CN101831262B - Special corn biomass-based adhesive and method for preparing same - Google Patents
Special corn biomass-based adhesive and method for preparing same Download PDFInfo
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- CN101831262B CN101831262B CN2010101783392A CN201010178339A CN101831262B CN 101831262 B CN101831262 B CN 101831262B CN 2010101783392 A CN2010101783392 A CN 2010101783392A CN 201010178339 A CN201010178339 A CN 201010178339A CN 101831262 B CN101831262 B CN 101831262B
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Abstract
The present invention relates to a special corn biomass-based adhesive, and belongs to the field of deep processing of corn starch. The adhesive is prepared from the following components in part by mass: 80 to 120 parts of waxy corn oxidized-hydroxypropyl starch, 150 and 250 parts of deionized water, 3 to 4 parts of sodium hydroxide, 10 to 15 parts of vinyl acetate, 4 to 8 parts of polyvinyl alcohol, 0.5to 1 part of boric acid, 3 to 5 parts of urea and 2 to 3 parts of preservative. The method for preparing the adhesive comprises pulp blending, gelatinization and graft copolymerization. The adhesive of the invention has the advantages of good viscosity stability, long shelf life and high fluidity and transparency. In the adhesive produced by the method, 90 percent of solids are degradable, and if the special corn biomass-based adhesive of the invention is used for replacing the polymer adhesive, pollution can be greatly reduced, and the environmental protection requirements on the production process and the using process are met.
Description
Technical field
The invention belongs to W-Gum deep processing field.
Background technology
Entered since 21st century, the kind of adhesive products and usage quantity have obtained along with great demand increasing fast, have all obtained extensive utilization in building, packing, petrochemical industry, metallurgy, weaving, papermaking, medical treatment, clothes and shoemaking, space flight and aviation and daily life.Almost anyone, any article all be unable to do without tackiness agent, and the effect of its performance and the benefit of generation are also more and more significant, are bringing into play the effect that becomes more and more important in Economic development.The adhesive industry of China is started in the 1950's, entered since the nineties in last century, the sector has obtained the development of advancing by leaps and bounds, tackiness agent has become the staple product of field of fine chemical, its Application Areas progressively enlarges, technology content further improves, and economic benefit of enterprises also increases substantially.2007, the tackiness agent ultimate production of China reached more than 400 ten thousand tons, and average growth rate per annum remains at 8～10%.
Starch adhesive is as the important branch of tackiness agent, it is the tackiness agent kind of usage quantity maximum in packaging industry, paper industry, textile industry, mounting industry, garment manufacturing industry and the daily life, along with continually developing of starch new variety, improving constantly of starch quality, the continuous use of new technology, the Application Areas of starch adhesive is more and more wider, and usage quantity is increasing.Entered since the new millennium, along with in the society to the enhancing of environmental consciousness in industrial production and the daily life with to the raising of product environmental requirement, people more and more favor in this pollution-free, degradable of starchiness base, reproducible green adhesive products, the enterprise of association area and scientific and technical personnel, according to the market requirement, when guaranteeing its original Application Areas, take new technology and technology, be devoted to improve the performance of product, enlarge new Application Areas.Be devoted to partly or entirely to replace the often research of synthetic macromolecular compounds such as the polyvinyl alcohol of use, polyvinyl acetate (PVA) in the water accack with starch in some field, when guaranteeing original use properties, reduce product cost, reduce the pollution of product to environment, and obtained sizable progress.In some Application Areas, replace non-renewable with reproducible natural polymer starch material and be that the synthesized polymer material of raw material is produced tackiness agent with the oil, be one of important directions of following adhesives industries development.
The biomass-based adhesive of main material production that traditional with starch is exists two big major defects: the one, and the flowability of tackiness agent is poor.The tackiness agent that with conventional corn starch is raw material is under the relative conditions of higher of solid content, and temperature is reduced to room temperature and is pasty state, is exactly so-called " paste ", makes the flowability of product can not get guaranteeing; The 2nd, the viscosity stability of tackiness agent is poor.Even the tackiness agent of many kinds is handled through some modifications, but in transportation and storage process in various degree the gelation or solid-liquid separation phenomenons of appearance tackiness agent all, the influence of environment is relatively more responsive to external world, makes the quality guaranteed period of product can not get guaranteeing.This two big defective has directly influenced the use range and the working conditions of starch adhesive, is the problem to be solved of killing.
Summary of the invention
The invention provides a kind of special corn biomass-based adhesive and preparation method thereof, is that the biomass-based adhesive of main material production exists: the problem of adhesive flow difference and viscosity stability difference with starch to solve traditional.The technical scheme that the present invention takes: it is to be made by the prescription of following ratio of quality and the number of copies and method:
Prescription:
80～120 parts of waxy corn oxidation-hydroxypropylated starchs
150～250 parts of deionized waters
3～4 parts in sodium hydroxide
10～15 parts of vinyl acetates
Polyvinyl alcohol 4-8 part
Boric acid 0.5-1 part
3～5 parts in urea
2～3 parts of sanitass;
Waxy corn oxidation-hydroxypropylated starch is made by following method in the prescription:
(a) size mixing: adding concentration is 2% alkali lye in closed reactor, waxy corn starch and alkali lye are dissolved in the sig water of reactor in 1: 2～2.5 ratio and stir, the back that stirs adds 5% alkali lye, and to adjust the pH of starch milk be 10～10.5;
(b) oxidizing reaction: closed reactor is warming up to 45～50 ℃ by water cycle, in adding H with 1: 10 ratio of alkali lye
2O
2, stirring reaction after 4～6 hours at the uniform velocity adds 2% HCl or sulfuric acid neutralization, washes then, suction filtration, obtains moisture 40% filter cake;
(c) etherification reaction: filter cake is sized mixing to the starch milk of 35-40%, inject closed reactor, the alkali lye with 5% is regulated pH to 10～10.5, adds the anhydrous sodium sulphate that accounts for starch butt weight 1.5～2% then, to suppress the swelling of starch granules; Be warming up to 45～50 ℃, stir starch milk was mixed in 30 minutes after, in reactor, charge into nitrogen, oxygen is got rid of; Injection and 1: 30 propylene oxide of alkali lye then evenly stirred and carried out etherification reaction, continues the alkali lye of adding 5% so that pH is stabilized in 10～10.5 in reaction process; After reaction finished, it was 6.8 that hydrochloric acid with 2% or 2% sulfuric acid are neutralized to pH, washed then, filtered, drying, made water content and be waxy corn oxidation-hydroxypropylated starch of 14%;
Method:
(1) size mixing: sodium hydroxide is dissolved in 75% the deionized water and forms alkali lye, waxy corn oxidation-hydroxypropylated starch mixes with sig water, after stirring, injects stainless steel cauldron;
(2) gelatinization: at the uniform velocity stir and be warming up to gelatinization point, 90 ℃～95 ℃ gelatinizations 1.5～2 hours, deionized water with 20% dissolves polyvinyl alcohol in another little reactor simultaneously, inject starch paste liquid after 1 hour in starch pasting, add boric acid in the mixing process and make initiator, promote the fusion of the two;
(3) graft copolymerization: take cooling water circulation to 30～40 ℃ after gelatinization is finished, the vinyl acetate that adds in the prescription carried out graft reaction 2～3 hours then;
(4) finished product: add the lysate of urea and sanitas, this lysate dissolves with 5% deionized water in filling a prescription and urea and sanitas and obtains, and finishes preparation after stirring, and the tackiness agent blowing is gone in the airtight packaging vessel.
One embodiment of the present invention is that sanitas adopts Sodium Benzoate, Whitfield's ointment, three potassium sorbates.
The present invention is raw material with the waxy corn starch, by oxidation-etherification complex denaturation technology, produces tackiness agent specific complex modified starch.With conventional corn starch---contain amylopectin about 73% and compare, waxy corn starch contains the amylopection content more than 97%, this situation compares to the effect that conventional corn starch has the good resistance gelation on physical property, stick with paste liquid and have good flowability and viscosity stability, after sex change, viscosity is than conventional corn starch adhesive height.Simultaneously, because average protein content is low than conventional corn starch in the waxy corn starch, therefore its transparency of products of tackiness agent and the anti-putridness of producing is all good than conventional corn starch adhesive.
Positively effect of the present invention: 1, the viscosity stability of tackiness agent is good, and long quality-guarantee period has good flowability and transparency.The tamanori of producing with this raw material and method is 40% in maximum solid content, when viscosity is 20～40Pas, still can keep good flowability, and the quality guaranteed period can reach 120 days, and thermostability and low-temperature stability can both reach respective standard.This performance is that conventional corn Starch Adhesive institute is inaccessible.2, the tackiness agent that goes out with this explained hereafter is when guaranteeing identical result of use, can replace at present packaging industry use with synthetic macromolecule tackiness agent such as polyvinyl alcohol, polyvinyl acetate emulsions, also can replace the plain tackiness agent of dried network that uses at packaging industry at present, can make the cost of product reduce by 30～50%.3, make the solid substance of the tackiness agent of producing in this way 90% have degradability, and present identical application target starch adhesive has the polymkeric substance about 50% not degrade, the replace polymeric tackiness agent can reduce pollution significantly, can reach the environmental protection standard in production technique and the use.
Embodiment
Embodiment 1
It is to be made by the prescription of following ratio of quality and the number of copies and method:
Prescription:
80 parts of waxy corn oxidation-hydroxypropylated starchs
150 parts of deionized waters
3 parts in sodium hydroxide
10 parts of vinyl acetates
4 parts of polyvinyl alcohol
0.5 part of boric acid
3 parts in urea
2 parts of sanitass;
Waxy corn oxidation-hydroxypropylated starch is made by following method in the prescription:
(a) size mixing: add concentration and be 2% NaOH alkali lye in closed reactor, waxy corn starch and alkali lye are dissolved in the sig water of reactor by 1: 2 ratio and stir, the pH of the alkali lye adjustment starch milk of the back adding 5% that stirs is 10;
(b) oxidizing reaction: closed reactor is warming up to 45～50 ℃ by water cycle, in adding H with 1: 10 ratio of alkali lye
2O
2, stirring reaction after 4 hours at the uniform velocity adds 2% HCl neutralization, washes then, suction filtration, obtains moisture 40% filter cake;
(c) etherification reaction: filter cake is sized mixing to 35% starch milk, inject closed reactor, the NaOH alkali lye with 5% is regulated pH to 10, adds the anhydrous sodium sulphate that accounts for starch butt weight 1.5% then, to suppress the swelling of starch granules; Be warming up to 45 ℃, stir starch milk was mixed in 30 minutes after, in reactor, charge into nitrogen, oxygen is got rid of; Injection and 1: 30 propylene oxide of alkali lye then evenly stirred and carried out etherification reaction, continues the NaOH alkali lye of adding 5% so that pH is stabilized in 10 in reaction process; After reaction finished, it was 6.8 that the hydrochloric acid with 2% is neutralized to pH, washed then, filtered, drying, made water content and be waxy corn oxidation-hydroxypropylated starch of 14%;
Method:
(1) size mixing: sodium hydroxide is dissolved in 75% the deionized water and forms alkali lye, waxy corn oxidation-hydroxypropylated starch mixes with sig water, after stirring, injects stainless steel cauldron;
(2) gelatinization: at the uniform velocity stir and be warming up to gelatinization point, 90 ℃ of gelatinizations 1.5 hours, the deionized water with 20% dissolved polyvinyl alcohol in another little reactor simultaneously, injects starch paste liquid after 1 hour in starch pasting, add boric acid in the mixing process and make initiator, promote the fusion of the two;
(3) graft copolymerization: take cooling water circulation to 30 ℃ after gelatinization is finished, the vinyl acetate that adds in the prescription carried out graft reaction 2 hours then;
(4) finished product: add the lysate of urea and Sodium Benzoate, this lysate dissolves with 5% deionized water in filling a prescription and urea and Sodium Benzoate and obtains, and finishes preparation after stirring, and the tackiness agent blowing is gone in the airtight packaging vessel.
Embodiment 2
It is to be made by the prescription of following ratio of quality and the number of copies and method:
Prescription:
100 parts of waxy corn oxidation-hydroxypropylated starchs
200 parts of deionized waters
3.5 parts in sodium hydroxide
12.5 parts of vinyl acetates
6 parts of polyvinyl alcohol
0.7 part of boric acid
4 parts in urea
2.5 parts of sanitass;
Waxy corn oxidation-hydroxypropylated starch is made by following method in the prescription:
(a) size mixing: add concentration and be 2% NaOH alkali lye in closed reactor, waxy corn starch and alkali lye are dissolved in the sig water of reactor by 1: 2.3 ratio and stir, the pH of the alkali lye adjustment starch milk of the back adding 5% that stirs is 10.2;
(b) oxidizing reaction: closed reactor is warming up to 47 ℃ by water cycle, in adding H with 1: 10 ratio of alkali lye
2O
2, stirring reaction after 5 hours at the uniform velocity adds 2% HCl neutralization, washes then, suction filtration, obtains moisture 40% filter cake;
(c) etherification reaction: filter cake is sized mixing to 37% starch milk, inject closed reactor, the NaOH alkali lye with 5% is regulated pH to 10.2, adds the anhydrous sodium sulphate that accounts for starch butt weight 1.7% then, to suppress the swelling of starch granules; Be warming up to 47 ℃, stir starch milk was mixed in 30 minutes after, in reactor, charge into nitrogen, oxygen is got rid of; Injection and 1: 30 propylene oxide of alkali lye then evenly stirred and carried out etherification reaction, continues the NaOH alkali lye of adding 5% so that pH is stabilized in 10.2 in reaction process; After reaction finished, it was 6.8 that the hydrochloric acid with 2% is neutralized to pH, washed then, filtered, drying, made water content and be waxy corn oxidation-hydroxypropylated starch of 14%;
Method:
(1) size mixing: sodium hydroxide is dissolved in 75% the deionized water and forms alkali lye, waxy corn oxidation-hydroxypropylated starch mixes with sig water, after stirring, injects stainless steel cauldron;
(2) gelatinization: at the uniform velocity stir and be warming up to gelatinization point, 92 ℃ of gelatinizations 1.7 hours, the deionized water with 20% dissolved polyvinyl alcohol in another little reactor simultaneously, injects starch paste liquid after 1 hour in starch pasting, add boric acid in the mixing process and make initiator, promote the fusion of the two;
(3) graft copolymerization: take cooling water circulation to 35 ℃ after gelatinization is finished, the vinyl acetate that adds in the prescription carried out graft reaction 2.5 hours then;
(4) finished product: add urea and salicylic lysate, this lysate dissolves with 5% deionized water in filling a prescription and urea and Whitfield's ointment and obtains, and finishes preparation after stirring, and the tackiness agent blowing is gone in the airtight packaging vessel.
Embodiment 3
It is to be made by the prescription of following ratio of quality and the number of copies and method:
Prescription:
120 parts of waxy corn oxidation-hydroxypropylated starchs
250 parts of deionized waters
4 parts in sodium hydroxide
15 parts of vinyl acetates
8 parts of polyvinyl alcohol
1 part of boric acid
5 parts in urea
3 parts of sanitass;
Waxy corn oxidation-hydroxypropylated starch is made by following method in the prescription:
(a) size mixing: add concentration and be 2% KOH alkali lye in closed reactor, waxy corn starch and alkali lye are dissolved in the sig water of reactor by 1: 2.5 ratio and stir, the pH of the alkali lye adjustment starch milk of the back adding 5% that stirs is 10.5;
(b) oxidizing reaction: closed reactor is warming up to 50 ℃ by water cycle, in adding H with 1: 10 ratio of alkali lye
2O
2, stirring reaction after 6 hours at the uniform velocity adds 2% sulfuric acid neutralization, washes then, suction filtration, obtains moisture 40% filter cake;
(c) etherification reaction: filter cake is sized mixing to 40% starch milk, inject closed reactor, the KOH alkali lye with 5% is regulated pH to 10.5, adds the anhydrous sodium sulphate that accounts for starch butt weight 2% then, to suppress the swelling of starch granules; Be warming up to 50 ℃, stir starch milk was mixed in 30 minutes after, in reactor, charge into nitrogen, oxygen is got rid of; Injection and 1: 30 propylene oxide of alkali lye then evenly stirred and carried out etherification reaction, continues the KOH alkali lye of adding 5% so that pH is stabilized in 10.5 in reaction process; After reaction finished, it was 6.8 that the sulfuric acid with 2% is neutralized to pH, washed then, filtered, drying, made water content and be waxy corn oxidation-hydroxypropylated starch of 14%;
Method:
(1) size mixing: sodium hydroxide is dissolved in 75% the deionized water and forms alkali lye, waxy corn oxidation-hydroxypropylated starch mixes with sig water, after stirring, injects stainless steel cauldron;
(2) gelatinization: at the uniform velocity stir and be warming up to gelatinization point, 95 ℃ of gelatinizations 2 hours, the deionized water with 20% dissolved polyvinyl alcohol in another little reactor simultaneously, injects starch paste liquid after 1 hour in starch pasting, add boric acid in the mixing process and make initiator, promote the fusion of the two;
(3) graft copolymerization: take cooling water circulation to 40 ℃ after gelatinization is finished, the vinyl acetate that adds in the prescription carried out graft reaction 3 hours then;
(4) finished product: add the lysate of urea and three potassium sorbates, this lysate dissolves with 5% deionized water in filling a prescription and urea and three potassium sorbates and obtains, and finishes preparation after stirring, and the tackiness agent blowing is gone in the airtight packaging vessel.
Claims (3)
1. special corn biomass-based adhesive, it is characterized in that: it is to be made by the prescription of following ratio of quality and the number of copies and method:
Prescription:
Waxy corn oxidation-hydroxypropylated starch is made by following method in the prescription:
(a) size mixing: adding concentration is 2% alkali lye in closed reactor, waxy corn starch and alkali lye are dissolved in the sig water of reactor in 1: 2～2.5 ratio and stir, the back that stirs adds 5% alkali lye, and to adjust the pH of starch milk be 10～10.5;
(b) oxidizing reaction: closed reactor is warming up to 45～50 ℃ by water cycle, in adding H with 1: 10 ratio of alkali lye
2O
2, at the uniform velocity behind stirring reaction 4～～6 hour, add 2% HCl or sulfuric acid neutralization, wash then, suction filtration, obtain moisture 40% filter cake;
(c) etherification reaction: filter cake is sized mixing to the starch milk of 35-40%, inject closed reactor, the alkali lye with 5% is regulated pH to 10～10.5, adds the anhydrous sodium sulphate that accounts for starch butt weight 1.5～2% then, to suppress the swelling of starch granules; Be warming up to 45～50 ℃, stir starch milk was mixed in 30 minutes after, in reactor, charge into nitrogen, oxygen is got rid of; Injection and 1: 30 propylene oxide of alkali lye then evenly stirred and carried out etherification reaction, continues the alkali lye of adding 5% so that pH is stabilized in 10～10.5 in reaction process; After reaction finished, it was 6.8 that hydrochloric acid with 2% or 2% sulfuric acid are neutralized to pH, washed then, filtered, drying, made water content and be waxy corn oxidation-hydroxypropylated starch of 14%;
Method:
(1) size mixing: sodium hydroxide is dissolved in 75% the deionized water and forms alkali lye, waxy corn oxidation-hydroxypropylated starch mixes with sig water, after stirring, injects stainless steel cauldron;
(2) gelatinization: at the uniform velocity stir and be warming up to gelatinization point, 90 ℃～95 ℃ gelatinizations 1.5～2 hours, deionized water with 20% dissolves polyvinyl alcohol in another little reactor simultaneously, inject starch paste liquid after 1 hour in starch pasting, add boric acid in the mixing process and make initiator, promote the fusion of the two;
(3) graft copolymerization: take cooling water circulation to 30～40 ℃ after gelatinization is finished, the vinyl acetate that adds in the prescription carried out graft reaction 2～3 hours then;
(4) finished product: add the lysate of urea and sanitas, this lysate dissolves with 5% deionized water in filling a prescription and urea and sanitas and obtains, and finishes preparation after stirring, and the tackiness agent blowing is gone in the airtight packaging vessel.
2. according to the described special corn biomass-based adhesive of claim 1, it is characterized in that: sanitas adopts Sodium Benzoate, Whitfield's ointment, potassium sorbate.
3. the preparation method of special corn biomass-based adhesive according to claim 1 is characterized in that comprising the prescription and the step of following ratio of quality and the number of copies:
Prescription:
Waxy corn oxidation-hydroxypropylated starch is made by following method in the prescription:
(a) size mixing: adding concentration is 2% alkali lye in closed reactor, waxy corn starch and alkali lye are dissolved in the sig water of reactor in 1: 2～2.5 ratio and stir, the back that stirs adds 5% alkali lye, and to adjust the pH of starch milk be 10～10.5;
(b) oxidizing reaction: closed reactor is warming up to 45～50 ℃ by water cycle, in adding H with 1: 10 ratio of alkali lye
2O
2, stirring reaction after 4～6 hours at the uniform velocity adds 2% HCl or sulfuric acid neutralization, washes then, suction filtration, obtains moisture 40% filter cake;
(c) etherification reaction: filter cake is sized mixing to the starch milk of 35-40%, inject closed reactor, the alkali lye with 5% is regulated pH to 10～10.5, adds the anhydrous sodium sulphate that accounts for starch butt weight 1.5～2% then, to suppress the swelling of starch granules; Be warming up to 45～50 ℃, stir starch milk was mixed in 30 minutes after, in reactor, charge into nitrogen, oxygen is got rid of; Injection and 1: 30 propylene oxide of alkali lye then evenly stirred and carried out etherification reaction, continues the alkali lye of adding 5% so that pH is stabilized in 10～10.5 in reaction process; After reaction finished, it was 6.8 that hydrochloric acid with 2% or 2% sulfuric acid are neutralized to pH, washed then, filtered, drying, made water content and be waxy corn oxidation-hydroxypropylated starch of 14%;
Step:
(1) size mixing: sodium hydroxide is dissolved in 75% the deionized water and forms alkali lye, waxy corn oxidation-hydroxypropylated starch mixes with sig water, after stirring, injects stainless steel cauldron;
(2) gelatinization: at the uniform velocity stir and be warming up to gelatinization point, 90 ℃～95 ℃ gelatinizations 1.5～2 hours, deionized water with 20% dissolves polyvinyl alcohol in another little reactor simultaneously, inject starch paste liquid after 1 hour in starch pasting, add boric acid in the mixing process and make initiator, promote the fusion of the two;
(3) graft copolymerization: take cooling water circulation to 30～40 ℃ after gelatinization is finished, the vinyl acetate that adds in the prescription carried out graft reaction 2～3 hours then;
(4) finished product: add the lysate of urea and sanitas, this lysate dissolves with 5% deionized water in filling a prescription and urea and sanitas and obtains, and finishes preparation after stirring, and the tackiness agent blowing is gone in the airtight packaging vessel.
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| Application Number | Priority Date | Filing Date | Title |
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| CN2010101783392A CN101831262B (en) | 2010-05-21 | 2010-05-21 | Special corn biomass-based adhesive and method for preparing same |
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| CN2010101783392A CN101831262B (en) | 2010-05-21 | 2010-05-21 | Special corn biomass-based adhesive and method for preparing same |
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| CN101831262B true CN101831262B (en) | 2011-09-28 |
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| CN102464963A (en) * | 2010-11-10 | 2012-05-23 | 吕继学 | Production process of transfer complex adhesive |
| CN102559107A (en) * | 2010-12-17 | 2012-07-11 | 浙江科技学院 | Preparation method of adhesive for producing corrugated cardboard |
| CN103242786B (en) * | 2013-04-22 | 2015-12-23 | 常州大学 | A kind of preparation method of environment-friendly modified starch cigarette glue |
| CN103614099B (en) * | 2013-10-28 | 2017-02-08 | 杭州美嘉保新材料科技有限公司 | Freeze-thaw resistant starch glue and preparation method thereof |
| CN104194673A (en) * | 2014-08-26 | 2014-12-10 | 安徽神舟飞船胶业有限公司 | Formula and preparation process of hydroxypropyl-polysiloxane sealant |
| CN104231175B (en) * | 2014-09-22 | 2017-10-17 | 广西民族大学 | A kind of preparation method of etherification oxidation graft polyol converted starch |
| CN104961838B (en) * | 2015-07-15 | 2017-03-01 | 河南恒瑞淀粉科技股份有限公司 | A kind of hydroxypropylation modified starch and preparation method thereof |
| CN104946163B (en) * | 2015-07-22 | 2019-06-11 | 钟博文 | High-speed cigarette machine modified starch base adhesive |
| CN108373892A (en) * | 2017-06-17 | 2018-08-07 | 赣州市金东门化工有限公司 | A kind of paster special-purpose adhesive and preparation method thereof |
| CN108715756A (en) * | 2018-07-20 | 2018-10-30 | 中国石油集团川庆钻探工程有限公司工程技术研究院 | A kind of modified starch filtration-control additive and its preparation method and application |
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| US4231803A (en) * | 1978-05-22 | 1980-11-04 | Anheuser-Busch Incorporated | Starch adhesive composition containing an oxidized waxy starch ester |
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|---|---|---|---|---|
| US4231803A (en) * | 1978-05-22 | 1980-11-04 | Anheuser-Busch Incorporated | Starch adhesive composition containing an oxidized waxy starch ester |
| CN1462786A (en) * | 2003-05-27 | 2003-12-24 | 郑正炯 | Method for preparing natural nontoxic adhesive for wood use |
| CN1840601A (en) * | 2005-03-31 | 2006-10-04 | 朱寿会 | Method for making adhesive made of starch and nontoxic high molecular polymer |
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| 陈军等.一种新型玉米淀粉粘合剂的研制.《中国胶粘剂》.1995,第4卷(第4期),第18页到第19页以及第24页. * |
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| CN101831262A (en) | 2010-09-15 |
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