CN116695484B - Cationic rosin/formaldehyde urea resin composite sizing agent and preparation method thereof - Google Patents
Cationic rosin/formaldehyde urea resin composite sizing agent and preparation method thereof Download PDFInfo
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- CN116695484B CN116695484B CN202310837460.9A CN202310837460A CN116695484B CN 116695484 B CN116695484 B CN 116695484B CN 202310837460 A CN202310837460 A CN 202310837460A CN 116695484 B CN116695484 B CN 116695484B
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- rosin
- urea resin
- cationic
- urea
- formaldehyde
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- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 title claims abstract description 67
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 title claims abstract description 66
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 229920001807 Urea-formaldehyde Polymers 0.000 title claims abstract description 52
- 125000002091 cationic group Chemical group 0.000 title claims abstract description 40
- 238000004513 sizing Methods 0.000 title claims abstract description 32
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 25
- ODGAOXROABLFNM-UHFFFAOYSA-N polynoxylin Chemical compound O=C.NC(N)=O ODGAOXROABLFNM-UHFFFAOYSA-N 0.000 title claims abstract description 15
- 239000000805 composite resin Substances 0.000 title claims abstract description 13
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 30
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000004202 carbamide Substances 0.000 claims abstract description 14
- OWEGMIWEEQEYGQ-UHFFFAOYSA-N 100676-05-9 Natural products OC1C(O)C(O)C(CO)OC1OCC1C(O)C(O)C(O)C(OC2C(OC(O)C(O)C2O)CO)O1 OWEGMIWEEQEYGQ-UHFFFAOYSA-N 0.000 claims abstract description 13
- GUBGYTABKSRVRQ-PICCSMPSSA-N Maltose Natural products O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@@H]1O[C@@H]1[C@@H](CO)OC(O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-PICCSMPSSA-N 0.000 claims abstract description 13
- 239000001530 fumaric acid Substances 0.000 claims abstract description 13
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 13
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000009775 high-speed stirring Methods 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 238000001816 cooling Methods 0.000 claims description 20
- 238000010438 heat treatment Methods 0.000 claims description 19
- 238000003756 stirring Methods 0.000 claims description 18
- 239000002131 composite material Substances 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 239000007787 solid Substances 0.000 claims description 8
- -1 cationic quaternary ammonium salt Chemical class 0.000 claims description 7
- 239000004094 surface-active agent Substances 0.000 claims description 7
- HSJKGGMUJITCBW-UHFFFAOYSA-N 3-hydroxybutanal Chemical compound CC(O)CC=O HSJKGGMUJITCBW-UHFFFAOYSA-N 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 5
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 4
- 239000004952 Polyamide Substances 0.000 claims description 4
- 229910021645 metal ion Inorganic materials 0.000 claims description 4
- 229920002647 polyamide Polymers 0.000 claims description 4
- 229920000768 polyamine Polymers 0.000 claims description 4
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 claims description 3
- 239000011654 magnesium acetate Substances 0.000 claims description 3
- 229940069446 magnesium acetate Drugs 0.000 claims description 3
- 235000011285 magnesium acetate Nutrition 0.000 claims description 3
- 238000013329 compounding Methods 0.000 claims 1
- 230000001276 controlling effect Effects 0.000 claims 1
- 230000001105 regulatory effect Effects 0.000 claims 1
- GZCGUPFRVQAUEE-SLPGGIOYSA-N aldehydo-D-glucose Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O GZCGUPFRVQAUEE-SLPGGIOYSA-N 0.000 abstract description 15
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 abstract description 9
- GUBGYTABKSRVRQ-QUYVBRFLSA-N beta-maltose Chemical compound OC[C@H]1O[C@H](O[C@H]2[C@H](O)[C@@H](O)[C@H](O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@@H]1O GUBGYTABKSRVRQ-QUYVBRFLSA-N 0.000 abstract description 8
- 239000000839 emulsion Substances 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 5
- STGGGMRYUUNYNC-UHFFFAOYSA-N furan-2-carbaldehyde;urea Chemical compound NC(N)=O.O=CC1=CC=CO1 STGGGMRYUUNYNC-UHFFFAOYSA-N 0.000 abstract description 4
- 238000006068 polycondensation reaction Methods 0.000 abstract description 4
- 229920005989 resin Polymers 0.000 abstract description 3
- 239000011347 resin Substances 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 231100000053 low toxicity Toxicity 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 238000000034 method Methods 0.000 description 6
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 239000000835 fiber Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- 229920001131 Pulp (paper) Polymers 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 2
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 2
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 230000001804 emulsifying effect Effects 0.000 description 2
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 2
- 229940078494 nickel acetate Drugs 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000004246 zinc acetate Substances 0.000 description 2
- 208000023445 Congenital pulmonary airway malformation Diseases 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000004026 adhesive bonding Methods 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 235000012222 talc Nutrition 0.000 description 1
- 229960000314 zinc acetate Drugs 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
- C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
- C08G12/04—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds
- C08G12/10—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds with acyclic compounds having the moiety X=C(—N<)2 in which X is O, S or —N
- C08G12/12—Ureas; Thioureas
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09F—NATURAL RESINS; FRENCH POLISH; DRYING-OILS; OIL DRYING AGENTS, i.e. SICCATIVES; TURPENTINE
- C09F1/00—Obtaining purification, or chemical modification of natural resins, e.g. oleo-resins
- C09F1/04—Chemical modification, e.g. esterification
-
- 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
- D21H17/46—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/47—Condensation polymers of aldehydes or ketones
- D21H17/49—Condensation polymers of aldehydes or ketones with compounds containing hydrogen bound to nitrogen
-
- 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
- D21H17/62—Rosin; Derivatives thereof
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- General Chemical & Material Sciences (AREA)
- Paper (AREA)
Abstract
The invention provides a cationic rosin/uronic urea resin composite sizing agent, which consists of cationic rosin, uronic urea resin and a proper amount of emulsifying agent, wherein the uronic urea resin accounts for 4-30% of the total weight of the cationic rosin and the uronic urea resin; the cationic rosin is maleic anhydride and fumaric acid modified rosin, and the urea formaldehyde resin is formed by polycondensation of urea and maltose. The preparation method comprises the steps of uniformly mixing the furfural urea resin and the cationic rosin, adding an emulsifying agent under high-speed stirring, and then adding hot water for phase inversion. According to the invention, the formaldehyde urea resin is introduced to replace part of cationic rosin, the formaldehyde resin formed by condensing maltose and urea has the advantages of low toxicity, environmental protection and low cost, the excellent performances of the formaldehyde urea resin and rosin are comprehensively utilized, the prepared sizing agent emulsion is stable and is not layered, the water resistance and printing adaptability of the paper after sizing are effectively improved, the raw materials of the formaldehyde urea resin are cheap and easily obtained, the price is not limited by seasons, and the sizing material cost is greatly reduced.
Description
Technical Field
The invention relates to the technical field of papermaking sizing agents, in particular to a composite sizing agent containing urea formaldehyde resin and a preparation method thereof.
Background
Rosin is a mixture of resin acid, a small amount of fatty acid, rosin anhydride and other substances, and is often used as an internal sizing agent in the papermaking field, mainly used for improving the water resistance of paper, preventing ink from penetrating and facilitating printing. Rosin has fluctuating price when affected by seasons, and the gluing cost is difficult to control, so that a rosin supplement with low cost and easy manufacture needs to be developed to relieve the influence caused by rosin price fluctuation.
Disclosure of Invention
The invention aims to provide a compound sizing agent of formaldehyde-urea resin capable of replacing or reducing rosin consumption and a preparation method thereof, wherein the formaldehyde-urea resin is formed by polycondensation of maltose and urea under the action of a catalyst, the novel sizing agent can be developed by replacing part of rosin to be applied to papermaking sizing agents, so that the stability and sizing effect of the novel sizing agent are improved, and the production cost is reduced.
The invention is realized by adopting the following technical scheme:
a cationic rosin/uronic urea resin composite sizing agent consists of cationic rosin, uronic urea resin and a proper amount of emulsifying agent, wherein the uronic urea resin accounts for 4-30% of the total weight of the cationic rosin and the uronic urea resin; the cationic rosin is maleic anhydride and fumaric acid modified rosin, and the urea formaldehyde resin is formed by polycondensation of urea and maltose.
The cationic rosin is prepared by methods conventional in the art, for example, by the following methods: 70-95 parts by weight of rosin is added into a reaction kettle, the temperature is raised to 180-220 ℃, 3.5-8 parts by weight of maleic anhydride and fumaric acid are added to modify the rosin, and the weight ratio of the maleic anhydride to the fumaric acid is 1: 1.
The urea and maltose in the formaldehyde urea resin are in a molar ratio of (1-4): (1-2) polycondensation. For example, the preparation method comprises the following steps: adding urea and maltose into a reaction kettle in proportion, starting stirring, heating to 70-110 ℃, adding a metal ion catalyst, reacting for 5-8 hours, and cooling to room temperature to obtain reddish brown viscous furfural urea resin.
The metal ion catalyst is at least one selected from zinc acetate, magnesium acetate, nickel acetate and copper acetate; the mass percent of the added additive is 0.1-2%.
The emulsifier used in the cationic rosin/formaldehyde urea resin composite sizing agent can be an emulsifier commonly used in the field, preferably a cationic emulsifier, and most preferably a composite cationic emulsifier consisting of a cationic quaternary ammonium salt surfactant and polyamide polyamine epichlorohydrin.
The inventor finds that after the urea formaldehyde resin is emulsified by the emulsifier, if the synergistic effect of the cationic rosin is not generated, the product can be layered in a short time, and a stable emulsion state can not be formed; when the substitution amount of the urea formaldehyde resin reaches more than 30%, the emulsifying effect is also poor, the color of the sizing material is deep, and brown small granular substances appear during the emulsifying process. Thus the optimum substitution amount of the aldol urea resin is between 4 and 30%.
The invention further provides a preparation method of the cationic rosin/formaldehyde urea resin composite sizing agent, which comprises the following steps:
S1, adding urea and maltose into a reaction kettle according to a proportion, starting stirring, heating to 70-110 ℃, adding a metal ion catalyst, reacting for 5-8 hours, and cooling to room temperature to obtain the aldol urea resin;
S2, adding rosin into a reaction kettle, heating to 180-220 ℃, and then adding maleic anhydride and fumaric acid to modify the rosin to obtain cationic rosin;
S3, cooling to 120-150 ℃, adding the furfural urea resin with the dosage of 5-30% of the mass of rosin, uniformly mixing, adding an emulsifying agent with the dosage of 10-30% of the mass of rosin under high-speed stirring, uniformly stirring at the temperature of 60-95 ℃, adding hot water for phase inversion, adjusting the solid content to 30-50%, and cooling to room temperature to obtain the cationic rosin/furfural urea resin composite sizing agent.
Preferably, the emulsifier is a composite emulsifier of cationic quaternary ammonium salt surfactant and polyamide polyamine epichlorohydrin, wherein the cationic quaternary ammonium salt surfactant accounts for 20-50% of the total weight of the composite emulsifier.
Preferably, in step S3, the stirring speed during the phase inversion of the hot water is controlled to be 1500-2000rpm/min.
Compared with the prior art, the invention has the beneficial effects that:
1) The invention introduces the urea formaldehyde resin to replace part of cationic rosin, the formaldehyde resin formed by condensing maltose and urea has the advantages of low toxicity, environmental protection and low cost, and has more hydroxyl groups, and the formaldehyde resin is added into rosin, thereby being more beneficial to the phase inversion emulsification of the rosin and leading the prepared emulsion to be more stable.
2) The formaldehyde-urea resin is adopted to prepare rosin size, not only is the carboxyl of rosin react with the hydroxyl of fibers, but also the emulsion can permeate into the fibers after being added into paper pulp, and dehydration condensation is carried out on the emulsion and the hydroxyl of the fibers, so that the slidability between the fibers of paper after the paper is soaked by water is reduced, the water resistance of the paper is improved, and a certain wet strength effect is also produced. The excellent properties of the urea formaldehyde resin and rosin are comprehensively utilized, the prepared sizing agent emulsion is stable and does not delaminate, and the water resistance and printing adaptability of the sized paper are effectively improved.
3) The raw materials of the formaldehyde urea resin are cheap and easy to obtain, the price is not limited by seasons, and the cost of the sizing material is greatly reduced.
Detailed Description
The following description is presented to enable one of ordinary skill in the art to make and use the invention. The preferred embodiments in the following description are by way of example only and are not intended to limit the scope of the invention, as other obvious variations will occur to those skilled in the art. The basic principles of the invention defined in the following description may be applied to other embodiments, variations, modifications, equivalents, and other technical solutions without departing from the spirit and scope of the invention.
The apparatus or materials of the present invention are not identified to the manufacturer and are conventional commercial apparatus or materials. Wherein the mass ratio of the maleic anhydride to the fumaric acid is 1:1, the composite cationic emulsifier adopts a composite emulsifier of cationic quaternary ammonium salt surfactant and polyamide polyamine epichlorohydrin, wherein the cationic quaternary ammonium salt surfactant accounts for 20 percent of the total weight of the composite emulsifier.
The detection indexes related to the embodiment of the invention are detected by adopting a conventional detection method in the field as not mentioned.
Example 1
Weighing 60g of urea and 342g of maltose into a dry reaction kettle, stirring, heating to 70 ℃, adding 8g of zinc acetate, reacting for 5 hours, and cooling to room temperature to obtain reddish brown viscous formaldehyde urea resin.
Adding 70g of rosin into a reaction kettle, heating to 180 ℃, adding 3.5g of maleic anhydride and fumaric acid to modify the rosin, cooling to 150 ℃, adding 3.5g of the urea formaldehyde resin synthesized in the first step, uniformly mixing, adding 21g of a composite cationic emulsifier under high-speed stirring, heating the emulsifier to 60 ℃, uniformly stirring, adding hot water to perform phase inversion, controlling the rotating speed at 1500rmp/min during phase inversion, adjusting the solid content to 30%, and cooling to room temperature to obtain the cationic rosin/urea formaldehyde resin composite sizing agent.
Example 2
120G of urea and 1000g of maltose are weighed and added into a dry reaction kettle, stirring is started, heating is carried out to 90 ℃, 1.12g of magnesium acetate is added, the reaction time is 8 hours, and the temperature is reduced to room temperature to obtain reddish brown viscous urea formaldehyde resin.
Adding 95g of rosin into a reaction kettle, heating to 180 ℃, adding 7.6g of maleic anhydride and fumaric acid to modify the rosin, cooling to 120 ℃, adding 19g of the urea formaldehyde resin synthesized in the first step, uniformly mixing, adding 28.5g of a composite cationic emulsifier under high-speed stirring, heating the emulsifier to 60 ℃, uniformly stirring, adding hot water to perform phase inversion, controlling the rotating speed at 1800rmp/min during phase inversion, adjusting the solid content to 40%, and cooling to room temperature to obtain the cationic rosin/urea formaldehyde resin composite sizing agent.
Example 3
Weighing 90g of urea and 1368g of maltose into a dry reaction kettle, stirring, heating to 110 ℃, adding 1.4g of nickel acetate, reacting for 6 hours, and cooling to room temperature to obtain reddish brown viscous urea formaldehyde resin.
Adding 80g of rosin into a reaction kettle, heating to 220 ℃, adding 4g of maleic anhydride and fumaric acid to modify the rosin, cooling to 130 ℃ after modification, adding 24g of the urea resin of the first step of synthesis, uniformly mixing, adding 16g of the composite cationic emulsifier under high-speed stirring, heating the emulsifier to 95 ℃, uniformly stirring, adding hot water to perform phase inversion, controlling the rotating speed at 2000rmp/min during phase inversion, adjusting the solid content to 40%, and cooling to room temperature to obtain the cationic rosin/urea resin composite sizing agent.
Example 4
Weighing 60g of urea and 1200g of maltose, adding the urea into a dry reaction kettle, starting stirring, heating to 100 ℃, adding 1.2g of copper acetate, reacting for 7 hours, and cooling to room temperature to obtain reddish brown viscous furfural urea resin.
Adding 80g of rosin into a reaction kettle, heating to 200 ℃, adding 4g of maleic anhydride and fumaric acid to modify the rosin, cooling to 140 ℃ after modification, adding 16g of the urea resin of the first step of synthesis, uniformly mixing, adding 8g of composite cationic emulsifier under high-speed stirring, heating the emulsifier to 80 ℃, uniformly stirring, adding hot water to perform phase inversion, controlling the rotating speed at 2000rmp/min during phase inversion, adjusting the solid content to 50%, and cooling to room temperature to obtain the cationic rosin/urea resin composite sizing agent.
Comparative example
Adding 80g of rosin into a reaction kettle, heating to 200 ℃, adding 4g of maleic anhydride and fumaric acid to modify the rosin, cooling to 140 ℃ after modification, adding 8g of composite cationic emulsifier under high-speed stirring, heating the emulsifier to 80 ℃, uniformly stirring, adding hot water to perform phase inversion, controlling the rotating speed at 2000rmp/min during phase inversion, adjusting the solid content to 40%, and cooling to room temperature to obtain the cationic rosin size.
Application examples
The sizing agents of examples 1-4 and comparative examples were applied to paper stock internal sizing at an add-on level of 9Kg/t paper.
The specific process is as follows:
Design and manufacture the ration 100g/m 2
The process comprises the following steps: slurry 85% + aluminum sulfate + rosin size + talc 15% + CPAM (200 ppm)
Rosin size 9kg/t paper (wet/dry, 35% solids for each sample added.)
According to the process, the pH value of blank paper pulp is adjusted to about 5.0 by using a dissolved 30% aluminum sulfate solution, rosin gum is added, talcum powder is added after stirring for 1min, retention aid is added after stirring for 1min, the prepared slurry is taken down after stirring for 1min, the slurry is sheet-formed by using a 73-62 semi-automatic sheet former, and after the value is pressed by using a 73-50 standard sheet press, the paper sample is dried by a glazing machine, and the value of the paper sample 1minCobb is detected. The test results are shown in Table 1.
Table 1 results of the test of the water absorption properties of paper after sizing with different sizing agents
From the water absorption value of the handsheet, the urea formaldehyde resin replaces part of the cationic rosin, and the water-resistant effect of the sizing agent prepared from the urea formaldehyde resin and all the cationic rosin is not obviously reduced and is enhanced.
It will be appreciated by persons skilled in the art that the above embodiments are by way of example only and not limiting of the invention. The objects of the present invention have been fully and effectively achieved. The function and principles of the present invention have been illustrated and described in the examples and embodiments of the present invention may be subject to any variations or modifications without departing from the principles.
Claims (1)
1. The cationic rosin/uronic urea resin composite sizing agent is characterized by comprising cationic rosin, uronic urea resin and a proper amount of emulsifying agent, and the preparation method comprises the following steps:
S1, adding 120g of urea and 1000g of maltose into a reaction kettle, starting stirring, heating to 90 ℃, adding a metal ion catalyst magnesium acetate, reacting for 8 hours, and cooling to room temperature to obtain the aldol urea resin;
S2, adding 95g of rosin into a reaction kettle, heating to 180 ℃, and adding 7.6g of maleic anhydride and fumaric acid to modify the rosin to obtain cationic rosin, wherein the mass ratio of the maleic anhydride to the fumaric acid is (1): 1, compounding;
S3, cooling to 120 ℃, adding the formaldehyde urea resin with the dosage of 19g, uniformly mixing, adding 28.5g of a composite cationic emulsifier under high-speed stirring, uniformly stirring at 60 ℃, adding hot water, switching phases, controlling the rotating speed to 1800rpm/min, regulating the solid content to 40%, and cooling to room temperature to obtain the cationic rosin/formaldehyde urea resin composite sizing agent; the composite cationic emulsifier adopts a composite emulsifier of cationic quaternary ammonium salt surfactant and polyamide polyamine epichlorohydrin, wherein the cationic quaternary ammonium salt surfactant accounts for 20% of the total weight of the composite emulsifier.
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| JP2864022B2 (en) * | 1989-05-31 | 1999-03-03 | 日本ピー・エム・シー株式会社 | Method for producing cationic rosin emulsion sizing agent |
| US6042691A (en) * | 1998-12-08 | 2000-03-28 | Plasmine Technology, Inc. | Cationic dispersions of fortified and modified rosins for use as paper sizing agents |
| JP2004044020A (en) * | 2002-07-12 | 2004-02-12 | Seiko Pmc Corp | Rosin emulsion sizing agent |
| CN103628356B (en) * | 2013-11-27 | 2015-10-28 | 杭州杭化哈利玛化工有限公司 | A kind of novel cation rosin sizing agent and application thereof |
| CN104725775B (en) * | 2015-03-18 | 2016-09-14 | 桂林兴松林化有限责任公司 | A kind of preparation method of the Abietyl modified Lauxite of nano silicon |
| CN107236133A (en) * | 2016-03-29 | 2017-10-10 | 上海东升新材料有限公司 | A kind of preparation method of cationic rosin size |
| CN106283850A (en) * | 2016-08-29 | 2017-01-04 | 上海东升新材料有限公司 | A kind of Reaction Cationic Rosin Sizing and preparation method thereof |
| CN111576082A (en) * | 2020-04-23 | 2020-08-25 | 上海东升新材料有限公司 | Cation dispersed rosin size and preparation method thereof |
| CN115058919A (en) * | 2022-06-30 | 2022-09-16 | 济宁明升新材料有限公司 | Preparation method of rosin substitute/cationic rosin sizing agent |
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| 王永贵 等."麦芽糖-尿素木材胶粘剂的合成与性能".《化工新型材料》.(第01期),正文前言、第1.2树脂胶粘剂的合成、第3结论部分. * |
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