CN104231175A - Method for preparing etherification-oxidation-grafting multiple-modified starches - Google Patents
Method for preparing etherification-oxidation-grafting multiple-modified starches Download PDFInfo
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Abstract
The invention discloses a method for preparing etherification-oxidation-grafting multiple-modified starches. The method comprises the following steps: using native starch as a raw material, adding an etherifying agent, an oxidizing agent and a composite catalyst, and completing etherification and oxidation reaction with one step by adopting a microwave semidry method; using the obtained etherified and oxidized starch as a raw material, adding an initiating agent, a basic catalyst and a composite vinyl monomer, and carrying out graft copolymerization reaction by adopting an open system method in a microwave reactor. The three modification methods of etherification, oxidation and grafting are organically combined, and a variety of reactive groups are grafted in the molecular structure of starch, the method enhances the advantages and avoid weaknesses and has complementary advantages. By regulating a process formula, the method can obtain a series of multiple-modified starches with different ratios of reactive groups and different grafting ratios. The multiple-modified starches have various good characteristics of carboxymethyl-etherified and/or hydroxyalkyl-etherified, oxidized and grafting starches and can be applied to the fields of papermaking, food, textile, daily chemical industry, polymeric flocculants, super absorbent materials, oilfield chemical materials, biodegradable mulch film and plastics and the like.
Description
Technical field
The invention belongs to technical field of modified starch, be specifically related to a kind of preparation method of etherificate-oxidation-graft polyol modified starch.
Background technology
Multicomponent modified starch refers to the starch connecting two or more reactive groups such as negatively charged ion, positively charged ion or nonionic in same starch molecule, it is the novel starch derivative grown up on the single modified starch basis such as yin, yang, nonionic, object is strengthening modified starch performance in a certain respect, and effect is more outstanding in actual applications, working conditions is wider, Application Areas is wider to make it.Select different reactive groups, different proportionings and different processing condition, the multicomponent modified starch product with different property can be prepared.In recent years, domestic many starch science research workers are active in the Synthesis and applications research work of multicomponent modified starch.
Through retrieval, we find some bibliographical informations relevant to multicomponent modified starch:
1, Chinese patent, [Application Number (patent)] CN200310112684.6[applying date] 2003.12.16[title] a kind of etherificate-crosslinked-pre-gelatinized ternary compound modified starch and its preparation method and application [application (patent right) people] Southern Yangtze University's [summary] a kind of etherificate-be cross-linked-pre-gelatinized ternary compound modified starch and its preparation method and application, belong to technical field of starch modification.Product application of the present invention to starch to carry out simultaneously etherificate, crosslinked, pre-gelatinized sex change method and obtain, make it have etherificate simultaneously, be cross-linked, the characteristic of pre-gelatinized starch.Product is used for the peracid in thick stabilization foodstuffs industry, high salt and frozen product, also can be used for the sizing agent of the industry such as papermaking, weaving.Advantage of the present invention is combined at etherificate, crosslinked, pre-gelatinized three kinds of denaturation methods, and technological design science is practical, and product performance are excellent, can the higher pectin, xanthan gum etc. of the current domestic price of Some substitute, easy to utilize.[principal claim] claims 1, a kind of etherificate-crosslinked-pre-gelatinized ternary compound modified starch, it is characterized in that applying preparation method starch being carried out simultaneously to etherificate, crosslinked, pre-gelatinized sex change, make it have the characteristic of etherification starch, cross-linking starch, pre-gelatinized starch simultaneously.The application of 2, as described in 1 three former composite modified starchs, is characterized in that being used as peracid, high salt and the frozen product in thick stabilization foodstuffs industry, also can be used for the sizing agent of the industry such as papermaking, weaving.
2, Chinese patent, [Application Number (patent)] CN2008100743403.3[applying date] 2008.1.4[title] multicomponent modified starch for papermaking and production method thereof [application (patent right) people] Guangxi Mingyang Biochemical Science and Technology Co., Ltd.'s [summary] the invention provides a kind of multicomponent modified starch for papermaking and production method thereof, it is a kind of " etherificate-oxidation-ester " multicomponent modified starch, concrete technology is: with the starch milk of water by starch furnishing 35 ~ 40% concentration, be, under the effect of 40 ~ 50 DEG C and 1# catalyzer, etherification reaction is carried out 1 ~ 2 hour to starch in temperature after adding etherifying agent, then oxygenant is added, react 3 ~ 5 hours under temperature is 30 ~ 45 DEG C and pH value is the condition of 8 ~ 12, add reductive agent again and carry out reduction treatment, finally add esterifying agent and 2# catalyzer, react 1 ~ 3 hour under temperature is 30 ~ 40 DEG C of conditions, and regulate pH value with acid, through washing, centrifuge dehydration, dry, obtain cohesive strength high, resistance to deterioration is good, good water-retaining property, good film-forming property, high density sticks with paste the good modified starch of the low temperature rheological behaviour of liquid.
3, Chinese patent, [Application Number (patent)] CN03132200.X[applying date] 2003.07.07[title] [application (patent right) people] Southern Yangtze University's [summary] is a kind of is oxidized-ester-grafting ternary compound modified starch and its preparation method and application for a kind of oxidation-ester-grafting ternary compound modified starch and its preparation method and application, belongs to technical field of starch modification.Product application of the present invention to starch to carry out simultaneously oxidative deformation, esterification sex change, grafting sex change preparation method and obtain, make it have the characteristic of oxidation, esterification, grafting modified starch simultaneously.Product is used as paper industry coating agent and sizing agent.Advantage of the present invention is when increasing equipment hardly, and oxidation, esterification, grafting three kinds of denaturation methods are combined, in Sumstar 190 production technique and equipment, a step has been come, technological design science, practicality.Product performance are better than the widely used modified starch kind of current paper industry, easy to utilize.[principal claim] claims 1, a kind of oxidation-ester-grafting ternary compound modified starch, it is characterized in that applying starch is oxidized simultaneously, esterification, grafting sex change preparation method, make it have the characteristic of oxidation, esterification, grafting modified starch simultaneously.
4, Chinese patent, [Application Number (patent)] CN99113918.6[applying date] 1999.07.27[title] non-wood fibre paper strengthening agent [application (patent right) people] Chemical Engineering Institute, HangZhou City [summary] the present invention relates to a kind of non-wood fibre paper strengthening agent, it is a kind of multicomponent modified starch derivative, by being obtained by reacting as follows: a) alkaline catalysts, cationic etherifying agent and starch carry out positively charged ion etherification reaction, its substitution value is made to be 0.010 ~ 0.035; B) spray anionic ester agent again, use phosphoric acid adjust pH, carry out anionization reaction, make substitution value be 0.005 ~ 0.030; C) strength assistant agent adding amount of starch 10% carries out helping strong reaction, and aftertreatment obtains product.Product of the present invention can make into fracture length and the bursting strength raising 15 ~ 20% of paper, and save wood pulp 10 ~ 20%, and have certain retention, drainage effect, the scope of application is wider.[principal claim] weighs claim 1, a kind of non-wood fibre paper strengthening agent, it is characterized in that by being obtained by reacting as follows: a) positively charged ion etherification reaction: under alkaline catalysts effect, cationic etherifying agent is sprayed on starch powder, make fully to be mixed evenly, temperature is at 50 ~ 80 DEG C, react 4 ~ 6 hours, make positively charged ion etherificate base substitution value be 0.010 ~ 0.035; B) anionization reaction: spray adds anionic ester agent below 50 DEG C, and adjust pH value to 4 ~ 8 with acid catalyst, after (miscellany pH value measures under 3% concentration) stirs, by air stream drying method, material moisture content is down to 5 ~ 8%, be warming up to 120 ~ 140 DEG C again, react 2 ~ 4 hours, make negatively charged ion esterification base substitution value be 0.005 ~ 0.030, be then cooled to 40 ~ 60 DEG C; C) help strong reaction: add the toughener of starch consumption 1 ~ 10% and be mixed evenly, react 1-3 hour under room temperature, aftertreatment, obtain non-wood fibre paper strengthening agent.
5, Chinese periodical: [autograph] semidrying Microwave-assisted firing prepares novel process research [author] Cui Yanru [tutor] Yin Yongguang [degree-conferring units] Jilin University [disciplines title] Processing and Storage of Agriculture Products [paper rank] master of multicomponent modified starch, Jilin University; Cui Yanru [time] 2005-08-26[makes a summary] there is employed herein semidrying in conjunction with the novel working method of Microwave-assisted firing to starch denaturalization, by esterification, etherificate two kinds of starch denaturalization technology, positively charged ion, negatively charged ion, neutral group are incorporated in starch polymer chain, have prepared a kind of multicomponent modified starch.Detect through papermaking application performance and show, it has good enhancing, retention aid and filter aid effect to paper.Have employed the technique of nonlinear multivariate regression equations to multicomponent modified starch to simulate, through inspection, regression equation is remarkable under the level of α=0.05.Have studied herein moisture content, microwave power, heat-up time, tripoly phosphate sodium STPP, urea, cupric chloride, 6TA, sodium hydroxide the processing condition such as content on the impact of multicomponent modified starch application performance; Have selected optimum technological parameters: moisture content (additional) 20%, microwave power 350W, reaction times 7min, pH value=4, the optimum addition of cupric chloride, tripoly phosphate sodium STPP, urea, GTA, sodium hydroxide is respectively 0.06 (g/g), 0.05 (g/g), 0.08 (g/g), 0.1134 (g/g), 0.05 (g/g); Reached a conclusion by papermaking application test: when the enhancing of multicomponent modified starch and retention and drainage effect reach the best, the positive and negative of corresponding multicomponent modified starch, the substitution value of neutral ion are respectively 0.017,0.019,0.017.
From open source literature, we can recognize, current multicomponent modified starch has: oxidation-ester-grafting ternary compound modified starch, etherificate-crosslinked-pre-gelatinized ternary compound modified starch, etherificate-oxidation-ester ternary compound modified starch, esterification-etherificate modified starches etc., report there are no the research about " etherificate-oxidation-grafting " multicomponent modified starch.
Summary of the invention
The object of the invention is: the preparation method that a kind of etherificate-oxidation-graft polyol modified starch is provided.Gained multicomponent modified starch molecular structure is with multiple reactive group, and have the multiple good characteristic of carboxymethyl etherification or hydroxyalkyl etherificate, oxidation, graft starch, effect is more outstanding, and range of application is wider.
Technical scheme of the present invention is:
Take ative starch as raw material, prepare multicomponent modified starch through carboxymethyl etherification and/or hydroxyalkyl etherificate, oxidation, the triple sex change of grafting.Its processing step is:
1) be added in ative starch by etherifying agent, oxygenant, composite catalyst under whipped state, gained mixture be placed in microwave reactor and carry out etherification oxidation reaction simultaneously, microwave power is 320W, and the microwave time is 1 ~ 10 minute, obtains etherification oxidation starch;
2) under whipped state, reductive agent is added step 1) in gains etherification oxidation starch, and fully mix;
3) under whipped state, basic catalyst, initiator and compound ethylene base monomer are added step 2) in gains, gained mixture being placed in microwave reactor adopts unlimited system method to carry out graft copolymerization, microwave power is 240W, and the microwave time is 2 ~ 20 minutes;
4) by step 3) products therefrom carries out aftertreatment, obtains product multicomponent modified starch of the present invention.
The key technical indexes of product of the present invention: etherificate base substitution value (DS or MS) is 0.010 ~ 0.50; Carboxyl-content is 0.1 ~ 5.0%; Percentage of grafting is 60 ~ 90%.
The present invention's ative starch used is one or both the mixture in tapioca (flour), yam starch.
Described etherifying agent is one or both the mixture in chloroethanol, Mono Chloro Acetic Acid, sodium chloroacetate, and consumption is 2 ~ 50% of ative starch quality.
Described oxygenant is one or both the mixture in hydrogen peroxide, Sodium Persulfate, and consumption is 0.2 ~ 5.0% of ative starch quality.
Described reductive agent is one or both mixture of S-WAT, sodium bisulfite, and consumption is 0.01 ~ 1.0% of ative starch oven-dry weight.
Described composite catalyst is one or both the mixture in copper sulfate and sodium hydroxide, sodium carbonate, potassium hydroxide, and consumption is 1 ~ 30% of ative starch quality.
Described basic catalyst is one or both the mixture in sodium hydroxide, sodium carbonate, potassium hydroxide, and consumption is 5 ~ 50% of ative starch quality.
Described initiator is hydrogen peroxide-ferrous sulfate system, and consumption is 0.1 ~ 10% of ative starch quality.
Described compound ethylene base monomer is the mixture of in vinyl acetate between to for plastic, acetate propylene, methacrylic alcohol acetic ester any two kinds, and consumption is 10 ~ 100% of ative starch quality.
Outstanding substantive distinguishing features of the present invention and significant progress:
(1) the present invention selects appropriate etherifying agent, oxygenant, catalyzer, under same microwave condition, carry out etherification reaction and oxidizing reaction simultaneously, connect in starch molecular structure etherificate substituent while starch oxidized generation carboxyl.
(2) etherificate, oxidation, grafting three kinds of denaturation methods organically combine by the present invention, multiple reactive group is connected in starch molecular structure, maximize favourable factors and minimize unfavourable ones, have complementary advantages, filled a prescription by adjusting process, can obtain the multicomponent modified starch that series reaction group proportioning is different, percentage of grafting is different, product has the multiple good characteristic of carboxymethyl etherification and/or hydroxyalkyl etherificate, oxidation, graft starch.
(3) to have gelatinization point low for product of the present invention, reaction control is stable, transparency is high, adhesive power is strong, good penetrability, retrogradation is weak, freeze-thaw stability is high, to the good stability of acid, alkali, salt, heat and oxygenant effect, stick with paste liquid good film-forming property, film is soft, smooth, the features such as thermoplastic property is excellent, stick with paste the performance in the multi-field application such as thickening material, daily-use chemical industry, polymeric flocculant, high-absorbent material, oilfield chemistry material, degradable mulch and plastics with excellence at paper industry auxiliary agent, foodstuffs industry additive, textile sizing agent, textile printing.
(4) starch adopts unlimited system method to carry out graft copolymerization in microwave reactor, eliminate the water quench of conventional graft copolymerization, heating in water bath, pass into the operations such as nitrogen, utilize id reaction heat to cause and maintain starch-grafted reaction to a certain extent, the required microwave power of reaction is low, and energy consumption is low.
(5) present method realizes the combination of multiple denaturation method, and the reaction times is short, and the transformation efficiency of reagent is high, basic three-waste free discharge, the harm that the waste that significantly can reduce chemical reaction generation causes environment, and environmental protection contribution is outstanding.
Embodiment
Below by embodiment, technical scheme of the present invention is further described in detail, but not as limitation of the present invention.
Embodiment 1
Tapioca (flour) 100g, sodium carbonate 1.1g, sodium hydroxide 1g, copper sulfate 0.02g, hydrogen peroxide 1.5g, chloroethanol 5g are fully mixed, gained mixture is placed in microwave reactor and carries out microwave reaction, microwave power is 320W, and the microwave time is 3 minutes, obtains hydroxyethyl etherificate Sumstar 190; Add S-WAT 0.13g reduction residual oxidizing agent, add sodium carbonate 25g, hydrogen peroxide-ferrous sulfate initiator system 11g, vinyl acetic monomer 25g, acetate propylene 10g, and fully mix, gained mixture being placed in microwave reactor adopts unlimited system method to carry out graft copolymerization, microwave power is 240W, the microwave time is 6 minutes, and products therefrom, through aftertreatment, obtains product of the present invention.
Embodiment 2
Tapioca (flour) 100g, sodium hydroxide 18g, copper sulfate 0.05g, hydrogen peroxide 4.5g, Mono Chloro Acetic Acid 45g are fully mixed, gained mixture is placed in microwave reactor and carries out microwave reaction, microwave power is 320W, and the microwave time is 6 minutes, obtains carboxymethyl etherification Sumstar 190; Add S-WAT 0.2g reduction residual oxidizing agent, add sodium carbonate 20g, potassium hydroxide 10g, hydrogen peroxide-ferrous sulfate initiator system 17g, vinyl acetate between to for plastic 45g, methacrylic alcohol acetic ester 12g, and fully mix, gained mixture being placed in microwave reactor adopts unlimited system method to carry out graft copolymerization, microwave power is 240W, the microwave time is 12 minutes, and products therefrom, through aftertreatment, obtains product of the present invention.
Embodiment 3
Tapioca (flour) 100g, potassium hydroxide 2.8g, copper sulfate 0.05g, Sodium Persulfate 1g, chloroethanol 9g are fully mixed, gained mixture is placed in microwave reactor and carries out microwave reaction, microwave power is 320W, and the microwave time is 4 minutes, obtains hydroxyethyl etherificate Sumstar 190; Add sodium bisulfite 0.35g reduction residual oxidizing agent, add sodium carbonate 22g, hydrogen peroxide-ferrous sulfate initiator system 12g, acetate propylene 45g, methacrylic alcohol acetic ester 21g, and fully mix, gained mixture being placed in microwave reactor adopts unlimited system method to carry out graft copolymerization, microwave power is 240W, the microwave time is 6 minutes, and products therefrom, through aftertreatment, obtains product of the present invention.
Embodiment 4
Yam starch 100g, sodium hydroxide 15g, copper sulfate 0.02g, Sodium Persulfate 1.5g, sodium chloroacetate 35g are fully mixed, gained mixture is placed in microwave reactor and carries out microwave reaction, microwave power is 320W, and the microwave time is 3 minutes, obtains carboxymethyl etherification Sumstar 190; Add S-WAT 0.2g reduction residual oxidizing agent, add sodium carbonate 20g, potassium hydroxide 5g, hydrogen peroxide-ferrous sulfate initiator system 16g, vinyl acetate between to for plastic 35g, acetate propylene 12g, and fully mix, gained mixture being placed in microwave reactor adopts unlimited system method to carry out graft copolymerization, microwave power is 240W, the microwave time is 8 minutes, and products therefrom, through aftertreatment, obtains product of the present invention.
Embodiment 5
Yam starch 100g, sodium hydroxide 8g, copper sulfate 0.02g, hydrogen peroxide 2.5g, chloroethanol 15g are fully mixed, gained mixture is placed in microwave reactor and carries out microwave reaction, microwave power is 320W, and the microwave time is 3 minutes, obtains hydroxyethyl etherificate Sumstar 190; Add S-WAT 0.2g reduction residual oxidizing agent, add sodium carbonate 20g, potassium hydroxide 10g, hydrogen peroxide-ferrous sulfate initiator system 13g, vinyl acetate between to for plastic 35g, methacrylic alcohol acetic ester 8g, and fully mix, gained mixture being placed in microwave reactor adopts unlimited system method to carry out graft copolymerization, microwave power is 240W, the microwave time is 12 minutes, and products therefrom, through aftertreatment, obtains product of the present invention.
Embodiment 6
Yam starch 100g, sodium hydroxide 15g, sodium carbonate 10g, copper sulfate 0.03g, hydrogen peroxide 3g, Mono Chloro Acetic Acid 25g, sodium chloroacetate 20g are fully mixed, gained mixture is placed in microwave reactor and carries out microwave reaction, microwave power is 320W, the microwave time is 3 minutes, obtains carboxymethyl etherification Sumstar 190; Add sodium bisulfite 0.3g reduction residual oxidizing agent, add sodium carbonate 15g, potassium hydroxide 10g, hydrogen peroxide-ferrous sulfate initiator system 11g, vinyl acetate between to for plastic 20g, acetate propylene 30g, and fully mix, gained mixture being placed in microwave reactor adopts unlimited system method to carry out graft copolymerization, microwave power is 240W, the microwave time is 18 minutes, and products therefrom, through aftertreatment, obtains product of the present invention.
Claims (1)
1. a preparation method for etherificate-oxidation-graft polyol modified starch, is characterized in that, its processing step is:
1) be added in ative starch by etherifying agent, oxygenant, composite catalyst under whipped state, gained mixture be placed in microwave reactor and carry out etherification oxidation reaction simultaneously, microwave power is 320W, and the microwave time is 1 ~ 10 minute, obtains etherification oxidation starch;
2) under whipped state, reductive agent is added step 1) in gains etherification oxidation starch, and fully mix;
3) under whipped state, basic catalyst, initiator and compound ethylene base monomer are added step 2) in gains, gained mixture being placed in microwave reactor adopts unlimited system method to carry out graft copolymerization, microwave power is 240W, and the microwave time is 2 ~ 10 minutes;
And
4) by step 3) products therefrom carries out aftertreatment, obtains product multicomponent modified starch of the present invention, wherein:
Described etherifying agent is one or both the mixture in chloroethanol, Mono Chloro Acetic Acid, sodium chloroacetate, and consumption is 2 ~ 50% of ative starch quality;
Described oxygenant is one or both the mixture in hydrogen peroxide, Sodium Persulfate, and consumption is 0.2 ~ 5.0% of ative starch quality;
Described reductive agent is one or both mixture of S-WAT, sodium bisulfite, and consumption is 0.01 ~ 1.0% of ative starch oven-dry weight;
Described composite catalyst is one or both the mixture in copper sulfate and sodium hydroxide, sodium carbonate, potassium hydroxide, and consumption is 1 ~ 30% of ative starch quality;
Described basic catalyst is one or both the mixture in sodium hydroxide, sodium carbonate, potassium hydroxide, and consumption is 5 ~ 50% of ative starch quality;
Described initiator is hydrogen peroxide-ferrous sulfate system, and consumption is 0.1 ~ 10% of ative starch quality;
Described compound ethylene base monomer is the mixture of in vinyl acetate between to for plastic, acetate propylene, methacrylic alcohol acetic ester any two kinds, and consumption is 10 ~ 100% of ative starch quality.
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| CN107573424A (en) * | 2016-11-21 | 2018-01-12 | 广西大学 | A kind of method that semidry method prepares phosphate ester starch |
| CN108070056A (en) * | 2017-12-14 | 2018-05-25 | 成都新柯力化工科技有限公司 | A kind of laser modified method for preparing the special thermoplastic starch of biodegradable plastic |
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| CN105061676A (en) * | 2015-07-29 | 2015-11-18 | 封开县嘉诚纸业有限公司 | Composite modified starch for emulsification of surface sizing agent, preparation method and application thereof |
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| CN106905488B (en) * | 2017-04-12 | 2018-10-23 | 广西民族大学 | A kind of preparation method of more carboxy starch composite high water absorption resins |
| CN107334141A (en) * | 2017-06-21 | 2017-11-10 | 许昌学院 | A kind of sweet potato oxidized starch and preparation method thereof |
| CN108070056A (en) * | 2017-12-14 | 2018-05-25 | 成都新柯力化工科技有限公司 | A kind of laser modified method for preparing the special thermoplastic starch of biodegradable plastic |
| CN108070056B (en) * | 2017-12-14 | 2019-12-03 | 合肥科拜耳新材料有限公司 | A kind of laser modified method for preparing the dedicated thermoplastic starch of biodegradable plastic |
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Application publication date: 20141224 Assignee: GUANGXI STATE FARMS MINGYANG BIOCHEMICAL Group Inc. Assignor: GUANGXI University FOR NATIONALITIES Contract record no.: X2020450000019 Denomination of invention: A preparation method of etherification oxidation graft multi modified starch Granted publication date: 20171017 License type: Exclusive License Record date: 20200804 |