CN108018739A - A kind of nano-starch adhesive and preparation method thereof - Google Patents
A kind of nano-starch adhesive and preparation method thereof Download PDFInfo
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- CN108018739A CN108018739A CN201711339430.6A CN201711339430A CN108018739A CN 108018739 A CN108018739 A CN 108018739A CN 201711339430 A CN201711339430 A CN 201711339430A CN 108018739 A CN108018739 A CN 108018739A
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H19/00—Coated paper; Coating material
- D21H19/36—Coatings with pigments
- D21H19/44—Coatings with pigments characterised by the other ingredients, e.g. the binder or dispersing agent
- D21H19/54—Starch
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B31/00—Preparation of derivatives of starch
- C08B31/02—Esters
- C08B31/04—Esters of organic acids, e.g. alkenyl-succinated starch
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B31/00—Preparation of derivatives of starch
- C08B31/18—Oxidised starch
- C08B31/185—Derivatives of oxidised starch, e.g. crosslinked oxidised starch
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H19/00—Coated paper; Coating material
- D21H19/36—Coatings with pigments
- D21H19/44—Coatings with pigments characterised by the other ingredients, e.g. the binder or dispersing agent
- D21H19/64—Inorganic compounds
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/06—Paper forming aids
- D21H21/12—Defoamers
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
- D21H21/16—Sizing or water-repelling agents
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
- D21H21/18—Reinforcing agents
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Biochemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Paper (AREA)
Abstract
The invention discloses a kind of nano-starch adhesive and preparation method thereof, preparation method includes the following steps：Ative starch and tap water are stirred, heating adds oxidant and reacted, and after reaction, adds reducing agent, reduces the oxidant not reacted, then adjust pH with sodium bicarbonate solution, carries out esterification.After reaction, neutralized with acid, clear water washing, is filtered by vacuum and is dried into starch granules；The starch granules of gained is deployed into starch milk, appropriate dispersant, defoamer and water are added after gelatinization, and to be made into starch adhesive spare；The starch adhesive of gained is poured into rod pin type nanometer sand mill and carries out wet grinding, abrasive media is zirconium oxide bead, through multiple circular grinding, is discharged through big flow separator, finally obtains nano-starch adhesive.Nano-starch adhesive of the present invention, it is characterised in that there is stronger cohesion, chemistry and mechanical stability, free from extraneous odour, makes paper have more preferable water-resistance and tensile strength.
Description
Technical field
The invention belongs to papermaking coating auxiliary agent technical field, and in particular to a kind of nano-starch adhesive and its preparation side
Method.
Background technology
In order to improve the various qualities of paper, it has to rely on various papermaking chemical products, general way is in copy paper system
Papermaking chemical product is added in system, such as paper making intensifier, sizing agent.But papermaking chemical product is added in wet end, is often caused white
Water l oad aggravates, and paper waste reuse is difficult；On the other hand, the chemical assistant of wet end addition, a part outflow with water, a part
Consumed by the rubbish in system, the using effect of chemical assistant is had a greatly reduced quality.For this reason, more and more papermaking enterprise selection tables
The mode of face sizing coating improves the quality of paper.
The performance of coating paper depends primarily upon coating, the main component of coating be pigment, adhesive and other auxiliary agents and
Water.Adhesive is the important component of coating, its effect is pigment is mutually bonded, while pigment is glued with body paper surface
Close, secondly adhesive can also adjust the absorption of printing ink, to obtain the balance of ink solidification and ink gloss, in addition adhesive
The effect of protecting colloid is also acted as in coating, control coating stability and mobility therefore, the master as coating for paper
The adhesive of one of component is wanted to play decisive role to the quality of coating and paper.
Starch base nanometer adhesive is a kind of adhesive product based on biology, and nanoscale is formed by starch conversion
Grain, has stable spacial framework.The volume of native starch particle is about 30 μm, by modified and mechanism by this
A little particles are converted into the nano particle of 400~500nm, and under such volume, the surface area of nano-particle is than natural grain
The more hundreds of times of son, therefore there is stronger cohesion, chemistry and mechanical stability, free from extraneous odour, makes paper have more preferable water-resistance
And tensile strength.
The content of the invention
The present invention wants the key problem in technology problem that emphasis solves to improve the cohesive force and water-resistance of starch base nanometer adhesive：
Natural or unmodified ative starch has very high viscosity, and property is unstable, easy aging, and water-resistance is poor, it is difficult to directly as
The adhesive of coating using, it is necessary to carry out denaturation treatment to it, and combine follow-up mechanical treatment come reach improve cohesive force and
Water-resistance.Therefore, the present invention provides a kind of new preparation method of nano-starch adhesive.Nano-starch glue of the present invention
Glutinous agent, it is characterised in that there is stronger cohesion, chemistry and mechanical stability, free from extraneous odour, makes paper have more preferable water-resistance
And tensile strength.
For this reason, the present invention adopts the following technical scheme that：A kind of nano-starch adhesive and preparation method thereof, including it is following
Step：
（1）Ative starch and tap water are stirred, are deployed into 40% starch milk, pH value is adjusted to 7- with sodium hydroxide solution
11, it is warming up to 30-60 DEG C, adds oxidant and reacted, pH value is maintained in 7-11 with sodium hydroxide solution in reaction process,
Insulation reaction 1h, after reaction, adds reducing agent, reduces the oxidant not reacted, react 10 minutes, then use bicarbonate
Sodium solution adjusts pH in 7-11, adds esterifying agent, be adjusted to 30-60 DEG C of reaction 0.5-3 it is small when, after reaction, neutralized with acid,
Clear water washs, and is filtered by vacuum and is dried into starch granules at 30-50 DEG C；
The ative starch is the one or more in tapioca, cornstarch, wheaten starch and farina.
The oxidant is the one or more in sodium hypochlorite, hydrogen peroxide, potassium permanganate and ammonium persulfate.
The esterifying agent is the one or more in vinylacetate and acetic anhydride.
The reducing agent is sodium hydrogensulfite, the one or more in sodium sulfite, sodium sulphate and ferrous sulfate.
The acid is the one or more in hydrochloric acid, sulfuric acid, phosphoric acid and acetic acid.
First ative starch is modified, is specifically first aoxidized, carries out acetylated modification afterwards, the purpose of oxidation is to make shallow lake
Powder molecular chain rupture, is easy to follow-up working process, the purpose of acetylation is to introduce lipophilic group i.e. hydrophobic grouping, so as to improve
The water-resistance and adhesion strength of starch.The hydrophobically modified of starch mainly introduces alkyl fatty acid in starch molecular chain, reacts
Based on esterification.Acetate starch is aoxidized in addition to possessing the advantages of general modified starch, there is strong affinity to fiber
Can, it can be kept firmly on fiber, simultaneously because introducing hydrophobic group, after carrying out Paper Coating with it, can improve
Paper water repelling property；And the surface strength of paper can be improved and fiber and interfibrous combination power, the printing for improving paper are fitted
Ying Xing.
The oxidizer is the 2%-10% of ative starch oven-dry weight.
The esterifying agent dosage is the 4%-8% of ative starch oven-dry weight.
The reducing agent dosage is the 1%-5% of ative starch oven-dry weight.
（2）By step（1）The starch granules of gained is deployed into 40-50% starch milks, and pH value is adjusted to 6.5-7.5 after gelatinization,
Adding appropriate dispersant, defoamer and water, to be made into starch adhesive spare.
The dispersant is nonionic surfactant PE-6200, surfactant D ynol60, wetting dispersing agent
One or more in CF-10 and nonionic surfactant LF900.
The defoamer is water-soluble organic silicon class Q-119, Y-610, the siliceous class DF-886 of oiliness and the siliceous class of oiliness
One or more in DF-133.
The dispersant dosage is the 0.05%-3% of ative starch oven-dry weight.
The defoamer dosage is the 0.05%-1% of ative starch oven-dry weight.
（3）By step（2）The amylan of gained pours into rod pin type nanometer sand mill and carries out wet grinding, and abrasive media is
The zirconium oxide bead of 0.3-0.4mm, equipment rotating speed are 2000-4000rpm, by multiple circular grinding, are arranged through big flow separator
Go out, finally obtain the nano-starch adhesive that particle diameter is 300-500nm, milling time is 80-180 minutes, solid content 20-
30%。
The advantage of the invention is that：Starch granules is converted into by receiving for 400~500nm by modified and mechanism
Rice grain, under such volume, the surface area of the nano-particle hundreds of times more than natural particulates, therefore cohered with stronger
Power, chemistry and mechanical stability, free from extraneous odour, makes paper have more preferable water-resistance and tensile strength.
Embodiment
By the embodiment content that the present invention is further explained, and protection scope of the present invention be not intended to be limited to it is following
Embodiment, is not limitation of the invention.
Embodiment 1
（1）200g tapiocas, 200g tap water are added in the three-necked flask of electric mixer and constant temperature water bath apparatus is equipped with
With 72.7g sodium hypochlorite（Effective chlorine density 5.5%）It is stirred, adjusts pH value to 9 with sodium hydroxide solution, be warming up to 50 DEG C
Reacted, maintain pH value 9 with sodium hydroxide solution in reaction process, insulation reaction 1h.After reaction, it is sub- to add 2g
Niter cake, reduces the sodium hypochlorite that does not react, reacts 10 minutes, then adjusts pH 9 with sodium bicarbonate solution, adds 8g
Vinylacetate, be adjusted to 30 DEG C reaction 2 it is small when.After reaction, it is neutralized with hydrochloric acid, clear water washing, filters and in 40 DEG C of bakings
It is dry, obtain starch granules 160g（Loss about 20%）；
（2）By step（1）The 160g starch granules of gained adds 240g water and is deployed into 40% starch milk, is adjusted to pH value after gelatinization
It is spare that 7, addition 1.6g surfactant, 0.8g defoamers and 138g water are made into 30% starch adhesive；
（3）By step（2）The amylan of gained pours into rod pin type nanometer sand mill and carries out wet grinding, prepares 40g water and is grinding
Midway is diluted according to sample state, and abrasive media is the zirconium oxide bead of 0.3-0.4mm, and equipment rotating speed is 2500rpm, is passed through
Multiple circular grinding, is discharged through big flow separator, finally obtains the nano-starch glue that particle diameter is 345nm, milling time 135
Minute, nano-starch adhesive solid content is about 28%.
Embodiment 2
（1）180g tapiocas, 100g tap water are added in the three-necked flask of electric mixer and constant temperature water bath apparatus is equipped with
With 181.8g sodium hypochlorite（Effective chlorine density 5.5%）It is stirred, adjusts pH value to 10 with sodium hydroxide solution, be warming up to 60
DEG C reacted, maintain pH value 10 with sodium hydroxide solution in reaction process, insulation reaction 1h.After reaction, add
3.6g sodium hydrogensulfites, reduce the sodium hypochlorite that does not react, react 10 minutes, then adjust pH 9 with sodium bicarbonate solution,
Add 8g vinylacetates, be adjusted to 30 DEG C reaction 1 it is small when.After reaction, be neutralized with hydrochloric acid, clear water washing, filter and
40 DEG C of drying, obtain starch granules 145g（Loss about 20%）；
（2）By step（1）The 145g starch granules of gained adds 218g water and is deployed into 40% starch milk, is adjusted to pH value after gelatinization
It is spare that 7, addition 1.4g surfactant, 0.7g defoamers and 118g water are made into 30% starch adhesive；
（3）By step（2）The amylan of gained pours into rod pin type nanometer sand mill and carries out wet grinding, prepares 97g water and is grinding
Midway is diluted according to sample state, and abrasive media is the zirconium oxide bead of 0.3-0.4mm, and equipment rotating speed is 2400rpm, is passed through
Multiple circular grinding, is discharged through big flow separator, finally obtains the nano-starch glue that particle diameter is 349nm, milling time 130
Minute, nano-starch adhesive solid content is about 25%.Embodiment 3
（1）200g tapiocas, 100g tap water are added in the three-necked flask of electric mixer and constant temperature water bath apparatus is equipped with
With 218.2g sodium hypochlorite（Effective chlorine density 5.5%）It is stirred, adjusts pH value to 9 with sodium hydroxide solution, be warming up to 40
DEG C reacted, maintain pH value 9 with sodium hydroxide solution in reaction process, insulation reaction 1h.After reaction, 6g is added
Sodium hydrogensulfite, reduces the sodium hypochlorite that does not react, reacts 10 minutes, then adjusts pH 10 with sodium bicarbonate solution, adds
12g vinylacetates, be adjusted to 35 DEG C reaction 2 it is small when.After reaction, it is neutralized with hydrochloric acid, clear water washing, filters and 40
DEG C drying, obtain starch granules 160g（Loss about 20%）；
（2）By step（1）The 160g starch granules of gained adds 240g water and is deployed into 40% starch milk, is adjusted to pH value after gelatinization
It is spare that 7, addition 1.6g surfactant, 0.8g defoamers and 138g water are made into 30% starch adhesive；
（3）By step（2）The amylan of gained pours into rod pin type nanometer sand mill and carries out wet grinding, prepares 40g water and is grinding
Midway is diluted according to sample state, and abrasive media is the zirconium oxide bead of 0.3-0.4mm, and equipment rotating speed is 2500rpm, is passed through
Multiple circular grinding, is discharged through big flow separator, finally obtains the nano-starch glue that particle diameter is 375nm, milling time 123
Minute, nano-starch adhesive solid content is about 28%.
Claims (8)
1. a kind of nano-starch adhesive and preparation method thereof, it is characterised in that comprise the following steps：
（1）Ative starch and tap water are stirred, are deployed into 40% starch milk, pH value is adjusted to 7- with sodium hydroxide solution
11, it is warming up to 30-60 DEG C, adds oxidant and reacted, pH value is maintained in 7-11 with sodium hydroxide solution in reaction process,
Insulation reaction 1h, after reaction, adds reducing agent, reduces the oxidant not reacted, react 10 minutes, then use bicarbonate
Sodium solution adjusts pH in 7-11, adds esterifying agent, be adjusted to 30-60 DEG C of reaction 0.5-3 it is small when, after reaction, neutralized with acid,
Clear water washs, and is filtered by vacuum and is dried into starch granules at 30-50 DEG C；
（2）By step（1）The starch granules of gained is deployed into 40-50% starch milks, and pH value is adjusted to 6.5-7.5 after gelatinization, adds
It is spare that appropriate dispersant, defoamer and water are made into starch adhesive；
（3）By step（2）The starch adhesive of gained pours into rod pin type nanometer sand mill and carries out wet grinding, and abrasive media is
The zirconium oxide bead of 0.3-0.4mm, equipment rotating speed are 2000-4000rpm, by multiple circular grinding, are arranged through big flow separator
Go out, finally obtain the nano-starch adhesive that particle diameter is 300-500nm, milling time is 80-180 minutes, solid content 20-
30%。
A kind of 2. nano-starch adhesive according to claim 1 and preparation method thereof, it is characterised in that：Step（1）Institute
The ative starch stated is the one or more in tapioca, cornstarch, wheaten starch and farina.
A kind of 3. nano-starch adhesive according to claim 1 and preparation method thereof, it is characterised in that：Step（1）Institute
The oxidant stated is the one or more in sodium hypochlorite, hydrogen peroxide, potassium permanganate and ammonium persulfate, and dosage is formed sediment to be former
The 2%-10% of powder oven-dry weight.
A kind of 4. nano-starch adhesive according to claim 1 and preparation method thereof, it is characterised in that：The esterification
Agent is the one or more in vinylacetate and acetic anhydride, and dosage is the 4%-8% of ative starch oven-dry weight.
A kind of 5. nano-starch adhesive according to claim 1 and preparation method thereof, it is characterised in that：Step（1）Institute
The reducing agent stated is sodium hydrogensulfite, the one or more in sodium sulfite, sodium sulphate and ferrous sulfate, and dosage is formed sediment to be former
The 1%-5% of powder oven-dry weight.
A kind of 6. nano-starch adhesive according to claim 1 and preparation method thereof, it is characterised in that：Step（1）Institute
The acid stated is the one or more in hydrochloric acid, sulfuric acid, phosphoric acid and acetic acid.
A kind of 7. nano-starch adhesive according to claim 1 and preparation method thereof, it is characterised in that：Step（2）Institute
The dispersant stated is nonionic surfactant PE-6200, surfactant D ynol60, wetting dispersing agent CF-10 and it is non-from
One or more in sub- surfactant LF900, dosage are the 0.05%-3% of ative starch oven-dry weight.
A kind of 8. nano-starch adhesive according to claim 1 and preparation method thereof, it is characterised in that：Step（2）Institute
The defoamer stated is in water-soluble organic silicon class Q-119, Y-610, the siliceous class DF-886 of oiliness and the siliceous class DF-133 of oiliness
One or more, dosage are the 0.05%-1% of ative starch oven-dry weight.
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Cited By (9)
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| CN108824078A (en) * | 2018-07-01 | 2018-11-16 | 王琪宇 | A kind of preparation method of corrugated paper top sizing new material |
| CN108978211A (en) * | 2018-08-01 | 2018-12-11 | 江西博世达科技有限公司 | Recompounded multielement method starch size and preparation method thereof |
| CN109186368A (en) * | 2018-11-08 | 2019-01-11 | 东信烟花集团有限公司 | A kind of packaging method of fireworks and firecrackers nozzle |
| CN109811587A (en) * | 2019-03-20 | 2019-05-28 | 中冶纸业银河有限公司 | A kind of fluting medium surface size and its preparation method and application |
| CN110343485A (en) * | 2019-08-16 | 2019-10-18 | 严佳飞 | A kind of preparation method aoxidizing anticoagulant precipitating powder adhesive |
| CN112111017A (en) * | 2020-09-03 | 2020-12-22 | 绿色轻化科技发展(北京)有限公司 | Degradable cassava acetate starch, resin thereof, preparation method and application of degradable cassava acetate starch and resin |
| CN112259734A (en) * | 2020-10-21 | 2021-01-22 | 常州大学 | Lithium ion battery negative electrode polymer binder and preparation method and application thereof |
| CN112482083A (en) * | 2020-11-24 | 2021-03-12 | 中国制浆造纸研究院有限公司 | Starch-based compound capable of improving oil resistance of paper |
| CN115678467A (en) * | 2022-11-08 | 2023-02-03 | 江苏兴达文具集团有限公司 | Nano starch type solid gum and production method thereof |
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Cited By (13)
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| CN108824078A (en) * | 2018-07-01 | 2018-11-16 | 王琪宇 | A kind of preparation method of corrugated paper top sizing new material |
| CN108978211A (en) * | 2018-08-01 | 2018-12-11 | 江西博世达科技有限公司 | Recompounded multielement method starch size and preparation method thereof |
| CN109186368B (en) * | 2018-11-08 | 2021-06-22 | 东信烟花集团有限公司 | Packaging method for firework and firecracker barrel opening |
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