CN114855503B - Biodegradable water-based plastic-replacing oil and preparation method thereof - Google Patents
Biodegradable water-based plastic-replacing oil and preparation method thereof Download PDFInfo
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- CN114855503B CN114855503B CN202210573244.3A CN202210573244A CN114855503B CN 114855503 B CN114855503 B CN 114855503B CN 202210573244 A CN202210573244 A CN 202210573244A CN 114855503 B CN114855503 B CN 114855503B
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- water
- oxidized starch
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 239000001254 oxidized starch Substances 0.000 claims abstract description 52
- 235000013808 oxidized starch Nutrition 0.000 claims abstract description 52
- 239000003921 oil Substances 0.000 claims abstract description 41
- 238000002156 mixing Methods 0.000 claims abstract description 35
- 229920002472 Starch Polymers 0.000 claims abstract description 31
- 239000000839 emulsion Substances 0.000 claims abstract description 31
- 229920002635 polyurethane Polymers 0.000 claims abstract description 31
- 239000004814 polyurethane Substances 0.000 claims abstract description 31
- 239000008107 starch Substances 0.000 claims abstract description 31
- 235000019698 starch Nutrition 0.000 claims abstract description 31
- 239000002131 composite material Substances 0.000 claims abstract description 27
- 229920003023 plastic Polymers 0.000 claims abstract description 26
- 239000004033 plastic Substances 0.000 claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- 239000000945 filler Substances 0.000 claims abstract description 19
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 15
- 239000007787 solid Substances 0.000 claims abstract description 12
- 239000002518 antifoaming agent Substances 0.000 claims abstract description 10
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 9
- 239000004970 Chain extender Substances 0.000 claims abstract description 7
- 239000002270 dispersing agent Substances 0.000 claims abstract description 7
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 7
- 229920001228 polyisocyanate Polymers 0.000 claims abstract description 7
- 238000004132 cross linking Methods 0.000 claims abstract description 6
- 230000001804 emulsifying effect Effects 0.000 claims abstract description 6
- 239000003054 catalyst Substances 0.000 claims abstract description 5
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 5
- 229920005862 polyol Polymers 0.000 claims abstract description 5
- 150000003077 polyols Chemical class 0.000 claims abstract description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 22
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical class O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 13
- -1 polybutylene adipate Polymers 0.000 claims description 11
- 238000009835 boiling Methods 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 8
- 229920001451 polypropylene glycol Polymers 0.000 claims description 8
- 239000006185 dispersion Substances 0.000 claims description 7
- JVYDLYGCSIHCMR-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)butanoic acid Chemical group CCC(CO)(CO)C(O)=O JVYDLYGCSIHCMR-UHFFFAOYSA-N 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 6
- 229910052710 silicon Inorganic materials 0.000 claims description 6
- 239000010703 silicon Substances 0.000 claims description 6
- 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 6
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 5
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical group CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 5
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 5
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 5
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 claims description 4
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical group O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 claims description 4
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 4
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 3
- 229920000909 polytetrahydrofuran Polymers 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- JCVQBRUGOCZZJD-UHFFFAOYSA-N CC(C)CCCCCCCC(C)C.N=C=O.N=C=O Chemical compound CC(C)CCCCCCCC(C)C.N=C=O.N=C=O JCVQBRUGOCZZJD-UHFFFAOYSA-N 0.000 claims description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 2
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 2
- 229940077388 benzenesulfonate Drugs 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 2
- 229920000921 polyethylene adipate Polymers 0.000 claims description 2
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 2
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims description 2
- 150000005846 sugar alcohols Polymers 0.000 claims description 2
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 8
- 239000000123 paper Substances 0.000 abstract description 8
- 238000000576 coating method Methods 0.000 abstract description 4
- 239000011248 coating agent Substances 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 19
- 239000000463 material Substances 0.000 description 8
- 229910004298 SiO 2 Inorganic materials 0.000 description 6
- 239000000126 substance Substances 0.000 description 5
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000002390 adhesive tape Substances 0.000 description 2
- 239000011111 cardboard Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000013530 defoamer Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000002715 modification method Methods 0.000 description 2
- 238000002464 physical blending Methods 0.000 description 2
- 229920005749 polyurethane resin Polymers 0.000 description 2
- 230000003014 reinforcing effect Effects 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- PBIDWHVVZCGMAR-UHFFFAOYSA-N 1-methyl-3-prop-2-enyl-2h-imidazole Chemical compound CN1CN(CC=C)C=C1 PBIDWHVVZCGMAR-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- FAHRLXDLULNUTF-UHFFFAOYSA-N 2-n-ethenylbenzene-1,2-diamine Chemical compound NC1=CC=CC=C1NC=C FAHRLXDLULNUTF-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011127 biaxially oriented polypropylene Substances 0.000 description 1
- 229920006378 biaxially oriented polypropylene Polymers 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 239000006184 cosolvent Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000009501 film coating Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000011087 paperboard Substances 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229920002577 polybenzoxazole Polymers 0.000 description 1
- 239000011527 polyurethane coating Substances 0.000 description 1
- 229920006264 polyurethane film Polymers 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 230000003678 scratch resistant effect Effects 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 238000004383 yellowing 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
- 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
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
- C08G18/348—Hydroxycarboxylic acids
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4825—Polyethers containing two hydroxy groups
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/6692—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/34
-
- 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
- D21H19/385—Oxides, hydroxides or carbonates
-
- 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
-
- 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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W90/00—Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
- Y02W90/10—Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polyurethanes Or Polyureas (AREA)
- Biological Depolymerization Polymers (AREA)
Abstract
The invention belongs to the technical field of environment-friendly water-based printing ink, and discloses biodegradable water-based plastic-replacing oil and a preparation method thereof. The water-based plastic replacing oil comprises the following components in percentage by weight: 48-90% of starch-based composite waterborne polyurethane emulsion; 6 to 20 percent of matte filler; 0.2 to 2 percent of dispersant; 0.5 to 2 percent of defoaming agent; the balance of water. The starch-based composite waterborne polyurethane emulsion is prepared by the following method: mixing polyisocyanate and polyol for reaction, adding a hydrophilic chain extender and a catalyst for continuous reaction to obtain a polyurethane prepolymer with a terminal-NCO group, mixing and emulsifying the polyurethane prepolymer with an oxidized starch solution, dropwise adding a cross-linking agent for cross-linking reaction, and adding pure water after neutralization to adjust the solid content to 35-65% to obtain a product. The water-based plastic replacing oil can obviously enhance the biodegradability of the coated paper, and can obviously improve the adhesiveness, the matte effect and the transparency of the coating.
Description
Technical Field
The invention belongs to the technical field of environment-friendly water-based printing ink, and particularly relates to biodegradable water-based plastic replacing oil and a preparation method thereof.
Background
The existing film covering process is to print ink on a paper substrate and then to cover a BOPP film (the film is already made with matte or touch effect and the like) by glue; however, because the film is not easy to degrade, plastic-limiting instructions are provided in a plurality of countries and regions internationally.
The water-based plastic-replacing oil is a mature novel environment-friendly thermoplastic water-based polyurethane material which is supposed to be transported by the global plastic-limiting order, has the characteristics of excellent high tension, high tensile force, toughness, wear resistance, folding and explosion resistance, water resistance, aging resistance, environment friendliness and the like, and has good adhesion with ink, no after-tack and excellent cohesiveness. The oil-coated paper has good glossiness and good film surface yellowing resistance, is widely applied to packaging paperboard coatings of medical treatment, electronic equipment, cosmetics, education and the like, can achieve the effects of approximate plastic film coating and the like when being applied to the printing industry, and is suitable for equipment such as printing online machines, full-page UV machines, common oil coating machines, thin paper local UV machines and the like.
Patent CN 113278352A discloses a water-based plastic-replacing oil, which comprises 60-80 parts by weight of water-based polyurethane emulsion, 10-20 parts by weight of water-based acrylic emulsion, 2-4 parts by weight of wax powder, 2-4 parts by weight of matting powder, 0.5-2 parts by weight of organic silicon and 20-40 parts by weight of water. Patent CN 114015336A discloses a scratch-resistant wear-resistant folding-resistant explosion-proof water-based plastic-replacing oil which is prepared from the following components in parts by weight: 55-70 parts of a sulfonate-terminated hyperbranched waterborne polyurethane emulsion, 20-30 parts of a functional copolymer, 3-6 parts of sulfonated polybenzoxazole, 3-5 parts of an emulsifier, 1-2 parts of a defoaming agent, 2-4 parts of a dispersant, 5-8 parts of a cosolvent and 25-45 parts of water; the functional copolymer is prepared by performing free radical polymerization reaction on tert-butyldimethyl ((2- (4, 5-tetramethyl-1, 3, 2-dioxaborolan-2-yl) allyl) oxo) silane, N-bis (2-hydroxyethyl) -N' - (ALPHA, ALPHA-dimethyl-3-isopropenylbenzene) urea, N-vinyl-o-phenylenediamine, N-trimethylol methacrylamide and 1-allyl-3-methyl imidazole chloride. However, the polyurethane coating formed by the aqueous polyurethane emulsion still has the defect of difficult degradation.
Starch-based degradable composite materials generally refer to materials whose composition contains starch or its derivatives, as well as materials in which natural starch is used as a filler and materials in which natural starch or its derivatives are used as a blending system. The preparation method of the starch-based degradable composite material mainly comprises a physical blending method and a chemical grafting modification method. The physical blending method mainly comprises the processes of stirring and blending, extrusion, hot pressing, injection molding and the like. The chemical grafting modification method mainly utilizes a large number of hydroxyl groups contained in starch molecules to carry out chemical reaction with active groups on the composite material, thereby realizing the compounding of chemical bond connection. the-NCO functional group in the polyurethane prepolymer and the hydroxyl group in the starch have high reaction activity, so that the development of the starch-based composite waterborne polyurethane emulsion suitable for waterborne plastic oil replacement has obvious practical significance.
Disclosure of Invention
Aiming at the defects and shortcomings of the prior art, the invention mainly aims to provide biodegradable water-based plastic replacement oil. The water-based plastic replacing oil disclosed by the invention adopts biodegradable starch-based materials to carry out blending and chemical grafting modification on polyurethane resin, so that the biodegradability of the film-coated paper can be obviously enhanced.
The invention also aims to provide a preparation method of the biodegradable water-based plastic replacement oil.
The purpose of the invention is realized by the following technical scheme:
a biodegradable water-based plastic-replacing oil comprises the following components in percentage by weight:
the starch-based composite waterborne polyurethane emulsion is prepared by the following method:
(1) Mixing polyisocyanate and polyol for reaction, and then adding a hydrophilic chain extender and a catalyst for continuous reaction to obtain a-NCO-terminated polyurethane prepolymer;
(2) Mixing oxidized starch with water, heating and boiling until the oxidized starch is completely dissolved, then adding ethanol to reduce the viscosity, and cooling to 60-80 ℃ to obtain an oxidized starch solution;
(3) And (3) mixing and emulsifying the polyurethane prepolymer obtained in the step (1) and the oxidized starch solution obtained in the step (2), dripping a cross-linking agent at the temperature of 60-80 ℃ for cross-linking reaction, and adding pure water after neutralization to adjust the solid content to 35-65% to obtain the starch-based composite aqueous polyurethane emulsion.
Further preferably, the polyisocyanate in step (1) is at least one selected from the group consisting of toluene diisocyanate, isophorone diisocyanate, diisohexylmethane diisocyanate, and hexamethylene diisocyanate.
Further preferably, the polyhydric alcohol in the step (1) is at least one selected from polyoxypropylene glycol, polytetrahydrofuran ether glycol, polybutylene adipate glycol, and polyethylene adipate glycol having a molecular weight range of 1000 to 4000.
Further preferably, in the step (1), the hydrophilic chain extender is dimethylol butyric acid or dimethylol propionic acid, and the catalyst is dibutyltin dilaurate or stannous octoate.
Further preferably, the molar ratio of the polyisocyanate to the polyol and the hydrophilic chain extender in step (1) is 1.05 to 1.35:1.
Further preferably, the solid content of the oxidized starch solution in the step (2) is 10-35%, and the mass ratio of ethanol to water in the oxidized starch solution is 0.15-0.3: 1.
Further preferably, the mass ratio of the polyurethane prepolymer and the oxidized starch solution in the step (3) is 0.1-0.8: 1.
Further preferably, the crosslinking agent in step (3) is glutaraldehyde or epichlorohydrin.
Further, the matte filler is at least one of nano-scale silicon dioxide powder, titanium dioxide powder and calcium carbonate powder.
Further preferably, the matte filler is a crosslinked oxidized starch modified silica matte filler, which is prepared by the following method:
mixing oxidized starch with water, heating and boiling until the oxidized starch is completely dissolved, then adding ethanol and alkali liquor, uniformly mixing, and cooling to 60-90 ℃ to obtain an oxidized starch solution; and then uniformly stirring and mixing the oxidized starch solution and the silica sol, adding a cross-linking agent, keeping the temperature at 60-90 ℃ for reaction, washing, drying and crushing the obtained product to obtain the cross-linked oxidized starch modified silica matte filler.
Further preferably, the mass ratio of the oxidized starch solution to the silica sol by stirring and mixing is 1: 2-2: 1 calculated by the oxidized starch and the silica; the cross-linking agent is glutaraldehyde or epichlorohydrin.
Further, the dispersing agent is any one or a mixture of more than two of alkyl sodium sulfonate, sodium alkyl benzene sulfonate, alkylphenol polyoxyethylene and fatty alcohol polyoxyethylene ether ammonium sulfate; the defoaming agent is an organic silicon defoaming agent.
The preparation method of the biodegradable water-based plastic replacement oil comprises the following steps:
adding the starch-based composite aqueous polyurethane emulsion, the matte filler, the dispersing agent, the defoaming agent and water into a dispersion machine, and uniformly stirring and dispersing to obtain the biodegradable aqueous plastic-replacing oil.
Compared with the prior art, the invention has the beneficial effects that:
(1) The water-based plastic replacing oil disclosed by the invention adopts biodegradable starch-based materials to carry out blending and chemical grafting modification on polyurethane resin, so that the biodegradability of the film-coated paper can be obviously enhanced.
(2) The invention adopts the specific starch-based composite aqueous polyurethane emulsion as the connecting material, has better bonding strength with paper base materials and better dispersion stability for matte filling compared with the conventional aqueous polyurethane emulsion, and can obviously improve the adhesiveness, matte effect and transparency of the coating.
(3) The invention further adopts the cross-linked oxidized starch modified silicon dioxide prepared by a specific method as the matte filler, so that better reinforcing effect and matte effect can be achieved.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto.
Example 1
The biodegradable water-based plastic replacement oil comprises the following components in percentage by weight:
the biodegradable water-based plastic replacement oil is prepared by the following method:
1. preparing a starch-based composite waterborne polyurethane emulsion:
(1) Adding isophorone diisocyanate and polyoxypropylene glycol (PPG-2000) into a reactor, stirring and mixing uniformly, reacting at normal temperature for 1h, adding dimethylolbutyric acid and dibutyltin dilaurate, and continuing to react for 2h, wherein the molar ratio of the isophorone diisocyanate to the PPG-2000 to the dimethylolbutyric acid is 1.15: 1, so as to obtain the-NCO-terminated polyurethane prepolymer.
(2) Mixing oxidized starch with water, heating and boiling until the oxidized starch is completely dissolved, then adding ethanol with the mass of 20% of that of the water to reduce the viscosity, and cooling to 70-75 ℃ to obtain an oxidized starch solution with the solid content of 20%.
(3) And (2) mixing and emulsifying the polyurethane prepolymer obtained in the step (1) and the oxidized starch solution obtained in the step (2) according to the mass ratio of 0.5: 1, then dropwise adding epoxy chloropropane at the temperature of 70-75 ℃ to perform crosslinking reaction and grafting reaction for 3h, then adding ethylenediamine for neutralization, and then adding pure water to adjust the solid content to 45% to obtain the starch-based composite waterborne polyurethane emulsion.
2. Preparing water-based plastic replacing oil:
proportionally mixing starch-base composite aqueous polyurethane emulsion and gas-phase SiO 2 Adding alkylphenol polyoxyethylene, organic silicon defoamer and water into a dispersion machine, stirring and dispersing uniformly to obtain biodegradable water-based plastic-replacing oil.
Example 2
The biodegradable water-based plastic replacement oil comprises the following components in percentage by weight:
the biodegradable water-based plastic replacement oil is prepared by the following method:
1. preparing starch-based composite waterborne polyurethane emulsion:
(1) Adding toluene diisocyanate and polyoxypropylene glycol (PPG-2000) into a reactor, stirring and mixing uniformly, reacting at normal temperature for 1h, adding dimethylolbutyric acid and dibutyltin dilaurate, and continuing to react for 2h, wherein the molar ratio of the toluene diisocyanate to the PPG-2000 to the dimethylolbutyric acid is 1.3: 1, so as to obtain the-NCO-terminated polyurethane prepolymer.
(2) Mixing oxidized starch with water, heating and boiling until the oxidized starch is completely dissolved, then adding ethanol with the mass of 15% of that of the water to reduce the viscosity, and cooling to 70-75 ℃ to obtain an oxidized starch solution with the solid content of 15%.
(3) And (3) mixing and emulsifying the polyurethane prepolymer obtained in the step (1) and the oxidized starch solution obtained in the step (2) according to the mass ratio of 0.3:1, then dropwise adding epoxy chloropropane at the temperature of 70-75 ℃ to perform crosslinking reaction and grafting reaction for 3 hours, and then adding ethylenediamine to neutralize to obtain the starch-based composite waterborne polyurethane emulsion with the solid content of about 35%.
2. Preparing water-based plastic replacing oil:
proportionally mixing starch-base composite aqueous polyurethane emulsion and gas-phase SiO 2 Adding alkylphenol polyoxyethylene and organic silicon defoaming agent into a dispersion machine, stirring and dispersing uniformly to obtain the biodegradable water-based plastic-replacing oil.
Example 3
The biodegradable water-based plastic-replacing oil comprises the following components in percentage by weight:
the biodegradable water-based plastic replacement oil is prepared by the following method:
1. preparing a starch-based composite waterborne polyurethane emulsion:
(1) Adding toluene diisocyanate and polytetrahydrofuran ether glycol (PTMEG-1000) into a reactor, stirring and mixing uniformly, reacting at normal temperature for 1h, then adding dimethylolpropionic acid and dibutyltin dilaurate, and continuing to react for 2h, wherein the molar ratio of the toluene diisocyanate to the PTMEG-1000 to the dimethylolpropionic acid is 1.1: 1, so as to obtain the polyurethane prepolymer with terminal-NCO groups.
(2) Mixing oxidized starch with water, heating and boiling until the oxidized starch is completely dissolved, then adding ethanol with the water mass of 30% to reduce the viscosity, and cooling to 70-75 ℃ to obtain an oxidized starch solution with the solid content of 35%.
(3) And (3) mixing and emulsifying the polyurethane prepolymer obtained in the step (1) and the oxidized starch solution obtained in the step (2) according to the mass ratio of 0.8:1, then dropwise adding epoxy chloropropane at the temperature of 70-75 ℃ to perform a crosslinking reaction and a grafting reaction for 3 hours, then adding ethylenediamine for neutralization, and then adding pure water to adjust the solid content to 55% to obtain the starch-based composite waterborne polyurethane emulsion.
2. Preparing water-based plastic replacing oil:
proportionally mixing starch-base composite aqueous polyurethane emulsion and gas-phase SiO 2 Adding alkylphenol polyoxyethylene, organic silicon defoamer and water into a dispersion machine, stirring and dispersing uniformly to obtain biodegradable water-based plastic-replacing oil.
Example 4
Compared with the embodiment 1, the embodiment adopts the cross-linked oxidized starch modified silica matte filler with the same adding amount to replace gas-phase SiO 2 And the rest is the same. The crosslinked oxidized starch modified silicon dioxide matte filler is prepared by the following method:
mixing oxidized starch with water, heating and boiling until the oxidized starch is completely dissolved, then adding ethanol with the mass of 15% of the solution and 0.5% of sodium hydroxide solution, uniformly mixing, and cooling to 75 ℃ to obtain an oxidized starch solution with the mass concentration of 15%; and then uniformly stirring and mixing the oxidized starch solution and silica sol (with the solid content of 15%) according to the mass ratio of 1: 1, adding an epichlorohydrin solution, carrying out heat preservation reaction for 2 hours at the temperature of 75 ℃, washing the obtained product with water and ethanol in sequence, carrying out vacuum drying, and crushing to obtain the cross-linked oxidized starch modified silica matte filler.
Comparative example 1
Compared with the embodiment 1, the conventional aqueous polyurethane emulsion with the same addition amount is adopted to replace the starch-based composite aqueous polyurethane emulsion, and the rest is the same.
The adhesion of the aqueous plastic replacement oil obtained in the above examples (after curing the aqueous plastic replacement oil on a gray cardboard, the adhesive tape was repeatedly stuck on a gray cardboard with a 3M600 adhesive tape and peeled off at an angle of 90 degrees, and the number of peeling-off times when the film layer was peeled off was recorded), the rub resistance (the number of rubbing times when scratches occurred was recorded by a 4-pound abrasion tester), the rub resistance (the aqueous plastic replacement oil was applied to a 10 μ M wire rod and then subjected to a folding test, and the number of folding times when cracks occurred) and the appearance and transparency of the paint film (GB 1721 "determination of appearance and transparency of varnish, oil and diluent"). The results are shown in table 1 below.
TABLE 1
As can be seen from the results in Table 1, the adhesion of the invention can be significantly improved by using the specific starch-based composite aqueous polyurethane emulsion as a binder compared with the conventional aqueous polyurethane emulsion, because the starch-based modified polyurethane film has better bonding strength with the paper substrate. And the matte effect and the transparency can be improved to a certain extent, probably because the starch-based composite aqueous polyurethane emulsion has better dispersion stability for the matte filler. In addition, it can be further seen from the results of example 4 that the crosslinked oxidized starch modified silica prepared by the specific method is used as matte filler, compared with the conventional gas-phase SiO 2 The filler can further remarkably improve the adhesiveness, the friction resistance, the rubbing resistance and the transparency, which shows that the crosslinked oxidized starch modified silicon dioxide is compared with the conventional gas-phase SiO 2 The reinforcing effect and the matte effect of the starch-based composite waterborne polyurethane emulsion are better.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (6)
1. The biodegradable water-based plastic replacing oil is characterized by comprising the following components in percentage by weight:
48-90% of starch-based composite waterborne polyurethane emulsion;
6% -20% of matte filler;
0.2% -2% of a dispersant;
0.5% -2% of defoaming agent;
the balance of water;
the starch-based composite waterborne polyurethane emulsion is prepared by the following method:
(1) Mixing polyisocyanate and polyol for reaction, and then adding a hydrophilic chain extender and a catalyst for continuous reaction to obtain a-NCO-terminated polyurethane prepolymer;
(2) Mixing oxidized starch with water, heating and boiling until the oxidized starch is completely dissolved, then adding ethanol for reducing the viscosity, and cooling to 60-80 ℃ to obtain an oxidized starch solution;
(3) Mixing and emulsifying the polyurethane prepolymer obtained in the step (1) and the oxidized starch solution obtained in the step (2), dripping a cross-linking agent at the temperature of 60-80 ℃ for cross-linking reaction, adding pure water after neutralization to adjust the solid content to 35-65% to obtain the starch-based composite waterborne polyurethane emulsion;
the mass ratio of the polyurethane prepolymer to the oxidized starch solution in the step (3) is 0.1 to 0.8; the cross-linking agent is glutaraldehyde or epichlorohydrin;
the matte filler is a crosslinked oxidized starch modified silicon dioxide matte filler and is prepared by the following method:
mixing oxidized starch with water, heating and boiling until the oxidized starch is completely dissolved, then adding ethanol and alkali liquor, uniformly mixing, and cooling to 60-90 ℃ to obtain an oxidized starch solution; then uniformly stirring and mixing the oxidized starch solution and the silica sol, then adding a cross-linking agent for heat preservation reaction at 60-90 ℃, washing, drying and crushing the obtained product to obtain the cross-linked oxidized starch modified silica matte filler;
the mass ratio of the oxidized starch solution to the silica sol by stirring and mixing is 1; the cross-linking agent is glutaraldehyde or epichlorohydrin.
2. The biodegradable aqueous plastic replacement oil as claimed in claim 1, wherein the polyisocyanate in step (1) is at least one selected from toluene diisocyanate, isophorone diisocyanate, diisohexylmethane diisocyanate, and hexamethylene diisocyanate; the polyalcohol is at least one of polypropylene oxide glycol, polytetrahydrofuran ether glycol, polybutylene adipate glycol and polyethylene adipate glycol with the molecular weight range of 1000 to 4000; the hydrophilic chain extender is dimethylolbutyric acid or dimethylolpropionic acid, and the catalyst is dibutyltin dilaurate or stannous octoate.
3. The biodegradable aqueous plastic replacement oil as claimed in claim 1, wherein the molar ratio of the polyisocyanate to the polyol and the hydrophilic chain extender in step (1) is 1.05 to 1.35.
4. The biodegradable aqueous plastic replacement oil as claimed in claim 1, wherein the solid content of the oxidized starch solution in the step (2) is 10% -35%, and the mass ratio of ethanol to water in the oxidized starch solution is 0.15 to 0.3.
5. The biodegradable aqueous plastic replacement oil as claimed in claim 1, wherein the dispersant is any one or a mixture of more than two of sodium alkyl sulfonate, sodium alkyl benzene sulfonate, alkylphenol ethoxylates and fatty alcohol-polyoxyethylene ether ammonium sulfate; the defoaming agent is an organic silicon defoaming agent.
6. The preparation method of the biodegradable water-based plastic replacement oil as claimed in any one of claims 1 to 5, which is characterized by comprising the following steps:
adding the starch-based composite aqueous polyurethane emulsion, the matte filler, the dispersing agent, the defoaming agent and water into a dispersion machine, and uniformly stirring and dispersing to obtain the biodegradable aqueous plastic-replacing oil.
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| CN101935951A (en) * | 2010-09-16 | 2011-01-05 | 湖北达雅化工技术发展有限公司 | Textile size combination |
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| CN101215451A (en) * | 2007-12-26 | 2008-07-09 | 华南农业大学 | A kind of starch-based adhesive and preparation method thereof |
| CN101935951A (en) * | 2010-09-16 | 2011-01-05 | 湖北达雅化工技术发展有限公司 | Textile size combination |
| CN113278352A (en) * | 2021-06-01 | 2021-08-20 | 惠州德斯坤化工有限公司 | Water-based plastic replacement oil and preparation method thereof |
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