CN103665173A - Method for preparing high-substitution-degree cation starch emulsifier - Google Patents
Method for preparing high-substitution-degree cation starch emulsifier Download PDFInfo
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- CN103665173A CN103665173A CN201310751990.8A CN201310751990A CN103665173A CN 103665173 A CN103665173 A CN 103665173A CN 201310751990 A CN201310751990 A CN 201310751990A CN 103665173 A CN103665173 A CN 103665173A
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Abstract
The invention discloses a method for preparing a high-substitution-degree cation starch emulsifier. The method comprises the following steps: mixing starch, an emulsifier, amylase and water to obtain starch milk, heating to 45-60 DEG C, preserving heat for 0.5-2 hours, adding a solution slowing agent while stirring, and adding a catalyst; adding a cation etherifying agent aqueous solution, reacting for 4-7 hours, and adjusting the pH of a system to 2.0-4.0 with a neutralizing agent to obtain the high-substitution-degree anion starch emulsifier. The method for preparing the high-substitution-degree cation starch emulsifier has the advantages of simple process, mild reaction conditions and low cost; the prepared high-substitution-degree cation starch emulsifier is high in substitution degree and dispersity, is used for emulsifying an alkyl ketene dimer (AKD), and has the advantages of stronger fiber bonding force, higher water resistance and higher storage stability when compared with an ordinary AKD emulsion.
Description
Technical field
The present invention relates to a kind of method of preparing cationic starch with high substitution degree emulsifying agent, be applied to emulsification alkyl ketene dimer (AKD).
Background technology
1948, first Sauer synthesized AKD.Downoy develops in nineteen fifty-two the AKD emulsion that paper-making sizing is used.Tyrreily, wemer etc. are used for AKD with CaCO first
3glue used in paper-making for filler.U.S. Herecules company in 1956 founds the factory to go into operation and produces AKD, and nineteen fifty-seven starts to supply AKD latex (commodity are called " Aquapel "), and in nineteen fifty-seven and nineteen sixty first for the production of good quality paper and canned milk paperboard in.Yet due to the chemical such as retention aid and cationic starch at that time, not yet invent, stability of emulsion is poor, sizing material retention is low, so do not obtain widespread use.Hercules company in 1972 releases cation AKD neutral gum in Europe, its retention at paper pulp increases, but still has the problems such as the slow and rubber material using quantity of applying glue speed is more.
Because AKD is the light yellow waxy solid of a kind of low melting point (generally between 43～55 ℃), water insoluble, for AKD is easily added in paper stock, and be uniformly distributed, must be changed into the molecule that can be scattered in water, be by AKD emulsification.The tensio-active agent that is used as at present AKD emulsifying agent mainly contains the fatty alcohol-polyoxyethylene ether of non-ionic type, alkylphenol polyoxyethylene etc.; The sodium alkyl sulfate of anionic, alkyl sodium sulfonate and quaternary ammonium cation type; Also have higher fatty acid, high fatty alcohol and their ester.Have data to point out, HLB value (hydrophile-lipophile balance value of tensio-active agent) is that 14 emulsifier effect is better.For avoiding reactive hydrogen to react with AKD quaternary lactonic ring, emulsifying agent used can not contain reactive hydrogen, can not contain active hydroxyl.
Cationic starch can prevent the interior cyclic ester hydrolysis of alkyl ketene dimer, and low price.Therefore the early stage multiplex cationic starch of AKD emulsion is made emulsifying agent, plays the effect of protective colloid.And the existence because cationic starch is stuck with paste liquid, makes AKD particulate band cationic charge, and forms diffusion double layer, makes AKD emulsion have certain Zeta potential, makes to have electrostatic repulsion between AKD particulate.The mutual trial of strength of the attractive interaction between particulate and electrostatic repulsion has just determined the stability of emulsion.Cationic starch can be as the desirable retention aid of AKD applying glue.But industrial AKD carrys out emulsification with cationic starch and tensio-active agent, poor stability, at room temperature stablizes and stores about one month only.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of method of preparing cationic starch with high substitution degree emulsifying agent, the above-mentioned defect existing to overcome prior art.
For solving the problems of the technologies described above, the present invention adopts following technical scheme to realize:
The present invention prepares the method for cationic starch with high substitution degree emulsifying agent, comprises the steps: starch, emulsifying agent, amylase and water to mix, and obtains starch milk, intensification 45-60 ℃, and insulation 0.5-2h, adds retarding solvent under stirring, adds catalyzer; Then add the cationic etherifying agent aqueous solution, reaction 4-7h, with neutralizing agent regulation system PH to 2.0-4.0, obtains cationic starch with high substitution degree emulsifying agent.
The parts by weight of each component are:
Described starch is a kind of in W-Gum, wheat starch, tapioca (flour) and yam starch;
Described emulsifying agent is nonionic emulsifying agent, and nonionic emulsifying agent is selected from Witconol AL 69-66, anhydrous sorbitol tristearate (this dish 65), glycol fatty acid ester, propylene glycol fatty acid ester, anhydrous sorbitol list hard fatty acid ester (this dish 60), sorbitan monooleate (span 80), Diethylene Glycol fatty acid ester, anhydrous sorbitol monopalmitate (this dish 40), polyoxytrimethylene hard fatty acid ester, sorbitan mono-laurate (this dish 20), polyoxyethylene hard fatty acid ester, lauric acid polyoxyethylene ester, polyoxyethylene (4) anhydrous sorbitol list hard fatty acid ester (Tween61), polyoxyethylene (5) sorbitan monooleate (sorbimacrogol oleate100), polyoxyethylene (20) anhydrous sorbitol tristearate (polysorbate65), polyoxyethylene (20) Witconol AL 69-66 (polysorbate85), polyoxyethylene monoleate, fatty alcohol amine polyoxyethylene ether, alkylphenol polyoxyethylene, polyoxyethylene mono-laurate, polyoxyethylene castor oil, polyoxyethylene (4) sorbitan mono-laurate (tween 21), polyoxyethylene (20) anhydrous sorbitol list hard fatty acid ester (polysorbate60), polyoxyethylene (20) sorbitan monooleate (tween 80), polyoxyethylene (20) anhydrous sorbitol monopalmitate (polysorbate40), at least one in polyoxyethylene (20) sorbitan mono-laurate (polysorbas20), preferably sorbitan monooleate (span 80), polyoxyethylene (20) sorbitan monooleate (tween 80), sorbitan mono-laurate (this dish 20).
Described amylase is a kind of in α-amylase, beta-amylase, gamma amylase, isoamylase.
Described retarding solvent is a kind of in sodium sulfate, sodium-chlor or potassium sulfate, and add-on is the 5-10% of starch weight.
Described catalyzer is a kind of in sodium hydroxide, potassium hydroxide, ammoniacal liquor.
Described etherifying agent is a kind of in the chloro-2-hydroxypropyl-trimethyl ammonium chloride of 3-or 2,3-epoxypropyl ammonium chloride.
Described neutralizing agent is one or more in hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, formic acid or Glacial acetic acid.
The invention has the advantages that:
1, prepare the method technique of cationic starch with high substitution degree emulsifying agent simple, reaction conditions is gentle, and cost is low;
2, the cationic starch with high substitution degree emulsifying agent substitution value high (0.2-0.4) of preparation, good dispersity;
3, for emulsification alkyl ketene dimer (AKD), to compare with common AKD emulsion,, water resisting property strong with fibrous binding force and stability in storage are all better.
Embodiment
Provide preferred embodiment of the present invention below, to describe technical scheme of the present invention in detail.
Embodiment 1
In the four-hole boiling flask of prolong, stirring, thermometer is housed, add 185g deionized water, 4g sorbitan monooleate (span 80), 1g α-amylase and 100g W-Gum, heat up 60 ℃, insulation 1h, under stirring, add retarding solvent anhydrous sodium sulphate 5g, to add weight concentration be 32% sodium hydroxide to the PH of solution be 11.0, in another beaker, add the chloro-2-hydroxypropyl-trimethyl ammonium chloride of 10g water dissolution 7g3-, then join in starch milk, reaction 4h, be cooled to 30 ℃, with hydrochloric acid regulation system PH to 4.0, recording substitution value is 0.311.
Embodiment 2
In the four-hole boiling flask of prolong, stirring, thermometer is housed, add 150g deionized water, 10g polyoxyethylene (20), 1g beta-amylase and 100g W-Gum, heat up 55 ℃, insulation 2h, under stirring, add retarding solvent sodium-chlor 8g, to add weight concentration be 32% sodium hydroxide to the PH of solution be 12.0, in another beaker, add 10g water dissolution 9g2,3-epoxypropyl ammonium chloride, then join in starch milk, reaction 6h, is cooled to 30 ℃, with phosphoric acid regulation system PH to 3.0, recording substitution value is 0.351.
Embodiment 3
Prolong is being housed, stir, in the four-hole boiling flask of thermometer, add 170g deionized water, 8g sorbitan mono-laurate (this dish 20), 1g gamma amylase-amylase and 100g wheat starch, heat up 45 ℃, insulation 2h, under stirring, add retarding solvent anhydrous sodium sulphate 5g, to add weight concentration be 32% sodium hydroxide to the PH of solution be 12.5, in another beaker, add the chloro-2-hydroxypropyl-trimethyl ammonium chloride of 10g water dissolution 10g3-, then join in starch milk, reaction 5h, be cooled to 30 ℃, with acetic acid regulation system PH to 4.0, recording substitution value is 0.372.
Claims (9)
1. a method of preparing cationic starch with high substitution degree emulsifying agent, is characterized in that, comprises the steps: starch, emulsifying agent, amylase and water to mix, and obtains starch milk, intensification 45-60 ℃, and insulation 0.5-2h, adds retarding solvent under stirring, adds catalyzer; Then add the cationic etherifying agent aqueous solution, reaction 4-7h, with neutralizing agent regulation system PH to 2.0-4.0, obtains described cationic starch with high substitution degree emulsifying agent.
2. method according to claim 1, is characterized in that, the parts by weight of each component are as follows:
3. method according to claim 1, is characterized in that, described starch is a kind of in W-Gum, wheat starch, tapioca (flour) and yam starch.
4. method according to claim 1, is characterized in that, described emulsifying agent is nonionic emulsifying agent, and nonionic emulsifying agent is selected from Witconol AL 69-66, anhydrous sorbitol tristearate (this dish 65), glycol fatty acid ester, propylene glycol fatty acid ester, anhydrous sorbitol list hard fatty acid ester (this dish 60), sorbitan monooleate (span 80), Diethylene Glycol fatty acid ester, anhydrous sorbitol monopalmitate (this dish 40), polyoxytrimethylene hard fatty acid ester, sorbitan mono-laurate (this dish 20), polyoxyethylene hard fatty acid ester, lauric acid polyoxyethylene ester, polyoxyethylene (4) anhydrous sorbitol list hard fatty acid ester (Tween61), polyoxyethylene (5) sorbitan monooleate (sorbimacrogol oleate100), polyoxyethylene (20) anhydrous sorbitol tristearate (polysorbate65), polyoxyethylene (20) Witconol AL 69-66 (polysorbate85), polyoxyethylene monoleate, fatty alcohol amine polyoxyethylene ether, alkylphenol polyoxyethylene, polyoxyethylene mono-laurate, polyoxyethylene castor oil, polyoxyethylene (4) sorbitan mono-laurate (tween 21), polyoxyethylene (20) anhydrous sorbitol list hard fatty acid ester (polysorbate60), polyoxyethylene (20) sorbitan monooleate (tween 80), polyoxyethylene (20) anhydrous sorbitol monopalmitate (polysorbate40), at least one in polyoxyethylene (20) sorbitan mono-laurate (polysorbas20), preferably sorbitan monooleate (span 80), polyoxyethylene (20) sorbitan monooleate (tween 80), sorbitan mono-laurate (this dish 20).
5. method according to claim 1, is characterized in that, described amylase is a kind of in α-amylase, beta-amylase, gamma amylase, isoamylase.
6. method according to claim 1, is characterized in that, described retarding solvent is a kind of in sodium sulfate, sodium-chlor or potassium sulfate, and add-on is the 5-10% of starch weight.
7. method according to claim 1, is characterized in that, described catalyzer is a kind of in sodium hydroxide, potassium hydroxide, ammoniacal liquor.
8. method according to claim 1, is characterized in that, described etherifying agent is a kind of in the chloro-2-hydroxypropyl-trimethyl ammonium chloride of 3-or 2,3-epoxypropyl ammonium chloride.
9. method according to claim 1, is characterized in that, described neutralizing agent is one or more in hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, formic acid or Glacial acetic acid.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105088861A (en) * | 2015-08-13 | 2015-11-25 | 合肥龙发包装有限公司 | Emulsifier making AKD glue fast cured |
| CN105544293A (en) * | 2015-12-31 | 2016-05-04 | 邢仁卫 | Cationic macromolecule-based liquid AKD sizing agent and preparation method thereof |
| CN105986514A (en) * | 2015-02-28 | 2016-10-05 | 上海东升新材料有限公司 | Sizing agent for corrugated paper and preparation method of sizing agent |
| CN106032657A (en) * | 2015-03-20 | 2016-10-19 | 上海东升新材料有限公司 | Enhanced surface sizing agent and preparing method thereof |
| CN106819546A (en) * | 2016-12-30 | 2017-06-13 | 安徽众盛农业发展有限公司 | A kind of wild duck fodder of good palatability |
| CN108686575A (en) * | 2018-05-15 | 2018-10-23 | 江南大学 | A kind of compound emulsifying agent with magnetic responsiveness energy |
| CN108951148A (en) * | 2018-07-28 | 2018-12-07 | 黄勇 | A kind of preparation method of fabric stiffening agent |
| CN109988246A (en) * | 2019-04-19 | 2019-07-09 | 广州天赐高新材料股份有限公司 | A kind of high degree of substitution cationic starch and preparation method thereof |
| CN110172105A (en) * | 2019-05-22 | 2019-08-27 | 华南理工大学 | A method of improving dry method/semidry method starch and etherifying agent reaction efficiency |
| CN111118951A (en) * | 2019-12-25 | 2020-05-08 | 上海东升新材料有限公司 | Starch emulsifier, preparation method and anionic AKD surface sizing agent prepared by emulsifier |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101168569A (en) * | 2007-12-04 | 2008-04-30 | 天津科技大学 | Method for preparing cationic starch with high substitution degree |
| CN101525856A (en) * | 2009-03-06 | 2009-09-09 | 天津科技大学 | Control of waste paper stock micro-adhesive material by using low molecular weight and high cation substituted ratio starch |
| CN102517991A (en) * | 2011-12-31 | 2012-06-27 | 上海东升新材料有限公司 | Modified starch for surface sizing of paper, as well as the preparation method and the application of the modified starch |
| CN102627734A (en) * | 2012-05-04 | 2012-08-08 | 陕西科技大学 | Preparation method of amphoteric alkyl ketene dimer (AKD) neutral/alkaline sizing agent without sizing lag |
-
2013
- 2013-12-31 CN CN201310751990.8A patent/CN103665173B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101168569A (en) * | 2007-12-04 | 2008-04-30 | 天津科技大学 | Method for preparing cationic starch with high substitution degree |
| CN101525856A (en) * | 2009-03-06 | 2009-09-09 | 天津科技大学 | Control of waste paper stock micro-adhesive material by using low molecular weight and high cation substituted ratio starch |
| CN102517991A (en) * | 2011-12-31 | 2012-06-27 | 上海东升新材料有限公司 | Modified starch for surface sizing of paper, as well as the preparation method and the application of the modified starch |
| CN102627734A (en) * | 2012-05-04 | 2012-08-08 | 陕西科技大学 | Preparation method of amphoteric alkyl ketene dimer (AKD) neutral/alkaline sizing agent without sizing lag |
Non-Patent Citations (4)
| Title |
|---|
| 张可喜等: "《淀粉的改性及其应用》", 30 June 2008, 海南出版公司 * |
| 徐兆瑜: ""阳离子淀粉与醚化剂开发前景广阔"", 《造纸化学品》 * |
| 王尚玲: ""改性AKD施胶剂的制备及其施胶机理的研究"", 《中国优秀硕士学位论文全文数据库 工程辑I辑》 * |
| 陈启杰等: ""高取代度阳离子淀粉的制备与应用"", 《中国造纸》 * |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105986514A (en) * | 2015-02-28 | 2016-10-05 | 上海东升新材料有限公司 | Sizing agent for corrugated paper and preparation method of sizing agent |
| CN106032657A (en) * | 2015-03-20 | 2016-10-19 | 上海东升新材料有限公司 | Enhanced surface sizing agent and preparing method thereof |
| CN105088861A (en) * | 2015-08-13 | 2015-11-25 | 合肥龙发包装有限公司 | Emulsifier making AKD glue fast cured |
| CN105544293A (en) * | 2015-12-31 | 2016-05-04 | 邢仁卫 | Cationic macromolecule-based liquid AKD sizing agent and preparation method thereof |
| CN106819546A (en) * | 2016-12-30 | 2017-06-13 | 安徽众盛农业发展有限公司 | A kind of wild duck fodder of good palatability |
| CN108686575A (en) * | 2018-05-15 | 2018-10-23 | 江南大学 | A kind of compound emulsifying agent with magnetic responsiveness energy |
| CN108951148A (en) * | 2018-07-28 | 2018-12-07 | 黄勇 | A kind of preparation method of fabric stiffening agent |
| CN109988246A (en) * | 2019-04-19 | 2019-07-09 | 广州天赐高新材料股份有限公司 | A kind of high degree of substitution cationic starch and preparation method thereof |
| CN110172105A (en) * | 2019-05-22 | 2019-08-27 | 华南理工大学 | A method of improving dry method/semidry method starch and etherifying agent reaction efficiency |
| CN110172105B (en) * | 2019-05-22 | 2021-09-21 | 华南理工大学 | Method for improving reaction efficiency of dry/semi-dry starch and etherifying agent |
| CN111118951A (en) * | 2019-12-25 | 2020-05-08 | 上海东升新材料有限公司 | Starch emulsifier, preparation method and anionic AKD surface sizing agent prepared by emulsifier |
| CN111118951B (en) * | 2019-12-25 | 2022-06-24 | 上海东升新材料有限公司 | Starch emulsifier, preparation method and anionic AKD surface sizing agent prepared by emulsifier |
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Denomination of invention: Method for preparing cationic starch emulsifier with high degree of substitution Effective date of registration: 20210728 Granted publication date: 20160817 Pledgee: Bank of Hangzhou Limited by Share Ltd. Shanghai branch Pledgor: SHANGHAI CHANGFA NEW MATERIAL Co.,Ltd. Registration number: Y2021310000054 |
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