CN105085830A - Preparation method of high-water-resistant anti-freezing PUA resin - Google Patents
Preparation method of high-water-resistant anti-freezing PUA resin Download PDFInfo
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- CN105085830A CN105085830A CN201510497050.XA CN201510497050A CN105085830A CN 105085830 A CN105085830 A CN 105085830A CN 201510497050 A CN201510497050 A CN 201510497050A CN 105085830 A CN105085830 A CN 105085830A
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Abstract
The invention discloses a preparation method of high-water-resistant anti-freezing PUA resin. The method comprises the steps of polyurethane prepolymer preparation, double-bond end-sealing type polyurethane prepolymer preparation, double-bond end-sealing type polyurethane dispersion preparation, high-water-resistant anti-freezing PUA resin preparation and the like. A method for preparing high-water-resistant anti-freezing PUA resin comprises two steps of pre-emulsion preparation and emulsion polymerization, and a method for preparing polyurethane prepolymers comprises two steps of preparing a polyurethane prepolymer A and preparing a polyurethane prepolymer B. According to the preparation method of the high-water-resistant anti-freezing PUA resin, by controlling over the monomer ratio and adopting a method of using polyurethane for conducting graft modification of polyacrylic emulsion, the low-temperature self-crosslinking anti-freezing high-water-resistant PUA resin with a core-shell structure and the solid content ranging from 45% to 65% is synthesized, a solvent and an additional emulsifying agent are not needed in the synthesis reaction process, and environmental protection and energy saving are better achieved; the film-forming surface of the obtained high-water-resistant anti-freezing PUA resin is drier and makes a person feel more comfortable, the handfeel is softer, and the obtained high-water-resistant anti-freezing PUA resin is excellent in water-resistant performance, good in low-temperature-resistant performance and stronger in adhesive force.
Description
Technical field
The invention belongs to a kind of method that polyurethane-modified acrylic acid prepares PUA emulsion, be specifically related to the preparation method of the water-fast antifreeze PUA resin of height of a kind of printing mortar or spinning coating.Background technology
Current existing printing mortar and the following shortcoming of spinning coating ubiquity: 1, poor water resistance, particularly alkaline-resisting water poor performance; 2, to the poor adhesive force of waterproof nylon cloth, woven dacron; 3, surface is more sticky, not dry-ness, and feel is partially hard; 4, antifreeze ability.
Summary of the invention
For the deficiencies in the prior art, the present invention aims to provide that a kind of film formation surface is dry and comfortable, soft, resistance to low temperature is good, water resistance is high and the preparation method of the printing mortar be prepared into by polyurethane-modified acrylic acid of strong adhesion or the high water-fast antifreeze PUA resin of spinning coating.
For achieving the above object, the present invention adopts following technical scheme:
A preparation method for high water-fast antifreeze PUA resin, comprises the following steps:
Prepared by a, base polyurethane prepolymer for use as, by the building-up reactions acquisition base polyurethane prepolymer for use as under certain catalytic condition according to a certain percentage such as isocyanic ester, polyester polyol, polyether glycol, BDO, glycerol, DMPA;
Prepared by b, double bond terminated polyurethane prepolymer, namely adopt the base polyurethane prepolymer for use as synthesizing acquisition in Hydroxyethyl acrylate, hydroxypropyl acrylate, Isosorbide-5-Nitrae-butylene glycol and above-mentioned steps a to carry out end capping acquisition;
Prepared by c, double bond end-sealed type polyurethane dispersions, turn water by the double bond terminated polyurethane prepolymer obtained in step b with triethylamine, trolamine salify, obtained double bond end-sealed type polyurethane dispersions;
D, high water-fast antifreeze PUA resin-made are standby, namely using the obtained double bond end-sealed type polyurethane dispersions of step c as emulsifying agent, add vinylformic acid, ethyl propenoate, Hydroxyethyl acrylate, the monomer emulsifications such as methyl methacrylate, diethylene glycol acrylate, acrylamide are even, carry out emulsion polymerization, prepare high water-fast antifreeze PUA resin.
Further, the high water-fast antifreeze PUA resin-made of described steps d is standby comprises pre-emulsion preparation and emulsion polymerization two steps, namely pre-emulsion preparation adds vinylformic acid, ethyl propenoate in the double bond end-sealed type polyurethane dispersions that step c is obtained, Hydroxyethyl acrylate, the monomers such as methyl methacrylate, diethylene glycol acrylate, acrylamide, add deionized water under high velocity agitation and carry out dispersion and emulsion acquisition pre-emulsion;
Namely letex polymerization gets the pre-emulsion of above-mentioned 20% as seed emulsion, drip initiator simultaneously and remain 80% pre-emulsion and carry out letex polymerization, control temperature of reaction at 80 DEG C, 3 hours reinforced terminate follow-up continuation of insurance temperature 2 hours and adjust ph of lowering the temperature be 6-7 to reacting end, obtain the water-fast antifreeze PUA resin of height.
Further, described step a base polyurethane prepolymer for use as preparation comprises base polyurethane prepolymer for use as A preparation and base polyurethane prepolymer for use as B prepares two steps, base polyurethane prepolymer for use as A preparation isocyanic ester and polyester polyol, polyether glycol is synthesized by a certain percentage to obtain base polyurethane prepolymer for use as A under the catalyzed reaction of catalyzer, base polyurethane prepolymer for use as B preparation is that the building-up reactionss such as base polyurethane prepolymer for use as A and BDO, glycerol, DMPA are obtained base polyurethane prepolymer for use as B.
Further, described base polyurethane prepolymer for use as B and Hydroxyethyl acrylate, hydroxypropyl acrylate, Isosorbide-5-Nitrae-butylene glycol carry out end capping and obtain double bond terminated polyurethane prepolymer.
The present invention has following beneficial effect:
The preparation method of a kind of high water-fast antifreeze PUA resin of the present invention, solvent-free in its synthetic reaction process, without additional emulsifying agent, more environmental protection and energy saving; The structure that the water-fast antifreeze PUA resin of its height prepared is simultaneously take urethane as shell, vinylformic acid is core, film formation surface is dryer and comfortableer, feel is more soft, there is excellent water resistance and good resistance to low temperature, advantage that sticking power is stronger, be applicable to printing mortar or spinning coating, current printing mortar and poor, the antifreeze ability of the ubiquitous water resistance of spinning coating, poor adhesive force and dry-ness inadequate problem can be solved.
Accompanying drawing explanation
Fig. 1 is its preparation flow schematic diagram of preparation method of a kind of high water-fast antifreeze PUA resin of the present invention;
Fig. 2 is its concrete preparation flow schematic diagram of preparation method of a kind of high water-fast antifreeze PUA resin of the present invention.
Embodiment
Below in conjunction with drawings and the specific embodiments, the invention will be further described, understands the technological thought of application claims protection so that clearer.
The preparation method of a kind of high water-fast antifreeze PUA resin of the present invention as shown in Figure 1-2, comprises the following steps:
Prepared by a, base polyurethane prepolymer for use as, by the building-up reactions acquisition base polyurethane prepolymer for use as under certain catalytic condition according to a certain percentage such as isocyanic ester, polyester polyol, polyether glycol, BDO, glycerol, DMPA;
Prepared by b, double bond terminated polyurethane prepolymer, namely adopt the base polyurethane prepolymer for use as synthesizing acquisition in Hydroxyethyl acrylate, hydroxypropyl acrylate, Isosorbide-5-Nitrae-butylene glycol and above-mentioned steps a to carry out end capping acquisition;
Prepared by c, double bond end-sealed type polyurethane dispersions, turn water by the double bond terminated polyurethane prepolymer obtained in step b with triethylamine, trolamine salify, obtained double bond end-sealed type polyurethane dispersions;
D, high water-fast antifreeze PUA resin-made are standby, namely using the obtained double bond end-sealed type polyurethane dispersions of step c as emulsifying agent, add vinylformic acid, ethyl propenoate, Hydroxyethyl acrylate, the monomer emulsifications such as methyl methacrylate, diethylene glycol acrylate, acrylamide are even, carry out emulsion polymerization, prepare high water-fast antifreeze PUA resin.
Wherein more specifically, the high water-fast antifreeze PUA resin-made of steps d is standby comprises pre-emulsion preparation and emulsion polymerization two steps, namely pre-emulsion preparation adds vinylformic acid, ethyl propenoate in the double bond end-sealed type polyurethane dispersions that step c is obtained, Hydroxyethyl acrylate, the monomers such as methyl methacrylate, diethylene glycol acrylate, acrylamide, add deionized water under high velocity agitation and carry out dispersion and emulsion acquisition pre-emulsion;
Namely letex polymerization gets the pre-emulsion of above-mentioned 20% as seed emulsion, drip initiator simultaneously and remain 80% pre-emulsion and carry out letex polymerization, control temperature of reaction at 80 DEG C, 3 hours reinforced terminate follow-up continuation of insurance temperature 2 hours and adjust ph of lowering the temperature be 6-7 to reacting end, obtain the water-fast antifreeze PUA resin of height.
The preparation of step a base polyurethane prepolymer for use as comprises base polyurethane prepolymer for use as A preparation and base polyurethane prepolymer for use as B prepares two steps, base polyurethane prepolymer for use as A preparation isocyanic ester and polyester polyol, polyether glycol is synthesized by a certain percentage to obtain base polyurethane prepolymer for use as A under the catalyzed reaction of catalyzer, base polyurethane prepolymer for use as B preparation is that the building-up reactionss such as base polyurethane prepolymer for use as A and BDO, glycerol, DMPA are obtained base polyurethane prepolymer for use as B.Base polyurethane prepolymer for use as B and Hydroxyethyl acrylate, hydroxypropyl acrylate, Isosorbide-5-Nitrae-butylene glycol carry out end capping and obtain double bond terminated polyurethane prepolymer.
Principle of the present invention is: by the control of monomer ratio, adopt the method for polyurethane grafted modified acrylic acid emulsion, synthesize a kind of PUA resin with the antifreeze enhanced water resistance energy of nucleocapsid structure, the solid content low-temperature self-crosslinking type between 45%-65%, by adding the end-capping reagents such as excessive Hydroxyethyl acrylate in end capping, both ensure that thoroughly carrying out fast of end capping, again reduce the viscosity of base polyurethane prepolymer for use as, avoid the use of solubility promoter, be conducive to environmental protection and energy-conservation; Use as reactive emulsifier using double bond end-sealed type polyurethane dispersions in emulsion process, avoid additional emulsifying agent and both saved reaction cost, also improve the water resistance of the finished product; In reaction process, hydrophilic radical is mainly introduced in urethane end, can to obtain with urethane is shell, PUA emulsion that vinylformic acid is core, more can embody the dry and comfortable feature of polyaminoester emulsion film formation surface; Urethane, to acrylic acid modification, can promote the low temperature resistant performance of emulsion, and the introducing of crosslinked at low temperature monomer also makes this emulsion have low-temperature self-crosslinking.
When utilizing the water-fast antifreeze PUA resin embody rule of the height prepared by the inventive method, through inspection indices all by being up to the standards, concrete check data sees attached list 1-2:
Table 1:
Table 2:
For a person skilled in the art, according to technical scheme described above and design, other various corresponding change and distortion can be made, and all these change and distortion all should belong within the protection domain of the claims in the present invention.
Claims (4)
1. a preparation method for high water-fast antifreeze PUA resin, comprises the following steps:
Prepared by a, base polyurethane prepolymer for use as, by the building-up reactions acquisition base polyurethane prepolymer for use as under certain catalytic condition according to a certain percentage such as isocyanic ester, polyester polyol, polyether glycol, BDO, glycerol, DMPA;
Prepared by b, double bond terminated polyurethane prepolymer, namely adopt the base polyurethane prepolymer for use as synthesizing acquisition in Hydroxyethyl acrylate, hydroxypropyl acrylate, Isosorbide-5-Nitrae-butylene glycol and above-mentioned steps a to carry out end capping acquisition;
Prepared by c, double bond end-sealed type polyurethane dispersions, turn water by the double bond terminated polyurethane prepolymer obtained in step b with triethylamine, trolamine salify, obtained double bond end-sealed type polyurethane dispersions;
D, high water-fast antifreeze PUA resin-made are standby, namely using the obtained double bond end-sealed type polyurethane dispersions of step c as emulsifying agent, add vinylformic acid, ethyl propenoate, Hydroxyethyl acrylate, the monomer emulsifications such as methyl methacrylate, diethylene glycol acrylate, acrylamide are even, carry out emulsion polymerization, prepare high water-fast antifreeze PUA resin.
2. the preparation method of a kind of high water-fast antifreeze PUA resin as claimed in claim 1, is characterized in that:
The high water-fast antifreeze PUA resin-made of described steps d is standby comprises pre-emulsion preparation and emulsion polymerization two steps, namely pre-emulsion preparation adds vinylformic acid, ethyl propenoate in the double bond end-sealed type polyurethane dispersions that step c is obtained, Hydroxyethyl acrylate, the monomers such as methyl methacrylate, diethylene glycol acrylate, acrylamide, add deionized water under high velocity agitation and carry out dispersion and emulsion acquisition pre-emulsion;
Namely letex polymerization gets the pre-emulsion of above-mentioned 20% as seed emulsion, drip initiator simultaneously and remain 80% pre-emulsion and carry out letex polymerization, control temperature of reaction at 80 DEG C, 3 hours reinforced terminate follow-up continuation of insurance temperature 2 hours and adjust ph of lowering the temperature be 6-7 to reacting end, obtain the water-fast antifreeze PUA resin of height.
3. the preparation method of a kind of high water-fast antifreeze PUA resin as claimed in claim 1, it is characterized in that: described step a base polyurethane prepolymer for use as preparation comprises base polyurethane prepolymer for use as A preparation and base polyurethane prepolymer for use as B prepares two steps, base polyurethane prepolymer for use as A preparation isocyanic ester and polyester polyol, polyether glycol is synthesized by a certain percentage to obtain base polyurethane prepolymer for use as A under the catalyzed reaction of catalyzer, base polyurethane prepolymer for use as B preparation is that the building-up reactionss such as base polyurethane prepolymer for use as A and BDO, glycerol, DMPA are obtained base polyurethane prepolymer for use as B.
4. the preparation method of a kind of high water-fast antifreeze PUA resin as claimed in claim 3, it is characterized in that: described base polyurethane prepolymer for use as B and Hydroxyethyl acrylate, hydroxypropyl acrylate, Isosorbide-5-Nitrae-butylene glycol carry out end capping and obtain double bond terminated polyurethane prepolymer.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107938357A (en) * | 2017-12-04 | 2018-04-20 | 上海雅运纺织助剂有限公司 | A kind of Fabric Style finishing agent composition and preparation method thereof |
| CN109048698A (en) * | 2018-06-22 | 2018-12-21 | 阳江市伟艺抛磨材料有限公司 | A kind of polyurethane rubbing down wheel and preparation method thereof |
| CN114411429A (en) * | 2021-12-15 | 2022-04-29 | 安徽大学 | Electron beam cured waterproof moisture-permeable waterborne polyurethane fabric coating adhesive and preparation method thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101165075A (en) * | 2007-09-07 | 2008-04-23 | 香港生产力促进局 | Polyurethane-acrylic ester composite emulsion and preparation method thereof |
| CN101759841A (en) * | 2010-01-08 | 2010-06-30 | 合肥聚合辐化技术有限公司 | Method for polymerizing core-shell type aqueous polyurethane-polyacrylate (PUA) emulsion by in-situ radiation |
| CN101906192A (en) * | 2010-08-04 | 2010-12-08 | 中山大学 | Method for preparing aqueous polyurethane-acrylate composite emulsion |
| CN102093516A (en) * | 2010-12-28 | 2011-06-15 | 东莞市英科水墨有限公司 | Waterborne polyurethane-acrylate emulsion prepared by seed emulsion polymerization method |
| CN102492383A (en) * | 2011-11-18 | 2012-06-13 | 合肥工业大学 | Preparation method of nuclear shell water-based polyurethane-acrylate composite emulsion adhesive for polyolefin film composition |
| CN102838712A (en) * | 2012-09-20 | 2012-12-26 | 江苏荣昌新材料科技有限公司 | Preparation method of hydroxyl-terminated aqueous core shell emulsion for anticorrosive paint |
| CN102898592A (en) * | 2012-09-11 | 2013-01-30 | 青岛文创科技有限公司 | Preparation method for acrylate-modified waterborne polyurethane |
-
2015
- 2015-08-13 CN CN201510497050.XA patent/CN105085830A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101165075A (en) * | 2007-09-07 | 2008-04-23 | 香港生产力促进局 | Polyurethane-acrylic ester composite emulsion and preparation method thereof |
| CN101759841A (en) * | 2010-01-08 | 2010-06-30 | 合肥聚合辐化技术有限公司 | Method for polymerizing core-shell type aqueous polyurethane-polyacrylate (PUA) emulsion by in-situ radiation |
| CN101906192A (en) * | 2010-08-04 | 2010-12-08 | 中山大学 | Method for preparing aqueous polyurethane-acrylate composite emulsion |
| CN102093516A (en) * | 2010-12-28 | 2011-06-15 | 东莞市英科水墨有限公司 | Waterborne polyurethane-acrylate emulsion prepared by seed emulsion polymerization method |
| CN102492383A (en) * | 2011-11-18 | 2012-06-13 | 合肥工业大学 | Preparation method of nuclear shell water-based polyurethane-acrylate composite emulsion adhesive for polyolefin film composition |
| CN102898592A (en) * | 2012-09-11 | 2013-01-30 | 青岛文创科技有限公司 | Preparation method for acrylate-modified waterborne polyurethane |
| CN102838712A (en) * | 2012-09-20 | 2012-12-26 | 江苏荣昌新材料科技有限公司 | Preparation method of hydroxyl-terminated aqueous core shell emulsion for anticorrosive paint |
Non-Patent Citations (5)
| Title |
|---|
| 徐培林 等: "《聚氨酯材料手册》", 31 July 2002, 北京：化学工业出版社 * |
| 朱万强: "《涂料基础教程》", 30 June 2012, 成都：西南交通大学出版社 * |
| 王国建 等: "《建筑涂料与涂装》", 30 April 2002, 北京：中国轻工业出版社 * |
| 耿耀宗: "《现代水性涂料：工艺 配方 应用》", 31 March 2003, 北京：中国石化出版社 * |
| 耿耀宗: "《现代水性涂料工艺 配方 应用 第二版》", 30 April 2013, 北京：中国石化出版社 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107938357A (en) * | 2017-12-04 | 2018-04-20 | 上海雅运纺织助剂有限公司 | A kind of Fabric Style finishing agent composition and preparation method thereof |
| CN107938357B (en) * | 2017-12-04 | 2020-01-10 | 上海雅运新材料有限公司 | Fabric style finishing agent composition and preparation method thereof |
| CN109048698A (en) * | 2018-06-22 | 2018-12-21 | 阳江市伟艺抛磨材料有限公司 | A kind of polyurethane rubbing down wheel and preparation method thereof |
| CN114411429A (en) * | 2021-12-15 | 2022-04-29 | 安徽大学 | Electron beam cured waterproof moisture-permeable waterborne polyurethane fabric coating adhesive and preparation method thereof |
| CN114411429B (en) * | 2021-12-15 | 2023-06-20 | 安徽大学 | Electron beam curing waterproof moisture-permeable aqueous polyurethane fabric coating adhesive and preparation method thereof |
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Application publication date: 20151125 |