CN102399516A - Preparation for heat-resistant crosslinking cationic starch adhesive - Google Patents
Preparation for heat-resistant crosslinking cationic starch adhesive Download PDFInfo
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- CN102399516A CN102399516A CN2011104495692A CN201110449569A CN102399516A CN 102399516 A CN102399516 A CN 102399516A CN 2011104495692 A CN2011104495692 A CN 2011104495692A CN 201110449569 A CN201110449569 A CN 201110449569A CN 102399516 A CN102399516 A CN 102399516A
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Abstract
The invention relates to a new preparation method for a heat-resistant crosslinking cationic starch adhesive. The method comprises the following steps of: reacting starch with paraphthaloyl chloride; and reacting with a cationic etherifying agent to obtain the crosslinking cationic starch adhesive capable of resisting higher temperature. The synthetic process is simple; cost is low; and pollution is avoided. Meanwhile, the crosslinking cationic starch adhesives with different heat resistance and different viscosity can be obtained by changing the using amount of the paraphthaloyl chloride and the cationic etherifying agent, so development of the crosslinking cationic starch adhesives in China can be promoted, renewable resources are recycled, and good social and economic benefits are achieved.
Description
Technical field
The present invention relates to a kind of preparation method of heat-resisting cross-linked cationic starch sizing agent, belong to the technical field of the production of fine chemistry industry.
Background technology
Cationic starch has characteristics such as degradability, good water dispersible, low retrogradation property, biocidal property; Particularly it has positive charge; The fiber that has negative charge, the solid particulate in the suspension-s etc. are had good avidity, be applied in a lot of fields, as being used as wet end additive, Surface Size, coating adhesive etc. in paper industry; Textile industry is as the fiber sizing agent; Petroleum industry is used as the hydrate inhibitor of oil field fluid loss agent, emulsion splitter, clay and shale etc., and WWT and coal mining industries are as flocculation agent, and the flotation of ores aspect is used as ore dressing sinking agent etc.In addition etherificate type and esterification type cationic starch household chemicals and medical aspect also as additive.
Cross-linking starch is the alcoholic extract hydroxyl group of starch and the product with linking agent generation crosslinking reaction of two or more functional groups, is the hyperspace network structure, promptly through two ehter bonds or diester linkage, with " bridge formation " between two or more starch molecules together.Through crosslinking reaction introduce in the starch cross-linked dosage normally seldom, general per 100～3000 glucose units contain a cross-link bond.Linking agent commonly used has: epoxy chloropropane, formaldehyde, POCl3, three inclined to one side (or trimerization) sodium phosphates etc.The cross-linking chemistry bonding strength of cross-linking starch is far above hydrogen bond; The intensity of grain pattern improves, and makes cross-linking starch be difficult for gelatinization, has higher anti-shearing force; Thermotolerance and to the stability of soda acid, its stability is also variant along with the difference of crosslinking chemical bond and crosslinking degree.In addition, cross-linking starch also has higher freeze-stable property and freeze-thaw stability.Cross-linking starch can be used as sizing agent, tackiness agent, foodstuff additive, lubricant etc.
The linking agent that uses at present makes crosslinkedization of cationic starch, and the resistance toheat of resultant sizing agent increases, but can not satisfy the higher field of some temperature, like the requirement of the production of iron smelting pellets etc.Therefore, the present invention will adopt a kind of new aromatic base compounds p-phthaloyl chloride as linking agent, in the hope of obtaining a kind of new high temperature resistant gluing agent.
Summary of the invention
The objective of the invention is to be to provide a kind of new preparation process of heat-resisting cross-linked cationic starch sizing agent, this explained hereafter cost is low, product yield is high, process is pollution-free.
The present invention is a preparation process of realizing heat-resisting cross-linked cationic starch sizing agent through following technical scheme.It is characterized in that; Be reflected under dry method, the normal pressure and carry out, starch is under agitation joined in the certain amount of alkaline solution, place the thermostat water bath of certain temperature then; Drip a certain amount of p-phthaloyl chloride, be stirred to the reaction specified time at a certain temperature.After reaction finishes, pH is transferred to 6.0～7.0, leave standstill for some time, after filtration, washing, suction filtration, oven dry, promptly get cross-linking starch with sulphuric acid soln.Then a certain amount of cross-linking starch is put into there-necked flask, add zero(ppm) water, stir; Place thermostat water bath then, add a certain amount of massfraction and be 40% KOH solution, simultaneously; Add a certain amount of 2; 3-epoxypropyl trimethylammonium chloride ammonium (cationic etherifying agent GTA) after reaction for some time, is cooled to room temperature with reaction solution; The volume(tric)fraction that use contains small amount of acetic acid be 70% ethanol to be neutralized to pH be 6.5, after filtering, use volume(tric)fraction to be 70% washing with alcohol, washing, suction filtration, oven dry, promptly get cross-linked cationic starch.
The invention has the advantages that reaction efficiency is high, production technique is simple, can not produce harmful effect to human body, animal and environment, can not destroy ecology and environment.
Embodiment
Embodiment one
Take by weighing the 100g W-Gum, under agitation join in the sodium hydroxide solution of 120mL 20%, place 50 ℃ thermostat water bath then, drip 40mL Diluted Alcohol solution (containing the 1.5g paraphenylene terephthalamide) in the 5min, under 50 ℃, be stirred to reaction 3 hours.After reaction finishes, use concentration pH to be transferred to 6.0～7.0, leave standstill for some time, after filtration, washing, suction filtration, oven dry, promptly get cross-linking starch as the sulphuric acid soln of 3mol/L.
In the tubular vial of whisking appliance is housed; Add 10g cross-linking starch and 10mL 5% sodium hydroxide solution, stir 20min under the room temperature, add 2g 2 again; 3-epoxypropyl trimethylammonium chloride ammonium (cationic etherifying agent GTA); After continuing under the room temperature to stir 10min, reacted 3 hours down, obtain semi-solid thick product at 50 ℃.Thick product soaks with 70% aqueous ethanolic solution that contains an amount of acetate, through filter, the use volume(tric)fraction is 70% washing with alcohol, promptly get cross-linked cationic starch after the washing, suction filtration, oven dry.
Embodiment two
Take by weighing the 100g W-Gum, under agitation join in the sodium hydroxide solution of 100mL 25%, place 40 ℃ thermostat water bath then, drip 40mL Diluted Alcohol solution (containing the 2g paraphenylene terephthalamide) in the 5min, under 40 ℃, be stirred to reaction 3 hours.After reaction finishes, use concentration pH to be transferred to 6.0～7.0, leave standstill for some time, after filtration, washing, suction filtration, oven dry, promptly get cross-linking starch as the sulphuric acid soln of 3mol/L.
Take by weighing the 10g cross-linking starch and put into there-necked flask, add 6mL zero(ppm) water, stir; Place thermostat water bath then, the massfraction that adds 4mL is 20% sodium hydroxide solution, simultaneously; Add 1.5g 2; 3-epoxypropyl trimethylammonium chloride ammonium (cationic etherifying agent GTA) after reaction for some time, is cooled to room temperature with reaction solution; The volume(tric)fraction that use contains small amount of acetic acid be 70% ethanol to be neutralized to pH be 6.5, after filtering, use volume(tric)fraction to be 70% washing with alcohol, washing, suction filtration, oven dry, promptly get cross-linked cationic starch.
Embodiment three
Take by weighing the 100g W-Gum, under agitation join in the sodium hydroxide solution of 100mL 20%, place 50 ℃ thermostat water bath then, drip 30mL Diluted Alcohol solution (containing the 1g paraphenylene terephthalamide) in the 5min, under 50 ℃, be stirred to reaction 2 hours.After reaction finishes, use concentration pH to be transferred to 6.0～7.0, leave standstill for some time, after filtration, washing, suction filtration, oven dry, promptly get cross-linking starch as the sulphuric acid soln of 3mol/L.
In the tubular vial of whisking appliance is housed; Add 10g cross-linking starch and 10mL 10% sodium hydroxide solution, stir 20min under the room temperature, add 1g 2 again; 3-epoxypropyl trimethylammonium chloride ammonium (cationic etherifying agent GTA); After continuing under the room temperature to stir 10min, reacted 3 hours down, obtain semi-solid thick product at 50 ℃.Thick product soaks with 70% aqueous ethanolic solution that contains an amount of acetate, through filter, the use volume(tric)fraction is 70% washing with alcohol, promptly get cross-linked cationic starch after the washing, suction filtration, oven dry.
Claims (1)
1. one kind prepares the method for heat-resisting cross-linked cationic starch sizing agent with p-phthaloyl chloride as linking agent, it is characterized in that may further comprise the steps:
A, under liquid phase, normal pressure, with starch under alkaline condition; Under agitation p-phthaloyl chloride is added in the mixture of a certain amount of starch and water, then reactor drum is placed the thermostat water bath of 20～100 ℃ of temperature, after mixing; To wherein dripping basic soln, reacted 1～6 hour down at 20～100 ℃ again, after having reacted; With sulphuric acid soln pH is transferred to 6.0～7.0, leave standstill for some time, after filtration, washing, suction filtration, oven dry, promptly get cross-linking starch;
B; Get a certain amount of cross-linking starch and water and insert in the tubular vial of belt stirrer, under 20～100 ℃ of water-baths, stir 20min, add an amount of 2 again; 3-epoxypropyl trimethylammonium chloride ammonium (cationic etherifying agent GTA); After continuing under the room temperature to stir 5～30min, reacted 1～6 hour down at 20～100 ℃ again, obtain semi-solid thick product.
C, using the volume(tric)fraction contain small amount of acetic acid is that 70% ethanol neutralization reactant to pH value is 6.5, after filtration, use volume(tric)fraction are 70% washing with alcohol, washing, suction filtration, oven dry, promptly gets cross-linked cationic starch sizing agent.
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| Application Number | Priority Date | Filing Date | Title |
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| CN2011104495692A CN102399516A (en) | 2011-12-29 | 2011-12-29 | Preparation for heat-resistant crosslinking cationic starch adhesive |
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| CN2011104495692A CN102399516A (en) | 2011-12-29 | 2011-12-29 | Preparation for heat-resistant crosslinking cationic starch adhesive |
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| CN102399516A true CN102399516A (en) | 2012-04-04 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103509125A (en) * | 2012-06-21 | 2014-01-15 | 中国石油化工股份有限公司 | Preparation method for hydrophobically modified carboxymethyl starch used for drilling fluid |
| CN106674362A (en) * | 2016-11-21 | 2017-05-17 | 华南理工大学 | Method for preparing paraphthaloyl chloride crosslinked starch by using ethanol solvent |
| CN108842059A (en) * | 2018-07-13 | 2018-11-20 | 山西太钢不锈钢股份有限公司 | The manufacturing method of green pellets |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0346752A1 (en) * | 1988-06-15 | 1989-12-20 | National Starch and Chemical Investment Holding Corporation | Improved starch based corrugating adhesives |
| CN1110296A (en) * | 1994-04-13 | 1995-10-18 | 北京万事通电子技术有限公司 | Method for preparing adhesive from corn starch |
| CN1310751A (en) * | 1998-07-23 | 2001-08-29 | 马铃薯及衍生产品合作销售生产阿韦贝公司 | Adhesive composition |
-
2011
- 2011-12-29 CN CN2011104495692A patent/CN102399516A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0346752A1 (en) * | 1988-06-15 | 1989-12-20 | National Starch and Chemical Investment Holding Corporation | Improved starch based corrugating adhesives |
| CN1110296A (en) * | 1994-04-13 | 1995-10-18 | 北京万事通电子技术有限公司 | Method for preparing adhesive from corn starch |
| CN1310751A (en) * | 1998-07-23 | 2001-08-29 | 马铃薯及衍生产品合作销售生产阿韦贝公司 | Adhesive composition |
Non-Patent Citations (1)
| Title |
|---|
| 何文等: "阿司匹林鼻粘膜给药淀粉微球的制备工艺及其质量控制", 《中国医院药学杂志》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103509125A (en) * | 2012-06-21 | 2014-01-15 | 中国石油化工股份有限公司 | Preparation method for hydrophobically modified carboxymethyl starch used for drilling fluid |
| CN103509125B (en) * | 2012-06-21 | 2016-04-20 | 中国石油化工股份有限公司 | The drilling fluid preparation method of hydrophobically modified carboxy methyl starch |
| CN106674362A (en) * | 2016-11-21 | 2017-05-17 | 华南理工大学 | Method for preparing paraphthaloyl chloride crosslinked starch by using ethanol solvent |
| CN108842059A (en) * | 2018-07-13 | 2018-11-20 | 山西太钢不锈钢股份有限公司 | The manufacturing method of green pellets |
| CN108842059B (en) * | 2018-07-13 | 2019-11-08 | 山西太钢不锈钢股份有限公司 | The manufacturing method of green pellets |
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