CN108383944B - Preparation method of cationic starch/nano-cellulose-based water-resistant reinforced composite emulsion - Google Patents
Preparation method of cationic starch/nano-cellulose-based water-resistant reinforced composite emulsion 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
Abstract
The invention provides a preparation method of cationic starch/nano cellulose base water-resistant reinforced composite emulsion, which comprises the steps of starch oxidation, mixed monomer preparation, initiator preparation and reaction. The reaction comprises the following steps: introducing oxidized starch into a reaction kettle, heating the oxidized starch, and then simultaneously dropwise adding an initiator A and an initiator B; after the initiator is dripped for 0.5 to 2 minutes, the mixed monomer is dripped; after the reaction is finished, the dodecyl glycol ester is dripped, and the temperature is reduced after the dripping is finished, so that the starch/nano cellulose base high-water-resistance reinforced composite emulsion is obtained. The composite emulsion prepared by the invention has the functions of strengthening and resisting water, has good water-resisting effect and obvious strengthening effect, and can obviously improve the quality and the grade of paper.
Description
Technical Field
The invention relates to a preparation method of cationic starch/nano-cellulose-based water-resistant reinforced composite emulsion, belonging to the technical field of papermaking.
Background
In the process of rapid development of the paper industry in China, a series of problems are encountered while the paper industry is developed. The use of the paper-making reinforcing agent provides an effective solution to the problems of the insufficient performance of the waste paper raw material and the strength loss caused by high filler.
Early used enhancers were mainly starch and natural vegetable gums; later, starch derivatives such as oxidized starch, cationic starch, anionic starch, amphoteric starch, and the like have been developed; water-soluble cellulose derivatives, such as carboxymethyl cellulose, methyl cellulose, hydroxyethyl cellulose and the like, effectively improve the strength of the paper. Later, high polymer polymers such as polyacrylamide and polyamine and water-soluble resin are applied to the paper industry, and a better reinforcing effect is achieved.
At present, the general trend in sizing medium and high grade paper is to use neutral sizing. Neutral sizing agents widely applied at home and abroad mainly comprise AKD, ASA and the like. The use of such sizing agents improves water resistance to some extent, but the improvement in strength is weak.
The cationic starch/nano cellulose base water-resistant reinforced composite emulsion is a starch/nano cellulose base product, has good stability, does not form gel and is insensitive to pH value change. The surface water-resistant reinforcing agent can be used as a surface water-resistant reinforcing agent in the papermaking process, and has the functions of a sizing agent and a reinforcing agent. Especially, the nano-cellulose has the advantages of high crystallinity, high purity, high Young modulus, high strength, high hydrophilicity, superfine structure, high transparency and the like, so that the nano-cellulose has very important application in the aspect of reinforcement. Because the nano-cellulose has larger specific surface area and abundant hydroxyl groups, the nano-cellulose can be added into paper to improve the bonding between pulp fibers, thereby improving the bonding force between the pulp fibers, and can be used as a reinforcing agent in the pulping and papermaking process, and the research on the reinforcing aspect draws more and more attention.
Disclosure of Invention
The invention aims to solve the problems and provides a preparation method of cationic starch/nano cellulose base water-resistant reinforced composite emulsion, which realizes the following purposes:
the composite emulsion of the invention can obviously improve the water resistance and the filler retention rate of paper, improve the ring crush strength and reduce the Cobb value.
In order to realize the purpose of the invention, the following technical scheme is adopted:
a preparation method of cationic starch/nano cellulose base water-resistant reinforced composite emulsion comprises the following steps:
step 1, starch oxidation
The raw materials comprise: cationic starch, AKD wax flakes, nano-cellulose suspension, ferrous sulfate and hydrogen peroxide, wherein the mass ratio is as follows: 250: 25: 500 to 750: 1-2.5: 75.
the cationic starch is corn starch, and the substitution degree of the cationic starch is 0.02-0.04;
the model of the AKD wax sheet is 1860;
the solid content of the nano-cellulose suspension is 1%; the nano-cellulose is cotton pulp nano-cellulose and is prepared by a sulfuric acid hydrolysis method, and the average particle size is 150-200 nm.
Mixing cationic starch and AKD wax sheets, heating to 60-70 ℃, and stirring for 30 minutes at a stirring speed of 120 rpm/min; then adding the nano-cellulose suspension, and heating to 72 ℃; then, adding ferrous sulfate and 30% solid content hydrogen peroxide, and stirring for 1 hour at a stirring speed of 120 rpm/min; so that the starch is fully oxidized and degraded to obtain the oxidized starch.
Step 2, preparing mixed monomer
Diallyl amine pretreatment: adjusting the pH value of diallylamine to 4-5 with acetic acid to obtain the pretreated diallylamine.
Mixing monomers: mixing 3- (methacryloyloxy) propyltrimethoxysilane, trifluoropropylmethylcyclotrisiloxane, acrylamide, diallyldimethylammonium chloride, ethyleneimine, styrene and butyl acrylate to obtain a mixed solution; and adding the pretreated diallylamine into the mixed solution to obtain a mixed monomer.
The 3- (methacryloyloxy) propyltrimethoxysilane: trifluoropropylmethylcyclotrisiloxane: acrylamide: diallyl dimethyl ammonium chloride: pretreatment of diallylamine: ethylene imine: styrene: the mass ratio of butyl acrylate is 10: 1-5: 5-10: 10: 1: 3-5: 80: 60.
step 3, preparing an initiator
The initiator comprises an initiator A and an initiator B.
And dissolving 30% hydrogen peroxide in a certain amount of water, wherein the mass ratio of hydrogen peroxide to water is 1: 10-20, and thus obtaining the initiator A.
And dissolving benzoyl peroxide in ethyl acetate, wherein the mass ratio of the benzoyl peroxide to the ethyl acetate is 1: 50-100, so as to obtain an initiator B.
Step 4, reaction
Introducing oxidized starch into a reaction kettle, heating the oxidized starch to 85 ℃, and then simultaneously dropwise adding an initiator A and an initiator B;
after the initiator was added dropwise for 1 minute, the dropping of the mixed monomer was started, the dropping time of the mixed monomer was 4.5 hours, and the dropping time of the initiator was 5 hours.
The oxidized starch: the mass ratio of the mixed monomers is 1: 1-2.
The dosage of the initiator A is 1 to 1.5 percent of the mass of the mixed monomer, and the dosage of the initiator B is 0.3 to 0.5 percent of the mass of the mixed monomer. And during dripping, the initiator A and the initiator B are dripped together at different dripping speeds, valves are adjusted according to the dosage in the production process, and the dripping time is controlled to be the same.
After the reaction is finished, the temperature is reduced to 40 ℃, and the decaglycol ester is slowly dripped for 15 minutes.
Dripping the decaglycol ester, stirring for 10 minutes, and cooling to 25 ℃ to obtain the starch/nano cellulose base high-water-resistance reinforced composite emulsion.
The dosage of the dodecyl glycol ester is 1 to 5 percent of the mass of the starch/nano cellulose based high water-resistant reinforced composite emulsion.
Compared with the prior art, the technical scheme of the invention has the following beneficial effects:
(1) compared with the traditional sizing agent and reinforcing agent, the composite emulsion prepared by the invention has the functions of reinforcing and resisting water, has good water-resisting effect and obvious reinforcing effect, and can obviously improve the quality and the grade of paper. The ring crush strength of the paper is improved, the Cobb value is reduced, and the product can reach 25g/m2(ii) a The surface sizing Cobb value of the AKD emulsion in the traditional technology is 30g/m2Left and right. The ring crush strength index of the product can reach 6.0N m/g, the AKD emulsion surface sizing of the traditional technology is adopted, and the transverse ring crush strength is 5.2N m/g.
(2) The emulsion prepared by the invention can also be used for enhancing the water resistance in the slurry, and has the advantages of high retention rate, high sizing efficiency, good enhancing effect, stable emulsion and the like. The product can improve the retention rate of the filler by 2 percent. AKD internal sizing Cobb value: the product can reach 30g/m2In the case of traditional AKD emulsion, the Cobb value of internal sizing of the AKD emulsion can reach 35g/m2Left and right.
(3) The invention has simple process, mild reaction condition, less investment and good economic benefit.
(4) The invention is used for surface sizing of corrugated paper, and when the dosage of the composite emulsion is 0.5 percent, the degree of sizing of the paper is 25.6g/m2The water-resistant effect is obvious, and the ring crush index is 7.8 N.m/g; a tensile index of 42.7 N.m/g and a burst index of 1.9 kPa.m2/g；
The invention is used for adding in the sanitary paper pulp, the dosage is 1.5%, the tensile strength of the sanitary paper is 59.4N/m in the longitudinal and transverse directions on average, and the standard of A and the like is achieved;
the invention is used for surface sizing of corrugated paper, the dosage of each ton of paper is 5kg, the opacity of the paper reaches 85, the folding endurance is 8 times, the longitudinal tensile index is 42 N.m/g, and the absorptivity is 38.6g/m2And the standard of superior products is achieved.
Detailed Description
Example 1 preparation method of cationic starch/nano-cellulose-based water-resistant reinforced composite emulsion
Step 1, starch oxidation
The raw materials comprise: corn starch, AKD wax sheets, nano cellulose suspension, ferrous sulfate and hydrogen peroxide.
The cationic starch is corn starch, and the substitution degree of the cationic starch is 0.02;
the model of the AKD wax sheet is 1860;
the solid content of the nano-cellulose suspension is 1%; the nano-cellulose is cotton pulp nano-cellulose and is prepared by a sulfuric acid hydrolysis method, and the average particle size is 150 nm.
Adding 100kg of corn starch into a reaction kettle; then adding 10kg of AKD wax sheets, mixing, heating to 60 ℃, stirring for 30 minutes at the stirring speed of 120 rpm/min; then 200kg of nano-cellulose suspension is added, and the temperature is raised to 72 ℃; then, 0.4kg of ferrous sulfate and 30kg of hydrogen peroxide with the solid content of 30 percent are added, and the mixture is stirred for 1 hour at the stirring speed of 120 rpm/min; so that the starch is fully oxidized and degraded to obtain the oxidized starch.
Step 2, preparing mixed monomer
Diallyl amine pretreatment: adjusting the pH of diallylamine to 4-5 with acetic acid to obtain the pretreated diallylamine.
Mixing: respectively weighing 10kg, 1kg, 5kg, 10kg, 1kg, 3kg, 80kg and 60kg of 3- (methacryloyloxy) propyltrimethoxysilane, trifluoropropylmethylcyclotrisiloxane, acrylamide, diallyldimethylammonium chloride, pretreated diallylamine, ethyleneimine, styrene and butyl acrylate; and mixing the monomers to obtain a mixed monomer.
Step 3, preparing an initiator
The initiator comprises an initiator A and an initiator B.
17kg of hydrogen peroxide with a solid content of 30% is weighed and dissolved in 170kg of water to obtain the initiator A.
0.5kg of benzoyl peroxide was weighed out and dissolved in 25kg of ethyl acetate to obtain initiator B.
Step 4, reaction
Introducing oxidized starch into a reaction kettle, heating the oxidized starch to 85 ℃, and then simultaneously dropwise adding an initiator A and an initiator B.
After the initiator was added dropwise for 1 minute, the dropping of the mixed monomer was started, the dropping time of the mixed monomer was 4.5 hours, and the dropping time of the initiator was 5 hours.
The oxidized starch: the mass ratio of the mixed monomers is 1: 1; the dosage of the initiator A is 1% of the mass of the mixed monomer, and the dosage of the initiator B is 0.3% of the mass of the mixed monomer. And during dripping, the initiator A and the initiator B are dripped together at different dripping speeds, valves are adjusted according to the dosage in the production process, and the dripping time is controlled to be the same.
After the reaction is finished, the temperature is reduced to 40 ℃, and 10kg of glycol tridecanoate is slowly dripped for 15 minutes.
And dropwise adding the dodecyl glycol ester, stirring for 10 minutes, and cooling to 25 ℃ to obtain 1000kg of the starch/nano cellulose based highly water-resistant reinforced composite emulsion.
The finished composite emulsion prepared in example 1 is used for surface sizing of corrugated paper. The results are as follows:
the composite emulsion of this example was mixed with surface sizing starch for surface sizing of corrugated board and compared to conventional polyacrylamide reinforcing agents.
The test result shows that:
when the amount of the composite emulsion in the embodiment is 0.5 percent, the paper sizing degree is 25.6g/m2The water-resistant effect is obvious, and the ring crush index is 7.8 N.m/g; a tensile index of 42.7 N.m/g and a burst index of 1.9 kPa.m2/g；
When the polyacrylamide reinforcing agent is used, the degree of sizing of the paper is 97.5 g/m when the dosage is 0.5 percent2Water resistance and ring pressure index of 6.4 N.m/g; the tensile index is 38.2 N.m/g, and the burst index is 1.6 kPa.m2/g；
Therefore, the composite emulsion has the advantages of obvious sizing effect, obvious reinforcing effect and good water resistance, and obviously improves the overall quality of paper.
Example 2 preparation method of cationic starch/nano-cellulose-based water-resistant reinforced composite emulsion
Step 1, starch oxidation
The raw materials comprise: cationic starch, AKD wax sheets, nano cellulose suspension, ferrous sulfate and hydrogen peroxide. The cationic starch is corn starch, and the substitution degree of the cationic starch is 0.03;
the model of the AKD wax sheet is 1860;
the solid content of the nano-cellulose suspension is 1%; the nano-cellulose is cotton pulp nano-cellulose and is prepared by a sulfuric acid hydrolysis method, and the average particle size is 180 nm.
Adding 100kg of corn starch into a reaction kettle, wherein the substitution degree is 0.03; then adding 10kg of AKD wax sheets, heating to 60 ℃, and stirring for 30 minutes at the stirring speed of 120 rpm/min; then adding 250kg of nano cellulose suspension, and heating to 72 ℃; then adding 0.8 kg of ferrous sulfate and 30kg of hydrogen peroxide with the solid content of 30%, and stirring for 1 hour at the stirring speed of 120 rpm/min; so that the starch is fully oxidized and degraded to obtain the oxidized starch.
Step 2, preparing mixed monomer
Diallyl amine pretreatment: adjusting the pH value of diallylamine to 4-5 with acetic acid to obtain the pretreated diallylamine.
Mixing: respectively weighing 10kg, 2.5kg, 7.5kg, 10kg, 1kg, 4kg, 80kg and 60kg of 3- (methacryloyloxy) propyltrimethoxysilane, trifluoropropylmethylcyclotrisiloxane, acrylamide, diallyldimethylammonium chloride, pretreated diallylamine, ethyleneimine, styrene and butyl acrylate; and mixing the monomers to obtain a mixed monomer.
Step 3, preparing an initiator
The initiator comprises an initiator A and an initiator B.
22kg of hydrogen peroxide is weighed and dissolved in 330kg of water to obtain the initiator A.
0.7kg of benzoyl peroxide was weighed out and dissolved in 53kg of ethyl acetate to obtain initiator B.
Initiator A and initiator B serve as the initiating system for the reaction of the invention.
Step 4, reaction
Introducing oxidized starch into a reaction kettle, heating the oxidized starch to 85 ℃, and then simultaneously dropwise adding an initiator A and an initiator B;
after the initiator was added dropwise for 1 minute, the dropping of the mixed monomer was started, the dropping time of the mixed monomer was 4.5 hours, and the dropping time of the initiator was 5 hours.
The oxidized starch: the mass ratio of the mixed monomers is 1: 1.5.
The dosage of the initiator A is 1.2 percent of the mass of the mixed monomer, and the dosage of the initiator B is 0.4 percent of the mass of the mixed monomer. And during dripping, the initiator A and the initiator B are dripped together at different dripping speeds, valves are adjusted according to the dosage in the production process, and the dripping time is controlled to be the same.
After the reaction is finished, the temperature is reduced to 40 ℃, 25kg of glycol tridecanoate is slowly dripped, and the dripping time is 15 minutes. And dropwise adding the dodecyl glycol ester, stirring for 10 minutes, and cooling to 25 ℃ to obtain 1000kg of the starch/nano cellulose based highly water-resistant reinforced composite emulsion.
The composite emulsion of this example was used for in-pulp application in hygiene paper and was compared to conventional polyamide polyamine epichlorohydrin.
The test result shows that:
the composite emulsion of the embodiment is added into sanitary paper pulp with the dosage of 1.5 percent and is compared with the traditional polyamide polyamine epichlorohydrin.
The test result shows that:
after 1.5% of the composite emulsion in the embodiment is added, the tensile strength of 150-drawer/double-layer toilet paper is 59.4N/m on average in the longitudinal direction and the transverse direction, and the standards such as A are achieved; under the same dosage, after the polyamide polyamine epichlorohydrin is added, the tensile strength of the 150/double-layer toilet paper is 54.0N/m on average in the longitudinal direction and the transverse direction;
the composite emulsion of the invention obviously improves the wet strength of paper.
Example 3 preparation method of cationic starch/nano-cellulose-based water-resistant reinforced composite emulsion
Step 1, starch oxidation
The raw materials comprise: cationic starch, AKD wax sheets, nano cellulose suspension, ferrous sulfate and hydrogen peroxide; the cationic starch is corn starch, and the substitution degree of the cationic starch is 0.04;
the model of the AKD wax sheet is 1860;
the solid content of the nano-cellulose suspension is 1%; the nano-cellulose is cotton pulp nano-cellulose and is prepared by a sulfuric acid hydrolysis method, and the average particle size is 200 nm.
Adding 100kg of corn starch into a reaction kettle, then adding 10kg of AKD, mixing, heating to 60 ℃, stirring for 30 minutes at the stirring speed of 120 rpm/min; then adding 300kg of nano cellulose suspension, and heating to 72 ℃; then, adding 1kg of ferrous sulfate and 30kg of hydrogen peroxide with the solid content of 30%, and stirring for 1 hour at the stirring speed of 120 rpm/min; so that the starch is fully oxidized and degraded to obtain the oxidized starch.
Step 2, preparing mixed monomer
Diallyl amine pretreatment: adjusting the pH value of diallylamine to 4-5 with acetic acid to obtain the pretreated diallylamine.
Mixing: respectively weighing 10kg, 5kg, 10kg, 1kg, 5kg, 80kg and 60kg of 3- (methacryloyloxy) propyltrimethoxysilane, trifluoropropylmethylcyclotrisiloxane, acrylamide, diallyldimethylammonium chloride, pretreated diallylamine, ethyleneimine, styrene and butyl acrylate, and mixing the monomers to obtain a mixed monomer.
Step 3, preparing an initiator
The initiator comprises an initiator A and an initiator B.
27kg of hydrogen peroxide solution was weighed and dissolved in 540kg of water to obtain initiator A.
0.9kg of benzoyl peroxide was weighed out and dissolved in 90kg of ethyl acetate to obtain initiator B.
Step 4, reaction
Introducing oxidized starch into a reaction kettle, heating the oxidized starch to 85 ℃, and then simultaneously dropwise adding an initiator A and an initiator B;
after the initiator was added dropwise for 1 minute, the dropping of the mixed monomer was started, the dropping time of the mixed monomer was 4.5 hours, and the dropping time of the initiator was 5 hours.
The oxidized starch: the mass ratio of the mixed monomers is 1: 2.
The dosage of the initiator A is 1.5 percent of the mass of the mixed monomer, and the dosage of the initiator B is 0.5 percent of the mass of the mixed monomer. And during dripping, the initiator A and the initiator B are dripped together at different dripping speeds, valves are adjusted according to the dosage in the production process, and the dripping time is controlled to be the same.
After the reaction is finished, the temperature is reduced to 40 ℃, and 50kg of glycol tridecanoate is slowly dripped for 15 minutes. And dropwise adding the dodecyl glycol ester, stirring for 10 minutes, and cooling to 25 ℃ to obtain 1000kg of the starch/nano cellulose based highly water-resistant reinforced composite emulsion.
The composite emulsion finished product of the embodiment is used for corrugated paper. The results are as follows:
the composite emulsion of this example was mixed with surface sizing starch for surface sizing of corrugated board and compared to AKD sizing emulsions.
The test result shows that: the dosage of each ton of paper is 5kg, after the composite emulsion of the embodiment is used, the opacity of the paper reaches 85, the folding endurance is 8 times, the longitudinal tensile index is 42 N.m/g, and the absorbency is 38.6g/m2The standard of superior products is achieved;
under the same dosage, after AKD is used for surface sizing, the opacity of the paper reaches 80, the folding endurance is 6 times, the longitudinal tensile index is 40 N.m/g, and the absorbency is 39.52g/m2；
Therefore, the emulsion of the invention has the effects of obviously enhancing the opacity, folding endurance and tensile index of paper and reducing the absorptivity.
Except for special description, the percentages are mass percentages, and the ratios are mass ratios.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (5)
1. A preparation method of cationic starch/nano cellulose base water-resistant reinforced composite emulsion is characterized by comprising the following steps: comprises the steps of oxidizing starch, preparing mixed monomers, preparing an initiator and reacting;
the oxidized starch: the raw materials comprise cationic starch, AKD wax flakes, nano cellulose suspension, ferrous sulfate and hydrogen peroxide, and the mass ratio is as follows: 250: 25: 500 to 750: 1-2.5: 75;
the prepared mixed monomer: comprising diallylamine pretreatment and monomer mixing; the monomer mixing: mixing 3- (methacryloyloxy) propyltrimethoxysilane, trifluoropropylmethylcyclotrisiloxane, acrylamide, diallyldimethylammonium chloride, ethyleneimine, styrene and butyl acrylate to obtain a mixed solution; adding the pretreated diallylamine into the mixed solution to obtain a mixed monomer;
the 3- (methacryloyloxy) propyltrimethoxysilane: trifluoropropylmethylcyclotrisiloxane: acrylamide: diallyl dimethyl ammonium chloride: pretreatment of diallylamine: ethylene imine: styrene: the mass ratio of butyl acrylate is 10: 1-5: 5-10: 10: 1: 3-5: 80: 60, adding a solvent to the mixture;
the preparation of the initiator comprises the following steps: the initiator is a composite initiator and comprises an initiator A and an initiator B;
the reaction steps are as follows: introducing the oxidized starch into a reaction kettle, heating the oxidized starch, and then simultaneously dropwise adding an initiator A and an initiator B; after the initiator is dripped for 0.5 to 2 minutes, the mixed monomer is dripped; after the reaction is finished, adding the dodecyl alcohol ester dropwise, and cooling after the addition is finished to obtain the cationic starch/nano cellulose base water-resistant reinforced composite emulsion.
2. The method for preparing the cationic starch/nano cellulose based water-resistant reinforced composite emulsion according to claim 1, wherein the method comprises the following steps: the initiator A: dissolving 30% hydrogen peroxide in a certain amount of water to obtain an initiator A, wherein the mass of the hydrogen peroxide and the water is 1: 10-20.
3. The method for preparing the cationic starch/nano cellulose based water-resistant reinforced composite emulsion according to claim 1, wherein the method comprises the following steps: the initiator B: and dissolving benzoyl peroxide in ethyl acetate to obtain an initiator B, wherein the mass ratio of the benzoyl peroxide to the ethyl acetate is 1: 50-100.
4. The method for preparing the cationic starch/nano cellulose based water-resistant reinforced composite emulsion according to claim 1, wherein the method comprises the following steps: the oxidized starch: the mass ratio of the mixed monomers is 1: 1-2.
5. The method for preparing the cationic starch/nano cellulose based water-resistant reinforced composite emulsion according to claim 1, wherein the method comprises the following steps: the dosage of the initiator A is 1 to 1.5 percent of the mass of the mixed monomer, and the dosage of the initiator B is 0.3 to 0.5 percent of the mass of the mixed monomer.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
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| 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 |
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2018
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| 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 |
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