CN114853971A - Degradable waterborne polyurethane and preparation method thereof - Google Patents
Degradable waterborne polyurethane and preparation method thereof Download PDFInfo
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- CN114853971A CN114853971A CN202210428680.1A CN202210428680A CN114853971A CN 114853971 A CN114853971 A CN 114853971A CN 202210428680 A CN202210428680 A CN 202210428680A CN 114853971 A CN114853971 A CN 114853971A
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- degradable
- chain extender
- aqueous polyurethane
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- waterborne polyurethane
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- 239000004814 polyurethane Substances 0.000 title claims abstract description 50
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title abstract description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000004970 Chain extender Substances 0.000 claims abstract description 24
- 239000004626 polylactic acid Substances 0.000 claims abstract description 19
- 229920000747 poly(lactic acid) Polymers 0.000 claims abstract description 18
- 150000002009 diols Chemical class 0.000 claims abstract description 13
- 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 claims abstract description 11
- 239000008103 glucose Substances 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 11
- 229920005862 polyol Polymers 0.000 claims abstract description 11
- 150000003077 polyols Chemical class 0.000 claims abstract description 11
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000003054 catalyst Substances 0.000 claims abstract description 8
- 125000005442 diisocyanate group Chemical group 0.000 claims abstract description 8
- 229920001610 polycaprolactone Polymers 0.000 claims abstract description 8
- 239000004632 polycaprolactone Substances 0.000 claims abstract description 8
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical group CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 8
- 238000004945 emulsification Methods 0.000 claims description 7
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 6
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 claims description 5
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 5
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 claims description 5
- 230000001804 emulsifying effect Effects 0.000 claims description 5
- 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 5
- 238000002156 mixing Methods 0.000 claims description 5
- 238000010008 shearing Methods 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 claims description 4
- 230000003472 neutralizing effect Effects 0.000 claims description 4
- 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 4
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 claims description 3
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 claims description 3
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 3
- 229960002887 deanol Drugs 0.000 claims description 3
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 3
- 239000012972 dimethylethanolamine Substances 0.000 claims description 3
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 2
- JVYDLYGCSIHCMR-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)butanoic acid Chemical compound CCC(CO)(CO)C(O)=O JVYDLYGCSIHCMR-UHFFFAOYSA-N 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- 239000006185 dispersion Substances 0.000 claims description 2
- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 claims description 2
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 150000003384 small molecules Chemical group 0.000 claims description 2
- 239000002904 solvent Substances 0.000 abstract description 7
- 239000000463 material Substances 0.000 abstract description 5
- 239000002313 adhesive film Substances 0.000 abstract description 3
- 238000004132 cross linking Methods 0.000 abstract description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 3
- 239000003960 organic solvent Substances 0.000 abstract description 3
- 238000013329 compounding Methods 0.000 abstract description 2
- 230000007547 defect Effects 0.000 abstract description 2
- 239000000839 emulsion Substances 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000002689 soil Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 239000003292 glue Substances 0.000 description 3
- 238000003475 lamination Methods 0.000 description 3
- -1 polyhexamethylene Polymers 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 229920002472 Starch Polymers 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 238000006065 biodegradation reaction Methods 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 239000003337 fertilizer Substances 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 230000000813 microbial effect Effects 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000008107 starch Substances 0.000 description 2
- 235000019698 starch Nutrition 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 238000007648 laser printing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000011527 polyurethane coating Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000006467 substitution reaction Methods 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
- 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
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4202—Two or more polyesters of different physical or chemical nature
-
- 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
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
- C08G18/4269—Lactones
- C08G18/4277—Caprolactone and/or substituted caprolactone
-
- 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
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
- C08G18/428—Lactides
-
- 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
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6659—Compounds of group C08G18/42 with compounds of group C08G18/34
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/06—Polyurethanes from polyesters
-
- 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
- C08G2150/00—Compositions for coatings
-
- 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
-
- 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
Abstract
The invention discloses degradable waterborne polyurethane and a preparation method thereof, wherein the degradable waterborne polyurethane comprises the following components: diisocyanate, polyol, an internal crosslinking agent, a small molecular chain extender, a catalyst, a hydrophilic chain extender, a neutralizer and a post chain extender. The invention improves the defects that the polylactic acid polyurethane material is difficult to form a film and has lower tensile strength by compounding the polycaprolactone diol and the polylactic acid diol; meanwhile, glucose is used as a cross-linking agent, and contains five active hydroxyl groups, so that the cross-linking degree of the aqueous polyurethane can be improved, and the water resistance and the solvent resistance of the adhesive film are improved; the degradable waterborne polyurethane disclosed by the invention is simple in process, is easy to remove and does not cause organic solvent pollution, and only a small amount of low-boiling-point acetone is used as a solvent.
Description
Technical Field
The invention relates to the technical field of fine polymer materials, in particular to degradable waterborne polyurethane and a preparation method thereof.
Background
Compared with an oily product, the waterborne polyurethane does not use and generate a solvent, partially solves the problem of environmental pollution, improves the working environment of workers in related industries, but still has the difficult problem of difficult degradation, and under the condition, the development of a rapid and efficient degradable material is urgently required to solve the problem. Polylactic acid (PLA) is one of the most representative biodegradable materials. It is made up by using starch raw material provided by renewable plant resource (for example corn, etc.). The starch raw material is made into lactic acid through a fermentation process, and then is converted into polylactic acid through chemical synthesis. The source of the microbial fertilizer is wide, the price is low, and the microbial fertilizer can be completely degraded by microorganisms finally without burden on the environment. However, the source and synthesis process of polylactic acid determine the characteristic of relatively wide molecular mass distribution, and polylactic acid is a linear polymer, so that the resin synthesized by using polylactic acid as polyol has low strength and certain limitations in the practical application process.
The degradable waterborne polyurethane of the invention is added with polycaprolactone diol while polylactic acid is used as polyol, and glucose is used as a cross-linking agent to synthesize the high-strength degradable waterborne polyurethane, thereby widening the application range of the polylactic acid synthesized waterborne polyurethane.
Disclosure of Invention
Aiming at the problems in the related art, the invention provides degradable waterborne polyurethane and a preparation method thereof, aiming at overcoming the technical problems in the prior related art, and aiming at improving the defects of difficult film formation and low tensile strength of a polylactic acid polyurethane material which is singly used by compounding polycaprolactone diol and polylactic acid diol; meanwhile, glucose is used as a cross-linking agent, and contains five active hydroxyl groups, so that the cross-linking degree of the aqueous polyurethane can be improved, and the water resistance and the solvent resistance of the adhesive film are improved; the degradable waterborne polyurethane disclosed by the invention is simple in process, is easy to remove and does not cause organic solvent pollution, and only a small amount of low-boiling-point acetone is used as a solvent.
In order to achieve the purpose, the invention provides the following technical scheme:
the degradable waterborne polyurethane comprises the following components in parts by weight: 80-120 parts of diisocyanate, 480 parts of polyol 240-480, 0.1-0.8 part of internal crosslinking agent, 1-3 parts of micromolecular chain extender, 0.01-0.1 part of catalyst, 12-24 parts of hydrophilic chain extender, 11-16 parts of neutralizer and 12-24 parts of post chain extender.
Preferably, the diisocyanate is one or more of isophorone diisocyanate and dicyclohexylmethane diisocyanate.
By adopting the technical scheme, the diisocyanate accounts for 15-25% of the synthetic prepolymer.
Preferably, the polyol is a mixture of polycaprolactone diol and polylactic acid diol.
By adopting the technical scheme, the polyol accounts for 65-75% in the synthetic prepolymer, wherein the proportion of the polylactic acid in the polyol is not less than 70%.
Preferably, the internal crosslinking agent is glucose.
By adopting the technical scheme, the internal cross-linking agent accounts for 0-2.5% in the synthesis of the prepolymer.
Preferably, the small-molecule chain extender is one or more of 1, 4-butanediol and 1, 6-hexanediol.
By adopting the technical scheme, the small molecular chain extender accounts for 0.5-3% of the synthetic prepolymer.
Preferably, the catalyst is one of dibutyl tin dilaurate and stannous octoate.
By adopting the technical scheme, the catalyst accounts for 0.01-0.05% in the synthesis of the prepolymer.
Preferably, the hydrophilic chain extender is one or more of dimethylolpropionic acid and dimethylolbutyric acid.
By adopting the technical scheme, the hydrophilic chain extender accounts for 3.3-4.5% of the synthetic prepolymer.
Preferably, the neutralizing agent is triethylamine or N, N-dimethylethanolamine.
By adopting the technical scheme, the neutralization degree is 90-100%.
Preferably, the rear chain extender is one of hydrazine hydrate, ethylenediamine and isophorone diamine.
By adopting the technical scheme, the adding amount of the post chain extender is that the molar ratio of the residual isocyanate in the system is 0.2-0.4: 1.
In order to achieve the purpose, the invention provides the following technical scheme:
a preparation method of degradable waterborne polyurethane comprises the following steps:
(1) pre-polymerization: under the protection of dry high-purity nitrogen, putting diisocyanate into a four-neck flask containing vacuum dehydrated polyol, and reacting in the presence of a catalyst to prepare a prepolymer, wherein the reaction temperature is 80-90 ℃ and the reaction time is 1-2 hours; reducing the temperature of a reaction system to 50-70 ℃, adding a small molecular chain extender, a hydrophilic chain extender and glucose, simultaneously adding a proper amount of acetone into the reaction system to control the viscosity of the system, heating to 70-80 ℃, and mixing for reaction for 2-3 hours;
(2) emulsification: introducing the prepolymer into an emulsifying kettle, adding a proper amount of triethylamine or dimethylethanolamine as a neutralizing agent, adding deionized water under high-speed shearing for emulsification, and finally adding a rear chain extender for uniform dispersion;
(3) and removing the acetone in vacuum to obtain the degradable waterborne polyurethane.
Compared with the prior art, the invention has the beneficial effects that:
(1) the invention is a degradable waterborne polyurethane and its preparation method, the degradable waterborne polyurethane emulsion that the invention provides, through polyhexamethylene lactone diol and polylactic acid diol compound use improve use polylactic acid polyurethane material only difficult to film, the disadvantage of lower tensile strength;
(2) the invention relates to degradable waterborne polyurethane and a preparation method thereof, glucose is used as a cross-linking agent, and contains five active hydroxyl groups, so that the cross-linking degree of the waterborne polyurethane can be improved, and the water resistance and the solvent resistance of a glue film are improved;
(3) the degradable waterborne polyurethane disclosed by the invention is simple in process, is easy to remove by only using a small amount of low-boiling-point acetone as a solvent, and does not cause organic solvent pollution.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
A preparation method of degradable waterborne polyurethane comprises the following steps:
the method comprises the following steps: adding 300g of polylactic acid diol and 110g of polycaprolactone diol into a four-neck flask provided with a stirrer and a thermometer, heating to 110 ℃, vacuumizing for dehydration, wherein the vacuum degree is-0.08 MPa, cooling to below 75 ℃ after 1.5h, replacing a vacuum tube opening with a condensation reflux tube, adding 103.00g of isophorone diisocyanate, adding 0.09g of dibutyl tin dilaurate, uniformly mixing, heating to 85-90 ℃, and reacting for 2 h;
step two: reducing the temperature of the obtained prepolymer to 60 ℃, adding 2.70g of 1, 6-hexanediol, 0.50g of glucose and 18.2g of dimethylolpropionic acid, simultaneously adding acetone to control the viscosity of a reaction system, and carrying out chain extension reaction at the temperature of 70-75 ℃ for 3 hours to obtain the prepolymer;
step three: transferring the prepolymer into an emulsifying kettle, adding 13.60g of triethylamine, adding water under high-speed shearing for emulsification, adding 18.83g of ethylenediamine 10% aqueous solution at 20-25 ℃, uniformly dispersing, and removing acetone in vacuum to obtain the degradable aqueous polyurethane emulsion.
The resulting emulsion had a solids content of 43%, a viscosity of 90mPa.s, a pH: 7.35.
example 2
A preparation method of degradable waterborne polyurethane comprises the following steps:
the method comprises the following steps: adding 187.50g of polylactic acid glycol and 62.5g of polycaprolactone glycol into a four-neck flask provided with a stirrer and a thermometer, heating to 120 ℃, vacuumizing for dehydration, wherein the vacuum degree is-0.09 Mpa, cooling to below 75 ℃ after 1.5h, changing the opening of a vacuum tube into a condensation reflux tube, adding 46.00g of isophorone diisocyanate and 42.00g of dicyclohexylmethane diisocyanate, adding 0.09g of stannous octoate, uniformly mixing, heating to 85-90 ℃, and reacting for 2 h;
step two: reducing the temperature of the obtained prepolymer to 60 ℃, adding 2.10g of 1, 4-butanediol, 0.4g of glucose and 15.20g of dimethylolpropionic acid, simultaneously adding acetone to control the viscosity of a reaction system, and carrying out chain extension reaction at the temperature of 70-75 ℃ for 3 hours to obtain the prepolymer;
step three: and transferring the prepolymer into an emulsifying kettle, adding 11.45g of triethylamine, adding water under high-speed shearing for emulsification, adding 13.28g of ethylenediamine 10% aqueous solution at the water temperature of 20-25 ℃, uniformly dispersing, and removing acetone in vacuum to obtain the degradable aqueous polyurethane emulsion.
The resulting emulsion had a solids content of 38%, a viscosity of 90mpa.s, a pH: 7.28.
example 3
A preparation method of degradable waterborne polyurethane comprises the following steps:
the method comprises the following steps: adding 252g of polylactic acid diol and 63g of polycaprolactone diol into a four-mouth flask provided with a stirrer and a thermometer, heating to 120 ℃, vacuumizing for dehydration, wherein the vacuum degree is-0.08 Mpa, cooling to below 75 ℃ after 1.5h, changing the mouth of a vacuum tube into a condensation reflux tube, adding 99.00g of isophorone diisocyanate, adding 0.08g of stannous octoate, uniformly mixing, heating to 80-85 ℃, and reacting for 1.5;
reducing the temperature of the obtained prepolymer to 60 ℃, adding 2.32g of 1, 6-hexanediol, 0.4g of glucose and 15.00g of dimethylolpropionic acid, simultaneously adding acetone to control the viscosity of a reaction system, and carrying out chain extension reaction at the temperature of 70-75 ℃ for 2.5 hours to obtain the prepolymer;
and transferring the prepolymer into an emulsifying kettle, adding 9.57g of dimethylethanolamine, adding water under high-speed shearing for emulsification, adding 35.31g of an isophorone diamine 10% aqueous solution, uniformly dispersing, and removing acetone in vacuum to obtain the degradable waterborne polyurethane emulsion.
The resulting emulsion had a solids content of 38%, a viscosity of 80mpa.s, a pH: 7.27.
PHA cards are coated by the degradable waterborne polyurethane prepared in the examples 1-3, and the obtained card coatings are subjected to physicochemical property tests at normal temperature and normal pressure, wherein the main indexes are shown in Table 1:
TABLE 1 main indexes of analysis test of coating after degradable waterborne polyurethane coating PHA card
The coated cards from examples 1-3 were printed with other polyurethane coated cards using an OKIC711DN color printer, and the results are shown in table 2:
TABLE 2 comparison of Main Properties of different coated cards after laser printing
The biodegradation effect of the coating films of examples 1 to 3 was determined by the soil burying method: the glue film is buried in the soil, and the glue film is gradually eroded by microorganisms and water molecules, so that polyurethane molecules are degraded. The degradable waterborne polyurethane prepared in the embodiment, the common aliphatic waterborne polyurethane and the common aromatic waterborne polyurethane are respectively coated on the same PVC film, the dry basis thickness is 16 mu m, the degradable waterborne polyurethane and the common aliphatic waterborne polyurethane are laminated with the PVC card with the same thickness of 200 mu m, and the lamination is carried out on the same laminating machine at the temperature of 150 ℃ and the pressure of 4 MPa. The three prepared cards were cut into 50mm × 50mm standard specimens, and buried in garden soil to a depth of 20 cm. The lamination instant peeling time is counted to be 0 week, the lamination card is taken out once every other week to carry out peeling strength attenuation test, and the larger the degradation degree is, the faster the peeling strength attenuation is correspondingly. The main indexes are shown in the table 3:
TABLE 3 soil burying method for testing main biodegradation indexes of adhesive films in examples 1 to 3
Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, and not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it should be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (10)
1. The degradable waterborne polyurethane is characterized by comprising the following components in parts by weight: 80-120 parts of diisocyanate, 480 parts of polyol 240-480, 0.1-0.8 part of internal crosslinking agent, 1-3 parts of micromolecular chain extender, 0.01-0.1 part of catalyst, 12-24 parts of hydrophilic chain extender, 11-16 parts of neutralizer and 12-24 parts of post chain extender.
2. The degradable aqueous polyurethane of claim 1, wherein the diisocyanate is one or more of isophorone diisocyanate and dicyclohexylmethane diisocyanate.
3. The degradable aqueous polyurethane of claim 1, wherein the polyol is a mixture of polycaprolactone diol and polylactic acid diol.
4. The degradable aqueous polyurethane of claim 1, wherein the internal crosslinking agent is glucose.
5. The degradable aqueous polyurethane of claim 1, wherein the small-molecule chain extender is one or more of 1, 4-butanediol and 1, 6-hexanediol.
6. The degradable aqueous polyurethane of claim 1, wherein the catalyst is one of dibutyl tin dilaurate and stannous octoate.
7. The degradable aqueous polyurethane of claim 1, wherein the hydrophilic chain extender is one or more of dimethylolpropionic acid and dimethylolbutyric acid.
8. The degradable aqueous polyurethane of claim 1, wherein the neutralizing agent is triethylamine or N, N-dimethylethanolamine.
9. The degradable aqueous polyurethane of claim 1, wherein the post-chain extender is one of hydrazine hydrate, ethylenediamine and isophorone diamine.
10. A method for preparing the degradable aqueous polyurethane of any one of claims 1 to 9, comprising the steps of:
(1) pre-polymerization: under the protection of dry high-purity nitrogen, putting diisocyanate into a four-neck flask containing vacuum dehydrated polyol, and reacting in the presence of a catalyst to prepare a prepolymer, wherein the reaction temperature is 80-90 ℃ and the reaction time is 1-2 hours; reducing the temperature of a reaction system to 50-70 ℃, adding a small molecular chain extender, a hydrophilic chain extender and glucose, simultaneously adding a proper amount of acetone into the reaction system to control the viscosity of the system, heating to 70-80 ℃, and mixing for reaction for 2-3 hours;
(2) emulsification: introducing the prepolymer into an emulsifying kettle, adding a proper amount of triethylamine or dimethylethanolamine as a neutralizing agent, adding deionized water under high-speed shearing for emulsification, and finally adding a rear chain extender for uniform dispersion;
(3) and removing acetone in vacuum to obtain the degradable waterborne polyurethane.
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