CN105254812A - Grafted starch slurry preparation method based on enzymatic cascade reaction - Google Patents
Grafted starch slurry preparation method based on enzymatic cascade reaction Download PDFInfo
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Abstract
The invention discloses a grafted starch slurry preparation method based on an enzymatic cascade reaction. The method comprises the steps of firstly, adopting a modification technology for cross-linking lactate oxidase with horse radish peroxidase, and forming joint modification enzyme; preparing a solution with a certain concentration through starch, adding lactic acid and acrylic acid monomer to the solution, raising the temperature to 70-95 DEG C, conducting gelatinization for 0.1-1 hour, adjusting the temperature to 40-80 DEG C, finally adding the joint modification enzyme to the starch solution, and conducting a reaction for 1-10 hours while the temperature is preserved. According to the grafted starch slurry preparation method, preparation of grafted starch through a biological method is achieved through the enzymatic cascade reaction, the graft polymerization reaction is easy to control, a product has synthetic macromolecule characteristics and starch characteristics at the same time, and adhesiveness of the obtained grafted starch to cotton is greater than 70 N and to polyester is greater than 90 N; torsion resistance of a slurry film is greater than 500 times; strength of the slurry film ranges from 20.0 N/mm<2> to 33.5 N/mm<2>; elongation of the slurry film ranges from 3.5% to 5.9%, and viscosity stability of slurry liquid is greater than 90%.
Description
Technical field
The present invention relates to a kind of grafting starch preparation method based on enzymatic cascade reaction, belong to textile technology field.
Background technology
Starch is a kind of abundance, can regenerate, can biological degradation, low cost, the natural polysaccharide material that world wide extensively exists.But it compares synthetic polymer in performance, there are some shortcomings, such as its thermostability, solvability, ion exchangeable etc.Oxidation, hydrolysis, esterification, grafting is taked to carry out chemical modification to starch and obtained and study widely.Carrying out graft modification to starch is the one effectively means changing starch process based prediction model, the performances such as its film-forming flexibility, thermostability, metal ion binding capacity, resistance to biological corrosion can be improved by introducing flexible chain on starch stiff backbone, enhance its industrial applicibility, expand its range of application.
Graft starch mainly adopts free radical initiation grafting copolymerization method to prepare, and free radical causes can be divided into again chemical initiator initiation method and Co
60the physics such as ray, light, microwave radiation cause method.When chemical initiator causes, chemical reagent often remains in reactant, makes troubles to subsequent disposal, but because of its be easy to get, easy to operate and be widely used, study also comparatively extensive.Mainly containing of studying adopts cerium salt (as ceric ammonium nitrate), persulfuric acid salt, manganese salt and the oxidation system such as potassium permanganate and Diisopropyl azodicarboxylate and H
2o
2-FeSO
4graft copolymerization is carried out in the combination causing the monomer such as starch and vinyl cyanide, vinylformic acid, acrylamide, (methyl) methyl acrylate, butyl acrylate, vinylbenzene, vinyl-acetic ester, dimethyl fumarate and different monomers etc. redox system.CN102643390B discloses a kind of oxidization-reduction type initiator system adopting assembly voluntarily, cause rapidly at normal temperatures cationic starch simultaneously with the cationic grafted starch preparation method of wetting ability, lipophilicity and amphiphilic monomer terpoiymer graft copolymerization; CN102329404B complex denaturation graft starch disclosing a kind of spinning sizing agent and preparation method thereof, is grafted on starch polymer under spirit solvent condition by acrylamide, vinylformic acid, vinyl acetate between to for plastic ternary mix monomer.CN101353393B discloses a kind of graft starch radical polymerization preparation method having improvement side shoot and form; CN101481441B discloses the method that a kind of chemical initiator initiation instantaneous polymerization prepares acrylic monomer grafting starch; It is that the chemical initiator of solvent causes and prepares the method for graft starch with ethanol that CN100402567C discloses a kind of; CN102051015A discloses a kind of method of ultrasonic-microwave method synthesizing methyl acrylate grafting starch; CN102212169B discloses one and first carries out 60Co-γ irradiation acquisition irradiated starch, then processes irradiated starch with debranching factor, the method for the synthesis grafting starch then reacted with alpha-olefin; CN101735392B discloses a kind of preparation method being beneficial to microwave radiation and the coefficient vinylformic acid of chemical initiator, butyl methacrylate Grafted Starch.
Warp sizing is the critical process in textile manufacturing, directly affects weaving efficiency and quality product.In order to adapt to the requirements of weaving process of high speed loom and ramuscule high density fabric, sizing agent (slurry) used requires good film-forming property, and pliable and tough, wear-resisting, anti-flexing is tired, stretching property and good springiness by force, and requires there is good adhesion property to by pulp fibres.Ative starch and general modified starch are difficult to meet this requirement, so also have in textile warp starching use destarch poor performance in a large number, and are difficult to biodegradable polyvinyl alcohol pulp.In order to improve the performance of starch size, improving the ratio of replacing for polyvinyl alcohol slurry, studying using grafting modified starch as spinning sizing agent both at home and abroad, and once becoming the focus of research.Acrylic size has good film-forming properties, and serous coat is soft, and environmentally safe, is widely used in warp sizing.But acrylic size has larger moisture absorption viscosity again, can not be used alone as main slurry, can only be the auxiliary slurry in main slurry.Compare ative starch, acrylic acid grafted starch viscosity degradation, serous coat obdurability is good, and the storage modulus of film is high, avoids the shortcomings such as ative starch slurry is crisp, hard, viscosity is large, can meet to wash/starching the requirement of silk/cotton blended yarn, can be used as slashing size.First anticipate again with acrylic acid-grafted to starch in addition, the size film property of graft starch is better.
Although graft starch is paid much attention to, and carried out large quantity research, but because existing various synthetic method exists many defects such as grafting conditions harshness, grafting process be wayward all in various degree, particularly be subject to the restriction (mainly the impact of amylopectin) of starch self composition and structure, product film forming properties improves remarkable, has a strong impact on its effect in film forming material.As in spinning sizing agent, current graft starch cannot replace completely or at high proportion and be difficult to biodegradable polyvinyl alcohol pulp.Therefore, the bottleneck how broken through in graft starch synthetic method and Molecular Structure Design is the urgent problem that the research of this type of material foundation faces.
The invention provides a kind of grafting starch preparation method based on enzymatic cascade reaction, namely adopt co-modified technology by Lactate Oxidase and horseradish peroxidase crosslinked together, form co-modified enzyme, again it is mixed with starch, lactic acid, acrylic monomer, react under certain condition, utilize Lactate Oxidase catalysis lactic acid Hydrogen Peroxide, under horseradish peroxidase effect, acrylic monomer is grafted in starch molecular structure again, the obtained starch graft polyacrylate base polymer that can be used as spinning sizing agent.This Biological preparation graft starch technique that the present invention proposes is a kind of environmentally friendly graft starch preparation method.
Summary of the invention
The invention provides a kind of grafting starch preparation method based on enzymatic cascade reaction, the method comprises the following steps:
(1) co-modified enzyme preparation: Lactate Oxidase and horseradish peroxidase are dissolved in deionized water, add natural biological linking agent genipin, in system, Lactate Oxidase, horseradish peroxidase and genipin mass concentration are respectively 0.01-10%, 0.01-15% and 1-5%, then at 30-55 DEG C, react 1-8h; After reaction terminates, reaction solution is down to room temperature stand-by;
(2) graft starch preparation: starch is made into 10-30% mass concentration solution, and adds 0.1-2% mass concentration lactic acid and 1-20% mass concentration acrylic monomer, after being warming up to 70-95 DEG C of gelatinization 0.1-1 hour, temperature is adjusted to 40-80 DEG C;
(3) co-modified enzyme liquid obtained in step (1) is joined in step (2) mixing starch solution, then 40-80 DEG C of insulation reaction 1-10 hour; Be down to room temperature after reaction terminates, obtain starch graft polyacrylate base polymer.
Starch for the preparation of starch graft polyacrylate base polymer can be cereal starch, potato starch and treated starch thereof or play composition.Cereal starch comprises W-Gum, wheat starch; Potato starch comprises tapioca (flour), sweet potato starch, yam starch, konjak starch, banana lily starch etc.; Modified starch comprises cationic starch, carboxymethyl starch, Sumstar 190, acidified starch, hydroxyalkyl starch, phosphate ester starch, acetate starch.
Acrylic monomer comprises vinylformic acid, methacrylic acid, acrylamide, vinyl cyanide, vinyl acetate, methyl acrylate, ethyl propenoate, butyl acrylate, methyl methacrylate, β-dimethyl-aminoethylmethacrylate, butyl methacrylate.
Described Lactate Oxidase, horseradish peroxidase and genipin concentration preferred 0.01-1%, 0.01-1% and 1-2%.
6-8h is reacted at the preferred 30-40 of preparation technology DEG C of described co-modified enzyme.
Described starch concentration is 10-15% preferably.
Described lactic acid and acrylic monomer add concentration preferably 1-2% and 5-10%.
The inventive method realizes graft starch Biological preparation by enzymatic cascade reaction, graft polymerization reaction easily controls, product has synthesis polymer and starch feature concurrently, can be used for spinning sizing agent, has, serous coat elasticity good to fiber adhesion and degree of stretching is good, serum viscosity stablizes advantage.
Embodiment
Embodiment 1 is based on the grafting starch preparation method of enzymatic cascade reaction
(1) co-modified enzyme preparation: Lactate Oxidase and horseradish peroxidase are dissolved in deionized water, add natural biological linking agent genipin, in system, Lactate Oxidase, horseradish peroxidase and genipin mass concentration are respectively 0.01,15% and 5%, then at 30 DEG C, react 1; After reaction terminates, reaction solution is down to room temperature stand-by;
(2) graft starch preparation: cereal starch is made into mass concentration 10%, and adds 2% mass concentration lactic acid and 1% mass concentration acrylic monomer, be warming up to 70 DEG C of gelatinizations after 0.1 hour, temperature be adjusted to 80 DEG C;
(3) co-modified enzyme liquid obtained in step (1) is joined in step (2) mixing starch solution, then 40 DEG C of insulation reaction 10 hours; Be down to room temperature after reaction terminates, obtain starch graft polyacrylate base polymer.
Acrylic monomer comprises vinylformic acid, methacrylic acid, acrylamide, vinyl cyanide, vinyl acetate, methyl acrylate, ethyl propenoate, butyl acrylate, methyl methacrylate, β-dimethyl-aminoethylmethacrylate, butyl methacrylate or its composition.
The percentage of grafting of obtained graft starch is 50-60%, grafting efficiency 80-90%.To fiber adhesion: cotton > 70N, wash > 90N; The resistance to bent tropism > of serous coat 500 times; Film phonograph strength: 20.0-30.5N/mm
2, serous coat elongation: 3.5-5.5%, serum viscosity stability: > 90%.
Embodiment 2 is based on the grafting starch preparation method of enzymatic cascade reaction
(1) co-modified enzyme preparation: Lactate Oxidase and horseradish peroxidase are dissolved in deionized water, add natural biological linking agent genipin, in system, Lactate Oxidase, horseradish peroxidase and genipin mass concentration are respectively 10%, 0.01% and 1%, then at 55 DEG C, react 8h; After reaction terminates, reaction solution is down to room temperature stand-by;
(2) graft starch preparation: potato starch is made into mass concentration 30%, and adds 0.1% mass concentration lactic acid and 20% mass concentration acrylic monomer, be warming up to 95 DEG C of gelatinizations after 1 hour, temperature be adjusted to 40 DEG C;
(3) co-modified enzyme liquid obtained in step (1) is joined in step (2) mixing starch solution, then 80 DEG C of insulation reaction 1 hour; Be down to room temperature after reaction terminates, obtain starch graft polyacrylate base polymer.
The percentage of grafting of obtained graft starch is 52-64%, grafting efficiency 85-90%.To fiber adhesion: cotton > 80N, wash > 90N; The resistance to bent tropism > of serous coat 500 times; Film phonograph strength: 25.0-30.6N/mm
2, serous coat elongation: 3.9-5.5%, serum viscosity stability: > 92%.
Embodiment 3 is based on the grafting starch preparation method of enzymatic cascade reaction
(1) co-modified enzyme preparation: Lactate Oxidase and horseradish peroxidase are dissolved in deionized water, add natural biological linking agent genipin, in system, Lactate Oxidase, horseradish peroxidase and genipin mass concentration are respectively 0.5%, 10% and 2%, then at 45 DEG C, react 2h; After reaction terminates, reaction solution is down to room temperature stand-by;
(2) graft starch preparation: starch is made into mass concentration 20% strength solution, and adds 0.4% mass concentration lactic acid and 14% mass concentration acrylic monomer, be warming up to 85 DEG C of gelatinizations after 0.5 hour, temperature be adjusted to 60 DEG C;
(3) co-modified enzyme liquid obtained in step (1) is joined in step (2) mixing starch solution, then 60 DEG C of insulation reaction 8 hours; Be down to room temperature after reaction terminates, obtain starch graft polyacrylate base polymer.
The percentage of grafting of obtained graft starch is 58-64%, grafting efficiency 80-90%.To fiber adhesion: cotton > 90N, wash > 90N; The resistance to bent tropism > of serous coat 625 times; Film phonograph strength: 25.0-30.5N/mm
2, serous coat elongation: 4.1-5.5%, serum viscosity stability: > 92%.
Embodiment 4 is based on the grafting starch preparation method of enzymatic cascade reaction
(1) co-modified enzyme preparation: Lactate Oxidase and horseradish peroxidase are dissolved in deionized water, add natural biological linking agent genipin, in system, Lactate Oxidase, horseradish peroxidase and genipin mass concentration are respectively 8.5%, 5% and 3%, then at 50 DEG C, react 2h; After reaction terminates, reaction solution is down to room temperature stand-by;
(2) graft starch preparation: starch is made into 25% mass concentration solution, and adds mass concentration 1.2% lactic acid and mass concentration 14.3% acrylic monomer, be warming up to 75 DEG C of gelatinizations after 0.4 hour, temperature be adjusted to 50 DEG C;
(3) co-modified enzyme liquid obtained in step (1) is joined in step (2) mixing starch solution, then 70 DEG C of insulation reaction 2 hours; Be down to room temperature after reaction terminates, obtain starch graft polyacrylate base polymer.
The percentage of grafting of obtained graft starch is 50-60%, grafting efficiency 85-90%.To fiber adhesion: cotton > 70N, wash > 90N; The resistance to bent tropism > of serous coat 500 times; Film phonograph strength: 30.0-33.5N/mm
2, serous coat elongation: 4.2-5.9%, serum viscosity stability: > 90%.
Although the present invention with preferred embodiment openly as above; but it is also not used to limit the present invention, any person skilled in the art, without departing from the spirit and scope of the present invention; all can do various changes and modification, what therefore protection scope of the present invention should define with claims is as the criterion.
Claims (7)
1., based on a grafting starch preparation method for enzymatic cascade reaction, the method comprises the following steps:
(1) co-modified enzyme preparation: Lactate Oxidase and horseradish peroxidase are dissolved in deionized water, add natural biological linking agent genipin, in system, Lactate Oxidase, horseradish peroxidase and genipin mass concentration are respectively 0.01-10%, 0.01-15% and 1-5%, then at 30-55 DEG C, react 1-8h; After reaction terminates, reaction solution is down to room temperature stand-by;
(2) graft starch preparation: starch is made into mass concentration 10-30%, and adds mass concentration 0.1-2% lactic acid and 1-20% acrylic monomer, after being warming up to 70-95 DEG C of gelatinization 0.1-1 hour, temperature is adjusted to 40-80 DEG C;
(3) co-modified enzyme liquid obtained in step (1) is joined in step (2) mixing starch solution, then 40-80 DEG C of insulation reaction 1-10 hour; Be down to room temperature after reaction terminates, obtain starch graft polyacrylate base polymer.
2. preparation method according to claim 1, is characterized in that starch can be cereal starch, potato starch and treated starch thereof or its composition; Cereal starch comprises W-Gum, wheat starch; Potato starch comprises tapioca (flour), sweet potato starch, yam starch, konjak starch, banana lily starch etc.; Modified starch comprises cationic starch, carboxymethyl starch, Sumstar 190, acidified starch, hydroxyalkyl starch, phosphate ester starch, acetate starch.
3. preparation method according to claim 1, is characterized in that described acrylic monomer comprises vinylformic acid, methacrylic acid, acrylamide, vinyl cyanide, vinyl acetate, methyl acrylate, ethyl propenoate, butyl acrylate, methyl methacrylate, β-dimethyl-aminoethylmethacrylate, butyl methacrylate or its composition.
4. preparation method according to claim 1, is characterized in that described Lactate Oxidase, horseradish peroxidase and genipin concentration preferred 0.01-1%, 0.01-1% and 1-2%.
5. the preparation method described in claim 1 or 4, reacts 6-8h at it is characterized in that the preferred 30-40 of preparation technology DEG C of described co-modified enzyme.
6. the preparation method described in claim 1 or 4, is characterized in that the preferred 10-15% of described starch concentration.
7. preparation method according to claim 1, is characterized in that described lactic acid and acrylic monomer add preferred 1-2% and 5-10% of concentration.
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| CN110548491A (en) * | 2019-07-31 | 2019-12-10 | 浙江大学 | Efficient adsorption material for adsorbing toxic substances in cigarette smoke |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5512149A (en) * | 1978-07-11 | 1980-01-28 | Nichiden Kagaku Kk | Preparation of starch-polyvinyl alcohol graft copolymer |
| CN101274975A (en) * | 2008-05-08 | 2008-10-01 | 江南大学 | Method for improving grafting efficiency of grafting starch syrup |
| CN103045702A (en) * | 2012-12-11 | 2013-04-17 | 淄博兰雁集团有限责任公司 | Method for producing modified starch size through bio-enzyme |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5512149A (en) * | 1978-07-11 | 1980-01-28 | Nichiden Kagaku Kk | Preparation of starch-polyvinyl alcohol graft copolymer |
| CN101274975A (en) * | 2008-05-08 | 2008-10-01 | 江南大学 | Method for improving grafting efficiency of grafting starch syrup |
| CN103045702A (en) * | 2012-12-11 | 2013-04-17 | 淄博兰雁集团有限责任公司 | Method for producing modified starch size through bio-enzyme |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110548491A (en) * | 2019-07-31 | 2019-12-10 | 浙江大学 | Efficient adsorption material for adsorbing toxic substances in cigarette smoke |
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