CN101962518A - Starch bonding agent, and preparation method and use thereof - Google Patents
Starch bonding agent, and preparation method and use thereof Download PDFInfo
- Publication number
- CN101962518A CN101962518A CN2010101192405A CN201010119240A CN101962518A CN 101962518 A CN101962518 A CN 101962518A CN 2010101192405 A CN2010101192405 A CN 2010101192405A CN 201010119240 A CN201010119240 A CN 201010119240A CN 101962518 A CN101962518 A CN 101962518A
- Authority
- CN
- China
- Prior art keywords
- starch
- preparation
- modified starch
- sodium hydroxide
- modified
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Landscapes
- Polysaccharides And Polysaccharide Derivatives (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Paper (AREA)
Abstract
The invention provides a preparation method for a starch bonding agent, which comprises the following steps of: performing crosslinking treatment on starch by adopting a crosslinker to form modified starch A, performing oxidation with sodium hypochlorite, esterification with butanedioic anhydride and treatment with a cationic etherifying agent on the starch to form modified starch B, and mixing the modified starch A and the modified starch B according to a certain proportion to form the modified starch bonding agent. The preparation method has the advantage of ensuring higher bonding power, firm bonding, high hardness of bonded paper products, high drying speed, low viscosity of paste, high flowability and wettability, convenience of coating, high storage stability and difficulty in gel production.
Description
Technical field
The application relates to a kind of chemical industry technical field of adhesive, in particular to a kind of modified starch tackiness agent and preparation method thereof and purposes.
Background of invention
Fluting board normally adopts tackiness agent that paperboard is bonded in and makes behind the corrugated Corrugating Base Paper, it is mainly used in the package packing supplies of article, such as carton, list, multiple layer paper bag etc., the package packing supplies that uses fluting board to make has utilized the resiliency that fluting board has and has made the article of being taken care of package packing supplies in avoid damaging.
For the tackiness agent of fluting board, early stage, most of life-time service bubble flower alkali, its conjunctiva is fast, and price is low, but spends the easy moisture absorption accumulation of salt in the surface soil of alkali adherent carton with bubble, destroys the compressive resistance of case face, and degumming phenomenon happens occasionally, even corrosion internal packing commodity.Before more than ten years, people begin to adopt the tackiness agent of starch as fluting board, because starch is pollution-free, can long-term storage and binding property does not change, advantages such as suitable use at normal temperatures, the use of Starch Adhesive has obtained very big development, at present, the preparation method of Starch Adhesive mainly contains following several:
1. alkali is stuck with paste method: this method is that water is mixed with starch, diluted alkaline, is warmed up to 40 ℃, continuously stirring.This method technology is simple, and used starting material are few, but because the functional group of starch does not change, bounding force is undesirable, uses less;
2. dextrin method: this method is with starch direct roasting (190～230 ℃), or in the presence of small amount of hydrochloric acid, nitric acid in 110～140 ℃ of roastings, or undergo microbial fermentation and form.The mobile performance of the tackiness agent of making is good, pH value is near neutral, corrodibility is little, but the functional group of starch is changed, cohesive force and anticorrosion mildew-resistant ability, can not store, technology is complicated, and terminal point is difficult to control, and the big minor swing of relative molecular mass is big, the quality instability, present application is also fewer;
3. main body-support methods: this method is with small amounts starch hydro-oxidation sodium, magma thing after the gelatinization is a carrier, starch or Sumstar 190 with ungelatinized mixes as main body again, will give birth to starch or Sumstar 190 explosion and gelatinization by the unexpected high temperature after the gluing.The fluting board quality that this method is produced is better; But only suitable high-speed and continuous machine is produced.
4. Sumstar 190 method: this method is to utilize oxygenant with starch oxidation, make the hydroxyl on 6 carbon of glucose unit of original starch become aldehyde radical and carboxyl, the variation of this functional group had both increased the cohesive force of starch and paper fiber, improved its anticorrosion mildew-resistant ability, simultaneous oxidation can make the long molecular chain of starch become short molecular chain again, make the mobile property raising of the tackiness agent that makes, be convenient on machine, be coated with.Though this method is comparatively more superior than first three methods, cohesive force is still strong inadequately, and viscosity stability is not good, poor storage stability, and easily gel is crispaturaed tendency greatly.
In order to overcome prior art starch is made the existing various shortcoming of tackiness agent, the inventor is through discovering in earnest for a long time, use crosslinked, oxidation, esterification and the MULTIPLE COMPOSITE of cationization simultaneously, composite means are modified, make the Starch Adhesive that obtains, not only solved all defect that Starch Adhesive exists in the prior art, and improved the performance of tackiness agent significantly, thereby finished the present invention.
Summary of the invention
An object of the present invention is to provide a kind of preparation method of Starch Adhesive, it comprises
(1) preparation of modified starch A: adopt linking agent that starch is carried out crosslinking Treatment, obtain modified starch A;
(2) preparation of modified starch B: starch is adopted hypochlorite oxidation, succinic anhydride esterification, cationic etherifying agent etherificate successively, obtain modified starch B;
(3) composite: with modified starch A and modified starch B with 6: 4-5: 5, preferred 11: 9 weight part mixes, and can obtain the composite modified starch tackiness agent.
Alternatively, after preparing finished product, can carry out processing such as pre-gelatinization, cold water swelling and granulation to finished product, wherein pre-gelatinization or cold water swelling treatment can improve the water-absorbent and the film-forming properties of starch, improve the convenience of using; Granulation can improve the disperse properties of starch in water, avoids occurring meeting drawbacks such as water lumps, viscosity is inhomogeneous.This handles and destroys the original form of starch simultaneously, and the partial analysis detection method was lost efficacy, thereby covers the source or the processing mode of starch, has certain commercial value.
In the above-described embodiment, described starch can be selected from yam starch, tapioca (flour), conventional corn starch, rye starch, wheat starch, oat starch etc., preferred yam starch, because amylopection content is higher in the yam starch, the cohesive force of the Starch Adhesive for preparing according to method of the present invention is stronger.
In the above-described embodiment, described linking agent can be selected from phosphorus oxychloride, Trisodium trimetaphosphate, epoxy chloropropane etc., preferred phosphorus oxychloride; Described cationic etherifying agent can adopt the cationic etherifying agent that is selected from 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride or β-chloroethyldiethylamine to carry out etherificate and handle, preferred 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride.
In the above-described embodiment, in preparation modified starch A, linking agent accounts for 2 ‰ (w/w)-3 ‰ (w/w) of starch weight, preferred 2.5 ‰ (w/w) (total amount in starch among the modified starch A is 100% (w/w)); In preparation modified starch B, clorox, Succinic anhydried, cationic etherifying agent account for 2% (w/w)-3% (w/w), 3 ‰ (w/w)-6 ‰ (w/w), the 4-10% (w/w) of the weight of starch respectively, and preferred point is respectively 2.3% (w/w), 4 ‰ (w/w), 6% (w/w) (total amount in starch among the modified starch B is 100% (w/w)).
In a preferred embodiment, the invention provides a kind of preparation method of Starch Adhesive, it comprises the steps:
The preparation of modified starch
(1) preparation of modified starch A
Will be to the sodium sulfate of starch wet basis 2% (w/w)-5% (w/w), 0.2% (w/w)-1% (w/w) sodium hydroxide is dissolved in the water about 1.5 times to the starch wet basis, stirs it is fully dissolved;
To wherein adding starch, regulate pH value to 11-12 with sodium hydroxide solution (preferred 4% (w/w)), stir and obtain starch milk; To the phosphorus oxychloride that wherein adds based on starch wet basis 2-3 ‰ (w/w), at room temperature reacted 3-5 hour, 0.5-1 hour domestic demand of reaction beginning replenished the sodium hydroxide of 4% (w/w), to keep the stable of PH again;
Afterwards, be neutralized to PH 6-7 with hydrochloric acid soln (preferred 10% (w/w)); Wash to electricity with soft water (pure water, distilled water all can) and to lead＜2000us/cm, drying, moisture content of finished products is controlled at 17% (w/w)-19% (w/w), pulverizes, crosses 100 mesh sieves and get final product;
(2) preparation of modified starch B
1. oxidation:
Starch is soluble in water, stir and obtain starch milk; In 45-50 ℃ of water-bath, transfer pH value to 9.0-9.5 with sodium hydroxide solution (preferred 4% (w/w)), then add available chlorine based on starch wet basis 2-3% (w/w) (in the consumption of available chlorine, usually the effective chlorine density of clorox is 5-10% (w/w)), reacted 2-3 hour, the reaction beginning replenished 4% (w/w) sodium hydroxide solution in 0.5-1 hour, keep pH value at 9.0-9.5, after 2-3 hour, add an amount of S-WAT dechlorination, do not develop the color for qualified with starch-KI test paper, be cooled to room temperature, stand-by;
2. esterification:
After sample after treating 1. to handle is reduced to room temperature, add 10% (w/w) hydrochloric acid and pull back to pH value 8.0-9.0, add 3-6 ‰ (w/w) Succinic anhydried again, replenish 4% (w/w) sodium hydroxide simultaneously and keep pH value in the 8.0-9.0 scope, question response finishes back (pH value tends towards stability), and is stand-by;
3. cationization
To place 45-50 ℃ of water-bath again through the sample after 2. handling, transfer pH value to 11.0-12.0 with sodium hydroxide solution (4% (w/w)), adding is based on the 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride of starch wet basis 4-10% (w/w), reacted 5-8 hour, add acid afterwards and regulate PH and be about 6.0-7.0, wash to electricity with soft water (pure water, distilled water all can) and lead＜2000us/cm PH6.0-7.0, and dry, pulverize, cross 100 mesh sieves, promptly obtain modified starch B;
Starch composite:
Starch A and starch B preferably with 11: 9 mass parts thorough mixing, are promptly obtained the modified starch tackiness agent.
In above-mentioned, the starch wet basis is meant the starch product that contains a certain amount of moisture, and general conventional starch product all contains certain moisture, contains about moisture 19% (w/w) as yam starch on the market, and the starch butt is meant the starch that does not contain moisture.
In the preparation method of Starch Adhesive of the present invention, the peak viscosity of the modified starch A that obtains is≤100BU (measuring during starch concentration 10% (w/w)), the peak viscosity of the modified starch B that obtains is 250-350BU (measuring during starch concentration 10% (w/w)), and the peak viscosity of the modified starch tackiness agent finished product that obtains is 100-150BU (measuring during starch concentration 10% (w/w)).
Another object of the present invention provides according to the modified starch tackiness agent of preparation method's acquisition of Starch Adhesive of the present invention and the purposes that this modified starch tackiness agent is used to prepare the corrugation paperboard, is used to prepare carton, cardboard, list, multiple layer paper bag, label, poster etc. especially.In addition, Starch Adhesive of the present invention can also be used for suitable any other purposes in this area.
After obtaining modified starch tackiness agent of the present invention, can be made into composite adhesive, such as with behind itself and the complexing agent separated pulverizing, mix in proportion, add weighting agent (siccative) and paste agent (sodium hydroxide) after pulverizing, and as required, can also add an amount of auxiliary agent such as defoamer, softening agent, sanitas etc., the total amount of these auxiliary agents is no more than 3% (w/w) of tackiness agent, is finished product after the packing.Wherein paste agent refers to sodium hydroxide; Complexing agent refers to borax; Weighting agent (siccative) refers to light calcium carbonate, wilkinite, kaolin, diatomite etc.
Compare with tackiness agent of the prior art, the modified starch tackiness agent that obtains according to the preparation method of Starch Adhesive has stronger cohesive force, bonding firmly, bonding back paper product hardness height, rate of drying is fast; The paste fluid viscosity is low, and good fluidity, wettability height are convenient to coating, and the stability in storage height is not prone to gelatin phenomenon; Can adopt the form of solid adhesive, be convenient to transportation, deposit and visual real needs and the flexible proportioning of other auxiliary agents; In the time of on being applied in fluting board, avoid occurring the phenomenon of hacking of fluting board, be difficult for gelation, obviously improve coating performance; And make to have the less tendency of crispaturaing, do not influence the paper product quality.
Description of drawings
Fig. 1 is the viscosimetric analysis data plot according to the modified starch A of embodiments of the invention 1 preparation, wherein peak viscosity≤100BU (measuring during starch concentration 10% (w/w)).
Fig. 2 is the viscosimetric analysis data plot according to the modified starch B of embodiments of the invention 1 preparation, and wherein peak viscosity is 250-350BU (measuring during starch concentration 10% (w/w)).
Fig. 3 is the viscosimetric analysis data plot according to the modified starch tackiness agent finished product of embodiments of the invention 1 preparation, and wherein peak viscosity is 100-150BU (measuring during starch concentration 10% (w/w)).
Embodiment
Further elaborate the present invention with reference to embodiment below, but it will be appreciated by those skilled in the art that but the present invention is not limited to the method for these embodiment and use.And those skilled in the art can be equal to replacement, combination, improvement or modification to the present invention according to description of the invention, but these all will comprise within the scope of the invention.
Embodiment 1: the preparation of modified starch tackiness agent
1. the preparation of modified starch
(1) preparation of modified starch A
With the sodium sulfate of 2g, 0.2g sodium hydroxide is dissolved in the water of 150g, stirs it is fully dissolved, and treats that fully the dissolving back adds the 100g yam starch, regulates pH value to 11.5 with 4% (w/w) sodium hydroxide solution, stirs and obtains starch milk; Again to the phosphorus oxychloride that wherein adds 0.2g, replenish the sodium hydroxide of 4% (w/w) within 0.5 hour, fluctuate at 11.0-11.5 to keep PH, at room temperature clock reaction is 3 hours.
Reaction is neutralized to PH 6.8 with 10% (w/w) hydrochloric acid soln after finishing; Lead 1200us/cm with soft water washing three times to electricity, moisture content of finished products is controlled at 17% (w/w)-19% (w/w), and 100 mesh sieves are pulverized, crossed to 45 ℃ of oven dryings 2 hours.
(2) preparation of modified starch B
1. oxidation:
The 100g yam starch is dissolved in the 120g water, stirs and obtain starch milk; In 45-50 ℃ of water-bath, transfer pH value to 9.2 with 4% (w/w) sodium hydroxide, then add the chlorine bleach liquor of 17ml, replenish the sodium hydroxide of 4% (w/w) within 0.5 hour, fluctuate at 9.0-9.5 to keep PH, at room temperature clock reaction is 3 hours.Add the dechlorination of 0.1g S-WAT after 3 hours, do not develop the color for qualified, be cooled to room temperature with starch-KI test paper, stand-by;
2. esterification:
After sample after treating 1. to handle is reduced to room temperature, add 10% (w/w) hydrochloric acid and pull back to pH value 8.5, add the 0.5g Succinic anhydried again, replenish 4% (w/w) sodium hydroxide simultaneously and keep pH value in the 8.2-8.7 scope, question response finishes back (pH value tends towards stability), and is stand-by;
3. cationization
To place 45-50 ℃ of water-bath again through the sample after 2. handling, transfer pH value to 11.3 with 4% (w/w) sodium hydroxide solution, the 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride that adds 6g, reacted 6 hours, and used 10% (w/w) hydrochloric acid to be neutralized to PH to 6.0 afterwards, soft water washing three times, electricity is led 1800us/cm,, 45 ℃ of oven dryings are pulverized after 2 hours, are crossed 100 mesh sieves, promptly obtain modified starch B;
2. starch is composite
With starch A and starch B mass parts thorough mixing, promptly obtain the modified starch tackiness agent with 11: 9.
The preparation of embodiment 2 modified starch tackiness agents
1. the preparation of modified starch
(1) preparation of modified starch A
With the sodium sulfate of 3g, 0.5g sodium hydroxide is dissolved in the water of 120g, stirs it is fully dissolved, and treats that fully the dissolving back adds the 100g yam starch, regulates pH value to 11.6 with 4% (w/w) sodium hydroxide solution, stirs and obtains starch milk; To wherein adding the 0.23g phosphorus oxychloride, replenish the sodium hydroxide of 4% (w/w) within 0.5 hour again, fluctuate at 11.2-11.8 to keep PH, at room temperature clock reaction is 3 hours.
Reaction is neutralized to PH 6.5 with 10% (w/w) hydrochloric acid soln after finishing; With soft water washing three times, electricity is led 1500us/cm, and 100 mesh sieves are pulverized, crossed to 45 ℃ of oven dryings 2 hours.
(2) preparation of modified starch B
1. oxidation:
The 100g yam starch is dissolved in the 100g water, stirs and obtain starch milk; In 45-50 ℃ of water-bath, transfer pH value to 9.5 with 4% (w/w) sodium hydroxide, then add the chlorine bleach liquor of 22ml, replenish the sodium hydroxide of 4% (w/w) within 0.5 hour, fluctuate at 9.2-9.6 to keep PH, at room temperature clock reaction is 3 hours.Add the dechlorination of 0.15g S-WAT after 3 hours, do not develop the color for qualified, be cooled to room temperature with starch-KI test paper, stand-by;
2. esterification:
After sample after treating 1. to handle is reduced to room temperature, add 10% (w/w) hydrochloric acid and pull back to pH value 8.5, add the 0.4g Succinic anhydried again, replenish 4% (w/w) sodium hydroxide simultaneously and keep pH value in the 8.2-8.7 scope, question response finishes back (pH value tends towards stability), and is stand-by;
3. cationization
To place 45-50 ℃ of water-bath again through the sample after 2. handling, transfer pH value to 11.5 with 4% (w/w) sodium hydroxide solution, the 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride that adds 5g, reacted 6 hours, and used 10% (w/w) hydrochloric acid to be neutralized to PH to 6.0 afterwards, soft water washing three times, electricity is led 1583us/cm,, 45 ℃ of oven dryings are pulverized after 2 hours, are crossed 100 mesh sieves, promptly obtain modified starch B;
2 starch composite
With starch A and starch B mass parts thorough mixing, promptly obtain the modified starch tackiness agent with 1: 1.
The preparation of embodiment 3 modified starch tackiness agents
1. the preparation of modified starch
(1) preparation of modified starch A
With the sodium sulfate of 2.8g, 0.28g sodium hydroxide is dissolved in the water of 125g, stirs it is fully dissolved, and treats that fully the dissolving back adds the 100g tapioca (flour), regulates pH value to 11.0 with 4% (w/w) sodium hydroxide solution, stirs and obtains starch milk; Again to the phosphorus oxychloride that wherein adds 0.3g, replenish the sodium hydroxide of 4% (w/w) within 0.5 hour, fluctuate at 11.0-11.5 to keep PH, at room temperature clock reaction is 3 hours.
Reaction is neutralized to PH 7.0 with 10% (w/w) hydrochloric acid soln after finishing; Lead 1600us/cm with soft water washing three times to electricity, 100 mesh sieves are pulverized, crossed to 45 ℃ of oven dryings 2 hours.
(2) preparation of modified starch B
1. oxidation:
The 100g tapioca (flour) is dissolved in the 150g water, stirs and obtain starch milk; In 45-50 ℃ of water-bath, transfer pH value to 9.7 with 4% (w/w) sodium hydroxide, then add the chlorine bleach liquor of 25ml, replenish the sodium hydroxide of 4% (w/w) within 0.5 hour, fluctuate at 9.4-9.8 to keep PH, at room temperature clock reaction is 3 hours.Add the dechlorination of 0.11g S-WAT after 3 hours, do not develop the color for qualified, be cooled to room temperature with starch-KI test paper, stand-by;
2. esterification:
After sample after treating 1. to handle is reduced to room temperature, add 10% (w/w) hydrochloric acid and pull back to pH value 8.0, add the 0.56g Succinic anhydried again, replenish 4% (w/w) sodium hydroxide simultaneously and keep pH value in the 8.0-8.5 scope, question response finishes back (pH value tends towards stability), and is stand-by;
3. cationization
To place 45-50 ℃ of water-bath again through the sample after 2. handling, transfer pH value to 11.2 with 4% (w/w) sodium hydroxide solution, β-the chloroethyldiethylamine that adds 7g, reacted 6 hours, and used 10% (w/w) hydrochloric acid to be neutralized to PH to 6.0 afterwards, soft water washing three times, electricity is led 1940us/cm,, 45 ℃ of oven dryings are pulverized after 2 hours, are crossed 100 mesh sieves, promptly obtain modified starch B;
2. starch is composite
With starch A and starch B mass parts thorough mixing, promptly obtain the modified starch tackiness agent with 3: 2.
The preparation of embodiment 4 modified starch tackiness agents
1. the preparation of modified starch
(1) preparation of modified starch A
With the sodium sulfate of 4g, 0.36g sodium hydroxide is dissolved in the water of 130g, stirs it is fully dissolved, and treats that fully the dissolving back adds the 100g W-Gum, regulates pH value to 11.2 with 4% (w/w) sodium hydroxide solution, stirs and obtains starch milk; Again to the Trisodium trimetaphosphate that wherein adds 0.26g, replenish the sodium hydroxide of 4% (w/w) within 0.5 hour, fluctuate at 11.0-11.5 to keep PH, at room temperature clock reaction is 3 hours.
Reaction is neutralized to PH6.3 with 10% (w/w) hydrochloric acid soln after finishing; With soft water washing three times, electricity is led 1370us/cm, and 100 mesh sieves are pulverized, crossed to 45 ℃ of oven dryings 2 hours.
(2) preparation of modified starch B
1. oxidation:
The 100g W-Gum is dissolved in the 120g water, stirs and obtain starch milk; In 45-50 ℃ of water-bath, transfer pH value to 9.5 with 4% (w/w) sodium hydroxide, then add the chlorine bleach liquor of 30ml, replenish the sodium hydroxide of 4% (w/w) within 0.5 hour, fluctuate at 9.4-9.6 to keep PH, at room temperature clock reaction is 3 hours.Add the dechlorination of 0.25g S-WAT after 3 hours, do not develop the color for qualified, be cooled to room temperature with starch-KI test paper, stand-by;
2. esterification:
After sample after treating 1. to handle is reduced to room temperature, add 10% (w/w) hydrochloric acid and pull back to pH value 8.7, add the 0.38g Succinic anhydried again, replenish 4% (w/w) sodium hydroxide simultaneously and keep pH value in the 8.3-8.9 scope, question response finishes back (pH value tends towards stability), and is stand-by;
3. cationization
To place 45-50 ℃ of water-bath again through the sample after 2. handling, transfer pH value to 11.4 with 4% (w/w) sodium hydroxide solution, the 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride that adds 9g, reacted 6 hours, and used 10% (w/w) hydrochloric acid to be neutralized to PH to 6.7 afterwards, soft water washing three times, electricity is led 1440us/cm,, 45 ℃ of oven dryings are pulverized after 2 hours, are crossed 100 mesh sieves, promptly obtain modified starch B;
2 starch composite
With starch A and starch B mass parts thorough mixing, promptly obtain the modified starch tackiness agent with 6: 5.
The preparation of embodiment 5 modified starch tackiness agents
1. the preparation of modified starch
(1) preparation of modified starch A
With the sodium sulfate of 5g, 0.4g sodium hydroxide is dissolved in the water of 150g, stirs it is fully dissolved, and treats that fully the dissolving back adds the 100g yam starch, regulates pH value to 11.5 with 4% (w/w) sodium hydroxide solution, stirs and obtains starch milk; Again to the phosphorus oxychloride that wherein adds 0.25g, replenish the sodium hydroxide of 4% (w/w) within 0.5 hour, fluctuate at 11.3-11.8 to keep PH, at room temperature clock reaction is 3 hours.
Reaction is neutralized to PH6.5 with 10% (w/w) hydrochloric acid soln after finishing; With soft water washing three times, electricity is led 1230us/cm, and 100 mesh sieves are pulverized, crossed to 45 ℃ of oven dryings 2 hours.
(2) preparation of modified starch B
1. oxidation:
The 100g yam starch is dissolved in the 120g water, stirs and obtain starch milk; In 45-50 ℃ of water-bath, transfer pH value to 9.6 with 4% (w/w) sodium hydroxide, then add the chlorine bleach liquor of 28ml, replenish the sodium hydroxide of 4% (w/w) within 0.5 hour, fluctuate at 9.4-9.8 to keep PH, at room temperature clock reaction is 3 hours.Add the dechlorination of 0.23g sodium sulfate after 3 hours, do not develop the color for qualified, be cooled to room temperature with starch-KI test paper, stand-by;
2. esterification:
After sample after treating 1. to handle is reduced to room temperature, add 10% (w/w) hydrochloric acid and pull back to pH value 8.5, add the 0.6g Succinic anhydried again, replenish 4% (w/w) sodium hydroxide simultaneously and keep pH value in the 8.3-8.8 scope, question response finishes back (pH value tends towards stability), and is stand-by;
3. cationization
To place 45-50 ℃ of water-bath again through the sample after 2. handling, transfer pH value to 11.3 with 4% (w/w) sodium hydroxide solution, the 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride that adds 10g, reacted 6 hours, and used 10% (w/w) hydrochloric acid to be neutralized to PH to 6.0 afterwards, soft water washing three times, electricity is led 1890us/cm,, 45 ℃ of oven dryings are pulverized after 2 hours, are crossed 100 mesh sieves, promptly obtain modified starch B;
2 starch composite
With starch A and starch B mass parts thorough mixing, promptly obtain the modified starch tackiness agent with 11: 9.
Embodiment 6 composite adhesives
Constituent mass part
The modified starch 50 of embodiment 1
Borax 0.5
Sodium hydroxide 5
With above each component and 40 ℃ of water in 1: ratio (8-9) is mixed with thick liquid and promptly obtains composite adhesive.
Embodiment 7 composite adhesives
Constituent mass part
The modified starch 14 of embodiment 2
Sodium hydroxide 1.8
Wilkinite 7
Water 77.2
Modified starch and the wilkinite of above embodiment 2 are dissolved in a certain amount of water by mass parts, stir and be emulsion form, then sodium hydroxide is made into the alkali lye of 10% (w/w)-30% (w/w) with surplus water, join in the emulsion while stirring, leave standstill about 10 minutes, treat that its abundant gelatinization promptly gets the glue finished product.
Claims (8)
1. the preparation method of a Starch Adhesive, it comprises:
(1) preparation of modified starch A: adopt linking agent that starch is carried out crosslinking Treatment, obtain modified starch A;
(2) preparation of modified starch B: starch is adopted hypochlorite oxidation, succinic anhydride esterification, cationic etherifying agent etherificate successively, obtain modified starch B;
(3) composite: with modified starch A and modified starch B with mass parts 6: 4-5: 5 thorough mixing can obtain the composite modified starch tackiness agent.
2. the preparation method of the Starch Adhesive of claim 1, described starch is selected from yam starch, tapioca (flour), conventional corn starch, rye starch, wheat starch, oat starch, preferred yam starch.
3. the preparation method of the Starch Adhesive of claim 1, wherein said linking agent is selected from phosphorus oxychloride, Trisodium trimetaphosphate, epoxy chloropropane etc., preferred phosphorus oxychloride; Described cationic etherifying agent can be selected from 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride or β-chloroethyldiethylamine, preferred 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride.
4. the preparation method of the Starch Adhesive of claim 1, wherein in preparation modified starch A, linking agent accounts for 2 ‰ (w/w)-3 ‰ (w/w) of starch weight, preferred 2.5 ‰ (w/w); In preparation modified starch B, clorox, Succinic anhydried, cationic etherifying agent account for 2% (w/w)-3% (w/w), 3 ‰ (w/w)-6 ‰ (w/w), the 4-10% (w/w) of starch weight respectively, preferably are respectively 2.3% (w/w), 4 ‰ (w/w), 6% (w/w).
5. the preparation method of the Starch Adhesive of claim 1 is characterized in that, it comprises the steps:
(1) preparation of described modified starch A:
Will be to the sodium sulfate of starch wet basis 2% (w/w)-5% (w/w), 0.2% (w/w)-1% (w/w) sodium hydroxide is dissolved in the water to 1.5 times of starch wet basis weight, stirs it is fully dissolved;
To wherein adding starch, regulate pH value to 11-12 with sodium hydroxide solution, stir and obtain starch milk; To the phosphorus oxychloride that wherein adds based on starch wet basis 2-3 ‰ (w/w), at room temperature reacted 3-5 hour again, keep pH value to 11-12 with sodium hydroxide solution between the reaction period;
Afterwards, be neutralized to PH 6-7 with hydrochloric acid soln; Wash to electricity with soft water and to lead＜2000us/cm, drying, moisture content of finished products is controlled at 17% (w/w)-19% (w/w), pulverizes, sieving gets final product.
(2) preparation of described modified starch B:
1. oxidation:
Starch is soluble in water, stir and obtain starch milk; In 45-50 ℃ of water-bath, transfer pH value to 9.0-9.5 with sodium hydroxide solution, then add available chlorine based on starch wet basis 2-3% (w/w), reacted 2-3 hour, keep PH at 9.0-9.5 with sodium hydroxide solution between the reaction period, after 2-3 hour, add an amount of S-WAT dechlorination, do not develop the color for qualified with starch-KI test paper, be cooled to room temperature, stand-by;
2. esterification:
After sample after treating 1. to handle is reduced to room temperature, add 10% (w/w) hydrochloric acid and pull back to pH value 8.0-9.0, add 3-6 ‰ (w/w) Succinic anhydried again, the hydrogen make-up sodium oxide is kept pH value in the 8.0-9.0 scope simultaneously, and is after question response finishes, stand-by;
3. cationization
To place 45-50 ℃ of water-bath again through the sample after 2. handling, transfer pH value to 11.0-12.0 with sodium hydroxide solution, adding is based on the 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride of starch wet basis 4-10% (w/w), reacted 5-8 hour, adding acid afterwards, to regulate PH be 6.0-7.0, washs to electricity with soft water and lead＜2000us/cm, regulates and guarantee PH 6.0-7.0 with hydrochloric acid soln, and dry, pulverize, sieve, promptly obtain modified starch B;
(3) starch is composite:
With modified starch A and modified starch B with 6: 4-5: 5, preferably, promptly obtain the modified starch tackiness agent with 11: 9 mass parts thorough mixing.
6. the preparation method of the Starch Adhesive of claim 5 is characterized in that, in the preparation of described (2) modified starch B, described available chlorine is in the consumption of available chlorine, and the effective chlorine density of clorox is 5-10% (w/w) usually.
7. the modified starch tackiness agent for preparing according to each method among the claim 1-6.
8. the purposes of the modified starch tackiness agent of claim 7 in preparation corrugation paperboard is used to prepare Corrugated Box, cardboard, list, multiple layer paper bag, label, poster especially.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010101192405A CN101962518B (en) | 2010-02-03 | 2010-02-03 | Starch bonding agent, and preparation method and use thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010101192405A CN101962518B (en) | 2010-02-03 | 2010-02-03 | Starch bonding agent, and preparation method and use thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101962518A true CN101962518A (en) | 2011-02-02 |
| CN101962518B CN101962518B (en) | 2012-09-05 |
Family
ID=43515573
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2010101192405A Expired - Fee Related CN101962518B (en) | 2010-02-03 | 2010-02-03 | Starch bonding agent, and preparation method and use thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101962518B (en) |
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102391797A (en) * | 2011-07-09 | 2012-03-28 | 山西大学 | Corn starch adhesive for building and preparation method thereof |
| CN102585726A (en) * | 2012-03-10 | 2012-07-18 | 广东天银化工实业有限公司 | Preparation method for starch-based biomass latex adhesive |
| CN102732186A (en) * | 2012-07-12 | 2012-10-17 | 华东理工大学 | Modified starch adhesive and method for preparing same |
| CN103773273A (en) * | 2012-10-20 | 2014-05-07 | 中国烟草总公司郑州烟草研究院 | Novel amyloid cigarette adhesive based on esterified gelatinized starch and non-gelatinized starch |
| CN104017134A (en) * | 2014-06-12 | 2014-09-03 | 上海东升新材料有限公司 | Preparation method and application of amphoteric biological high polymer binder |
| CN104031295A (en) * | 2014-05-09 | 2014-09-10 | 广西农垦明阳生化集团股份有限公司 | Preparation method for cassava starch modified by combining three kinds of modification processes |
| CN104231973A (en) * | 2014-09-05 | 2014-12-24 | 句容市给力包装制品厂 | Quick dry adhesive for corrugated paper box and preparation method of quick dry adhesive |
| CN103773277B (en) * | 2012-10-20 | 2016-04-06 | 中国烟草总公司郑州烟草研究院 | A kind of based on etherificate class-pasted starch and the amyloid starchiness cigarette glue of non-gelatinization |
| CN105947409A (en) * | 2016-05-04 | 2016-09-21 | 太仓市源创包装材料厂 | Anti-microbial type food packaging paper |
| CN107502229A (en) * | 2017-09-07 | 2017-12-22 | 滁州市光威化工有限公司 | A kind of nanocrystal cellulose enhancing maize-starch adhesive modified with oxidizing for making-cigarette and preparation method |
| CN108165204A (en) * | 2018-02-06 | 2018-06-15 | 罗绍庆 | A kind of preparation method of wood-based plate amylum adhesive |
| CN109320619A (en) * | 2018-11-24 | 2019-02-12 | 蚌埠学院 | A kind of preparation method of crosslinking-oxidization jointly modified starch |
| CN111945466A (en) * | 2020-07-08 | 2020-11-17 | 广东冠豪高新技术股份有限公司 | Water-binding adhesive paper and preparation method thereof |
| CN113088218A (en) * | 2021-05-25 | 2021-07-09 | 佛山市南海华昊华丰淀粉有限公司 | Preparation method and application of starch adhesive for environment-friendly paper bags |
| CN113292949A (en) * | 2021-05-25 | 2021-08-24 | 佛山市南海华昊华丰淀粉有限公司 | Starch adhesive for environment-friendly paper bags, preparation method and application |
| US11603483B2 (en) | 2019-08-16 | 2023-03-14 | Hongsheng Technology (Beijing) Co., Ltd | Environment-friendly oxidation-resisting carton binder and preparation method therefor |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4374217A (en) * | 1981-01-14 | 1983-02-15 | Hohnen Oil Co., Ltd. | Cold-setting starch adhesive |
| EP1109873B1 (en) * | 1998-07-23 | 2005-06-08 | Coöperatieve Verkoop- en Productievereniging van Aardappelmeel en Derivaten 'AVEBE' B.A. | Adhesive composition |
| US6379447B1 (en) * | 1999-04-05 | 2002-04-30 | National Starch And Chemical Investment Holding Corporation | Polysaccharide adhesives for multi-ply paper products |
| CN1227407C (en) * | 2004-03-15 | 2005-11-16 | 江南大学 | Method for preparing printing paste of compound modified starch with adjustable viscosity |
| CN101195978B (en) * | 2008-01-04 | 2010-06-02 | 广西明阳生化科技股份有限公司 | Multicomponent modified starch for papermaking and producing method thereof |
-
2010
- 2010-02-03 CN CN2010101192405A patent/CN101962518B/en not_active Expired - Fee Related
Cited By (24)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102391797B (en) * | 2011-07-09 | 2013-04-24 | 山西大学 | Corn starch adhesive for building and preparation method thereof |
| CN102391797A (en) * | 2011-07-09 | 2012-03-28 | 山西大学 | Corn starch adhesive for building and preparation method thereof |
| CN102585726A (en) * | 2012-03-10 | 2012-07-18 | 广东天银化工实业有限公司 | Preparation method for starch-based biomass latex adhesive |
| CN102585726B (en) * | 2012-03-10 | 2013-04-10 | 广东天银化工实业有限公司 | Preparation method for starch-based biomass latex adhesive |
| CN102732186A (en) * | 2012-07-12 | 2012-10-17 | 华东理工大学 | Modified starch adhesive and method for preparing same |
| CN102732186B (en) * | 2012-07-12 | 2013-12-25 | 华东理工大学 | Modified starch adhesive and method for preparing same |
| CN103773273B (en) * | 2012-10-20 | 2016-02-24 | 中国烟草总公司郑州烟草研究院 | A kind of based on esterification class-pasted starch and the amyloid starchiness cigarette glue of non-gelatinization |
| CN103773273A (en) * | 2012-10-20 | 2014-05-07 | 中国烟草总公司郑州烟草研究院 | Novel amyloid cigarette adhesive based on esterified gelatinized starch and non-gelatinized starch |
| CN103773277B (en) * | 2012-10-20 | 2016-04-06 | 中国烟草总公司郑州烟草研究院 | A kind of based on etherificate class-pasted starch and the amyloid starchiness cigarette glue of non-gelatinization |
| CN104031295B (en) * | 2014-05-09 | 2016-08-24 | 广西农垦明阳生化集团股份有限公司 | A kind of preparation method of tri compound modified tapioca starch |
| CN104031295A (en) * | 2014-05-09 | 2014-09-10 | 广西农垦明阳生化集团股份有限公司 | Preparation method for cassava starch modified by combining three kinds of modification processes |
| CN104017134A (en) * | 2014-06-12 | 2014-09-03 | 上海东升新材料有限公司 | Preparation method and application of amphoteric biological high polymer binder |
| CN104231973A (en) * | 2014-09-05 | 2014-12-24 | 句容市给力包装制品厂 | Quick dry adhesive for corrugated paper box and preparation method of quick dry adhesive |
| CN105947409A (en) * | 2016-05-04 | 2016-09-21 | 太仓市源创包装材料厂 | Anti-microbial type food packaging paper |
| CN107502229A (en) * | 2017-09-07 | 2017-12-22 | 滁州市光威化工有限公司 | A kind of nanocrystal cellulose enhancing maize-starch adhesive modified with oxidizing for making-cigarette and preparation method |
| CN108165204B (en) * | 2018-02-06 | 2019-12-13 | 江西宏大化工有限公司 | Preparation method of starch adhesive for artificial board |
| CN108165204A (en) * | 2018-02-06 | 2018-06-15 | 罗绍庆 | A kind of preparation method of wood-based plate amylum adhesive |
| CN109320619A (en) * | 2018-11-24 | 2019-02-12 | 蚌埠学院 | A kind of preparation method of crosslinking-oxidization jointly modified starch |
| US11603483B2 (en) | 2019-08-16 | 2023-03-14 | Hongsheng Technology (Beijing) Co., Ltd | Environment-friendly oxidation-resisting carton binder and preparation method therefor |
| CN111945466A (en) * | 2020-07-08 | 2020-11-17 | 广东冠豪高新技术股份有限公司 | Water-binding adhesive paper and preparation method thereof |
| CN111945466B (en) * | 2020-07-08 | 2024-06-07 | 广东冠豪高新技术股份有限公司 | Water-stick gummed paper and preparation method thereof |
| CN113088218A (en) * | 2021-05-25 | 2021-07-09 | 佛山市南海华昊华丰淀粉有限公司 | Preparation method and application of starch adhesive for environment-friendly paper bags |
| CN113292949A (en) * | 2021-05-25 | 2021-08-24 | 佛山市南海华昊华丰淀粉有限公司 | Starch adhesive for environment-friendly paper bags, preparation method and application |
| CN113292949B (en) * | 2021-05-25 | 2022-02-22 | 佛山市南海华昊华丰淀粉有限公司 | Starch adhesive for environment-friendly paper bags, preparation method and application |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101962518B (en) | 2012-09-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101962518B (en) | Starch bonding agent, and preparation method and use thereof | |
| ES2289734T5 (en) | Adhesive, aqueous composition, containing a mixture product based on legume starch | |
| CN101945928B (en) | Thermosetting polysaccharides | |
| US4941922A (en) | Starch-based corrugating adhesive containing fibers | |
| CN103038303A (en) | Starch-based compositions for latex replacement | |
| CN101195692B (en) | Diversification premixing method modified starch and producing method thereof | |
| CN101892022A (en) | Starch adhesive for producing corrugated board and preparation method thereof | |
| CN101175808A (en) | Cationic crosslinked starch containing starch compositions and use thereof | |
| CN103030698B (en) | By composite modified starch prepared by four kinds of denaturation methods | |
| CN1911966B (en) | Pretreatment method of starch | |
| CN1816592B (en) | Cationic liquid starchy composition and uses thereof | |
| CN101429743B (en) | Production method of surface sizing agent, sizing agent and use thereof | |
| US4359341A (en) | Starch based adhesives and method therefor | |
| CN102852041B (en) | Preparation method for writing paper | |
| CN101326233A (en) | Lecithin-starches compositions, preparation thereof and paper products having oil and grease resistance, and/or release properties | |
| CN104452448A (en) | Starch surface sizing liquid production process and starch surface sizing liquid | |
| Liu et al. | Functional properties and enzymatic digestibility of cationic and cross-linked cationic ae, wx, and normal maize starch | |
| CN101886352B (en) | Preparation method of starch solution for papermaking surface sizing | |
| CN113429909A (en) | Alkali-gelatinized wet glue and preparation method and application thereof | |
| CN104861849B (en) | Preparation method of high-impact-resistance environment-friendly thermal-insulation textile coating | |
| CN1665900A (en) | Procede de traitement d'ennoblissement d'une nappe fibreuse au moyen d'une composition adhesive a base de polymere(s), contenant une combinaison particuliere de saccharides | |
| CN1522279A (en) | Binding agent composition for roller paste preparation | |
| JP2646135B2 (en) | Adhesive for cardboard | |
| CA2611403A1 (en) | Adhesive composition | |
| CN105860877A (en) | Addition agent for starch adhesive and preparation method and application method of addition agent for starch adhesive |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20120905 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |