CN104403046B - A kind of polymer emulsified thickener and preparation method thereof - Google Patents
A kind of polymer emulsified thickener and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of polymer emulsified thickener and preparation method thereof.The polymer emulsified thickener contains multiple polymerized monomers, and polymerized monomer is containing anionic monomer 30.0 99.9% and amphipathic cationic monomer 0.1 10.0% by mass percentage;Anionic monomer is the one kind or at least two in acrylic acid, methacrylic acid or the methyl propane sulfonic acid of 2 acrylamide 2;Amphipathic cationic monomer is N, N dimethyl N dodecyl methyls allyl ammonium chloride, N, N dimethyl N tetradecylmethyls allyl ammonium chloride, N, one kind or at least two in N dimethyl N sodium dodecyl allyls ammonium chloride or N, N dimethyl N myristyl allyl ammonium chlorides;The weight average molecular weight of polymer emulsified thickener is 200 600 ten thousand.The product is thickened and emulsifying effectiveness is good, good salt tolerance, swelling quick, and its preparation cost is low, can be used for big production.
Description
Technical field
The invention belongs to the synthesis technical field in polymer chemistry, more particularly to a kind of polymer emulsified thickener and its
Preparation method.
Background technology
The thickened systems configured using polymer emulsified thickener have that viscosity stability is good, emulsifying effectiveness is good, tool thixotroping
Property, the features such as limiting viscosity is high, and the change of viscosity with temperature and time is smaller, and this causes polymer emulsified thickener in day
The industries such as change, oil field, coating and printing ink, adhesive, food additives have increasingly be widely applied.
Studying more synthetic polymer emulsifing thickener at present has acrylic acid, methacrylic acid, 2- acrylamide -2- first
The homopolymers and copolymer of base propane sulfonic acid, acrylamide and acrylate, acrylic polymer thickener due to lipophile compared with
Weak, the emulsifying effectiveness to oily matter is more general;2- acrylamide-2-methyl propane sulfonics and acrylamide lipophile slightly have increasing
Plus, it is but generally still on the weak side, and acrylamide due to toxicity it is larger, residual quantity must be controlled in very low level;Acrylic acid
Type thickener lipophile is good, but thickening properties are relatively poor.
Chinese patent CN100418990C discloses a kind of acrylate emulsifying thickening agent and production method, its 2% white slurry
Viscosity be 2400 centipoises, viscosity is relatively low;Chinese patent CN101974134A discloses a kind of association type acrylate and increases
Thick dose and preparation method and application, polymer viscosity highest prepared by embodiment 3,3% viscosity is 9500mpa.s (NDJ-
1,3# rotor, 6r/min), viscosity is also relatively low;Chinese patent CN103183765A discloses a kind of powdered polyacrylic and increases
Thick dose of preparation method, the 85-397s of the aqueous solution of sample 0.5% prepared by embodiment, viscosity is 1500-59000mPa.s,
The technique uses a large amount of low boiling point organic solvents, and production is dangerous higher, and cost is also higher.
The content of the invention
Primary and foremost purpose of the invention is to overcome shortcoming present in prior art with deficiency, there is provided a kind of polymer emulsified
Thickener.
Preparation method another object of the present invention is to provide described polymer emulsified thickener.
The purpose of the present invention is achieved through the following technical solutions:A kind of polymer emulsified thickener, it is single containing multiple polymerization
Body, described polymerized monomer contains anionic monomer 30.0-99.9% and amphipathic cationic monomer by mass percentage
0.1-10.0%;
Described anionic monomer be acrylic acid, methacrylic acid or the methyl propane sulfonic acid of 2- acrylamides -2 in one kind or
At least two;
Described amphipathic cationic monomer is N, N- Dimethyl-N-dodecyl methacrylic chlorinations ammonium, N, N- bis-
Methyl-N- tetradecylmethyls allyl ammonium chloride, N, N- Dimethyl-N-dodecyls allyl ammonium chloride or N, N- diformazan
One kind or at least two in base-N- myristyl allyl ammonium chlorides;The Weight-average molecular of described polymer emulsified thickener
It is 200-600 ten thousand to measure.
Described polymer emulsified thickener has both sexes structure, and intermolecular force is stronger, and thickening effect is more preferable;It is described
Polymer emulsified thickener also have amphipathic structure, emulsifying effectiveness more preferably, salt tolerance is also more preferable.
Described polymer emulsified thickener, is prepared by the component counted by weight as follows:Anionic monomer
9.0-29.9 parts, amphipathic cationic monomer 0.03-3.0 parts, 0-30.0 parts of other monomers, alkali 0.6-35.0 parts, chelating agent
0.005-0.5 parts, initiator 0.001-0.5 parts, emulsifying agent 0.5-10.0 parts, crosslinking agent 0.001-0.1 parts, water 30.0-65.0
Part and organic phase 15.0-40.0 parts.
Other described monomers are the one kind or at least two in acrylamide, vinyl pyrrolidone and vinyl imidazole
Kind;
Described alkali is NaOH, potassium hydroxide, ammoniacal liquor, ammonia, sodium carbonate, potassium carbonate, sodium acid carbonate and bicarbonate
One kind in potassium or at least two;The consumption of alkali be it is pure after consumption.
Described chelating agent is sodium ethylene diamine tetracetate and/or diethylenetriamine pentaacetic acid sodium;
Described initiator is sodium peroxydisulfate, ammonium persulfate, potassium peroxydisulfate, hydrogen peroxide, TBHP, isopropyl
Benzene hydrogen peroxide, sodium sulfite, sodium pyrosulfite, sodium hydrogensulfite, ferrous sulfate, azodiisobutyronitrile, AMBN,
One kind or at least two in benzoyl peroxide, peroxidized t-butyl perbenzoate and azo diisobutyl amidine dihydrochloride;
Described emulsifying agent is AEO, tristerin, polyethylene glycol stearate diester, dehydration mountain
Pears alcohol monoleate, sorbitan monostearate, polyoxyethylene 20 sorbitan monooleate and polyoxyethylene sorbitan mountain
One kind or at least two in pears alcohol monostearate;
Described crosslinking agent is pentaerythritol triacrylate, pentaerythritol triallyl ether, trimethylolpropane tris third
Olefin(e) acid ester, trimethylolpropane diacrylate, methylene-bisacrylamide, polyethyleneglycol diacrylate and polyethylene glycol two
One kind in methacrylate or at least two;
Described organic phase is the one kind or at least two in White Mineral Oil, isomery White Mineral Oil and polyisobutene;
Described water is running water, deionized water or distilled water.
Preferably, described polymer emulsified thickener contains the chain-transferring agent for accounting for total quality of material 0.00001-0.1%;
After adding appropriate chain-transferring agent, can make to prevent the polymer produced during initial polymerization because molecular weight is excessive cause it is water-soluble and
Thickening properties are deteriorated.
Described total material be anionic monomer+amphipathic cationic monomer+other monomer+alkali+chelating agent+initiators+
Emulsifying agent+crosslinking agent+water+organic phase+chain-transferring agent;
Described chain-transferring agent is sulfurous organic compound and/or inorganic chain-transferring agent;
Preferably, described sulfurous organic compound is n-butyl mercaptan, tert-butyl mercaptan, n-octyl mercaptan, mercaptoethanol, sulfydryl second
One kind in acid, mercaptopropionic acid, alkyl thioglycollate and alkyl mercaptopropionates or at least two.
Preferably, described inorganic chain-transferring agent is sulfurous acid, sulphite, hypophosphorous acid, hypophosphites, phosphorous acid and Asia
One kind in phosphate or at least two.
The preparation method of described polymer emulsified thickener, comprises the following steps:
(1) by anionic monomer 9.0-29.9 parts, amphipathic cationic monomer 0.03-3.0 parts and other monomers 0-30.0
Part is dissolved in 30.0-65.0 parts of water, adds 0.6-35.0 parts of alkali, controls the pH value of solution for 5.0-8.0, is subsequently adding chelating agent
0.005-0.5 parts and crosslinking agent 0.001-0.1 parts, stir, obtain water phase;
(2) by 0.2-6.0 parts of emulsifying agent 15.0-40.0 parts of organic phase of addition, stir, obtain oil phase;
(3) water phase respectively to step (1), the oil phase of step (2) carry out logical nitrogen deoxygenation, under nitrogen protection, while stirring
Mix side the water of step (1) is mutually added dropwise in the oil phase of step (2), mixing speed is 10-30000 revs/min, is subsequently adding and draws
0.001-0.5 parts of agent of hair carries out polymerisation, obtains polymer emulsified thickener;
Above-mentioned number is parts by weight.
In step (3):
Described time for adding is 5-60min;
Described polymerisation is adopted to be carried out with the following method:Start reaction in 5-50 DEG C, be warming up to by 0.01-40 hours
Continue to react 0.1-10 hours after 60-80 DEG C, be then cooled to less than 40 DEG C, add 0.2-6.0 parts of emulsifying agent, stir.
Preferably, described polymerisation is carried out under ultraviolet light.Can be dropped using ultraviolet light supplemental polymeric
The decomposition temperature of low initiator, so as to prepare the polymer of higher molecular weight at lower temperatures;Meanwhile, when polymerization exotherm mistake
When causing temperature to be difficult to control to soon, stopping ultraviolet light being greatly reduced polymerization speed, so as to control polymerization temperature.
Described polymer emulsified thickener can apply to the technologies such as household chemicals, oil field, coating and printing ink, adhesive
Field.
The present invention has the following advantages and effect relative to prior art:Polymer emulsified thickener of the invention has
Both sexes structure, intermolecular force is stronger, and more preferably, salt tolerance is also more preferable for thickening effect and emulsifying effectiveness.The polymer emulsified increasing
Thick dose the characteristics of there is Fast-swelling, substantially without insoluble matter.Preparation method of the invention stablizes controllable, safer, cost
It is relatively low, can be applied to big production.
Specific embodiment
With reference to embodiment, the present invention is described in further detail, but embodiments of the present invention not limited to this.
Embodiment 1
(1) by 161g acrylic acid, the methyl propane sulfonic acid of 50g 2- acrylamides -2 and 6g N, N- Dimethyl-N-dodecyls
Methacrylic chlorination ammonium is dissolved in 500g running water, add 38.3g ammonias, control temperature be less than 10 DEG C, regulation pH value to
6.5-6.8, is subsequently adding 0.001g mercaptoethanols, 0.3g sodium ethylene diamine tetracetates and 0.15g trimethylolpropane diacrylates
Ester, stirs, and obtains water phase;
(2) by 3.5g tristerins and 15.5g sorbitan monooleates addition 205g White Mineral Oils, stirring is equal
It is even, obtain oil phase;
(3) water phase respectively to step (1), the oil phase of step (2) carry out logical nitrogen deoxygenation 25-30min, in nitrogen protection
Under, the water of step (1) is mutually added dropwise in the oil phase of step (2) while stirring, 28000 revs/min of mixing speed, time for adding
It is 25-30min;0.1g azodiisobutyronitriles are subsequently adding, 7g1% ammonium persulfate aqueous solutions are added dropwise simultaneously afterwards and 7g1% is burnt
Sodium sulfite aqueous solution, is added dropwise 4-5min, carries out polymerisation, obtains polymer emulsified thickener 1, its theoretical active thing content
It is 24.7%.
Polymerisation is adopted to be carried out with the following method:Start in 6-7 DEG C reaction, by 1h be gradually heating to 70-75 DEG C it is follow-up
Continuous reaction 2h, is then cooled to less than 35-40 DEG C, adds 42g AEO -7, stirs.
Embodiment 2
(1) by 100g methacrylic acids, 200g acrylamides and 3g N, N- dimethyl-N-tetradecyl ylmethyl pi-allyls
Ammonium chloride is dissolved in 455g deionized waters, adds 17.8g ammonias, and control temperature is less than 10 DEG C, adjusts pH value to 5.5-5.8, so
0.00016g TGAs, 0.4g diethylenetriamine pentaacetic acids sodium and 0.1g pentaerythritol triallyl ethers are added afterwards, are stirred,
Obtain water phase;
(2) 2.1g AEOs -3,15g sorbitan monooleates are added into 200g isomery White Mineral Oils
In, stir, obtain oil phase;
(3) water phase respectively to step (1), the oil phase of step (2) carry out logical nitrogen deoxygenation 35-40min, in nitrogen protection
Under, the water of step (1) is mutually added dropwise in the oil phase of step (2) while stirring, 1000 revs/min of mixing speed, time for adding
It is 5-7min;0.4g AMBNs are subsequently adding, the azo diisobutyl amidine dihydrochlorides of 20g 1% are added afterwards, carried out
Polymerisation, obtains polymer emulsified thickener 2, and its theoretical active thing content is 31.1%.
Polymerisation is adopted to be carried out with the following method:Start reaction in 30-35 DEG C, after 40h is gradually heating to 70-75 DEG C
Continue to react 0.1h, be then cooled to less than 35-40 DEG C, add 19g polyoxyethylene 20 sorbitan monooleates, stirring is equal
It is even.
Embodiment 3
(1) by 100g acrylic acid, 174g vinyl pyrrolidones and 1.4g N, N- Dimethyl-N-dodecyl methyl alkene
Propyl ammonium chloride is dissolved in 314g distilled water, adds 66.3g sodium carbonate, and control temperature is less than 10 DEG C, regulation pH value to 6.0-
6.5,0.01g mercaptoethanols, 2g sodium ethylene diamine tetracetates and 0.95g polyethyleneglycol diacrylates are subsequently adding, stir,
Obtain water phase;
(2) by 3.3g sorbitan monooleates addition 400g polyisobutene, stir, obtain oil phase;
(3) water phase respectively to step (1), the oil phase of step (2) carry out logical nitrogen deoxygenation 25-30min, in nitrogen protection
Under, the water of step (1) being mutually added dropwise in the oil phase of step (2) while stirring, 100 revs/min of mixing speed, time for adding is
25-30min;0.5g azodiisobutyronitriles are added, the TBHP aqueous solution of 3g 1% and 3g 1% is added dropwise simultaneously afterwards
Aqueous solution of sodium bisulfite, is added dropwise 4-5min, carries out polymerisation, obtains polymer emulsified thickener 3, and its theoretical active thing contains
Measure is 29.4%.
Polymerisation is adopted to be carried out with the following method:Start reaction in 6-7 DEG C, 70-75 DEG C is gradually heating to instead by 1.5h
0.5h is answered, is then cooled to less than 35-40 DEG C, add 2.8g AEO -9, stirred.
Embodiment 4
(1) by the methyl propane sulfonic acid of 190g 2- acrylamides -2,80g vinyl imidazoles and 0.4g N, N- dimethyl-N-ten
Dialkyl methyl allyl ammonium chloride is dissolved in 353g running water, adds the sodium hydroxide solutions of 91.7g 40%, and control temperature is low
In 10 DEG C, regulation pH value is subsequently adding 0.95g n-butyl mercaptans, 0.06g sodium ethylene diamine tetracetates and 0.013g sub- to 7.0-7.5
Bisacrylamide, stirs, and obtains water phase;
(2) 2.5g sorbitan monostearates, 16.7g sorbitan monooleates are added into 280g White Mineral Oils
In, stir, obtain oil phase;
(3) water phase respectively to step (1), the oil phase of step (2) carry out logical nitrogen deoxygenation 25-30min, in nitrogen protection
Under, the water of step (1) being mutually added dropwise in the oil phase of step (2) while stirring, 800 revs/min of mixing speed, time for adding is
25-30min;Completion of dropping adjusts rotating speed to 10 revs/min, is subsequently adding the persulfate aqueous solutions of 5g 0.2% and 5g 0.2%
Metabisulfite solution, is added dropwise 4-5min, carries out polymerisation, obtains polymer emulsified thickener 4, and its theoretical active thing contains
Measure is 28.1%.
Polymerisation is adopted to be carried out with the following method:Start reaction in 6-7 DEG C, after 0.7h is gradually heating to 70-75 DEG C
Continue to react 3h, be then cooled to less than 35-40 DEG C, add 9.5g AEO -7, stir.
Embodiment 5
(1) by 113g acrylic acid and 10g N, N- Dimethyl-N-dodecyl methacrylic chlorination ammoniums and 20gN, N- bis-
Methyl-N- myristyl allyl ammonium chlorides are dissolved in 653g deionized waters, add 70.7g sodium carbonate, and control temperature is less than 30
DEG C, regulation pH value is subsequently adding 0.05g n-octyl mercaptans, 4.8g sodium ethylene diamine tetracetates and 0.07g di-2-ethylhexylphosphine oxides to 5.5-5.8
Acrylamide, stirs, and obtains water phase;
(2) by 2g polyethylene glycol stearate diesters, 14.5g sorbitan monooleates addition 160g White Mineral Oils, stir
Mix uniform, obtain oil phase;
(3) water phase respectively to step (1), the oil phase of step (2) carry out logical nitrogen deoxygenation 25-30min, in nitrogen protection
Under, the water of step (1) is mutually added dropwise in the oil phase of step (2) while stirring, 1000 revs/min of mixing speed, time for adding
It is 55-60min;0.2g AMBNs are subsequently adding, the azo diisobutyl amidine dihydrochlorides of 12g 1% are added dropwise simultaneously afterwards
The aqueous solution, is added dropwise 5-10min, carries out polymerisation, obtains polymer emulsified thickener 5, and its theoretical active thing content is
16.8%.
Polymerisation is adopted to be carried out with the following method:Start reaction in 49-50 DEG C, 60-65 DEG C is gradually heating to instead by 20h
10h is answered, is then cooled to less than 35-40 DEG C, add 14g polyoxyethylene 20 sorbitan monooleates, stirred.
Embodiment 6
(1) by the methyl propane sulfonic acid of 98g 2- acrylamides -2,179g acrylamides and 3g N, N- dimethyl-N-dodecyls
Ylmethyl allyl ammonium chloride is dissolved in 380g deionized waters, adds the potassium hydroxide solutions of 66.3g 40%, and control temperature is less than
10 DEG C, regulation pH value is subsequently adding 0.05g TGAs ethyl ester, 0.4g sodium ethylene diamine tetracetates and 0.09g to 5.5-5.8
Trimethylolpropane diacrylate, stirs, and obtains water phase;
(2) by 5.4g tristerins, 54g sorbitan monooleates addition 200g White Mineral Oils, stir,
Obtain oil phase;
(3) water phase respectively to step (1), the oil phase of step (2) carry out logical nitrogen deoxygenation 25-30min, in nitrogen protection
Under, the water of step (1) being mutually added dropwise in the oil phase of step (2) while stirring, 600 revs/min of mixing speed, time for adding is
25-30min;4.6g azodiisobutyronitriles are subsequently adding, the 10g1% azo diisobutyl amidine dihydrochloride aqueous solution are added dropwise afterwards,
4-5min is added dropwise, polymerisation is carried out, polymer emulsified thickener 6 is obtained, its theoretical active thing content is 29.3%.
Polymerisation is adopted to be carried out with the following method:Start reaction in 25-30 DEG C, after 8h is gradually heating to 75-80 DEG C
Continue to react 0.5h, be then cooled to 35-40 DEG C, add 41g AEO -9, stir.
Polymerisation is carried out (the temporary close uviol lamp if temperature rising is too fast) under ultraviolet light.
Embodiment 7
(1) by the methyl propane sulfonic acid of 300g 2- acrylamides -2 and 2g N, N- Dimethyl-N-dodecyl methacrylics
Ammonium chloride is dissolved in 484g running water, adds 24.7g ammonias, and control temperature is less than 10 DEG C, adjusts pH value to 6.5-6.8, then
0.3g sodium ethylene diamine tetracetates and 0.15g pentaerythritol triallyl ethers are added, is stirred, obtain water phase;
(2) 3.5g sorbitan monostearates, 15.9g sorbitan monooleates are added into 162g White Mineral Oils
In, stir, obtain oil phase;
(3) water phase respectively to step (1), the oil phase of step (2) carry out logical nitrogen deoxygenation 25-30min, in nitrogen protection
Under, the water of step (1) is mutually added dropwise in the oil phase of step (2) while stirring, 10000 revs/min of mixing speed, time for adding
It is 25-30min;The isopropyl benzene hydroperoxide aqueous solution of 5g 0.2% and the ferrous sulfate aqueous solutions of 5g 0.2% are subsequently adding, are added dropwise
5-10min, carries out polymerisation, obtains polymer emulsified thickener 7, and its theoretical active thing content is 31.6%.
Polymerisation is adopted to be carried out with the following method:Start in 6-7 DEG C reaction, by 2h be gradually heating to 70-75 DEG C it is follow-up
Continuous reaction 1 hour, is then cooled to less than 35-40 DEG C, adds 32g AEO -7, stirs.
Embodiment 8
(1) by the methyl propane sulfonic acid of 100g 2- acrylamides -2,300g acrylamides and 7g N, N- dimethyl-N-dodecyls
Base allyl ammonium chloride is dissolved in 400g running water, adds 8.2g ammonias, and control temperature is less than 10 DEG C, regulation pH value to 5.5-
5.8,0.004g phosphorous acid, 0.7 sodium ethylene diamine tetracetate and 0.13g polyethylene glycol dimethacrylates are subsequently adding, stir
Uniformly, water phase is obtained;
(2) by 2g tristerins, 10g sorbitan monooleates addition 195g White Mineral Oils, stir, obtain
To oil phase;
(3) water phase respectively to step (1), the oil phase of step (2) carry out logical nitrogen deoxygenation 25-30min, in nitrogen protection
Under, the water of step (1) is mutually added dropwise in the oil phase of step (2) while stirring, 15000 revs/min of mixing speed, time for adding
It is 25-30min;The azo diisobutyl amidine dihydrochloride aqueous solution of 15g 2% is subsequently adding, 4-5min is added dropwise, be polymerized instead
Should, polymer emulsified thickener 8 is obtained, its theoretical active thing content is 39.6%.
Polymerisation is adopted to be carried out with the following method:Start reaction in 25-30 DEG C, after 30h is gradually heating to 70-75 DEG C
Continue to react 1h, be then cooled to less than 35-40 DEG C, add 11g AEO -9, stir.
Polymerisation is carried out (the temporary close uviol lamp if temperature rising is too fast) under ultraviolet light.
Embodiment 9
(1) 252g acrylic acid and 1g N, N- Dimethyl-N-dodecyl methacrylic chlorination ammoniums are dissolved in 463g originally
In water, 332.8g saleratus is added, control temperature is less than 10 DEG C, and regulation pH value is subsequently adding 0.03g phosphorous to 6.5-7.0
Sour sodium, 0.4g sodium ethylene diamine tetracetates and 0.11g trimethylolpropane diacrylates, stir, and obtain water phase;
(2) by 1g tristerins, 9g sorbitan monooleates addition 160g White Mineral Oils, stir, obtain
To oil phase;
(3) water phase respectively to step (1), the oil phase of step (2) carry out logical nitrogen deoxygenation 25-30min, in nitrogen protection
Under, the water of step (1) being mutually added dropwise in the oil phase of step (2) while stirring, 800 revs/min of mixing speed, time for adding is
5-10min;2.6g azodiisobutyronitriles are subsequently adding, the ammonium persulfate aqueous solutions of 5g 1% and the sulfurous of 5g 1% is added dropwise simultaneously afterwards
Sour hydrogen sodium water solution, is added dropwise 4-5min, carries out polymerisation, obtains polymer emulsified thickener 9, and its theoretical active thing content is
36.7%.
Polymerisation is adopted to be carried out with the following method:Start reaction in 6-7 DEG C, after 0.02h is gradually heating to 70-75 DEG C
Continue to react 2 hours, be then cooled to less than 35-40 DEG C, add 8g AEO -9, stir.
Comparative example 1
(1) 167g acrylic acid and the methyl propane sulfonic acid of 50g 2- acrylamides -2 are dissolved in 500g running water, add 39.7g
Ammonia, control temperature is less than 10 DEG C, and regulation pH value is subsequently adding 0.001g mercaptoethanols, 0.3g ethylenediamine tetrems to 6.5-6.8
Sour sodium and 0.15g trimethylolpropane diacrylates, stir, and obtain water phase;
(2) by 3.5g tristerins and 15.5g sorbitan monooleates addition 205g White Mineral Oils, stirring is equal
It is even, obtain oil phase;
(3) water phase respectively to step (1), the oil phase of step (2) carry out logical nitrogen deoxygenation 25-30min, in nitrogen protection
Under, the water of step (1) is mutually added dropwise in the oil phase of step (2) while stirring, 28000 revs/min of mixing speed, time for adding
It is 25-30min;0.1g azodiisobutyronitriles are subsequently adding, 7g1% ammonium persulfate aqueous solutions are added dropwise simultaneously afterwards and 7g1% is burnt
Sodium sulfite aqueous solution, is added dropwise 4-5min, carries out polymerisation, obtains comparative sample 1, and its theoretical active thing content is
24.7%.
Polymerisation is adopted to be carried out with the following method:0.2h is reacted in 6-7 DEG C, 70-75 DEG C of reaction is gradually heating to by 1h
2h, is then cooled to less than 35-40 DEG C, adds 42g AEO -7, stirs.
Effect example
The sample and tested viscosity of 1% active matter are configured with deionized water, thickening properties, the emulsibility of each polymer is contrasted
Energy and salt resistant character, as a result as shown in table 1:
The polymer emulsified thickener prepared using the embodiment of the present invention is can be seen that from following test results, product is total
Body performance is superior to import sample, is even more compared with domestic sample and is improved largely.
The viscosity of each polymer of table 1, thickening properties, emulsifiability and salt resistant character result
Above-described embodiment is the present invention preferably implementation method, but embodiments of the present invention are not by above-described embodiment
Limitation, it is other it is any without departing from Spirit Essence of the invention and the change, modification, replacement made under principle, combine, simplification,
Equivalent substitute mode is should be, is included within protection scope of the present invention.
Claims (7)
1. a kind of polymer emulsified thickener, it is characterised in that containing multiple polymerized monomers, described polymerized monomer contains by matter
Measure the anionic monomer 30.0-99.9% and amphipathic cationic monomer 0.1-10.0% of percentages;Described anion list
Body is the one kind or at least two in acrylic acid, methacrylic acid or the methyl propane sulfonic acid of 2- acrylamides -2;Described is amphipathic
Cationic monomer is N, N- Dimethyl-N-dodecyl methacrylic chlorinations ammonium, N, N- dimethyl-N-tetradecyl ylmethyl alkene
Propyl ammonium chloride, N, N- Dimethyl-N-dodecyls allyl ammonium chloride or N, N- dimethyl-N-tetradecyl base pi-allyl chlorination
One kind in ammonium or at least two;The weight average molecular weight of described polymer emulsified thickener is 200-600 ten thousand;
The preparation method of above-mentioned polymer emulsified thickener, comprises the following steps:
(1) it is anionic monomer 9.0-29.9 parts, amphipathic cationic monomer 0.03-3.0 parts and 0-30.0 parts of other monomers is molten
In 30.0-65.0 parts of water, 0.6-35.0 parts of alkali is added, control the pH value of solution for 5.0-8.0, be subsequently adding chelating agent
0.005-0.5 parts and crosslinking agent 0.001-0.1 parts, stir, obtain water phase;
(2) by 0.2-6.0 parts of emulsifying agent 15.0-40.0 parts of organic phase of addition, stir, obtain oil phase;
(3) water phase respectively to step (1), the oil phase of step (2) carry out logical nitrogen deoxygenation, under nitrogen protection, while stirring
The water of step (1) is mutually added dropwise in the oil phase of step (2), 10-30000 revs/min of mixing speed is subsequently adding initiator
0.001-0.5 parts carries out polymerisation, obtains polymer emulsified thickener;
Above-mentioned number is parts by weight;
Time for adding described in step (3) is 5-60min;Described polymerisation is adopted to be carried out with the following method:In 5-50 DEG C
Start reaction, continue to react 0.1-10h after 0.01-40h is warming up to 60-80 DEG C, be then cooled to less than 40 DEG C, add
0.2-6.0 parts of emulsifying agent, stirs.
2. polymer emulsified thickener according to claim 1, it is characterised in that other described monomers are acryloyl
One kind in amine, vinyl pyrrolidone and vinyl imidazole or at least two;
Described alkali is in NaOH, potassium hydroxide, ammoniacal liquor, ammonia, sodium carbonate, potassium carbonate, sodium acid carbonate and saleratus
One kind or at least two;
Described chelating agent is sodium ethylene diamine tetracetate and/or diethylenetriamine pentaacetic acid sodium;
Described initiator is sodium peroxydisulfate, ammonium persulfate, potassium peroxydisulfate, hydrogen peroxide, TBHP, isopropylbenzene mistake
Hydrogen oxide, sodium sulfite, sodium pyrosulfite, sodium hydrogensulfite, ferrous sulfate, azodiisobutyronitrile, AMBN, peroxide
Change the one kind or at least two in benzoyl, peroxidized t-butyl perbenzoate and azo diisobutyl amidine dihydrochloride;
Described emulsifying agent is AEO, tristerin, polyethylene glycol stearate diester, anhydrous sorbitol
Monoleate, sorbitan monostearate, polyoxyethylene 20 sorbitan monooleate and polyoxyethylene sorbitan
One kind in monostearate or at least two;
Described crosslinking agent is pentaerythritol triacrylate, pentaerythritol triallyl ether, trimethylolpropane tris acrylic acid
Ester, trimethylolpropane diacrylate, methylene-bisacrylamide, polyethyleneglycol diacrylate and polyethylene glycol dimethyl
One kind in acrylate or at least two;
Described organic phase is the one kind or at least two in White Mineral Oil, isomery White Mineral Oil and polyisobutene;
Described water is running water, deionized water or distilled water.
3. polymer emulsified thickener according to claim 2, it is characterised in that described polymer emulsified thickener contains
There is the chain-transferring agent of the 0.00001-0.1% for accounting for total quality of material.
4. polymer emulsified thickener according to claim 3, it is characterised in that described chain-transferring agent is that sulfur-bearing is organic
Thing and/or inorganic chain-transferring agent.
5. polymer emulsified thickener according to claim 4, it is characterised in that described sulfurous organic compound is positive fourth sulphur
Alcohol, tert-butyl mercaptan, n-octyl mercaptan, mercaptoethanol, TGA, mercaptopropionic acid, alkyl thioglycollate and mercaptopropionic acid alkyl
One kind in ester or at least two;Described inorganic chain-transferring agent is sulfurous acid, sulphite, hypophosphorous acid, hypophosphites, phosphorous
One kind or at least two in acid and phosphite.
6. polymer emulsified thickener according to claim 1, it is characterised in that described polymerisation is in ultraviolet lighting
Penetrate down carry out.
7. the polymer emulsified thickener described in any one of claim 1-2 be applied to household chemicals, oil field, coating and printing ink and
Technical field of adhesive.
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CN104963220A (en) * | 2015-07-23 | 2015-10-07 | 百宁纺织化工(中山)有限公司 | Emulsifying agent formula |
CN105969368A (en) * | 2016-05-16 | 2016-09-28 | 四川恒泽建材有限公司 | Foaming agent for shield tunnelling machine and preparation method of foaming agent |
CN109762105B (en) * | 2019-03-21 | 2021-03-16 | 东营宝莫环境工程有限公司 | Emulsified dispersed thickened polymer for petroleum exploitation and preparation method thereof |
CN112708012A (en) * | 2019-10-25 | 2021-04-27 | 中国石油化工股份有限公司 | Emulsion polymer for fracturing and preparation method and application thereof |
CN112252057B (en) * | 2020-07-29 | 2022-04-26 | 爱森(中国)絮凝剂有限公司 | Preparation method of composite anionic polyacrylamide printing and dyeing thickener |
CN112876596B (en) * | 2021-01-06 | 2022-12-13 | 广州市东雄化工有限公司 | Solution type alcohol disinfection gel thickening agent and preparation method thereof |
CN113563535B (en) * | 2021-09-26 | 2021-11-30 | 山东诺尔生物科技有限公司 | Temperature-sensitive self-assembly tackifying dispersion and preparation method thereof |
CN114134732A (en) * | 2021-11-24 | 2022-03-04 | 杭州传化精细化工有限公司 | Compound thickener and preparation method thereof |
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CN102532410A (en) * | 2011-12-22 | 2012-07-04 | 中国海洋石油总公司 | Hydrophobically associating polymer, preparation method and application thereof |
CN103320114A (en) * | 2013-05-10 | 2013-09-25 | 北京爱普聚合科技有限公司 | Multiple association type polymer cleaning fracturing fluid thickening agent and preparation method thereof |
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CN102532410A (en) * | 2011-12-22 | 2012-07-04 | 中国海洋石油总公司 | Hydrophobically associating polymer, preparation method and application thereof |
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