CN1068339A - The manufacture method of High hydrophilous resin - Google Patents
The manufacture method of High hydrophilous resin Download PDFInfo
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- CN1068339A CN1068339A CN 91107241 CN91107241A CN1068339A CN 1068339 A CN1068339 A CN 1068339A CN 91107241 CN91107241 CN 91107241 CN 91107241 A CN91107241 A CN 91107241A CN 1068339 A CN1068339 A CN 1068339A
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- starch
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- graft copolymer
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
With starch is raw material, with currently known methods with acrylonitrile grafting to starch, starch-acrylonitrile graft copolymer.The present invention provides a kind of dispersion system of forming with immiscible organic solvent of water and strong alkali aqueous solution, above-mentioned graft copolymer is particulate state is scattered in saponification in the organic solvent, add tensio-active agent and prevent particle bond, 70～100 ℃ of range of reaction temperature.Present method can directly obtain widely used granular product.Method is simple, save trouble, and cost is low, the production efficiency height.
Description
The present invention relates to a kind of manufacture method of High hydrophilous resin starch-acrylonitrile graft copolymer.This High hydrophilous resin with a large amount of absorptions or irreducible water has extensive use in a lot of fields, and water-keeping material is applied to breeding, raising seedling, drought resisting increases income, prevents erosion and the desert transformation aspect, has all obtained bigger success as being used as.
According to U.S.Pat.No2,922,768 reports, with starch is raw material, acrylonitrile grafting constitutes the further polyacrylonitrile side chain of hydrolysis to starch, be dispersed in saponification in the big water gaging, it is the important method of present industrial production water absorbent polymer, this method has that the product water regain is big, raw material is easy to get, low cost and other advantages, but weak point is graftomer and is dispersed in the full-bodied gelinite of the easy formation of saponification in the water that product contains a large amount of moisture content, makes stirring, discharging and product drying difficulty, generally all want specific installation to handle at present, cause the technical process complexity.Though if change into the problem that saponification in lower alcohol-highly basic mixed solution can avoid occurring the high-viscosity gel body; But saponification temperature is lower, thereby influences the saponification effect, and has the problem of recovery aspect with lower alcohol.
The purpose of this invention is to provide a kind of starch-acrylonitrile graft copolymer with the immiscible organic solvent of water in the saponified method.
Concrete technical measures of the present invention are to be raw material with pasty state or granular starch, acrylonitrile grafting is to starch, formation is the polyacrylonitrile side chain of hydrolysis further, starch mainly plays skeleton function, the amount ratio of vinyl cyanide and starch has the range changing of broad, the general mole ratio that adopts 4: 1 to 6: 1 in the reality.Select for use a kind of not miscible organic solvent (for example aliphatics and aromatic hydrocarbons compounds benzene,toluene,xylene, petroleum naphtha, white oil etc.) and the dispersion of strong base solution composition not to be then with water, above-mentioned pearl starch-acrylonitrile graft copolymer is dispersed in saponification in the organic medium, for preventing particle bond or closing with fixed attention, can add consumption and be the thousandth to ten ten thousand of organic medium weight/ tensio-active agent in wherein, strong alkali aqueous solution then infiltrates granule interior with the hydrolysis of polyacrylonitrile side chain.Suitable temperature of reaction is 70-100 ℃, reacts after several hours, removes by filter organic solvent, and drying can directly obtain the particulate state High hydrophilous resin, and organic solvent must not handled with regard to recyclable utilization.
The manufacture method of hydrolyzed starch-acrylonitrile graft copolymer provided by the invention has the following advantages: 1, high viscosity does not appear in reaction system; 2, local alkali concn height, speed of response is fast, and saponification is more complete; 3, organic solvent easily separates with product; 4, organic solvent can directly be recycled; 5, the low drying that is easy to of product water content; 6, can directly provide granulated product; 7, product color is light; 8, equipment is simple, and it is low to consume energy, the efficient height, and cost is low.
The embodiment of the inventive method is:
Embodiment 1
33g dried corn starch dispersed with stirring in 570ml water, is blown into nitrogen, is warming up to 85 ℃ of pre-gelatinizations 1 hour.Add 34ml0.1M ceric ammonium nitrate solution (being dissolved in the 1N nitric acid) after being chilled to 25 ℃, mixed 15 minutes, the more distilled again vinyl cyanide of 60g is added, remain on 33 ℃ of reactions 3 hours.Product neutralizes with diluted alkaline, filters and washes with water, 45 ℃ of oven dry, pulverizes standby.
Dissolving 0.27g Sodium dodecylbenzene sulfonate in the 405ml200# solvent oil stirs the graft copolymer that adds gained down gradually and 45ml water and makes and be uniformly dispersed.Slowly heating up about 80 ℃ adds the 189g25% aqueous sodium hydroxide solution, continues elevated temperature to 98-100 ℃ of reaction 3 hours.Be chilled to room temperature, filtered and recycled solvent oil product washs with lower alcohol, and the every gram in oven dry back absorbs distilled water 400ml.
Embodiment 2
Synthesizing of this routine used starch-acrylonitrile graft copolymer original material is identical with example 1, be dispersed in hydrolysis in the 405ml toluene that contains the 0.009g sodium abietate by same operation, be reflected at reflux temperature and carried out 2.5 hours, the every gram of drying products absorbs distilled water 340ml.
Embodiment 3
8% starch water slurry 313g is stirred swelling 1.5 hours at 60 ℃, be blown into nitrogen simultaneously.Be chilled to 25 ℃ and add 12ml0.1M ceric ammonium nitrate solution (being dissolved in the 1N nitric acid).Stir and added vinyl cyanide 37g in 15 minutes, 28 ℃ of reactions 3 hours.
Graft copolymer is through neutralization, washing, and suction filtration stirs to add gradually down and contains in the 270ml200# solvent oil of 0.18g Sodium dodecylbenzene sulfonate to 114g.Saponification was carried out 3 hours at 98-100 ℃, and temperature rises to and adds 40% hydrogen sodium nitride aqueous solution 75g about 80 ℃.Product elimination solvent oil washs with lower alcohol, and the every gram of drying products absorbs distilled water 180ml.
Claims (4)
1, a kind of high-hydroscopicity can hydrolyzed starch--manufacture method of acrylonitrile graft copolymer is characterized in that: starch--acrylonitrile graft copolymer be dispersed in be added with tensio-active agent with the immiscible organic medium of water in saponification.
2, manufacture method according to claim 1 is characterized in that: the organic medium of employing can be aliphatics and aromatic hydrocarbons compounds.
3, manufacture method according to claim 1 is characterized in that: the dosage of surfactant scope of employing be the thousandth to ten ten thousand of organic solvent weight/.
4, manufacture method according to claim 1 is characterized in that: the saponification temperature scope is 70-100 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 91107241 CN1068339A (en) | 1991-07-08 | 1991-07-08 | The manufacture method of High hydrophilous resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 91107241 CN1068339A (en) | 1991-07-08 | 1991-07-08 | The manufacture method of High hydrophilous resin |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1068339A true CN1068339A (en) | 1993-01-27 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 91107241 Pending CN1068339A (en) | 1991-07-08 | 1991-07-08 | The manufacture method of High hydrophilous resin |
Country Status (1)
| Country | Link |
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| CN (1) | CN1068339A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100368608C (en) * | 2005-09-30 | 2008-02-13 | 中国石油化工股份有限公司 | Method for preparing copolymerized acrylonitrile high water-absorption fiber |
| CN100447189C (en) * | 2006-01-19 | 2008-12-31 | 江南大学 | Production of easily biological-degradable built-up starch-base high water-absorption resin |
| CN104804138A (en) * | 2015-05-12 | 2015-07-29 | 苏州市湘园特种精细化工有限公司 | Super absorbent resin and preparation method thereof |
| WO2020157643A1 (en) * | 2019-01-29 | 2020-08-06 | Upl Ltd | A process for preparation of superabsorbent polymer |
| WO2021165842A1 (en) * | 2020-02-20 | 2021-08-26 | Upl Limited | A process for preparation of superabsorbent polymer |
-
1991
- 1991-07-08 CN CN 91107241 patent/CN1068339A/en active Pending
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100368608C (en) * | 2005-09-30 | 2008-02-13 | 中国石油化工股份有限公司 | Method for preparing copolymerized acrylonitrile high water-absorption fiber |
| CN100447189C (en) * | 2006-01-19 | 2008-12-31 | 江南大学 | Production of easily biological-degradable built-up starch-base high water-absorption resin |
| CN104804138A (en) * | 2015-05-12 | 2015-07-29 | 苏州市湘园特种精细化工有限公司 | Super absorbent resin and preparation method thereof |
| WO2020157643A1 (en) * | 2019-01-29 | 2020-08-06 | Upl Ltd | A process for preparation of superabsorbent polymer |
| CN113316606A (en) * | 2019-01-29 | 2021-08-27 | Upl有限公司 | Method for preparing superabsorbent polymer |
| US20220097022A1 (en) * | 2019-01-29 | 2022-03-31 | Upl Ltd | A process for preparation of superabsorbent polymer |
| WO2021165842A1 (en) * | 2020-02-20 | 2021-08-26 | Upl Limited | A process for preparation of superabsorbent polymer |
| US20230074309A1 (en) * | 2020-02-20 | 2023-03-09 | Upl Limited | A process for preparation of superabsorbent polymer |
| US11958925B2 (en) * | 2020-02-20 | 2024-04-16 | Upl Ltd | Process for preparation of superabsorbent polymer |
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