CN114108371A - UV-cured paper surface sizing agent and preparation and application thereof - Google Patents
UV-cured paper surface sizing agent and preparation and application thereof Download PDFInfo
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- CN114108371A CN114108371A CN202111502414.0A CN202111502414A CN114108371A CN 114108371 A CN114108371 A CN 114108371A CN 202111502414 A CN202111502414 A CN 202111502414A CN 114108371 A CN114108371 A CN 114108371A
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- Prior art keywords
- paper
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- surface sizing
- sizing agent
- stirring
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- 238000004513 sizing Methods 0.000 title claims abstract description 68
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000000123 paper Substances 0.000 claims abstract description 122
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 103
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 67
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 54
- 238000003848 UV Light-Curing Methods 0.000 claims abstract description 38
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 34
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 32
- 239000005543 nano-size silicon particle Substances 0.000 claims abstract description 31
- 229920000728 polyester Polymers 0.000 claims abstract description 31
- XLPJNCYCZORXHG-UHFFFAOYSA-N 1-morpholin-4-ylprop-2-en-1-one Chemical compound C=CC(=O)N1CCOCC1 XLPJNCYCZORXHG-UHFFFAOYSA-N 0.000 claims abstract description 18
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 14
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000011248 coating agent Substances 0.000 claims abstract description 10
- 238000000576 coating method Methods 0.000 claims abstract description 10
- 238000001723 curing Methods 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims description 49
- 239000000377 silicon dioxide Substances 0.000 claims description 35
- 238000010438 heat treatment Methods 0.000 claims description 34
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 30
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 22
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 22
- JOXIMZWYDAKGHI-UHFFFAOYSA-N p-toluenesulfonic acid Substances CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 22
- 239000000839 emulsion Substances 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 18
- 238000001816 cooling Methods 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 14
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Substances CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 13
- 238000010992 reflux Methods 0.000 claims description 13
- 239000003054 catalyst Substances 0.000 claims description 12
- MBHINSULENHCMF-UHFFFAOYSA-N n,n-dimethylpropanamide Chemical compound CCC(=O)N(C)C MBHINSULENHCMF-UHFFFAOYSA-N 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 10
- 238000006116 polymerization reaction Methods 0.000 claims description 10
- 239000000843 powder Substances 0.000 claims description 10
- 239000000725 suspension Substances 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- 239000012452 mother liquor Substances 0.000 claims description 9
- ZDQNWDNMNKSMHI-UHFFFAOYSA-N 1-[2-(2-prop-2-enoyloxypropoxy)propoxy]propan-2-yl prop-2-enoate Chemical group C=CC(=O)OC(C)COC(C)COCC(C)OC(=O)C=C ZDQNWDNMNKSMHI-UHFFFAOYSA-N 0.000 claims description 8
- GTELLNMUWNJXMQ-UHFFFAOYSA-N 2-ethyl-2-(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical class OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.CCC(CO)(CO)CO GTELLNMUWNJXMQ-UHFFFAOYSA-N 0.000 claims description 8
- WILBZOKCISUVDL-UHFFFAOYSA-M benzyl-dimethyl-tridecylazanium;bromide Chemical compound [Br-].CCCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 WILBZOKCISUVDL-UHFFFAOYSA-M 0.000 claims description 8
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 8
- 239000001361 adipic acid Substances 0.000 claims description 7
- 235000011037 adipic acid Nutrition 0.000 claims description 7
- 239000003112 inhibitor Substances 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 7
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 5
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 5
- 238000001354 calcination Methods 0.000 claims description 5
- 239000004202 carbamide Substances 0.000 claims description 5
- 239000003085 diluting agent Substances 0.000 claims description 5
- 238000007599 discharging Methods 0.000 claims description 5
- 238000004821 distillation Methods 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 5
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- 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 description 5
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 5
- -1 4-methylthiophenyl Chemical group 0.000 claims description 4
- GUCYFKSBFREPBC-UHFFFAOYSA-N [phenyl-(2,4,6-trimethylbenzoyl)phosphoryl]-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C(=O)C1=C(C)C=C(C)C=C1C GUCYFKSBFREPBC-UHFFFAOYSA-N 0.000 claims description 4
- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 claims description 4
- 239000003292 glue Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 229920001897 terpolymer Polymers 0.000 claims description 3
- 125000000687 hydroquinonyl group Chemical group C1(O)=C(C=C(O)C=C1)* 0.000 claims description 2
- 230000001678 irradiating effect Effects 0.000 claims description 2
- 125000005489 p-toluenesulfonic acid group Chemical group 0.000 claims description 2
- 239000003995 emulsifying agent Substances 0.000 abstract description 12
- 239000000835 fiber Substances 0.000 abstract description 11
- 239000000126 substance Substances 0.000 abstract description 8
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 abstract description 5
- 238000010521 absorption reaction Methods 0.000 abstract description 5
- 239000001257 hydrogen Substances 0.000 abstract description 3
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 3
- 230000009467 reduction Effects 0.000 abstract description 3
- 230000008961 swelling Effects 0.000 abstract description 2
- 239000003513 alkali Substances 0.000 abstract 1
- 238000010008 shearing Methods 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 11
- 238000012512 characterization method Methods 0.000 description 8
- 238000001514 detection method Methods 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 239000011436 cob Substances 0.000 description 7
- 239000003960 organic solvent Substances 0.000 description 6
- 230000009172 bursting Effects 0.000 description 5
- 239000002131 composite material Substances 0.000 description 5
- 229920000620 organic polymer Polymers 0.000 description 5
- 239000002313 adhesive film Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 238000000016 photochemical curing Methods 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
- 230000002035 prolonged effect Effects 0.000 description 3
- 230000037303 wrinkles Effects 0.000 description 3
- 229920001661 Chitosan Polymers 0.000 description 2
- 230000002745 absorbent Effects 0.000 description 2
- 239000002250 absorbent Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000007306 functionalization reaction Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000011087 paperboard Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- NNAHKQUHXJHBIV-UHFFFAOYSA-N 2-methyl-1-(4-methylthiophen-2-yl)-2-morpholin-4-ylpropan-1-one Chemical compound CC1=CSC(C(=O)C(C)(C)N2CCOCC2)=C1 NNAHKQUHXJHBIV-UHFFFAOYSA-N 0.000 description 1
- 208000010392 Bone Fractures Diseases 0.000 description 1
- 206010017076 Fracture Diseases 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 208000013201 Stress fracture Diseases 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000011111 cardboard Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910003471 inorganic composite material Inorganic materials 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000010413 mother solution Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000011863 silicon-based powder Substances 0.000 description 1
- XJKVPKYVPCWHFO-UHFFFAOYSA-N silicon;hydrate Chemical compound O.[Si] XJKVPKYVPCWHFO-UHFFFAOYSA-N 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Classifications
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- 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
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
-
- 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
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/10—Esters
- C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
- C08F222/106—Esters of polycondensation macromers
- C08F222/1061—Esters of polycondensation macromers of alcohol terminated polyesters or polycarbonates, e.g. polyester (meth)acrylates
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H19/00—Coated paper; Coating material
- D21H19/36—Coatings with pigments
- D21H19/38—Coatings with pigments characterised by the pigments
- D21H19/40—Coatings with pigments characterised by the pigments siliceous, e.g. clays
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H19/00—Coated paper; Coating material
- D21H19/36—Coatings with pigments
- D21H19/44—Coatings with pigments characterised by the other ingredients, e.g. the binder or dispersing agent
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H19/00—Coated paper; Coating material
- D21H19/36—Coatings with pigments
- D21H19/44—Coatings with pigments characterised by the other ingredients, e.g. the binder or dispersing agent
- D21H19/46—Non-macromolecular organic 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
- D21H19/00—Coated paper; Coating material
- D21H19/36—Coatings with pigments
- D21H19/44—Coatings with pigments characterised by the other ingredients, e.g. the binder or dispersing agent
- D21H19/62—Macromolecular organic compounds or oligomers thereof obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
-
- 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
- D21H21/50—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 form
- D21H21/52—Additives of definite length or shape
- D21H21/54—Additives of definite length or shape being spherical, e.g. microcapsules, beads
Abstract
The invention relates to a UV-cured paper surface sizing agent and preparation and application thereof, belonging to the technical field of paper surface sizing agents. The acryloyl morpholine, the organic functional dendritic nano silicon dioxide and the polyester acrylate prepolymer are used as main components, the polar acryloyl morpholine is used for replacing the traditional styrene and acrylic acid, the polar acryloyl morpholine can be combined with fiber hydrogen bonds in paper, and the high-temperature resistant, saline-alkali resistant, shearing resistant, high curing speed and other excellent characteristics are achieved. The addition of the nano silicon dioxide endows the surface sizing agent with excellent water resistance, mechanical property and heat resistance, and improves the ultraviolet absorptivity. After UV curing, the polyester acrylate prepolymer is polymerized and crosslinked to form a high-molecular net structure, so that the bonding force among fibers is enhanced, the compactness of a coating film is improved, and the smoothness and the wet strength of the surface of paper can be improved. By adopting UV curing, an emulsifier is not needed, so that the problems of reduction of physical and mechanical properties and chemical properties of paper, water absorption and swelling in water and the like caused by the residual emulsifier can be avoided.
Description
Technical Field
The invention relates to a UV curing paper surface sizing agent and a preparation and application method thereof, in particular to a UV curing paper surface sizing agent containing acryloyl morpholine and a preparation and application method thereof, belonging to the technical field of paper surface sizing agents.
Background
Surface sizing is an important way for treating the surface of paper to improve the application performance of the paper, and the application of the surface sizing agent is more and more extensive with the continuous improvement of the technical level of the paper-making production process and the upgrading and updating of paper-making equipment. The surface sizing has the advantages of low sizing cost, capability of reducing the strength reduction of paper caused by sizing agents in pulp, paper machine dirt, net water white water load and the like, and can obviously improve the surface properties of the paper, such as surface strength, water resistance and the like. The surface sizing agent becomes an effective method for changing the performance of paper and producing paper with high added value, and is also an effective method for solving the problem of paper product quality, and is increasingly concerned and applied by paper-making workers. For example, chinese patent CN108690159A discloses a polymer surface sizing agent, which is prepared by dispersing styrene monomer and acrylate monomer as main monomers in an emulsifier and polymerizing under the action of an initiator, wherein the surface sizing agent prepared by the invention can improve the surface strength of paper, but the components are complex, and the surface sizing agent is easy to foam during surface sizing, and the organic solvent is used as a reaction medium during polymerization, thereby polluting the environment and having higher cost. Chinese patent CN106283869A discloses an organic/inorganic composite surface sizing agent, silica sol is prepared by reacting simple substance silicon powder and water under the catalysis of sodium hydroxide, and the mass ratio of chitosan oligomer to silica sol is 2:3-1: 9. The organic/inorganic composite surface sizing agent improves the water resistance and the surface strength of the surface sizing agent by preparing nano silica sol and compounding oligomeric chitosan, but the silica sol in the system is easy to be condensed to form gel, and the shrinkage and the fracture can occur in the paper making and drying process, thereby affecting the performance index of the paper.
In the prior art, the surface sizing agent is mostly prepared by adopting an emulsion polymerization process, the polymer surface sizing agent can better meet the special requirements of high-performance paper, however, the residual emulsifier in a polymerization product can influence the water resistance and chemical corrosion resistance of an adhesive film, pinholes can easily appear in the adhesive film, the physical mechanical property and the chemical property are reduced, in addition, the emulsifier molecules in the adhesive film can easily migrate to the surface, a non-chemical bonding emulsifier layer is formed on the surface of the film, and the emulsifier layer can absorb water and swell when meeting water, has complex components and higher cost. When inorganic nano materials such as nano silicon dioxide and the like are compounded with organic polymers for use, the surface strength and the water resistance of paper and the printing performance of the paper can be effectively improved, and the cost is reduced. However, the nano particles have the characteristics of large specific surface energy, strong polarity and the like, and are easy to agglomerate and promote sedimentation in the preparation and treatment processes, so that the nano silicon dioxide has poor dispersion stability in organic molecules, cannot achieve a good composite effect, and influences the service performance.
In order to overcome the defects of the paper surface sizing agent in the prior art that the physical and mechanical properties and the chemical properties of paper are reduced and water absorption swelling is caused by the residual emulsifier, the paper surface sizing agent capable of improving the dispersibility of nano silicon dioxide and organic polymer in composite use and improving the product performance, and the preparation and application methods thereof are in urgent need of development.
Disclosure of Invention
In order to solve the defects of the prior art, the invention provides a UV-cured paper surface sizing agent and a preparation method and application thereof, wherein organic functional dendritic nano-silica is used as an inorganic composite material, and a UV curing process is adopted, so that the influence of the use residue of an emulsifier in a polymerization product on the performance of the surface sizing agent is avoided, and the UV-cured paper surface sizing agent has the advantages of improving the smoothness of the paper surface, the printing adaptability of paper, the surface strength, the bursting strength, the folding strength, the wet strength and the like.
The technical scheme adopted by the invention for solving the technical problems is as follows: the UV-curing paper surface sizing agent is prepared from the following components in parts by weight:
the organic functionalized dendritic nano-silica is dendritic porous nano-silica with the particle size of 100-200 nm, and the preparation method comprises the following steps:
a. preparing dendritic nano silicon dioxide:
adding 30.2-45.5 g of ethyl orthosilicate and 60-80 ml of absolute ethyl alcohol into the reactor A, keeping the temperature to 30-40 ℃, and fully stirring to form a solution. And adding 70.5-80.8 g of deionized water, 0.2-1.3 g of dodecyl benzyl trimethyl ammonium bromide and 0.5-2.6g of urea into the reactor B, fully stirring, and mixing with the solution in the reactor A to form a reaction mother solution. Carrying out hydrothermal synthesis on the mother liquor in a homogeneous reactor, heating to 120-125 ℃, reacting for 4-5 h, and stirring at a speed of 60r/min to obtain a stable white emulsion.
And centrifugally separating the obtained white emulsion, washing the white emulsion for 3 times by using acetone and deionized water respectively, and drying the white emulsion at the temperature of 70 ℃ to obtain white powder. And placing the white powder in a muffle furnace, heating to 500 ℃, calcining for 6-7 h, and removing the template agent dodecyl benzyl trimethyl ammonium bromide to obtain the dendritic nano silicon dioxide.
b. Organically functionalizing the dendritic nano silicon dioxide:
dispersing 10.5-20.5 g of dendritic nano-silica in an organic solvent, and performing ultrasonic dispersion for 20min to obtain a uniformly dispersed suspension. Adding the suspension into a three-neck flask, slowly dropping 70.2-80.5 g of 80.5g N, N-dimethylpropionamide, 70.2-80.5 g of toluene-2, 4-diisocyanate and 5.5-10.6 g of dibutylene dilaurate at the temperature of 70-80 ℃, reacting for 2-3 h, cooling to 45-55 ℃, adding 2.5-5 g of hydroquinone, and dropping a mixture of 70-80 g of hydroxyethyl acrylate and 70-80 g of N, N-dimethylpropionamide. And after reacting for 2-3 h, drying the product in a vacuum box at the drying temperature of 30-40 ℃, and fully grinding to obtain the organic functionalized silicon dioxide with active double bonds on the surface, namely the organic functionalized dendritic nano-silicon dioxide.
Preferably, the organic solvent in step b is N, N-dimethylpropionamide.
The polyester acrylate prepolymer is an acrylic acid-terminated terpolymer of adipic acid, diethylene glycol and maleic anhydride, and is prepared from the following components in parts by weight:
preferably, the catalyst is p-toluenesulfonic acid.
Preferably, the polymerization inhibitor is hydroquinone.
The polyester acrylate prepolymer is prepared by the following steps:
adding 60-70 parts of toluene, 30-40 parts of adipic acid, 80-90 parts of diethylene glycol and 30-40 parts of maleic anhydride into a four-neck flask, adding 0.2-0.4 part of catalyst p-toluenesulfonic acid, heating under the protection of nitrogen, stirring while heating at a stirring speed of 120r/min to fully dissolve the components, heating to 125-135 ℃, refluxing for 2-3 hours, and distributing water, wherein the reaction equation is as follows:
and when the reaction temperature is reduced to 100-105 ℃, adding 25-30 parts of acrylic acid and 0.01-0.02 part of polymerization inhibitor hydroquinone, keeping the stirring speed at 120r/min, continuously heating, refluxing when the temperature is increased to 135-145 ℃, distributing water after refluxing for 2-3 h until no water is distilled off, and cooling and discharging. Washing the product with water to remove the catalyst p-toluenesulfonic acid, and removing toluene and unreacted acrylic acid by reduced pressure distillation to obtain the polyester acrylate prepolymer, wherein the reaction equation is as follows:
wherein n is more than or equal to 4 and less than or equal to 8.
The characterization shows that the viscosity of the polyester acrylate prepolymer at 25 ℃ is 10000-13000 mPa & s.
A UV curing paper surface sizing agent is prepared by the following steps:
(1) preparing the organic functional dendritic nano silicon dioxide.
(2) Preparing a polyester acrylate prepolymer.
(3) Preparing a UV curing paper surface sizing agent:
under the condition of room temperature, firstly adding 20-40 parts of reactive diluent, 20-30 parts of acryloyl morpholine and 50-80 parts of polyester acrylate prepolymer, starting stirring, controlling the rotating speed at 100-200 r/min, heating to 75-85 ℃, stirring for 20min, adding 10-15 parts of organic functionalized dendritic nano-silica, continuing stirring for 30-40 min, cooling to 48-52 ℃, adding 1-4 parts of photoinitiator, and stirring for 30-40 min to obtain the UV cured paper surface sizing agent.
Preferably, the reactive diluent is a combination of tripropylene glycol diacrylate and ethoxylated trimethylolpropane triacrylate. The mass ratio of the tripropylene glycol diacrylate to the ethoxylated trimethylolpropane triacrylate is 1: 1-3.
Preferably, the photoinitiator is: 2-benzyl-2-dimethylamine-1- (4-morpholine benzyl phenyl) butanone, 2,4, 6-trimethylbenzoyl-diphenyl phosphine oxide, phenyl bis (2,4, 6-trimethylbenzoyl) phosphine oxide and one or more of 2-methyl-1- (4-methylthiophenyl) -2-morpholinyl-1-propanone in any proportion.
The UV-curing paper surface sizing agent is applied to surface sizing of paper, and comprises the following steps:
and (3) adopting an ST-1-260 type coating machine to glue the surface sizing agent of the UV-cured paper on the surface of the paper, and then adopting an ultraviolet curing machine with the power of 3kW to irradiate for UV curing.
Preferably, the coating amount of the coating machine on the surface of the paper is 0.8-1.4 g/m2。
The invention has the advantages of
(1) Compared with the paper surface sizing agent in the prior art, the UV curing paper surface sizing agent has the advantages that no emulsifier is needed in the UV curing, the physical and mechanical properties and chemical properties of paper are reduced due to the residual emulsifier, and the problems that a non-chemically bonded emulsifier layer is formed on the surface of a film, and the film absorbs water and swells when meeting water are solved.
(2) The polar acryloyl morpholine component is adopted to replace the traditional styrene and acrylic acid component, and the acryloyl morpholine has higher polarity and can be combined with fiber hydrogen bonds in paper. The side chain is a heterocyclic structure containing nitrogen elements and oxygen elements, has good adhesive force, has the rigidity of a six-membered ring and certain flexibility, has excellent characteristics of high temperature resistance, saline and alkaline resistance, shear resistance, high curing speed and the like as a UV curing monomer, and can ensure that paper can quickly absorb ink after being applied with glue, the tensile strength is high and no curling occurs.
(3) After UV curing, the polyester acrylate prepolymer free radical polymerization crosslinking forms a high-molecular net structure, the fibers are fixed in the polyester acrylate net through the hydrogen bond combination of hydrophilic groups in the acryloyl morpholine and the fibers, the bonding force among the fibers is enhanced, the free movement of single fibers is restrained, the fiber arrangement form is more regular, and the surface wrinkles of the paper are reduced and are smoother. In addition, according to a photo-curing mechanism, a cross-linked network structure can be formed after curing, the compactness of a coating film is improved, the smoothness of the surface of the paper can be improved, and the wet strength of the paper is improved.
(4) Dendritic nano-silica prepared by adding dodecyl benzyl trimethyl ammonium bromide as a template agent: firstly, the addition of the nano silicon dioxide endows the surface sizing agent with excellent water resistance, mechanical property, heat resistance and extremely strong absorption characteristic to ultraviolet rays. Secondly, the dendritic nano-silica has a three-dimensional radial dendritic superstructure, a large number of active functional groups exist on the surface, and a large number of carbon-carbon double bonds with photochemical activity are introduced on the surface of the dendritic nano-silica through organic modification, so that the UV curing rate is improved. Thirdly, under the action of the photoinitiator, chemical bonds combined with the organic polymer are increased, firm binding force is generated, the affinity and the internal stability between the nano silicon dioxide and the organic polymer are improved, and a good composite effect is achieved. Fourthly, the dendritic nano silicon dioxide has a three-dimensional center radial porous structure, so that the density of the dendritic nano silicon dioxide is reduced, and the weight of the surface sizing agent is reduced.
(5) The polyester acrylate prepolymer is added with maleic anhydride, so that the density of C ═ C double bonds in the prepolymer structure is increased, and the photocuring speed is improved. In addition, the introduction of ether bond in diglycol in the polyester acrylate prepolymer improves the adhesion with paper.
Detailed Description
In order to better understand the invention, the following examples further illustrate the content of the invention, but the content of the invention is not limited to the following examples, and the examples should not be construed as limiting the scope of the invention.
Example 1
The UV-curing paper surface sizing agent is prepared from the following components in parts by weight:
the preparation method of the UV curing paper surface sizing agent comprises the following steps:
(1) preparing organic functional dendritic nano-silica:
a. preparing dendritic nano silicon dioxide: 30.2g of ethyl orthosilicate and 60ml of absolute ethanol are added into a reactor A, the temperature is kept constant to 30 ℃, and the mixture is fully stirred to form a solution. And adding 70.5-80.8 g of deionized water, 0.2-1.3 g of dodecyl benzyl trimethyl ammonium bromide and 0.5-2.6g of urea into the reactor B, fully stirring, and mixing with the solution in the reactor A to form reaction mother liquor. Carrying out hydrothermal synthesis on the mother liquor in a homogeneous reactor, heating to 120-125 ℃, reacting for 4 hours at a stirring speed of 60r/min, and obtaining the stable white emulsion.
And centrifugally separating the obtained white emulsion, washing the white emulsion for 3 times by using acetone and deionized water respectively, and drying the white emulsion at the temperature of 70 ℃ to obtain white powder. And placing the white powder in a muffle furnace, heating to 500 ℃, calcining for 6h, and removing the template agent to obtain the dendritic nano silicon dioxide.
b. Organically functionalizing the dendritic nano silicon dioxide: dispersing 10.5g of dendritic nano-silica in an organic solvent, and performing ultrasonic dispersion for 20min to obtain a uniformly dispersed suspension. Adding the suspension into a reaction vessel, slowly dropping 70.2g of N, N-dimethylpropionamide, 70.2g of toluene-2, 4-diisocyanate and 5.5g of dibutylene dilaurate at 70 ℃, reacting for 2h, cooling to 45 ℃, adding 2.5g of hydroquinone, and dropwise adding a mixture of 70g of hydroxyethyl acrylate and 70g of N, N-dimethylpropionamide. After reacting for 2h, drying the product in a vacuum oven at the drying temperature of 30 ℃, and fully grinding to obtain the organic functionalized silicon dioxide with active double bonds on the surface. The characterization shows that the particle size of the organic functionalized dendritic nano silicon dioxide is 100-200 nm.
(2) Preparation of polyester acrylate prepolymer:
the polyester acrylate prepolymer is prepared from the following components in parts by weight:
the preparation method comprises the following steps:
adding 60 parts of toluene, 30 parts of adipic acid, 80 parts of diethylene glycol and 30 parts of maleic anhydride into a four-neck flask, adding 0.2 part of catalyst p-toluenesulfonic acid, heating under the protection of nitrogen at a stirring speed of 120r/min while stirring to fully dissolve the components, heating to 125-135 ℃, refluxing for 2 hours, and dividing water.
When the reaction temperature is reduced to 100 ℃, adding 25 parts of acrylic acid and 0.01 part of polymerization inhibitor hydroquinone, keeping the stirring speed at 120r/min, continuing heating, heating to 135 ℃, refluxing for 2h, then distributing water until no water is distilled off, cooling and discharging. And washing the product with water to remove the catalyst p-toluenesulfonic acid, and removing toluene and unreacted acrylic acid by reduced pressure distillation to obtain the polyester acrylate prepolymer. The characterization shows that the viscosity of the polyester acrylate prepolymer at 25 ℃ is 10000-11000 mPa & s.
(3) Preparing a UV curing paper surface sizing agent:
under the condition of room temperature, firstly adding 10 parts of tripropylene glycol diacrylate, 10 parts of ethoxylated trimethylolpropane triacrylate, 20 parts of acryloyl morpholine and 50 parts of prepolymer, starting stirring, controlling the rotating speed at 60r/min, heating to 75 ℃, stirring for 20min, adding 10 parts of organic functionalized dendritic nano-silica, continuing stirring for 30min, cooling to 48-52 ℃, adding 0.5 part of 2-benzyl-2-dimethylamine-1- (4-morpholine benzyl phenyl) butanone and 0.5 part of 2-methyl-1- (4-methylthiophenyl) -2-morpholinyl-1-acetone photoinitiator, and stirring for 30min to obtain the UV-cured paper surface sizing agent.
Example 2
The UV-curing paper surface sizing agent is prepared from the following components in parts by weight:
the preparation method of the UV curing paper surface sizing agent comprises the following steps:
(1) preparing organic functional dendritic nano-silica:
a. preparing dendritic nano silicon dioxide: 38.6g of ethyl orthosilicate and 700ml of absolute ethanol are added to the reactor A, the temperature is kept constant to 35 ℃, and the mixture is fully stirred to form a solution. 75.8g of deionized water, 0.8g of dodecylbenzyltrimethylammonium bromide and 1.8g of urea are added into the reactor B, and the mixture is fully stirred and then mixed with the solution to form reaction mother liquor. Carrying out hydrothermal synthesis on the mother liquor in a homogeneous reactor, heating to 120-125 ℃, reacting for 4.5h, and stirring at the speed of 60r/min to obtain the stable white emulsion.
And centrifugally separating the obtained white emulsion, washing the white emulsion for 3 times by using acetone and deionized water respectively, and drying the white emulsion at the temperature of 70 ℃ to obtain white powder. And then placing the white powder in a muffle furnace, heating to 500 ℃, calcining for 6.5h, and removing the template agent to obtain the dendritic nano silicon dioxide.
b. Organically functionalizing the dendritic nano silicon dioxide: dispersing 18.6g of dendritic nano-silica in an organic solvent, and performing ultrasonic dispersion for 20min to obtain a uniformly dispersed suspension. Adding the suspension into a reaction vessel, slowly dropping 76.5g of N, N-dimethylpropionamide, 75.6g of toluene-2, 4-diisocyanate and 8.5g of dibutylene dilaurate at 75 ℃, reacting for 2.5h, cooling to 50 ℃, adding 4.5g of hydroquinone, and dropwise adding a mixture of 75g of hydroxyethyl acrylate and 75g of N, N-dimethylpropionamide. After 2.5h of reaction, the product is dried in a vacuum oven, the drying temperature is 35 ℃, and the organic functionalized silicon dioxide with active double bonds on the surface is obtained after full grinding. The characterization shows that the particle size of the organic functionalized dendritic nano silicon dioxide is 100-200 nm.
(2) Preparation of polyester acrylate prepolymer:
the polyester acrylate prepolymer is prepared from the following components in parts by weight:
the preparation method comprises the following steps:
adding 65 parts of toluene, 35 parts of adipic acid, 85 parts of diethylene glycol and 35 parts of maleic anhydride into a four-neck flask, adding 0.3 part of catalyst p-toluenesulfonic acid, heating under the protection of nitrogen at a stirring speed of 120r/min while stirring to fully dissolve the components, heating to 130 ℃, refluxing for 2.5 hours, and dividing water.
When the reaction temperature is reduced to 100 ℃, adding 27 parts of acrylic acid and 0.015 part of polymerization inhibitor hydroquinone, keeping the stirring speed at 120r/min, continuing to heat, heating to 130 ℃, refluxing for 2.5h, then distributing water until no water is distilled off, cooling and discharging. And washing the product with water to remove the catalyst p-toluenesulfonic acid, and removing toluene and unreacted acrylic acid by reduced pressure distillation to obtain the polyester acrylate prepolymer. The characterization shows that the viscosity of the polyester acrylate prepolymer at 25 ℃ is 11000-12000 mPa & s.
(3) Preparing a UV curing paper surface sizing agent:
under the condition of room temperature, firstly adding 10 parts of tripropylene glycol diacrylate, 15 parts of ethoxylated trimethylolpropane triacrylate, 25 parts of acryloyl morpholine and 60 parts of prepolymer, starting stirring, controlling the rotating speed at 160r/min, heating to 80 ℃, stirring for 20min, adding 12 parts of organic functionalized dendritic nano-silica, continuing stirring for 35min, cooling to 48-52 ℃, adding 1 part of 2-benzyl-2-dimethylamine-1- (4-morpholine benzyl phenyl) butanone, 1 part of 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide and 1 part of phenyl bis (2,4, 6-trimethylbenzoyl) phosphine oxide photoinitiator, and stirring for 35min to obtain the UV-cured paper surface sizing agent.
Example 3
The UV-curing paper surface sizing agent is prepared from the following components in parts by weight:
the preparation method of the UV curing paper surface sizing agent comprises the following steps:
(1) preparing organic functional dendritic nano-silica:
a. preparing dendritic nano silicon dioxide: 45.5g of tetraethoxysilane and 80ml of absolute ethanol are added to the reactor A, the temperature is kept constant to 40 ℃, and the mixture is fully stirred to form a solution. 80.8g of deionized water, 1.3g of dodecylbenzyltrimethylammonium bromide and 2.6g of urea are added into the reactor B, fully stirred and mixed with the solution in the reactor A to form reaction mother liquor. Carrying out hydrothermal synthesis on the mother liquor in a homogeneous reactor, heating to 120-125 ℃, reacting for 5 hours at a stirring speed of 60r/min, and obtaining the stable white emulsion.
And centrifugally separating the obtained white emulsion, washing the white emulsion for 3 times by using acetone and deionized water respectively, and drying the white emulsion at the temperature of 70 ℃ to obtain white powder. And placing the white powder in a muffle furnace, heating to 500 ℃, calcining for 7h, and removing the template agent to obtain the dendritic nano silicon dioxide.
b. Organically functionalizing the dendritic nano silicon dioxide: dispersing 20.5g of dendritic nano-silica in an organic solvent, and performing ultrasonic dispersion for 20min to obtain a uniformly dispersed suspension. Adding the suspension into a reaction vessel, slowly dripping 80.5g of N, N-dimethylpropionamide, 80.5g of toluene-2, 4-diisocyanate and 10.6g of dibutylene dilaurate at the temperature of 80 ℃, reacting for 3h, cooling to 55 ℃, adding 5g of hydroquinone, and dripping a mixture of 80g of hydroxyethyl acrylate and 80g of N, N-dimethylpropionamide. After reacting for 3h, drying the product in a vacuum oven at 40 ℃, and fully grinding to obtain the organic functionalized silicon dioxide with active double bonds on the surface. The characterization shows that the particle size of the organic functionalized dendritic nano silicon dioxide is 100-200 nm.
(2) Preparation of polyester acrylate prepolymer:
the polyester acrylate prepolymer is prepared from the following components in parts by weight:
the preparation method comprises the following steps:
adding 70 parts of toluene, 40 parts of adipic acid, 90 parts of diethylene glycol and 40 parts of maleic anhydride into a four-neck flask, adding 0.4 part of catalyst p-toluenesulfonic acid, heating under the protection of nitrogen at a stirring speed of 120r/min while stirring to fully dissolve the components, heating to 135 ℃, refluxing for 3 hours, and distributing water.
When the reaction temperature is reduced to 100 ℃, adding 30 parts of acrylic acid and 0.02 part of polymerization inhibitor hydroquinone, keeping the stirring speed at 120r/min, continuously heating, refluxing when the temperature is increased to 135 ℃, distributing water after refluxing for 3h until no water is distilled off, cooling and discharging. And washing the product with water to remove the catalyst p-toluenesulfonic acid, and removing toluene and unreacted acrylic acid by reduced pressure distillation to obtain the polyester acrylate prepolymer. The characterization shows that the viscosity of the polyester acrylate prepolymer at 25 ℃ is 12000-13000 mPa & s.
(3) Preparing a UV curing paper surface sizing agent:
under the condition of room temperature, firstly adding 10 parts of tripropylene glycol diacrylate, 30 parts of ethoxylated trimethylolpropane triacrylate active diluent, 30 parts of acryloyl morpholine and 80 parts of prepolymer, starting stirring, controlling the rotating speed at 300r/min, heating to 85 ℃, stirring for 20min, adding 15 parts of organic functionalized dendritic nano-silica, continuing stirring for 40min, cooling to 48-52 ℃, adding 1 part of 2-benzyl-2-dimethylamine-1- (4-morpholine benzyl phenyl) butanone, 1 part of 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide, 1 part of phenyl bis (2,4, 6-trimethylbenzoyl) phosphine oxide and 1 part of 2-methyl-1- (4-methylthiophenyl) -2-morpholinyl-1-acetone photoinitiator, stirring for 40min to obtain the UV curing paper surface sizing agent.
And (3) comparison test:
comparative example 1
The preparation process of the UV curing paper surface sizing agent is as follows, and the rest is the same as the example 1.
Under the condition of room temperature, firstly adding 10 parts of tripropylene glycol diacrylate, 10 parts of ethoxylated trimethylolpropane triacrylate, 20 parts of acryloyl morpholine and 50 parts of prepolymer, starting stirring, controlling the rotating speed at 60r/min, heating to 75 ℃, stirring for 20min, adding 10 parts of organic functionalized dendritic nano-silica, continuing stirring for 30min, cooling to 48-52 ℃, adding 2 parts of potassium persulfate initiator, and stirring for 30min to obtain the surface sizing agent.
Comparative example 2
The same procedure as in example 1 was followed except that only the organofunctionalized dendritic nanosilica was replaced with the dendritic nanosilica which had not been organofunctionalized.
Comparative example 3
The same procedure as in example 1 was followed except that only the organic functionalized dendritic nanosilica was replaced with the commercially available silica cabot white carbon black CAB-O-SIL TS-530 fumed silica.
Comparative example 4
The procedure of example 1 was otherwise the same as in the preparation of the UV-curable paper surface sizing agent except that acryloyl morpholine alone was not used.
Comparative example 5
The procedure is as in example 1 except that the photoinitiator is replaced with a single component of 2-phenylbenzyl-2-dimethylamine-1- (4-morpholinobenzylphenyl) butanone.
Detection, characterization and comparison:
the UV-cured paper surface sizing agents prepared in the examples 1-3 and the comparative examples 1-5 are respectively used for sizing the paper surface by using an ST-1-260 type coating machine, UV curing is carried out by irradiating an ultraviolet curing machine with the power of 3kW, and the paper is subjected to detection of tensile strength, CoBB value, surface strength and smoothness, wherein the detection items are as follows:
(1) CoBB value
The CoBB value refers to the surface absorbency of paper and board, also known as the surface absorbent weight of the paper, with a higher weight generally indicating a higher absorbency of the paper. The test method comprises the following steps: cutting the paper to be tested into 10cm2And (3) pouring 100ml of water into the paper, pouring the water after 45 seconds of absorption, and drying the water on the surface of the paper by using absorbent paper, wherein the weight difference of the paper before and after comparison.
(2) Tensile strength
The tensile strength of paper is usually the maximum tensile force that can be borne when a paper sample with a certain width is subjected to stress fracture, the tensile strength represents the toughness and the tensile force of the paper, and also represents the bonding force between fibers and the strength of the fibers, and the tensile strength performance test of the paper is one of the performances which must be tested in paper production enterprises and use industries. The detection method comprises the following steps: 10 test pieces each having a width of 15mm were cut with a sample cutter in the longitudinal and transverse directions of the paper sheet, and the length of each test piece was 250 mm. The tensile strength is tested by using a tensile strength tester, and the test length of the position of a clamping head of the tester device is adjusted to be 180mm +/-1 mm. Adjusting the stretching speed to be 20mm/min +/-5 mm/min; the sample is held in the test jaw and the tensile tester is started to pull the sample at a rate of 20mm/min + -5 mm/min until the sample breaks. The maximum tensile force applied was recorded. The sample breaks within 10mm of the grip distance during the test, and all readings should be discarded. The calculation formula is as follows:
t- -tensile index, N.m/g;
GPabsolute tensile strength, N/m;
w- -quantitative, g/m2。
(3) Paper bursting strength
During testing, according to the pressure transmission principle, the paper pattern is gradually raised under the action of pressure until the paper pattern is finally broken, and the maximum pressure borne by the paper pattern in the process is the bursting strength of the test sample. Burst is the burst strength of paper, representing the overall strength, uniformity and toughness of the paper. The detection method comprises the following steps: a standard sample of 100 square centimeters to be tested is cut, and an NP-1 electronic paper bursting strength tester is used for displaying a stable input layer numerical value and a quantitative value. The sample is arranged on the clamp, the automatic key is pressed, the pressing ring on the instrument is slowly pressed down, the pressure reaches a certain degree, and the pressing is stopped. The hydraulic piston starts to move, pressure is applied to the center of the sample through the adhesive film and gradually increases until the sample is broken, the upper pressing ring and the piston return to the initial position, and the display window displays the burst strength and the test times. The calculation formula is as follows:
b- -burst index, KPa.m2/g；
p- -absolute burst, KPa.
(4) Wet strength of paper
Paper strength is highly susceptible to moisture and paper saturated with water typically loses 95% or more of its tensile strength, with the remainder of the strength often referred to as wet strength. The detection method comprises the following steps: cutting a test sample according to GB/T450, cutting the paper to be tested into a test sample with the diameter of 15mm multiplied by 100mm on a paper cutter, respectively soaking paper strips in deionized water for 10min under a dry condition, absorbing excessive moisture on the surface by using filter paper, and quickly measuring by using a ZL-300A type paper and paperboard tensile testing machine, wherein the speed of the testing machine is 40 rpm. The calculation formula is as follows:
w- -Wet Strength, KPa;
d- -Dry Strength, KPa.
(5) Folding strength of paper
Folding endurance is one of the basic mechanical properties of paper and is used to indicate the ability of paper to resist folding back and forth. The folding strength of a sheet is measured as the number of folds, expressed in number of times, in terms of double folds, required for the sheet to be broken by being folded back and forth after being stretched under a certain force. The detection method comprises the following steps: 10 test specimens 15mm by 100mm are cut out according to GB/T450, measured using a Shoebert refractometer, and the specimens are placed in a chuck, clamped parallel between the two chucks of the tester, and the spring cartridge is pulled apart until the pin locks the spring cartridge, applying tension to the specimens. And (4) returning the counter to zero, starting the instrument to enable the sample to start to be folded until the sample is broken, automatically stopping counting by the instrument, and recording the reading.
(6) Paper smoothness inspection
The smoothness of the paper is the time required for a certain amount of air to escape from the atmosphere between the sample side and the annular plate side under a specific contact condition and a certain pressure difference. The measurement was carried out by placing paper and cardboard on a glass plate, applying a specific pressure to generate a semi-vacuum, thereby sucking air and passing the air through the contact surface, and measuring the time required for the degree of vacuum to vary within a prescribed range. The detection method comprises the following steps: sampling according to the GB/T450 specification. On the extracted large sheets, enough samples for each of the front and back sides to be tested 10 times are cut out uniformly along the cross-web 15mm from the edge, the area of the sample is at least 60mm x 60mm, and the samples are ensured to be free of folds, wrinkles, visible cracks or other paper defects. For testing, the test sample was placed with its measuring side against a glass plate, and then a rubber pad and top platen were placed on the test sample, applying a pressure of (100. + -. 2) kPa and creating a vacuum of 50.66kPa in a large vacuum vessel. The time, expressed in seconds, required for the vacuum to drop from 50.66kPa to 48.00kPa was measured and recorded. Such as over 300 s. The small volume is used instead and the test is retested with additional samples. If the time is less than 15s, the time required for the vacuum to drop from 50.66kPa to 29.33kPa is measured with another sample. The time from the loading of the sample to the start of the timing should be about 60 s.
Δ P- -poor smoothness on both sides,%;
Pbig (a)-a greater smoothness measurement, S;
PsmallA less smooth determination, S.
The specific experimental results are shown in the following table:
the comparison results show that: the paper surface sizing agent prepared by the UV curing process can restrict the free movement of single fiber, so that the surface wrinkles of the paper are reduced, a cross-linked network structure can be formed after curing, the compactness of a coating film is improved, the smoothness of the surface of the paper is improved, and the wet strength of the paper is improved. Without the UV curing process, the paper smoothness decreased significantly, the water absorption value CoBB increased, and the wet strength decreased, see comparative example 1.
After the organic functionalized dendritic nano-silica is replaced by the dendritic nano-silica which is not subjected to organic functionalization, the nano-silica which is not subjected to organic functionalization is extremely easy to agglomerate, and double bonds are not formed on the surface of the nano-silica, so that the nano-silica cannot participate in the photocuring reaction of the system, the UV curing time of the system is prolonged, the smoothness of the paper is reduced, and the mechanical properties (tensile index, burst index and folding strength) and the water resistance (CoBB rising and wet strength reducing) of the paper are reduced, as shown in a comparative example 2.
Compared with the commercially available nano-silica, the dendritic nano-silica prepared by the method has the advantages that a large number of carbon-carbon double bonds with photochemical activity are introduced into the surface of the dendritic nano-silica, so that the UV curing rate can be obviously improved, the internal stability with organic polymers can be enhanced, the dispersity is improved, the smoothness of paper is improved, and the mechanical properties (tensile index, burst index and folding strength) and the water resistance (CoBB reduction and wet strength increase) of the paper are improved, as shown in a comparative example 3.
The side chain of the acryloyl morpholine is a six-membered ring structure containing nitrogen and oxygen, when the acryloyl morpholine is applied to a UV curing paper surface sizing agent, a copolymer of the acryloyl morpholine has good adhesion, not only has rigidity, but also has certain flexibility, when the acryloyl morpholine is not used, the UV curing time is prolonged, the paper smoothness is reduced, and the mechanical properties (tensile index, bursting index and folding endurance) of the paper are reduced, as shown in a comparative example 4.
When only a single component photoinitiator, 2-phenylbenzyl-2-dimethylamine-1- (4-morpholinebenzyl) butanone, was used, the UV curing time was prolonged, the smoothness was reduced, the CoBB was increased, and the wet strength was reduced, as shown in comparative example 5.
Claims (10)
1. The UV-curing paper surface sizing agent is characterized by being prepared from the following components in parts by weight:
wherein the organic functionalized dendritic nano-silica is dendritic porous nano-silica with the particle size of 100-200 nm;
wherein the polyester acrylate prepolymer is acrylic acid-terminated terpolymer of adipic acid, diethylene glycol and maleic anhydride, and the structural formula of the terpolymer is as follows:
wherein n is more than or equal to 4 and less than or equal to 8.
2. A UV-curable paper surface sizing agent according to claim 1, characterized in that: the active diluent is a composition of tripropylene glycol diacrylate and ethoxylated trimethylolpropane triacrylate, and the mass ratio of the tripropylene glycol diacrylate to the ethoxylated trimethylolpropane triacrylate is 1: 1-3.
3. A UV-curable paper surface sizing agent according to claim 1, characterized in that: the photoinitiator is one or more of 2-phenylbenzyl-2-dimethylamine-1- (4-morpholine benzyl phenyl) butanone, 2,4, 6-trimethylbenzoyl-diphenyl phosphine oxide, phenyl bis (2,4, 6-trimethylbenzoyl) phosphine oxide and 2-methyl-1- (4-methylthiophenyl) -2-morpholinyl-1-acetone in any proportion.
4. A process for the preparation of the organofunctionalized arborescent nanosilica according to claim 1, characterized in that it comprises the following steps:
a. preparing dendritic nano silicon dioxide: adding 30.2-45.5 g of ethyl orthosilicate and 60-80 ml of absolute ethyl alcohol into the reactor A, keeping the temperature to 30-40 ℃, and fully stirring to form a solution; adding 70.5-80.8 g of deionized water, 0.2-1.3 g of template agent dodecyl benzyl trimethyl ammonium bromide and 0.5-2.6g of urea into a reactor B, fully stirring, and mixing with the solution in the reactor A to form reaction mother liquor; carrying out hydrothermal synthesis on the mother liquor in a homogeneous reactor, heating to 120-125 ℃, reacting for 4-5 h, and stirring at a speed of 60r/min to obtain a stable white emulsion;
centrifugally separating the obtained white emulsion, washing the white emulsion for 3 times by using acetone and deionized water respectively, and drying the white emulsion at the temperature of 70 ℃ to obtain white powder; placing the white powder in a muffle furnace, heating to 500 ℃, calcining for 6-7 h, and removing a template agent, namely dodecyl benzyl trimethyl ammonium bromide to obtain dendritic nano silicon dioxide;
b. organically functionalizing the dendritic nano silicon dioxide: dispersing 10.5-20.5 g of the dendritic nano silicon dioxide prepared in the step a in N, N-dimethyl propionamide, and performing ultrasonic dispersion for 20min to obtain a uniformly dispersed suspension; adding the suspension into a three-neck flask, slowly dropping 70.2-80.5 g of 80.5g N, N-dimethylpropionamide, 70.2-80.5 g of toluene-2, 4-diisocyanate and 5.5-10.6 g of dibutylene dilaurate at the temperature of 70-80 ℃, reacting for 2-3 h, cooling to 45-55 ℃, adding 2.5-5 g of hydroquinone, and dropping a mixture of 70-80 g of hydroxyethyl acrylate and 70-80 g of N, N-dimethylpropionamide; and after reacting for 2-3 h, drying the product in a vacuum box at the drying temperature of 30-40 ℃, and fully grinding to obtain the organic functionalized dendritic nano-silica with the surface provided with the active double bonds.
5. The polyester acrylate prepolymer of claim 1 prepared from the following components in parts by weight:
6. a polyester acrylate prepolymer according to claim 5 wherein: the catalyst is p-toluenesulfonic acid, and the polymerization inhibitor is hydroquinone.
7. A process for preparing the polyester acrylate prepolymer according to any one of claims 5 or 6, characterized by comprising the steps of:
adding 60-70 parts of toluene, 30-40 parts of adipic acid, 80-90 parts of diethylene glycol and 30-40 parts of maleic anhydride into a four-neck flask, adding 0.2-0.4 part of catalyst p-toluenesulfonic acid, heating under the protection of nitrogen, stirring while heating at a stirring speed of 120r/min to fully dissolve the components, heating to 125-135 ℃, refluxing for 2-3 hours, and distributing water, wherein the reaction equation is as follows:
when the reaction temperature is reduced to 100-105 ℃, adding 25-30 parts of acrylic acid and 0.01-0.02 part of polymerization inhibitor hydroquinone, keeping the stirring speed at 120r/min, continuously heating, refluxing when the temperature is increased to 135-145 ℃, distributing water after refluxing for 2-3 h until no water is distilled off, cooling and discharging; washing the product with water to remove the catalyst p-toluenesulfonic acid, and removing toluene and unreacted acrylic acid by reduced pressure distillation to obtain the polyester acrylate prepolymer, wherein the reaction equation is as follows:
wherein n is more than or equal to 4 and less than or equal to 8.
8. A method for preparing the UV-curable paper surface sizing agent according to claim 1, characterized by comprising the steps of:
1) preparing organic functional dendritic nano silicon dioxide;
2) preparing a polyester acrylate prepolymer;
3) preparing a UV curing paper surface sizing agent: under the condition of room temperature, firstly adding 20-40 parts of reactive diluent, 20-30 parts of acryloyl morpholine and 50-80 parts of polyester acrylate prepolymer, starting stirring, controlling the rotating speed at 100-200 r/min, heating to 75-85 ℃, stirring for 20min, adding 10-15 parts of organic functionalized dendritic nano-silica, continuing stirring for 30-40 min, cooling to 48-52 ℃, adding 1-4 parts of photoinitiator, and stirring for 30-40 min to obtain the UV cured paper surface sizing agent.
9. The use of a UV-curable paper surface sizing agent according to claim 1 for surface sizing paper, wherein: and (3) applying glue on the surface of the paper by using a UV curing paper surface sizing agent by using a coating machine, and irradiating by using an ultraviolet curing machine to perform UV curing.
10. The use of a UV-curable paper surface sizing agent according to claim 9, characterized in that: the coating amount of the coating machine on the surface of the paper is 0.8-1.4 g/m2。
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