1 madeThe mixture of monomer A CE, 2g acrylic acid and the 6.7g peroxidized t-butyl perbenzoate obtaining, at the uniform velocity drips, and in 3.5 hours, dripsComplete, be incubated after 1 hour, add 1.6g peroxidized t-butyl perbenzoate, continue insulation 2～3 hours, be cooled to 80 DEG C, addEnter 80g dimethylbenzene and dilute,, dispersed with stirring obtains water white Hydroxylated acrylic resin. The parameter index of embodiment 3 is shown inFollowing table:
Table 3
| Solid hydroxyl value | 86mgKOH/g |
| Solid acid number | 3.9mgKOH/g |
| Solid content (gross data) | 60% |
| Viscosity | 1932mPa·s-1 |
Embodiment 5
Table 4 is with Hydroxylated acrylic resin of the present invention, collocation polyisocyanate curing agent, and preparation can overcoating two component polyurethaneThe formula of coating, table 5 item is corresponding performance indications.
Table 4 aqueous two-component polyurethane lacquer formulation
The above-mentioned performance indications that can overcoating bicomponent polyurethane coating of table 5
* the adhesion test method of overcoating: carry out making sheet after joining paint, prepared model is dry 24h under the condition of 23 ± 2 DEG C,Then dried model is placed in to 80 ± 2 DEG C of baking ovens 3 days, takes out model and apply second paint, the condition of 23 ± 2 DEG CDry 24h, tests its adhesive force by cross-hatching down.
Claims (10)
1. can overcoating polyurethane coating by the preparation method of Hydroxylated acrylic resin, it is characterized in that: described Hydroxylated acrylic resin is prepared as follows:
(1) drip not mix monomer a and the initator of hydroxy acryl acid ester, through reacting a synthetic long-chain free radical;
(2) in the long-chain free radical generating, drip mix monomer b and the initator of hydroxy acryl acid ester, after reaction, obtain described can overcoating polyurethane coating Hydroxylated acrylic resin;
In the described mix monomer a of not hydroxy acryl acid ester and the mix monomer b of hydroxy acryl acid ester, all comprise a kind of particular monomers, this particular monomers is reacted and is formed with acrylic acid by tertiary carbonic acid glycidyl ester, it is a kind of mixture, be called monomer A CE, monomer A CE comprises following two kinds of primary structures:
Wherein, R1、R2For alkyl, R1In carbon number+R2In carbon number=7;
The mix monomer a of described not hydroxy acryl acid ester comprises (methyl) alkyl acrylate, particular monomers ACE, unsaturated carboxylic acid and other vinyl monomer; The mix monomer b of described hydroxy acryl acid ester comprises (methyl) alkyl acrylate, particular monomers ACE, (methyl) acrylic acid hydroxy alkyl ester, unsaturated carboxylic acid and other vinyl monomer; The described raw material of preparing Hydroxylated acrylic resin forms by percentage to the quality, comprising:
Component title consumption
Solvent 30～60 quality %
In mix monomer a component
In mix monomer b component
According to claim 1 can overcoating polyurethane coating by the preparation method of Hydroxylated acrylic resin, it is characterized in that: described (methyl) alkyl acrylate is selected from one or more in ethyl acrylate, n-butyl acrylate, isobutyl acrylate, acrylic acid-2-ethyl caproite, acrylic acid stearyl, methyl methacrylate, EMA, n-BMA, isobutyl methacrylate, isobornyl methacrylate monomer; Described (methyl) acrylic acid hydroxy alkyl ester is selected from one or more in hydroxy-ethyl acrylate, hydroxypropyl acrylate, acrylic acid hydroxy butyl ester, hydroxyethyl methacrylate, hydroxy propyl methacrylate, methacrylic acid hydroxy butyl ester; Described unsaturated carboxylic acid is selected from one or more in acrylic acid, methacrylic acid; Other described vinyl monomer is selected from one or more in styrene, acrylonitrile.
According to claim 1 can overcoating polyurethane coating by the preparation method of Hydroxylated acrylic resin, it is characterized in that: described initator is selected from one or several in azodiisobutyronitrile, dibenzoyl peroxide, peroxidized t-butyl perbenzoate, peroxide-2-ethyl hexanoic acid tert-butyl, peroxidating-2 ethyl hexanoic acid tert-pentyl ester, di-tert-butyl peroxide, two t-amyl peroxy things.
According to claim 1 can overcoating polyurethane coating by the preparation method of Hydroxylated acrylic resin, it is characterized in that: described solvent is selected from a kind of in dimethylbenzene, butyl acetate, Solvesso100,1-Methoxy-2-propyl acetate, 2-Butoxyethyl acetate or several.
According to claim 1 can overcoating polyurethane coating by the preparation method of Hydroxylated acrylic resin, it is characterized in that: in step (1), the quality of the mix monomer a of hydroxy acryl acid ester is not 1:3～1:8 with the mass ratio of the mix monomer b of the middle hydroxy acryl acid ester of step (2).
According to claim 1 can overcoating polyurethane coating by the preparation method of Hydroxylated acrylic resin, it is characterized in that: in step (1), the quality of the mix monomer a of hydroxy acryl acid ester is not 1:4～1:6 with the mass ratio of the mix monomer b of the middle hydroxy acryl acid ester of step (2).
According to claim 1 can overcoating polyurethane coating by the preparation method of Hydroxylated acrylic resin, it is characterized in that: the reaction temperature of selecting in step (1) and step (2) is the half-life of initator used in the polymerisation decomposition temperature that is 0.5～2h.
According to claim 1 can overcoating polyurethane coating by the preparation method of Hydroxylated acrylic resin, it is characterized in that: in step (1), the time for adding of monomer and initator is 25～50 minutes, in step (2), the time for adding of monomer and initator is 150～220 minutes.
According to claim 1 can overcoating polyurethane coating by the preparation method of Hydroxylated acrylic resin, it is characterized in that: can set the solid acid number with 2～5mgKOH/g, the solid hydroxyl value of 66～88mgKOH/g by overcoating polyurethane coating hydroxy acrylic acid by what obtain after step (1) and (2) reaction.
According to claim 1 can overcoating polyurethane coating by the preparation method of Hydroxylated acrylic resin, it is characterized in that, described preparation can overcoating polyurethane coating by the concrete steps of Hydroxylated acrylic resin be:
(A) in reactor, add solvent, pass into nitrogen, stirring is warming up to assigned temperature, start to drip mix monomer a, comprise the mixture of (methyl) alkyl acrylate, monomer A CE, unsaturated carboxylic acid and other vinyl monomer and initator, at the appointed time interior dripping off, a synthetic long-chain free radical;
(B) in the synthetic long-chain free radical of step (1), drip mix monomer b, comprise the mixture of (methyl) alkyl acrylate, monomer A CE, (methyl) acrylic acid hydroxy alkyl ester, unsaturated carboxylic acid and other vinyl monomer and initator, drip off at the appointed time;
(C) after dropping finishes, at this temperature, be incubated 30min, add initator, keep temperature-resistant, continue insulation 2～4h;
(D) be cooled to 70～80 DEG C, be blended into solvent dilution, make water white hydroxyl polyacrylic resin.
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Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104031233B (en) * | 2014-05-26 | 2016-04-13 | 北京红狮漆业有限公司 | A kind of acroleic acid polyurethane emulsion and its preparation method and application |
| CN106220784A (en) * | 2016-07-27 | 2016-12-14 | 无锡市虎皇漆业有限公司 | E 10 modified thermoset type acrylic resin and preparation method thereof |
| CN106749852B (en) * | 2016-11-29 | 2019-01-18 | 上海华谊精细化工有限公司 | A kind of high corrosion-resistant acrylate and preparation method thereof |
| CN106750129B (en) * | 2016-12-28 | 2019-12-27 | 中昊北方涂料工业研究设计院有限公司 | Low dielectric loss polyurethane resin and preparation method thereof |
| CN107828012A (en) * | 2017-11-15 | 2018-03-23 | 立邦工业涂料(上海)有限公司 | A kind of acrylate polymer, preparation method and applications |
| CN109053947B (en) * | 2018-07-17 | 2021-05-14 | 万华化学集团股份有限公司 | Thermosetting acrylic resin with high hardness and deep drawing resistance and synthesis method and application thereof |
| CN112708321B (en) * | 2020-12-27 | 2022-04-05 | 山东齐鲁漆业有限公司 | Modified acrylic resin finish paint for railway building materials and preparation method thereof |
| CN114085332B (en) * | 2021-11-26 | 2023-08-08 | 上海华谊涂料有限公司 | High-solid hydroxyl acrylic resin and preparation method and application thereof |
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