CN102504079B - The preparation method of spherical polyacrylic resin - Google Patents
The preparation method of spherical polyacrylic resin Download PDFInfo
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- CN102504079B CN102504079B CN201110315133.4A CN201110315133A CN102504079B CN 102504079 B CN102504079 B CN 102504079B CN 201110315133 A CN201110315133 A CN 201110315133A CN 102504079 B CN102504079 B CN 102504079B
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Abstract
The invention provides the preparation method of spherical polyacrylic resin, relate in particular to a kind of personal care articles, the preparation method of spherical polyacrylic resin that medicine and other fields uses as rheology modified thickening material.It discloses the method by inverse suspension polymerization, by water,
Description
Technical field
The present invention relates to the preparation method of spherical polyacrylic resin.Specifically, the present invention relates to personal care articles, the preparation method of spherical polyacrylic resin that medicine and other fields uses as rheology modified thickening material.
Background technology
Polyacrylic resin is as water miscible rheology modified thickening material, and the viscosity being commonly used to regulates liquid, the thixotropic property improving gelling system and stability, be widely used in personal care articles.At the polyacrylic resin that makeup, field of medicaments use, normally appropriately crosslinked polyacrylic resin or alkyl-modified polyacrylic resin.
Patent US2798053 describes with (methyl) vinylformic acid, (methyl) acrylate, with a kind of energy dissolved monomer, the organic solvent of dissolve polymer, if the one such as heptane, cyclohexane, dimethylbenzene or its mixture are for reaction solvent, does not obtain polyacrylic resin by the method for precipitation polymerization.This resin is unbodied white powder body, though have certain thickening capabilities, the swelling time of the aqueous solution is longer.
Patent US4062817 describe with (methyl) vinylformic acid be monomer basis on add another monomer C
10-30long-chain (methyl) acrylate and C
2-8short chain (methyl) acrylate, obtain polyacrylic resin with precipitation polymerization method.Though this polyacrylic resin has good salt tolerant and thickening capabilities, resin is still unbodied white powder body, easy conglomeration and the swelling time of the aqueous solution is longer.
Patent US54689797 reports in the process preparing polyacrylic resin, by adding the tensio-active agent of low surface tension as the tensio-active agent containing fluorine or silicon, improves the swelling time of product.But this resin is still unbodied white powder body, and tap density is little, in use easily conglomeration.
In addition, patent CN200710032560.5 reports a kind of physical modification method of polyacrylic resin, by polyacrylic resin powder at room temperature to be obtained the resin of modification through ball milling with certain speed, this polyacrylic resin swelling time is very fast, but still be unbodied white powder body, tap density is little, there is the harm of dust to human body in use procedure.
Above-mentioned polyacrylic resin product is all unbodied white powder, easy conglomeration when being dispersed in water, and in use the swelling time of the aqueous solution is longer.Meanwhile, above-mentioned polyacrylic resin is owing to being subacidity powder, and easy static electrification lotus, plays powder serious, there is the harm of dust to human body in use procedure when material shifts.In addition, it is little that the polyacrylic resin of micropowder also exists tap density, and stock takes up space large and problems such as transportation cost increase.Therefore, wait in expectation and modification is carried out to existing polyacrylic resin.
Application number CN200880020880.1 reports a kind of manufacture method of particulate polypropylene acid resin, first obtains slurry with precipitation polymerization method, and redistillation removing inert solvent, then drying under reduced pressure, obtain the polyacrylic resin of micropowder; Then make polyacrylic resin suck polar organic solvent to manufacture the aggregate of polymer particle, finally again aggregate pulverized, sieve, obtain the particulate polypropylene acid resin that median particle diameter is 300-800 um.Although the product that above-mentioned manufacture method obtains has larger loose density and shorter swelling time, solve the harm of powder dust, stock takes up space the problem such as large, but the method manufacturing this product be by the gel process in later stage and further dry, pulverize, operation is sieved in classification, operate relatively loaded down with trivial details; In addition, because pulverizing is carry out under mechanical friction or impact force action, cause resin to be cleaved into irregularly shaped, there is particle diameter and differ in product, frangible.
Summary of the invention
The present invention in order to overcome the defect of above-mentioned prior art, provide a kind of compared with manufacture easily tap density greatly, the preparation method of easily swelling spherical polyacrylic resin.
Object of the present invention is achieved through the following technical solutions: by the method for inverse suspension polymerization, by water,
, alkali lye, linking agent, initiator form aqueous phase; Oil phase is formed by petroleum hydrocarbon dispersion medium, tensio-active agent, macromolecule dispersing agent; At certain temperature and stirring velocity, react certain hour, then through dehydration, filtration, drying, namely obtain spherical polyacrylic resin; Its concrete technology step is:
(1) aqueous phase preparation: after alkali is made into the certain density aqueous solution, a neutralization part
, add linking agent and initiator and dissolve, being uniformly mixed;
(2) oil phase preparation: tensio-active agent, macromolecule dispersing agent are placed in petroleum hydrocarbon dispersion medium, stirring and dissolving;
(3) in five mouthfuls of reaction flasks with thermometer, reflux exchanger, logical nitrogen, add oil phase, start stirring, logical nitrogen, adds aqueous phase, stirs until the uniform dispersion suspension liquid of System forming, starts to heat up, reaction certain hour;
(4) dewater, filter or do not filter convection drying and namely obtain spherical polyacrylic resin.
Preparation method of the present invention obtains spherical polyacrylic resin, and it has following characteristic:
1) examine under a microscope the outward appearance of particle for spherical uniformly, its diameter is 100-400 um;
2) tap density is more than 0.50g/ml;
3) 0.5% resin aqueous solution swelling time is at below 35min.
The above
for vinylformic acid, methacrylic acid, toxilic acid, methylene-succinic acid; Separately above-mentioned
use or use with the mixture of at least two kinds.
The above
with basic metal neutralization,
the degree of neutralization of middle carboxyl is 10 ~ 70 % by mole.Above-mentioned basic metal comprises some lithiums, sodium, potassium; Relative to 100 mass parts
, in system, the consumption of water is 100 ~ 300 mass parts; After neutralization, the liquid pH of viscous fluid is 6.5 ~ 7.8.
Linking agent of the present invention is ethylene glycol, propylene glycol, polyoxyethylene glycol, glycerine, Polyglycerine, TriMethylolPropane(TMP), tetramethylolmethane, sucrose or the Sorbitol Powder that two of the polyvalent alcohol of the compound with two or more ethylenic unsaturated group replaces in above esters of acrylic acid, or two of above-mentioned polyvalent alcohol replace Phthalic acid, diallyl ester, allyl methacrylate(AMA), adipic acid divinyl ester, 1,5-hexadiene or divinylbenzene in above allyl ether series; Relative to 100 mass parts
, the consumption of linking agent is 0.1 ~ 1.2 mass parts.
Described initiator is water-soluble free radical initiator and sulphite, comprises, the Potassium Persulphate in persulphate, ammonium persulphate, Sodium Persulfate; Hydrogen peroxide in superoxide; In azo-compound 2,2
,-azo two (2-amidine propane) dihydrochloride; Above-mentioned water-soluble radical polymerization initiator is used alone or uses with the mixture of at least two kinds; Relative to 100 mass parts
, the consumption of water-soluble free radical initiator is 0.05 ~ 0.7 %.
Tensio-active agent of the present invention comprises above, the sorbitan fatty(acid)ester in nonionogenic tenside, polyglycerol fatty acid ester, sucrose fatty ester; Alkylbenzene sulfonate in anion surfactant example, Voranol EP 2001 sulfonate; Above-mentioned tensio-active agent is used alone or uses with the mixture of at least two kinds;
Described macromolecule dispersing agent is with hydrophilic radical with polymkeric substance, the maleic anhydride modified polymkeric substance containing polyethylene oxide segment in the segmented copolymer of hydrophobic grouping; Above-mentioned macromolecule dispersing agent is used alone or uses with the mixture of at least two kinds;
Relative to 100 mass parts
; The total amount that adds of above-mentioned tensio-active agent and macromolecule dispersing agent is 0.3 ~ 1.0 %.
The above petroleum hydrocarbon dispersion medium comprises normal hexane, normal heptane in aliphatic hydrocarbon example; Pentamethylene in clicyclic hydrocarbon, cyclohexane; Benzene in aromatic hydrocarbons, toluene and dimethylbenzene; Relative to 100 mass parts
, above-mentioned petroleum hydrocarbon dispersion Jie is 100 ~ 600 mass parts.
The above anti-phase suspension liquid temperature of reaction is 35 ~ 80 DEG C, and the reaction times is 0.5 ~ 5 hour; After inverse suspension polymerization terminates, heat up and remove moisture content, the amount of removing of moisture content is the 70-95 % of moisture content quality in inverse suspension polymerization system; After preparation terminates, gained spherical polyacrylic resin, by filtering, to realize the initial gross separation of solvent and material, obtains slurry; Or directly enter next procedure without filtration.
Manufacturing method according to the invention, can obtain the more uniform spherical polyacrylic resin of outward appearance compared with unbodied powder, the feature such as has a tap density greatly, easily swelling, dust pollution is little.In addition, after the spherical polyacrylic resin utilizing preparation method of the present invention to obtain is mixed with the certain density aqueous solution, with alkali as after the neutralization such as trolamine, potassium hydroxide, sodium hydroxide, obtain that smooth surface, transparency are high, thickening property and suspension good in and viscous fluid.
Preparation method's inverse suspension polymerization method of spherical polyacrylic resin of the present invention.
Described
class is not particularly limited, and such as, can enumerate vinylformic acid, methacrylic acid, toxilic acid, methylene-succinic acid etc.These can be used alone or use with the mixture of at least two kinds.It should be noted that, vinylformic acid and (methyl) vinylformic acid are referred to as vinylformic acid by the present invention.
Described
can neutralize with basic metal, the aspect such as disadvantage from the performance and the issuable any safety of excessive basic metal of the Stability Control of reaction process, product, preferably
the degree of neutralization of middle carboxyl is 10 ~ 70 % by mole.Above-mentioned basic metal comprises some lithiums, sodium, potassium etc.Among them, sodium and potassium are preferred.
Relative to 100 mass parts
, in system, the consumption of water is 100 ~ 300 mass parts.
It should be noted that, in the present invention, in what is called, mean that the pH of this liquid is 6.5 ~ 7.8 with viscous fluid.
Linking agent used in the present invention is the compound with two or more ethylenic unsaturated group, be not particularly limited, such as can enumerate the polyvalent alcohols such as ethylene glycol, propylene glycol, polyoxyethylene glycol, glycerine, Polyglycerine, TriMethylolPropane(TMP), tetramethylolmethane, sucrose, Sorbitol Powder two replace above esters of acrylic acid; Two of above-mentioned polyvalent alcohol replaces above allyl ether series; Phthalic acid, diallyl ester, allyl methacrylate(AMA), adipic acid divinyl ester, 1,5-hexadiene, divinylbenzene etc.
Relative to 100 mass parts
, the consumption of linking agent is preferably 0.1 ~ 1.2 mass parts.When the consumption of linking agent is less than 0.1 mass parts, likely reduce with the viscosity of viscous fluid in being prepared by obtained spherical polyacrylic resin.When the consumption of linking agent is greater than 1.2 mass parts, in being prepared by obtained spherical polyacrylic resin and viscous fluid be likely easy to generate insoluble gel.
Described initiator is water-soluble free radical initiator, comprises, and persulphate is Potassium Persulphate such as, ammonium persulphate, Sodium Persulfate; Superoxide is hydrogen peroxide such as; Azo-compound such as 2,2
,-azo two (2-amidine propane) dihydrochloride etc.Water-soluble free radical initiator can be used as reductionoxidation polymerization initiator together with sulphite etc.Among them, from easily obtaining the viewpoint with stability in storage excellence, Potassium Persulphate, ammonium persulphate, Sodium Persulfate and 2,2
,-azo two (2-amidine propane) dihydrochloride is preferred.Above-mentioned water-soluble radical polymerization initiator can be used alone or uses with the mixture of at least two kinds.
Relative to 100 mass parts
, from shortening the poly-reaction times and preventing sudden and violent poly-viewpoint, consumption preferably 0. 05 ~ 0.7 % of water-soluble free radical initiator.
Tensio-active agent used in the present invention comprises, such as: nonionogenic tenside is as sorbitan fatty(acid)ester, polyglycerol fatty acid ester, sucrose fatty ester; Anion surfactant is alkylbenzene sulfonate, Voranol EP 2001 sulfonate etc. such as.Among them, preferred sorbitan fatty(acid)ester, polyglycerol fatty acid ester, sucrose fatty ester.These tensio-active agents can be used alone or use with the mixture of at least two kinds.
Described macromolecule dispersing agent is with hydrophilic radical and the segmented copolymer with hydrophobic grouping, such as, polymkeric substance, maleic anhydride modified polymkeric substance etc. containing polyethylene oxide segment.These macromolecule dispersing agents can be used alone or use with the mixture of at least two kinds.
Relative to 100 mass parts
, above-mentioned tensio-active agent and macromolecule dispersing agent add total amount preferably 0.3 ~ 1.0 %.
Above-mentioned petroleum hydrocarbon dispersion medium comprises, and such as, aliphatic hydrocarbon is normal hexane, normal heptane etc. such as; Clicyclic hydrocarbon is pentamethylene, cyclohexane etc. such as; Aromatic hydrocarbons is benzene, toluene and dimethylbenzene etc. such as.Among them, quality stability ready availability from the viewpoint of industry and cheap, normal hexane, normal heptane and cyclohexane are preferred.
Relative to 100 mass parts
, from removing polymerization heat and the easy viewpoint controlling polymerization temperature, above-mentioned petroleum hydrocarbon dispersion medium preferably 100 ~ 600 mass parts.
The temperature of reaction of above-mentioned polyreaction is different according to the radical polymerization initiator used.From carrying out reacting, being convenient to the viewpoint removing polymerization heat and reacting balance and carry out fast, anti-phase suspension liquid temperature of reaction is preferably 35 ~ 80 DEG C.Reaction times is generally 0.5 ~ 5 hour.
After inverse suspension polymerization terminates, heat up and remove moisture content, the amount of removing of moisture content is the 70-95 % of moisture content quality in inverse suspension polymerization system.
By filtering, to realize the initial gross separation of solvent and material, obtain slurry; Or directly enter next procedure without filtration.
Drying installation for drying is not particularly limited, such as, can enumerates pressure Reduction Dryer.Drying temperature is 40 ~ 130 DEG C.When drying temperature is less than 40 DEG C, likely need to carry out drying for a long time.During more than 130 DEG C, the solvability of the spherical polyacrylic resin obtained in water is likely impaired.From guaranteeing the application performance of resin and the viewpoints such as consolidated block not occurring after using, dried water ratio is preferably less than 5 quality %.
The diameter of spherical polyacrylic resin of the present invention is preferably 100-400um.When diameter is less than 100um, easily have dust during use, and easily lump in swelling process, swelling time is long; And diameter is when being greater than 400um, although easily process, until polymer material all in water swelling needs expend time in.
The tap density of spherical polyacrylic resin of the present invention is preferably more than 0.50g/ml, when tap density is less than 0.50g/ml, tap density is not very enough large compared with existing powdered polypropylene acid resin, does not solve the increase of transportation cost and needs the problems such as a large amount of site of storages.
" tap density " refers to the value that the quality of spherical polyacrylic resin obtains divided by the volume of the resin of this quality.
Below, enumerate embodiment and comparative example illustrates the present invention, but the present invention is by any restriction of these embodiments.
Embodiment 1
The acrylic acid aqueous solution of 90g 80 wt % is added in 500 mL Erlenmeyer flasks, under ice bath, in this Erlenmeyer flask, dropwise adds the aqueous sodium hydroxide solution of 66.7g 30 wt%, with in and the vinylformic acid of 50 % moles.Then in this Erlenmeyer flask, add the water of 35g further, 0.144g water-soluble free radical initiator potassium persulfate and 0.288g linking agent cane sugar allyl ether, to obtain the aqueous phase for being polymerized;
Separate with aforesaid operations, the sorbitan monooleate (sorbester p17) of 500g cyclohexane and 0.144g and the polyoxyethylene 30 dimerization hydroxy stearic acid ester of 0.144g is added in the 1000mL five mouthfuls of flasks being furnished with agitator, reflux exchanger, dropping funnel, thermometer and nitrogen ingress pipe, dispersed mixture in flask, ready for use is oil phase;
Under agitation aqueous phase is added in above-mentioned five mouthfuls of flasks, and dispersed mixture, logical nitrogen, intensification, stirring are that 70 DEG C of polyreactions carry out 4 hours at system temperature;
When being polymerized termination, raising system temperature, azeotropic dehydration being carried out to the mixture of heating, 80g water is steamed;
Obtain wet stock after suction filtration, be placed on further vacuum drying oven internal pressure be-0.095 Mpa, at temperature 100 DEG C dry 8 hours, obtain spherical polyacrylic resin 79.7g.
Embodiment 2
Except the aqueous sodium hydroxide solution by dropwise adding 66.7g 30 wt% in embodiment 1 in this Erlenmeyer flask, with in and the vinylformic acid of 50% mole, then in this Erlenmeyer flask, add the water of 35g further, change the aqueous sodium hydroxide solution dropwise adding 40.0g 30 wt% in this Erlenmeyer flask into, with in and the vinylformic acid of 30 % moles, then, beyond the water adding 54g in this Erlenmeyer flask further, carry out with the step identical with embodiment 1, obtain 75.9g spherical polyacrylic resin.
Embodiment 3
Except the aqueous sodium hydroxide solution by dropwise adding 66.7g 30 wt% in embodiment 1 in this Erlenmeyer flask, with in and the vinylformic acid of 50 % moles, then in this Erlenmeyer flask, add the water of 35g further, change the aqueous sodium hydroxide solution dropwise adding 13.3g 30wt% in this Erlenmeyer flask into, with in and the vinylformic acid of 10% mole, then, beyond the water adding 72.7g in this Erlenmeyer flask further, carry out with the step identical with embodiment 1, obtain 71.2g spherical polyacrylic resin.
Embodiment 4
Except the aqueous sodium hydroxide solution by dropwise adding 66.7g 30 wt% in embodiment 1 in this Erlenmeyer flask, with in and the vinylformic acid of 50 % moles, then in this Erlenmeyer flask, add the water of 35g further, change the aqueous sodium hydroxide solution dropwise adding 93.3g 30 wt% in this Erlenmeyer flask into, with in and the vinylformic acid of 70 % moles, then, beyond the water adding 16.7g in this Erlenmeyer flask further, carry out with the step identical with embodiment 1, obtain 84.6g spherical polyacrylic resin.
Embodiment 5
Except 0.288g linking agent cane sugar allyl ether in embodiment 1 being changed into 0.576g and the polyoxyethylene 30 dimerization hydroxy stearic acid ester of the sorbitan mono-oleic acid ester (sorbester p17) of the 0.144g in embodiment 1 and 0.144g being changed into except the polyoxyethylene 30 dimerization hydroxy stearic acid ester of 0.288g sorbitan mono-oleic acid ester (sorbester p17) and 0.288g, carry out with the step identical with embodiment 1, obtain 80.2g spherical polyacrylic resin.
Embodiment 6
Except 0.288g linking agent cane sugar allyl ether in embodiment 1 being changed into 0.876g and the polyoxyethylene 30 dimerization hydroxy stearic acid ester of the sorbitan mono-oleic acid ester (sorbester p17) of the 0.144g in embodiment 1 and 0.144g being changed into except the polyoxyethylene 30 dimerization hydroxy stearic acid ester of 0.36 sorbitan mono-oleic acid ester (sorbester p17) and 0.36g, carry out with the step identical with embodiment 1, obtain 81.1g spherical polyacrylic resin.
Embodiment 7
Except the polyoxyethylene 30 dimerization hydroxy stearic acid ester of the sorbitan mono-oleic acid ester (sorbester p17) of the 0.144g in embodiment 1 and 0.144g being changed into the polyoxyethylene 30 dimerization hydroxy stearic acid ester of 0.144 sorbitan mono-oleic acid ester (sorbester p17) and 0.072g, carry out with the step identical with embodiment 1, obtain 79.8g spherical polyacrylic resin.
Embodiment 8
Except 0.288g linking agent cane sugar allyl ether in embodiment 1 is changed into except 0.072g tetramethylolmethane triolefin acrylate, carry out with the step identical with embodiment 1, obtain 78.8g spherical polyacrylic resin.
Comparative example 1
Except 0.288g linking agent cane sugar allyl ether in embodiment 1 is changed into except 0.936g tetramethylolmethane triolefin acrylate, carry out with the step identical with embodiment 1, obtain 72.2g spherical polyacrylic resin.
Comparative example 2
Except 0.288g linking agent cane sugar allyl ether in embodiment 1 is changed into except 0.036g, carry out with the step identical with embodiment 1, obtain 71.1g spherical polyacrylic resin.
Comparative example 3
Except the polyoxyethylene 30 dimerization hydroxy stearic acid ester of the sorbitan mono-oleic acid ester (sorbester p17) of the 0.144g in embodiment 1 and 0.144g being changed into the polyoxyethylene 30 dimerization hydroxy stearic acid ester of 0.072 sorbitan mono-oleic acid ester (sorbester p17) and 0.036g, carry out with the step identical with embodiment 1, obtain 71.0g spherical polyacrylic resin.
Comparative example 4
Except the polyoxyethylene 30 dimerization hydroxy stearic acid ester of the sorbitan mono-oleic acid ester (sorbester p17) of the 0.144g in embodiment 1 and 0.144g being changed into the polyoxyethylene 30 dimerization hydroxy stearic acid ester of 0.432 pears alcohol acid anhydride monoleate (sorbester p17) and 0.432g, carry out with the step identical with embodiment 1, obtain 71.1g spherical polyacrylic resin.
Comparative example 5
Except by the aqueous sodium hydroxide solution dropwise adding 66.7g 30 wt% in this Erlenmeyer flask in embodiment 1, with in and the vinylformic acid of 50% mole, then in this Erlenmeyer flask, add the water of 35g further, change the aqueous sodium hydroxide solution dropwise adding 6.67g 30 wt% in this Erlenmeyer flask into, with in and the vinylformic acid of 5% mole, in this Erlenmeyer flask, then add the water of 77.3g further, in addition, carry out with the step identical with embodiment 1, obtain 58.1g spherical polyacrylic resin.
Comparative example 6
Except dropwise 66.7g(0.5mol will be added in embodiment 1 in this Erlenmeyer flask) aqueous sodium hydroxide solution of 30wt%, with in and the vinylformic acid of 50% mole, then in this Erlenmeyer flask, add the water of 35g further, change into and dropwise add 100g(0.75mol in this Erlenmeyer flask) aqueous sodium hydroxide solution of 30wt%, with in and the vinylformic acid of 75% mole, then in this Erlenmeyer flask, add the water of 12g further, in addition, carry out with the step identical with embodiment 1, obtain 71.1g spherical polyacrylic resin.
The spherical polyacrylic resin obtained in each embodiment and each comparative example is assessed according to following evaluation method.
Evaluation method
1. the diameter of spherical polyacrylic resin
Take a certain amount of spherical polyacrylic resin, spread over equably and carry on thin slice, examine under a microscope form and the size of ion.
2. tap density
The resin-like (g) taking certain mass is loaded on a clean drying and in the 500mL graduated cylinder of weighing, to fill gently as degree, tightly seals immediately with preservative film, and tighten with rubber, weigh, be then contained on tap density tester, setting jolt ramming frequency is 250 times/min, shakes 6000 times.Take off graduated cylinder, read the volume (ml) of sample in graduated cylinder, be tap density by the value calculated divided by volume shared by it by the quality of polyacrylic resin.
3. the swelling time of 0.5% resin aqueous solution
Be 250ml at volume, add 100ml deionized water in diameter 6.3cm beaker, water temperature is remained on 25 DEG C, the polyacrylic resin taking 2.5g spreads after on the water surface of the deionized water left standstill, and measures polyacrylic resin particle whole swelling required time.In addition, when judging that spherical polyacrylic resin is swelling in water, time dry by visual judgement, the polymer particle of white is swelled into white translucent to judge in water.
The spherical polyacrylic resin obtained in each embodiment and each comparative example measures diameter, tap density, 0.5% resin aqueous solution swelling time.Result is provided in table 1, table 2 and table 3.
Table 1
Table 2
Table 3
Known from the result table 1, table 2 and table 3, the tap density of the spherical polyacrylic resin utilizing manufacture method of the present invention to obtain is large, and swelling in water in the short period of time.
Industrial applicibility
Manufacturing method according to the invention, can to obtain compared with the polyacrylic resin of micronized in water easily swelling, dust is few, the spherical polyacrylic resin of excellent performance when using.In addition, the spherical polyacrylic resin utilizing manufacture method of the present invention to obtain being dissolved in after in water, by utilizing the alkali such as sodium hydroxide, trolamine to neutralize, can obtaining in smooth surface, thickening property and transmittance excellence and viscous fluid with the short period of time.
Claims (1)
1. the preparation method of spherical polyacrylic resin, is characterized in that the method by inverse suspension polymerization, and by water, α, beta-unsaturated acid, alkali lye, linking agent, initiator form aqueous phase; Oil phase is formed by petroleum hydrocarbon dispersion medium, tensio-active agent, macromolecule dispersing agent; At certain temperature and stirring velocity, react certain hour, then through dehydration, filtration, drying, namely obtain spherical polyacrylic resin; Its concrete technology step is:
(1) aqueous phase preparation: after alkali is made into the certain density aqueous solution, neutralize a part of α, beta-unsaturated acid, adds linking agent and initiator and dissolves, being uniformly mixed;
(2) oil phase preparation: tensio-active agent, macromolecule dispersing agent are placed in petroleum hydrocarbon dispersion medium, stirring and dissolving;
(3) in five mouthfuls of reaction flasks with thermometer, reflux exchanger, logical nitrogen, add oil phase, start stirring, logical nitrogen, adds aqueous phase, stirs until the uniform dispersion suspension liquid of System forming, starts to heat up, reaction certain hour;
(4) dewater, filter or do not filter convection drying and namely obtain spherical polyacrylic resin;
Described preparation method obtains spherical polyacrylic resin, and it has following characteristic:
1) examine under a microscope the outward appearance of particle for spherical uniformly, its diameter is 100-400um;
2) tap density is more than 0.50g/ml;
3) 0.5% resin aqueous solution swelling time is at below 35min;
Described α, beta-unsaturated acid is vinylformic acid, methacrylic acid, toxilic acid, methylene-succinic acid; Above-mentioned α, beta-unsaturated acid is used alone or uses with the mixture of at least two kinds;
Described α, beta-unsaturated acid sodium hydroxide solution neutralizes, α, and in beta-unsaturated acid, the degree of neutralization of carboxyl is 10 ~ 70 % by mole;
Relative to the α of 100 mass parts, beta-unsaturated acid, in system, the consumption of water is 100 ~ 300 mass parts; After neutralization, the liquid pH of viscous fluid is 6.5 ~ 7.8;
Be cane sugar allyl ether or tetramethylolmethane triolefin acrylate for linking agent of the present invention; Relative to the α of 100 mass parts, beta-unsaturated acid, the consumption of linking agent is 0.1 ~ 1.2 mass parts;
Described initiator is Potassium Persulphate, ammonium persulphate, Sodium Persulfate; Hydrogen peroxide; 2,2
,-azo two (2-amidine propane) dihydrochloride; Above-mentioned initiator is used alone or uses with the mixture of at least two kinds; Relative to the α of 100 mass parts, beta-unsaturated acid, the consumption of initiator is 0.05 ~ 0.7%;
Described tensio-active agent is sorbitan fatty(acid)ester, polyglycerol fatty acid ester, sucrose fatty ester, alkylbenzene sulfonate, Voranol EP 2001 sulfonate; Above-mentioned tensio-active agent is used alone or uses with the mixture of at least two kinds;
Described macromolecule dispersing agent is with hydrophilic radical with polymkeric substance, the maleic anhydride modified polymkeric substance containing polyethylene oxide segment in the segmented copolymer of hydrophobic grouping; Above-mentioned macromolecule dispersing agent is used alone or uses with the mixture of at least two kinds; Relative to the α of 100 mass parts, beta-unsaturated acid; The total amount that adds of above-mentioned tensio-active agent and macromolecule dispersing agent is 0.3 ~ 1.0%;
Described petroleum hydrocarbon dispersion medium is normal hexane, normal heptane, pentamethylene, cyclohexane, benzene, toluene or dimethylbenzene; Relative to the α of 100 mass parts, beta-unsaturated acid, above-mentioned petroleum hydrocarbon dispersion Jie is 100 ~ 600 mass parts;
Described anti-phase suspension liquid temperature of reaction is 35 ~ 80 DEG C, and the reaction times is 0.5 ~ 5 hour; After inverse suspension polymerization terminates, heat up and remove moisture content, the amount of removing of moisture content is the 70-95% of moisture content quality in inverse suspension polymerization system; After preparation terminates, gained spherical polyacrylic resin, by filtering, to realize the initial gross separation of solvent and material, obtains slurry; Or directly enter next procedure without filtration.
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| CN1903893A (en) * | 2006-07-19 | 2007-01-31 | 浙江大学 | Antisticking agent in preparation of reversed phase suspension polymerization polypropylene high water absorption resin |
| CN101466740A (en) * | 2006-04-24 | 2009-06-24 | 住友精化株式会社 | Process for production of water-absorbable resin particle, and water-absorbable resin particle produced by the process |
| CN101688001A (en) * | 2007-06-19 | 2010-03-31 | 住友精化株式会社 | Method for producing granulated carboxyl group-containing polymer particle and granulated carboxyl group-containing polymer particle |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101466740A (en) * | 2006-04-24 | 2009-06-24 | 住友精化株式会社 | Process for production of water-absorbable resin particle, and water-absorbable resin particle produced by the process |
| CN1903893A (en) * | 2006-07-19 | 2007-01-31 | 浙江大学 | Antisticking agent in preparation of reversed phase suspension polymerization polypropylene high water absorption resin |
| CN101688001A (en) * | 2007-06-19 | 2010-03-31 | 住友精化株式会社 | Method for producing granulated carboxyl group-containing polymer particle and granulated carboxyl group-containing polymer particle |
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