CN103183765A - Preparation method of powdery polyacrylic acid thickener - Google Patents
Preparation method of powdery polyacrylic acid thickener Download PDFInfo
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Abstract
A preparation method of a powdery polyacrylic acid thickener comprises the following steps: at room temperature, adding organic solvent, polymeric monomers, comonomers, neutralizers and cross linking agents in a reaction kettle in sequence, introducing nitrogen to remove all oxygen, starting stirring to cause the reactants to be uniformly mixed, rising the temperature to the reaction temperature, dissolving initiators in the organic solvent having the same reaction system as the initiators, dripping off for 15-30 min, preserving the reaction temperature for 3-6 hours, cooling, filtering, washing with the organic solvent, removing unreacted raw materials in the product, and vacuum-drying a filter cake for 24-48 hours at the temperature of 40-50 DEG C to obtain white powder. The preparation method has the advantages of simple preparation process, environmental friendliness, low energy consumption and low cost.
Description
Technical field
The invention belongs to a kind of preparation method of Powdered polyacrylic thickening material.
Background technology
Nineteen fifty-three polyacrylic thickening material Carbomer 934 has introduced since the market, and is more and more wider in the application of coating, weaving, pharmacy, building materials, washing composition and makeup.In recent years, along with the needs of modernization industry, the acrylic thickener development is very fast, and the development and application of the synthetic method that it is new has caused scientific worker's concern.
At present, the preparation method of polyacrylic thickening material mainly adopts three kinds of emulsion polymerization, reversed emulsion polymerization and the precipitator method.The speed of response of emulsion polymerization is very fast, and the molecular weight of polymkeric substance is higher, and the viscosity of material is low, is easy to conduct heat and mix, and produces control easily.The shortcoming of letex polymerization is that emulsifying agent of adding in the polymerization process etc. influences product properties.For obtaining solid polymer, need through technological processs such as cohesion, separation, washing, production cost height.
The antiphase emulsifiable method rate of polymerization is fast, reaction conditions is gentle, obtains product and exists with emulsion form, and is easy to use.But because building-up process has been used a large amount of organic solvents, product is the water-in-oil emulsion, is not suitable for preparing the thickening material of powder shaped.
Solution polymerization process claims precipitation polymerization method again, and this polyreaction must be carried out in organic solvent, and after polymerization was finished, unpolymerized vinylformic acid and esters monomer thereof, impurity can be removed by solvent wash, and drying can obtain the higher acrylic thickener of purity.But, big, the higher organic solvent of boiling point of the most of employing of this method toxicity, as aromatic hydrocarbon and hydrochloric ether, thereby cause the drying temperature height, granularity and color and luster to product have bigger influence, and be mingled with trace toxic solvent, color in the product easily and slightly displaing yellow, dissolution rate is slow and cause thickening properties not ideal enough in water, and its range of application is very limited.
US Patent No. 20070072788A1 disclosed the method that a kind of solvent method prepares Polyacrylate thickeners in 2007.This method selects for use benzene, methyl chloride, hexane, ethyl acetate etc. to be solvent, be initiator with benzoyl peroxide, dilauroyl peroxide, peroxy dicarbonate diethyl ester, be that monomer, pentaerythritol triallyl ether are linking agent with vinylformic acid, in solution, add sodium-chlor or anhydrous Na
2SO
4Deng inorganic salt ionogen and organic silicon surfactant, prepared in reaction Polyacrylate thickeners at a certain temperature.Synthetic thickening material is white powder, can be divided in water can in 5 minutes, dissolve, dissolve in 10 minutes, be partly dissolved in 10 minutes with 10 minutes undissolved water-wet performances be excellent, good, in, differ from four kinds of thickening materials.It is solvent with methylene dichloride or benzene that European patent EP 1 767 568 A1 in 2007 disclose employing, vinylformic acid and/or Fatty Alcohol(C12-C14 and C12-C18) (C
18-C
22) acrylate is that monomer, tetramethylolmethane Vinyl Ether are linking agent, superoxide is initiator, polymerization prepares acrylic thickener in reactor.The thickening material that these methods make has all been selected the bigger organic solvents of toxicity such as benzene class aromatic hydrocarbon and hydrochloric ether for use, and production technique is comparatively complicated, and dissolution rate is slower in water.
Summary of the invention
The present invention is directed to the deficiency that powdery acrylic thickener preparation method exists, the preparation method of the polyacrylic thickening material that provide that a kind of preparation technology is succinct, environmental protection, energy consumption and cost is low.
Avoid selecting for use the organic solvent except benzene class aromatic hydrocarbon and hydrochloric ether among the present invention.Because alcoholic solvent has dissolving and swelling action to acrylic thickener, can not select for use; Organic solvent volatilization easily in reaction process that boiling point is lower, reaction needs to carry out in autoclave, brought the inconvenience of producing, and the higher organic solvent of boiling point need drying be removed under higher temperature, can not select for use.Therefore, the present invention preferably uses the normal hexane that toxicity is less, boiling point is lower (50-90 ℃), hexanaphthene, organic solvents such as acetone, ethyl acetate.
Technical scheme provided by the invention is as follows:
Under the room temperature, add organic solvent, polymerization single polymerization monomer, comonomer, neutralizing agent, linking agent successively in reactor, logical nitrogen 20～30 min are with the oxygen in the Ex-all reaction system; Open and stir, reactant is mixed, be warming up to temperature of reaction, by initiator: organic solvent is 1 gram: 40mL, dissolves in the organic solvent that initiator is identical with reaction system, and in 15～30min, be added dropwise in the reactor, behind insulation reaction temperature 3～6h, cool off, filter, use organic solvent washing, remove unreacted raw material in the product, filter cake at 40～50 ℃ of following vacuum-drying 24～48 h, is obtained white powder; Wherein the weight percent of material is organic solvent 45～65%, polymerization single polymerization monomer 5%～25%, comonomer 0～10%, neutralizing agent 0.01%～8%, linking agent 0.01%～6%, initiator 0.01%～6%, wherein initiator is peroxidation class or azo class, temperature of reaction when being initiator with the peroxidation class is 60～80 ℃, and temperature of reaction is 50～70 ℃ during with azo-initiator.
Aforesaid organic solvent is one or more in ethyl acetate, normal hexane, hexanaphthene, acetone, the ethyl acetate.
Aforesaid polymerization single polymerization monomer is the carboxylic acid monomer of containing the alkene key of a free redical polymerization, is vinylformic acid, methacrylic acid or butene dioic acid.
Aforesaid linking agent is pentaerythrite allyl ether, multi-functional acrylate's (as tetramethylolmethane triolefin acrylate, dipentaerythrityl ether five acrylate, dipentaerythrityl ether six acrylate), polyfunctional group methacrylic ester (as trimethylolpropane trimethacrylate, two contracting trihydroxy methyl propane tetraacrylate) or the silicone couplet that contains vinyl.
Aforesaid alkaline neutraliser is sodium bicarbonate, sodium hydroxide or trolamine.
Aforesaid comonomer is C
3～C
18Alkyl acrylate or C
3～C
18Alkyl methacrylate.
Aforesaid initiator is selected peroxidation class initiator (as dilauroyl peroxide or dibenzoyl peroxide) or azo-initiator (as Diisopropyl azodicarboxylate or 2,2'-Azobis(2,4-dimethylvaleronitrile)) for use.
The measuring method of acrylic thickener:
Synthetic Polyacrylate thickeners powder 1～2g is scattered in the sample pool that fills 120 mL ethanol, measures its particle diameter and size-grade distribution thereof with laser particle analyzer.
Get polypropylene-base thickening material powder, use deionized water, be made into 0.5% the aqueous solution, (900～1000r/min) to dissolving fully, and measures its dissolution time with stopwatch 25 ℃ of stirrings;
In above-mentioned solution, regulate pH 7～9 with the sodium hydroxide solution of concentration 30%, with UV～1600 ultraviolet-visible pectrophotometers survey its transmittance (under the room temperature, λ=425nm);
Survey its viscosity with NDJ～8S rotational viscosimeter (25 ℃, No. 4 rotors, 6 r/min).
The Powdered Polyacrylate thickeners that the present invention synthesizes is the caustic solubility thickening material, in use should regulate its pH value of aqueous solution to neutrality or slight alkalinity, and pH is 7～9.
Compared with prior art, the present invention has the following advantages:
It is 1, of the present invention that preparation is simple, the solvent low toxicity of use, environmental protection, and drying is removed easily, and can recycle by underpressure distillation or air distillation; 2, by in vinylformic acid, adding the material of alkalescence such as a small amount of sodium bicarbonate, trolamine or sodium hydroxide, by the part acrylic acid carboxyl is become salt, the carboxylic ions that generates is mutually exclusive, thereby reach the mitigation polyreaction, be conducive to control molecular weight and the crosslinking degree of acrylic polymer, thereby make molecular weight and particle size distribution even, make its dissolution rate in water fast, and the viscosity of product and transmittance are improved;
3, the initiator feed way is selected to drip with slow, overcomes easy sudden and violent poly-or excessive crosslinked phenomenon in vinylformic acid (ester) and the linking agent polymerization process effectively, and the vinylformic acid that improves and the transformation efficiency of ester class thereof; Control viscosity and the transmittance of product by the consumption of regulating linking agent and initiator;
4, the acrylate by introducing pentaerythrite allyl ether, many officials group or methacrylic ester and organo-silicon coupling agent make the three-dimensional netted three-dimensional arrangement of polymer formation complexity, have effectively brought up to the thickening capabilities of product
5, adopt the acrylic thickener even particle size distribution of this method preparation, the dissolution rate in water is fast, and aqueous solution viscosity is big, and the transmittance height can satisfy service requirements.
Embodiment
In order to make purpose of the present invention, technical scheme and advantage are clearer, and below in conjunction with concrete embodiment, the present invention is described in detail.
To be described in detail the present invention by specific embodiment below.
Embodiment 1:
Agitator is being housed, thermometer, add 200 mL ethyl acetate successively in the 500 mL four-hole boiling flasks of reflux exchanger, 35g vinylformic acid, the 5g Jia Jibingxisuanyizhi, 0.07g pentaerythritol triallyl ether, logical nitrogen 30 min open and stir, and are warming up to 70 ℃, the 0.14g dilauroyl peroxide is dissolved in the 6ml ethyl acetate, drip in 15～17min with the normal pressure funnel, add the 2g sodium bicarbonate again, to relax polyreaction, the control temperature of reaction is at 71～73 ℃, and to be triggered dose dripped off insulation reaction 4 hours fully.Be cooled to room temperature, filter, with ethyl acetate washing 2 times, suction filtration is removed unreacted raw material in the polymkeric substance, and filter cake is placed in the porcelain dish, at 45 ℃ of following vacuum-drying 24h, obtains white powder, and yield is 96.8%; Its average particle size distribution is about 0.5 μ m, and the dissolution time of surveying its 0.5% aqueous solution is 135s, and transmittance is 95～97%, and viscosity is 1500～1700mPa ﹒ S.
Embodiment 2:
Agitator is being housed, thermometer, add 150 mL ethyl acetate and 100mL hexanaphthene successively in the 500 mL four-hole boiling flasks of reflux exchanger, the 30g methacrylic acid, the 14g butyl acrylate, 0.28g trimethylolpropane trimethacrylate, logical nitrogen 30min opens and stirs, and is warming up to 70 ℃, the 0.35g dibenzoyl peroxide is dissolved in the 14ml ethyl acetate, drip in 20～23min with the normal pressure funnel, add the 3g trolamine again, to relax polyreaction, the control temperature of reaction is at 73～75 ℃, and to be triggered dose dripped off insulation reaction 5 hours fully.Be cooled to room temperature, filter, with hexanaphthene washing 3 times, remove unreacted raw material in the polymkeric substance, suction filtration is placed on filter cake in the porcelain dish, at 40 ℃ of following vacuum-drying 30h, obtain white fine and smooth powder, yield is 98.2%, and its average particle size distribution is about 0.4 μ m, and the dissolution time of surveying its 0.5% aqueous solution is 397s, transmittance is 92～93%, and viscosity is 58000～59000mPa ﹒ S.
Embodiment 3:
Agitator is being housed, thermometer, add 150 mL ethyl acetate successively in the 500 mL four-hole boiling flasks of reflux exchanger, the 80mL normal hexane, the 40g butene dioic acid, the 2g dodecyl acrylate, 0.28g pentaerythritol triallyl ether, logical nitrogen 30min opens and stirs, be warming up to 50 ℃, the 0.56g Diisopropyl azodicarboxylate is dissolved in the 23ml ethyl acetate, drips in 25～27min with the normal pressure funnel, add 3.5g sodium bicarbonate and 1g sodium hydroxide again and relax polyreaction, the control temperature of reaction is at 56～58 ℃, and to be triggered dose dripped off insulation reaction 5 hours fully.Be cooled to room temperature, filter, with ethyl acetate washing 2 times, remove unreacted raw material in the polymkeric substance, suction filtration is placed on filter cake in the porcelain dish, at 50 ℃ of following vacuum-drying 36h, obtain white fine and smooth powder, yield is 97.8%, and its average particle size distribution is about 0.6 μ m, and surveying its 0.5% aqueous solution dissolution time is 345s, transmittance is 93～94%, and viscosity is 31000～32000mPa ﹒ S.
Embodiment 4:
Agitator is being housed, and thermometer adds the acetone of 250 mL successively in the 500 mL four-hole boiling flasks of reflux exchanger, 30g vinylformic acid, 5g butyl acrylate, 0.35g tetramethylolmethane triolefin acrylate, logical nitrogen 30min opens and stirs, and is warming up to 50 ℃, the 0.42g 2,2'-Azobis(2,4-dimethylvaleronitrile) is dissolved in 17ml acetone, drip in 23～25min with the normal pressure funnel, add the 2g sodium bicarbonate again, relax polyreaction, the control temperature of reaction is at 58～60 ℃, and to be triggered dose dripped off insulation reaction 5 hours fully.Be cooled to room temperature, filter, use washing with acetone 2 times, remove unreacted raw material in the polymkeric substance, suction filtration is placed on filter cake in the disk, at 50 ℃ of following vacuum-drying 30h, obtain white powder, yield is 97.8%, and its average particle size distribution is about 0.5 μ m, and the dissolution time of surveying its 0.5% aqueous solution is 287s, transmittance is 95～96%, and viscosity is 44000～45000m Pa ﹒ S.
Embodiment 5:
Agitator is being housed, thermometer, add 80 mL ethyl acetate and 100mL hexanaphthene successively in the 500 mL four-hole boiling flasks of reflux exchanger, the 40g methacrylic acid, the 8g Jia Jibingxisuanyizhi, 0.07g methacryloxypropyl trimethoxy silane, 0.09g deionized water, logical nitrogen 30min, stirred 1 hour earlier, make the methacryloxypropyl trimethoxy silane hydrolysis complete, be warming up to 70 ℃, the 0.21g dilauroyl peroxide is dissolved in the 9ml ethyl acetate, drip in 15～17min with the normal pressure funnel, add 2g sodium hydroxide and 1.5g sodium bicarbonate again, to relax polyreaction, the control temperature of reaction is at 71～73 ℃, and to be triggered dose dripped off insulation reaction 3 hours fully.Be cooled to room temperature, filter, ethyl acetate washing 3 times, remove unreacted raw material in the polymkeric substance, suction filtration is placed on filter cake in the porcelain dish, at 40 ℃ of following vacuum-drying 40h, obtain white powder, yield is 98.6%, and its median size is about 0.24 μ m, and the dissolution time of surveying its 0.5% aqueous solution is 85s, transmittance is 97～98%, and viscosity is 4600～4700mPa ﹒ S.
Embodiment 6:
Agitator is being housed, thermometer, add 120 mL ethyl acetate and 40mL normal hexane successively in the 500 mL four-hole boiling flasks of reflux exchanger, 36g vinylformic acid, the 10g dodecyl acrylate,, 0.42 g, two contracting trihydroxy methyl propane tetraacrylate, logical nitrogen 30min, stirred 30 minutes earlier, be warming up to 50 ℃ again, the 0.42g 2,2'-Azobis(2,4-dimethylvaleronitrile) is dissolved in the 17ml ethyl acetate, drip in 20～22min with the normal pressure funnel, add 2g trolamine and 1g sodium hydroxide again and relax polyreaction, prevent implode, avoid elevating the temperature because of the polyreaction heat release, the control temperature of reaction is at 55～57 ℃, and to be triggered dose dripped off insulation reaction 6 hours fully.Reaction is cooled to room temperature after finishing, and filters, ethyl acetate washing 2 times, suction filtration is placed on filter cake in the porcelain dish, at 45 ℃ of following vacuum-drying 45h, obtain white powder, yield is 98.5%, and its median size is about 0.23 μ m, and the dissolution time of surveying its 0.5% aqueous solution is 199s, transmittance is 96～96.%, and viscosity is 28000～29000m Pa ﹒ S.
Embodiment 7:
Agitator is being housed, thermometer, add the ethyl acetate of 60mL and the acetone of 100mL successively in the 500 mL four-hole boiling flasks of reflux exchanger, 35g vinylformic acid, 7g butyl acrylate, 0.35g methacryloxypropyl trimethoxy silane, 0.07g pentaerythritol triallyl ether, 0.28g deionized water, nitrogen 30min stirred 30 minutes earlier, be warming up to 60 ℃ again, the 0.21g dilauroyl peroxide is dissolved in the 9ml ethyl acetate, drips in 17～19min with the normal pressure funnel, add the 6g trolamine again, relax polyreaction,, the control temperature of reaction is at 73～75 ℃, and to be triggered dose dripped off insulation reaction 5 hours fully.Be cooled to room temperature, filter ethyl acetate washing 3 times, suction filtration, filter cake is placed in the porcelain dish, at 50 ℃ of following vacuum-drying 36h, obtain white powder, yield is 98.8%, its median size is about 0.3 μ m, surveying its 0.5% aqueous solution dissolution time is 267s, and transmittance is 91～92%, and viscosity is 10000～11000m Pa ﹒ S.
Embodiment 8:
Agitator is being housed, thermometer, add 120mL hexanaphthene and 30mL normal hexane successively in the 500 mL four-hole boiling flasks of reflux exchanger, 30g vinylformic acid, the 14g octadecyl acrylate, 0.14g methacryloxypropyl trimethoxy silane, 0.14g tetramethylol methane tetraacrylate, 0.35g deionized water, logical nitrogen 30min stirred 30 minutes earlier, be warming up to 50 ℃ again, the 0.42g Diisopropyl azodicarboxylate is dissolved in the 17ml cyclohexane, drips in 25～27min with the normal pressure funnel, add 1.5g sodium bicarbonate and 0.5g sodium hydroxide again and relax polyreaction, prevent implode, avoid because the polyreaction heat release elevates the temperature, the control temperature of reaction is at 55～57 ℃, and to be triggered dose dripped off insulation reaction 4 hours fully.Be cooled to room temperature, filter ethyl acetate washing 3 times, suction filtration, filter cake is placed in the porcelain dish, at 45 ℃ of following vacuum-drying 40h, obtain white powder, yield is 98.6%, its median size is about 0.34 μ m, survey its 0.5% aqueous solution dissolution time by being 228s, transmittance is 94～95%, and viscosity is 18000～19000m Pa ﹒ S.
Embodiment 9:
Agitator is being housed, thermometer, add 180mL acetone successively in the 500 mL four-hole boiling flasks of reflux exchanger, the 42g methacrylic acid, the 7g tetradecyl acrylate, 0.14g methacryloxypropyl trimethoxy silane, 0.35g two contracting trihydroxy methyl propane tetraacrylate, 0.21g deionized water, logical nitrogen 30min stirred 30 minutes earlier, be warming up to 50 ℃ again, the 0.42g 2,2'-Azobis(2,4-dimethylvaleronitrile) is dissolved in 17ml acetone, drips in 28～30min with the normal pressure funnel, add 3g trolamine and 0.5g sodium hydroxide again and relax polyreaction, prevent implode, avoid because the polyreaction heat release elevates the temperature, the control temperature of reaction is at 58～60 ℃, and to be triggered dose dripped off insulation reaction 5 hours fully.Be cooled to room temperature, filter ethyl acetate washing 2 times, suction filtration, filter cake is placed in the porcelain dish, at 50 ℃ of following vacuum-drying 24h, obtain white powder, yield is 98.6%, its average particle size distribution is about 0.38 μ m, survey its 0.5% aqueous solution dissolution time by being 195s, transmittance is 95～96%, and viscosity is 37000～38000m Pa ﹒ S.
Embodiment 10:
Agitator is being housed, thermometer, add 80mL normal hexane and 140mL ethyl acetate successively in the 500 mL four-hole boiling flasks of reflux exchanger, the butene dioic acid of 40g, the dodecyl acrylate of 2g, 0.28g methacryloxypropyl trimethoxy silane, 0.28g two contracting trihydroxy methyl propane tetraacrylate, the deionized water of 0.35g, logical nitrogen 30min, stirred 30 minutes earlier, be warming up to 70 ℃ again, the dibenzoyl peroxide of 0.28g is dissolved in the 12ml ethyl acetate, drip in 20～22min with the normal pressure funnel, add 2.5g sodium bicarbonate and 0.5g trolamine again, relax polyreaction, prevent implode, avoid elevating the temperature because of the polyreaction heat release, the control temperature of reaction is at 72～75 ℃, and to be triggered dose dripped off insulation reaction 4 hours fully.Be cooled to room temperature, filter ethyl acetate washing 2 times, suction filtration, filter cake is placed in the porcelain dish, at 40 ℃ of following vacuum-drying 48h, obtain white powder, yield is 98.6%, its average particle size distribution is about 0.36 μ m, survey its 0.5% aqueous solution dissolution time by being 268s, transmittance is 92～93%, and viscosity is 55000～56000m Pa ﹒ S.
Claims (9)
1. the preparation method of a Powdered polyacrylic thickening material is characterized in that comprising the steps:
Under the room temperature, add organic solvent, polymerization single polymerization monomer, comonomer, neutralizing agent, linking agent successively in reactor, logical nitrogen 20～30 min are with the oxygen in the Ex-all reaction system; Open and stir, reactant is mixed, be warming up to temperature of reaction, by initiator: organic solvent is 1 gram: 40mL, dissolves in the organic solvent that initiator is identical with reaction system, and in 15～30min, be added dropwise in the reactor, behind insulation reaction temperature 3～6h, cool off, filter, use organic solvent washing, remove unreacted raw material in the product, filter cake at 40～50 ℃ of following vacuum-drying 24～48 h, is obtained white powder; Wherein the weight percent of material is organic solvent 45～65%, polymerization single polymerization monomer 5%～25%, comonomer 0～10%, neutralizing agent 0.01%～8%, linking agent 0.01%～6%, initiator 0.01%～6%, wherein initiator is peroxidation class or azo class, temperature of reaction when being initiator with the peroxidation class is 60～80 ℃, and temperature of reaction is 50～70 ℃ during with azo-initiator.
2. the preparation method of a kind of Powdered polyacrylic thickening material as claimed in claim 1 is characterized in that described organic solvent is one or more in ethyl acetate, normal hexane, hexanaphthene, acetone, the ethyl acetate.
3. the preparation method of a kind of Powdered polyacrylic thickening material as claimed in claim 1 is characterized in that described polymerization single polymerization monomer is the carboxylic acid monomer of containing the alkene key of a free redical polymerization, is vinylformic acid, methacrylic acid or butene dioic acid.
4. the preparation method of a kind of Powdered polyacrylic thickening material as claimed in claim 1, it is characterized in that described linking agent be pentaerythrite allyl ether, multi-functional acrylate's (as tetramethylolmethane triolefin acrylate, dipentaerythrityl ether five acrylate, dipentaerythrityl ether six acrylate), polyfunctional group methacrylic ester (as trimethylolpropane trimethacrylate,, two contracting trihydroxy methyl propane tetraacrylate) or contain the silicone couplet of vinyl.
5. the preparation method of a kind of Powdered polyacrylic thickening material as claimed in claim 4 is characterized in that described multi-functional acrylate is trimethylolpropane trimethacrylate or two contracting trihydroxy methyl propane tetraacrylate for tetramethylolmethane triolefin acrylate, dipentaerythrityl ether five acrylate or dipentaerythrityl ether six acrylate, polyfunctional group methacrylic ester.
6. the preparation method of a kind of Powdered polyacrylic thickening material as claimed in claim 1 is characterized in that described neutralizing agent is sodium bicarbonate, sodium hydroxide or trolamine.
7. the preparation method of a kind of Powdered polyacrylic thickening material as claimed in claim 1 is characterized in that described comonomer is C
3～C
18Alkyl acrylate or C
3～C
18Alkyl methacrylate.
8. the preparation method of a kind of Powdered polyacrylic thickening material as claimed in claim 1 is characterized in that described peroxidation class initiator is dilauroyl peroxide or dibenzoyl peroxide.
9. the preparation method of a kind of Powdered polyacrylic thickening material as claimed in claim 1 is characterized in that described azo-initiator is Diisopropyl azodicarboxylate or 2,2'-Azobis(2,4-dimethylvaleronitrile).
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| CN109957062A (en) * | 2017-12-22 | 2019-07-02 | 万华化学（宁波）有限公司 | High cross-linked acrylic acid lipin polymer and preparation method thereof and purposes as thickener |
| CN111057338A (en) * | 2019-12-17 | 2020-04-24 | 南京天之房节能科技有限公司 | Thickening agent for suspension |
| CN112538132A (en) * | 2020-12-08 | 2021-03-23 | 南京紫鸿生物科技有限公司 | Preparation method of thickening polymer suitable for alcohol system |
| CN112592425A (en) * | 2020-12-21 | 2021-04-02 | 合肥艾普拉斯环保科技有限公司 | Preparation method of novel thickener polyacrylate |
| CN113387582A (en) * | 2021-08-17 | 2021-09-14 | 佛山市三水区康立泰无机合成材料有限公司 | Glaze for ultrathin ceramic rock plate and preparation method and application thereof |
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| CN114456299A (en) * | 2021-12-30 | 2022-05-10 | 国科温州研究院(温州生物材料与工程研究所) | Preparation method and application of polyacrylic acid thickening agent |
| CN116063609A (en) * | 2021-11-03 | 2023-05-05 | 马鞍山科思化学有限公司 | Preparation method of thickener acrylic polymer |
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| CN109957062A (en) * | 2017-12-22 | 2019-07-02 | 万华化学（宁波）有限公司 | High cross-linked acrylic acid lipin polymer and preparation method thereof and purposes as thickener |
| CN111057338A (en) * | 2019-12-17 | 2020-04-24 | 南京天之房节能科技有限公司 | Thickening agent for suspension |
| CN111057338B (en) * | 2019-12-17 | 2022-05-10 | 南京敬邺达新型建筑材料有限公司 | Thickening agent for suspension |
| CN113896823A (en) * | 2020-07-06 | 2022-01-07 | 山东泰和水处理科技股份有限公司 | Preparation method of polyacrylic acid crosslinked resin |
| CN113896823B (en) * | 2020-07-06 | 2022-09-27 | 山东泰和水处理科技股份有限公司 | Preparation method of polyacrylic acid crosslinked resin |
| CN112538132A (en) * | 2020-12-08 | 2021-03-23 | 南京紫鸿生物科技有限公司 | Preparation method of thickening polymer suitable for alcohol system |
| CN112592425A (en) * | 2020-12-21 | 2021-04-02 | 合肥艾普拉斯环保科技有限公司 | Preparation method of novel thickener polyacrylate |
| CN113387582A (en) * | 2021-08-17 | 2021-09-14 | 佛山市三水区康立泰无机合成材料有限公司 | Glaze for ultrathin ceramic rock plate and preparation method and application thereof |
| CN116063609A (en) * | 2021-11-03 | 2023-05-05 | 马鞍山科思化学有限公司 | Preparation method of thickener acrylic polymer |
| CN114292359A (en) * | 2021-12-02 | 2022-04-08 | 合肥艾普拉斯环保科技有限公司 | Preparation method of novel efficient thickener polyacrylate copolymer |
| CN114456299A (en) * | 2021-12-30 | 2022-05-10 | 国科温州研究院(温州生物材料与工程研究所) | Preparation method and application of polyacrylic acid thickening agent |
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Application publication date: 20130703 |