CN102504228A - Method for preparing non-ionic hyperbranched linear polymer emulsifier - Google Patents
Method for preparing non-ionic hyperbranched linear polymer emulsifier Download PDFInfo
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- CN102504228A CN102504228A CN2011103521295A CN201110352129A CN102504228A CN 102504228 A CN102504228 A CN 102504228A CN 2011103521295 A CN2011103521295 A CN 2011103521295A CN 201110352129 A CN201110352129 A CN 201110352129A CN 102504228 A CN102504228 A CN 102504228A
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- hyperbranched
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- trimethylolpropane
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Abstract
The invention relates to a method for preparing a non-ionic hyperbranched linear polymer emulsifier. The invention adopts a technical scheme which comprises: 1, a step of preparing a hyperbranched polymer monomer, which is to drip methyl acrylate into a methanol solution of diethanol amine according to a molar ratio of methyl acrylate to diethanol amine of (1-3):1, stir the solution for 3 to 6 hours at 15 to 60 DEG C, and vacuumize for 1 hour under a pressure of 0.01 to 1MPa; 2, a step of preparing hyperbranched polymer, which is to mix trimethylolpropane and an acid catalyst at 115 DEG C with stirring, drip the monomer into the trimethylolpropane according to a monomer to trimethylolpropane ratio of (9-3):1, react the monomer with the trimethylolpropane for 1 to 2 hours at 100 to 130 DEG C with stirring, and rotationally evaporate the reaction solution at 120 to 150 DEG C under a pressure of 0.01 to 1MPa; and 3, a step of reacting a hydroxyl-terminated hyperbranched polymer with a hydrophobic group with a long chain in the presence of an acid catalyst to obtain the non-ionic hyperbranched linear polymer emulsifier.
Description
Technical field
The present invention relates to a kind of preparation method of hyperbranched polymer emulsifying agent, particularly a kind of non-ionic type is hyperbranched-preparation method of linear polymer emulsifying agent.
Background technology
Emulsifying agent is meant and improves the surface tension between the various compositions in the emulsification system, forms the material of dispersed system or emulsification system, is one type of tensio-active agent with hydrophilic group and hydrophobic group.Since coming out, get more and more people's extensive concerning always, the every field from common daily necessities to industry has all obtained using widely.But Along with people's improves constantly various product demand, and emulsifier type has also obtained continuous expansion.Wherein polymeric surface active agent has all shown emulsifying capacity and emulsifying stability preferably all the time; In addition; Polymeric surface active agent also has good distribution, cohesion, compatibilization ability, water retention, thickening power, film-forming properties and adhesive power; The application widely that obtains in the emulsifying agent field, as: the polyoxyethylene sorbitan fatty ester of tween series has all obtained good application in a lot of fields.But macromolecule emulsifier shows lower surfactivity usually; Higher viscosity; Relatively poor flowability and soil removability; Foaming power and seepage force are also all good inadequately, this for polymeric surface active agent some field application brought very big inconvenience, and these shortcomings all have very confidential relation with high molecular long-chain shape structure.Traditional emulsifying agent all is based on the lipophilic chain surfactant structure of the hydrophilic end of an end, perhaps has the tensio-active agent of two hydrophilic and oleophilic groups as Gemini surface active agent.
Summary of the invention
The purpose of this invention is to provide a kind of hyperbranched-preparation method of linear polymer emulsifying agent, good inadequately to improve in the macromolecule emulsifier seepage force, viscosity is big, and is mobile bad, shortcomings such as molecular chain easy entanglement.
A kind of non-ionic type is hyperbranched-preparation method of linear polymer emulsifying agent, and its process step is following successively:
1, the monomer of hyperbranched polymer preparation: the mol ratio of methyl acrylate according to methyl acrylate and diethylolamine 1 ~ 3:1 is added drop-wise in the methanol solution of diethylolamine; 15 ~ 60 ℃ were stirred 3 ~ 6 hours down; 0.01 vacuumized under ~ 1MPa the pressure 1 hour; Obtain the monomer of hyperbranched polymer, subsequent use.
2, the preparation of hyperbranched polymer: mix with under 115 ℃ of TriMethylolPropane(TMP) and an acidic catalysts; Be that the ratio of 9 ~ 3:1 drips monomer to TriMethylolPropane(TMP) according to above-mentioned monomer and TriMethylolPropane(TMP) mol ratio then; 100 ~ 130 ℃ of following stirring reactions 1 ~ 2 hour change Rotary Evaporators at 120 ~ 150 ℃, and 0.01 ~ 1MPa pressure underspin steamed 1 ~ 3 hour; Obtain the superbrnaching end-hydroxy polymkeric substance, wherein the massfraction of an acidic catalyst is 0.5 ~ 4% of a total mass;
3, the preparation of hyperbranched polymer emulsifying agent: the superbrnaching end-hydroxy polymkeric substance that obtains in the said step 2 under an acidic catalyst catalysis and the hydrophobic grouping reaction that has a long-chain to make a kind of hydrophilic radical be hydroxyl, hydrophobic grouping be the non-ionic type of long chain alkane hyperbranched-the linear polymer emulsifying agent.
As 1; The hydrophobic grouping that has long-chain in above-mentioned the 3rd step be meant the lipid acid that contains carboxyl or acyl chlorides or fat acyl chloride and can with the long chain alkyl group of hydroxyl reaction; With the hyperbranched polymer of terminal hydroxy group type with have the mixed in molar ratio of the hydrophobic grouping of long-chain by 1 ~ 9:1; At 100 ~ 150 ℃, reacted under 0.01 ~ 1MPa condition 1 ~ 5 hour, make a kind of non-ionic type hyperbranched-the linear polymer emulsifying agent.
Above-mentioned an acidic catalyst is meant the vitriol oil, tosic acid or exsiccant hydrochloric acid.
With respect to prior art, the present invention introduces the hydrophobic grouping that has long-chain on the end group top of synthetic superbrnaching end-hydroxy polymkeric substance, utilizes the hydrophobic performance of hyperbranched polymer terminal hydroxy group wetting ability and long-chain, in solution, forms stable emulsion.Because the spheroid shape structure of hyperbranched polymer forms stable unimolecular micelle easily, the hydrophilic hydrophobic characteristic of multiterminal makes it have tensio-active agent preferably simultaneously, and the cavity structure of hyperbranched polymer can well be realized emulsive stability.Thereby obtain the hydrophilic hydrophobic hyperbranched-linear polymer emulsifying agent of multiterminal.
Embodiment:
Instance 1:
At first the 1mol diethylolamine is dissolved in a certain amount of methyl alcohol, drips the 2mol methyl acrylate, 35 ℃ were stirred 4 hours down, and vacuum filtration is 1 hour under the 0.08MPa, obtains preparing the monomer of hyperbranched polymer.
Mix under 115 ℃ of TriMethylolPropane(TMP) and the tosic acid; Be that the ratio of 6:1 drips monomer to TriMethylolPropane(TMP) according to above-mentioned monomer and TriMethylolPropane(TMP) mol ratio then; 100 ℃ of following stirring reactions 1 hour change Rotary Evaporators at 120 ℃, and 0.01MPa pressure underspin steamed 3 hours; Obtain the superbrnaching end-hydroxy polymkeric substance, wherein the massfraction of tosic acid is 2% of a total mass;
With the mixed in molar ratio that superbrnaching end-hydroxy polymkeric substance and oleic acid are pressed 3:1, at 100 ℃, pressure is that 0.01MPa pressure underspin steamed 3 hours.Obtain non-ionic type hyperbranched-the linear polymer emulsifying agent.
Instance 2:
The 1mol diethylolamine is dissolved in a certain amount of methyl alcohol, drips the 3mol methyl acrylate, 15 ℃ of stirring reactions 6 hours vacuumized under the 0.5MPa pressure 1 hour, obtained preparing the monomer of hyperbranched polymer,
Mix under 115 ℃ of TriMethylolPropane(TMP) and the tosic acid; Be that the ratio of 4:1 drips monomer to TriMethylolPropane(TMP) according to above-mentioned monomer and TriMethylolPropane(TMP) mol ratio then; 110 ℃ of following stirring reactions 1.5 hours change Rotary Evaporators at 130 ℃, and 0.1MPa pressure underspin steamed 1.5 hours; Obtain the superbrnaching end-hydroxy polymkeric substance, wherein the massfraction of tosic acid is 0.5% of a total mass;
With hyperbranched polymer and the Triple Pressed Stearic Acid ratio in 2:1, at 140 ℃, 0.05MPa pressure underspin steamed 5 hours, obtain non-ionic type hyperbranched-the linear polymer emulsifying agent.
Instance 3:
Diethylolamine is dissolved in a certain amount of methyl alcohol; Is that the ratio of 2:1 drops in the methanol solution of diethylolamine with methyl acrylate according to methyl acrylate and diethylolamine mol ratio; 35 ℃ were stirred 4 hours down; Pressure is to vacuumize 1 hour under the pressure of 0.1MPa, obtains preparing the monomer of hyperbranched polymer.
Mix under 115 ℃ of TriMethylolPropane(TMP) and the exsiccant hydrochloric acid; Be that the ratio of 3:1 drips monomer to TriMethylolPropane(TMP) according to above-mentioned monomer and TriMethylolPropane(TMP) mol ratio then; 130 ℃ of following stirring reactions 1.5 hours change Rotary Evaporators at 150 ℃, and 0.5MPa pressure underspin steamed 3 hours; Obtain the superbrnaching end-hydroxy polymkeric substance, wherein the massfraction of tosic acid is 4% of a total mass;
Is that the ratio of 5:1 adds in the flask with palmityl chloride according to superbrnaching end-hydroxy polymkeric substance and palmityl chloride mol ratio, and 150 ℃, rotary evaporation is 1 hour under the 1MPa pressure, obtain non-ionic type hyperbranched-the linear polymer tensio-active agent.
Instance 4:
Is that the mixed of 1:1 is even with diethylolamine and methyl alcohol according to volume ratio, the dropwise addition of acrylic acid methyl esters, and wherein methyl acrylate and diethylolamine mol ratio are 3:1; Stirring reaction is 3 hours under 45 ℃ of conditions; Vacuumized under the 1MPa pressure 1 hour, and obtained the monomer of hyperbranched polymer, subsequent use.
Mix under 115 ℃ of TriMethylolPropane(TMP) and the vitriol oils; Be that the ratio of 3:1 drips monomer to TriMethylolPropane(TMP) according to above-mentioned monomer and TriMethylolPropane(TMP) mol ratio then; 115 ℃ of following stirring reactions 1.5 hours change Rotary Evaporators at 130 ℃, and 1MPa pressure underspin steamed 1 hour; Obtain the superbrnaching end-hydroxy polymkeric substance, wherein the massfraction of the vitriol oil is 2% of a total mass;
With oleoyl chloride and superbrnaching end-hydroxy polymkeric substance mol ratio is that the oleoyl chloride of 3:1 is added drop-wise in the above-mentioned hyperbranched polymer, and 110 ℃, reaction is 2 hours under the 0.01MPa condition, obtain non-ionic type hyperbranched-the linear polymer emulsifying agent.
Instance 5:
Is that the mixed of 1:2 is even with diethylolamine and methyl alcohol according to volume ratio, the dropwise addition of acrylic acid methyl esters, and wherein methyl acrylate and diethylolamine mol ratio are 2:1; Stirring reaction is 3 hours under 60 ℃ of conditions; 0.01MPa vacuumized under the pressure 1 hour, obtain the monomer of hyperbranched polymer, subsequent use.
Mix under 115 ℃ of TriMethylolPropane(TMP) and the vitriol oils; Be that the ratio of 9:1 drips monomer to TriMethylolPropane(TMP) according to above-mentioned monomer and TriMethylolPropane(TMP) mol ratio then; 115 ℃ of following stirring reactions 2 hours change Rotary Evaporators at 130 ℃, and 0.05MPa pressure underspin steamed 1 hour; Obtain the superbrnaching end-hydroxy polymkeric substance, wherein the massfraction of the vitriol oil is 3% of a total mass;
With stearoyl chlorine and superbrnaching end-hydroxy polymkeric substance mol ratio is that the stearoyl chlorine of 5:1 is added drop-wise in the above-mentioned hyperbranched polymer, and 115 ℃, reaction is 4 hours under the 0.01MPa condition, obtain non-ionic type hyperbranched-the linear polymer emulsifying agent.
Claims (3)
- A non-ionic type hyperbranched-preparation method of linear polymer emulsifying agent, it is characterized in that: its process step is following successively:1) monomer of hyperbranched polymer preparation: the mol ratio of methyl acrylate according to methyl acrylate and diethylolamine 1 ~ 3:1 is added drop-wise in the methanol solution of diethylolamine; 15 ~ 60 ℃ were stirred 3 ~ 6 hours down; 0.01 suction filtration is 1 hour under the ~ 1MPa pressure, obtains the monomer of hyperbranched polymer, and is subsequent use;2) preparation of hyperbranched polymer: mix with under 115 ℃ of TriMethylolPropane(TMP) and an acidic catalysts; Be that the ratio of 9 ~ 3:1 drips monomer to TriMethylolPropane(TMP) according to above-mentioned monomer and TriMethylolPropane(TMP) mol ratio then; 100 ~ 130 ℃ of following stirring reactions 1 ~ 2 hour change Rotary Evaporators at 120 ~ 150 ℃, and 0.01 ~ 1MPa pressure underspin steamed 1 ~ 3 hour; Obtain the superbrnaching end-hydroxy polymkeric substance, wherein the massfraction of an acidic catalyst is 0.5 ~ 4% of a total mass;3) preparation of hyperbranched polymer emulsifying agent: the superbrnaching end-hydroxy polymkeric substance that obtains in the said step 2 under an acidic catalyst catalysis and the hydrophobic grouping reaction that has a long-chain to make a kind of hydrophilic radical be hydroxyl, hydrophobic grouping be the non-ionic type of long chain alkane hyperbranched-the linear polymer emulsifying agent.
- 2. a kind of non-ionic type as claimed in claim 1 is hyperbranched-preparation method of linear polymer emulsifying agent; It is characterized in that: the above-mentioned the 3rd) hydrophobic grouping that has long-chain in the step be meant the lipid acid that contains carboxyl or acyl chlorides or fat acyl chloride and can with the long chain alkyl group of hydroxyl reaction; With the hyperbranched polymer of terminal hydroxy group type with have the mixed in molar ratio of the hydrophobic grouping of long-chain by 1 ~ 9:1; At 100 ~ 150 ℃; 0.01 reacted under ~ 1MPa the condition 1 ~ 5 hour, make a kind of non-ionic type hyperbranched-the linear polymer emulsifying agent.
- According to claim 1 or claim 2 a kind of non-ionic type hyperbranched-preparation method of linear polymer emulsifying agent, it is characterized in that: said an acidic catalyst is meant the vitriol oil, tosic acid or exsiccant hydrochloric acid.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106832312A (en) * | 2016-12-16 | 2017-06-13 | 济南大学 | A kind of application of hyperbranched emulsion in soil-less breeding |
| CN110330638A (en) * | 2019-07-09 | 2019-10-15 | 陕西科技大学 | A kind of epoxy terminated dissaving polymer, preparation method and application |
| CN115466035A (en) * | 2022-08-15 | 2022-12-13 | 中国石油大学(北京) | Composition for reduction treatment of oily sludge and reduction treatment method of oily sludge |
| CN118684840A (en) * | 2024-08-22 | 2024-09-24 | 余姚市远东化工有限公司 | Easily-separated rubber release agent and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101240072A (en) * | 2008-01-08 | 2008-08-13 | 上海大学 | Method for synthesizing polyurethane/polyacrylate ionomer emuldion |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101240072A (en) * | 2008-01-08 | 2008-08-13 | 上海大学 | Method for synthesizing polyurethane/polyacrylate ionomer emuldion |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106832312A (en) * | 2016-12-16 | 2017-06-13 | 济南大学 | A kind of application of hyperbranched emulsion in soil-less breeding |
| CN106832312B (en) * | 2016-12-16 | 2020-04-03 | 济南大学 | Application of hyperbranched emulsion in soilless culture |
| CN110330638A (en) * | 2019-07-09 | 2019-10-15 | 陕西科技大学 | A kind of epoxy terminated dissaving polymer, preparation method and application |
| CN115466035A (en) * | 2022-08-15 | 2022-12-13 | 中国石油大学(北京) | Composition for reduction treatment of oily sludge and reduction treatment method of oily sludge |
| CN115466035B (en) * | 2022-08-15 | 2023-12-19 | 中国石油大学(北京) | Composition for reducing oily sludge and method for reducing oily sludge |
| CN118684840A (en) * | 2024-08-22 | 2024-09-24 | 余姚市远东化工有限公司 | Easily-separated rubber release agent and preparation method thereof |
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