CN101857654B - Synthetic method of reactive emulsifier - Google Patents
Synthetic method of reactive emulsifier Download PDFInfo
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- CN101857654B CN101857654B CN2010102016186A CN201010201618A CN101857654B CN 101857654 B CN101857654 B CN 101857654B CN 2010102016186 A CN2010102016186 A CN 2010102016186A CN 201010201618 A CN201010201618 A CN 201010201618A CN 101857654 B CN101857654 B CN 101857654B
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Abstract
The invention discloses a synthetic method of a reactive emulsifier, which comprises the following steps: adding a hydroxyl-contained emulsifier, a carboxyl-contained unsaturated monomer, a dehydrating agent, a polymerization inhibitor, a catalyst and the like into a reaction kettle at room temperature, wherein the molar ratio of the hydroxyl-contained emulsifier to the carboxyl-contained unsaturated monomer is 1:1 to 2; then heating to reflux temperature, and controlling the reflux speed to enable the reflux speed to be smaller than 1 drop/second; heating to the temperature of 120 to 190 DEG C step by step, preserving heat for 1 to 2 hours, and measuring a hydroxyl value to be qualified; and finally cooling to the temperature of lower than 45 DEG C, and discharging to obtain the reactive emulsifier. The synthetic method of the reactive emulsifier of the invention has fewer steps and simple operation, is applicable for the method for synthesizing the reactive emulsifier through raw materials, such as all carboxyl-contained unsaturated monomers, hydroxyl-contained emulsifiers and the like, has less equipment investment and economic feasibility and is easy to realize industrialized production.
Description
Technical field
The present invention relates to fine chemical technology, be specifically related to a kind of compound method of reactive emulsifier.
Background technology
Along with the growing tension of the energy and increasingly sharpening of environmental issue, the Water-borne modification problem of needed vinyl resin of all industries such as weaving, leather, packing, coating, printing ink and auxiliary agent is urgent day by day.But there are the difference of many performances in aqueous product and traditional oil product, and like poor adhesive force, to store unstable, gloss relatively poor or the like, this improves with regard to the emulsifying agent that needs some specific functions.
The production of water-base resin in the market is many to be main with the free emulsifying agent, and the existence of free emulsifying agent tends to paint film in the system gloss, water tolerance exert an influence.
Summary of the invention
Goal of the invention: in order to overcome the deficiency that exists in the prior art; The present invention provides a kind of compound method of reactive emulsifier; A kind of reactive emulsifier of this method synthetic replaces part free emulsifying agent, for the water-borne acrylic resin series products provides special functional type raw material.
Technical scheme: for realizing above-mentioned purpose, the compound method of a kind of reactive emulsifier of the present invention is characterized in that may further comprise the steps:
(1) emulsifying agent of hydroxyl, carboxylic unsaturated monomer and dewatering agent, stopper, catalyzer are added reaction kettle, the emulsifying agent of said hydroxyl and the mol ratio of carboxylic unsaturated monomer are 1: 1～2;
(2) reaction kettle is warming up to reflux temperature, the control return velocity;
(3) progressively be warming up to 120～190 ℃, be incubated 1～2 hour, it is qualified to survey hydroxyl value to hydroxyl value, and promptly hydroxyl value is less than 5;
(4) be cooled to below 45 ℃, discharging promptly gets reactive emulsifier.
Said carboxylic unsaturated monomer is acrylic or methacrylic acid; Said dewatering agent is toluene, YLENE or hexanaphthene; Said stopper is one or both in Resorcinol or the p-ten.-butylcatechol; Said catalyzer is one or more in the dibutyl tin laurate vitriol oil, tosic acid, the heteropolyacid; Said return velocity is less than 1 droplet/second, and this moment, reaction relatively relaxed; Said reflux temperature is 78～180 ℃.
Beneficial effect: the compound method step of a kind of reactive emulsifier of the present invention is few; Simple to operate, emulsifying agent that is applicable to all carboxylic unsaturated monomers, hydroxyl etc. is the method for raw material building-up reactions property emulsifying agent, and facility investment is few; Economically feasible, easy realization of industrial production.
Embodiment
Below in conjunction with embodiment the present invention is done explanation further.
Embodiment 1
A kind of compound method of reactive emulsifier, composition of raw materials is following: NP-15:380g, vinylformic acid: 56g, dibutyl tin laurate T12:1.2g, Resorcinol: 3.5g, toluene: 300g.
A kind of compound method of reactive emulsifier, step is following:
In the time of (1) 17 ℃, in the 1000ml four-hole boiling flask, add 380g NP-15,300g toluene successively, add vinylformic acid, Resorcinol, warming while stirring down in stirring; When being warming up to 75 ℃, add T12, continue to heat up;
(2) when temperature rises to 115 ℃, begin to reflux, be incubated 0.5 hour;
(3) progressively be warming up to 117 ℃, reflux less this moment; Continue to heat up, the control return velocity is less than 1 droplet/second; When temperature arrives 132 ℃, distillate liquid 260g, be incubated 0.5 hour; Temperature arrives 134 ℃, continues slowly to heat up while stirring; When temperature arrives 162 ℃, be incubated 1 hour; When temperature reaches 167 ℃, measure hydroxyl value; When temperature reaches 152 ℃, hydroxyl value=4.8, cooling;
(4) when temperature was reduced to 45 ℃, discharging promptly got reactive emulsifier.
Embodiment 2
A kind of compound method of reactive emulsifier, composition of raw materials is following: NP-40:800g, methylacrylic acid: 70g, composite catalyst (mass ratio of tosic acid and heteropolyacid is 1: 1): 1.4g, composite polymerzation inhibitor (mass ratio of Resorcinol and p-ten.-butylcatechol is 2: 1): 1.5g, dewatering agent (mass ratio of toluene and YLENE is 2: 1): 350g
A kind of compound method of reactive emulsifier, step is following:
In the time of (1) 21 ℃, in the 2000ml four-hole boiling flask, add 800g NP-40,350g dewatering agent successively, add methylacrylic acid, composite polymerzation inhibitor, warming while stirring down in stirring; When temperature rises to 70 ℃, add composite catalyst, continue to heat up;
(2) when temperature rises to 113 ℃, begin to reflux, be incubated 0.5 hour;
(3) progressively be warming up to 115 ℃, reflux less this moment; Continue to heat up, the control return velocity is less than 1 droplet/second; When temperature arrives 134 ℃, distillate liquid 292g, be incubated 0.5 hour; Temperature reaches 134 ℃, continues slowly to heat up while stirring; When temperature reaches 172 ℃, be incubated 1 hour; When temperature arrives 171 ℃, measure hydroxyl value; When temperature reaches 172 ℃, hydroxyl value=3.7, cooling;
(4) when temperature was reduced to 45 ℃, discharging promptly got reactive emulsifier.
Embodiment 3
A kind of compound method of reactive emulsifier, composition of raw materials is following: AEO-9 (C12-14 alcohol mixture, EO=9): 700g, methylacrylic acid: 120g, the vitriol oil: 3.0g, composite polymerzation inhibitor (mass ratio of Resorcinol and p-ten.-butylcatechol is 1: 1): 2.0g, hexanaphthene: 600g
A kind of compound method of reactive emulsifier, step is following:
In the time of (1) 19 ℃, in the 2000ml four-hole boiling flask, add 700g AEO-9,600g hexanaphthene successively, add methylacrylic acid, composite polymerzation inhibitor, warming while stirring down in stirring; When temperature rises to 70 ℃, add concentrated sulfuric acid catalyst, continue to heat up;
(2) when temperature rises to 79 ℃, begin to reflux, be incubated 2 hours;
(3) progressively heating up, (the control return velocity is less than 1 droplet/second) to 110 ℃, reflux less this moment; Continue to heat up, when temperature arrives 140 ℃, do not have the liquid of distillating basically, be incubated 0.5 hour; Continue slowly to heat up while stirring; When temperature reaches 170 ℃, be incubated 1 hour; Measure hydroxyl value, hydroxyl value=4.2, cooling;
(4) when temperature was reduced to 45 ℃, discharging promptly got reactive emulsifier.
The above only is a preferred implementation of the present invention; Be noted that technician for the present technique field; Under the prerequisite that does not break away from the principle of the invention, can also make some improvement and retouching, these improvement and retouching also should be regarded as protection scope of the present invention.
Claims (5)
1. the compound method of a reactive emulsifier is characterized in that may further comprise the steps:
(1) emulsifying agent of hydroxyl, carboxylic unsaturated monomer and dewatering agent, stopper, catalyzer are added reaction kettle, the emulsifying agent of said hydroxyl and the mol ratio of carboxylic unsaturated monomer are 1: 1～2;
(2) reaction kettle is warming up to reflux temperature, the control return velocity;
(3) progressively be warming up to 120～190 ℃, be incubated 1～2 hour, survey hydroxyl value to hydroxyl value less than 5;
(4) be cooled to below 45 ℃, discharging promptly gets reactive emulsifier;
Said catalyzer is: one or more in dibutyl tin laurate, the vitriol oil, tosic acid, the heteropolyacid;
Said carboxylic unsaturated monomer is: acrylic or methacrylic acid.
2. the compound method of a kind of reactive emulsifier according to claim 1, it is characterized in that: said dewatering agent is: toluene, YLENE or hexanaphthene.
3. the compound method of a kind of reactive emulsifier according to claim 1, it is characterized in that: said stopper is: one or both in Resorcinol or the p-ten.-butylcatechol.
4. the compound method of a kind of reactive emulsifier according to claim 1 is characterized in that: return velocity is for less than 1 droplet/second in the said step (2).
5. the compound method of a kind of reactive emulsifier according to claim 1 is characterized in that: reflux temperature is 78～180 ℃ in the said step (2).
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| CN2010102016186A CN101857654B (en) | 2010-06-13 | 2010-06-13 | Synthetic method of reactive emulsifier |
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| CN101857654B true CN101857654B (en) | 2012-05-23 |
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| CN104030947B (en) * | 2014-06-12 | 2016-01-13 | 青岛科技大学 | A kind of sulfonate type reactive polymer emulsifying agent and its preparation method and application |
| CN106893518A (en) * | 2017-01-20 | 2017-06-27 | 南通苏宝建筑节能科技有限公司 | A kind of self-adhering-type glass fiber reticular cloth repaired for exterior-wall heat insulation |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1844211A (en) * | 2006-03-17 | 2006-10-11 | 中国科学院长春应用化学研究所 | Drip agent containing high active double bond and its preparation method and use |
| CN101497569A (en) * | 2008-12-30 | 2009-08-05 | 浙江皇马科技股份有限公司 | Method for synthesizing allyl alcohol polyoxyethylene ether methacrylate |
| CN101619543A (en) * | 2009-07-27 | 2010-01-06 | 成都德美精英化工有限公司 | Thickening agent synthesized by acrylic ester and preparation method thereof |
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2010
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1844211A (en) * | 2006-03-17 | 2006-10-11 | 中国科学院长春应用化学研究所 | Drip agent containing high active double bond and its preparation method and use |
| CN101497569A (en) * | 2008-12-30 | 2009-08-05 | 浙江皇马科技股份有限公司 | Method for synthesizing allyl alcohol polyoxyethylene ether methacrylate |
| CN101619543A (en) * | 2009-07-27 | 2010-01-06 | 成都德美精英化工有限公司 | Thickening agent synthesized by acrylic ester and preparation method thereof |
Non-Patent Citations (2)
| Title |
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| 张洁辉等."烷基酚聚氧乙烯醚丙烯酸酯共聚物表面活性剂的合成与性质".《精细石油化工》.1998,(第3期),14-19. |
| 李艳华等.《AM/AE/AA三元共聚物的合成》.《沈阳工业大学学报》.2000,第22卷(第6期),535-537. * |
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Application publication date: 20101013 Assignee: Changshou City spring polyurethane products Co., Ltd. Assignor: Suzhou Bona Chemical Technology Co., Ltd. Contract record no.: 2015320010130 Denomination of invention: Synthetic method of reactive emulsifier Granted publication date: 20120523 License type: Exclusive License Record date: 20150817 |
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