CN1390868A - Amphiprotic starch graft copolymer and its one-step preparing process - Google Patents
Amphiprotic starch graft copolymer and its one-step preparing process Download PDFInfo
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- CN1390868A CN1390868A CN 02134335 CN02134335A CN1390868A CN 1390868 A CN1390868 A CN 1390868A CN 02134335 CN02134335 CN 02134335 CN 02134335 A CN02134335 A CN 02134335A CN 1390868 A CN1390868 A CN 1390868A
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Abstract
A process for preparing the graft copolymer of amphiprotic starch prepared by one-step method includes such steps as preparing amphiprotic starch by both cationic and anionic reaction at 20-60 deg.C, where mixed water-alcohol solvent is used as reaction medium, tripolyphosphate or pyrophosphate as anionic reagent and 3-Cl-dihydroxytrimethylamine hydrochloride as cationic reagent, the graft copolymerizing between amphiprotic starch and acrylamide at 5-60 deg.C in water phase, and cationic reacting for the graft chain of said graft copolymer at 2-50 deg.C in water phase. Its advantages are better network structure, and high stability.
Description
Technical field
The present invention relates to chemical field, specifically being that preparation is a kind of is reaching the starch product that has functional structure and network structure simultaneously on the grafted chain skeleton on the starch chain skeleton.This technology is used in modified starch manufacturing enterprise, and the amphiprotic starch graft copolymer product of Sheng Chaning then can be applicable to extensively industry and field such as papermaking, weaving, chemical industry, pharmacy, oil, environmental protection, agricultural and mining industry thus.
Background technology
Starch is a kind of natural high moleculer eompound, and synthetic by photosynthesis by plant, its basic composition is a carbohydrate, and the starch based product mainly is meant the modified starch of naturally occurring ative starch and process various physics, chemistry and biological method modification.Amphoteric starch and starch graft copolymer are two big series products in numerous modified starch products.
The amphoteric starch of producing both at home and abroad all adopts two-step approach to carry out at present, promptly adopt wet processing on starch molecular chain, to introduce cation group earlier, and then on starch molecular chain, introduce anionic group by dry process, the characteristics of its product on molecular structure are different positionss that the yin, yang ionic group is in same starch molecular chain.The kind of starch graft copolymer product is then more, but all is to be the starch graft copolymer of grafting parent with the ative starch basically.
Though the modified starch product that with the ative starch is the starch graft copolymer of parent is widely used, they structurally also exist big deficiency and defective.Starch graft copolymer comprises starch chain and grafted chain two portions from structure.This product partly has functional structure at the grafted chain skeleton, but still keeps the ative starch chain structure in starch chain skeleton part, and does not have functional structure, so directly affects the performance of product.
With the amphoteric starch is the amphiprotic starch graft copolymer of grafting parent, not only has networked structure, and on starch chain parent and grafted chain skeleton, have functional structure simultaneously, and be the modified starch product of a kind of more fully functionalization, networking, have stable and excellent more performance.
Because the preparation of amphoteric starch at present all is to adopt method of fractional steps production, its complicated process of preparation, the production cycle is long, equipment requirements is high, preparation cost is high, unstable product quality, therefore be the restriction that the preparation of the amphiprotic starch graft copolymer product of grafting parent is subjected to very big degree with the two-step approach amphoteric starch, cause the suitability for industrialized production of this product and application to can not get promoting.
Summary of the invention
The objective of the invention is to shortcoming, a kind of preparation method of single stage method amphiprotic starch graft copolymer is provided at the prior art existence.Simplify preparation technology, shorten the production cycle, equipment requirements is low.
The present invention also aims to provide the amphiprotic starch graft copolymer of this method production.
The preparation method of single stage method amphiprotic starch graft copolymer of the present invention comprises:
(1) the synthetic amphoteric starch of single stage method is a reaction medium with water-pure mixed solvent promptly, and tri-polyphosphate or pyrophosphate salt are anionization reagent, and 3-chloro-2 hydroxypropyl trimethylamine hydrochlorides are cationic reagent, carry out the yin, yang ion reaction simultaneously at 20-60 ℃;
(2) amphoteric starch and acrylic amide graft copolymerization, be that parent, acrylamide are that grafted monomer is initiator at aqueous phase with cerium salt or cerium salt and Potassium Persulphate etc. promptly with the single stage method amphoteric starch, in nitrogen or carbon dioxide environment system, 5-60 ℃ is carried out graft copolymerization;
(3) cationization of the grafted chain of amphoteric starch and acrylamide grafted copolymer, the cationic reagent so that formaldehyde (or trioxymethylene) and dimethylamine reaction generate carries out the cationization reaction at aqueous phase 2-50 ℃.
Described starch material is the common starch raw material, as corn, cassava, potato, wheat, Ipomoea batatas wherein one or more.
During the one-step synthesis of amphoteric starch, require the anionization reaction of starch and cationization to react and carry out simultaneously; Amphoteric starch and acrylic amide graft copolymerization then are that the amphoteric starch for preparing with single stage method is the graft copolymerization of grafting parent; The grafted chain modification of amphoteric starch and acrylamide grafted copolymer then is to carry out the cationization reaction and introduce the cationic functional base on the grafted chain skeleton at the grafted chain of aqueous phase to amphoteric starch and acrylamide grafted copolymer.
Amphiprotic starch graft copolymer through above process preparation, can remove behind freshen and the impurity as the gel-like prod packing through neutralization, dialysis, also can further separate, the processing of postorder operations such as washing, purifying, dehydration, drying, pulverizing, screening and packing obtains powdery product.
The more specifically production method of amphiprotic starch graft copolymer of the present invention comprises: at constant temperature in 20-60 ℃ thermostatic water-circulator bath reactor or other isothermal reactor, keep continuously stirring, is corn ative starch volume ratio that water-pure blending agent of 0.1～2.0 is made into 5%～85% starch milk, 0.5%～15% the strong base solution that adds 1%～30% 3-chloro-2-hydroxypropyl trimethylamine hydrochloride of starch butt quality and starch butt quality, activation 1-120min, 0.5%～30% the tripoly phosphate sodium STPP dilute alkaline soln that adds starch butt quality, reaction 0.5～8h.Reaction Bi Zhonghe is to neutral, filter, the amphoteric starch water of preparation is made into 1%～40% starch milk, be warming up to 65～95 ℃ of gelatinization 10-120min, be cooled to 5-60 ℃, with the nitric acid adjust pH is 2～7, after feeding nitrogen or carbonic acid gas 10～40min, adding system concentration is cerium salt initiators or cerium salt and the Potassium Persulphate composite initiator of 0.5～10.0mmol/L, induces 10～60min, adds 20%～400% acrylamide amine of starch quality, reaction 1～6h, be neutralized to neutrality, add 2%～50% the formaldehyde (or trioxymethylene) of acrylamide quality and the cationic reagent of dimethylamine, reaction 0.5～4h 2～25 ℃ of preparations.
Different with two-step process, one-step technology has that technology is simple, with short production cycle, equipment requirements is simple, preparation cost is low, for the industrial production and the application of amphiprotic starch graft copolymer product provides great convenience.In addition, amphoteric starch that one-step technology obtained and two-step approach product exist the qualitative difference on the molecular structure, and promptly the yin, yang ionic group of two-step approach amphoteric starch is the different positions that is connected on starch molecular chain respectively, are two independently side chains; And the yin, yang ionic group of single stage method amphoteric starch is to be on the same side chain, in the same position of starch molecular chain.Therefore, has functional structure simultaneously on the starch chain skeleton of single stage method amphoteric starch and the grafted chain skeleton.
The present invention compared with prior art has following advantage: single stage method amphiprotic starch graft copolymer provided by the invention promptly is different from traditional starch graft copolymer product, also is different from two-step approach amphiprotic starch graft copolymer product.Be primarily characterized in that on starch chain skeleton and the grafted chain skeleton to have functional group simultaneously, and the yin, yang ionic group of amphoteric starch is positioned on the same side chain.Compare with starch graft copolymer, because the starch chain skeleton has been introduced yin, yang ion functional group simultaneously on same side chain, its functional structure is more complete, more even, make the good networked structure of the easier formation of single stage method amphiprotic starch graft copolymer, under equally distributed yin, yang ionic interacts, have better stability and better application performance.Enforcement of the present invention can bring direct economic benefit for modified starch factory.Simultaneously, also can bring indirect economic benefit for the Application Areas such as the industries such as papermaking, weaving, chemical industry, pharmacy, oil, environmental protection, agricultural and mining industry of modified starch.Can bring more social benefit for people's clothing, food, lodging and transportion--basic necessities of life and for the human survival and development.
Embodiment
Embodiment 1
At constant temperature in 20 ℃ thermostatic water-circulator bath reactor or other isothermal reactor, keep continuously stirring, is corn ative starch volume ratio that water-pure blending agent of 0.6 is made into 30% starch milk, 3.5% the strong base solution that adds 5.8% 3-chloro-2-hydroxypropyl trimethylamine hydrochloride of starch butt quality and starch butt quality, activation 10min, 5.5% the tripoly phosphate sodium STPP dilute alkaline soln that adds starch butt quality, reaction 3h.Reaction Bi Zhonghe is to neutral, filter, the amphoteric starch of preparation is made into 4% starch milk with deionized water, be warming up to 90 ℃ of gelatinization 40min, be cooled to 40 ℃, with the nitric acid adjust pH is 5, after feeding nitrogen or carbonic acid gas 30min, adding system concentration is the cerium salt initiators of 2.5mmol/L, induces 10min, 100% the acrylamide amine that adds starch quality, reaction 3h is neutralized to neutrality, adds 50% formaldehyde 15 ℃ of preparations (or trioxymethylene) of acrylamide quality and the cationic reagent of dimethylamine, reaction 2h, product is purified, dry, pulverizing waits the postorder operation promptly to get the sex change product of powdery amphoteric starch graft copolymer.
Embodiment 2
At constant temperature in 40 ℃ thermostatic water-circulator bath reactor or other isothermal reactor, keep continuously stirring, is corn ative starch volume ratio that water-pure blending agent of 1.0 is made into 40% starch milk, add and 3.5% strong base solution of starch butt quality, activation 10min, 2.5% the tripoly phosphate sodium STPP dilute alkaline soln that adds 10% 3-chloro-2-hydroxypropyl trimethylamine hydrochloride of starch butt quality and starch butt quality, reaction 1h.The reaction post neutralization is to neutral, filter, the amphoteric starch of preparation is made into 8% starch milk with deionized water, be warming up to 70 ℃ of gelatinization 20min, be cooled to 50 ℃, with the nitric acid adjust pH is 3, after feeding nitrogen or carbonic acid gas 10min, adding system concentration is the cerium salt initiators of 4.0mmol/L, induces 30min, 20% the acrylamide amine that adds starch quality, reaction 4h is neutralized to neutrality, adds 25% formaldehyde 15 ℃ of preparations (or trioxymethylene) of acrylamide quality and the cationic reagent of dimethylamine, reaction 4h, product is purified, get the sex change product of gluey amphiprotic starch graft copolymer.
Embodiment 3
At constant temperature in 50 ℃ thermostatic water-circulator bath reactor or other isothermal reactor, keep continuously stirring, is corn ative starch volume ratio that water-pure blending agent of 1.2 is made into 5% starch milk, 7% the strong base solution that adds 20% 3-chloro-2-hydroxypropyl trimethylamine hydrochloride of starch butt quality and starch butt quality, activation 5min, 20% the tripoly phosphate sodium STPP dilute alkaline soln that adds starch butt quality, reaction 4h.Reacted the neutrality that neutralizes, filter, the amphoteric starch of preparation is made into 4% starch milk with deionized water, be warming up to 90 ℃ of gelatinization 20min, be cooled to 20 ℃, with the nitric acid adjust pH is 5, after feeding nitrogen or carbonic acid gas 30min, adding system concentration is cerium salt initiators and the 4.0mmol/L Potassium Persulphate of 2.0mmol/L, induce 10min, 200% the acrylamide amine that adds starch quality, reaction 3h is neutralized to neutrality, adds 5% formaldehyde 15 ℃ of preparations (or trioxymethylene) of acrylamide quality and the cationic reagent of dimethylamine, reaction 2h, product is purified, dry, pulverizing waits the postorder operation promptly to get the sex change product of powdery amphoteric starch graft copolymer.
Claims (3)
1, a kind of preparation method of single stage method amphiprotic starch graft copolymer is characterized in that comprising:
(1) the synthetic amphoteric starch of single stage method is a reaction medium with water-pure mixed solvent promptly, and tri-polyphosphate or pyrophosphate salt are anionization reagent, and 3-chloro-2 hydroxypropyl trimethylamine hydrochlorides are cationic reagent, carry out the yin, yang ion reaction simultaneously at 20-60 ℃;
(2) amphoteric starch and acrylic amide graft copolymerization, be that parent, acrylamide are that grafted monomer is initiator at aqueous phase with cerium salt or cerium salt and Potassium Persulphate etc. promptly with the single stage method amphoteric starch, in nitrogen or carbon dioxide environment system, 5-60 ℃ is carried out graft copolymerization;
(3) cationization of the grafted chain of amphoteric starch and acrylamide grafted copolymer, the cationic reagent with formaldehyde or trioxymethylene and dimethylamine reaction generation carries out the cationization reaction at aqueous phase 2-50 ℃.
2, the preparation method of single stage method amphiprotic starch graft copolymer according to claim 1 is characterized in that described starch material is the common starch raw material, as corn, cassava, potato, wheat, Ipomoea batatas wherein one or more.
3, the preparation method of single stage method amphiprotic starch graft copolymer according to claim 1, it is characterized in that at constant temperature in 20-60 ℃ thermostatic water-circulator bath reactor or other isothermal reactor, keep continuously stirring, is corn ative starch volume ratio that water-pure blending agent of 0.1～2.0 is made into 5%～85% starch milk, 0.5%～15% the strong base solution that adds 1%～30% 3-chloro-2-hydroxypropyl trimethylamine hydrochloride of starch butt quality and starch butt quality, activation 1-120min, 0.5%～30% the tripoly phosphate sodium STPP dilute alkaline soln that adds starch butt quality, reaction 0.5～8h; Reaction Bi Zhonghe is to neutral, filter, the amphoteric starch water of preparation is made into 1%～40% starch milk, be warming up to 65～95 ℃ of gelatinization 10-120min, be cooled to 5-60 ℃, with the nitric acid adjust pH is 2～7, after feeding nitrogen or carbonic acid gas 10～40min, adding system concentration is cerium salt initiators or cerium salt and the Potassium Persulphate composite initiator of 0.5～10.0mmol/L, induces 10～60min, adds 20%～400% acrylamide amine of starch quality, reaction 1～6h, be neutralized to neutrality, add 2%～50% the formaldehyde (or trioxymethylene) of acrylamide quality and the cationic reagent of dimethylamine, reaction 0.5～4h 2～25 ℃ of preparations.
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| CNB021343357A CN1182168C (en) | 2002-07-11 | 2002-07-11 | Amphiprotic starch graft copolymer and its one-step preparing process |
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| CNB021343357A CN1182168C (en) | 2002-07-11 | 2002-07-11 | Amphiprotic starch graft copolymer and its one-step preparing process |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102050881A (en) * | 2010-10-27 | 2011-05-11 | 烟台大学 | Method for preparing special intumescent starch flame retardants for leather |
| CN102898665A (en) * | 2012-11-07 | 2013-01-30 | 桂林理工大学 | Method for preparing adsorptive double cross-linked amphoteric cassava starch |
| CN102898666A (en) * | 2012-11-07 | 2013-01-30 | 桂林理工大学 | Method for preparing high-degree double-crosslinked amphoteric grafted tapioca starch resin |
| CN104804139A (en) * | 2015-05-21 | 2015-07-29 | 南京大学 | Flocculation sterilization difunctional grafting starch water treatment agent and preparation method thereof |
| CN108530652A (en) * | 2018-03-29 | 2018-09-14 | 钦州学院 | A kind of converted starch plural gel and its preparation method and application |
-
2002
- 2002-07-11 CN CNB021343357A patent/CN1182168C/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102050881A (en) * | 2010-10-27 | 2011-05-11 | 烟台大学 | Method for preparing special intumescent starch flame retardants for leather |
| CN102050881B (en) * | 2010-10-27 | 2012-05-23 | 烟台大学 | Method for preparing special intumescent starch flame retardants for leather |
| CN102898665A (en) * | 2012-11-07 | 2013-01-30 | 桂林理工大学 | Method for preparing adsorptive double cross-linked amphoteric cassava starch |
| CN102898666A (en) * | 2012-11-07 | 2013-01-30 | 桂林理工大学 | Method for preparing high-degree double-crosslinked amphoteric grafted tapioca starch resin |
| CN102898666B (en) * | 2012-11-07 | 2014-01-08 | 桂林理工大学 | Method for preparing high-degree double-crosslinked amphoteric grafted tapioca starch resin |
| CN102898665B (en) * | 2012-11-07 | 2014-01-08 | 桂林理工大学 | Method for preparing adsorptive double cross-linked amphoteric cassava starch |
| CN104804139A (en) * | 2015-05-21 | 2015-07-29 | 南京大学 | Flocculation sterilization difunctional grafting starch water treatment agent and preparation method thereof |
| CN108530652A (en) * | 2018-03-29 | 2018-09-14 | 钦州学院 | A kind of converted starch plural gel and its preparation method and application |
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| CN1182168C (en) | 2004-12-29 |
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Assignee: Foshan Shunde Digital Paint Co., Ltd. Assignor: South China University of Technology Contract fulfillment period: 2007.10.31 to 2012.10.30 contract change Contract record no.: 2009440001623 Denomination of invention: Amphiprotic starch graft copolymer and its one-step preparing process Granted publication date: 20041229 License type: Exclusive license Record date: 20091016 |
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Free format text: EXCLUSIVE LICENSE; TIME LIMIT OF IMPLEMENTING CONTACT: 2007.10.31 TO 2012.10.30; CHANGE OF CONTRACT Name of requester: FOSHAN CITY SHUNDE DISTRICT DIGITAL COLOR COATING Effective date: 20091016 |
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Granted publication date: 20041229 Termination date: 20120711 |