CN104403046A - Polymer emulsifying and thickening agent and preparation method thereof - Google Patents
Polymer emulsifying and thickening agent and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a polymer emulsifying and thickening agent and a preparation method thereof. The polymer emulsifying and thickening agent contains a plurality of polymerization monomers, wherein each polymerization monomer contains the following components in percentage by mass: 30.0-99.9% of anionic monomers and 0.1-10.0% of amphoteric cationic monomers; the anionic monomers are one or at least two selected from acrylic acid, methacrylic acid and 2-acrylamide-2-methylacrylsulfonate; the amphoteric cationic monomers are one or at least two selected from N, N-dimethyl-N-dodecyl methylallyl ammonium chloride, N, N-dimethyl-N-tetradecyl methylallyl ammonium chloride, N, N-dimethyl-N-dodecyl allyl ammonium chloride and N, N-dimethyl-N-dodecyl tetradecyl allyl ammonium chloride; and the weight-average molecular weight of the polymer emulsifying and thickening agent is 2000-6000 thousands. The polymer emulsifying and thickening agent is good in thickening and emulsifying effects and salt resistance, high in swelling speed and low in preparation cost and can be produced on a large scale.
Description
Technical field
The invention belongs to the synthesis technical field in polymer chemistry, particularly polymer emulsified thickening material of one and preparation method thereof.
Background technology
The thickened systems using polymer emulsified thickening material to configure has that viscosity stability is good, emulsify well, tool thixotropy, limiting viscosity high, and the change of viscosity with temperature and time is less, this makes polymer emulsified thickening material have in industries such as daily use chemicals, oil field, coating and printing ink, tackiness agent, foodstuff additive to apply more and more widely.
The more synthetic polymer emulsifing thickener of current research has homopolymer and the multipolymer of vinylformic acid, methacrylic acid, 2-acrylamide-2-methyl propane sulfonic, acrylamide and acrylate, acrylic polymers thickening material due to lipophilicity more weak, more general to the emulsifying effectiveness of oily matter; 2-acrylamide-2-methyl propane sulfonic and acrylamide lipophilicity slightly increase, but still on the weak side generally, and acrylamide due to toxicity comparatively large, residual quantity must control in very low level; Acrylic ester thickener lipophilicity is good, but thickening properties is relatively poor.
Chinese patent CN100418990C discloses a kind of acrylate emulsifying thickening agent and production method, and its 2% viscosity of starching in vain is 2400 centipoises, and viscosity is relatively low; Chinese patent CN101974134A discloses a kind of association type acrylate thickening agent and preparation method thereof and application, polymer viscosity prepared by embodiment 3 is the highest, and 3% viscosity is 9500mpa.s (NDJ-1,3# rotor, 6r/min), viscosity is also on the low side; Chinese patent CN103183765A discloses a kind of preparation method of powdery polyacrylic acid thickener, the 85-397s of sample 0.5% aqueous solution prepared by embodiment, viscosity is 1500-59000mPa.s, this technique adopts a large amount of low boiling point organic solvent, production danger is higher, and cost is also higher.
Summary of the invention
Primary and foremost purpose of the present invention is to overcome the shortcoming that exists in prior art with not enough, provides a kind of polymer emulsified thickening material.
Another object of the present invention is to provide the preparation method of described polymer emulsified thickening material.
Object of the present invention is achieved through the following technical solutions: a kind of polymer emulsified thickening material, and containing multiple polymerization single polymerization monomer, described polymerization single polymerization monomer contains anionic monomer 30.0-99.9% by mass percentage and amphipathic cationic monomer 0.1-10.0%;
Described anionic monomer is one in vinylformic acid, methacrylic acid or 2-acrylamide-2 methyl propane sulfonic acid or at least two kinds;
Described amphipathic cationic monomer is N, N-Dimethyl-N-dodecyl methacrylic chlorination ammonium, N, N-dimethyl-N-tetradecyl ylmethyl allyl ammonium chloride, N, one in N-Dimethyl-N-dodecyl allyl ammonium chloride or N, N-dimethyl-N-tetradecyl base allyl ammonium chloride or at least two kinds; The weight-average molecular weight of described polymer emulsified thickening material is 200-600 ten thousand.
Described polymer emulsified thickening material has both sexes structure, and Intermolecular Forces is stronger, and thickening effectiveness is better; Described polymer emulsified thickening material also has amphipathic structure, and emulsifying effectiveness is better, and salt tolerance is also better.
Described polymer emulsified thickening material, is prepared by the component counted by weight as follows: anionic monomer 9.0-29.9 part, amphipathic cationic monomer 0.03-3.0 part, other monomer 0-30.0 part, alkali 0.6-35.0 part, sequestrant 0.005-0.5 part, initiator 0.001-0.5 part, emulsifying agent 0.5-10.0 part, linking agent 0.001-0.1 part, water 30.0-65.0 part and organic phase 15.0-40.0 part.
Other described monomer is one in acrylamide, vinyl pyrrolidone and vinyl imidazole or at least two kinds;
Described alkali is one in sodium hydroxide, potassium hydroxide, ammoniacal liquor, ammonia, sodium carbonate, salt of wormwood, sodium bicarbonate and saleratus or at least two kinds; The consumption of alkali be pure after consumption.
Described sequestrant is sodium ethylene diamine tetracetate and/or diethylenetriamine pentaacetic acid sodium;
Described initiator is one in Sodium Persulfate, ammonium persulphate, Potassium Persulphate, hydrogen peroxide, tertbutyl peroxide, isopropyl benzene hydroperoxide, S-WAT, Sodium Pyrosulfite, sodium bisulfite, ferrous sulfate, Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile), benzoyl peroxide, peroxidized t-butyl perbenzoate and azo diisobutyl amidine dihydrochloride or at least two kinds;
Described emulsifying agent is one in fatty alcohol-polyoxyethylene ether, stearin, Triglycol distearate, sorbitan monooleate, sorbitan monostearate, polyoxyethylene 20 sorbitan monooleate and polyoxyethylene 20 sorbitan monostearate or at least two kinds;
Described linking agent is one in pentaerythritol triacrylate, pentaerythritol triallyl ether, Viscoat 295, trimethylolpropane diacrylate, methylene-bisacrylamide, polyethyleneglycol diacrylate and polyethylene glycol dimethacrylate or at least two kinds;
Described organic phase is one in white mineral oil, isomery white mineral oil and polyisobutene or at least two kinds;
Described water is tap water, deionized water or distilled water.
Preferably, described polymer emulsified thickening material contains the chain-transfer agent accounting for total quality of material 0.00001-0.1%; After adding appropriate chain-transfer agent, the polymkeric substance produced when preventing initial polymerization can be made because molecular weight is excessive to cause water-soluble and thickening properties variation.
Described total material is anionic monomer+amphipathic cationic monomer+other monomer+alkali+sequestrant+initiator+emulsifying agent+linking agent+water+organic phase+chain-transfer agent;
Described chain-transfer agent is sulfurous organic compound and/or inorganic chain-transfer agent;
Preferably, described sulfurous organic compound is one in n-butyl mercaptan, tert-butyl mercaptan, octyl mercaptan, mercaptoethanol, Thiovanic acid, thiohydracrylic acid, alkyl thioglycollate and alkyl mercaptopropionates or at least two kinds.
Preferably, described inorganic chain-transfer agent is one in sulfurous acid, sulphite, Hypophosporous Acid, 50, hypophosphite, phosphorous acid and phosphite or at least two kinds.
The preparation method of described polymer emulsified thickening material, comprises the steps:
(1) anionic monomer 9.0-29.9 part, amphipathic cationic monomer 0.03-3.0 part and other monomer 0-30.0 part are dissolved in 30.0-65.0 part water, add alkali 0.6-35.0 part, the pH value controlling solution is 5.0-8.0, then sequestrant 0.005-0.5 part and linking agent 0.001-0.1 part is added, stir, obtain aqueous phase;
(2) 0.2-6.0 part emulsifying agent is added in organic phase 15.0-40.0 part, stir, obtain oil phase;
(3) respectively logical nitrogen deoxygenation is carried out to the aqueous phase of step (1), the oil phase of step (2), under nitrogen protection, while stirring the aqueous phase of step (1) is added dropwise in the oil phase of step (2), stirring velocity is 10-30000 rev/min, then add initiator 0.001-0.5 part and carry out polyreaction, obtain polymer emulsified thickening material;
Above-mentioned number is parts by weight.
In step (3):
Described time for adding is 5-60min;
Described polyreaction is adopted and is carried out with the following method: start reaction in 5-50 DEG C, continues reaction 0.1-10 hour, be then cooled to lower than 40 DEG C, add 0.2-6.0 part emulsifying agent, stir after 0.01-40 hour is warming up to 60-80 DEG C.
Preferably, described polyreaction is carried out under UV-irradiation.Use UV-irradiation supplemental polymeric can reduce the decomposition temperature of initiator, thus prepare the polymkeric substance of more high molecular at lower temperatures; Meanwhile, when polymerization exotherm is too fast cause difficult control of temperature time, stop UV-irradiation significantly can reduce polymerization velocity, thus control polymerization temperature.
Described polymer emulsified thickening material can be applied to the technical fields such as household chemicals, oil field, coating and printing ink, tackiness agent.
The present invention has following advantage and effect relative to prior art: polymer emulsified thickening material of the present invention has both sexes structure, and Intermolecular Forces is stronger, and better, salt tolerance is also better for thickening effectiveness and emulsifying effectiveness.This polymer emulsified thickening material has the feature of Fast-swelling, does not substantially have insolubles.Preparation method of the present invention stablizes controlled, safer, and cost is lower, can be applicable to large production.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail, but embodiments of the present invention are not limited thereto.
Embodiment 1
(1) by 161g vinylformic acid, 50g 2-acrylamide-2 methyl propane sulfonic acid and 6g N, N-Dimethyl-N-dodecyl methacrylic chlorination ammonium is dissolved in 500g tap water, add 38.3g ammonia, control temperature is lower than 10 DEG C, adjust ph is to 6.5-6.8, then add 0.001g mercaptoethanol, 0.3g sodium ethylene diamine tetracetate and 0.15g trimethylolpropane diacrylate, stir, obtain aqueous phase;
(2) 3.5g stearin and 15.5g sorbitan monooleate are added in 205g white mineral oil, stir, obtain oil phase;
(3) respectively logical nitrogen deoxygenation 25-30min is carried out to the aqueous phase of step (1), the oil phase of step (2), under nitrogen protection, while stirring the aqueous phase of step (1) is added dropwise in the oil phase of step (2), stirring velocity 28000 revs/min, time for adding is 25-30min; Then add 0.1g Diisopropyl azodicarboxylate, drip 7g1% ammonium persulfate aqueous solution and 7g1% metabisulfite solution afterwards simultaneously, drip 4-5min, carry out polyreaction, obtain polymer emulsified thickening material 1, its theoretical active thing content is 24.7%.
Polyreaction is adopted and is carried out with the following method: start reaction in 6-7 DEG C, continues reaction 2h, be then cooled to lower than 35-40 DEG C, add 42g fatty alcohol-polyoxyethylene ether-7, stir after 1h is warming up to 70-75 DEG C gradually.
Embodiment 2
(1) by 100g methacrylic acid, 200g acrylamide and 3g N, N-dimethyl-N-tetradecyl ylmethyl allyl ammonium chloride is dissolved in 455g deionized water, add 17.8g ammonia, control temperature is lower than 10 DEG C, adjust ph is to 5.5-5.8, then add 0.00016g Thiovanic acid, 0.4g diethylenetriamine pentaacetic acid sodium and 0.1g pentaerythritol triallyl ether, stir, obtain aqueous phase;
(2) 2.1g fatty alcohol-polyoxyethylene ether-3,15g sorbitan monooleate are added in 200g isomery white mineral oil, stir, obtain oil phase;
(3) respectively logical nitrogen deoxygenation 35-40min is carried out to the aqueous phase of step (1), the oil phase of step (2), under nitrogen protection, while stirring the aqueous phase of step (1) is added dropwise in the oil phase of step (2), stirring velocity 1000 revs/min, time for adding is 5-7min; Then add 0.4g 2,2'-Azobis(2,4-dimethylvaleronitrile), add 20g 1% azo diisobutyl amidine dihydrochloride afterwards, carry out polyreaction, obtain polymer emulsified thickening material 2, its theoretical active thing content is 31.1%.
Polyreaction is adopted and is carried out with the following method: start reaction in 30-35 DEG C, continues reaction 0.1h, be then cooled to lower than 35-40 DEG C, add 19g polyoxyethylene 20 sorbitan monooleate, stir after 40h is warming up to 70-75 DEG C gradually.
Embodiment 3
(1) by 100g vinylformic acid, 174g vinyl pyrrolidone and 1.4g N, N-Dimethyl-N-dodecyl methacrylic chlorination ammonium is dissolved in 314g distilled water, add 66.3g sodium carbonate, control temperature is lower than 10 DEG C, adjust ph is to 6.0-6.5, then add 0.01g mercaptoethanol, 2g sodium ethylene diamine tetracetate and 0.95g polyethyleneglycol diacrylate, stir, obtain aqueous phase;
(2) 3.3g sorbitan monooleate is added in 400g polyisobutene, stir, obtain oil phase;
(3) respectively logical nitrogen deoxygenation 25-30min is carried out to the aqueous phase of step (1), the oil phase of step (2), under nitrogen protection, while stirring the aqueous phase of step (1) is added dropwise in the oil phase of step (2), stirring velocity 100 revs/min, time for adding is 25-30min; Add 0.5g Diisopropyl azodicarboxylate, drip the 3g 1% tertbutyl peroxide aqueous solution and 3g 1% aqueous solution of sodium bisulfite afterwards simultaneously, drip 4-5min, carry out polyreaction, obtain polymer emulsified thickening material 3, its theoretical active thing content is 29.4%.
Polyreaction is adopted and is carried out with the following method: start reaction in 6-7 DEG C, is warming up to 70-75 DEG C of reaction 0.5h gradually, is then cooled to lower than 35-40 DEG C, adds 2.8g fatty alcohol-polyoxyethylene ether-9, stir through 1.5h.
Embodiment 4
(1) by 190g 2-acrylamide-2 methyl propane sulfonic acid, 80g vinyl imidazole and 0.4g N, N-Dimethyl-N-dodecyl methacrylic chlorination ammonium is dissolved in 353g tap water, add 91.7g 40% sodium hydroxide solution, control temperature is lower than 10 DEG C, adjust ph is to 7.0-7.5, then add 0.95g n-butyl mercaptan, 0.06g sodium ethylene diamine tetracetate and 0.013g methylene-bisacrylamide, stir, obtain aqueous phase;
(2) 2.5g sorbitan monostearate, 16.7g sorbitan monooleate are added in 280g white mineral oil, stir, obtain oil phase;
(3) respectively logical nitrogen deoxygenation 25-30min is carried out to the aqueous phase of step (1), the oil phase of step (2), under nitrogen protection, while stirring the aqueous phase of step (1) is added dropwise in the oil phase of step (2), stirring velocity 800 revs/min, time for adding is 25-30min; Dropwise adjustment rotating speed to 10 rev/min, then add 5g 0.2% persulfate aqueous solution and 5g 0.2% metabisulfite solution, drip 4-5min, carry out polyreaction, obtain polymer emulsified thickening material 4, its theoretical active thing content is 28.1%.
Polyreaction is adopted and is carried out with the following method: start reaction in 6-7 DEG C, continues reaction 3h, be then cooled to lower than 35-40 DEG C, add 9.5g fatty alcohol-polyoxyethylene ether-7, stir after 0.7h is warming up to 70-75 DEG C gradually.
Embodiment 5
(1) by 113g vinylformic acid and 10g N, N-Dimethyl-N-dodecyl methacrylic chlorination ammonium and 20gN, N-dimethyl-N-tetradecyl base allyl ammonium chloride is dissolved in 653g deionized water, add 70.7g sodium carbonate, control temperature is lower than 30 DEG C, and adjust ph, to 5.5-5.8, then adds 0.05g octyl mercaptan, 4.8g sodium ethylene diamine tetracetate and 0.07g methylene-bisacrylamide, stir, obtain aqueous phase;
(2) 2g Triglycol distearate, 14.5g sorbitan monooleate are added in 160g white mineral oil, stir, obtain oil phase;
(3) respectively logical nitrogen deoxygenation 25-30min is carried out to the aqueous phase of step (1), the oil phase of step (2), under nitrogen protection, while stirring the aqueous phase of step (1) is added dropwise in the oil phase of step (2), stirring velocity 1000 revs/min, time for adding is 55-60min; Then add 0.2g 2,2'-Azobis(2,4-dimethylvaleronitrile), drip the 12g 1% azo diisobutyl amidine dihydrochloride aqueous solution afterwards, drip 5-10min, carry out polyreaction, obtain polymer emulsified thickening material 5, its theoretical active thing content is 16.8% simultaneously.
Polyreaction is adopted and is carried out with the following method: start reaction in 49-50 DEG C, is warming up to 60-65 DEG C of reaction 10h gradually, is then cooled to lower than 35-40 DEG C, adds 14g polyoxyethylene 20 sorbitan monooleate, stir through 20h.
Embodiment 6
(1) by 98g 2-acrylamide-2 methyl propane sulfonic acid, 179g acrylamide and 3g N, N-Dimethyl-N-dodecyl methacrylic chlorination ammonium is dissolved in 380g deionized water, add 66.3g 40% potassium hydroxide solution, control temperature is lower than 10 DEG C, adjust ph is to 5.5-5.8, then add 0.05g Thiovanic acid ethyl ester, 0.4g sodium ethylene diamine tetracetate and 0.09g trimethylolpropane diacrylate, stir, obtain aqueous phase;
(2) 5.4g stearin, 54g sorbitan monooleate are added in 200g white mineral oil, stir, obtain oil phase;
(3) respectively logical nitrogen deoxygenation 25-30min is carried out to the aqueous phase of step (1), the oil phase of step (2), under nitrogen protection, while stirring the aqueous phase of step (1) is added dropwise in the oil phase of step (2), stirring velocity 600 revs/min, time for adding is 25-30min; Then add 4.6g Diisopropyl azodicarboxylate, drip the 10g1% azo diisobutyl amidine dihydrochloride aqueous solution afterwards, drip 4-5min, carry out polyreaction, obtain polymer emulsified thickening material 6, its theoretical active thing content is 29.3%.
Polyreaction is adopted and is carried out with the following method: start reaction in 25-30 DEG C, continues reaction 0.5h, be then cooled to 35-40 DEG C, add 41g fatty alcohol-polyoxyethylene ether-9, stir after 8h is warming up to 75-80 DEG C gradually.
Polyreaction is carried out under UV-irradiation (as the too fast then temporary close ultraviolet lamp of temperature rising).
Embodiment 7
(1) by 300g 2-acrylamide-2 methyl propane sulfonic acid and 2g N, N-Dimethyl-N-dodecyl methacrylic chlorination ammonium is dissolved in 484g tap water, add 24.7g ammonia, control temperature is lower than 10 DEG C, adjust ph is to 6.5-6.8, then add 0.3g sodium ethylene diamine tetracetate and 0.15g pentaerythritol triallyl ether, stir, obtain aqueous phase;
(2) 3.5g sorbitan monostearate, 15.9g sorbitan monooleate are added in 162g white mineral oil, stir, obtain oil phase;
(3) respectively logical nitrogen deoxygenation 25-30min is carried out to the aqueous phase of step (1), the oil phase of step (2), under nitrogen protection, while stirring the aqueous phase of step (1) is added dropwise in the oil phase of step (2), stirring velocity 10000 revs/min, time for adding is 25-30min; Then add the 5g 0.2% isopropyl benzene hydroperoxide aqueous solution and 5g 0.2% ferrous sulfate aqueous solution, drip 5-10min, carry out polyreaction, obtain polymer emulsified thickening material 7, its theoretical active thing content is 31.6%.
Polyreaction is adopted and is carried out with the following method: start reaction in 6-7 DEG C, continue reaction 1 hour, be then cooled to lower than 35-40 DEG C, add 32g fatty alcohol-polyoxyethylene ether-7, stir after 2h is warming up to 70-75 DEG C gradually.
Embodiment 8
(1) by 100g 2-acrylamide-2 methyl propane sulfonic acid, 300g acrylamide and 7g N, N-Dimethyl-N-dodecyl allyl ammonium chloride is dissolved in 400g tap water, add 8.2g ammonia, control temperature is lower than 10 DEG C, adjust ph is to 5.5-5.8, then add 0.004g phosphorous acid, 0.7 sodium ethylene diamine tetracetate and 0.13g polyethylene glycol dimethacrylate, stir, obtain aqueous phase;
(2) 2g stearin, 10g sorbitan monooleate are added in 195g white mineral oil, stir, obtain oil phase;
(3) respectively logical nitrogen deoxygenation 25-30min is carried out to the aqueous phase of step (1), the oil phase of step (2), under nitrogen protection, while stirring the aqueous phase of step (1) is added dropwise in the oil phase of step (2), stirring velocity 15000 revs/min, time for adding is 25-30min; Then add the 15g 2% azo diisobutyl amidine dihydrochloride aqueous solution, drip 4-5min, carry out polyreaction, obtain polymer emulsified thickening material 8, its theoretical active thing content is 39.6%.
Polyreaction is adopted and is carried out with the following method: start reaction in 25-30 DEG C, continues reaction 1h, be then cooled to lower than 35-40 DEG C, add 11g fatty alcohol-polyoxyethylene ether-9, stir after 30h is warming up to 70-75 DEG C gradually.
Polyreaction is carried out under UV-irradiation (as the too fast then temporary close ultraviolet lamp of temperature rising).
Embodiment 9
(1) by 252g vinylformic acid and 1g N, N-Dimethyl-N-dodecyl methacrylic chlorination ammonium is dissolved in 463g tap water, add 332.8g saleratus, control temperature is lower than 10 DEG C, adjust ph is to 6.5-7.0, then add 0.03g sodium phosphite, 0.4g sodium ethylene diamine tetracetate and 0.11g trimethylolpropane diacrylate, stir, obtain aqueous phase;
(2) 1g stearin, 9g sorbitan monooleate are added in 160g white mineral oil, stir, obtain oil phase;
(3) respectively logical nitrogen deoxygenation 25-30min is carried out to the aqueous phase of step (1), the oil phase of step (2), under nitrogen protection, while stirring the aqueous phase of step (1) is added dropwise in the oil phase of step (2), stirring velocity 800 revs/min, time for adding is 5-10min; Then add 2.6g Diisopropyl azodicarboxylate, drip 5g 1% ammonium persulfate aqueous solution and 5g 1% aqueous solution of sodium bisulfite afterwards simultaneously, drip 4-5min, carry out polyreaction, obtain polymer emulsified thickening material 9, its theoretical active thing content is 36.7%.
Polyreaction is adopted and is carried out with the following method: start reaction in 6-7 DEG C, continue reaction 2 hours, be then cooled to lower than 35-40 DEG C, add 8g fatty alcohol-polyoxyethylene ether-9, stir after 0.02h is warming up to 70-75 DEG C gradually.
Comparative example 1
(1) 167g vinylformic acid and 50g 2-acrylamide-2 methyl propane sulfonic acid are dissolved in 500g tap water, add 39.7g ammonia, control temperature is lower than 10 DEG C, adjust ph is to 6.5-6.8, then 0.001g mercaptoethanol, 0.3g sodium ethylene diamine tetracetate and 0.15g trimethylolpropane diacrylate is added, stir, obtain aqueous phase;
(2) 3.5g stearin and 15.5g sorbitan monooleate are added in 205g white mineral oil, stir, obtain oil phase;
(3) respectively logical nitrogen deoxygenation 25-30min is carried out to the aqueous phase of step (1), the oil phase of step (2), under nitrogen protection, while stirring the aqueous phase of step (1) is added dropwise in the oil phase of step (2), stirring velocity 28000 revs/min, time for adding is 25-30min; Then add 0.1g Diisopropyl azodicarboxylate, drip 7g1% ammonium persulfate aqueous solution and 7g1% metabisulfite solution afterwards simultaneously, drip 4-5min, carry out polyreaction, obtain comparative sample 1, its theoretical active thing content is 24.7%.
Polyreaction is adopted and is carried out with the following method: in 6-7 DEG C of reaction 0.2h, is warming up to 70-75 DEG C of reaction 2h gradually, is then cooled to lower than 35-40 DEG C, adds 42g fatty alcohol-polyoxyethylene ether-7, stir through 1h.
Effect example
Configure the sample of 1% actives and tested viscosity with deionized water, contrast the thickening properties of each polymkeric substance, emulsifying property and salt resistant character, result is as shown in table 1:
As can be seen from following test result, use polymer emulsified thickening material prepared by the embodiment of the present invention, overall product performance is all better than import sample, is improved largely especially compared with domestic sample.
The viscosity of each polymkeric substance of table 1, thickening properties, emulsifying property and salt resistant character result
Above-described embodiment is the present invention's preferably embodiment; but embodiments of the present invention are not restricted to the described embodiments; change, the modification done under other any does not deviate from spirit of the present invention and principle, substitute, combine, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (10)
1. a polymer emulsified thickening material, is characterized in that, containing multiple polymerization single polymerization monomer, described polymerization single polymerization monomer contains anionic monomer 30.0-99.9% by mass percentage and amphipathic cationic monomer 0.1-10.0%; Described anionic monomer is one in vinylformic acid, methacrylic acid or 2-acrylamide-2 methyl propane sulfonic acid or at least two kinds; Described amphipathic cationic monomer is N, N-Dimethyl-N-dodecyl methacrylic chlorination ammonium, N, N-dimethyl-N-tetradecyl ylmethyl allyl ammonium chloride, N, one in N-Dimethyl-N-dodecyl allyl ammonium chloride or N, N-dimethyl-N-tetradecyl base allyl ammonium chloride or at least two kinds; The weight-average molecular weight of described polymer emulsified thickening material is 200-600 ten thousand.
2. polymer emulsified thickening material according to claim 1, it is characterized in that, described polymer emulsified thickening material, is prepared by the component counted by weight as follows: anionic monomer 9.0-29.9 part, amphipathic cationic monomer 0.03-3.0 part, other monomer 0-30.0 part, alkali 0.6-35.0 part, sequestrant 0.005-0.5 part, initiator 0.001-0.5 part, emulsifying agent 0.5-10.0 part, linking agent 0.001-0.1 part, water 30.0-65.0 part and organic phase 15.0-40.0 part.
3. polymer emulsified thickening material according to claim 2, is characterized in that, other described monomer is one in acrylamide, vinyl pyrrolidone and vinyl imidazole or at least two kinds;
Described alkali is one in sodium hydroxide, potassium hydroxide, ammoniacal liquor, ammonia, sodium carbonate, salt of wormwood, sodium bicarbonate and saleratus or at least two kinds;
Described sequestrant is sodium ethylene diamine tetracetate and/or diethylenetriamine pentaacetic acid sodium;
Described initiator is one in Sodium Persulfate, ammonium persulphate, Potassium Persulphate, hydrogen peroxide, tertbutyl peroxide, isopropyl benzene hydroperoxide, S-WAT, Sodium Pyrosulfite, sodium bisulfite, ferrous sulfate, Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile), benzoyl peroxide, peroxidized t-butyl perbenzoate and azo diisobutyl amidine dihydrochloride or at least two kinds;
Described emulsifying agent is one in fatty alcohol-polyoxyethylene ether, stearin, Triglycol distearate, sorbitan monooleate, sorbitan monostearate, polyoxyethylene 20 sorbitan monooleate and polyoxyethylene 20 sorbitan monostearate or at least two kinds;
Described linking agent is one in pentaerythritol triacrylate, pentaerythritol triallyl ether, Viscoat 295, trimethylolpropane diacrylate, methylene-bisacrylamide, polyethyleneglycol diacrylate and polyethylene glycol dimethacrylate or at least two kinds;
Described organic phase is one in white mineral oil, isomery white mineral oil and polyisobutene or at least two kinds;
Described water is tap water, deionized water or distilled water.
4. the polymer emulsified thickening material according to Claims 2 or 3, is characterized in that, described polymer emulsified thickening material contains the chain-transfer agent of the 0.00001-0.1% accounting for total quality of material.
5. polymer emulsified thickening material according to claim 4, is characterized in that, described chain-transfer agent is sulfurous organic compound and/or inorganic chain-transfer agent.
6. polymer emulsified thickening material according to claim 5, it is characterized in that, described sulfurous organic compound is one in n-butyl mercaptan, tert-butyl mercaptan, octyl mercaptan, mercaptoethanol, Thiovanic acid, thiohydracrylic acid, alkyl thioglycollate and alkyl mercaptopropionates or at least two kinds; Described inorganic chain-transfer agent is one in sulfurous acid, sulphite, Hypophosporous Acid, 50, hypophosphite, phosphorous acid and phosphite or at least two kinds.
7. the preparation method of the polymer emulsified thickening material described in any one of claim 1-3, is characterized in that, comprise the steps:
(1) anionic monomer 9.0-29.9 part, amphipathic cationic monomer 0.03-3.0 part and other monomer 0-30.0 part are dissolved in 30.0-65.0 part water, add alkali 0.6-35.0 part, the pH value controlling solution is 5.0-8.0, then sequestrant 0.005-0.5 part and linking agent 0.001-0.1 part is added, stir, obtain aqueous phase;
(2) 0.2-6.0 part emulsifying agent is added in organic phase 15.0-40.0 part, stir, obtain oil phase;
(3) respectively logical nitrogen deoxygenation is carried out to the aqueous phase of step (1), the oil phase of step (2), under nitrogen protection, while stirring the aqueous phase of step (1) is added dropwise in the oil phase of step (2), stirring velocity 10-30000 rev/min, then add initiator 0.001-0.5 part and carry out polyreaction, obtain polymer emulsified thickening material;
Above-mentioned number is parts by weight.
8. the preparation method of polymer emulsified thickening material according to claim 7, is characterized in that, the time for adding described in step (3) is 5-60min; Described polyreaction is adopted and is carried out with the following method: start reaction in 5-50 DEG C, continues reaction 0.1-10h, be then cooled to lower than 40 DEG C, add 0.2-6.0 part emulsifying agent, stir after 0.01-40h is warming up to 60-80 DEG C.
9. the preparation method of the polymer emulsified thickening material according to claim 7 or 8, is characterized in that, described polyreaction is carried out under UV-irradiation.
10. the polymer emulsified thickening material described in any one of claim 1-3 is applied to household chemicals, oil field, coating and printing ink and technical field of adhesive.
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