CN101481441A - Preparation of grafting starch sizing agent by instantaneous polymerization - Google Patents
Preparation of grafting starch sizing agent by instantaneous polymerization Download PDFInfo
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- CN101481441A CN101481441A CNA2009100210920A CN200910021092A CN101481441A CN 101481441 A CN101481441 A CN 101481441A CN A2009100210920 A CNA2009100210920 A CN A2009100210920A CN 200910021092 A CN200910021092 A CN 200910021092A CN 101481441 A CN101481441 A CN 101481441A
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Abstract
The invention discloses a method for preparing grafting starch slurry through instantaneous polymerization, comprising the flowing steps: acrylic acid is added into NaOH solution for obtaining sodium acrylate solution with pH value of 5-6; acrylic ester which accounts for 30-45 percent (in terms of mass) of acrylic acid is added into the sodium acrylate solution for obtaining sodium acrylate-acrylic ester solution; then, starch milk is added in the sodium acrylate-acrylic ester solution for obtaining sodium acrylate-acrylic ester-starch solution; in the solution, the mass of the starch is 100-130 percent of the sodium acrylate-acrylic ester solution; ammonium persulfate aqueous solution and sodium sulfite aqueous solution are sequentially added into the sodium acrylate-acrylic ester solution-starch solution respectively for reaction, thus obtaining loose grafting starch product; and the loose grafting starch product is crashed and sieved for obtaining the grafting starch slurry. The grafting starch slurry prepared according to the method has high grafting rate and convenient usage; and in addition, the preparation process is reliable, the energy consumption is low, the cost is low and the method causes no environment pollution.
Description
Technical field
The invention belongs to field of polymer material preparing technology, relate to a kind of preparation method of grafting starch, be specifically related to the method that a kind of instantaneous polymerization prepares grafting starch.
Background technology
Grafting starch is the novel high polymer material that starch is formed by graft copolymerization, with wetting ability, semirigid starch polymer is skeleton, utilize physico-chemical process to cause and produce free radical, with the vinyl monomer copolyreaction, by introducing different functional groups and regulating ratio hydrophilic, the oleophylic segmented structure, make it have compound of polysaccharide, Intermolecular Forces and reactivity, machinery and the stability of biological action and the developing power of linear approach structure of synthetic macromolecule arranged again.Be widely used in aspects such as weaving, papermaking, oil field chemical, degradative plastic film, polymeric flocculant, water-absorbing material, plastics.Suspension method at present commonly used, the grafting starch for preparing be for liquid, uses inconveniently, and long reaction time, energy consumption is big, percentage of grafting is low, cost is high.
Summary of the invention
The purpose of this invention is to provide the method that a kind of instantaneous polymerization prepares grafting starch, be used for the preparation of grafting starch, the grafting starch that makes is loose shape graft copolymer, the convenient use, and also the reaction times is short, percentage of grafting is high, cut down the consumption of energy and cost.
The technical solution adopted in the present invention is, a kind of instantaneous polymerization prepares the method for grafting starch, adopt redox initiation system, instantaneous initiation sodium acrylate, acrylate and the starch-grafted thing of starch-grafted formation under the normal temperature, through crushing screening, make grafting starch, this method is specifically carried out according to the following steps:
Step 1: get vinylformic acid and NaOH solution respectively, NaOH solution is added in the vinylformic acid, obtain sodium acrylate solution, the pH value of controlling this solution is 5～6;
Step 2: get 30%～45% of vinylformic acid quality and get acrylate for 1 set by step, and under agitation condition, add in the sodium acrylate solution that step 1 makes, obtain sodium acrylate-acrylate solution;
Step 3: press mass ratio 1:1.5～2, get starch and water respectively, starch is added in the entry, stir, obtain starch milk;
Step 4: the starch milk that step 3 is made adds under agitation condition in sodium acrylate-acrylate solution that step 2 makes, obtain sodium acrylate-acrylate-starch mixed solution, the quality of controlling starch in this mixed solution is 100%～130% of sodium acrylate-acrylate solution quality;
Step 5: press mass ratio 1:1, get Ammonium Persulfate 98.5 and water respectively, Ammonium Persulfate 98.5 is dissolved in the water, form the Ammonium Persulfate 98.5 aqueous solution;
Step 6: press mass ratio 1:1, get S-WAT and water respectively, S-WAT is dissolved in the water, form sodium sulfite aqueous solution;
Step 7: press mass ratio 1:0.5～1, get the sodium sulfite aqueous solution that the Ammonium Persulfate 98.5 aqueous solution that step 5 makes and step 6 make respectively, then, the Ammonium Persulfate 98.5 aqueous solution and sodium sulfite aqueous solution are added under agitation condition in sodium acrylate-acrylate-starch mixed solution that step 4 obtains successively, the control Ammonium Persulfate 98.5 aqueous solution and the total mass of sodium sulfite aqueous solution and the mass ratio of sodium acrylate-acrylate-starch mixed solution total mass are 3～4:50, and reaction obtains loose shape graft starch product;
Step 8: the loose shape graft starch product crushing screening with step 7 obtains makes grafting starch.
Feature of the present invention also is,
Starch is selected W-Gum, yam starch, tapioca (flour), wheat starch or above-mentioned wherein a kind of treated starch for use in the step 3 wherein.
The inventive method adopts redox initiation system, and instantaneous at normal temperatures initiation vinylformic acid sodium salt and acrylate and the starch-grafted thing of starch-grafted formation have plurality of advantages such as simple and reliable process, low power consuming, low cost, non-environmental-pollution.
Embodiment
The present invention is described in detail below in conjunction with embodiment.
The inventive method, adopt initiator, make vinylformic acid, sodium acrylate, acrylate and starch generation graft copolymerization, utilize oxidation-reduction trigger system a large amount of heat energy that moment produces in the graft polymerization process, moisture evaporation in the reaction system is fallen, formed loose shape grafting starch copolymer.This method is specifically carried out according to the following steps:
Step 1: get vinylformic acid and NaOH solution respectively, NaOH solution is added in the vinylformic acid, obtain sodium acrylate solution, the pH value of controlling this solution is 5～6;
Step 2: get acrylate, its quality is that step 1 is got 30%～45% of vinylformic acid quality, and in the sodium acrylate solution that adding step 1 makes under stirring state, forms sodium acrylate-acrylate solution;
Step 3: press mass ratio 1:1.5～2, get starch and water respectively, starch is added in the entry, stir, obtain starch milk;
Starch is selected a kind of or a kind of treated starch in W-Gum, yam starch, tapioca (flour) or the wheat starch for use.
Step 4: the starch milk that step 3 is made adds under agitation condition in sodium acrylate-acrylate solution that step 2 makes, obtain sodium acrylate-acrylate-starch mixed solution, the quality of controlling starch in this mixed solution is 100%～130% of sodium acrylate-acrylate solution quality;
Step 5: press mass ratio 1:1, get Ammonium Persulfate 98.5 and water respectively, Ammonium Persulfate 98.5 is dissolved in the water, form the Ammonium Persulfate 98.5 aqueous solution;
Step 6: press mass ratio 1:1, get S-WAT and water respectively, S-WAT is dissolved in the water, form sodium sulfite aqueous solution;
Step 7: press mass ratio 1:0.5～1, get the sodium sulfite aqueous solution that the Ammonium Persulfate 98.5 aqueous solution that step 5 makes and step 6 make respectively, then, the Ammonium Persulfate 98.5 aqueous solution and sodium sulfite aqueous solution are added under agitation condition in sodium acrylate-acrylate-starch mixed solution that step 4 obtains successively, the mass ratio of the total mass of the Ammonium Persulfate 98.5 aqueous solution and sodium sulfite aqueous solution and sodium acrylate-acrylate-starch mixed solution total mass is 3～4:50, and reaction obtains loose shape graft starch product;
Step 8: the loose shape graft starch product crushing screening with step 7 obtains makes grafting starch.
Vinylformic acid, NaOH solution, acrylate, Ammonium Persulfate 98.5 and S-WAT are the commercially available prod.
Ammonium Persulfate 98.5 that adopts in the inventive method and S-WAT form oxidation-reduction trigger system, this initiator system not only causes sodium acrylate and acrylate and starch generation graft copolymerization, and in the graft polymerization process, produce a large amount of heat energy, moisture evaporation in the reaction system is fallen, obtained loose shape graft starch product.
The inventive method, instantaneous polymerization prepares grafting starch, its graft polymerization principle:
With vinylformic acid with sodium hydroxide neutralize to the pH value be 5～6, then, under agitation condition, add acrylate and starch milk, add the Ammonium Persulfate 98.5 solution for preparing again, make the mixed solution of certain flowability.
2. the activation energy of oxidation-reduction trigger system generation free radical is lower, at low temperatures just can initiated polymerization.
3. the sodium sulfite solution for preparing is joined in vinylformic acid sodium salt, acrylate and the starch mixed solution that has prepared, reaction will begin, carrying out along with thermopositive reaction, temperature can raise rapidly, the reaction meeting was acutely carried out fast in moment, vinylformic acid sodium salt and acrylic ester graftedly form graft starch to starch.
Concrete graft polymerization reaction process is as follows:
1) redox initiation system forms free radical:
The oxygenant reduction initiating is:
(NH
4)
2S
2O
8/NaHSO
3
If only adopt the oxygenant initiator system, being decomposed into of this initiator system:
The oxygenant initiator system decomposes the back and produces two free radicals, and the decomposition activation energy of this free radical is 140kJmol
-1, can not initiation reaction when temperature is low, and can not produce a large amount of heat energy moment with the moisture evaporation in the reaction solution.
Adopt oxidation-reduction trigger system, being decomposed into of this initiator system:
The redox initiation system decomposition also produces two free radicals, but the decomposition activation energy of this free radical is 41.90kJmol
-1, what the oxygenant initiator system will be low relatively is many, therefore, and just energy initiation reaction when temperature is low, and react a large amount of heat energy of instantaneous generation, the moisture in the reaction solution is evaporated, obtain the graft starch product of loose shape.
2) chain initiation:
In the formula, St-OH is a starch, and M is vinylformic acid, methacrylic acid, acrylate, methacrylic ester, acrylate or methacrylate.
3) chainpropagation:
4) chain termination:
5) chain transfer:
6) oxidizing reaction:
Embodiment 1
Get vinylformic acid and NaOH solution respectively, NaOH solution is added in the vinylformic acid, obtain sodium acrylate solution, the pH value of controlling this solution is 5～6; Get the acrylate of used vinylformic acid quality 30%, and in the sodium acrylate solution that under stirring state, makes, form sodium acrylate-acrylate solution; Pressed mass ratio 1: 1.5, extracting corn starch and water add W-Gum in the entry respectively, stir, and obtain corn starch milk; The corn starch milk that makes is added in the sodium acrylate-acrylate solution that makes under agitation condition, obtain sodium acrylate-acrylate-starch mixed solution, the quality of controlling starch in this mixed solution is 100% of sodium acrylate-acrylate solution quality; Press mass ratio 1:1, get Ammonium Persulfate 98.5 and water respectively, Ammonium Persulfate 98.5 is dissolved in the water, form the Ammonium Persulfate 98.5 aqueous solution; Press mass ratio 1:1, get S-WAT and water respectively, S-WAT is dissolved in the water, form sodium sulfite aqueous solution; Press mass ratio 1:0.5, get the Ammonium Persulfate 98.5 aqueous solution and the sodium sulfite aqueous solution that make respectively, then, under agitation condition, add in the sodium acrylate-acrylate-starch mixed solution that obtains successively the Ammonium Persulfate 98.5 aqueous solution and sodium sulfite aqueous solution, the mass ratio of the total mass of the Ammonium Persulfate 98.5 aqueous solution and sodium sulfite aqueous solution and sodium acrylate-acrylate-starch mixed solution total mass is 3:50, and reaction obtains loose shape graft starch product; Loose shape graft starch product crushing screening with obtaining makes grafting starch.This grafting starch is 6% in mass concentration, when temperature is 95 ℃, the viscosity of dextrin is 12cp, thermoviscosity stability 〉=90%, the percentage of grafting of product are 20.1%.
Embodiment 2
Get vinylformic acid and NaOH solution respectively, NaOH solution is added in the vinylformic acid, obtain sodium acrylate solution, the pH value of controlling this solution is 5～6; Get the acrylate of used vinylformic acid quality 45%, and under stirring state, add in the sodium acrylate solution that makes, form sodium acrylate-acrylate solution; Press mass ratio 1:2, get yam starch and water respectively, yam starch is added in the entry, stir, obtain the yam starch breast; Under agitation condition, add the yam starch breast that makes in the sodium acrylate-acrylate solution that makes, obtain sodium acrylate-acrylate-starch mixed solution, the quality of controlling yam starch in this mixed solution is 130% of sodium acrylate-acrylate solution quality; Press mass ratio 1:1, get Ammonium Persulfate 98.5 and water respectively, Ammonium Persulfate 98.5 is dissolved in the water, form the Ammonium Persulfate 98.5 aqueous solution; Press mass ratio 1:1, get S-WAT and water respectively, S-WAT is dissolved in the water, form sodium sulfite aqueous solution; Press mass ratio 1:1, get the Ammonium Persulfate 98.5 aqueous solution and the sodium sulfite aqueous solution that make respectively, then, under agitation condition, add in the sodium acrylate-acrylate-starch mixed solution that obtains successively the Ammonium Persulfate 98.5 aqueous solution and sodium sulfite aqueous solution, the mass ratio of the total mass of the Ammonium Persulfate 98.5 aqueous solution and sodium sulfite aqueous solution and sodium acrylate-acrylate-starch mixed solution total mass is 4:50, and reaction obtains loose shape graft starch product; Loose shape graft starch product crushing screening with obtaining makes grafting starch.This grafting starch is 6% in mass concentration, when temperature is 95 ℃, the viscosity degree of dextrin is 15cp, viscosity stability 〉=90%, the percentage of grafting of product are 18.6%.
Embodiment 3
Get vinylformic acid and NaOH solution respectively, NaOH solution is added in the vinylformic acid, obtain sodium acrylate solution, the pH value of controlling this solution is 5～6; Get the acrylate of used vinylformic acid quality 37.5%, and under stirring state, add in the sodium acrylate solution that makes, form sodium acrylate-acrylate solution; Press mass ratio 1:1.75, get wheat starch and water respectively, wheat starch is added in the entry, stir, obtain the wheat starch breast; Under agitation condition, add the wheat starch breast that makes in the sodium acrylate-acrylate solution that makes, obtain sodium acrylate-acrylate-starch mixed solution, the quality of controlling wheat starch in this mixed solution is 115% of sodium acrylate-acrylate solution quality; Press mass ratio 1:1, get Ammonium Persulfate 98.5 and water respectively, Ammonium Persulfate 98.5 is dissolved in the water, form the Ammonium Persulfate 98.5 aqueous solution, press mass ratio 1:1, get S-WAT and water respectively, S-WAT is dissolved in the water, form sodium sulfite aqueous solution; Pressed mass ratio 1: 0.75, get the Ammonium Persulfate 98.5 aqueous solution and the sodium sulfite aqueous solution that make respectively, then, under agitation condition, add in the sodium acrylate-acrylate-starch mixed solution that obtains successively the Ammonium Persulfate 98.5 aqueous solution and sodium sulfite aqueous solution, the mass ratio of the total mass of the Ammonium Persulfate 98.5 aqueous solution and sodium sulfite aqueous solution and sodium acrylate-acrylate-starch mixed solution total mass is 3.5:50, and reaction obtains loose shape graft starch product; Loose shape graft starch product crushing screening with obtaining makes grafting starch.This grafting starch is 6% in mass concentration, when temperature is 95 ℃, the viscosity degree of dextrin is 12cp, viscosity stability 〉=90%, the percentage of grafting of product are 18.4%.
The inventive method adopts redox initiation system, instantaneous at normal temperatures initiation vinylformic acid sodium salt and acrylate and the starch-grafted thing of starch-grafted formation, this starch-grafted thing makes grafting starch through crushing screening, simple and reliable process, and consume energy low, cost is low, non-environmental-pollution.
Claims (2)
1. an instantaneous polymerization prepares the method for grafting starch, adopt redox initiation system, instantaneous initiation sodium acrylate, acrylate and the starch-grafted thing of starch-grafted formation under the normal temperature, through crushing screening, make grafting starch, it is characterized in that this method is specifically carried out according to the following steps:
Step 1: get vinylformic acid and NaOH solution respectively, NaOH solution is added in the vinylformic acid, obtain sodium acrylate solution, the pH value of controlling this solution is 5～6;
Step 2: get 30%～45% of vinylformic acid quality and get acrylate for 1 set by step, and under agitation condition, add in the sodium acrylate solution that step 1 makes, obtain sodium acrylate-acrylate solution;
Step 3: press mass ratio 1:1.5～2, get starch and water respectively, starch is added in the entry, stir, obtain starch milk;
Step 4: the starch milk that step 3 is made adds under agitation condition in sodium acrylate-acrylate solution that step 2 makes, obtain sodium acrylate-acrylate-starch mixed solution, the quality of controlling starch in this mixed solution is 100%～130% of sodium acrylate-acrylate solution quality;
Step 5: press mass ratio 1:1, get Ammonium Persulfate 98.5 and water respectively, Ammonium Persulfate 98.5 is dissolved in the water, form the Ammonium Persulfate 98.5 aqueous solution;
Step 6: press mass ratio 1:1, get S-WAT and water respectively, S-WAT is dissolved in the water, form sodium sulfite aqueous solution;
Step 7: press mass ratio 1:0.5～1, get the sodium sulfite aqueous solution that the Ammonium Persulfate 98.5 aqueous solution that step 5 makes and step 6 make respectively, then, the Ammonium Persulfate 98.5 aqueous solution and sodium sulfite aqueous solution are added under agitation condition in sodium acrylate-acrylate-starch mixed solution that step 4 obtains successively, the control Ammonium Persulfate 98.5 aqueous solution and the total mass of sodium sulfite aqueous solution and the mass ratio of sodium acrylate-acrylate-starch mixed solution total mass are 3～4:50, and reaction obtains loose shape graft starch product;
Step 8: the loose shape graft starch product crushing screening with step 7 obtains makes grafting starch.
2. the method for preparing grafting starch according to claim 1 is characterized in that, starch is selected W-Gum, yam starch, tapioca (flour), wheat starch or above-mentioned wherein a kind of treated starch for use in the described step 3.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101935951A (en) * | 2010-09-16 | 2011-01-05 | 湖北达雅化工技术发展有限公司 | Textile size combination |
| CN102926198A (en) * | 2012-10-26 | 2013-02-13 | 无锡裕通织造有限公司 | Spinning sizing agent |
| CN109295721A (en) * | 2018-08-29 | 2019-02-01 | 中纺院（浙江）技术研究院有限公司 | The slurry and slashing technique of a kind of polyester and high proportion polyester blended yarn |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1094131C (en) | 1998-11-24 | 2002-11-13 | 唐山博亚科技工业开发中心 | High hygrophanous resin and its synthesizing process by controlling terms one by one |
| CN1557849A (en) | 2003-12-30 | 2004-12-29 | 江西东永实业有限公司 | Corn starch and methyl acrylate initiated with cerium salt, and acrylic acid graft copolymer |
| CN100513425C (en) | 2007-07-17 | 2009-07-15 | 江南大学 | Starch pretreatment method for raising graft efficiency for grafting starch slurry |
-
2009
- 2009-02-11 CN CN2009100210920A patent/CN101481441B/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101935951A (en) * | 2010-09-16 | 2011-01-05 | 湖北达雅化工技术发展有限公司 | Textile size combination |
| CN102926198A (en) * | 2012-10-26 | 2013-02-13 | 无锡裕通织造有限公司 | Spinning sizing agent |
| CN109295721A (en) * | 2018-08-29 | 2019-02-01 | 中纺院（浙江）技术研究院有限公司 | The slurry and slashing technique of a kind of polyester and high proportion polyester blended yarn |
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