CN110922531A - A kind of starch grafted fluorescent copolymer emulsion and its preparation method and application - Google Patents
A kind of starch grafted fluorescent copolymer emulsion and its preparation method and application Download PDFInfo
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- 229920002472 Starch Polymers 0.000 title claims abstract description 64
- 235000019698 starch Nutrition 0.000 title claims abstract description 64
- 239000008107 starch Substances 0.000 title claims abstract description 64
- 239000000839 emulsion Substances 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 229920001114 fluorescent copolymer Polymers 0.000 title claims abstract description 22
- 239000000178 monomer Substances 0.000 claims abstract description 59
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical group C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 29
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 23
- 238000004513 sizing Methods 0.000 claims abstract description 17
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims abstract description 15
- 240000003183 Manihot esculenta Species 0.000 claims abstract description 12
- 235000016735 Manihot esculenta subsp esculenta Nutrition 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 12
- 238000004383 yellowing Methods 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 36
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- MGNCLNQXLYJVJD-UHFFFAOYSA-N cyanuric chloride Chemical compound ClC1=NC(Cl)=NC(Cl)=N1 MGNCLNQXLYJVJD-UHFFFAOYSA-N 0.000 claims description 23
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 22
- 239000002253 acid Substances 0.000 claims description 20
- 239000000243 solution Substances 0.000 claims description 20
- 238000001816 cooling Methods 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 11
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 11
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 11
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 11
- CCJAYIGMMRQRAO-UHFFFAOYSA-N 2-[4-[(2-hydroxyphenyl)methylideneamino]butyliminomethyl]phenol Chemical compound OC1=CC=CC=C1C=NCCCCN=CC1=CC=CC=C1O CCJAYIGMMRQRAO-UHFFFAOYSA-N 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 238000004821 distillation Methods 0.000 claims description 9
- 239000012153 distilled water Substances 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 9
- 238000000967 suction filtration Methods 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 150000003384 small molecules Chemical class 0.000 claims description 4
- 238000005516 engineering process Methods 0.000 claims description 3
- 230000000977 initiatory effect Effects 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 2
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 claims 1
- 230000002087 whitening effect Effects 0.000 abstract description 8
- 229920001577 copolymer Polymers 0.000 abstract description 3
- 230000002401 inhibitory effect Effects 0.000 abstract description 3
- 230000005764 inhibitory process Effects 0.000 abstract description 2
- 239000003999 initiator Substances 0.000 abstract description 2
- 238000010534 nucleophilic substitution reaction Methods 0.000 abstract 1
- 150000003254 radicals Chemical class 0.000 abstract 1
- 239000006081 fluorescent whitening agent Substances 0.000 description 9
- PJANXHGTPQOBST-VAWYXSNFSA-N Stilbene Natural products C=1C=CC=CC=1/C=C/C1=CC=CC=C1 PJANXHGTPQOBST-VAWYXSNFSA-N 0.000 description 5
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical compound C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 description 5
- 235000021286 stilbenes Nutrition 0.000 description 5
- 230000032683 aging Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 230000007547 defect Effects 0.000 description 2
- 238000002284 excitation--emission spectrum Methods 0.000 description 2
- 229920000578 graft copolymer Polymers 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229920001131 Pulp (paper) Polymers 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 230000032912 absorption of UV light Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000007697 cis-trans-isomerization reaction Methods 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006862 quantum yield reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Images
Classifications
-
- 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
-
- 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
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
-
- 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
- D21H17/21—Macromolecular organic compounds of natural origin; Derivatives thereof
- D21H17/24—Polysaccharides
- D21H17/28—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
- 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
- D21H21/30—Luminescent or fluorescent substances, e.g. for optical bleaching
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Paper (AREA)
- Graft Or Block Polymers (AREA)
Abstract
一种淀粉接枝荧光共聚乳液及其制备方法及其应用，此类荧光乳液的特点是将荧光单体通过与淀粉、功能单体进行自由基接枝共聚，从而制得一种施胶性能良好且具有荧光增白、抑制返黄以及表面施胶性能的多功能共聚乳液。其制备方法为：首先通过三步亲核取代法制备荧光单体，再糊化木薯淀粉并作为初始原料与荧光单体、丙烯酰胺、苯乙烯单体，通过氧化还原体系引发剂进行接枝共聚反应，得到一种淀粉接枝荧光共聚乳液。本方法制得的荧光乳液可直接进行纸张表面施胶，具有增白、抑制返黄以及同时可提高纸张表面强度等多重作用，特别对高得率浆的文化纸有效。
A starch grafted fluorescent copolymer emulsion, a preparation method and application thereof, the characteristics of this type of fluorescent emulsion are that a fluorescent monomer is subjected to free radical graft copolymerization with starch and functional monomers to obtain a kind of good sizing performance. And it is a multifunctional copolymer emulsion with fluorescent whitening, yellowing inhibition and surface sizing properties. The preparation method is as follows: firstly, a fluorescent monomer is prepared by a three-step nucleophilic substitution method, then tapioca starch is gelatinized and used as an initial raw material, and the fluorescent monomer, acrylamide and styrene monomer are used for graft copolymerization through a redox system initiator. reaction to obtain a starch grafted fluorescent copolymer emulsion. The fluorescent emulsion prepared by the method can directly sizing the paper surface, has multiple functions such as whitening, inhibiting yellowing and improving the surface strength of the paper at the same time, and is especially effective for the cultural paper with high yield pulp.
Description
Technical Field
The invention relates to the technical field of fluorescent whitening agents and surface sizing agents, and particularly relates to a starch grafted fluorescent copolymer emulsion as well as a preparation method and application thereof.
Background
Based on the problem of wood raw material shortage in China, high-yield pulp is popular in the papermaking industry due to the advantages of small fiber damage, high yield, small environmental pollution and the like, but the problems of poor paper-making strength, easy yellowing and the like limit the expanded application of the pulp. The stilbene fluorescent whitening agent is used as the most widely applied fluorescent whitening agent in the papermaking industry, and has the advantages of good whitening effect and high fluorescence quantum yield. The traditional stilbene fluorescent whitening agent has the defects of serious light-induced cis-trans isomerization phenomenon, poor binding force with paper and the like, so that the application range of the stilbene fluorescent whitening agent is greatly limited. Researchers have prevented cis-trans isomerism by incorporating uv absorbers into optical brighteners to reduce the absorption of uv light by the optical brighteners, but this does not substantially ameliorate the disadvantages of photo-cis-trans isomerism. Macromolecules are also adopted to modify the fluorescent whitening agent, so that the structural stability and the light stability of the compound are improved, but the loss of the fluorescent whitening agent is serious.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide the starch graft copolymerization emulsion and the preparation method and the application thereof.
In order to achieve the purpose, the invention adopts the technical scheme that:
a starch graft copolymerization fluorescent emulsion is prepared by carrying out multi-component graft copolymerization on a fluorescent monomer containing double bonds and other monomers by a starch graft copolymerization technology to prepare the starch graft copolymerization fluorescent emulsion with the functions of fluorescent whitening, yellowing inhibition and paper surface strength enhancement, wherein the fluorescent monomer in the starch graft copolymerization fluorescent emulsion has the structure as follows:
a preparation method of starch graft fluorescent copolymer emulsion comprises the following steps:
step 1: placing cyanuric chloride in a three-neck flask, adding acetone with the mass 10 times that of cyanuric chloride to dissolve cyanuric chloride at the temperature of 0-5 ℃ (ice bath), slowly adding DSD acid into the three-neck flask after dissolving the DSD acid with 1% sodium hydroxide solution with the mass 20 times that of the DSD acid, and adjusting the pH value to 5-6, wherein the reaction time is 1.5-2.5 h; then heating to 35-40 ℃, dropwise adding diethanolamine, controlling the pH to be 6-7, and reacting for 2-3 h; heating to 90-95 ℃, adding N-hydroxymethyl acrylamide, controlling the pH value to be 7-8, simultaneously installing a distillation device to evaporate acetone, continuously reacting for 4-6 hours, cooling the product to room temperature after the reaction is finished, performing suction filtration, washing with absolute ethyl alcohol to remove unreacted raw materials, and drying to obtain the double-bonded small-molecule fluorescent monomer; the preparation route is shown in figure 1.
Step 2: dissolving cassava starch in a certain amount of distilled water, placing the cassava starch in a three-neck flask with stirring, gelatinizing the cassava starch at 65-85 ℃ for 25-40 min to prepare 10% starch paste, cooling, keeping the temperature at 55-65 ℃, and introducing N2Sequentially adding ammonium persulfate and total monomers in the atmosphere, dropwise adding sodium bisulfite for 30min, continuously reacting for 2-3 h, adjusting the pH to 6-7, and adjusting the solid content to be 25% -30%, thereby obtaining the starch graft copolymerization fluorescent emulsion. The preparation route can be seen in fig. 2.
When the fluorescent monomer is prepared in the step 1, the molar ratio of the four raw materials, namely DSD acid, cyanuric chloride, diethanolamine and N-hydroxymethyl acrylamide, is 1 (2.0-2.1) to (1.5-2.0).
The total monomers in the step 2 are fluorescent monomers, acrylamide and styrene, the mass of the total monomers is the sum of the mass of the fluorescent monomers, the mass of the acrylamide and the mass of the styrene, and the mass ratio of the cassava starch to the total monomers is 1: 2-1: 4.
In the step 2, the dosage of the fluorescent monomer is 20-30% of the total monomer mass, the dosage of the acrylamide is 50-60% of the total monomer mass, and the dosage of the styrene is 20-30% of the total monomer mass.
In the step 2, a redox system consisting of ammonium persulfate and sodium bisulfite in the initiation system has a molar ratio of 1:1, 10% aqueous solution is prepared respectively, and the initiator is 0.5-1.0% of the total monomer mass.
The starch graft fluorescent copolymer emulsion is applied to surface sizing of paper, whitens the paper, inhibits yellowing, improves the surface strength of the paper, and is particularly effective to surface sizing of high-yield pulp culture paper.
The invention has the beneficial effects that:
the invention has the advantages that the three functions of whitening paper, inhibiting yellowing and improving surface strength are combined together to prepare the starch graft fluorescent copolymer emulsion. The starch in the starch graft copolymerization fluorescent emulsion can greatly improve the film forming property of the polymer emulsion and prevent the loss of the fluorescent monomer, and styrene and acrylamide monomers are introduced into the copolymer through starch graft copolymerization, so that the surface physical strength and the sizing property of paper are improved. The method has the advantages of synthesis temperature below 100 ℃, simple and convenient operation, energy conservation and convenient industrial implementation.
Drawings
FIG. 1 is a scheme of fluorescent small molecule preparation and modification.
FIG. 2 is a preparation route diagram of a starch graft copolymerization fluorescent emulsion.
FIG. 3 is an excitation-emission spectrum of a starch graft fluorescent copolymer emulsion.
FIG. 4 is a graph of whiteness and yellowness index as a function of aging time after paper sizing.
Detailed Description
The present invention will be described in further detail with reference to examples.
A preparation method of starch graft fluorescent copolymer emulsion comprises the following steps:
step 1: placing cyanuric chloride in a three-neck flask, adding acetone with the mass 10 times that of cyanuric chloride to dissolve cyanuric chloride at the temperature of 0-5 ℃ (ice bath), slowly adding DSD acid into the three-neck flask after dissolving the DSD acid with 1% sodium hydroxide solution with the mass 20 times that of the DSD acid, and adjusting the pH value to 5-6, wherein the reaction time is 1.5-2.5 h; then heating to 35-40 ℃, dropwise adding diethanolamine, controlling the pH to be 6-7, and reacting for 2-3 h; heating to 90-95 ℃, adding N-hydroxymethyl acrylamide, controlling the pH value to be 7-8, simultaneously installing a distillation device to evaporate acetone, continuously reacting for 4-6 hours, cooling the product to room temperature after the reaction is finished, performing suction filtration, washing with absolute ethyl alcohol to remove unreacted raw materials, and drying to obtain the double-bonded small-molecule fluorescent monomer; the preparation route is shown in figure 1.
Step 2: dissolving cassava starch in a certain amount of distilled water, placing the cassava starch in a three-neck flask with stirring, gelatinizing the cassava starch at 65-85 ℃ for 25-40 min to prepare 10% starch paste, cooling, keeping the temperature at 55-65 ℃, and introducing N2Sequentially adding ammonium persulfate and total monomers in the atmosphere, dropwise adding sodium bisulfite for 30min, continuously reacting for 2-3 h, adjusting the pH to 6-7, and adjusting the solid content to be 25% -30%, thereby obtaining the starch graft copolymerization fluorescent emulsion. The preparation route can be seen in fig. 2.
Example 1
The method comprises the following steps: placing 4.82g (0.026mol) of cyanuric chloride in a three-neck flask, adding 48ml of acetone to completely dissolve the cyanuric chloride at 0-5 ℃ (ice bath), dissolving 4.81g (0.013mol) of DSD acid with 96ml of 1% sodium hydroxide solution, slowly adding the dissolved DSD acid into the three-neck flask, dropwise adding for 30min, adjusting the pH value to 5-6, and reacting for 2 h. And then heating to 40 ℃, dropwise adding 2.75g (0.026mol) of diethanolamine, controlling the pH to be 6-7, and reacting for 3 hours. And finally, heating to 90 ℃, adding 2.23g (0.02mol) of N-hydroxymethyl acrylamide, adjusting the pH value to 7-8, simultaneously installing a distillation device to evaporate acetone, and continuing to react for 5 hours. And after the reaction is finished, cooling the product to room temperature, carrying out suction filtration, washing with absolute ethyl alcohol to remove unreacted raw materials, and drying to obtain the double-bonded micromolecule fluorescent monomer. The preparation route is shown in figure 1.
Step two: dissolving 30g starch in 200ml distilled water, and standingThe mixture was stirred at 85 ℃ in a flask and gelatinized for 30 min. Then cooling to 55 ℃ under the condition of N2Sequentially adding 0.22g of ammonium persulfate and 60g of total monomers in a certain mass ratio (the mass of FBs monomer: styrene: acrylamide is respectively 10g, 15g and 35g) in an atmosphere, dropwise adding 0.08g of sodium bisulfite for 30min, continuously reacting for 2h, adjusting the pH to 6-7, and adjusting the solid content to 30% to obtain the starch graft fluorescent copolymer emulsion, wherein the preparation route can be shown in FIG. 2.
Example 2
The method comprises the following steps: placing 5.04g (0.027mol) of cyanuric chloride in a three-neck flask, adding 50ml of acetone to completely dissolve the cyanuric chloride at 0-5 ℃ (ice bath), dissolving 4.81g (0.013mol) of DSD acid with 96ml of 1% sodium hydroxide solution, slowly adding the solution into the three-neck flask, dropwise adding for 30min, adjusting the pH value to 5-6, and reacting for 1.5 h. Then heating to 35 ℃, dropwise adding 2.73g (0.026mol) of diethanolamine, controlling the pH value to be 6-7, and reacting for 3.5 h. And finally, heating to 95 ℃, adding 2.23g (0.02mol) of N-hydroxymethyl acrylamide, adjusting the pH value to 7-8, simultaneously installing a distillation device to evaporate acetone, and continuing to react for 5 hours. And after the reaction is finished, cooling the product to room temperature, carrying out suction filtration, washing with absolute ethyl alcohol to remove unreacted raw materials, and drying to obtain the double-bonded micromolecule fluorescent monomer. The preparation route is shown in figure 1.
Step two: 30g of starch is dissolved in 200ml of distilled water and placed in a three-neck flask, and the mixture is stirred and gelatinized for 25min at 80 ℃. Then cooling to 60 ℃ under the condition of N2Sequentially adding 0.44g of ammonium persulfate and 60g of total monomers in a certain mass ratio (the mass of FBs monomer: styrene: acrylamide is 15g, 15g and 30g respectively) in an atmosphere, dropwise adding 0.16g of sodium bisulfite for 30min, continuously reacting for 2.5h, adjusting the pH to 6-7, and adjusting the solid content to 30% to obtain the starch graft fluorescent copolymer emulsion, wherein the preparation route can be shown in FIG. 2.
Example 3
The method comprises the following steps: placing 4.82g (0.026mol) of cyanuric chloride in a three-neck flask, adding 48ml of acetone to completely dissolve the cyanuric chloride at 0-5 ℃ (ice bath), dissolving 4.81g (0.013mol) of DSD acid with 96ml of 1% sodium hydroxide solution, slowly adding the dissolved DSD acid into the three-neck flask, dropwise adding for 30min, adjusting the pH value to 5-6, and reacting for 2.5 h. Then heating to 40 ℃, dropwise adding 2.73g (0.026mol) of diethanolamine, controlling the pH value to be 6-7, and reacting for 2.5 h. And finally, heating to 90 ℃, adding 2.32g (0.023mol) of N-hydroxymethyl acrylamide, adjusting the pH value to 7-8, simultaneously installing a distillation device to distill out acetone, and continuing to react for 5 hours. And after the reaction is finished, cooling the product to room temperature, carrying out suction filtration, washing with absolute ethyl alcohol to remove unreacted raw materials, and drying to obtain the double-bonded micromolecule fluorescent monomer. The preparation route is shown in figure 1.
Step two: dissolving 15g of starch in 180ml of distilled water, placing the solution in a three-neck flask, and stirring and gelatinizing the solution at 75 ℃ for 35 min. Then cooling to 65 ℃ under the condition of N2Sequentially adding 0.165g of ammonium persulfate and 45g of total monomers (the mass of FBs monomer: styrene: acrylamide is respectively 10g, 10g and 25g) in a certain mass ratio in an atmosphere, dripping 0.06g of sodium bisulfite for 30min, continuously reacting for 3h, adjusting the pH to 6-7, and adjusting the solid content to 25% to obtain the starch graft fluorescent copolymer emulsion, wherein the preparation route can be shown in figure 2.
Example 4
The method comprises the following steps: placing 5.04g (0.027mol) of cyanuric chloride in a three-neck flask, adding 50ml of acetone to completely dissolve the cyanuric chloride at 0-5 ℃ (ice bath), dissolving 4.81g (0.013mol) of DSD acid with 96ml of 1% sodium hydroxide solution, slowly adding the solution into the three-neck flask, dropwise adding for 30min, adjusting the pH value to 5-6, and reacting for 2.5 h. And then heating to 35 ℃, dropwise adding 2.84g (0.027mol) of diethanolamine, controlling the pH to be 6-7, and reacting for 3 hours. And finally, heating to 95 ℃, adding 2.32g (0.023mol) of N-hydroxymethyl acrylamide, adjusting the pH value to 7-8, simultaneously installing a distillation device to distill out acetone, and continuing to react for 6 hours. And after the reaction is finished, cooling the product to room temperature, carrying out suction filtration, washing with absolute ethyl alcohol to remove unreacted raw materials, and drying to obtain the double-bonded micromolecule fluorescent monomer. The preparation route is shown in figure 1.
Step two: dissolving 15g of starch in 180ml of distilled water, placing the solution in a three-neck flask, and stirring and gelatinizing the solution at 70 ℃ for 25 min. Then cooling to 55 ℃ under the condition of N20.33g of ammonium persulfate and 45g of total monomers with a certain mass ratio are sequentially added in the atmosphere (the mass of FBs monomer: styrene: acrylamide is respectively 10g,15g, 35g), then dropwise adding 0.12g of sodium bisulfite for 30min, continuing to react for 2h, adjusting the pH to 6-7, and adjusting the solid content to 25% to obtain the starch graft fluorescent copolymer emulsion, wherein the preparation route can be shown in figure 2.
Example 5
The method comprises the following steps: placing 4.82g (0.026mol) of cyanuric chloride in a three-neck flask, adding 48ml of acetone to completely dissolve the cyanuric chloride at 0-5 ℃ (ice bath), dissolving 4.81g (0.013mol) of DSD acid with 96ml of 1% sodium hydroxide solution, slowly adding the dissolved DSD acid into the three-neck flask, dropwise adding for 30min, adjusting the pH value to 5-6, and reacting for 1.5 h. And then heating to 40 ℃, dropwise adding 2.84g (0.027mol) of diethanolamine, controlling the pH to be 6-7, and reacting for 3.5 h. And finally, heating to 90 ℃, adding 2.62g (0.026mol) of N-hydroxymethyl acrylamide, adjusting the pH value to 7-8, simultaneously installing a distillation device to evaporate acetone, and continuing to react for 6 hours. And after the reaction is finished, cooling the product to room temperature, carrying out suction filtration, washing with absolute ethyl alcohol to remove unreacted raw materials, and drying to obtain the double-bonded micromolecule fluorescent monomer. The preparation route is shown in figure 1.
Step two: dissolving 15g of starch in 180ml of distilled water, placing the solution in a three-neck flask, and stirring and gelatinizing the solution at 65 ℃ for 40 min. Then cooling to 60 ℃ under the condition of N2Sequentially adding 0.22g of ammonium persulfate and 60g of total monomers in a certain mass ratio (the mass of FBs monomer: styrene: acrylamide is respectively 10g, 15g and 35g) in an atmosphere, dripping 0.08g of sodium bisulfite for 30min, continuously reacting for 2.5h, adjusting the pH to 6-7, and adjusting the solid content to 30% to obtain the starch graft fluorescent copolymer emulsion, wherein the preparation route can be shown in FIG. 2.
Example 6
The method comprises the following steps: placing 5.04g (0.027mol) of cyanuric chloride in a three-neck flask, adding 50ml of acetone to completely dissolve the cyanuric chloride at 0-5 ℃ (ice bath), dissolving 4.81g (0.013mol) of DSD acid with 96ml of 1% sodium hydroxide solution, slowly adding the solution into the three-neck flask, dropwise adding for 30min, adjusting the pH value to 5-6, and reacting for 2.5 h. And then heating to 35 ℃, dropwise adding 2.84g (0.027mol) of diethanolamine, controlling the pH to be 6-7, and reacting for 2.5 h. And finally, heating to 95 ℃, adding 2.62g (0.026mol) of N-hydroxymethyl acrylamide, adjusting the pH value to 7-8, simultaneously installing a distillation device to evaporate acetone, and continuing to react for 6 hours. And after the reaction is finished, cooling the product to room temperature, carrying out suction filtration, washing with absolute ethyl alcohol to remove unreacted raw materials, and drying to obtain the double-bonded micromolecule fluorescent monomer. The preparation route is shown in figure 1.
Step two: dissolving 15g of starch in 180ml of distilled water, placing the solution in a three-neck flask, and stirring and gelatinizing the solution at 85 ℃ for 30 min. Then cooling to 65 ℃ under the condition of N2Sequentially adding 0.44g of ammonium persulfate and 60g of total monomers with a certain mass ratio (the mass of FBs monomer: styrene: acrylamide is respectively 10g, 15g and 35g) in an atmosphere, dripping 0.16g of sodium bisulfite for 30min, continuously reacting for 3h, adjusting the pH to 6-7, and adjusting the solid content to 30% to obtain the starch graft fluorescent copolymer emulsion, wherein the preparation route can be shown in figure 2.
Starch is used as a natural, cheap, green and environment-friendly surface sizing agent, and the sizing performance of emulsion is generally improved by graft copolymerization; the stilbene type fluorescent whitening agent is grafted to molecular chains of starch, and sizing is carried out in a surface sizing mode, so that the surface strength of paper can be improved, the whiteness of the paper can be effectively improved, and the paper yellowing is inhibited, and the stilbene type fluorescent whitening agent is a multifunctional paper surface sizing agent. According to the invention, a starch graft copolymerization technology is adopted to introduce a fluorescent monomer, acrylamide and styrene into starch macromolecules, so that the starch graft copolymerization fluorescent emulsion which has the effects of whitening paper and inhibiting yellowing and can improve the surface strength of the paper is prepared. The technical scheme has important theoretical significance and practical value in the fields of fluorescent whitening and starch graft copolymerization.
As can be seen from FIG. 3, the copolymer emulsion has a good peak-type mirror symmetry of the excitation-emission spectrum, the maximum excitation wavelength is 335nm, the maximum emission wavelength is 433nm, and the peak-type mirror symmetry is located in the blue light region, which indicates that the fluorescent group in the starch graft copolymer fluorescent emulsion can absorb ultraviolet light of 320-400 nm and emit 433nm blue fluorescence, and the blue light is complementary to the yellow light of paper in optical color, so that the paper has a whitening effect.
As can be seen from FIG. 4, the initial whiteness of the sized paper is 11.33% ISO higher than that of the blank paper, and after 48h ultraviolet aging test, the yellowing value of the sized paper is 1.46 lower than that of the blank paper, which indicates that the starch graft copolymerization fluorescent emulsion can improve the whiteness of the paper and inhibit the yellowing of the paper.
Examples comparison of application effects:
paper pulp at high yield (100 g/m) using the example samples2) Before and after sizing, the whiteness, the surface napping speed, the smoothness, the tensile strength and the yellowing value (PC value) of the paper are measured through a 48-hour ageing box accelerated ageing test, and the implementation effect of the technical scheme is illustrated. The following are some performance tests of the starch graft copolymer fluorescent emulsion and the attached drawings:
TABLE 1 comparison of the properties of the paper after sizing
Claims (7)
1. A starch graft fluorescence copolymerization emulsion is characterized in that a fluorescence monomer and other functional monomers are subjected to multi-component graft copolymerization by a starch graft copolymerization technology, and the structure of the fluorescence monomer in the graft copolymerization emulsion is as follows:
2. a preparation method of starch graft fluorescent copolymer emulsion comprises the following steps:
step 1: placing cyanuric chloride in a three-neck flask, adding acetone with the mass 10 times that of cyanuric chloride to dissolve cyanuric chloride at the temperature of 0-5 ℃ (ice bath), slowly adding DSD acid into the three-neck flask after dissolving the DSD acid with 1% sodium hydroxide solution with the mass 20 times that of the DSD acid, and adjusting the pH value to 5-6, wherein the reaction time is 1.5-2.5 h; then heating to 35-40 ℃, dropwise adding diethanolamine, controlling the pH to be 6-7, and reacting for 2-3 h; and heating to 90-95 ℃, adding N-hydroxymethyl acrylamide, controlling the pH value to be 7-8, simultaneously installing a distillation device to evaporate acetone, continuously reacting for 4-6 hours, cooling the product to room temperature after the reaction is finished, performing suction filtration, washing with absolute ethyl alcohol to remove unreacted raw materials, and drying to obtain the double-bonded small-molecule fluorescent monomer.
Step 2: dissolving cassava starch in a certain amount of distilled water, placing the cassava starch in a three-neck flask with stirring, gelatinizing the cassava starch at 65-85 ℃ for 20-40 min to prepare 10% starch paste, cooling, keeping the temperature at 55-65 ℃, and introducing N2Sequentially adding ammonium persulfate and total monomers in the atmosphere, dropwise adding sodium bisulfite for 30min, continuously reacting for 2-3 h, adjusting the pH to 6-7, and adjusting the solid content to 25% -30% to obtain the starch graft copolymerization fluorescent emulsion.
3. The method for preparing a starch-grafted fluorescent copolymer emulsion as claimed in claim 2, wherein the molar ratio of the DSD acid, cyanuric chloride, diethanolamine, and N-methylolacrylamide is 1 (2.0-2.1) to (1.5-2.0) respectively when the fluorescent monomer is prepared in step 1.
4. The preparation method of the starch-grafted fluorescent copolymer emulsion as claimed in claim 2, wherein the total monomers in the step 2 are fluorescent monomers, acrylamide and styrene, the total mass of the monomers is the sum of the fluorescent monomers, the acrylamide and the styrene, and the mass ratio of the tapioca starch to the total monomers is 1: 2-1: 4.
5. The method for preparing the starch-grafted fluorescent copolymer emulsion according to claim 2, wherein the amount of the fluorescent monomer used in the step 2 is 20-30% of the total mass of the monomers, the amount of the acrylamide used is 50-60% of the total mass of the monomers, and the amount of the styrene used is 20-30% of the total mass of the monomers.
6. The method for preparing starch graft fluorescent copolymer emulsion according to claim 2, wherein in the step 2, the initiating system ammonium persulfate and sodium bisulfite are prepared into 10% aqueous solutions respectively with a molar ratio of 1:1, and the amount of the initiating agent is 0.5-1.0% of the total mass of the monomers.
7. The starch graft fluorescent copolymer emulsion is applied to surface sizing of paper, whitens the paper, inhibits yellowing, improves the surface strength of the paper, and is particularly effective to surface sizing of high-yield pulp culture paper.
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