CN115417964B - Degradable polyurethane, preparation method thereof and garden water pipe prepared from degradable polyurethane - Google Patents
Degradable polyurethane, preparation method thereof and garden water pipe prepared from degradable polyurethane Download PDFInfo
- Publication number
- CN115417964B CN115417964B CN202211147169.0A CN202211147169A CN115417964B CN 115417964 B CN115417964 B CN 115417964B CN 202211147169 A CN202211147169 A CN 202211147169A CN 115417964 B CN115417964 B CN 115417964B
- Authority
- CN
- China
- Prior art keywords
- polyurethane
- starch
- lignin
- reaction kettle
- parts
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000004814 polyurethane Substances 0.000 title claims abstract description 113
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 109
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title abstract description 20
- 229920005610 lignin Polymers 0.000 claims abstract description 73
- 229920002472 Starch Polymers 0.000 claims abstract description 64
- 235000019698 starch Nutrition 0.000 claims abstract description 63
- 239000008107 starch Substances 0.000 claims abstract description 63
- 239000012948 isocyanate Substances 0.000 claims abstract description 23
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 22
- -1 isocyanate compound Chemical class 0.000 claims abstract description 22
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 22
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 16
- 239000012975 dibutyltin dilaurate Substances 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims description 43
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 20
- 239000003513 alkali Substances 0.000 claims description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 12
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 12
- 230000008569 process Effects 0.000 claims description 10
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 10
- 240000003183 Manihot esculenta Species 0.000 claims description 8
- 235000016735 Manihot esculenta subsp esculenta Nutrition 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 7
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 3
- 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 3
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 2
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 claims 1
- 238000001125 extrusion Methods 0.000 abstract description 8
- 150000001875 compounds Chemical class 0.000 abstract description 4
- 239000002699 waste material Substances 0.000 abstract 1
- 239000000463 material Substances 0.000 description 34
- 230000000052 comparative effect Effects 0.000 description 12
- 238000012360 testing method Methods 0.000 description 12
- 239000002131 composite material Substances 0.000 description 8
- 229920003023 plastic Polymers 0.000 description 8
- 239000004033 plastic Substances 0.000 description 8
- 238000005452 bending Methods 0.000 description 6
- 230000004048 modification Effects 0.000 description 6
- 238000012986 modification Methods 0.000 description 6
- 230000008961 swelling Effects 0.000 description 6
- 125000003118 aryl group Chemical group 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000005056 polyisocyanate Substances 0.000 description 5
- 229920001228 polyisocyanate Polymers 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 230000001965 increasing effect Effects 0.000 description 4
- 229920005862 polyol Polymers 0.000 description 4
- 150000003077 polyols Chemical class 0.000 description 4
- 229920002261 Corn starch Polymers 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 239000008120 corn starch Substances 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 3
- 150000002483 hydrogen compounds Chemical class 0.000 description 3
- 125000001165 hydrophobic group Chemical group 0.000 description 3
- 238000003973 irrigation Methods 0.000 description 3
- 230000002262 irrigation Effects 0.000 description 3
- 150000002513 isocyanates Chemical class 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 229920001592 potato starch Polymers 0.000 description 3
- 241000196324 Embryophyta Species 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000004075 alteration Effects 0.000 description 2
- 150000001412 amines Chemical group 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 230000006870 function Effects 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 150000008442 polyphenolic compounds Chemical class 0.000 description 2
- 235000013824 polyphenols Nutrition 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 description 2
- 239000012279 sodium borohydride Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000009864 tensile test Methods 0.000 description 2
- 238000002411 thermogravimetry Methods 0.000 description 2
- 229920000945 Amylopectin Polymers 0.000 description 1
- 229920000856 Amylose Polymers 0.000 description 1
- 239000004970 Chain extender Substances 0.000 description 1
- 239000004593 Epoxy Chemical class 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 244000017020 Ipomoea batatas Species 0.000 description 1
- 235000002678 Ipomoea batatas Nutrition 0.000 description 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 241000592342 Tracheophyta Species 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- WQZGKKKJIJFFOK-UHFFFAOYSA-N alpha-D-glucopyranose Natural products OCC1OC(O)C(O)C(O)C1O WQZGKKKJIJFFOK-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-DVKNGEFBSA-N alpha-D-glucose Chemical group OC[C@H]1O[C@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-DVKNGEFBSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 235000014633 carbohydrates Nutrition 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 210000002421 cell wall Anatomy 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 229920006237 degradable polymer Polymers 0.000 description 1
- 230000017858 demethylation Effects 0.000 description 1
- 238000010520 demethylation reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000009778 extrusion testing Methods 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 229940100445 wheat starch Drugs 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- 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
-
- 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
- C08G18/16—Catalysts
- C08G18/22—Catalysts containing metal compounds
- C08G18/24—Catalysts containing metal compounds of tin
- C08G18/242—Catalysts containing metal compounds of tin organometallic compounds containing tin-carbon bonds
-
- 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
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4081—Mixtures of compounds of group C08G18/64 with other macromolecular compounds
-
- 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
- C08G18/4833—Polyethers containing oxyethylene units
-
- 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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
-
- 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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
-
- 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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
- C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
- F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
- F16L11/00—Hoses, i.e. flexible pipes
- F16L11/04—Hoses, i.e. flexible pipes made of rubber or flexible plastics
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
- F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
- F16L57/00—Protection of pipes or objects of similar shape against external or internal damage or wear
- F16L57/02—Protection of pipes or objects of similar shape against external or internal damage or wear against cracking or buckling
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
- F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
- F16L57/00—Protection of pipes or objects of similar shape against external or internal damage or wear
- F16L57/06—Protection of pipes or objects of similar shape against external or internal damage or wear against wear
-
- 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
- C08G2230/00—Compositions for preparing biodegradable polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/06—Biodegradable
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/18—Applications used for pipes
Abstract
The invention relates to the technical field of organic high molecular compounds, in particular to degradable polyurethane, a preparation method thereof, a garden water pipe prepared from the degradable polyurethane, a preparation method and application thereof. The invention aims at providing a degradable and high-flexibility PU, discloses the composition of the degradable PU, and discloses a preparation method of the degradable PU. The polyurethane comprises 50-100 parts of isocyanate compound, 100-200 parts of polyethylene glycol and 0.5-1 part of dibutyltin dilaurate, and is characterized in that: the method also comprises 25-50 parts of lignin and 15-30 parts of starch, and can be used for preparing garden water pipes, wherein the diameter of the prepared garden water pipes is 16-38mm, and the pipe wall thickness is 1.5-3mm. The garden water pipe prepared by the invention has extremely high tensile strength, can effectively resist the extrusion of past vehicles such as bicycles and pedestrians without damage, and is a biodegradable product with good performance, wherein the degree of biodegradability of the waste garden water pipe is more than 90 percent.
Description
Technical Field
The invention relates to the technical field of organic high molecular compounds, in particular to degradable polyurethane, a preparation method thereof, a garden water pipe prepared from the degradable polyurethane, a preparation method and application thereof.
Technical Field
Garden water pipes are prepared for the purpose of watering flowers and plants in the garden planting process, and can be divided into corrugated hoses, rubber hoses and plastic hoses according to materials. The main functions of the garden water pipe need to be satisfied: a. bendable to facilitate movement during irrigation and storage after irrigation work is completed; b. extrusion resistance, because the traffic road is often blocked by the use scene, the automobile is extruded by the pedestrians and vehicles in the past, and the automobile can meet the normal use only by having a certain degree of extrusion resistance; c. rebound after extrusion, only the garden water pipe resistant to extrusion can influence water flow and then the irrigation process if deformation cannot be eliminated by itself.
Polyurethane (PU) is an organic high molecular compound prepared from polyisocyanate, polyol, various amine chain extenders and the like, has more excellent mechanical properties compared with common rubber and plastic, and is suitable for being used as a raw material for preparing garden water pipes. However, based on environmental requirements of public growing attention, garden water pipes made of degradable materials are increasingly accepted by environmental policies established by local governments, and thus have higher competitiveness in the market place. While PU has the potential to be modified into a degradable material because the synthesis of PU is that isocyanate groups (-NCO) in isocyanate react with active hydrogen compounds in polyol, and the biodegradability of PU can be imparted by introducing either of these bio-based substitutions, however, combining the progress of the existing bio-based PU research capable of replacing non-renewable raw materials, replacing-NCO seems to present a greater challenge, and the inventors are more inclined to introduce other bio-based as a source of active hydrogen compounds because of the wide variety of active hydrogen compounds that can react with-NCO to produce PU, including but not limited to: alcohols, water, phenols, amines, carboxylic acids, epoxy compounds, urea, and the like.
Lignin (Lignin) is a natural type of polyphenol with a three-dimensional network structure, often found in the supporting tissues of vascular plants, which forms an important component of the plant cell wall, and is inferior to cellulose in reserves in nature, and raw materials are readily available and inexpensive. Based on the characteristics of pure nature and high mechanical strength, researchers have considered how lignin is combined with polyurethane to give the PU degradable effect. For example, CN107383307a, the first publication of chinese patent No. 2017-11-24 discloses a method for preparing a modified lignin reinforced rigid polyurethane material, which comprises extracting lignin from papermaking black liquor, pre-modifying lignin with silicate, increasing the number of silicon hydroxyl groups on the surface of lignin, performing secondary modification with sodium borohydride, reducing carbonyl groups on lignin branched chains to aliphatic hydroxyl groups with sodium borohydride, and accompanying polymerization and demethylation, the number of reactive hydroxyl groups on reduced lignin is obviously improved, thus the reactivity of lignin is also obviously improved, and the polymerization degree of modified lignin and isocyanate is also obviously enhanced.
However, the inventor finds that in practical use, the PU material prepared by the preparation method provided by the invention has the advantages that the prepared garden water pipe is too hard, and has the effect of resisting the extrusion of pedestrians and vehicles, but the bending effect is not ideal, so that the PU material is not beneficial to storage or use. The inventors believe that based on the above prior art, PU materials still have the potential to further improve flexibility.
Disclosure of Invention
In order to solve the technical problems, the inventor of the application has conducted intensive analysis and research on improving the flexibility of the biologically modified PU material so as to further improve the bending degree of the garden water pipe prepared by the biologically modified PU material.
The specific technical scheme is as follows:
a degradable polyurethane comprising the following components by weight:
50-100 parts of isocyanate compound, 100-200 parts of polyethylene glycol and 0.5-1 part of dibutyltin dilaurate, and is characterized in that: also comprises 25-50 parts of lignin and 15-30 parts of starch.
In the technical scheme, adding starch into lignin modified PU is one of the core ideas of the inventor, and the ideas are mainly reflected in the discovery of the specific defects in the prior art by the inventor: the lignin modified PU has lower flexibility degree, and has no bending capability when being used for preparing pipeline components, and is especially applied to the raw materials of garden water pipes, and the garden water pipes with higher lengths are inconvenient to use and inconvenient to store.
Dibutyl tin dilaurate (Dibutyltin dilaurate, DBTDL) is an organotin-containing catalyst which is insoluble in water but soluble in organic solvents such as toluene, tetrahydrofuran, N-dimethylformamide, and the like, and exhibits a colorless or pale yellow oily liquid at ordinary temperatures and white crystals at low temperatures. DBTDL is widely used as an acidic catalyst in the process of synthesizing unsaturated polyester resin, and can overcome a series of defects in the traditional process production on the premise of not influencing the product color and not causing corrosion to equipment, so that the synthesis speed is increased, the process period is shortened, and the product quality is improved.
Lignin is a polyphenol having a three-dimensional network structure formed by connecting a basic structural unit of p-hydroxyphenyl, guaiacyl or syringyl through an ester bond and a carbon-carbon bond. The polyurethane resin can provide rigid aromatic groups for PU materials, thereby enhancing the mechanical properties of polymers, and in addition, the lignin also comprises groups such as phenol, carboxyl, carbonyl and the like as reaction sites, and can be used for replacing petroleum-based polyol to a certain extent to react with isocyanate compounds to generate bio-based PU.
Starch (amyl) molecules are natural polyol substances, are cheap and easy to obtain, have good biodegradation function, and the inventor finds that the softness of the starch modified PU material is greatly improved. Therefore, the inventor selects starch to be additionally added into lignin modified PU, and the PU added with the starch has stronger mechanical property, can be bent at will and has good degradability.
Further, regulating the lignin to starch ratio in PU is another important concept of the inventors: starch is added into lignin modified PU to improve the flexibility of the PU within a certain range, however, too much starch can reduce the mechanical strength of the PU too much, so that the PU breaks when in use or is easily crushed by running vehicles or pedestrians. In view of the above, the addition of not more than 5 parts by weight of starch per 100 parts by weight of isocyanate compound does not cause a problem of deterioration in mechanical strength.
The Isocyanate compound (Isocyanate) is widely classified into aromatic polyisocyanates, aliphatic polyisocyanates, alicyclic polyisocyanates, and the like according to the molecular structure. Preferably, the PU obtained by adopting hexamethylene diisocyanate and polyethylene glycol in aliphatic polyisocyanate through a two-step process of low-temperature prepolymerization and high-temperature curing is of a linear structure, so that a cross-linked network is formed with a lignin structure, and the toughness of the PU composite material is further improved.
Alkali lignin fiber (Alkali lignin) is one of lignin classified according to the extraction mode, is extracted by adopting a caustic soda method pulping process, and compared with the condition that the molecular weight of other lignin is higher than 10000, the molecular weight of Alkali lignin is generally 1000-2000, and the inventor discovers that PU modified by the Alkali lignin has higher rebound resilience performance and is more suitable for the application of garden water pipes.
Starch is a high molecular carbohydrate, a polysaccharide polymerized from glucose molecules. The basic constituent unit is alpha-D-glucopyranose, and the molecular formula is (C 6 H 10 O 5 ) n . Starch is of two types, amylose and amylopectin, the former is of an unbranched helix structure; the latter is formed by connecting 24-30 glucose residues end to end through alpha-1, 4-glycosidic bonds, and the alpha-1, 6-glycosidic bonds are arranged at branched chains. Starch can be classified into potato starch, corn starch, wheat starch, sweet potato starch and the like according to the types of raw materials, wherein tapioca starch is powder obtained by extracting tapioca starch and then dehydrating and drying, has the characteristics of excellent film forming property, strong permeability, high viscosity and the like, has lower protein content and ash content than most starch, and is suitable for producing degradable materials with starch as an additive.
The preparation method of the degradable polyurethane comprises the following steps:
s1, dissolving the isocyanate compound and the polyethylene glycol by using tetrahydrofuran, and then adding the dissolved isocyanate compound and the polyethylene glycol into a dry reaction kettle;
s2, heating the reaction kettle and keeping the temperature at 70-85 ℃ for 5-10min;
s3, adding the dibutyltin dilaurate into the reaction kettle, introducing nitrogen into the reaction kettle, and keeping for 15-25min to obtain polyurethane prepolymer;
s4, adding the lignin and the starch into the reaction kettle, and reacting for 30-60min to obtain polyurethane;
preferably, the starch is added into the reaction kettle at a constant speed for 10-15min.
Preferably, the lignin is added after the starch is completely added into the reaction kettle, and the adding time is 15-20min.
The degradable polyurethane prepared by the method can be applied to preparing garden water pipes, but is not limited to preparing garden water pipes, and the product can be applied to various outdoor or indoor use scenes according to actual requirements.
Preferably, when the degradable polyurethane is applied to the preparation of garden water pipes, the diameter of the garden water pipes is 16-38mm, and the pipe wall thickness is 1.5-3mm. The parameters limit the garden water pipe to have high water flow rate and simultaneously maintain high pressure resistance and bending performance.
Further or more detailed benefits will be described in connection with specific embodiments.
Drawings
FIG. 1 is a schematic view of a garden hose in a basic configuration and in a bent state;
FIG. 2 is a table of data relating to polyurethane performance testing;
FIG. 3 is a schematic diagram of the results of thermogravimetric analysis of polyurethane;
FIG. 4 is a three-dimensional schematic diagram of the tensile strength of the polyurethane obtained after adding lignin and starch in different proportions in example 1;
FIG. 5 is a table of data of FIG. 4;
FIG. 6 is a table showing the compressive tests of garden water pipes of different diameters and thicknesses prepared from the polyurethane prepared in example 1.
Detailed Description
The invention is further illustrated by the following examples:
the core technical problem faced by the technical solution of the embodiment of the present application comes from the discovery of specific defects in the prior art by the inventor: the traditional degradable polyurethane modified by lignin does not have good flexibility, so that the application of the degradable polyurethane to the preparation of garden water pipes is limited.
Therefore, further modification of polyurethane to provide good bending property is a technical problem to be solved by the inventor.
At the same time, improving the degradability of polyurethane is another creative contribution made by the inventor while solving the technical problems.
In the examples of the present invention, only representative chemical agents are selected as components of the degradable polyurethane, as will be readily appreciated by those skilled in the art: following the same basic principle, all chemical reagents having the same or similar chemical properties as those of the present embodiment can be used to prepare the polyurethane of the present invention, and the desired technical effect can be achieved.
Meanwhile, the application part of the embodiment of the invention only relates to garden water pipes, but the person skilled in the art can easily obtain that: following the same basic principle, the polyurethanes according to the invention are likewise suitable for other articles.
In order to facilitate comparison of technical effects, the reagents and preparation parameters which have little influence on the final bending performance and the degradability of polyurethane in the embodiment of the invention are kept consistent and are not changed, and the reagents and preparation parameters are also easily known by those skilled in the art: this does not mean that only the reagents and preparation parameters in the examples can be selected.
Accordingly, the following examples are not to be construed as limiting the scope of the invention:
example 1：
A degradable polyurethane comprising the following components by weight:
50 parts of isocyanate compound, 100 parts of polyethylene glycol, 0.5 part of dibutyltin dilaurate, 25 parts of lignin and 15 parts of starch, wherein:
the isocyanate compound is hexamethylene diisocyanate;
the lignin is alkali lignin;
the starch is tapioca starch.
The preparation method of the polyurethane comprises the following steps:
s1, dissolving hexamethylene diisocyanate and polyethylene glycol by using tetrahydrofuran, and then adding the dissolved hexamethylene diisocyanate and the polyethylene glycol into a dry reaction kettle;
s2, heating the reaction kettle and keeping the temperature at 70 ℃ for 5min;
s3, adding the dibutyltin dilaurate into the reaction kettle, introducing nitrogen into the reaction kettle, and keeping for 15min to obtain polyurethane prepolymer;
s4, adding alkali lignin and tapioca starch into the reaction kettle, adding the starch into the reaction kettle at a constant speed for 10min, adding the lignin after the starch is completely added into the reaction kettle, and reacting for 30min to obtain polyurethane.
Example 2:
a degradable polyurethane comprising the following components by weight:
100 parts of isocyanate compound, 200 parts of polyethylene glycol, 1 part of dibutyltin dilaurate, 50 parts of lignin and 30 parts of starch, wherein:
the isocyanate compound is diphenylmethane diisocyanate;
the lignin is alkali lignin;
the starch is potato starch.
The preparation method of the polyurethane comprises the following steps:
s1, dissolving hexamethylene diisocyanate and polyethylene glycol by using tetrahydrofuran, and then adding the dissolved hexamethylene diisocyanate and the polyethylene glycol into a dry reaction kettle;
s2, heating the reaction kettle and keeping the temperature at 85 ℃ for 10min;
s3, adding the dibutyltin dilaurate into the reaction kettle, introducing nitrogen into the reaction kettle, and keeping for 25min to obtain polyurethane prepolymer;
s4, adding alkali lignin and tapioca starch into the reaction kettle, adding the starch into the reaction kettle at a constant speed for 15min, adding the lignin after the starch is completely added into the reaction kettle, and reacting for 60min for 20min to obtain polyurethane.
Example 3:
a degradable polyurethane comprising the following components by weight:
70 parts of isocyanate compound, 150 parts of polyethylene glycol, 0.8 part of dibutyltin dilaurate, 32 parts of lignin and 24 parts of starch, wherein:
the isocyanate compound is isophorone diisocyanate;
the lignin is alkali lignin;
the starch is corn starch.
The preparation method of the polyurethane comprises the following steps:
s1, dissolving hexamethylene diisocyanate and polyethylene glycol by using tetrahydrofuran, and then adding the dissolved hexamethylene diisocyanate and the polyethylene glycol into a dry reaction kettle;
s2, heating the reaction kettle and keeping the temperature at 80 ℃ for 8min;
s3, adding the dibutyltin dilaurate into the reaction kettle, introducing nitrogen into the reaction kettle, and keeping for 21min to obtain polyurethane prepolymer;
s4, adding alkali lignin and tapioca starch into the reaction kettle, adding the starch into the reaction kettle at a constant speed for 12min, adding the lignin after the starch is completely added into the reaction kettle, and reacting for 45min for 18min to obtain polyurethane.
Example 4:
a degradable polyurethane comprising the following components by weight:
70 parts of isocyanate compound, 150 parts of polyethylene glycol, 0.8 part of dibutyltin dilaurate, 32 parts of lignin and 24 parts of starch, wherein:
the isocyanate compound is isophorone diisocyanate;
the lignin is alkali lignin;
the starch is corn starch.
The preparation method of the polyurethane comprises the following steps:
s1, dissolving hexamethylene diisocyanate and polyethylene glycol by using tetrahydrofuran, and then adding the dissolved hexamethylene diisocyanate and the polyethylene glycol into a dry reaction kettle;
s2, heating the reaction kettle and keeping the temperature at 80 ℃ for 8min;
s3, adding the dibutyltin dilaurate into the reaction kettle, introducing nitrogen into the reaction kettle, and keeping for 21min to obtain polyurethane prepolymer;
s4, adding alkali lignin and tapioca starch into the reaction kettle, adding the starch into the reaction kettle at a constant speed for 12min, adding the lignin after the starch is completely added into the reaction kettle, and reacting for 45min for 18min to obtain polyurethane.
Comparative example 1
The difference from example 1 is that: starch is not added in the polyurethane preparation process.
Comparative example 2
The difference from example 1 is that: starch and lignin are not added in the polyurethane preparation process.
< Properties of polyurethane >
The structure of the polyurethane was characterized and its properties were tested and the results are shown in fig. 2, wherein:
a. molecular weight
The molecular weight of the polyurethanes was tested using high performance liquid chromatography (Agilent LC 1100), and a solution of pure polyurethane 2-5mg/ml was prepared using tetrahydrofuran as the mobile phase and filtered, with a mobile phase flow rate of 1ml/min.
b. Swelling test
Soaking polyurethane in tetrahydrofuran for 36h, and observing the swelling state or dissolution state of the polyurethane. The linear high polymer can generate swelling or dissolution phenomenon in tetrahydrofuran, and the crosslinked reticular polymer only generates swelling but does not generate dissolution phenomenon, so that the polymerization structure of polyurethane can be judged.
The swelling ratio of polyurethane is inversely related to the crosslinking density, thus indirectly reflecting the integrity of the crosslinked network of polyurethane, and it can be seen that the molecular weight of the polyurethane prepared in comparative example 2 is only 23000, the pure polyurethane is prepared directly from hexamethylene diisocyanate with difunctional degree and polyethylene glycol, the corresponding crosslinked structure does not appear, while in examples 1-4 and comparative example 1, in which lignin is added, the corresponding crosslinked structure appears, the molecular weight also reaches about 50000, and the idea is also concomitantly demonstrated in the swelling test, namely, the crosslinked network is more perfect with the addition of lignin.
c. Tensile testing
The tensile properties of the polyurethane were tested using an SHK-A102 rubber tensile testing tensile machine (Suzhou examined Zhuo) in which the tensile bars were rectangular in structure and were 1.2X0.18X4.5 cm in size 3 The draw rate was 8mm/min, measured at least 10 times per set of samples, and averaged (one highest and one lowest was discarded).
Tensile strength of
According to the national standard GB/T228-1987, the tensile strength refers to a critical value of the transition of plastic deformation of a material from uniform plastic deformation direction change to local concentrated plastic deformation, namely the maximum bearing capacity of the material under the static stretching condition. The tensile strength is the resistance of the maximum uniform plastic deformation of the characterization material, the deformation of the tensile sample is uniform before the tensile sample bears the maximum tensile stress, but after the tensile sample exceeds the maximum tensile stress, the necking phenomenon of the metal begins to appear, namely the concentrated deformation is generated; for brittle materials with no or very little uniform plastic deformation, it reflects the fracture resistance of the material in MPa.
In the tensile process of the sample, the maximum force (Fb) born by the material in the tensile breaking process is obviously reduced along with the transverse cross section dimension after the material enters the strengthening stage after passing through the yield stage, and the unit is N/(MPa) after dividing the maximum force (Fb) by the stress (sigma) obtained by the original cross section area (So) of the sample. The method represents the maximum capability of the material to resist damage under the action of tensile force, and the calculation formula is as follows:
σ=Fb/So
wherein: fb—the maximum force that the test specimen will bear when broken, N (newton); so-original cross-sectional area of sample, mm.
Young's modulus
Young's modulus is a physical quantity that describes the ability of a solid material to resist deformation. When a metal wire with the length L and the cross section area S is stretched by delta L under the action of force F, F/S is called stress, and the physical meaning of the stress is that the unit cross section area of the material is subjected to the force with the unit of Mpa.
Elongation at break
When the material is broken by external force, the elongation (strain rate) of the material when the material stretches to break is called breaking elongation, and the unit is percent (%) by using e. Elongation at break can be expressed as the elongation deformation capacity of the fiber under maximum load, and the calculation formula is as follows:
e=(La-L 0 )/L 0
wherein: e-elongation at break,%; l0, the original length of the sample, mm; la-length of the sample when broken, mm.
As shown in FIG. 2, the tensile strength of the polyurethane composite material added with lignin is improved from about 6Mpa to about 12Mpa, which shows that the polyurethane with high crosslinking network has stronger tensile resistance, but it is noted that the Young's modulus of the polyurethane added with lignin is obviously improved when the results of comparative example 1 and comparative example 2 are compared, which shows that the strength of the polyurethane material is greatly improved when the lignin is added. In order to further obtain the flexibility of the material, the tensile fracture test is carried out on the material, and the results of comparative example 1 and comparative example 1 show that the polyurethane-lignin composite material without starch is lower in tensile strength than the polyurethane-lignin composite material after starch is added, so that the addition amount of the starch can greatly improve the flexibility degree of the material.
d. Thermogravimetric analysis
Testing pure polyurethane on N with thermal weightlessness analyzer (1100 SF) 2 The thermal weight loss percentage in the environment at different temperatures is 50-500 ℃, and the heating rate is 10 ℃/min.
According to industry standards, the initial thermal decomposition temperature is a temperature at which 5wt% of the weight is lost (T 5% ) As can be seen from FIG. 3, by comparing the results of comparative example 1 and comparative example 2, T of the lignin-added polyurethane material 5% About 385.4 ℃ and a polyurethane material without lignin added T 5% About 284.4 c, indicating that the addition of lignin produces some copolymerization with the polyurethane, laterally explaining the higher crosslink density characteristics of the lignin-added polyurethane. Comparing the lignin-polyurethane composite material with starch, T 5% About 432.1 c, it is shown that the addition of starch further increases the degree of copolymerization of the polyurethane, whereas comparative examples 1-4 and comparative example 1, it can be seen that the polyurethane composite material after the addition of starch, which is faster with increasing temperature, loses mass, shows that the addition of starch makes the polyurethane material more easily decomposed, which the inventors consider to have a more biodegradable potential.
e. Contact angle test
The water contact angle of the polyurethane material was measured using an optical contact angle meter (OCA 40) at 25 ℃ and wind speed <3.0m/s, at least 10 times per group of samples and averaged (one highest and one lowest value discarded). The interfacial work of adhesion between a liquid and a solid can be calculated by the following formula:
W α =Y L (1+cosθ)
wherein: w alpha-interfacial adhesion work, mJ/m 2 ，W；Y L -liquid surface tension, N/m; θ—contact angle, °.
Generally, the higher the contact angle θ, the lower the interfacial adhesion work, which indicates that the content of strong hydrophobic groups is lower, and the data in fig. 2 show that the contact angle of polyurethane added with lignin is greatly increased, which is thought to be caused by the strong hydrophobic groups contained in lignin, and through analyzing the strong hydrophobic groups possibly existing in lignin, the inventor considers that aromatic groups contained in lignin are also thought to be aromatic groups, and the aromatic rigid structure can also improve the integral mechanical strength of polyurethane, so that the mechanical test result of the polyurethane composite material can be explained.
< influence of starch/lignin addition on polyurethane flexibility >
The inventors have adjusted the addition amount of starch and lignin based on example 1, and tested the tensile strength of the polyurethane finally obtained, and as shown in fig. 4 and 5, it can be seen that when 50 parts of isocyanate compound and 100 parts of polyethylene glycol are used, the addition amount of lignin is 34-37 parts, 23-26 parts of starch can make the polyurethane finally prepared reach the optimal tensile strength, and 13.6Mpa, which indicates that the polyurethane has the advantages of high softness and high tensile strength at this ratio, and according to a large number of experiments, the inventors consider that the optimal addition ratio of lignin and starch is 1:0.714, and at this time, the polyurethane composite material with the best mechanical property can be obtained.
< influence of thickness, diameter on Garden Water pipe Properties >
Pouring the prepared polyurethane into a specific mould (such as polytetrafluoroethylene) to obtain garden water pipes with different specifications. Referring to a bellows collapse test in the national standard GB/T41486-2022 corrugated metal hose for domestic Drinking Water pipeline of the people's republic of China, the prepared garden water pipe is tested by the following method:
garden water pipes with different diameters and wall thicknesses prepared from the polyurethane prepared in the embodiment 1 are taken, two parallel pressing plates are placed between any position of the garden water pipes, the contact width of the pressing plates and the garden water pipes is 3cm to simulate the width of a bicycle tire, then a test piece is slowly extruded, the extrusion force is 200N to simulate the extrusion force of the bicycle to the water pipes, water is introduced, whether water leakage occurs or not is checked, and the result is shown in figure 5, wherein 'V' represents no water leakage. It can be seen that the water leakage phenomenon is not found in the extrusion test when the diameter of the garden water pipe is 16-38mm and the pipe wall thickness is 1.5-3mm.
< test for degradability of Garden Water tube >
The polyurethane prepared in example 1 is tested for the degradation capability of garden water pipes with the diameter of 25mm and the pipe wall thickness of 2.4mm by referring to the national standard GB/T20197-2006 for definition, classification, marking and degradation performance requirements of degradation plastics, and the biological decomposition rate of the water pipes is more than 90%, the disintegration degree is higher, and the polyurethane is a qualified degradable polymer product and has good environmental-friendly characteristics.
In the description of the present specification, reference to the terms "embodiment," "base embodiment," "preferred embodiment," "other embodiments," "example," "specific examples," or "some examples," etc., means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, schematic representations of the above terms do not necessarily refer to the same embodiments or examples. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
While preferred embodiments of the present invention have been described, additional variations and modifications in those embodiments may occur to those skilled in the art once they learn of the basic inventive concepts. It is therefore intended that the following claims be interpreted as including the preferred embodiments and all such alterations and modifications as fall within the scope of the invention.
It will be apparent to those skilled in the art that various modifications and variations can be made to the present invention without departing from the spirit or scope of the invention. Thus, it is intended that the present invention also include such modifications and alterations insofar as they come within the scope of the appended claims or the equivalents thereof.
Claims (5)
1. A garden hose made from a degradable polyurethane comprising by weight:
50-100 parts of isocyanate compound, 100-200 parts of polyethylene glycol and 0.5-1 part of dibutyltin dilaurate, and is characterized in that: also comprises 34-37 parts of alkali lignin and 23-26 parts of starch; the starch is tapioca starch; the mass ratio of the alkali lignin to the starch is 1: (0.7-0.75); the diameter of the garden water pipe is 16-38mm, and the pipe wall thickness is 1.5-3mm.
2. A garden hose as claimed in claim 1, wherein: the isocyanate compound is one of hexamethylene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate and dicyclohexyl methylene diisocyanate.
3. Garden hose according to claim 1 or 2, characterized in that the polyurethane is prepared by a process comprising the steps of:
s1, dissolving the isocyanate compound and the polyethylene glycol by using tetrahydrofuran, and then adding the dissolved isocyanate compound and the polyethylene glycol into a dry reaction kettle;
s2, heating the reaction kettle and keeping the temperature at 70-85 ℃ for 5-10min;
s3, adding the dibutyltin dilaurate into the reaction kettle, introducing nitrogen into the reaction kettle, and keeping for 15-25min to obtain polyurethane prepolymer;
s4, adding the alkali lignin and the starch into the reaction kettle, and reacting for 30-60min to obtain polyurethane.
4. A garden hose as claimed in claim 3, wherein: and S4, adding the starch into the reaction kettle at a constant speed for 10-15min.
5. A garden hose as claimed in claim 4, wherein: and S4, adding the alkali lignin after the starch is completely added into the reaction kettle, wherein the adding time is 15-20min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211147169.0A CN115417964B (en) | 2022-09-21 | 2022-09-21 | Degradable polyurethane, preparation method thereof and garden water pipe prepared from degradable polyurethane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211147169.0A CN115417964B (en) | 2022-09-21 | 2022-09-21 | Degradable polyurethane, preparation method thereof and garden water pipe prepared from degradable polyurethane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115417964A CN115417964A (en) | 2022-12-02 |
| CN115417964B true CN115417964B (en) | 2024-02-23 |
Family
ID=84203356
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211147169.0A Active CN115417964B (en) | 2022-09-21 | 2022-09-21 | Degradable polyurethane, preparation method thereof and garden water pipe prepared from degradable polyurethane |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115417964B (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB9205892D0 (en) * | 1991-09-30 | 1992-04-29 | Agency Ind Science Techn | Biodegradable composite material and process of producing same |
| WO1996038502A1 (en) * | 1995-06-01 | 1996-12-05 | Bayer Aktiengesellschaft | Polymer blends containing starch and polyurethane |
| JP2003064147A (en) * | 2001-02-28 | 2003-03-05 | National Institute Of Advanced Industrial & Technology | Lignin based polyurethane and method of production for the same |
| CN102977330A (en) * | 2012-11-14 | 2013-03-20 | 华北电力大学 | Preparation method for degradable polyurethane materials |
| CN112724430A (en) * | 2019-10-28 | 2021-04-30 | 中国石油化工股份有限公司 | Lignin-based polyurethane film and preparation method thereof |
-
2022
- 2022-09-21 CN CN202211147169.0A patent/CN115417964B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB9205892D0 (en) * | 1991-09-30 | 1992-04-29 | Agency Ind Science Techn | Biodegradable composite material and process of producing same |
| WO1996038502A1 (en) * | 1995-06-01 | 1996-12-05 | Bayer Aktiengesellschaft | Polymer blends containing starch and polyurethane |
| JP2003064147A (en) * | 2001-02-28 | 2003-03-05 | National Institute Of Advanced Industrial & Technology | Lignin based polyurethane and method of production for the same |
| CN102977330A (en) * | 2012-11-14 | 2013-03-20 | 华北电力大学 | Preparation method for degradable polyurethane materials |
| CN112724430A (en) * | 2019-10-28 | 2021-04-30 | 中国石油化工股份有限公司 | Lignin-based polyurethane film and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115417964A (en) | 2022-12-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Yin et al. | Improved wet shear strength in eco-friendly starch-cellulosic adhesives for woody composites | |
| Yang et al. | Reinforcement of ramie fibers on regenerated cellulose films | |
| CN101565602B (en) | Preparation method of water swelling polyurethane elastomer sealing product material | |
| Qi et al. | Hydrophobic, UV resistant and dielectric polyurethane-nanolignin composites with good reprocessability | |
| CN101831801A (en) | Durable cellulose fiber and application thereof | |
| CN111808334B (en) | Processing technology of biomass-based composite material for non-woven fabric with high degradability | |
| CN111073325A (en) | Lignin/fiber thermoplastic composite material and preparation method thereof | |
| CN115417964B (en) | Degradable polyurethane, preparation method thereof and garden water pipe prepared from degradable polyurethane | |
| WO2018220983A1 (en) | Method for producing biopolyether polyol, biopolyether polyol, and biopolyurethane resin | |
| CN111675854A (en) | Polyurethane toughened polypropylene composite material and preparation and detection method thereof | |
| CN114409921B (en) | Modified lignin polyol and preparation method of polyurethane hot melt adhesive thereof | |
| CN116376120A (en) | Degradable starch foaming buffer material and preparation method thereof | |
| US20230047011A1 (en) | Preparation method of ultraviolet (uv)-resistant and transparent lignin-based polyurethane (pu) elastomer | |
| CN113956522B (en) | Preparation method of high-strength polyurethane product | |
| CN111499826B (en) | Thermoplastic polyurethane elastomer and preparation method thereof | |
| CN111574705B (en) | Dual-curing nitrate polyether and synthetic method thereof | |
| CN115431620A (en) | Biodegradable garden water pipe | |
| CN114605615A (en) | High molecular weight crosslinking agent modified cationic waterborne polyurethane and preparation method thereof | |
| Xia et al. | Cellulose nanocrystal assisted dual-modification of starch and subsequent polyvinyl alcohol blends | |
| CN1314426A (en) | Modified polyurethane elastomer material and its preparing method and use | |
| CN114957574B (en) | High-temperature-resistant high-elasticity glass fiber composite material and preparation method thereof | |
| CN115537168B (en) | Preparation method of water-resistant bi-component natural biomass cellulose-based polyurethane building sealant and product thereof | |
| CN1273528C (en) | Half interpenetration polymer network materal and preparation process and application thereof | |
| Chowdhurya et al. | Cellulose-based materials foaming | |
| Qiao et al. | Preparation and Properties of Cellulose Nanocrystals Based Self-healing Polyurethane |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |