CN102358764A - Preparation method for liquid water-soluble resin - Google Patents
Preparation method for liquid water-soluble resin Download PDFInfo
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- CN102358764A CN102358764A CN2011102169044A CN201110216904A CN102358764A CN 102358764 A CN102358764 A CN 102358764A CN 2011102169044 A CN2011102169044 A CN 2011102169044A CN 201110216904 A CN201110216904 A CN 201110216904A CN 102358764 A CN102358764 A CN 102358764A
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Abstract
The present invention relates to a preparation method for a liquid water-soluble resin. The method is characterized by: carrying out alkali washing and water washing for a monomer mixture, adding an initiator to the mixture, stirring and dissolving to obtain a premixed monomer mixture, wherein the monomer mixture comprises (meth) acrylic acid or (meth) acrylic ester, at least one selected from a vinyl monomer and a allyl monomer, or the monomer mixture comprises (meth) acrylic acid or (meth) acrylic ester, at least one selected from a vinyl monomer and a allyl monomer, and maleic anhydride or a maleic anhydride derivative; heating a polymerization solvent and the initiator in a polymerization reactor until the polymerization solvent and the initiator are stably refluxed, then slowly adding the premixed monomer mixture to the polymerization reactor in a dropwise manner to carry out a reaction; after completing the reaction, adding a neutralizer and edible alcohol to the polymerization reactor, then filtering to obtain the finished product. According to the present invention, the process is reasonable; the prepared product is colorless, transparent, clarified and water-soluble, such that the prepared product can be directly diluted by adding tap water; the prepared resin has characteristics of good mechanical strength, good water wiping resistance, good after-tack resistance and strong versatility, and can be used for gravure printing ink, flexographic printing ink, lithographic printing ink and screen printing ink of paper, plastic, aluminum foil and other substrates, paints, coatings, and the like.
Description
Technical field
The present invention relates to a kind of preparation method of resin, particularly a kind of preparation method of liquid water soluble resin.
Background technology
In the prior art, be used for the water-base resin that is mostly that the intaglio plate of base materials such as paper, plastics, aluminium foil, gentle version, lithographic plate, screen painting printing ink prepare, and described water-base resin adopts all is " solid resin+emulsion " system.Its defective is: emulsion is easy breakdown of emulsion under high shearing action.The emulsion shelf lives is shorter, and tank farm stock can not be too many, may have the untimely situation of the supply of material.Water-base resin all is solid-state, and the printing ink that adopts water-base resin to produce cannot add water, but but water cut about 5% in the thinner, its PT is long, and energy consumption is more.
Summary of the invention
Technical problem to be solved by this invention is the deficiency to prior art, and the preparation method of a kind of technology liquid water soluble resin that more industry rationally, quality product and universal performance are good is provided.
Technical problem to be solved by this invention is to realize through following technical scheme.The present invention is a kind of preparation method of liquid water soluble resin, is characterized in, its step is following:
(1) be that basic soln and the monomer mixture of 3-10% drops in the purification tank and mix stirring with an amount of mass concentration, standing demix is after lower floor's buck layer emitted; In purification tank, add an amount of water, stir washing, standing demix; Lower aqueous layer is emitted, get the purifying monomer mixture; The initiator that in the purifying monomer mixture, adds the 0.5-2.5% of its weight, stirring and dissolving gets the premix monomer mixture; Described monomer mixture is by (methyl) vinylformic acid or its ester class, and at least a in vinyl monomer and the allyl monomer, perhaps adds the maleic anhydride or derivatives thereof again and forms, and the weight percent that each monomer accounts for monomer mixture is not less than 20%;
(2) in polymeric kettle, add the polymer solvent of the 10-50% of monomer mixture weight, the initiator of 0.1-0.5%; Be heated to stable the backflow, the premix monomer mixture slowly is added dropwise in the polymeric kettle, control reaction temperature is for stablizing reflux temperature; After drip finishing; Be incubated after 1-3 hour, in polymeric kettle, append the initiator of the 0.2-0.6% of monomer mixture weight, continue insulation 1-2 hour;
(3) material in the polymeric kettle is cooled to stops to reflux, in polymeric kettle, add neutralizing agent and the 40-60% edible ethanol of the 10-30% of monomer mixture weight again, filtration gets product.
In the described monomer mixture of above technical scheme, be not less than 20%, can select blending ratio on demand on this basis as long as each monomer accounts for the weight percent of monomer mixture.
In preparing method's technical scheme of liquid water soluble resin of the present invention, preferred technical characterictic is:
1, described vinyl monomer is preferably from ethene, vinyl toluene, vinylbenzene, vinylchlorid, divinyl, vinyl acetate between to for plastic, butyric acid ethene, Whitfield's ointment ethene, vinyl n-butyl ether, vinyl isobutyl ether, terepthaloyl moietie ethene ether, hydroxyl butyl vinyl ether; Described allyl monomer is preferably from allyl glyceroether, allyl group n-butyl ether; Described (methyl) esters of acrylic acid is preferably from (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) Bing Xisuandingzhi, (methyl) vinylformic acid n-propyl, (methyl) NSC 20949, (methyl) tert-butyl acrylate, the just own ester of (methyl) vinylformic acid, (methyl) octadecyl acrylate, (methyl) vinylformic acid ethoxy ethyl ester; Described maleic anhydride verivate is preferably from dibutyl maleinate, toxilic acid methyl esters, dimethyl maleate, ethyl maleate, itaconicacid.
2, described initiator is peroxide initiator or azo-initiator.The preferred Lucidol BPO of described peroxide initiator, Di Cumyl Peroxide 99, tertbutyl peroxide or peroxycarbonates; The preferred Diisopropyl azodicarboxylate AIBN of described azo-initiator, AMBN or ABVN.
3, the mixed solvent of one or more compositions in described polymer solvent preferred alcohol, propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol, propylene glycol monomethyl ether, Ucar 35 butyl ether, the dipropylene glycol methyl ether.
4, the preferred sodium hydroxide of described neutralizing agent, Pottasium Hydroxide, ammoniacal liquor, Monoethanolamine MEA BASF, diethylolamine, trolamine, N, N-dimethylethanolamine or triethylamine.
5, the preferred sodium hydroxide of described basic soln, Pottasium Hydroxide or lithium hydroxide solution.
Compared with prior art, technology of the present invention is more reasonable, and the liquid water soluble resin that adopts technology of the present invention to make possesses following advantage: colourless, transparent, the clarification of product; Its solid content can reach 40-60%.This liquid water soluble resin has water-soluble, can directly add tap water, and the dilution of available tap water; This liquid water soluble resin has excellent mechanical intensity, water-fast wiping and anti-after tack.This liquid water soluble resin highly versatile can be used for the intaglio plate of base materials such as paper, plastics, aluminium foil, gentle version, lithographic plate, screen painting printing ink, paint, coating etc.
Embodiment
Below further describe concrete technical scheme of the present invention,, and do not constitute restriction its right so that those skilled in the art understands the present invention further.
Embodiment 1, a kind of preparation method of liquid water soluble resin, and its step is following:
(1) be that 3% basic soln drops in the purification tank with monomer mixture and mixes stirring with an amount of mass concentration, standing demix is after lower floor's buck layer emitted; In purification tank, add an amount of water, stir washing, standing demix; Lower aqueous layer is emitted, get the purifying monomer mixture; 0.5% of its weight of adding initiator in the purifying monomer mixture, stirring and dissolving gets the premix monomer mixture; Described monomer mixture is by (methyl) vinylformic acid or its ester class, and vinyl monomer and allyl monomer, adds the maleic anhydride or derivatives thereof again and forms, and the weight percent that each monomer accounts for monomer mixture is 25%;
(2) 10% of adding monomer mixture weight polymer solvent, 0.1% initiator in polymeric kettle; Be heated to stable the backflow, the premix monomer mixture slowly is added dropwise in the polymeric kettle, control reaction temperature is for stablizing reflux temperature; Drip and finish; Be incubated after 1 hour, in polymeric kettle, append 0.2% initiator of monomer mixture weight, continue insulation 1 hour;
(3) material in the polymeric kettle is cooled to stops to reflux, in polymeric kettle, add 10% neutralizing agent and 40% edible ethanol of monomer mixture weight again, filtration gets product.
Embodiment 2, a kind of preparation method of liquid water soluble resin, and its step is following:
(1) be that 10% basic soln drops in the purification tank with monomer mixture and mixes stirring with an amount of mass concentration, standing demix is after lower floor's buck layer emitted; In purification tank, add an amount of water, stir washing, standing demix; Lower aqueous layer is emitted, get the purifying monomer mixture; 2.5% of its weight of adding initiator in the purifying monomer mixture, stirring and dissolving gets the premix monomer mixture; Described monomer mixture is by (methyl) vinylformic acid or its ester class, and vinyl monomer or allyl monomer, add the maleic anhydride or derivatives thereof again and form, each monomer respectively account for monomer mixture weight 1/3;
(2) 50% of adding monomer mixture weight polymer solvent, 0.5% initiator in polymeric kettle; Be heated to stable the backflow, the premix monomer mixture slowly is added dropwise in the polymeric kettle, control reaction temperature is for stablizing reflux temperature; Drip and finish; Be incubated after 3 hours, in polymeric kettle, append 0.6% initiator of monomer mixture weight, continue insulation 2 hours;
(3) material in the polymeric kettle is cooled to stops to reflux, in polymeric kettle, add 30% neutralizing agent and 60% edible ethanol of monomer mixture weight again, filtration gets product.
Embodiment 3, a kind of preparation method of liquid water soluble resin, and its step is following:
(1) be that 7% basic soln drops in the purification tank with monomer mixture and mixes stirring with an amount of mass concentration, standing demix is after lower floor's buck layer emitted; In purification tank, add an amount of water, stir washing, standing demix; Lower aqueous layer is emitted, get the purifying monomer mixture; 1.5% of its weight of adding initiator in the purifying monomer mixture, stirring and dissolving gets the premix monomer mixture; Described monomer mixture is by (methyl) vinylformic acid or its ester class; And vinyl monomer or allyl monomer composition; (methyl) vinylformic acid or its ester class account for monomer mixture weight percent 60%, vinyl monomer or allyl monomer account for monomer mixture weight percent 40%;
(2) 30% of adding monomer mixture weight polymer solvent, 0.25% initiator in polymeric kettle; Be heated to stable the backflow, the premix monomer mixture slowly is added dropwise in the polymeric kettle, control reaction temperature is for stablizing reflux temperature; After drip finishing; Be incubated after 2 hours, in polymeric kettle, append 0.4% initiator of monomer mixture weight, continue insulation 1.5 hours;
(3) material in the polymeric kettle is cooled to stops to reflux, in polymeric kettle, add 20% neutralizing agent and 50% edible ethanol of monomer mixture weight again, filtration gets product.
Among the embodiment 1,2,3:
Described vinyl monomer is selected from ethene, vinyl toluene, vinylbenzene, vinylchlorid, divinyl, vinyl acetate between to for plastic, butyric acid ethene, Whitfield's ointment ethene, vinyl n-butyl ether, vinyl isobutyl ether, terepthaloyl moietie ethene ether, hydroxyl butyl vinyl ether; Described allyl monomer is selected from allyl glyceroether, allyl group n-butyl ether; Described (methyl) esters of acrylic acid is selected from (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) Bing Xisuandingzhi, (methyl) vinylformic acid n-propyl, (methyl) NSC 20949, (methyl) tert-butyl acrylate, the just own ester of (methyl) vinylformic acid, (methyl) octadecyl acrylate, (methyl) vinylformic acid ethoxy ethyl ester; Described maleic anhydride verivate is selected from dibutyl maleinate, toxilic acid methyl esters, dimethyl maleate, ethyl maleate, itaconicacid.
Described initiator is peroxide initiator or azo-initiator.Described peroxide initiator is selected from Lucidol BPO, Di Cumyl Peroxide 99, tertbutyl peroxide or peroxycarbonates; Described azo-initiator is selected from Diisopropyl azodicarboxylate AIBN, AMBN or ABVN.
Described polymer solvent is selected from the mixed solvent of one or more compositions in ethanol, propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol, propylene glycol monomethyl ether, Ucar 35 butyl ether, the dipropylene glycol methyl ether.When using the mixed solvent of multiple composition, blending ratio can be mixed by arbitrary proportion.
Described neutralizing agent is selected from sodium hydroxide, Pottasium Hydroxide, ammoniacal liquor, Monoethanolamine MEA BASF, diethylolamine, trolamine, N, N-dimethylethanolamine or triethylamine.
Described basic soln is selected from sodium hydroxide, Pottasium Hydroxide or lithium hydroxide solution.
Get the liquid water soluble resin that embodiment 3 makes and detect, the result is following: this liquid water soluble resin detects viscosity through GB/T13217, detects solid content through GB/T1725, and pH is 7-9, and the correlation detection index is following:
| Color | Viscosity, s (25 ℃) | Solid content, % | First dryness mm | Attachment fastness % |
| Colourless | ≥25 | ≥40 | 25～50 | >;90 |
Claims (7)
1. the preparation method of a liquid water soluble resin is characterized in that, its step is following:
(1) be that basic soln and the monomer mixture of 3-10% drops in the purification tank and mix stirring with an amount of mass concentration, standing demix is after lower floor's buck layer emitted; In purification tank, add an amount of water, stir washing, standing demix; Lower aqueous layer is emitted, get the purifying monomer mixture; The initiator that in the purifying monomer mixture, adds the 0.5-2.5% of its weight, stirring and dissolving gets the premix monomer mixture; Described monomer mixture is by (methyl) vinylformic acid or its ester class, and at least a in vinyl monomer and the allyl monomer, perhaps adds the maleic anhydride or derivatives thereof again and forms, and the weight percent that each monomer accounts for monomer mixture is not less than 20%;
(2) in polymeric kettle, add the polymer solvent of the 10-50% of monomer mixture weight, the initiator of 0.1-0.5%; Be heated to stable the backflow, the premix monomer mixture slowly is added dropwise in the polymeric kettle, control reaction temperature is for stablizing reflux temperature; After drip finishing; Be incubated after 1-3 hour, in polymeric kettle, append the initiator of the 0.2-0.6% of monomer mixture weight, continue insulation 1-2 hour;
(3) material in the polymeric kettle is cooled to stops to reflux, in polymeric kettle, add neutralizing agent and the 40-60% edible ethanol of the 10-30% of monomer mixture weight again, filtration gets product.
2. the preparation method of liquid water soluble resin according to claim 1 is characterized in that: described vinyl monomer is selected from ethene, vinyl toluene, vinylbenzene, vinylchlorid, divinyl, vinyl acetate between to for plastic, butyric acid ethene, Whitfield's ointment ethene, vinyl n-butyl ether, vinyl isobutyl ether, terepthaloyl moietie ethene ether, hydroxyl butyl vinyl ether; Described allyl monomer is selected from allyl glyceroether, allyl group n-butyl ether; Described (methyl) esters of acrylic acid is selected from (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) Bing Xisuandingzhi, (methyl) vinylformic acid n-propyl, (methyl) NSC 20949, (methyl) tert-butyl acrylate, the just own ester of (methyl) vinylformic acid, (methyl) octadecyl acrylate, (methyl) vinylformic acid ethoxy ethyl ester; Described maleic anhydride verivate is selected from dibutyl maleinate, toxilic acid methyl esters, dimethyl maleate, ethyl maleate, itaconicacid.
3. the preparation method of liquid water soluble resin according to claim 1 is characterized in that: described initiator is peroxide initiator or azo-initiator.
4. the preparation method of liquid water soluble resin according to claim 3 is characterized in that: described peroxide initiator is selected from Lucidol BPO, Di Cumyl Peroxide 99, tertbutyl peroxide or peroxycarbonates; Described azo-initiator is selected from Diisopropyl azodicarboxylate AIBN, AMBN or ABVN.
5. the preparation method of liquid water soluble resin according to claim 1 is characterized in that: described polymer solvent is selected from the mixed solvent of one or more compositions in ethanol, propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol, propylene glycol monomethyl ether, Ucar 35 butyl ether, the dipropylene glycol methyl ether.
6. the preparation method of liquid water soluble resin according to claim 1 is characterized in that: described neutralizing agent is selected from sodium hydroxide, Pottasium Hydroxide, ammoniacal liquor, Monoethanolamine MEA BASF, diethylolamine, trolamine, N, N-dimethylethanolamine or triethylamine.
7. the preparation method of liquid water soluble resin according to claim 1 is characterized in that: described basic soln is selected from sodium hydroxide, Pottasium Hydroxide or lithium hydroxide solution.
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| Application Number | Priority Date | Filing Date | Title |
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| CN2011102169044A CN102358764A (en) | 2011-08-01 | 2011-08-01 | Preparation method for liquid water-soluble resin |
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| Application Number | Priority Date | Filing Date | Title |
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| CN2011102169044A CN102358764A (en) | 2011-08-01 | 2011-08-01 | Preparation method for liquid water-soluble resin |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102924648A (en) * | 2012-11-28 | 2013-02-13 | 常德市雄鹰科技有限责任公司 | Water-based resin for colouring aluminium-foil paper and preparation method for same |
| CN103084539A (en) * | 2012-12-07 | 2013-05-08 | 上海金兆节能科技有限公司 | Capillary mold oil for aluminum alloy casting crystallizer and preparation method of aluminum alloy casting capillary mold oil |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1997015604A1 (en) * | 1995-10-25 | 1997-05-01 | Elf Atochem S.A. | Finely particulate composite latices and use thereof in solvent-free paints |
| CN100999562A (en) * | 2006-12-29 | 2007-07-18 | 陕西科技大学 | Preparation process of non organic solvent type fluorine-containing soapless emulsion |
| CN102134296A (en) * | 2010-12-31 | 2011-07-27 | 江苏康泰氟化工有限公司 | Fluosilicic modification water-soluble acrylic resin dispersion and application thereof |
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2011
- 2011-08-01 CN CN2011102169044A patent/CN102358764A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1997015604A1 (en) * | 1995-10-25 | 1997-05-01 | Elf Atochem S.A. | Finely particulate composite latices and use thereof in solvent-free paints |
| CN100999562A (en) * | 2006-12-29 | 2007-07-18 | 陕西科技大学 | Preparation process of non organic solvent type fluorine-containing soapless emulsion |
| CN102134296A (en) * | 2010-12-31 | 2011-07-27 | 江苏康泰氟化工有限公司 | Fluosilicic modification water-soluble acrylic resin dispersion and application thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102924648A (en) * | 2012-11-28 | 2013-02-13 | 常德市雄鹰科技有限责任公司 | Water-based resin for colouring aluminium-foil paper and preparation method for same |
| CN102924648B (en) * | 2012-11-28 | 2014-05-07 | 常德市雄鹰科技有限责任公司 | Water-based resin for colouring aluminium-foil paper and preparation method for same |
| CN103084539A (en) * | 2012-12-07 | 2013-05-08 | 上海金兆节能科技有限公司 | Capillary mold oil for aluminum alloy casting crystallizer and preparation method of aluminum alloy casting capillary mold oil |
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Application publication date: 20120222 |