CN100564396C - The preparation method of oxidation cross-linked esterification triple modified starch - Google Patents
The preparation method of oxidation cross-linked esterification triple modified starch Download PDFInfo
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- CN100564396C CN100564396C CN 200710022111 CN200710022111A CN100564396C CN 100564396 C CN100564396 C CN 100564396C CN 200710022111 CN200710022111 CN 200710022111 CN 200710022111 A CN200710022111 A CN 200710022111A CN 100564396 C CN100564396 C CN 100564396C
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Abstract
The invention discloses a kind of preparation method of oxidation cross-linked esterification triple modified starch, it is characterized in that having following steps: be 1: 1～1: 2 mixing and stirring by weight with starch and water 1., add catalyzer, transferring to pH with basic solution is 6～9; 2. dropping oxidizing agent is carried out oxidizing reaction 1～2h and is reacted fully and carry out under 35 ℃～45 ℃ temperature, add terminator and destroy remaining oxygen; 3. the product after oxidizing reaction drips the esterification and crosslinking agent, carries out esterification and crosslinking reaction 1～2h under 35 ℃～45 ℃ temperature, and described esterification and crosslinking agent is the mixed solvent of acetic anhydride and di-carboxylic acid, and its weight ratio is 1: 1～1: 60; 4. the reacted product of esterification and crosslinking promptly gets oxidation cross-linked esterification triple modified starch through centrifuge dehydration after the oven dry.Oxidation cross-linked esterification triple modified starch of the present invention can be acidproof, alkaline-resisting, and shearing force, freeze-thaw stability are good, remedied the deficiency of existing treated starch performance.
Description
Technical field
The invention belongs to the treated starch technical field, be specifically related to a kind of preparation method of oxidation cross-linked esterification triple modified starch.
Background technology
Starch is a kind of natural polymers, and the starch size wide material sources are cheap, and hydrophilic natural fiber is had good adhesive performance.Owing to structural reason, the farinaceous size viscosity fluctuation is big, and serous coat is crisp hard, and it is very satisfied that its performance can not be made us, and therefore need carry out modification to obtain the various treated starches that satisfy market demands to starch.
Industrial production adopts the water law production technique of clorox as oxygenant basically at present, and this aerobicization of technology dosage is bigger, and it is 200kg that 1 ton of product of every production needs oxygenant, and the waste water that produces is many, big to environmental influence.
Chinese patent CN1257188C discloses starch size of a kind of quaternary complex denaturation and its production and application, its starch size is to add entry to be made into emulsion in starch, dropping oxidizing agent and esterifying agent carry out oxidative esterification reaction, add grafted monomer, initiator and linking agent again and carry out the graft crosslinking reaction, make through washing, dehydration, drying at last.Its oxygenant that adopts is a clorox, and its linking agent that adopts is a Trisodium trimetaphosphate, though adopt these linking agent product performance stable, speed of response is slower, and the production cycle is longer, and production efficiency is low, the energy consumption height, and linking agent is residual many.
Chinese patent CN1268647C discloses a kind of etherificate-crosslinked-pre-gelatinization ternary compound modified starch and its production and use, and its linking agent that adopts is the mixed solvent of hexanodioic acid and acetic anhydride, and ratio is 1: 45～1: 15.But acetic anhydride is excessive in this linking agent, and excessive acetic anhydride is bigger to whole system influence, has reduced reaction efficiency, and the price of acetic anhydride is also expensive in addition, has increased cost.
Summary of the invention
The object of the present invention is to provide a kind of cost lower, the preparation method of the oxidation cross-linked esterification triple modified starch that reaction efficiency is higher.
The technical scheme that realizes the object of the invention is: a kind of preparation method of oxidation cross-linked esterification triple modified starch, it is characterized in that having following steps: be 1: 1～1: 2 mixing and stirring by weight 1. with starch and water, add catalyzer, transferring to pH with basic solution is 6～9; 2. dropping oxidizing agent is carried out oxidizing reaction 1～2h and is reacted fully and carry out under 35 ℃～45 ℃ temperature, add terminator and destroy remaining oxygen; 3. the product after oxidizing reaction drips the esterification and crosslinking agent, carries out esterification and crosslinking reaction 1～2h under 35 ℃～45 ℃ temperature, and described esterification and crosslinking agent is the mixed solvent of acetic anhydride and di-carboxylic acid, and its weight ratio is 1: 1～1: 60; 4. the reacted product of esterification and crosslinking promptly gets oxidation cross-linked esterification triple modified starch through centrifuge dehydration after the oven dry.
The catalyzer of above-mentioned steps described in 1. is copper-bath, and its concentration is 2wt%～5wt%, and the consumption of copper-bath is 0.1%～2% of a starch weight.Described basic solution is sodium hydroxide solution, sodium carbonate solution or potassium hydroxide solution, and its concentration is 4wt%～6wt%.
The oxygenant of above-mentioned steps described in 2. is hydrogen peroxide solution, and its concentration is 25wt%～30wt%, and the consumption of hydrogen peroxide solution is 0.5%～5% of a starch weight.Described terminator is a hypo solution, and its concentration is 4wt%～6wt%, and the consumption of hypo solution is 3%～6% of a starch weight.
The 3. middle esterification and crosslinking reaction pH value of above-mentioned steps is 8～11.The consumption of described esterification and crosslinking agent is 0.01%～2% of a starch weight, and is preferred 0.01～1%, more preferably 0.01～0.1%.Di-carboxylic acid in the described esterification and crosslinking agent is a kind of in propanedioic acid, Succinic Acid, pentanedioic acid, hexanodioic acid, pimelic acid, the suberic acid, a kind of in preferred Succinic Acid, pentanedioic acid, the hexanodioic acid, more preferably Succinic Acid.The weight ratio of acetic anhydride and di-carboxylic acid is 1: 1～1: 30, preferred 1: 1～1: 15, and more preferably 1: 2～1: 5.
The positively effect that the present invention has: (1) the present invention becomes the ative starch modification by two chemical reactions the treated starch of oxidation cross-linked esterification triple performance, particularly adding a kind of special esterification and crosslinking agent makes crosslinked and esterification finish by a reaction, products obtained therefrom can be acidproof, alkaline-resisting, and shearing force, freeze-thaw stability are good, have remedied the deficiency of existing treated starch performance.(2) the esterification and crosslinking agent of the present invention's employing is mixed by acetic anhydride and di-carboxylic acid, and di-carboxylic acid is excessive, and dosage of crosslinking agent only is 0.02%, not only reduced cost, and improved reaction efficiency, transformation efficiency reaches more than 90%, speed of response is fast, only needs 1～2 hour.(3) the present invention can select different di-carboxylic acid to regulate and control the crosslinked carbon chain lengths and the degree of crosslinking of product as required, makes product performance meet the requirement of different user.(4) oxygenant of the present invention's employing is a hydrogen peroxide, and 1 ton of product of every production only needs oxygenant 10kg, greatly reduces cost; And be decomposed into water after the hydrogen peroxide reaction, and can not influence environment, be a comparatively ideal green production technique.(5) the present invention adopts Sulfothiorine to come the remaining oxygen of disruptive oxidation reaction as terminator, avoids these residual oxygen to influence the esterification and crosslinking reaction.
Embodiment
(embodiment 1)
The starch of 700kg and the water of 1000kg are stirred, and adding 5kg concentration is the copper-bath of 3wt%, is that to transfer to pH be 7 for the NaOH solution of 5wt% with concentration; Slowly Dropwise 5 .5kg concentration is the hydrogen peroxide solution of 27.5wt%, under 40 ℃, reacts 1.5 hours, reacts fully and carries out, and the hypo solution that adds 30kg concentration then and be 5wt% destroys remaining oxygen; Be under 10 the condition in the pH value, add the esterification and crosslinking agent of 0.15kg, the esterification and crosslinking agent of present embodiment is that acetic anhydride and hexanodioic acid are to mix at 1: 2 by weight, under 40 ℃ of temperature, reacts 1 hour, and transformation efficiency can reach 90%; After reaction finished, reaction product promptly got oxidation cross-linked esterification triple modified starch of the present invention through centrifuge dehydration, oven dry.The viscosity of the oxidation cross-linked esterification triple modified starch that present embodiment is produced (6%, 95 ℃) is 10～11mPas.
(embodiment 2～embodiment 4)
The preparation method is with embodiment 1, and each amounts of components and other data see Table 1.
(embodiment 5～embodiment 8)
The preparation method is with embodiment 1, and each amounts of components and other data see Table 2.
Table 1
Table 2
Claims (9)
1, a kind of preparation method of oxidation cross-linked esterification triple modified starch is characterized in that having following steps:
1. be 1: 1～1: 2 mixing and stirring by weight with starch and water, add catalyzer, transferring to pH with basic solution is 6～9;
2. dropping oxidizing agent is carried out oxidizing reaction 1～2h and is reacted fully and carry out under 35 ℃～45 ℃ temperature, add terminator and destroy remaining oxygen;
3. the product after oxidizing reaction drips the esterification and crosslinking agent, under 35 ℃～45 ℃ temperature, carry out esterification and crosslinking reaction 1～2h, the consumption of described esterification and crosslinking agent is 0.01%～2% of a starch weight, described esterification and crosslinking agent is the mixed solvent of acetic anhydride and di-carboxylic acid, and its weight ratio is 1: 1～1: 60;
4. the reacted product of esterification and crosslinking promptly gets oxidation cross-linked esterification triple modified starch through centrifuge dehydration after the oven dry.
2, the preparation method of oxidation cross-linked esterification triple modified starch according to claim 1, it is characterized in that: the catalyzer of step described in 1. is copper-bath, its concentration is 2wt%～5wt%, and the consumption of copper-bath is 0.1%～2% of a starch weight.
3, the preparation method of oxidation cross-linked esterification triple modified starch according to claim 1 is characterized in that: the basic solution of step described in 1. is sodium hydroxide solution, sodium carbonate solution or potassium hydroxide solution, and its concentration is 4wt%～6wt%.
4, the preparation method of oxidation cross-linked esterification triple modified starch according to claim 1, it is characterized in that: the oxygenant of step described in 2. is hydrogen peroxide solution, its concentration is 25wt%～30wt%, and the consumption of hydrogen peroxide solution is 0.5%～5% of a starch weight.
5, the preparation method of oxidation cross-linked esterification triple modified starch according to claim 1, it is characterized in that: the terminator of step described in 2. is hypo solution, its concentration is 4wt%～6wt%, and the consumption of hypo solution is 3%～6% of a starch weight.
6, the preparation method of oxidation cross-linked esterification triple modified starch according to claim 1 is characterized in that: the 3. middle esterification and crosslinking reaction pH value of step is 8～11.
7, the preparation method of oxidation cross-linked esterification triple modified starch according to claim 1, it is characterized in that: step 3. described in di-carboxylic acid in the esterification and crosslinking agent be a kind of in propanedioic acid, Succinic Acid, pentanedioic acid, hexanodioic acid, pimelic acid, the suberic acid, the weight ratio of acetic anhydride and di-carboxylic acid is 1: 1～1: 30.
8, the preparation method of oxidation cross-linked esterification triple modified starch according to claim 7, it is characterized in that: the consumption of described esterification and crosslinking agent is 0.01～1% of a starch weight, described di-carboxylic acid is a kind of in Succinic Acid, pentanedioic acid, the hexanodioic acid, and the weight ratio of acetic anhydride and di-carboxylic acid is 1: 1～1: 15.
9, the preparation method of oxidation cross-linked esterification triple modified starch according to claim 8, it is characterized in that: the consumption of described esterification and crosslinking agent is 0.01～0.1% of a starch weight, described di-carboxylic acid is a Succinic Acid, and the weight ratio of acetic anhydride and Succinic Acid is 1: 2～1: 5.
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Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102086233B (en) * | 2010-12-24 | 2012-10-03 | 陈明兴 | Manioc modified starch and production method thereof |
| CN102212142B (en) * | 2011-04-29 | 2012-06-27 | 成都海旺科技有限责任公司 | Dry-method preparation process for triple-modified starch |
| CN103642425A (en) * | 2013-09-29 | 2014-03-19 | 桐城市福润包装材料有限公司 | Production technology for starch adhesive |
| CN104031295B (en) * | 2014-05-09 | 2016-08-24 | 广西农垦明阳生化集团股份有限公司 | A kind of preparation method of tri compound modified tapioca starch |
| CN104262492A (en) * | 2014-09-22 | 2015-01-07 | 华南理工大学 | Preparation method of starch glutarate or modified starch glutarate |
| CN105399842A (en) * | 2015-12-07 | 2016-03-16 | 张自良 | Modified konjac starch and preparation process thereof |
| CN105367673B (en) * | 2015-12-19 | 2018-07-06 | 河南恒瑞淀粉科技股份有限公司 | A kind of oxidation cross-linked modified starch and preparation method thereof |
| CN105507032B (en) * | 2016-01-13 | 2017-12-19 | 北京中纺化工股份有限公司 | It is a kind of to be used to imitate printing gum of wax printing flower and preparation method thereof |
| CN107675551B (en) * | 2017-09-26 | 2020-12-04 | 江西虔研科技咨询有限公司 | Low-cost graphene filler special for high-grade coated paper and preparation method thereof |
| CN108003247A (en) * | 2017-12-19 | 2018-05-08 | 东莞东美食品有限公司 | A kind of preparation method of Wall paper adhesive converted starch |
| CN109369813A (en) * | 2018-10-23 | 2019-02-22 | 东莞东美食品有限公司 | A kind of dedicated cross-linked esterification oxidation ternary compound modified starch production method of Wall paper adhesive |
| CN110819402A (en) * | 2019-11-19 | 2020-02-21 | 安徽鑫固环保股份有限公司 | Starch modified comb-type coal water slurry dispersing agent and preparation method thereof |
| CN111533816B (en) * | 2020-06-05 | 2022-03-11 | 宁夏大学 | Starch-based fat substitute and method for preparing same |
| CN112106976B (en) * | 2020-08-27 | 2022-10-14 | 杭州纸友科技有限公司 | Preparation method of minced fillet product additive rich in modified nano-cellulose |
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Non-Patent Citations (2)
| Title |
|---|
| 变性淀粉生产与应用手册. 张友松，61-62，中国轻工业出版社. 2001 |
| 变性淀粉生产与应用手册. 张友松，61-62，中国轻工业出版社. 2001 * |
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Owner name: NANTONG JINNIU MACHINERY MANUFACTURE CO., LTD. Free format text: FORMER OWNER: JIANGSU TECHNOLOGY NORMAL COLLEGE Effective date: 20130807 Owner name: JIANGSU UNIVERSITY OF TECHNOLOGY Effective date: 20130807 |
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Effective date of registration: 20130807 Address after: 226600, Jiangsu province Nantong city Haian county old dam Town Industrial Park Patentee after: NANTONG JINNIU MACHINERY MANUFACTURE CO., LTD. Patentee after: Jiangsu University of Technology Address before: Changzhou City, Jiangsu province Yuying road 213001 No. 2 Patentee before: Jiangsu Teachers University of Technology |
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