CN103421183A - Reaction type greasy base degradable surfactant as well as synthetic method and application thereof - Google Patents
Reaction type greasy base degradable surfactant as well as synthetic method and application thereof Download PDFInfo
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Abstract
The invention discloses a reaction type greasy base degradable surfactant as well as a synthetic method and application thereof. Polyether blocks and unsaturated double bonds are introduced in grease, so that the prepared degradable surfactant can be used for conventional emulsion polymerization and miniemulsion polymerization, as a result, stable polymer latex can be obtained. According to the invention, the price of production raw material is low, the preparation process is simple and feasible and environment-friendly, and a new approach is provided for the preparation of biodegradable latex.
Description
Technical field
The present invention relates to a kind of tensio-active agent, relate in particular to a kind of response type fat-based degradable tensio-active agent and synthetic method and application.
Background technology
In the polymer latex preparation process, usually need to use tensio-active agent, emulsion particle can stably be scattered in water.But, even our recent research shows in latex the polymeric film that exists a small amount of tensio-active agent also can form latex and has a huge impact, existence due to tensio-active agent, make the easy moisture absorption of polymeric film and whiten, simultaneously, tensio-active agent is along with the volatilization of moisture is moved, and be enriched in polymer film surface, the polymeric film performance is sharply descended, as used the sodium lauryl sulphate of monomer consumption 4% in the polybutylacrylate latex polymerization, after moisture evaporation, the sodium lauryl sulphate concentration on butyl polyacrylate film surface is up to 28%, the tack of the pressure sensitive adhesive that uses this latex to prepare descends up to 75%.Therefore, scientists is called the tensio-active agent used in letex polymerization " necessary devil ".
In order to solve the negative impact of tensio-active agent to polymeric film, a large amount of scientific research personnel have set up the database of a system, for instructing people, are that polymerized emulsion is selected suitable emulsification system, to reducing migration and the enrichment problem of tensio-active agent.Yet, because tensio-active agent and polymkeric substance are ten hundreds of in the world, this work is wasted time and energy.
The effective way that the problems referred to above solve is to use response type surfactant active, it both can make emulsifying agent, again can with letex polymerization in monomer generation copolymerization, make tensio-active agent can be fixed on the latex particle surface, thereby effectively solve surfactant migration after the polymer latex film forming and the problem of enrichment.On this basis, the preparation by biomass for response type surfactant active, provide a kind of method of Biodegradable material being introduced to the latex polymer main chain.
But the most response type surfactant active is all because of the too high industrial applications that is unsuitable for of cost.
Summary of the invention
The object of the invention is to for the deficiencies in the prior art, a kind of response type fat-based degradable tensio-active agent and synthetic method and application are provided.
The objective of the invention is to be achieved through the following technical solutions: a kind of response type fat-based degradable tensio-active agent, it contains the response type group that can participate in radical polymerization, and its structural formula is as follows:
In formula, n=1-1000, y=1-3, x+2y+z=15.
A kind of synthetic method of above-mentioned response type fat-based degradable tensio-active agent comprises the following steps:
(1) hydrolysate oil: the acid catalyst that is 15-35% by 50 mass parts mass concentrations mixes with 30-70 mass parts ethanol, join in reactor, be warming up to 50-100 ℃, in in 0.5-12 hour, 20-60 part drip of grease being added to reactor while stirring, be cooled to room temperature after insulation reaction 0.5-24 hour, stratification, get upper strata liquid washing 5 times, obtains lipid acid;
(2) lipid acid and polyethers esterification: the lipid acid that 30-100 mass parts step 1 is obtained and be dissolved in 100 mass parts toluene with the polyethers of the molfractions such as lipid acid, add in reactor, splash into 0.01-0.5 mass parts acid catalyst, warming while stirring is to 50-150 ℃, stirring reaction 0.5-24 hour, after having reacted, 50-100 ℃ vacuumizes and removes toluene, then drips the NaHCO that massfraction is 30%
3The aqueous solution is until system no longer includes bubble formation; Add again 50-500 mass parts water and 50-500 mass parts CH
2Cl
2, stir, and add the NaCl aqueous solution that the mass concentration of 1-10 mass parts is 30%, stratification, taking precipitate, the MgSO that the mass concentration that adds while stirring the 1-10 mass parts is 30%
4The aqueous solution, finally, with deionized water washing 5 times, obtain the fatty acid polyglycol ether compound;
(3) 50-100 mass parts step 2 gained fatty acid polyglycol ether compound is dissolved in to 100 mass parts toluene, add in reactor, add while stirring with fatty acid polyglycol ether compound equimolar amount containing the carboxylic acid of unsaturated double-bond, containing the acid anhydrides of unsaturated double-bond or containing the acyl chlorides of unsaturated double-bond, add 0.01-0.5 mass parts acid catalyst and 0.01-0.1 mass parts Resorcinol, be heated to while stirring 50-150 ℃, insulation reaction 0.5-24 hour, obtain response type fat-based biodegradable tensio-active agent.
A kind of synthetic method of above-mentioned response type fat-based degradable tensio-active agent, the method is specially: by 50-100 mass parts PEG400-oleic acid acrylate, PEG400-linolic acid acrylate or PEG400-linolenic acid acrylate are dissolved in 100 mass parts toluene, add in reactor, add while stirring and PEG400-oleic acid acrylate, the carboxylic acid containing unsaturated double-bond of PEG400-linolic acid acrylate or PEG400-linolenic acid acrylate equimolar amount, containing the acid anhydrides of unsaturated double-bond or containing the acyl chlorides of unsaturated double-bond, add 0.01-0.5 mass parts acid catalyst and 0.01-0.1 mass parts Resorcinol, be heated to while stirring 50-150 ℃, insulation reaction 0.5-24 hour, obtain response type fat-based degradable tensio-active agent
.
Further, described acid catalyst is perchloric acid, hydroiodic acid HI, sulfuric acid, Hydrogen bromide, hydrochloric acid, nitric acid, acid iodide, oxalic acid, sulfurous acid, phosphoric acid, pyruvic acid, carbonic acid, nitrous acid, citric acid, hydrofluoric acid, oxysuccinic acid, gluconic acid, formic acid, acetic acid, propionic acid, butyric acid, valeric acid or caproic acid.
Further, described grease is vegetables oil or animal oil or their mixture, and vegetables oil comprises soybean oil, Viscotrol C, linseed oil, sunflower oil, Semen Maydis oil, rapeseed oil, Oleum Cocois, plam oil or Thistle oil or the mixture of the above grease; Animal oil comprises lard, butter, fish oil or sheep oil or the mixture of the above grease.
Further, the multipolymer that described polyethers is polyoxyethylene glycol (PEG), polypropylene glycol, ethylene glycol and propylene glycol or the blend of polyoxyethylene glycol and polypropylene glycol.
Further, the described carboxylic acid containing unsaturated double-bond is vinylformic acid, methacrylic acid, toxilic acid, fumaric acid or methylene-succinic acid; The described acid anhydrides containing unsaturated double-bond is acrylic anhydride, methacrylic anhydride, maleic anhydride, fumaric acid anhydride or itaconic anhydride; The described acyl chlorides containing unsaturated double-bond is acrylate chloride or methacrylic chloride.
A kind of application of above-mentioned response type fat-based degradable tensio-active agent, described response type fat-based degradable tensio-active agent can be used as the emulsifying agent of conventional emulsion polymerization or mini-emulsion polymerization, for the preparation of polymer emulsion; Application process is as follows: 100 mass parts monomers, 0.1-20 mass parts response type fat-based degradable tensio-active agent and 100-1000 mass parts water are mixed, after letting nitrogen in and deoxidizing, add while stirring 0.05-1 mass parts initiator, 30-90 ℃ of lower polymerase 10 .5-48 hour, obtain polymer emulsion.
Further, described monomer by vinylbenzene, vinyl acetate, vinyl ester, esters of acrylic acid, methyl acrylic ester, divinyl, isoprene,
One or more of-alkene, chloroprene, alpha-methyl styrene, vinylchlorid, vinylidene chloride, vinyl cyanide, vinylformic acid, methacrylic acid, maleic anhydride or alkyl vinyl ether mix and form by any proportioning.
Further, described initiator comprises peroxide initiator, azo-initiator, oxidation-reduction initiator, photochemical initiators etc.; Described peroxide initiator comprises ammonium persulphate, Potassium Persulphate etc.; Described azo-initiator comprises 4,4 '-azo two (4-cyanopentanoic acid), azo diisobutyl amidine hydrochlorides, azo di-isopropyl imidazoline salt hydrochlorate, azo di-isopropyl tetrahydroglyoxaline etc.; The compound system that described oxidation-reduction initiator is superoxide and reductive agent; Described superoxide is Potassium Persulphate, ammonium persulphate etc., and described reductive agent is S-WAT, sodium bisulfite, sodium formaldehyde sulphoxylate etc.; Described photochemical initiators is 2-hydroxyl-1-[4-(hydroxyl) phenyl]-2-methyl isophthalic acid-acetone.
The invention has the beneficial effects as follows: the present invention has synthesized a kind of novel surface reactive monomer of environmental protection, and, by emulsion polymerization way, prepares stable polymer latex.Cheap being easy to get of synthesis of surfactant cost of material that the present invention is synthetic, raw material sources extensively and environmental protection.Its preparation method is fairly simple to be easy to get.Prepared tensio-active agent has the biodegradable performance, is beneficial to environmental protection.Can be widely used in preparing various emulsions and latex, prepared emulsion and latex can be used for the product (Wound care dressing that medical facilities, stamp, adhesive tape, label, notepad directly contact with skin with some, ECG electrode, breathable adhesive tape, analgesic agent and dermatologic medicine paste), also can be used for micro-fluidic medical facilities or stamp.The present invention has positive promoter action to exploitation, protection of the environment and the letex polymerization industry of the tensio-active agent of letex polymerization.
Embodiment
The present invention is preparation feedback type fat-based biodegradable tensio-active agent and for conventional emulsion polymerization or mini-emulsion polymerization by the following method.
The synthetic method of a kind of fat-based degradable tensio-active agent provided by the invention comprises the following steps:
1. hydrolysate oil: the acid catalyst that is 15-35% by 50 mass parts mass concentrations mixes with 30-70 mass parts ethanol, join in reactor, be warming up to 50-100 ℃, in in 0.5-12 hour, 20-60 part drip of grease being added to reactor while stirring, be cooled to room temperature after insulation reaction 0.5-24 hour, stratification, get upper strata liquid washing 5 times, obtains lipid acid;
2. lipid acid and polyethers esterification: the lipid acid that 30-100 mass parts step 1 is obtained and be dissolved in 100 mass parts toluene with the polyethers of the molfractions such as lipid acid, add in reactor, splash into 0.01-0.5 mass parts acid catalyst, warming while stirring is to 50-150 ℃, stirring reaction 0.5-24 hour, after having reacted, 50-100 ℃ vacuumizes and removes toluene, then drips the NaHCO that massfraction is 30%
3The aqueous solution is until system no longer includes bubble formation.Add again 50-500 mass parts water and 50-500 mass parts CH
2Cl
2, stir, and add the NaCl aqueous solution that the mass concentration of 1-10 mass parts is 30%, stratification, taking precipitate, the MgSO that the mass concentration that adds while stirring the 1-10 mass parts is 30%
4Solution, finally, with deionized water washing 5 times, obtain the fatty acid polyglycol ether compound;
3. 50-100 mass parts step 2 gained fatty acid polyglycol ether compound is dissolved in to 100 mass parts toluene, add in reactor, add while stirring with fatty acid polyglycol ether compound equimolar amount containing the carboxylic acid of unsaturated double-bond, containing the acid anhydrides of unsaturated double-bond or containing the acyl chlorides of unsaturated double-bond, add 0.01-0.5 mass parts acid catalyst and 0.01-0.1 mass parts Resorcinol, be heated to while stirring 50-150 ℃, insulation reaction 0.5-24 hour, obtain response type fat-based biodegradable tensio-active agent;
Another kind of fat-based biodegradable tensio-active agent provided by the invention and synthetic method thereof, be specially: by 50-100 mass parts PEG400-oleic acid acrylate, PEG400-linolic acid acrylate or PEG400-linolenic acid acrylate are dissolved in 100 mass parts toluene, add in reactor, add while stirring and PEG400-oleic acid acrylate, the carboxylic acid containing unsaturated double-bond of PEG400-linolic acid acrylate or PEG400-linolenic acid acrylate equimolar amount, containing the acid anhydrides of unsaturated double-bond or containing the acyl chlorides of unsaturated double-bond, add 0.01-0.5 mass parts acid catalyst and 0.01-0.1 mass parts Resorcinol, be heated to while stirring 50-150 ℃, insulation reaction 0.5-24 hour, obtain response type fat-based degradable tensio-active agent
.
The acid catalyst that hydrolytic process is used is perchloric acid, hydroiodic acid HI, sulfuric acid, Hydrogen bromide, hydrochloric acid, nitric acid, acid iodide, oxalic acid, sulfurous acid, phosphoric acid, pyruvic acid, carbonic acid, nitrous acid, citric acid, hydrofluoric acid, oxysuccinic acid, gluconic acid, formic acid, acetic acid, propionic acid, butyric acid, valeric acid or caproic acid.
Grease is vegetables oil or animal oil or their mixture, and vegetables oil comprises soybean oil, Viscotrol C, linseed oil, sunflower oil, Semen Maydis oil, rapeseed oil, Oleum Cocois, plam oil or Thistle oil or the mixture of the above grease; Animal oil comprises lard, butter, fish oil or sheep oil or the mixture of the above grease.
The multipolymer that polyethers is polyoxyethylene glycol (PEG), polypropylene glycol, ethylene glycol and propylene glycol or the blend of polyoxyethylene glycol and polypropylene glycol.
Carboxylic acid containing unsaturated double-bond is vinylformic acid, methacrylic acid, toxilic acid, fumaric acid or methylene-succinic acid; Acid anhydrides containing unsaturated double-bond is acrylic anhydride, methacrylic anhydride, maleic anhydride, fumaric acid anhydride or itaconic anhydride; Acyl chlorides containing unsaturated double-bond is acrylate chloride or methacrylic chloride.
Response type fat-based degradable tensio-active agent prepared by the present invention contains the response type group that can participate in radical polymerization, and its structural formula is as follows:
In formula, n=1-1000, y=1-3, x+2y+z=15.
Response type fat-based degradable tensio-active agent of the present invention can be used as the emulsifying agent of conventional emulsion polymerization or mini-emulsion polymerization, prepares polymer emulsion.Application process is as follows: 100 mass parts monomers, 0.1-20 mass parts response type fat-based degradable tensio-active agent and 100-1000 mass parts water are mixed, after letting nitrogen in and deoxidizing, add while stirring 0.05-1 mass parts initiator, 30-90 ℃ of lower polymerase 10 .5-48 hour, obtain polymer emulsion.
Described monomer by vinylbenzene, vinyl acetate, vinyl ester, esters of acrylic acid, methyl acrylic ester, divinyl, isoprene,
One or more of-alkene, chloroprene, alpha-methyl styrene, vinylchlorid, vinylidene chloride, vinyl cyanide, vinylformic acid, methacrylic acid, maleic anhydride or alkyl vinyl ether mix and form by any proportioning.
Described initiator comprises peroxide initiator, azo-initiator, oxidation-reduction initiator, photochemical initiators etc.; Described peroxide initiator comprises ammonium persulphate, Potassium Persulphate etc.; Described azo-initiator comprises 4,4 '-azo two (4-cyanopentanoic acid), azo diisobutyl amidine hydrochlorides, azo di-isopropyl imidazoline salt hydrochlorate, azo di-isopropyl tetrahydroglyoxaline etc.; The compound system that described oxidation-reduction initiator is superoxide and reductive agent; Described superoxide is Potassium Persulphate, ammonium persulphate etc., and described reductive agent is S-WAT, sodium bisulfite, sodium formaldehyde sulphoxylate etc.; Described photochemical initiators is 2-hydroxyl-1-[4-(hydroxyl) phenyl]-2-methyl isophthalic acid-acetone etc.
Further illustrate the present invention program and result below by specific examples, but can not think that the present invention only limits in these examples.In an embodiment, except specified otherwise, all marks and percentage ratio are all weight ratios.
Embodiment 1:
The preparation of fat-based degradable tensio-active agent
1. hydrolysate oil: the sulfuric acid that is 15% by 50 gram concentration mixes with 30 gram ethanol, join in reactor, be warming up to 60 ℃, in in 1 hour, 20 gram soybean oil being dropped to reactor while stirring, insulation reaction was cooled to room temperature after 2 hours, after having reacted, and stratification, get upper strata liquid washing 5 times, obtain lipid acid;
2. lipid acid and polyethers esterification: lipid acid 30 grams that step 1 is obtained and be dissolved in 100 gram toluene with the polyethers of the molfractions such as lipid acid, add in reactor, splash into the 0.01 gram vitriol oil, warming while stirring to 60 ℃, stirring reaction 1 hour, after having reacted, 60 ℃ vacuumize and remove toluene, then drip the NaHCO that massfraction is 30%
3The aqueous solution is until no longer include bubble formation.Add again 60 gram water and 60 gram CH
2Cl
2, stir, and add the NaCl that the mass concentration of 1 gram is 30%.Stratification, taking precipitate adds the MgSO that the mass concentration of 1 gram is 30% while stirring
4Solution, finally, with deionized water washing 5 times, obtain the fatty acid polyglycol ether compound;
3. step 2 gained fatty acid polyglycol ether compound 50 grams are dissolved in to 100 gram toluene, add in reactor, add while stirring the vinylformic acid with fatty acid polyglycol ether compound equimolar amount, add the 0.01 gram vitriol oil and 0.01 gram Resorcinol, be heated to while stirring 60 ℃ of insulation reaction 1.5 hours, obtain response type fat-based biodegradable tensio-active agent;
The preparation of polymer emulsion:
100 gram butyl acrylates, 0.5 gram above-mentioned response type fat-based degradable tensio-active agent and 100 gram water are mixed, after letting nitrogen in and deoxidizing, add while stirring 0.05 gram ammonium persulphate, 80 ℃ of lower polymerizations 2 hours, obtain polymer emulsion.
Embodiment 2
The preparation of fat-based degradable tensio-active agent:
1. hydrolysate oil: the hydrochloric acid that is 20% by 50 gram mass concentration mixes with 50 gram ethanol, join in reactor, be warming up to 70 ℃, in in 4 hours, 50 parts of Pork Dripping being added to reactor while stirring, insulation reaction was cooled to room temperature after 2 hours, after having reacted, and stratification, get upper strata liquid washing 5 times, obtain lipid acid;
2. lipid acid and polyethers esterification: lipid acid 30 grams that step 1 is obtained and be dissolved in 100 parts of toluene with the polyethers of the molfractions such as lipid acid, add in reactor, splash into the 0.1 gram vitriol oil, warming while stirring to 90 ℃, stirring reaction 2 hours, after having reacted, 60 ℃ vacuumize and remove toluene, then drip the NaHCO that massfraction is 30%
3The aqueous solution is until no longer include bubble formation.Add again 300 gram water and 300 gram CH
2Cl
2, stir, and add the NaCl that the mass concentration of 4 grams is 30%.Stratification, taking precipitate adds the MgSO that the mass concentration of 4 grams is 30% while stirring
4Solution, finally, with deionized water washing 5 times, obtain the fatty acid polyglycol ether compound;
3. step 2 gained fatty acid polyglycol ether compound 75 grams are dissolved in to 100 gram toluene, add in reactor, add while stirring the methacrylic acid with fatty acid polyglycol ether compound equimolar amount, add the 0.1 gram vitriol oil and 0.05 gram Resorcinol, be heated to while stirring 90 ℃ of insulation reaction 8 hours, obtain response type fat-based biodegradable tensio-active agent;
The preparation of polymer emulsion:
100 gram methyl methacrylates, 4 gram response type fat-based degradable tensio-active agents and 300 gram water are mixed, after letting nitrogen in and deoxidizing, add while stirring 0.5 gram Potassium Persulphate, 80 ℃ of lower polymerizations 6 hours, obtain polymer emulsion.
Embodiment 3
The preparation of fat-based degradable tensio-active agent:
50 gram PEG400-oleic acid acrylate, be dissolved in 100 gram toluene, add in reactor, add while stirring the maleic anhydride with PEG400-oleic acid acrylate equimolar amount, add 0.01 gram phosphoric acid and 0.01 gram Resorcinol, limit is heated with stirring to 50 ℃ of insulation reaction 2 hours, obtains response type fat-based degradable tensio-active agent.
The preparation of polymer emulsion:
100 gram vinylbenzene, 0.5 gram response type fat-based degradable tensio-active agent and 100 gram water are mixed, after letting nitrogen in and deoxidizing, add while stirring 0.05-1 gram VA-044,50 ℃ of lower polyase 13s hour, obtain polymer emulsion.
Claims (10)
1. a response type fat-based degradable tensio-active agent, is characterized in that, it contains the response type group that can participate in radical polymerization, and its structural formula is as follows:
In formula, n=1-1000, y=1-3, x+2y+z=15.
2. the synthetic method of the described response type fat-based of claim 1 a degradable tensio-active agent, is characterized in that, comprises the following steps:
(1) hydrolysate oil: the acid catalyst that is 15-35% by 50 mass parts mass concentrations mixes with 30-70 mass parts ethanol, join in reactor, be warming up to 50-100 ℃, in in 0.5-12 hour, 20-60 part drip of grease being added to reactor while stirring, be cooled to room temperature after insulation reaction 0.5-24 hour, stratification, get upper strata liquid washing 5 times, obtains lipid acid;
(2) lipid acid and polyethers esterification: the lipid acid that 30-100 mass parts step 1 is obtained and be dissolved in 100 mass parts toluene with the polyethers of the molfractions such as lipid acid, add in reactor, splash into 0.01-0.5 mass parts acid catalyst, warming while stirring is to 50-150 ℃, stirring reaction 0.5-24 hour, after having reacted, 50-100 ℃ vacuumizes and removes toluene, then drips the NaHCO that massfraction is 30%
3The aqueous solution is until system no longer includes bubble formation; Add again 50-500 mass parts water and 50-500 mass parts CH
2Cl
2, stir, and add the NaCl aqueous solution that the mass concentration of 1-10 mass parts is 30%, stratification, taking precipitate, the MgSO that the mass concentration that adds while stirring the 1-10 mass parts is 30%
4The aqueous solution, finally, with deionized water washing 5 times, obtain the fatty acid polyglycol ether compound;
(3) 50-100 mass parts step 2 gained fatty acid polyglycol ether compound is dissolved in to 100 mass parts toluene, add in reactor, add while stirring with fatty acid polyglycol ether compound equimolar amount containing the carboxylic acid of unsaturated double-bond, containing the acid anhydrides of unsaturated double-bond or containing the acyl chlorides of unsaturated double-bond, add 0.01-0.5 mass parts acid catalyst and 0.01-0.1 mass parts Resorcinol, be heated to while stirring 50-150 ℃, insulation reaction 0.5-24 hour, obtain response type fat-based biodegradable tensio-active agent.
3. the synthetic method of the described response type fat-based of claim 1 a degradable tensio-active agent, it is characterized in that, the method is specially: by 50-100 mass parts PEG400-oleic acid acrylate, PEG400-linolic acid acrylate or PEG400-linolenic acid acrylate are dissolved in 100 mass parts toluene, add in reactor, add while stirring and PEG400-oleic acid acrylate, the carboxylic acid containing unsaturated double-bond of PEG400-linolic acid acrylate or PEG400-linolenic acid acrylate equimolar amount, containing the acid anhydrides of unsaturated double-bond or containing the acyl chlorides of unsaturated double-bond, add 0.01-0.5 mass parts acid catalyst and 0.01-0.1 mass parts Resorcinol, be heated to while stirring 50-150 ℃, insulation reaction 0.5-24 hour, obtain response type fat-based degradable tensio-active agent
.
4. according to the described synthetic method of claim 2 or 3, it is characterized in that, described acid catalyst is perchloric acid, hydroiodic acid HI, sulfuric acid, Hydrogen bromide, hydrochloric acid, nitric acid, acid iodide, oxalic acid, sulfurous acid, phosphoric acid, pyruvic acid, carbonic acid, nitrous acid, citric acid, hydrofluoric acid, oxysuccinic acid, gluconic acid, formic acid, acetic acid, propionic acid, butyric acid, valeric acid or caproic acid.
5. synthetic method according to claim 2, it is characterized in that, described grease is vegetables oil or animal oil or their mixture, and vegetables oil comprises soybean oil, Viscotrol C, linseed oil, sunflower oil, Semen Maydis oil, rapeseed oil, Oleum Cocois, plam oil or Thistle oil or the mixture of the above grease; Animal oil comprises lard, butter, fish oil or sheep oil or the mixture of the above grease.
6. synthetic method according to claim 2, is characterized in that, the multipolymer that described polyethers is polyoxyethylene glycol (PEG), polypropylene glycol, ethylene glycol and propylene glycol or the blend of polyoxyethylene glycol and polypropylene glycol.
7. according to the described synthetic method of claim 2 or 3, it is characterized in that, the described carboxylic acid containing unsaturated double-bond is vinylformic acid, methacrylic acid, toxilic acid, fumaric acid or methylene-succinic acid; The described acid anhydrides containing unsaturated double-bond is acrylic anhydride, methacrylic anhydride, maleic anhydride, fumaric acid anhydride or itaconic anhydride; The described acyl chlorides containing unsaturated double-bond is acrylate chloride or methacrylic chloride.
8. the application of the described response type fat-based of claim 1 a degradable tensio-active agent, is characterized in that, described response type fat-based degradable tensio-active agent can be used as the emulsifying agent of conventional emulsion polymerization or mini-emulsion polymerization, for the preparation of polymer emulsion; Application process is as follows: 100 mass parts monomers, 0.1-20 mass parts response type fat-based degradable tensio-active agent and 100-1000 mass parts water are mixed, after letting nitrogen in and deoxidizing, add while stirring 0.05-1 mass parts initiator, 30-90 ℃ of lower polymerase 10 .5-48 hour, obtain polymer emulsion.
9. application according to claim 8, is characterized in that, described monomer by vinylbenzene, vinyl acetate, vinyl ester, esters of acrylic acid, methyl acrylic ester, divinyl, isoprene,
One or more of-alkene, chloroprene, alpha-methyl styrene, vinylchlorid, vinylidene chloride, vinyl cyanide, vinylformic acid, methacrylic acid, maleic anhydride or alkyl vinyl ether mix and form by any proportioning.
10. application according to claim 8, is characterized in that, described initiator comprises peroxide initiator, azo-initiator, oxidation-reduction initiator, photochemical initiators etc.; Described peroxide initiator comprises ammonium persulphate, Potassium Persulphate etc.; Described azo-initiator comprises 4,4 '-azo two (4-cyanopentanoic acid), azo diisobutyl amidine hydrochlorides, azo di-isopropyl imidazoline salt hydrochlorate, azo di-isopropyl tetrahydroglyoxaline etc.; The compound system that described oxidation-reduction initiator is superoxide and reductive agent; Described superoxide is Potassium Persulphate, ammonium persulphate etc., and described reductive agent is S-WAT, sodium bisulfite, sodium formaldehyde sulphoxylate etc.; Described photochemical initiators is 2-hydroxyl-1-[4-(hydroxyl) phenyl]-2-methyl isophthalic acid-acetone.
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| CN113929838A (en) * | 2021-11-18 | 2022-01-14 | 西南石油大学 | Preparation of high-salt-resistant self-elasticizing type hydrophobically associating polymer and application of polymer in fracturing fluid |
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| AHMET ERDEM AND SELIM KUSEFOGLU: "SYNTHESIS OF OIL BASED LOW STYRENE EMISSION (LSE) AGENTS FOR POLYESTER", 《POLYMER PREPRINTS》, vol. 52, no. 2, 31 December 2011 (2011-12-31), pages 22 - 23 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109422825A (en) * | 2017-08-29 | 2019-03-05 | 中日合成化学股份有限公司 | Polymerizable surfactant and emulsion polymerization emulsion |
| CN109422825B (en) * | 2017-08-29 | 2021-06-08 | 中日合成化学股份有限公司 | Polymerizable surfactant and emulsion polymerization emulsion |
| CN113929838A (en) * | 2021-11-18 | 2022-01-14 | 西南石油大学 | Preparation of high-salt-resistant self-elasticizing type hydrophobically associating polymer and application of polymer in fracturing fluid |
Also Published As
| Publication number | Publication date |
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| CN103421183B (en) | 2015-12-02 |
| CN104861092A (en) | 2015-08-26 |
| CN104861092B (en) | 2016-06-29 |
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