CN108383944A - A kind of preparation method of cationic starch/nano-cellulose base water resistant enhancing complex emulsions - Google Patents
A kind of preparation method of cationic starch/nano-cellulose base water resistant enhancing complex emulsions Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F251/00—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F251/00—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof
- C08F251/02—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof on to cellulose or derivatives thereof
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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
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/33—Synthetic macromolecular compounds
- D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
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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
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/33—Synthetic macromolecular compounds
- D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/35—Polyalkenes, e.g. polystyrene
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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
- D21H19/10—Coatings without pigments
- D21H19/14—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
- D21H19/20—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12 comprising macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
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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
- D21H19/56—Macromolecular organic compounds or oligomers thereof obtained by reactions only involving carbon-to-carbon unsaturated bonds
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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
- 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
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Abstract
The present invention provides a kind of preparation method of cationic starch/nano-cellulose base water resistant enhancing complex emulsions, including starch oxidation, mix monomer is made, prepares initiator, reaction step.The reaction：Oxidized starch is introduced into reaction kettle, oxidized starch is heated up, then, while initiator A and initiator B is added dropwise；Initiator was added dropwise after 0.5 2 minutes, started that mix monomer is added dropwise；After the completion of reaction, lauryl alcohol ester is added dropwise, cool down after dripping enhances complex emulsions to get the high water resistant of starch/nano-cellulose base.Composite emulsion obtained by the present invention has had both enhancing and two kinds of functions of water resistant, and water resistant effect is good, and enhancing effect is notable, can significantly improve the quality and class of paper.
Description
Technical field
The present invention relates to the preparation methods that a kind of cationic starch/nano-cellulose base water resistant enhances complex emulsions, belong to
Pulp technology for making paper.
Background technology
During the paper industry in China is in rapid development, while Paper Industry Development, a system is also encountered
The problem of row.How the loss of strength of wastepaper as raw material performance deficiency and high packing belt is made up, and the use of paper making intensifier is then
Effective solution method is provided for the above problem.
The reinforcing agent of early application mainly has starch and natural plant；Starch derivatives was developed later, such as oxidation is formed sediment
Powder, cationic starch, anionic starch and amphoteric starch etc.；Water-soluble cellulose derivative, as carboxymethyl cellulose, methyl are fine
Dimension element and hydroxyethyl cellulose etc., effectively raise the intensity of paper.Later again using high scores such as polyacrylamide, polyamine
Sub- polymer, water-soluble resin are applied in paper industry, achieve better humidification.
Currently, it is to use neutral sizing that medium-to-high grade paper, which is glued total trend,.The extensive neutral sizing agent master of domestic and international application
There are AKD, ASA etc..The practicality of this kind of sizing agent improves water-resistance to a certain extent, but weaker to the raising of intensity.
This cationic starch/nano-cellulose base water resistant enhancing complex emulsions are one kind of starch/nano-cellulose base productions
Product, stability is good, not at gel, changes to pH value insensitive.It can be used as surface water resistant reinforcing agent in paper-making process to use, it is simultaneous
Has the effect of sizing agent and reinforcing agent.Especially nano-cellulose, due to high-crystallinity, high-purity, high Young's modulus,
The advantages that high intensity, high-hydrophilic, hyperfine structure and high grade of transparency, determines that nano-cellulose has very in terms of enhancing
Important application.Because nano-cellulose has larger specific surface area and abundant hydroxyl, paper can be improved by being added in paper
Combination between pulp fibres can be used as the reinforcing agent in pulping and papermaking processes to improve the binding force between paper pulp fiber,
Research in terms of enhancing causes more and more concerns.
Invention content
The problem to be solved in the present invention is to provide a kind of cationic starch/nano-cellulose base water resistant for the above deficiency
The preparation method for enhancing complex emulsions, realizes following goal of the invention：
Using complex emulsions of the present invention, hence it is evident that improve water-resistance, the filler retention of paper, improve ring crush intensity, reduce Cobb
Value.
For achieving the above object, using following technical scheme：
A kind of the step of preparation method of cationic starch/nano-cellulose base water resistant enhancing complex emulsions, preparation method is：
Step 1, starch oxidation
Raw material includes：Cationic starch, AKD wax disk(-sc)s, nano-cellulose suspension, ferrous sulfate, hydrogen peroxide, mass ratio are：
250：25：500~750：1~2.5：75.
The cationic starch is cornstarch, and the degree of substitution of cationic starch is 0.02~0.04；
The AKD wax disk(-sc)s model 1860；
The nano-cellulose suspension solid content is 1%；The nano-cellulose is cotton pulp nano-cellulose, using sulphur
Acid-hydrolysis method is made, and average grain diameter is 150~200nm.
Cationic starch is mixed with AKD wax disk(-sc)s, is heated to 60~70 DEG C, is stirred 30 minutes, mixing speed 120rpm/
min；Then nano-cellulose suspension is added, is warming up to 72 DEG C；Then, the hydrogen peroxide of ferrous sulfate and 30% solid content is added,
Stirring 1 hour, mixing speed 120rpm/min；Make the fully oxidized degradation of starch, obtains oxidized starch.
Mix monomer is made in step 2
Diallylamine pre-processes：The pH value of diallylamine is adjusted to 4-5 with acetic acid, obtains pretreatment diallylamine.
Monomer mixes：By 3- (methacryloxypropyl) propyl trimethoxy silicane, trifluoro propyl methyl cyclotrisiloxane, third
Acrylamide, diallyldimethylammonium chloride, aziridine, styrene, butyl acrylate mixing, obtain mixed liquor；It will locate in advance
It manages diallylamine to be added in above-mentioned mixed liquor, obtains mix monomer.
Described 3- (methacryloxypropyl) propyl trimethoxy silicane：Trifluoro propyl methyl cyclotrisiloxane：Acryloyl
Amine：Diallyldimethylammonium chloride：Pre-process diallylamine：Aziridine：Styrene：The mass ratio of butyl acrylate is
10：1~5：5~10：10：1：3~5：80：60.
Step 3 prepares initiator
The initiator includes initiator A and initiator B.
30% hydrogen peroxide is dissolved in a certain amount of water, dioxygen:The quality of water is 1:10~20, obtain initiator A.
Benzoyl peroxide is dissolved in ethyl acetate, benzoyl peroxide:The mass ratio of ethyl acetate is 1:50~
100, obtain initiator B.
Step 4, reaction
Oxidized starch is introduced into reaction kettle, oxidized starch is warming up to 85 DEG C, then, while initiator A and initiator is added dropwise
B；
After initiator is added dropwise 1 minute, start that mix monomer is added dropwise, mix monomer time for adding is 4.5 hours, and initiator is added dropwise
Time is 5 hours.
The oxidized starch：The mass ratio of mix monomer is 1:1~2.
The initiator A dosage is the 1%~1.5% of mix monomer quality, and initiator B dosage is mix monomer quality
0.3%~0.5%.When dropwise addition, initiator A and initiator B are added dropwise together, and the speed of dropwise addition is different, according to dosage in production process
Valve is adjusted, control time for adding is identical.
After the completion of above-mentioned reaction, 40 DEG C are cooled to, lauryl alcohol ester is slowly added dropwise, time for adding is 15 minutes.
Lauryl alcohol ester is dripped, is stirred 10 minutes, is cooled to 25 DEG C to get the high water resistant enhancing of starch/nano-cellulose base
Complex emulsions.
The dosage of the lauryl alcohol ester be the high water resistant of starch/nano-cellulose base enhance complex emulsions quality 1%~
5%。
Compared with prior art, technical solution of the present invention has the advantages that：
（1）Composite emulsion obtained by the present invention has had both enhancing and water resistant compared with traditional sizing agent and reinforcing agent
Two kinds of functions, and water resistant effect is good, and enhancing effect is notable, can significantly improve the quality and class of paper.Improve paper
Ring crush intensity, reduce Cobb values, this product can reach 25g/m2；The AKD emulsion surface sizing Cobb values of traditional technology are
30g/m2Left and right.The ring crush intensity index of this product is up to 6.0N*m/g, the AKD emulsion surface sizings of traditional technology, lateral loops
Compressive Strength is 5.2N*m/g.
（2）Lotion obtained by the present invention, it can also be used to which water resistant enhancing in slurry has retention height, sizing efficiency high, increases
The advantages that potent fruit is good and emulsion-stabilizing.This product can make filler retention improve 2%.AKD plasm-glue-blending Cobb values：This production
Product can reach 30g/m2, for traditional AKD lotions, using AKD lotion plasm-glue-blending Cobb values up to 35g/m2Left and right.
（3）Present invention process is simple, and reaction condition is mild, small investment, has good economic benefit.
（4）The present invention is used for corrugated paper top sizing, and when the dosage of complex emulsions is 0.5%, paper sizing degree is 25.6g/
m2, water resistant significant effect, ring crush index 7.8Nm/g；Tensile index is 42.7Nm/g, burst index 1.9kPam2/g；
The present invention is used for addition in hygienic paper pulp, dosage 1.5%, the tensile strength of toilet paper vertically and horizontally average out to 59.4N/m,
Reach the standards such as A；
The present invention is used for corrugated paper top sizing, and ton paper dosage is 5kg, and the opacity of paper reaches 85, and folding strength 8 times is indulged
It is 42Nm/g, absorbability 38.6g/m to tensile index2, reach high-class product standard.
Specific implementation mode
A kind of preparation method of 1 cationic starch of embodiment/nano-cellulose base water resistant enhancing complex emulsions
Step 1, starch oxidation
Raw material includes：Cornstarch, AKD wax disk(-sc)s, nano-cellulose suspension, ferrous sulfate, hydrogen peroxide.
The cationic starch is cornstarch, and the degree of substitution of cationic starch is 0.02；
The AKD wax disk(-sc)s model 1860；
The nano-cellulose suspension solid content is 1%；The nano-cellulose is cotton pulp nano-cellulose, using sulphur
Acid-hydrolysis method is made, average grain diameter 150nm.
100kg cornstarch is added in a kettle；Then 10kg AKD wax disk(-sc)s are added, after mixing, is warming up to 60 DEG C, stirs
It mixes 30 minutes, stir speed (S.S.) 120rpm/min；Then 200kg nano-cellulose suspension is added, is warming up to 72 DEG C；Then,
The hydrogen peroxide that 0.4kg ferrous sulfate and 30kg solid contents are 30% is added, stirs 1 hour, mixing speed 120rpm/min；Make
The fully oxidized degradation of starch, obtains oxidized starch.
Mix monomer is made in step 2
Diallylamine pre-processes：The pH value of diallylamine is adjusted to 4-5 with acetic acid, obtains pretreated diallyl
Amine.
Mixing：Weigh respectively 3- (methacryloxypropyl) propyl trimethoxy silicane, trifluoro propyl methyl cyclotrisiloxane,
The matter of acrylamide, diallyldimethylammonium chloride, pretreatment diallylamine, aziridine, styrene, butyl acrylate
Amount is 10kg, 1kg, 5kg, 10kg, 1kg, 3kg, 80kg, 60kg；Above-mentioned monomer is mixed, mix monomer is obtained.
Step 3 prepares initiator
The initiator includes initiator A and initiator B.
It weighs the hydrogen peroxide that 17kg solid contents are 30% to be dissolved in 170kg water, obtains initiator A.
It weighs 0.5kg benzoyl peroxides to be dissolved in 25kg ethyl acetate, obtains initiator B.
Step 4, reaction
Oxidized starch is introduced into reaction kettle, oxidized starch is warming up to 85 DEG C, then, while initiator A and initiator is added dropwise
B。
After initiator is added dropwise 1 minute, start that mix monomer is added dropwise, mix monomer time for adding is 4.5 hours, initiator
Time for adding is 5 hours.
The oxidized starch：The mass ratio of mix monomer is 1:1；The initiator A dosage is mix monomer quality
1%, initiator B dosage be mix monomer quality 0.3%.When dropwise addition, initiator A and initiator B are added dropwise together, the speed of dropwise addition
Degree is different, and valve is adjusted according to dosage in production process, and control time for adding is identical.
After the completion of above-mentioned reaction, 40 DEG C are cooled to, 10kg lauryl alcohol esters are slowly added dropwise, time for adding is 15 minutes.
Lauryl alcohol ester is dripped, stirs 10 minutes, is cooled to 25 DEG C, obtains the high water resistant enhancing of starch/nano-cellulose base
Complex emulsions 1000kg.
The complex emulsions finished product prepared using above-described embodiment 1 is used for corrugated paper top sizing.As a result as follows：
The present embodiment complex emulsions and surface sizing starch are mixed for corrugated paper top sizing, and with traditional polyacrylamide
Reinforcing agent is compared.
Test result shows：
When the dosage of the present embodiment complex emulsions is 0.5%, paper sizing degree is 25.6g/m2, water resistant significant effect, ring pressure refers to
Number 7.8Nm/g；Tensile index is 42.7Nm/g, burst index 1.9kPam2/g；
And polyacrylamide reinforcing agent is used, when dosage is 0.5%, paper sizing degree is 97.5 g/m2, do not have water-resistance, and
Ring crush index 6.4Nm/g；Tensile index is 38.2Nm/g, burst index 1.6kPam2/g；
As it can be seen that the sizing efficiency of complex emulsions of the present invention is notable, enhancing effect is apparent, and water-resistance is good, hence it is evident that improves paper
Total quality.
A kind of preparation method of 2 cationic starch of embodiment/nano-cellulose base water resistant enhancing complex emulsions
Step 1, starch oxidation
Raw material includes：Cationic starch, AKD wax disk(-sc)s, nano-cellulose suspension, ferrous sulfate, hydrogen peroxide.The cation
Starch is cornstarch, and the degree of substitution of cationic starch is 0.03；
The AKD wax disk(-sc)s model 1860；
The nano-cellulose suspension solid content is 1%；The nano-cellulose is cotton pulp nano-cellulose, using sulphur
Acid-hydrolysis method is made, average grain diameter 180nm.
100kg cornstarch, degree of substitution 0.03 are added in a kettle；Then 10kg AKD wax disk(-sc)s are added, are warming up to
It 60 DEG C, stirs 30 minutes, mixing speed 120rpm/min；Then 250kg nano-cellulose suspension is added, is warming up to 72
℃；Then the hydrogen peroxide that 0.8 kg ferrous sulfate and 30kg solid contents are 30% is added, stirs 1 hour, mixing speed is
120rpm/min；Make the fully oxidized degradation of starch, obtains oxidized starch.
Mix monomer is made in step 2
Diallylamine pre-processes：The pH value of diallylamine is adjusted to 4-5 with acetic acid, obtains pretreatment diallylamine.
Mixing：Weigh respectively 3- (methacryloxypropyl) propyl trimethoxy silicane, trifluoro propyl methyl cyclotrisiloxane,
The matter of acrylamide, diallyldimethylammonium chloride, pretreatment diallylamine, aziridine, styrene, butyl acrylate
Amount is 10kg, 2.5kg, 7.5kg, 10kg, 1kg, 4kg, 80kg, 60kg；Above-mentioned monomer is mixed, mix monomer is obtained.
Step 3 prepares initiator
The initiator includes initiator A and initiator B.
It weighs 22kg hydrogen peroxide to be dissolved in 330kg water, obtains initiator A.
It weighs 0.7kg benzoyl peroxides to be dissolved in 53kg ethyl acetate, obtains initiator B.
The initiation system that initiator A and initiator B are reacted as the present invention.
Step 4, reaction
Oxidized starch is introduced into reaction kettle, oxidized starch is warming up to 85 DEG C, then, while initiator A and initiator is added dropwise
B；
After initiator is added dropwise 1 minute, start that mix monomer is added dropwise, mix monomer time for adding is 4.5 hours, and initiator is added dropwise
Time is 5 hours.
The oxidized starch：The mass ratio of mix monomer is 1:1.5.
The initiator A dosage is the 1.2% of mix monomer quality, and initiator B dosage is mix monomer quality
0.4%.When dropwise addition, initiator A and initiator B are added dropwise together, and the speed of dropwise addition is different, and valve is adjusted according to dosage in production process
Door, control time for adding are identical.
After the completion of above-mentioned reaction, 40 DEG C are cooled to, 25kg lauryl alcohol esters are slowly added dropwise, time for adding is 15 minutes.It is added dropwise
Complete lauryl alcohol ester stirs 10 minutes, is cooled to 25 DEG C, obtains the high water resistant enhancing complex emulsions of starch/nano-cellulose base
1000kg。
The present embodiment complex emulsions are used in hygienic paper pulp apply, and are carried out with traditional Polyamide-Polyamsne-Epichlorohydrin
Comparison.
Test result shows：
Be added in hygienic paper pulp with the present embodiment complex emulsions, dosage 1.5%, and with traditional polyamide polyamines epoxy chlorine
Propane is compared.
Test result shows：
After the present embodiment complex emulsions of addition 1.5%, the tensile strength of 150 pumpings/two-ply toilet tissue vertically and horizontally average out to 59.4N/
M reaches the standards such as A；And under same dosage, after adding Polyamide-Polyamsne-Epichlorohydrin, the anti-tensile of 150/ two-ply toilet tissue is strong
Spend vertically and horizontally average out to 54.0N/m；
Illustrate that complex emulsions of the present invention significantly improve the wet strength of paper.
A kind of preparation method of 3 cationic starch of embodiment/nano-cellulose base water resistant enhancing complex emulsions
Step 1, starch oxidation
Raw material includes：Cationic starch, AKD wax disk(-sc)s, nano-cellulose suspension, ferrous sulfate, hydrogen peroxide；The cation
Starch is cornstarch, and the degree of substitution of cationic starch is 0.04；
The AKD wax disk(-sc)s model 1860；
The nano-cellulose suspension solid content is 1%；The nano-cellulose is cotton pulp nano-cellulose, using sulphur
Acid-hydrolysis method is made, average grain diameter 200nm.
100kg cornstarch is added in a kettle, 10kg AKD are then added, after mixing, is warming up to 60 DEG C, stirring 30
Minute, mixing speed 120rpm/min；Then 300kg nano-cellulose suspension is added, is warming up to 72 DEG C；Then, it is added
The hydrogen peroxide that 1kg ferrous sulfate and 30kg solid contents are 30%, is stirred 1 hour, mixing speed 120rpm/min；Starch is set to fill
Divide oxidative degradation, obtains oxidized starch.
Mix monomer is made in step 2
Diallylamine pre-processes：The pH value of diallylamine is adjusted to 4-5 with acetic acid, obtains pretreatment diallylamine.
Mixing：Weigh respectively 3- (methacryloxypropyl) propyl trimethoxy silicane, trifluoro propyl methyl cyclotrisiloxane,
The matter of acrylamide, diallyldimethylammonium chloride, pretreatment diallylamine, aziridine, styrene, butyl acrylate
Amount is 10kg, 5kg, 10kg, 10kg, 1kg, 5kg, 80kg, 60kg, and above-mentioned monomer is mixed, mix monomer is obtained.
Step 3 prepares initiator
The initiator includes initiator A and initiator B.
It weighs 27kg hydrogen peroxide to be dissolved in 540kg water, obtains initiator A.
It weighs 0.9kg benzoyl peroxides to be dissolved in 90kg ethyl acetate, obtains initiator B.
Step 4, reaction
Oxidized starch is introduced into reaction kettle, oxidized starch is warming up to 85 DEG C, then, while initiator A and initiator is added dropwise
B；
After initiator is added dropwise 1 minute, start that mix monomer is added dropwise, mix monomer time for adding is 4.5 hours, and initiator is added dropwise
Time is 5 hours.
The oxidized starch：The mass ratio of mix monomer is 1: 2.
The initiator A dosage is the 1.5% of mix monomer quality, and initiator B dosage is mix monomer quality
0.5%.When dropwise addition, initiator A and initiator B are added dropwise together, and the speed of dropwise addition is different, and valve is adjusted according to dosage in production process
Door, control time for adding are identical.
After the completion of above-mentioned reaction, 40 DEG C are cooled to, 50 kg lauryl alcohol esters are slowly added dropwise, time for adding is 15 minutes.It is added dropwise
Complete lauryl alcohol ester stirs 10 minutes, is cooled to 25 DEG C, obtains the high water resistant enhancing complex emulsions of starch/nano-cellulose base
1000kg。
The present embodiment complex emulsions finished product is used for corrugated paper.As a result as follows：
Be mixed for corrugated paper top sizing with the present embodiment complex emulsions and surface sizing starch, and with AKD sizing emulsions into
Row comparison.
Test result shows：Ton paper dosage is 5kg, and after the present embodiment complex emulsions, the opacity of paper reaches
85, folding strength 8 times, longitudinal tensile index is 42Nm/g, absorbability 38.6g/m2, reach high-class product standard；
And under same dosage, after carrying out top sizing using AKD, the opacity of paper reaches 80, folding strength 6 times, Zong Xiangkang
Tensile index is 40Nm/g, absorbability 39.52g/m2；
As it can be seen that lotion of the present invention has significant enhancing paper opacity, folding strength, tensile index, the effect of absorbability is reduced
Fruit.
In addition to specified otherwise, percentage of the present invention is mass percent, and the ratio is mass ratio.
Finally it should be noted that：The foregoing is only a preferred embodiment of the present invention, is not intended to restrict the invention,
It, for those skilled in the art, still can be with although describing the invention in detail with reference to the foregoing embodiments
Technical scheme described in the above embodiments is modified or equivalent replacement of some of the technical features.It is all
Within the spirit and principles in the present invention, any modification, equivalent replacement, improvement and so on should be included in the guarantor of the present invention
Within the scope of shield.
Claims (10)
1. a kind of preparation method of cationic starch/nano-cellulose base water resistant enhancing complex emulsions, it is characterised in that：Including
Starch oxidation is made mix monomer, prepares initiator, reaction step.
2. a kind of preparation side of cationic starch according to claim 1/nano-cellulose base water resistant enhancing complex emulsions
Method, it is characterised in that：The reaction：Oxidized starch is introduced into reaction kettle, oxidized starch is heated up, then, is added dropwise simultaneously
Initiator A and initiator B；After initiator is added dropwise 0.5-2 minutes, start that mix monomer is added dropwise；After the completion of reaction, it is added dropwise 12
Alcohol ester, cool down after dripping enhances complex emulsions to get the high water resistant of starch/nano-cellulose base.
3. a kind of preparation side of cationic starch according to claim 1/nano-cellulose base water resistant enhancing complex emulsions
Method, it is characterised in that：The obtained mix monomer：Including diallylamine pretreatment and monomer mixing；The monomer is mixed
It closes：By 3- (methacryloxypropyl) propyl trimethoxy silicane, trifluoro propyl methyl cyclotrisiloxane, acrylamide, two allyls
Base alkyl dimethyl ammonium chloride, aziridine, styrene, butyl acrylate mixing, obtain mixed liquor；Pretreatment diallylamine is added
Enter in above-mentioned mixed liquor, obtains mix monomer.
4. a kind of preparation side of cationic starch according to claim 3/nano-cellulose base water resistant enhancing complex emulsions
Method, it is characterised in that：Described 3- (methacryloxypropyl) propyl trimethoxy silicane：Trifluoro propyl methyl cyclotrisiloxane：
Acrylamide：Diallyldimethylammonium chloride：Pre-process diallylamine：Aziridine：Styrene：The matter of butyl acrylate
Amount is than being 10：1~5：5~10：10：1：3~5：80：60.
5. a kind of preparation side of cationic starch according to claim 1/nano-cellulose base water resistant enhancing complex emulsions
Method, it is characterised in that：Described prepares initiator：Initiator is composite initiator, including initiator A and initiator B.
6. a kind of preparation side of cationic starch according to claim 5/nano-cellulose base water resistant enhancing complex emulsions
Method, it is characterised in that：The initiator A：30% hydrogen peroxide is dissolved in a certain amount of water and obtains initiator A, dioxygen:The matter of water
Amount is 1:10~20.
7. a kind of preparation side of cationic starch according to claim 5/nano-cellulose base water resistant enhancing complex emulsions
Method, it is characterised in that：The initiator B：Benzoyl peroxide is dissolved in ethyl acetate and obtains initiator B, benzoyl peroxide
Formyl:The mass ratio of ethyl acetate is 1:50~100.
8. a kind of preparation side of cationic starch according to claim 1/nano-cellulose base water resistant enhancing complex emulsions
Method, it is characterised in that：The starch oxidation：Raw material includes cationic starch, AKD wax disk(-sc)s, nano-cellulose suspension, sulfuric acid Asia
Iron, hydrogen peroxide, mass ratio are：250：25：500~750：1~2.5：75.
9. a kind of preparation side of cationic starch according to claim 2/nano-cellulose base water resistant enhancing complex emulsions
Method, it is characterised in that：The oxidized starch：The mass ratio of mix monomer is 1:1~2.
10. a kind of preparation side of cationic starch according to claim 2/nano-cellulose base water resistant enhancing complex emulsions
Method, it is characterised in that：The initiator A dosage is the 1%~1.5% of mix monomer quality, and initiator B dosage is mix monomer
The 0.3%~0.5% of quality.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1323318A (en) * | 1998-10-16 | 2001-11-21 | 美国拜尔公司 | Improved paper sizing agents and methods of making the agents and sizing paper |
| EP0789725B1 (en) * | 1994-11-03 | 2004-03-24 | Hercules Incorporated | Cellulose ethers in emulsion polymerization dispersions |
| CN104894914A (en) * | 2015-05-05 | 2015-09-09 | 浙江宜佳新材料有限公司 | Preparation method of modified impregnated paper body paper |
| CN104988796A (en) * | 2015-05-29 | 2015-10-21 | 常州博润新材料科技有限公司 | Enhanced multifunctional surface sizing assistant for papermaking and preparation method thereof |
| CN106368059A (en) * | 2016-08-29 | 2017-02-01 | 上海东升新材料有限公司 | Preparing method of surface sizing agent for corrugated paper, product and application of surface sizing agent |
-
2018
- 2018-01-17 CN CN201810044910.8A patent/CN108383944B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0789725B1 (en) * | 1994-11-03 | 2004-03-24 | Hercules Incorporated | Cellulose ethers in emulsion polymerization dispersions |
| CN1323318A (en) * | 1998-10-16 | 2001-11-21 | 美国拜尔公司 | Improved paper sizing agents and methods of making the agents and sizing paper |
| CN104894914A (en) * | 2015-05-05 | 2015-09-09 | 浙江宜佳新材料有限公司 | Preparation method of modified impregnated paper body paper |
| CN104988796A (en) * | 2015-05-29 | 2015-10-21 | 常州博润新材料科技有限公司 | Enhanced multifunctional surface sizing assistant for papermaking and preparation method thereof |
| CN106368059A (en) * | 2016-08-29 | 2017-02-01 | 上海东升新材料有限公司 | Preparing method of surface sizing agent for corrugated paper, product and application of surface sizing agent |
Non-Patent Citations (1)
| Title |
|---|
| 姜雪松等: "《印刷材料及适性》", 31 August 2016, 东北林业大学出版社 * |
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