CN113045703A - Polymer and daily chemical - Google Patents
Polymer and daily chemical Download PDFInfo
- Publication number
- CN113045703A CN113045703A CN202110494757.0A CN202110494757A CN113045703A CN 113045703 A CN113045703 A CN 113045703A CN 202110494757 A CN202110494757 A CN 202110494757A CN 113045703 A CN113045703 A CN 113045703A
- Authority
- CN
- China
- Prior art keywords
- starch
- polymer
- acrylic acid
- sodium polyacrylate
- water
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229920000642 polymer Polymers 0.000 title claims abstract description 28
- 239000000126 substance Substances 0.000 title claims description 11
- 229920002472 Starch Polymers 0.000 claims abstract description 67
- 235000019698 starch Nutrition 0.000 claims abstract description 67
- 239000008107 starch Substances 0.000 claims abstract description 65
- 239000002245 particle Substances 0.000 claims abstract description 31
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 18
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 18
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 7
- 238000010557 suspension polymerization reaction Methods 0.000 claims abstract description 6
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 claims description 16
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 239000001341 hydroxy propyl starch Substances 0.000 claims description 12
- 235000013828 hydroxypropyl starch Nutrition 0.000 claims description 12
- 239000003999 initiator Substances 0.000 claims description 10
- 229920001592 potato starch Polymers 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 9
- 239000002270 dispersing agent Substances 0.000 claims description 8
- 239000003960 organic solvent Substances 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- 240000003183 Manihot esculenta Species 0.000 claims description 6
- 235000016735 Manihot esculenta subsp esculenta Nutrition 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- -1 rice starch Polymers 0.000 claims description 6
- 239000002562 thickening agent Substances 0.000 claims description 6
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- PQUXFUBNSYCQAL-UHFFFAOYSA-N 1-(2,3-difluorophenyl)ethanone Chemical compound CC(=O)C1=CC=CC(F)=C1F PQUXFUBNSYCQAL-UHFFFAOYSA-N 0.000 claims description 4
- AFABGHUZZDYHJO-UHFFFAOYSA-N 2-Methylpentane Chemical compound CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 claims description 4
- 244000017020 Ipomoea batatas Species 0.000 claims description 4
- 235000002678 Ipomoea batatas Nutrition 0.000 claims description 4
- 229910019142 PO4 Inorganic materials 0.000 claims description 4
- 235000003283 Pachira macrocarpa Nutrition 0.000 claims description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 4
- 240000001085 Trapa natans Species 0.000 claims description 4
- 235000014364 Trapa natans Nutrition 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 4
- 239000010452 phosphate Substances 0.000 claims description 4
- 235000009165 saligot Nutrition 0.000 claims description 4
- 229940047670 sodium acrylate Drugs 0.000 claims description 4
- 239000000725 suspension Substances 0.000 claims description 4
- 230000008719 thickening Effects 0.000 claims description 4
- 229920002261 Corn starch Polymers 0.000 claims description 3
- 239000008120 corn starch Substances 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical group C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 229940100486 rice starch Drugs 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-M Butyrate Chemical compound CCCC([O-])=O FERIUCNNQQJTOY-UHFFFAOYSA-M 0.000 claims description 2
- 235000000378 Caryota urens Nutrition 0.000 claims description 2
- 240000000163 Cycas revoluta Species 0.000 claims description 2
- 235000008601 Cycas revoluta Nutrition 0.000 claims description 2
- 244000151018 Maranta arundinacea Species 0.000 claims description 2
- 235000010804 Maranta arundinacea Nutrition 0.000 claims description 2
- 235000010103 Metroxylon rumphii Nutrition 0.000 claims description 2
- 240000002853 Nelumbo nucifera Species 0.000 claims description 2
- 235000006508 Nelumbo nucifera Nutrition 0.000 claims description 2
- 235000012419 Thalia geniculata Nutrition 0.000 claims description 2
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 claims description 2
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- WBJINCZRORDGAQ-UHFFFAOYSA-N formic acid ethyl ester Natural products CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 claims description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 2
- 239000003607 modifier Substances 0.000 claims description 2
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 claims description 2
- 239000001254 oxidized starch Substances 0.000 claims description 2
- 235000013808 oxidized starch Nutrition 0.000 claims description 2
- 229940090181 propyl acetate Drugs 0.000 claims description 2
- 239000006254 rheological additive Substances 0.000 claims description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 claims description 2
- 235000013312 flour Nutrition 0.000 claims 1
- 238000002834 transmittance Methods 0.000 abstract description 11
- 239000000499 gel Substances 0.000 abstract description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 abstract description 5
- 239000007787 solid Substances 0.000 abstract description 3
- 229940032147 starch Drugs 0.000 description 42
- 238000012360 testing method Methods 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 7
- 239000004005 microsphere Substances 0.000 description 6
- 239000000178 monomer Substances 0.000 description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 5
- 229920000881 Modified starch Polymers 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 235000019426 modified starch Nutrition 0.000 description 5
- 239000012071 phase Substances 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- 229940048053 acrylate Drugs 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000004132 cross linking Methods 0.000 description 4
- 239000000839 emulsion Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000004368 Modified starch Substances 0.000 description 3
- 229920002125 Sokalan® Polymers 0.000 description 3
- 238000005886 esterification reaction Methods 0.000 description 3
- 238000000593 microemulsion method Methods 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 3
- 239000004584 polyacrylic acid Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 239000006071 cream Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000003995 emulsifying agent Substances 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- QIZPVNNYFKFJAD-UHFFFAOYSA-N 1-chloro-2-prop-1-ynylbenzene Chemical compound CC#CC1=CC=CC=C1Cl QIZPVNNYFKFJAD-UHFFFAOYSA-N 0.000 description 1
- IQUCNXSZNHPPML-UHFFFAOYSA-N 2-chloro-n-[(4-chlorophenyl)-phenylmethyl]acetamide Chemical compound C=1C=C(Cl)C=CC=1C(NC(=O)CCl)C1=CC=CC=C1 IQUCNXSZNHPPML-UHFFFAOYSA-N 0.000 description 1
- 241000195940 Bryophyta Species 0.000 description 1
- SHBUUTHKGIVMJT-UHFFFAOYSA-N Hydroxystearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OO SHBUUTHKGIVMJT-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 229920001214 Polysorbate 60 Polymers 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- HVUMOYIDDBPOLL-XWVZOOPGSA-N Sorbitan monostearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O HVUMOYIDDBPOLL-XWVZOOPGSA-N 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229940099112 cornstarch Drugs 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 229940072106 hydroxystearate Drugs 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000004530 micro-emulsion Substances 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000003020 moisturizing effect Effects 0.000 description 1
- 235000011929 mousse Nutrition 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 125000000864 peroxy group Chemical group O(O*)* 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229940051841 polyoxyethylene ether Drugs 0.000 description 1
- 229920000056 polyoxyethylene ether Polymers 0.000 description 1
- 229920000136 polysorbate Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 229940116317 potato starch Drugs 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000000985 reactive dye Substances 0.000 description 1
- 239000012966 redox initiator Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 229940080313 sodium starch Drugs 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229940035023 sucrose monostearate Drugs 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- PZJJKWKADRNWSW-UHFFFAOYSA-N trimethoxysilicon Chemical compound CO[Si](OC)OC PZJJKWKADRNWSW-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F251/00—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/32—Polymerisation in water-in-oil emulsions
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/02—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to polysaccharides
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Graft Or Block Polymers (AREA)
- Cosmetics (AREA)
Abstract
The invention belongs to the field of polymers, in particular to a polymer, which is prepared by the reversed phase suspension polymerization of acrylic acid with the neutralization degree of 70-80% and starch in the presence of a water-soluble cross-linking agent; the starch is 10-30% by weight of the acrylic acid before neutralization. The polymer realizes the requirements on the relative performances such as light transmittance, viscosity and the like by optimizing the proportion of starch and acrylate and optimizing the neutralization degree of acrylic acid, and meanwhile, the product adopts reversed phase suspension polymerization, solid particles are obtained after drying, and gels with different handfeel can be obtained by crushing into different particle sizes, so that the polymer is suitable for different products.
Description
Technical Field
The invention relates to the field of polymers, in particular to a polymer and a daily chemical product.
Background
Sodium polyacrylate grafted starch: the project aims to combine sodium acrylate and starch together to obtain polyacrylic acid grafted starch water-absorbing resin with different particle sizes. The product can be thickened without neutralization, and has biodegradability. The materials in the market are mainly high water-absorbent resins, and are widely applied to personal hygiene products such as paper diapers and the like, the fields of agriculture and gardens (having various application scenes such as soil water retention, seed coating, seed dressing and seedling raising and the like), and the food industry for water absorption and fresh keeping.
The following information can be found for acrylic acid grafted starch:
CN201410775057.9 discloses a preparation method of self-crosslinking AM/AA grafting-esterification hydroxypropyl cassava starch microspheres and a preparation method thereof for Pb2+Adsorption of (3). The self-crosslinking AM/AA grafting-esterification hydroxypropyl cassava starch derivative microsphere with regular appearance, uniform granularity, developed internal pores and excellent adsorption performance is obtained by taking self-crosslinking AM/AA grafting-esterification hydroxypropyl cassava starch as a starting material and mixed solution of Span-60 and Tween-60 as an emulsifier under an alkaline condition and adopting a reverse micro-emulsion method through the process steps of emulsification dispersion, separation, washing, drying and the like, and the microsphere is subjected to Pb adsorption2+And (5) testing the performance. The starch derivative microspheres prepared from the compound modified cassava starch in the inverse emulsion have good space network structure, large specific surface area and good Pb resistance2+Has excellent adsorption performance. The method has high application value in the aspects of industrial sewage purification, heavy metal adsorption and the like.
CN201810094225.6 discloses a starch graft copolymerization nano-microsphere by a reverse microemulsion method, a preparation method and application thereof. The method specifically comprises the following steps: 1) mixing ethanol and hydroxypropyl starch, and dissolving in water to obtain a mixed solution of hydroxypropyl starch; 2) adding a water-soluble monomer into the mixed solution of the hydroxypropyl starch, and mixing to obtain an aqueous phase solution containing the water-soluble monomer and the hydroxypropyl starch; 3) adding cyclohexane, an emulsifier and an initiator into the water phase solution containing the water-soluble monomer and the hydroxypropyl starch, and mixing to obtain a water-in-oil type emulsion; 4) and (3) reacting the stable water-in-oil microemulsion to obtain the starch graft copolymerization nano-microsphere by the reverse microemulsion method. The preparation process is simple and convenient, easy to operate and low in production cost; the material has good shearing resistance, injection performance, temperature resistance, salt resistance and migration performance in a porous medium, and has the characteristics of acid and alkali resistance. The scheme is characterized in that: the mass ratio of the hydroxypropyl starch to the water-soluble monomer is 1: 1.5 to 2.75 and no crosslinking.
CN202011349403.9 discloses a thickening agent, which is prepared by grafting methacrylic acid and starch to prepare methacrylic acid grafted starch modified liquid, carrying out polymerization reaction on the methacrylic acid, the methacrylic acid grafted starch modified liquid and 3-methyl acrylic acid propyl tri (trimethoxy silicon) to prepare polyacrylic acid aqueous solution, and finally distilling under reduced pressure. The polyacrylic acid synthetic thickener prepared by the invention is used for printing reactive dyes on viscose fabrics, and the paste removal rate of the prepared printed fabrics is higher than 90%; the softness is good; the definition of the outline is high; the permeability is higher than 91%; the color fastness to dry rubbing and the soaping color change are high in grade, and the application prospect is good; the ratio of methacrylic acid to starch of the thickening agent is 1:10, and no crosslinking agent is used;
CN99805888.2 discloses starch stabilized polymer emulsions. The persulfate degrades the starch to the appropriate properties and then, substantially simultaneously, initiates polymerization with the monomer. The process allows the same reaction conditions to be used for the degradation step and the polymerization step and avoids the need to use metal ions such as iron ions. The scheme adopts nonionic unsaturated monomers for grafting and adopts an emulsion polymerization mode.
In general, the viscosity and light transmittance of modified starch are difficult to be particularly high, and the application of modified starch in daily chemicals is often very limited.
Therefore, the technical problem that the present scheme was solved is: how to improve the light transmittance and the viscosity of the modified starch.
Disclosure of Invention
The invention aims to provide a polymer and a daily chemical product, wherein the grafted starch meets the requirements on relative performances such as light transmittance, viscosity and the like by optimizing the proportion of starch and acrylate and the neutralization degree of the acrylate, and meanwhile, the product adopts reversed phase suspension polymerization, obtains solid particles after drying, and can obtain gels with different handfeel after being crushed into different particle sizes, so that the grafted starch can be suitable for different products.
As a further improvement of the invention, the optimal solution for light transmittance and viscosity is found by selecting the type of starch.
The specific scheme of the invention is as follows: the acrylic acid with the neutralization degree of 70-80 percent and starch are prepared by inverse suspension polymerization in the presence of a water-soluble cross-linking agent; the starch is 10-30% by weight of the acrylic acid before neutralization.
In the above polymer, the starch is a mixture of one or more of tapioca starch, corn starch, rice starch, potato starch, sweet potato starch, water chestnut starch, lotus root starch, water chestnut starch, sweet potato starch, arrowroot starch, sago palm starch, oxidized starch, carboxymethyl starch, hydroxypropyl starch, and hydroxypropyl starch phosphate.
In the above polymer, the crosslinking agent is N, N' -methylenebisacrylamide.
There are few water-soluble cross-linking agents, and in this case, only N, N' -methylenebisacrylamide is exemplified, but any potentially water-soluble cross-linking agent known in the art can be used in the present invention.
In the above-mentioned polymer, water is 1.5 to 3 times the weight of acrylic acid before neutralization in the reversed-phase suspension reaction system.
In the above-mentioned polymer, in the reversed-phase suspension reaction system, the organic solvent is 7 to 8 times the weight of acrylic acid before neutralization; the organic solvent is one or a mixture of n-hexane, cyclohexane, isohexane, cyclohexane, benzene, ethyl formate, propyl formate, butyl acetate, propyl acetate, ethyl acetate and methyl acetate.
In the above-mentioned polymer, the crosslinking agent is equivalent to 0.05% to 5% by weight of acrylic acid before neutralization.
Among the above polymers, the preparation method is:
step 1: putting starch into a flask, adding deionized water, stirring in a constant-temperature water bath at 60-90 ℃, and pasting to be transparent;
step 2: weighing acrylic acid, cooling the neutralized sodium acrylate aqueous solution to room temperature, and pouring into gelatinized starch;
and step 3: adding an organic solvent and a cross-linking agent and a dispersing agent into the system obtained in the step 2, and stirring and introducing nitrogen;
and 4, step 4: continuously stirring, adding an initiator, and reacting in a water bath at 50-70 ℃;
and 5: cooling to room temperature, filtering, drying and crushing to obtain the finished product.
In the above polymer, the daily chemical thickener is pulverized to 1 to 500. mu.m.
Meanwhile, the invention also discloses a daily chemical product which contains the sodium polyacrylate grafted starch with the particle size of 1-500 mu m.
In the above daily chemical, when the median particle diameter of the sodium polyacrylate grafted starch is 1 to 10 μm, the sodium polyacrylate grafted starch is used as a rheology modifier;
when the median particle diameter of the sodium polyacrylate grafted starch is 10-100 mu m, the sodium polyacrylate grafted starch is used as a thickening or skin feel modifier;
when the median particle diameter of the sodium polyacrylate grafted starch is 100-500 mu m, the sodium polyacrylate grafted starch is used as a friction agent.
It should be noted that the dispersant and the initiator are not limited in kind in the present invention, and actually the dispersant only functions as a stabilizing reaction in this example, what kind of dispersant has no substantial principle effect on the experimental results, and the kind and amount of the dispersant are selected mainly considering the formation of a stable emulsion.
The dispersant is selected from surfactants having an HLB within the range of about 3 to about 6, and may be selected from span, Tween, fatty alcohol polyoxyethylene ether, sucrose monostearate, polyethylene glycol hydroxystearate, triglycerol monostearate, and combinations thereof.
The initiator can be water-soluble initiator, generally a redox initiation system or a peroxy initiator is available, and the selection of the type and the amount of the initiator has no principle influence on the experimental result of the invention.
The initiator is selected from persulfates, perborates, percarbonates, and combinations thereof; persulfates are preferred.
Has the advantages that:
the grafted starch realizes the related performance requirements of light transmittance and viscosity by optimizing the proportion of starch and acrylate and optimizing the neutralization degree of acrylate, and meanwhile, the product adopts reversed phase suspension polymerization, obtains solid particles after drying, can obtain gels with different handfeel by crushing into different particle sizes, and is suitable for different products.
Repeated experimental research shows that the potato starch has the optimal performance on light transmittance and viscosity.
Drawings
FIG. 1 is a particle size distribution diagram of example 2 with a particle size of 1 to 10 μm;
FIG. 2 is a particle size distribution diagram of example 2 with a particle size of 10 to 100 μm;
FIG. 3 is a graph showing the particle size distribution of 100-500 μm in example 2.
Detailed Description
The technical solution of the present invention will be described in further detail with reference to the following embodiments, but the present invention is not limited thereto.
Example 1
In the polymer, the preparation method comprises the following steps: step 1: putting starch into a flask, adding deionized water, stirring in a water bath with constant temperature of 80 ℃ for 1h, and pasting to be transparent;
step 2: weighing acrylic acid, cooling the neutralized sodium acrylate aqueous solution to room temperature, and pouring into gelatinized starch;
and step 3: adding an organic solvent and a cross-linking agent and a dispersing agent into the system obtained in the step 2, and stirring and introducing nitrogen;
and 4, step 4: continuously stirring, adding an initiator, and reacting in a water bath at 60 ℃ for 3 hours;
and 5: cooling to room temperature, filtering, drying and crushing to obtain the finished product.
Examples 2 to 11
The preparation of examples 2 to 11 is referred to example 1, and the amounts of the respective examples are referred to table 1.
TABLE 1
Comparative examples 1 to 3
The formula is basically the same as example 2, and the differences are shown in the following table 2.
TABLE 2
Performance testing
The light transmittance and viscosity were measured mainly for examples and comparative examples.
The viscosity test is mainly to crush particles to the particle size range of 1-10 mu m, then 198g of deionized water is weighed in a 300mL beaker by a balance, the beaker is placed under an electric stirrer to be stirred at 800rpm, 2g of a sample is weighed, and the sample is slowly added into water to be stirred for 1h until the sample is completely and uniformly dissolved. The viscosity was measured with a brookfield rvt viscometer.
The method for testing the light transmittance comprises the following steps: samples were prepared according to the viscosity test requirements and then tested for light transmittance using an ultraviolet spectrophotometer.
The test results are shown in Table 3 below
Table 3 test results of viscosity and light transmittance of examples and comparative examples
By controlling the crushing time, products with different grain diameters can be obtained. The particle size distribution of the polymer of example 2 can be seen in FIGS. 1 to 3, where the peak positions of the curves in FIGS. 1 to 3 represent the particle size maximum distribution.
When the particle size is 1-10 mu m, the gel is super smooth and crystal-clear, and is mainly used as formula additives of super smooth gel, cream product thickening agent and moisturizing powder.
When the particle size is 10-100 mu m, the gel has micro powder texture and is mainly used as an additive for mousse additives and products such as skin care products, color cosmetics and the like.
When the particle size is 100-500 μm, the gel is transparent block gel, and can be used as body protecting and massage product additive.
Table 3 shows the viscosity at different particle size states as follows:
table 3 viscosity at different particle sizes of example 2
| Particle size of |
10 | 100 | 500 |
| Viscosity mpa.s | 27000 | 32000 | 15000 |
The following rules were followed, whether in the examples or in the comparative examples: when the particle size is too large, the product is granular, the gel is discontinuous, and the viscosity is low. When the particle size is too small, the molecular chain of the product is shortened, and the thickening capacity is slightly reduced.
For review: in this case, the most preferred starches are potato starch and hydroxypropyl starch phosphate, which require a suitable degree of neutralization and ratio of starch to acrylic acid to exhibit satisfactory viscosity and degree of neutralization.
In the present case, extensive performance testing was followed to confirm: hydroxypropyl starch phosphate is preferred over potato starch, potato starch over hydroxypropyl starch, and other starches such as corn starch, rice starch, and the like.
Application case
The polymer of example 2 above was applied to an air cream which showed good thickening and rheological properties, and the specific formulation was as follows:
the above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. A polymer is characterized in that acrylic acid with a neutralization degree of 70-80 percent and starch are prepared by reversed phase suspension polymerization in the presence of a water-soluble cross-linking agent; the starch is 10-30% by weight of the acrylic acid before neutralization.
2. The polymer of claim 1, wherein the starch is a mixture of one or more of tapioca starch, corn starch, rice starch, potato starch, sweet potato starch, water chestnut starch, lotus root starch, water chestnut starch, sweet potato flour, arrowroot flour, sago palm starch, oxidized starch, carboxymethyl starch, hydroxypropyl starch phosphate.
3. The polymer of claim 1, wherein the crosslinking agent is N, N' -methylenebisacrylamide.
4. The polymer according to claim 1, wherein the amount of water is 1.5 to 3 times the weight of acrylic acid before neutralization in the reaction system for reverse phase suspension.
5. The polymer according to claim 1, wherein the organic solvent is 7 to 8 times the weight of acrylic acid before neutralization in the reaction system of reverse phase suspension; the organic solvent is one or a mixture of n-hexane, cyclohexane, isohexane, cyclohexane, benzene, ethyl formate, propyl formate, butyl acetate, propyl acetate, ethyl acetate and methyl acetate.
6. The polymer of claim 1, wherein the crosslinking agent is present in an amount of 0.05% to 5% by weight based on the weight of the acrylic acid prior to neutralization.
7. The polymer according to any one of claims 1 to 6, characterized in that it is prepared by:
step 1: putting starch into a flask, adding deionized water, stirring in a constant-temperature water bath at 60-90 ℃, and pasting to be transparent;
step 2: weighing acrylic acid, cooling the neutralized sodium acrylate aqueous solution to room temperature, and pouring into gelatinized starch;
and step 3: adding an organic solvent and a cross-linking agent and a dispersing agent into the system obtained in the step 2, and stirring and introducing nitrogen;
and 4, step 4: continuously stirring, adding an initiator, and reacting in a water bath at 50-70 ℃;
and 5: cooling to room temperature, filtering, drying and crushing to obtain the finished product.
8. The polymer according to any one of claims 1 to 6, wherein the daily chemical thickener is pulverized to 1 to 500 μm.
9. A daily chemical comprising the sodium polyacrylate grafted starch according to any one of claims 1 to 8, wherein the sodium polyacrylate grafted starch is 1 to 500 μm.
10. The daily chemical according to claim 9, wherein the sodium polyacrylate grafted starch is used as a rheology modifier when the median particle diameter of the sodium polyacrylate grafted starch is 1 to 10 μm;
when the median particle diameter of the sodium polyacrylate grafted starch is 10-100 mu m, the sodium polyacrylate grafted starch is used as a thickening or skin feel modifier;
when the median particle diameter of the sodium polyacrylate grafted starch is 100-500 mu m, the sodium polyacrylate grafted starch is used as a friction agent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110494757.0A CN113045703A (en) | 2021-05-07 | 2021-05-07 | Polymer and daily chemical |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110494757.0A CN113045703A (en) | 2021-05-07 | 2021-05-07 | Polymer and daily chemical |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113045703A true CN113045703A (en) | 2021-06-29 |
Family
ID=76518546
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110494757.0A Pending CN113045703A (en) | 2021-05-07 | 2021-05-07 | Polymer and daily chemical |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113045703A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114149529A (en) * | 2021-12-31 | 2022-03-08 | 南京紫鸿生物科技有限公司 | Partially neutralized sodium polyacrylate and its preparation method and application |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4777232A (en) * | 1986-04-19 | 1988-10-11 | Starchem Gmbh | Method of manufacturing polysaccharide graft polymers which absorb water and are capable of swelling |
| CN102633943A (en) * | 2012-03-30 | 2012-08-15 | 广西大学 | Preparation method of starch super-absorbent resin |
-
2021
- 2021-05-07 CN CN202110494757.0A patent/CN113045703A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4777232A (en) * | 1986-04-19 | 1988-10-11 | Starchem Gmbh | Method of manufacturing polysaccharide graft polymers which absorb water and are capable of swelling |
| CN102633943A (en) * | 2012-03-30 | 2012-08-15 | 广西大学 | Preparation method of starch super-absorbent resin |
Non-Patent Citations (2)
| Title |
|---|
| 林润雄等: "反相悬浮聚合法淀粉接枝聚丙烯酸钠的研究", 《化工科技》 * |
| 辜英杰等: "淀粉-丙烯酸钠高吸水树脂的辐射反相悬浮法制备与性能", 《华南农业大学学报(自然科学版)》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114149529A (en) * | 2021-12-31 | 2022-03-08 | 南京紫鸿生物科技有限公司 | Partially neutralized sodium polyacrylate and its preparation method and application |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP3703539B2 (en) | High performance alkaline swellable rheological additive for water system and method for producing the same | |
| CA2532918C (en) | Aqueous dispersions of hydrosoluble polymerisates of ethylenically unsaturated anionic monomers, method for the production and use thereof | |
| CN103204968B (en) | High performance alkali swelling thickener and preparation method thereof | |
| PL199372B1 (en) | Method for making hydrophobically associative polymers, methods of use and compositions | |
| CN102958943B (en) | Surfactant-free alkali-swellable acrylic emulsions, use thereof in aqueous formulations and formulations containing same | |
| JPH09183806A (en) | Production of polymer by emulsion polymerization and aqueous polymer dispersion | |
| JP2000234003A (en) | Water-soluble or water-swellable polymer | |
| SG186114A1 (en) | Alkali-swellable acrylic emulsions comprising acrylic acid, use thereof in aqueous formulations and formulations containing same | |
| CN111848876B (en) | Preparation method of acrylic emulsion, prepared acrylic emulsion and application thereof | |
| US20080033129A1 (en) | Polymeric viscosity modifiers | |
| CN102911321A (en) | Pesticide suspension concentrate dispersing agent and novel preparation method thereof | |
| CN113045703A (en) | Polymer and daily chemical | |
| US5183872A (en) | Process for the peparation of finely divided, water-swellable polysaccharide graft polymers | |
| WO2022207696A1 (en) | Inverse emulsion thickeners | |
| KR20050022813A (en) | Process for preparing Bead-typed hydrogel | |
| JP7174043B2 (en) | Inverse emulsion thickener | |
| CN113563510B (en) | Temperature-resistant salt-resistant comb polymer fluid loss additive for drilling mud bentonite | |
| JP4908758B2 (en) | Method for producing vinylamide polymer composition for skin and hair composition | |
| JPH0798846B2 (en) | Cross-linked carboxylic acid copolymers useful as thickeners | |
| FR2710650A1 (en) | Water in oil thickening dispersions, their preparation process and their application in textile printing. | |
| JPH1160616A (en) | Dispersant for reverse-phase suspension polymerization and production of particulate polymer by using this dispersant | |
| EP0042678B1 (en) | Method of thickening | |
| JP6981963B2 (en) | Gel composition, cosmetics, and method for producing gel composition | |
| WO2012148951A1 (en) | Stimulus-responsive polymeric particle formulations | |
| JP4384135B2 (en) | Method for producing transparent bead-like superabsorbent resin colored without color transfer and sustained-release preparation containing the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20210629 |
|
| RJ01 | Rejection of invention patent application after publication |