CN115197434A - Paper product moisturizing emulsion, and preparation method and application thereof - Google Patents
Paper product moisturizing emulsion, and preparation method and application thereof Download PDFInfo
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- CN115197434A CN115197434A CN202210825637.9A CN202210825637A CN115197434A CN 115197434 A CN115197434 A CN 115197434A CN 202210825637 A CN202210825637 A CN 202210825637A CN 115197434 A CN115197434 A CN 115197434A
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- polyvinyl alcohol
- graft polymer
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- paper product
- emulsion
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- 239000000839 emulsion Substances 0.000 title claims abstract description 49
- 230000003020 moisturizing effect Effects 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 238000004945 emulsification Methods 0.000 title description 5
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 57
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 56
- 229920000578 graft copolymer Polymers 0.000 claims abstract description 50
- 238000006243 chemical reaction Methods 0.000 claims abstract description 45
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims abstract description 36
- 229920005862 polyol Polymers 0.000 claims abstract description 27
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 claims abstract description 20
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 18
- 239000000178 monomer Substances 0.000 claims abstract description 18
- 150000003077 polyols Chemical class 0.000 claims abstract description 17
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims abstract description 17
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 13
- -1 phthalic anhydride polyol Chemical class 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 6
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 6
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims abstract description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 42
- 238000010438 heat treatment Methods 0.000 claims description 24
- 239000003054 catalyst Substances 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 8
- 230000000379 polymerizing effect Effects 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 5
- 150000003384 small molecules Chemical class 0.000 abstract description 4
- 230000009467 reduction Effects 0.000 abstract description 2
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 44
- 230000000052 comparative effect Effects 0.000 description 11
- 150000005846 sugar alcohols Polymers 0.000 description 9
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 8
- 230000004888 barrier function Effects 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 5
- 229910052797 bismuth Inorganic materials 0.000 description 4
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 4
- 230000001804 emulsifying effect Effects 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229920002635 polyurethane Polymers 0.000 description 4
- 239000004814 polyurethane Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 3
- 230000008859 change Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000009194 climbing Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000003906 humectant Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920005906 polyester polyol Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
- C08G81/02—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers at least one of the polymers being obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C08G81/024—Block or graft polymers containing sequences of polymers of C08C or C08F and of polymers of C08G
-
- 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
- D21H19/12—Coatings without pigments applied as a solution using water as the only solvent, e.g. in the presence of acid or alkaline compounds
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Graft Or Block Polymers (AREA)
Abstract
The invention discloses a paper product moisturizing emulsion, and a preparation method and application thereof. The preparation method comprises the following steps: carrying out dehydration reaction on phthalic anhydride polyol and dimethylolpropionic acid to obtain a polyol monomer; carrying out polymerization reaction with toluene diisocyanate to obtain a graft polymer, wherein the terminal group of the graft polymer comprises an isocyanate group; and (3) carrying out an emulsion grafting reaction on the polyvinyl alcohol solution, triethylamine and the graft polymer, and grafting partial hydroxyl of the polyvinyl alcohol with the terminal group of the graft polymer to obtain the paper product moisturizing emulsion. According to the paper product moisturizing emulsion provided by the invention, a part of hydroxyl groups are grafted with the graft polymer which has certain rigidity and a plurality of branched chains through a high-molecular grafting method, so that the graft polymer has a certain steric hindrance effect, the bonding phenomenon caused by high temperature among polyvinyl alcohol molecular chains can be prevented, and the multi-branched structure cannot obstruct small molecules such as water molecules, so that the reduction of moisturizing performance and obstructing performance caused by grafting is avoided.
Description
Technical Field
The invention belongs to the technical field of polymer modification, and particularly relates to a paper product moisturizing emulsion, and a preparation method and application thereof.
Background
The statements in this section merely provide background information related to the present disclosure and may not constitute prior art.
In the current packaging material industry, in order to avoid the problems of paper warping, paper deformation and the like in the printing process, the purpose of keeping paper moisture is achieved by coating a layer of back coating emulsion on the back surface of paper, and the moisture of the paper is prevented from changing along with the change of a storage environment. The emulsion of the polyvinyl alcohol has good film forming property, barrier property, flexibility, smoothness and mechanical property, so that the emulsion is widely used as a paper humectant.
However, the inventor finds that in long-term production practice, under the high-temperature and high-humidity environment in summer, the PVA coating on the back of the paper sheet can be blocked, so that the paper sheet is blocked. The phenomenon can seriously affect the production efficiency of customer printing and even cause quality accidents.
Therefore, how to improve the anti-adhesion performance of the polyvinyl alcohol emulsion while ensuring the moisture retention performance and the barrier performance of the polyvinyl alcohol emulsion so as to avoid the hardening phenomenon is the key for solving the technical problems.
It should be noted that the above background description is only for the sake of clarity and complete description of the technical solutions of the present invention and for the understanding of those skilled in the art. These solutions are not considered to be known to the person skilled in the art merely because they are set forth in the background section of the invention.
Disclosure of Invention
The invention aims to provide a paper product moisturizing emulsion, and a preparation method and application thereof. The polyvinyl alcohol is grafted by the waterborne polyurethane to improve the defects of reverse adhesion and poor leveling of the polyvinyl alcohol back coating emulsion, and simultaneously, the excellent water retention performance and barrier property of the polyvinyl alcohol are maintained, so that the paper product is ensured to be moisturized, and the hardened adhesion caused by high temperature in summer is avoided.
In order to solve the technical problem, the invention provides a preparation method of a paper product moisturizing emulsion, which comprises the following steps:
1) Carrying out dehydration reaction on phthalic anhydride polyol and dimethylolpropionic acid to obtain a polyol monomer;
2) Polymerizing the polyol monomer and toluene diisocyanate to obtain a graft polymer, wherein the end group of the graft polymer comprises an isocyanate group;
3) And (2) carrying out an emulsion grafting reaction on a polyvinyl alcohol solution, triethylamine and the graft polymer, and grafting partial hydroxyl of the polyvinyl alcohol with the terminal group of the graft polymer to obtain the paper product moisturizing emulsion.
In the technical scheme, a branched polyol monomer with a plurality of hydroxyl groups is firstly generated and then has a polymerization reaction with toluene diisocyanate, and the obtained graft polymer of polyurethane is provided with certain rigidity caused by steric hindrance brought by a phthalic anhydride group and a plurality of branched chain structures brought by dimethylolpropionic acid, so that when the graft polymer is used for graft modification of the polyvinyl alcohol, rigid steric hindrance can be generated to prevent a plurality of polyvinyl alcohol molecular chains from approaching each other, adhesion is avoided, meanwhile, intermolecular force among the polyvinyl alcohol molecular chains is reduced, especially hydrogen bond interaction, and the fluidity of the polyvinyl alcohol is improved; meanwhile, the multi-branched structure does not hinder the interaction of the small molecules, namely water molecules, and hydroxyl, and the excellent moisture retention performance and the barrier performance of the polyvinyl alcohol to paper are kept.
Further, in the step 1), the molar ratio of the phthalic anhydride polyol to the dimethylolpropionic acid is 1. The setting of the molar ratio ensures that both ends of the polyol monomer have branched dihydroxy structures, improves the branching degree of the grafting group of the modified polyvinyl alcohol, and is favorable for preventing adhesion and keeping moisture.
Furthermore, the temperature of the dehydration reaction is 110-130 ℃, and the time is 0.5-2h.
Further, in the step 2), the mole number of the toluene diisocyanate is 1.1-1.4 times of that of the polyol monomer. The mole ratio ensures that the graft polymer has proper branching degree, if the mole ratio is too high, the polyol monomer has a plurality of hydroxyl groups, the graft polymer which is excessively crosslinked can be formed, the molecular chain appearance is more compact, the negative influence is generated on the water inlet and outlet, and the moisture retention is influenced; if the molar ratio is too low, an insufficient degree of polymerization may result, and the number of isocyanate terminal groups of the graft polymer may be insufficient to generate sufficient steric hindrance, thereby failing to produce an anti-blocking effect.
Further, the step 2) specifically comprises the following steps:
reacting the polyol monomer with a first reaction system consisting of toluene diisocyanate at 70-72 ℃ for 0.5-1h;
then adding an organic metal catalyst into the first reaction system, and reacting for 0.5-2h at the temperature of 80-85 ℃;
and then cooling the first reaction system to below 50 ℃, adding acetone, heating to 70-75 ℃ and reacting for 5-8h to complete the polymerization reaction.
Further, the step 3) specifically comprises the following steps:
fully mixing the polyvinyl alcohol solution, triethylamine and the grafted polymer to form a second reaction system, and reacting for 2-3h at 70-75 ℃;
then, acetone in the second reaction system was removed by heating.
Further, stirring and heating the mixture at 60-70 ℃ for 2-5h to remove the acetone in the second reaction system.
Further, the mass fraction of the polyvinyl alcohol solution is 10-15%;
in the second reaction system, the mass fraction of triethylamine is 2-5%, and the mass fraction of a graft polymer is 1-2%; the molecular weight of the polyvinyl alcohol in the polyvinyl alcohol solution is 2000-5000. When the mass fraction of the polymer is too low or too high, the anti-blocking effect is not preferable when the content is too low, and when the content of the graft polymer is too high, a large amount of hydroxyl groups are occupied by grafting, and moisture retention cannot be maintained.
The invention also provides a paper product moisturizing emulsion, which comprises water and modified polyvinyl alcohol, wherein the modified polyvinyl alcohol comprises a polyvinyl alcohol main chain, and a part of hydroxyl groups of the polyvinyl alcohol main chain are grafted with a graft polymer;
the graft polymer is prepared by polymerizing a polyol monomer and toluene diisocyanate, wherein the polyol monomer is prepared by dehydrating and condensing phthalic anhydride polyol and dimethylolpropionic acid.
The invention also provides application of the paper product moisturizing emulsion in a paper product back coating moisturizing agent.
By means of the technical scheme, the invention has the following beneficial effects:
according to the paper product moisturizing emulsion provided by the invention, a graft polymer which has certain rigidity and a plurality of branched chains is grafted on hydroxyl groups in partial polyvinyl alcohol by a high-molecular grafting method, so that on one hand, the paper product moisturizing emulsion has a certain steric hindrance effect and can prevent the adhesion phenomenon caused by high temperature between polyvinyl alcohol molecular chains, and on the other hand, the multi-branched structure can not obstruct small molecules such as water molecules, so that the reduction of moisturizing performance and obstructing performance caused by grafting is avoided.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention.
It should be noted that, in the description of the present invention, the terms "first", "second", and the like are used for descriptive purposes only and for distinguishing similar objects, and no precedence between the two is considered as indicating or implying relative importance. In addition, in the description of the present invention, "a plurality" means two or more unless otherwise specified.
The embodiment of the invention firstly provides a preparation method of a moisturizing emulsion for paper products, which comprises the following steps:
1) The phthalic anhydride polyalcohol and the dimethylolpropionic acid are subjected to dehydration reaction to obtain a polyalcohol monomer.
2) And (2) carrying out polymerization reaction on the polyol monomer and toluene diisocyanate to obtain the graft polymer, wherein the terminal group of the graft polymer comprises an isocyanate group.
3) And (2) carrying out an emulsion grafting reaction on a polyvinyl alcohol solution, triethylamine and the graft polymer, and grafting partial hydroxyl of the polyvinyl alcohol with the terminal group of the graft polymer to obtain the paper product moisturizing emulsion.
Meanwhile, the embodiment of the invention also provides the paper product moisturizing emulsion prepared by the preparation method and the application of the paper product moisturizing emulsion as a paper product back coating moisturizing agent directly or after being diluted or mixed with other functional components.
As an exemplary application, the method for preparing the moisturizing emulsion for paper products according to the present invention can be implemented by the following steps:
(1) the method comprises the following steps Dissolving the polyvinyl alcohol resin into a solution with the mass fraction of 10% by using water at 65 ℃ for later use.
(2) The method comprises the following steps Adding phthalic anhydride polyalcohol at 120 deg.C, and dehydrating with dimethylolpropionic acid for 1h.
(3) The method comprises the following steps Cooling to below 50 deg.C, adding toluene diisocyanate for reaction at 70-75 deg.C for 0.5h
(4) The method comprises the following steps Adding an organic bismuth catalyst, heating to 80 ℃, and reacting for 1h; it should be noted that the kind of the catalyst provided in the embodiments of the present invention is not limited to the scope of the present invention, and other catalysts capable of catalyzing polyurethane synthesis, such as organotin catalyst, etc., may be used, and are not described herein again.
(5) The method comprises the following steps Cooling to 50 ℃, adding acetone, heating to 70 ℃, introducing condensed water to continuously react for 6 hours to obtain a prepolymer, namely the solution of the graft polymer, wherein the addition amount of the acetone is preferably that the viscosity of a reaction system is proper and the rod climbing phenomenon does not occur.
(6) The method comprises the following steps Adding prepared polyvinyl alcohol resin solution and triethylamine into an emulsifying cylinder, and carrying out emulsification and grafting reaction with the prepolymer under high-speed dispersion for 2-3h
(7) The method comprises the following steps Putting the reacted materials into a reaction kettle, and removing acetone at 60-70 ℃.
(8) The method comprises the following steps After cooling, the discharge was filtered under a 300 mesh filter screen.
According to the technical scheme, the reverse adhesion of the polyvinyl alcohol back coating emulsion is improved by grafting the polyvinyl alcohol with the waterborne polyurethane, the defect of poor leveling is overcome, and the excellent water retention performance and barrier property of the polyvinyl alcohol are maintained, so that the paper product is ensured to be moisturized, and the hardened adhesion caused by high temperature in summer is avoided.
The technical solutions of the present invention are further illustrated by the following specific examples, however, the selected examples are merely representative of the numerous examples and are not meant to limit the scope of the present invention.
In addition, unless otherwise specified, the raw materials, catalysts, reagents and equipment in the following examples are commercially available and conventional in the art, and the technical means of heating, stirring and material transfer in the following examples are conventional in the art.
Example 1
This example illustrates a process for preparing a moisturizing emulsion for paper products, as follows:
adding phthalic anhydride polyalcohol and dimethylolpropionic acid into a reaction kettle, wherein the molar number of the phthalic anhydride polyalcohol is 100 parts, the dimethylolpropionic acid is 210 parts, heating to 110 ℃, and reacting for 2 hours.
After the reaction is finished, when the temperature is reduced to about 40 ℃, 110 parts of toluene diisocyanate is added, the temperature is raised to 70 ℃, and the reaction is carried out for 1 hour.
Adding a commercially available organic bismuth catalyst (DY-20) with the addition amount of 1 percent of the total mass of the reaction system, and heating to 80 ℃ for reaction for 2 hours.
After the reaction is finished, cooling to about 40 ℃, adding a proper amount of acetone, and then heating to 70 ℃ to continue the reaction for 8 hours.
Preparing 10wt% of polyvinyl alcohol solution, adding triethylamine in an amount of 2 wt% and 2 wt% of the graft polymer (the mass of the graft polymer cannot be accurately obtained because the graft polymer is co-dissolved with acetone), heating the graft polymer in an emulsifying cylinder to 70 ℃, and reacting for 3 hours.
Heating is then continued for 2h at 70 ℃ to remove the acetone, although in other embodiments higher temperatures and longer times may be used to remove the acetone.
Finally obtaining the paper product moisturizing emulsion.
Example 2
This example illustrates a process for preparing a moisturizing emulsion for paper products, which is specifically shown below:
adding phthalic anhydride polyalcohol and dimethylolpropionic acid into a reaction kettle, wherein the molar number of the phthalic anhydride polyalcohol is 100 parts, the dimethylolpropionic acid is 230 parts, heating to 130 ℃, and reacting for 0.5h.
After the reaction is finished, when the temperature is reduced to about 40 ℃, 140 parts of toluene diisocyanate is added, the temperature is raised to 75 ℃, and the reaction is carried out for 0.5h.
Adding a commercial organic bismuth catalyst (DY-20) with the addition amount of 3 percent of the total mass of the reaction system, and heating to 85 ℃ for reaction for 0.5h.
After the reaction is finished, cooling to about 40 ℃, adding a proper amount of acetone, then heating to 75 ℃ and continuing the reaction for 5 hours.
Preparing 15wt% of polyvinyl alcohol solution, then adding triethylamine in a mass ratio of 5% into the polyvinyl alcohol solution, and adding 1 wt% of the graft polymer in a mass ratio (the mass of the graft polymer cannot be accurately obtained because the graft polymer is dissolved with acetone, in the invention, the mass of the graft polymer is calculated by the total mass of the materials added, namely the total mass of the phthalic anhydride polyol, the dimethylolpropionic acid and the toluene diisocyanate), heating the mixture to 75 ℃ in an emulsifying cylinder, and reacting for 2 hours.
Heating is then continued for 5h at 60 ℃ to remove the acetone, although in other embodiments higher temperatures and longer times may be used to remove the acetone.
Finally obtaining the paper product moisturizing emulsion.
Example 3
This example illustrates a process for preparing a moisturizing emulsion for paper products, as follows:
adding phthalic anhydride polyalcohol and dimethylolpropionic acid into a reaction kettle, wherein the molar number of the phthalic anhydride polyalcohol is 100 parts, the dimethylolpropionic acid is 210 parts, heating to 120 ℃, and reacting for 1h.
After the reaction is finished, when the temperature is reduced to about 40 ℃, 130 parts of toluene diisocyanate is added, the temperature is raised to 70 ℃, and the reaction is carried out for 1 hour.
Adding a commercially available organic bismuth catalyst (DY-20) with the addition amount of 2 percent of the total mass of the reaction system, and heating to 80 ℃ for reaction for 1 hour.
After the reaction is finished, cooling to about 40 ℃, adding a proper amount of acetone, and then heating to 70 ℃ to continue the reaction for 6 hours.
Preparing 10wt% of polyvinyl alcohol solution, adding triethylamine into the polyvinyl alcohol solution in a mass ratio of 3%, and adding 1.5 wt% of the graft polymer (the mass of the graft polymer cannot be accurately obtained because the graft polymer is dissolved with acetone), wherein the mass of the graft polymer is calculated by the total mass of the materials, namely the total mass of the phthalic anhydride polyol, the dimethylolpropionic acid and the toluene diisocyanate), heating the mixture in an emulsifying cylinder to 75 ℃, and reacting for 3 hours.
Heating is then continued at 70 ℃ for 2h to remove the acetone, although in other embodiments higher temperatures and longer times may be used to remove the acetone.
Finally obtaining the paper product moisturizing emulsion.
Comparative example 1
This example illustrates the preparation of a moisturizing emulsion for paper products, which is substantially the same as example 1, except that:
the phthalic anhydride polyol is replaced by polyester polyol, and the rest steps and parameters are unchanged.
Comparative example 2
This example illustrates the preparation of a moisturizing emulsion for paper products, substantially the same as example 1, except that:
the adding amount of dimethylolpropionic acid is 100 parts, and the rest steps and parameters are unchanged.
Comparative example 3
This example illustrates the preparation of a moisturizing emulsion for paper products, substantially the same as example 1, except that:
dimethylolpropionic acid was not added, and the remaining steps and parameters were unchanged.
Comparative example 4
This example illustrates the preparation of a moisturizing emulsion for paper products, substantially the same as example 1, except that:
during the emulsification and grafting reaction, the graft polymer loading was 4wt%.
Comparative example 5
This example illustrates the preparation of a moisturizing emulsion for paper products, substantially the same as example 1, except that:
during the emulsification and grafting reaction, the graft polymer loading was 10wt%.
The 20 papers in each group were coated with ungrafted polyvinyl alcohol and grafted polyvinyl alcohol as provided in example 1 and comparative examples 1-5 above, and dried in an oven at 50 c for comparative testing.
Through the above experiments, it can be seen that the anti-blocking performance of the moisturizing emulsion formed by the grafted polyvinyl alcohol provided in example 1 is obviously improved compared with that of the common polyvinyl alcohol and the grafted polyvinyl alcohols provided in comparative examples 1 to 3.
The anti-blocking property of the moisturizing emulsions provided in comparative examples 4-5 is comparable to that of example 1, and may be even slightly better than that of example 1, but the moisturizing performance of the moisturizing emulsions provided in comparative examples 4-5 is severely reduced, dry wrinkles of the paper appear at 24h of drying, and the paper of example 1 is not excessively dried all the time.
The inventors also performed the same anti-adhesion performance test on the moisturizing emulsions of examples 2-4, which has the same test results as example 1 and will not be described herein.
Through the embodiments and the comparative examples, it is clear that the paper product moisturizing emulsion provided by the embodiments of the present invention, through a high molecular grafting method, makes part of the hydroxyl groups in the polyvinyl alcohol graft a graft polymer having a certain rigidity and a plurality of branched chains, on one hand, the graft polymer has a certain steric hindrance effect, and can prevent the adhesion phenomenon caused by high temperature between polyvinyl alcohol molecular chains, and on the other hand, the multi-branched structure does not cause barrier to a small molecule, i.e., a water molecule, thereby avoiding the decrease of moisturizing performance and barrier performance caused by grafting.
The above-mentioned embodiments are merely preferred embodiments for fully illustrating the present invention, and the scope of the present invention is not limited thereto. The equivalent substitution or change made by the technical personnel in the technical field on the basis of the invention is all within the protection scope of the invention. The protection scope of the invention is subject to the claims.
Claims (10)
1. A preparation method of a paper product moisturizing emulsion is characterized by comprising the following steps:
1) Carrying out dehydration reaction on phthalic anhydride polyol and dimethylolpropionic acid to obtain a polyol monomer;
2) Polymerizing the polyol monomer and toluene diisocyanate to obtain a graft polymer, wherein the end group of the graft polymer comprises an isocyanate group;
3) And (2) carrying out an emulsion grafting reaction on a polyvinyl alcohol solution, triethylamine and the graft polymer, and grafting partial hydroxyl of the polyvinyl alcohol with the terminal group of the graft polymer to obtain the paper product moisturizing emulsion.
2. The method according to claim 1, wherein the molar ratio of the phthalic anhydride polyol to the dimethylolpropionic acid in step 1) is 1.
3. The process according to claim 2, wherein the dehydration reaction is carried out at a temperature of 110 to 130 ℃ for a time of 0.5 to 2 hours.
4. The method according to claim 1, wherein the toluene diisocyanate is present in an amount of 1.1 to 1.4 times the molar amount of the polyol monomer in step 2).
5. The method according to claim 4, wherein the step 2) comprises:
reacting the polyol monomer with a first reaction system consisting of toluene diisocyanate at 70-75 ℃ for 0.5-1h;
then adding an organic metal catalyst into the first reaction system, and reacting for 0.5-2h at the temperature of 80-85 ℃;
and then cooling the first reaction system to below 50 ℃, adding acetone, heating to 70-75 ℃ and reacting for 5-8h to complete the polymerization reaction.
6. The method according to claim 5, wherein step 3) comprises:
fully mixing the polyvinyl alcohol solution, triethylamine and the grafted polymer to form a second reaction system, and reacting for 2-3h at 70-75 ℃;
then, acetone in the second reaction system was removed by heating.
7. The preparation method according to claim 6, wherein the acetone in the second reaction system is removed by stirring and heating at 60-70 ℃ for 2-5 h.
8. The preparation method according to claim 6, wherein the mass fraction of the polyvinyl alcohol solution is 10-15%;
in the second reaction system, the mass fraction of triethylamine is 2-5%, and the mass fraction of the graft polymer is 1-2%;
the molecular weight of the polyvinyl alcohol in the polyvinyl alcohol solution is 2000-5000.
9. The moisturizing emulsion for paper products prepared by the preparation method of any of claims 1 to 8, comprising water and modified polyvinyl alcohol, wherein the modified polyvinyl alcohol comprises a polyvinyl alcohol main chain, and a part of hydroxyl groups of the polyvinyl alcohol main chain is grafted with a graft polymer;
the graft polymer is prepared by polymerizing a polyol monomer and toluene diisocyanate, wherein the polyol monomer is prepared by dehydrating and condensing phthalic anhydride polyol and dimethylolpropionic acid.
10. Use of the paper product moisturizing emulsion of claim 9 in a moisturizing agent applied to the back of a paper product.
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CN103589135A (en) * | 2013-10-17 | 2014-02-19 | 常州大学 | Preparation method of polyvinyl alcohol modified waterborne polyurethane |
CN110003398A (en) * | 2019-04-28 | 2019-07-12 | 安徽匠星联创新材料科技有限公司 | A kind of polyvinyl alcohol modification water-based polyurethane-acrylate emulsion |
CN114395103A (en) * | 2021-09-30 | 2022-04-26 | 明新孟诺卡(江苏)新材料有限公司 | Microfiber synthetic leather waterborne polyurethane impregnated resin and preparation method thereof |
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Publication number | Priority date | Publication date | Assignee | Title |
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CN103589135A (en) * | 2013-10-17 | 2014-02-19 | 常州大学 | Preparation method of polyvinyl alcohol modified waterborne polyurethane |
CN110003398A (en) * | 2019-04-28 | 2019-07-12 | 安徽匠星联创新材料科技有限公司 | A kind of polyvinyl alcohol modification water-based polyurethane-acrylate emulsion |
CN114395103A (en) * | 2021-09-30 | 2022-04-26 | 明新孟诺卡(江苏)新材料有限公司 | Microfiber synthetic leather waterborne polyurethane impregnated resin and preparation method thereof |
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