CN117757032B - Self-catalytic bio-based aqueous polyurethane emulsion and preparation method and application thereof - Google Patents
Self-catalytic bio-based aqueous polyurethane emulsion and preparation method and application thereof Download PDFInfo
- Publication number
- CN117757032B CN117757032B CN202311760597.5A CN202311760597A CN117757032B CN 117757032 B CN117757032 B CN 117757032B CN 202311760597 A CN202311760597 A CN 202311760597A CN 117757032 B CN117757032 B CN 117757032B
- Authority
- CN
- China
- Prior art keywords
- bio
- chain extender
- preparation
- aqueous polyurethane
- polyurethane emulsion
- 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 53
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 53
- 239000000839 emulsion Substances 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 238000004945 emulsification Methods 0.000 title claims description 4
- 239000004970 Chain extender Substances 0.000 claims abstract description 39
- 238000006243 chemical reaction Methods 0.000 claims abstract description 39
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 claims abstract description 38
- 229920002472 Starch Polymers 0.000 claims abstract description 21
- 235000019698 starch Nutrition 0.000 claims abstract description 21
- 239000008107 starch Substances 0.000 claims abstract description 21
- 239000003054 catalyst Substances 0.000 claims abstract description 20
- 229940074391 gallic acid Drugs 0.000 claims abstract description 19
- 235000004515 gallic acid Nutrition 0.000 claims abstract description 19
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229920005862 polyol Polymers 0.000 claims abstract description 17
- 150000003077 polyols Chemical class 0.000 claims abstract description 17
- 125000005442 diisocyanate group Chemical group 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000000178 monomer Substances 0.000 claims abstract description 8
- AZIQALWHRUQPHV-UHFFFAOYSA-N prop-2-eneperoxoic acid Chemical compound OOC(=O)C=C AZIQALWHRUQPHV-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 6
- 230000003472 neutralizing effect Effects 0.000 claims abstract description 6
- 150000003384 small molecules Chemical group 0.000 claims abstract description 6
- 239000000853 adhesive Substances 0.000 claims abstract description 5
- 230000001070 adhesive effect Effects 0.000 claims abstract description 5
- 239000000976 ink Substances 0.000 claims abstract description 5
- 239000003973 paint Substances 0.000 claims abstract description 5
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical group CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 36
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 34
- 238000000034 method Methods 0.000 claims description 17
- 239000003960 organic solvent Substances 0.000 claims description 14
- 239000002202 Polyethylene glycol Substances 0.000 claims description 12
- 239000011259 mixed solution Substances 0.000 claims description 12
- 229920001223 polyethylene glycol Polymers 0.000 claims description 12
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 9
- 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 8
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 6
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 6
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 4
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 2
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 2
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 2
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 9
- 239000000203 mixture Substances 0.000 description 38
- 238000003756 stirring Methods 0.000 description 23
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 11
- 230000015572 biosynthetic process Effects 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 238000001514 detection method Methods 0.000 description 6
- 238000002329 infrared spectrum Methods 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 229920002593 Polyethylene Glycol 800 Polymers 0.000 description 5
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 239000012975 dibutyltin dilaurate Substances 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 230000015556 catabolic process Effects 0.000 description 4
- 238000006731 degradation reaction Methods 0.000 description 4
- 235000011187 glycerol Nutrition 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000012855 volatile organic compound Substances 0.000 description 4
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 231100000331 toxic Toxicity 0.000 description 3
- 230000002588 toxic effect Effects 0.000 description 3
- 229920002261 Corn starch Polymers 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- 239000007805 chemical reaction reactant Substances 0.000 description 2
- 239000008120 corn starch Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229940098779 methanesulfonic acid Drugs 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- IUGYQRQAERSCNH-UHFFFAOYSA-N pivalic acid Chemical compound CC(C)(C)C(O)=O IUGYQRQAERSCNH-UHFFFAOYSA-N 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- VUAXHMVRKOTJKP-UHFFFAOYSA-N 2,2-dimethylbutyric acid Chemical compound CCC(C)(C)C(O)=O VUAXHMVRKOTJKP-UHFFFAOYSA-N 0.000 description 1
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 230000003064 anti-oxidating effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 239000000287 crude extract Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000009775 high-speed stirring Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000000269 nucleophilic effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 150000008442 polyphenolic compounds Chemical class 0.000 description 1
- 235000013824 polyphenols Nutrition 0.000 description 1
- 229920006264 polyurethane film Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses an autocatalytic bio-based aqueous polyurethane emulsion and a preparation method and application thereof. Under the condition of no catalyst, starch-based polyol is used as a main reaction raw material, bio-based hydrophilic chain extender GA-MA synthesized by the monoesterification reaction of gallic acid and maleic anhydride is used as a hydrophilic chain extender, the bio-based hydrophilic chain extender GA-MA and diisocyanate, a small molecule chain extender and hydroxyl acrylate monomers are reacted together, a neutralizing agent is added for neutralization after the reaction to prepare a prepolymer, and finally the prepolymer is dispersed in water to prepare the self-catalyzed bio-based aqueous polyurethane emulsion. The bio-based aqueous polyurethane emulsion provided by the invention has high bio-based content and strong stability, and after being cured into a film, the cured film has good thermal stability, and can be widely applied to the fields of paint, ink, adhesive and the like, and can be applied to the preparation of paint, ink, adhesive and the like.
Description
Technical Field
The invention belongs to the technical field of aqueous polyurethane, and particularly relates to an autocatalytic bio-based aqueous polyurethane emulsion and a preparation method and application thereof.
Background
Volatile Organic Compounds (VOCs) such as toluene, xylene and formaldehyde are required to be used in the solvent-based polyurethane synthesis process, and serious emission of the volatile organic compounds can be caused in the production and application processes. In recent years, with the enhancement of environmental awareness, research on environment-friendly aqueous polyurethane (WPU) with water as a dispersant and without VOC emission is increasingly paid attention to. Conventional aqueous polyurethanes are typically prepared from dimethyl propionic acid (DMPA), dimethyl butyric acid (DMBA) and other petroleum-based chemical raw materials; with the enhancement of environmental awareness, the preparation of aqueous polyurethane by using bio-based raw materials instead of petroleum-based raw materials has become a mainstream trend.
In industry, the method for preparing the aqueous polyurethane is mainly based on an acetone method and a prepolymer mixing method, and highly toxic catalysts such as dibutyl tin dilaurate (DBTDL) and the like are required to be added in the whole reaction process to improve the reaction rate. However, industrial WPU dispersions do not appear to be as environmentally friendly due to the use of highly toxic catalysts in the preparation process, and the catalyst remains in the dried WPU film, which is prone to contact poisoning, especially when used as a coating agent. Therefore, the research and development of the catalyst-free waterborne polyurethane has very important theoretical and practical values.
Gallic Acid (GA) is a polyphenol substance extracted from crude extracts of fruits, nuts and flowers, contains three hydroxyl groups, has natural antioxidation effect, and is widely applied to the fields of food, chemical industry, biology, pharmacy and the like. Maleic Anhydride (MA) is the third largest anhydride raw material next to phthalic anhydride and acetic anhydride in the world at present, contains conjugated maleic acyl, has strong hydrophilicity after hydrolysis, has very active chemical property and is easy to generate esterification reaction.
Disclosure of Invention
A first object of the present invention is to provide a bio-based hydrophilic chain extender to solve at least one of the above technical problems.
The second object of the present invention is to provide an autocatalytic bio-based aqueous polyurethane emulsion to solve at least one of the above technical problems.
According to one aspect of the present invention, there is provided a bio-based hydrophilic chain extender, the preparation method of which comprises the steps of:
Mixing gallic acid, maleic anhydride, a catalyst and a first organic solvent, reacting for 5-7 hours at 70-90 ℃, and removing the first organic solvent to obtain the catalyst; wherein the molar ratio of gallic acid to maleic anhydride is (2.8-3.2): 1.
Under the condition of 70-90 ℃ and the catalysis of a catalyst, the hydroxyl of gallic acid and the epoxy of maleic anhydride are subjected to monoesterification reaction, so that the bio-based hydrophilic chain extender GA-MA is obtained.
In some embodiments, the catalyst may be selected from at least one of p-toluene sulfonic acid, tetrabutylammonium bromide.
In some embodiments, the catalyst may be used in an amount of 1% to 3% of the total mass of gallic acid and maleic anhydride.
In some embodiments, the first organic solvent may be selected from at least one of acetone, butanone.
In some embodiments, the mass ratio of the first organic solvent to the gallic acid may be (0.8-2): 1.
According to another aspect of the present invention, there is provided an autocatalytic bio-based aqueous polyurethane emulsion, the preparation method thereof comprising the steps of:
Mixing diisocyanate, the bio-based hydrophilic chain extender GA-MA and a second organic solvent, and reacting for 2-3 hours at the temperature of 60-80 ℃ to obtain a first reaction mixed solution;
adding starch-based polyol into the first reaction mixed solution, and reacting for 2-3 hours at the temperature of 60-80 ℃ to obtain a second reaction mixed solution;
adding a small molecular chain extender into the second reaction mixed solution, and reacting for 1-2 hours at the temperature of 60-80 ℃ to obtain a third reaction mixed solution;
Adding hydroxyl acrylate monomer into the third reaction mixed solution, reacting for 1-2h at 60-80 ℃, cooling to room temperature after the reaction is finished, and adding a neutralizer for neutralization to obtain a prepolymer;
Adding water into the prepolymer, and removing the second organic solvent in the emulsion after emulsification treatment.
When the bio-based hydrophilic chain extender GA-MA is applied to the preparation of the waterborne polyurethane, carboxylic acid in the GA-MA structure can activate electrophilic diisocyanate and nucleophilic alcohol (starch-based polyol) through hydrogen bonds, and the diisocyanate and the starch-based polyol can be subjected to acid catalytic reaction to generate ethyl carbamate, so that the catalyst such as dibutyltin dilaurate and the like is not needed in the synthesis process of the waterborne polyurethane provided by the invention, and the waterborne polyurethane can be synthesized in an autocatalytic mode.
In some embodiments, the amount of biobased hydrophilic chain extender may be from 5% to 8% of the total mass of the reaction starting materials (i.e., the total mass of diisocyanate, biobased hydrophilic chain extender, starch-based polyol, small molecule chain extender, and hydroxy acrylate monomer).
In some embodiments, the second organic solvent may be selected from at least one of acetone, butanone.
In some embodiments, the mass ratio of the second organic solvent to the diisocyanate may be (0.8-2): 1.
In some embodiments, the starch-based polyol may be used in an amount of 22% to 26% of the total mass of the reaction materials.
In some embodiments, the diisocyanate may be selected from at least one of isophorone diisocyanate, toluene diisocyanate, 4-methylenedicyclohexyl diisocyanate, hexamethylene diisocyanate.
In some embodiments, the small molecule chain extender may be selected from at least one of polyethylene glycol, 1, 4-butanediol.
In some embodiments, the hydroxy acrylate monomer may be selected from at least one of hydroxy ethyl acrylate, hydroxy ethyl 2-methacrylate.
In some embodiments, the polyethylene glycol may have a molecular weight of 400 to 800.
In some embodiments, the mass ratio of diisocyanate, bio-based hydrophilic chain extender, starch-based polyol, small molecule chain extender, hydroxy acrylate monomer may be (4.1-4.6): (0.5-0.8): (2.2-2.6): (1.0-1.2): (1.0-1.2).
In some embodiments, the neutralizing agent may be triethylamine.
In some embodiments, the molar ratio of neutralizing agent to bio-based hydrophilic chain extender may be (1.8-2.2): 1.
In some embodiments, the amount of water is 60 to 70% of the total mass of the reaction starting material and water.
The self-catalyzed bio-based aqueous polyurethane emulsion provided by the invention has good dispersibility and high stability, and the cured film obtained after curing has good thermal stability. The self-catalytic bio-based aqueous polyurethane emulsion provided by the invention can be widely applied to the fields of paint, ink, adhesive and the like, and particularly can be applied to the preparation of paint, ink, adhesive and the like.
The beneficial effects of the invention include:
(1) The hydrophilic chain extender provided by the invention belongs to a bio-based hydrophilic chain extender, is applied to preparation of aqueous polyurethane emulsion, and can improve the bio-based ratio of the aqueous polyurethane emulsion.
(2) The aqueous polyurethane provided by the invention mainly uses starch-based polyol as a synthetic raw material, and starch as the synthetic raw material and gallic acid for synthesizing the bio-based hydrophilic chain extender are renewable and cheap biological materials, so that the utilization of non-renewable petrochemical resources is reduced in the process of synthesizing the aqueous polyurethane, and the prepared aqueous polyurethane film has good degradation capability, safety and environmental friendliness.
(3) The waterborne polyurethane provided by the invention does not need to use toxic catalysts in the synthesis process, reduces the harm of the catalysts to the environment and human bodies, and is safe in production process.
(4) The preparation method of the waterborne polyurethane provided by the invention is simple, the reaction condition is mild, the reaction raw materials have no strong corrosiveness, the safety and the environment are protected, the reaction condition is simple and easy to realize, and the industrial production is facilitated.
Drawings
FIG. 1 is a synthetic scheme for the bio-based hydrophilic chain extender GA-MA according to the invention;
FIG. 2 is an infrared spectrum of Gallic Acid (GA), maleic Anhydride (MA), bio-based hydrophilic chain extender GA-MA;
FIG. 3 is a GA-MA nuclear magnetic resonance hydrogen spectrum of the bio-based hydrophilic chain extender;
FIG. 4 is an infrared spectrum of an intermediate product of different time periods in the synthesis process of the self-catalyzed bio-based aqueous polyurethane emulsion of the invention;
FIG. 5 is an infrared spectrum of an autocatalytic biobased aqueous polyurethane emulsion of the present invention and an aqueous polyurethane emulsion prepared with DMBA as a hydrophilic chain extender;
FIG. 6 is a graph showing the particle size distribution of the self-catalyzed bio-based aqueous polyurethane emulsion prepared in examples 2 to 5 of the present invention;
FIGS. 7 to 8 are thermogravimetric analysis diagrams of the self-catalyzed bio-based aqueous polyurethane emulsion prepared in examples 2 to 5 of the present invention after film formation;
FIG. 9 is a graph showing DMA analysis of the self-catalyzed bio-based aqueous polyurethane emulsion prepared in inventive examples 2 to 5 after film formation.
Detailed Description
The present invention will be described in further detail with reference to the following embodiments. The examples are for illustration only and are not intended to limit the invention in any way. The raw materials and reagents used in the examples were conventional products which were obtained commercially, unless otherwise specified; the experimental methods for which specific conditions are not specified in the examples are generally in accordance with the conditions conventional in the art or in accordance with the manufacturer's recommendations.
In the invention, the preparation method of starch-based polyol refers to the prior patent application CN116284682A starch-based aqueous polyurethane emulsion of the applicant and the preparation method and application thereof, and comprises the following steps:
Mixing glycerol and polyethylene glycol, stirring and heating to 90-100 ℃, then adding corn starch, stirring and heating to 120-140 ℃, preserving heat and stirring for 1-2 h, then adding methane sulfonic acid, stirring for 0.5-1 h at 120-140 ℃, then cooling to room temperature, and filtering out residues to obtain starch-based polyol; wherein the mass ratio of glycerin to polyethylene glycol is 3:7, the mass ratio of the corn starch to the total amount of glycerol and polyethylene glycol is 1:4, the dosage of methane sulfonic acid is 0.05 percent of the total mass of starch, glycerol and polyethylene glycol.
In the embodiment of the invention, the stirring speed is 200rpm, and the high-speed stirring and emulsifying speed is 1000rpm.
Example 1 preparation of biobased hydrophilic chain extenders
The method comprises the following steps:
29.400g of maleic anhydride, 17.012g of gallic acid, 17.000g of acetone and 0.6962g of p-toluenesulfonic acid are added into a reaction kettle, the temperature is raised to 80 ℃ by stirring, the temperature is kept for 5 hours by stirring, the solution is changed into orange red from pale yellow, the solution is cooled to room temperature, acetone is removed by rotary evaporation, the solid is put into a 60 ℃ oven, and the bio-based hydrophilic chain extender GA-MA is obtained by drying and grinding.
The synthetic route pattern of the bio-based hydrophilic chain extender GA-MA is shown in FIG. 1.
The Gallic Acid (GA), maleic Anhydride (MA) and bio-based hydrophilic chain extender GA-MA are subjected to infrared spectrum detection, and the detection result is shown in figure 2. Comparison of the infrared spectrograms of GA-MA and MA in FIG. 2 shows that the GA-MA has an associated O-H group at 3500cm -1～2800cm-1, wherein about 3500cm -1 is vibration absorption of carboxyl, and maleic anhydride characteristic peak of 1859cm -1～1781cm-1 disappears, thus proving that the ring opening of maleic anhydride is successful. 1614cm -1 in the figure is the absorption peak of c=c on the benzene ring, demonstrating successful connection of maleic anhydride and gallic acid. The above results indicate that GA-MA was successfully synthesized.
The bio-based hydrophilic chain extender GA-MA is subjected to nuclear magnetic resonance detection, the detection result is shown in figure 3, the peak of 5.66-6.40ppm represents-CH=CH-, and the peak of 6.72-7.15ppm represents the chemical shift of-CH-on the benzene ring of GA, the chemical shift of-CH=CH-appears at 6.27ppm in 1 H NMR spectrum of GA-MA, and the chemical shift of-CH-on the benzene ring appears at 6.92ppm, thus proving that GA-MA is successfully synthesized.
Example 2 preparation of an autocatalytic biobased aqueous polyurethane emulsion
The method comprises the following steps:
8.00g isophorone diisocyanate (IPDI), 1.00g (3.73 mmol) GA-MA and 8.00mL solvent acetone are added into a reaction kettle, the mixture is stirred and heated to 70 ℃, the mixture is stirred and reacted for 3 hours at the temperature of 70 ℃, then 4.50g starch-based polyol is dropwise added into the mixture by a constant pressure funnel, the mixture is stirred and reacted for 3 hours at the temperature of 70 ℃, then 2.00g polyethylene glycol (PEG 800) is dropwise added, the mixture is stirred and reacted for 1 hour at the temperature of 70 ℃, then 2.00g hydroxyethyl acrylate is added, the mixture is stirred and reacted for 2 hours at the temperature of 70 ℃, the mixture is cooled to room temperature, 0.755g Triethylamine (TEA) is added, the mixture is stirred and neutralized for 0.5 hour, then 33.90g deionized water is added, the mixture is stirred and emulsified for 2 hours at a high speed, and acetone is removed by spin evaporation from the reaction liquid after the reaction is completed, so that the aqueous polyurethane emulsion with the solid content of 35% is named as WPU1.
Example 3 preparation of an autocatalytic biobased aqueous polyurethane emulsion
The method comprises the following steps:
8.00g of isophorone diisocyanate (IPDI), 1.106g (4.12 mmol) of GA-MA and 8.00mL of solvent acetone are added into a reaction kettle, the temperature is raised to 70 ℃ by stirring, the mixture is reacted for 3 hours, then 4.50g of starch-based polyol is dropwise added by a constant pressure funnel, the mixture is reacted for 3 hours by stirring at 70 ℃, then 2.00g of polyethylene glycol (PEG 800) is dropwise added, the mixture is reacted for 1 hour by stirring at 70 ℃, then 2.00g of hydroxyethyl acrylate is added, the mixture is reacted for 2 hours by stirring at 70 ℃, the mixture is cooled to room temperature, 0.835g of Triethylamine (TEA) is added, the mixture is stirred and neutralized for 0.5 hours, then 34.25g of deionized water is added, the mixture is emulsified for 2 hours by stirring at a high speed, and after the reaction, the mixture is distilled to remove acetone by evaporation, so that the aqueous polyurethane emulsion with 35% of solid content is obtained, and the aqueous polyurethane emulsion is named WPU2.
Example 4 preparation of an autocatalytic biobased aqueous polyurethane emulsion
The method comprises the following steps:
8.00g of isophorone diisocyanate (IPDI), 1.155g (4.30 mmol) of GA-MA and 8.00mL of solvent acetone are added into a reaction kettle, the temperature is raised to 70 ℃ by stirring, the mixture is reacted for 3 hours, then 4.50g of starch-based polyol is dropwise added by a constant pressure funnel, the mixture is reacted for 3 hours by stirring at 70 ℃, then 2.00g of polyethylene glycol (PEG 800) is dropwise added, the mixture is reacted for 1 hour by stirring at 70 ℃, then 2.00g of hydroxyethyl acrylate is added, the mixture is reacted for 2 hours by stirring at 70 ℃, the mixture is cooled to room temperature, 0.871g of Triethylamine (TEA) is added, the mixture is reacted for 0.5 hour by stirring, then 34.93g of deionized water is added, the mixture is emulsified for 2 hours by stirring at a high speed, and acetone is removed by steaming the reaction liquid after the reaction is completed, so that the aqueous polyurethane emulsion with 35% of solid content is obtained and is named as WPU3.
Example 5 preparation of an autocatalytic biobased aqueous polyurethane emulsion
The method comprises the following steps:
8.00g of isophorone diisocyanate (IPDI), 1.320g (4.92 mmol) of GA-MA and 8.00mL of solvent acetone are added into a reaction kettle, the temperature is raised to 70 ℃ by stirring, the mixture is reacted for 3 hours, then 4.50g of starch-based polyol is dropwise added by a constant pressure funnel, the mixture is reacted for 3 hours by stirring at 70 ℃, then 2.00g of polyethylene glycol (PEG 800) is dropwise added, the mixture is reacted for 1 hour by stirring at 70 ℃, then 2.00g of hydroxyethyl acrylate is added, the mixture is reacted for 2 hours by stirring at 70 ℃, the mixture is cooled to room temperature, 0.996g of Triethylamine (TEA) is added, the mixture is stirred and neutralized for 0.5 hours, then 35.64g of deionized water is added, the mixture is emulsified for 2 hours by stirring at a high speed, and the mixture is distilled to remove acetone after the reaction, so that the aqueous polyurethane emulsion with the solid content of 35% is obtained, and the aqueous polyurethane emulsion is named as WPU4.
Comparative example 1
The method comprises the following steps:
8g of isophorone diisocyanate (IPDI), 1.105g of DMBA (the same molar mass of the carboxyl group of DMBA in this comparative example and the molar mass of the carboxyl group of GA-MA in example 1), 8mL of solvent acetone and 0.08g of catalyst dibutyltin dilaurate were added into a reaction kettle, stirred and heated to 70 ℃, stirred and reacted for 3 hours at 70 ℃, then 4.50g of starch-based polyol was dropwise added into the reaction kettle through a constant pressure funnel, stirred and reacted for 3 hours at 70 ℃, then 2.00g of polyethylene glycol (PEG 800) was dropwise added, stirred and reacted for 1 hour at 70 ℃, then 2.00g of hydroxyethyl acrylate was added, stirred and reacted for 2 hours at 70 ℃, cooled to room temperature, 0.754g of Triethylamine (TEA) was added and stirred and reacted for 0.5 hours, then 34.10g of deionized water was added, stirred and emulsified for 2 hours at a high speed, acetone was removed by spin evaporation after the reaction, and the aqueous polyurethane emulsion with 35% of solid content was obtained.
To verify the comprehensive properties of the bio-based aqueous polyurethane emulsion of the present invention, the performance test was performed on the bio-based aqueous polyurethane emulsion prepared in examples 2 to 5.
Test example 1
Example 2 during the reaction to synthesize WPU1, the reaction solution was taken at intervals of 2 hours from the start of the addition of isophorone diisocyanate and GA-MA, and infrared detection was performed, and the results are shown in fig. 4. As is apparent from FIG. 4, the (-NCO) absorption peak at 2250cm -1～2270cm-1 becomes progressively smaller, indicating that the reaction can be carried out efficiently without catalyst.
Fig. 5 is an infrared spectrum of WPU prepared by reacting GA-MA and DMBA using the same molar mass at the same temperature and time, i.e., WPU prepared in example 2 and comparative example 1, respectively designated as GA-MA (WPU) and DMBA (WPU), wherein dibutyltin dilaurate was used as a catalyst in the preparation of DMBA (WPU), no catalyst was used as GA-MA (WPU), and it can be seen from the figure that WPU using GA-MA as a hydrophilic chain extender and WPU using a catalyst had substantially the same infrared spectrum, and the vibration absorption peak at about 2270cm -1 (n=c=o) disappeared, confirming that the emulsion synthesis of the reactive WPU was successful.
Test example 2 stability characterization
The WPUs 1 to 4 prepared in examples 2 to 5 were subjected to stability characterization: the particle size distribution of the emulsion is detected, and the detection result is shown in figure 6, and from the figure, it can be seen that the particle size distribution of the starch-based aqueous polyurethane emulsion prepared in examples 2-5 is 10-100 nm, the particle size of the emulsion is small, the smaller the particle size, the better the stability, and the emulsion has better stability.
It can be seen from Table 1 that the absolute value of Zeta potential of each of WPUs 1 to 4 is greater than 30, so that each of WPUs 1 to 4 prepared in examples 2 to 5 has good stability, and it can be seen from Table 1 that the average particle diameter of the emulsion is reduced with the increase of the content of the hydrophilic chain extender, and the PDI value of the emulsion is less than 0.7, indicating good dispersibility.
TABLE 1 average particle size, zeta potential and PDI of WPU
Test example 3
1-3 Wt% of photoinitiator (2-hydroxy-2-methyl-1-phenyl acetone (PI-1173)) is added into the bio-based aqueous polyurethane emulsion prepared in the examples 2-5 respectively, the mixture is uniformly mixed, the mixture is coated on a glass plate by an applicator, the mixture is irradiated for 1min by an ultraviolet lamp, and after the solidification is successful, the photo-solidified film is cut into strips.
The thermal stability analysis and measurement of the cured films obtained by curing the WPUs 1 to 4 of examples 2 to 5 were performed, and the results are shown in fig. 7 to 8. As can be seen from fig. 7 to 8, the thermal degradation of the cured film is roughly divided into two stages, the first stage being the degradation of the hard segment at about 330 ℃ and the second stage being the degradation of the soft segment at about 400 ℃; and the carbon residue rate of the cured film at 700 ℃ is 10.85% -7.47%, and the cured film has good thermal stability.
Test example 4
1-3 Wt% of photoinitiator (2-hydroxy-2-methyl-1-phenyl acetone (PI-1173)) is added into the bio-based aqueous polyurethane emulsion prepared in the examples 2-5 respectively, the mixture is uniformly mixed, the mixture is coated on a glass plate by an applicator, the mixture is irradiated for 1min by an ultraviolet lamp, and after the solidification is successful, the photo-solidified film is cut into strips.
The dynamic thermo-mechanical properties of the cured films obtained by curing the WPUs 1 to 4 of examples 2 to 5 were analyzed, and the results are shown in fig. 9. It can be seen from fig. 9 that the cured film has a higher storage modulus in the low temperature region, and only one peak appears on the Tan delta curve, which indicates that the cured film is homogeneous, the temperature corresponding to the peak is the glass transition temperature of the cured film, and the glass transition temperature of the cured film is 71.1-85.2 ℃.
What has been described above is merely some embodiments of the present invention. It will be apparent to those skilled in the art that various modifications and improvements can be made without departing from the spirit of the invention.
Claims (10)
1. The preparation method of the bio-based hydrophilic chain extender is characterized by comprising the following steps:
Mixing gallic acid, maleic anhydride, a catalyst and a first organic solvent, reacting for 5-7 hours at the temperature of 70-90 ℃, and removing the first organic solvent to obtain the catalyst;
the molar ratio of the gallic acid to the maleic anhydride is (2.8-3.2): 1.
2. The preparation method according to claim 1, wherein the catalyst is at least one selected from the group consisting of p-toluenesulfonic acid and tetrabutylammonium bromide, and the amount thereof is 1% -3% of the total mass of gallic acid and maleic anhydride.
3. The preparation method according to claim 1 or 2, wherein the first organic solvent is at least one selected from acetone and butanone.
4. A bio-based hydrophilic chain extender prepared according to any one of claims 1 to 3.
5. The preparation method of the self-catalytic bio-based aqueous polyurethane emulsion is characterized by comprising the following steps:
mixing diisocyanate, the bio-based hydrophilic chain extender of claim 4 and a second organic solvent, and reacting for 2-3 hours at the temperature of 60-80 ℃ to obtain a first reaction mixed solution;
Adding starch-based polyol into the first reaction mixed solution, and reacting for 2-3 hours at the temperature of 60-80 ℃ to obtain a second reaction mixed solution;
adding a small molecular chain extender into the second reaction mixed solution, and reacting for 1-2 hours at the temperature of 60-80 ℃ to obtain a third reaction mixed solution;
adding a hydroxyl acrylate monomer into the third reaction mixed solution, reacting for 1-2 hours at the temperature of 60-80 ℃, cooling to room temperature after the reaction is finished, and adding a neutralizing agent for neutralization to obtain a prepolymer;
adding water into the prepolymer, and removing a second organic solvent in the emulsion after emulsification treatment to obtain the polyurethane emulsion;
Wherein the mass ratio of diisocyanate, bio-based hydrophilic chain extender, starch-based polyol, small molecule chain extender and hydroxyl acrylate monomer is (4.1-4.6): (0.5 to 0.8): (2.2 to 2.6): (1.0 to 1.2): (1.0 to 1.2).
6. The process according to claim 5, wherein the diisocyanate is at least one selected from isophorone diisocyanate, toluene diisocyanate, 4-methylenedicyclohexyl diisocyanate, and hexamethylene diisocyanate; the small molecule chain extender is selected from at least one of polyethylene glycol and 1, 4-butanediol; the hydroxyl acrylate monomer is at least one selected from hydroxyethyl acrylate and 2-hydroxyethyl methacrylate.
7. The preparation method according to claim 5 or 6, wherein the neutralizing agent is triethylamine, and the molar ratio of the neutralizing agent to the bio-based hydrophilic chain extender is (1.8-2.2): 1.
8. The method according to claim 7, wherein the second organic solvent is at least one selected from the group consisting of acetone and methyl ethyl ketone.
9. The self-catalyzed biobased aqueous polyurethane emulsion prepared by the preparation method according to any one of claims 5 to 8.
10. Use of the self-catalyzed biobased aqueous polyurethane emulsion according to claim 9 in the field of paints, inks or adhesives.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311760597.5A CN117757032B (en) | 2023-12-19 | 2023-12-19 | Self-catalytic bio-based aqueous polyurethane emulsion and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311760597.5A CN117757032B (en) | 2023-12-19 | 2023-12-19 | Self-catalytic bio-based aqueous polyurethane emulsion and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN117757032A CN117757032A (en) | 2024-03-26 |
| CN117757032B true CN117757032B (en) | 2024-06-14 |
Family
ID=90321651
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311760597.5A Active CN117757032B (en) | 2023-12-19 | 2023-12-19 | Self-catalytic bio-based aqueous polyurethane emulsion and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117757032B (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113026366A (en) * | 2021-05-06 | 2021-06-25 | 长春工业大学 | Bio-based polyurethane sizing agent and preparation method thereof |
| CN116284682A (en) * | 2023-02-28 | 2023-06-23 | 华南农业大学 | Starch-based aqueous polyurethane emulsion and preparation method and application thereof |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5682407B2 (en) * | 2010-03-31 | 2015-03-11 | 三菱化学株式会社 | Biomass resource-derived polyurethane and method for producing the same |
| CN103073693B (en) * | 2013-02-22 | 2014-12-03 | 华南师范大学 | Waterborne polyurethane and preparation method thereof |
| CN116462804A (en) * | 2022-01-12 | 2023-07-21 | 万华化学集团股份有限公司 | Method for preparing interpenetrating network type polyurethane modified acrylic ester dispersoid |
| CN116515283A (en) * | 2023-05-24 | 2023-08-01 | 东南大学 | Flame-retardant self-repairing polyurethane composite material and preparation method thereof |
-
2023
- 2023-12-19 CN CN202311760597.5A patent/CN117757032B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113026366A (en) * | 2021-05-06 | 2021-06-25 | 长春工业大学 | Bio-based polyurethane sizing agent and preparation method thereof |
| CN116284682A (en) * | 2023-02-28 | 2023-06-23 | 华南农业大学 | Starch-based aqueous polyurethane emulsion and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN117757032A (en) | 2024-03-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Liang et al. | Bio-based cationic waterborne polyurethanes dispersions prepared from different vegetable oils | |
| Mishra et al. | (UV/Oxidative) dual curing polyurethane dispersion from cardanol based polyol: Synthesis and characterization | |
| Saalah et al. | Waterborne polyurethane dispersions synthesized from jatropha oil | |
| Aung et al. | Synthesis and characterization of Jatropha (Jatropha curcas L.) oil-based polyurethane wood adhesive | |
| Zhang et al. | Polyurethanes from solvent-free vegetable oil-based polyols | |
| Cakić et al. | Glycolyzed poly (ethylene terephthalate) waste and castor oil-based polyols for waterborne polyurethane adhesives containing hexamethoxymethyl melamine | |
| Cakić et al. | Waterborne polyurethane-silica nanocomposite adhesives based on castor oil-recycled polyols: Effects of (3-aminopropyl) triethoxysilane (APTES) content on properties | |
| CN106866929A (en) | A kind of polyfunctionality castor oil-base light-cured resin and its preparation method and application | |
| Aung et al. | A comparative study of acrylate oligomer on Jatropha and Palm oil-based UV-curable surface coating | |
| Saravari et al. | Preparation and properties of urethane alkyd based on a castor oil/jatropha oil mixture | |
| US5990192A (en) | Radiation-curable water-dilutable urethane resins, preparation process and use | |
| CN112250850B (en) | Environment-friendly alkyd resin and preparation method and application thereof | |
| CN104119543B (en) | A kind of preparation method of nonionic ultraviolet light solidfication water polyurethane acrylate | |
| Huang et al. | A novel polyfunctional polyurethane acrylate prepolymer derived from bio-based polyols for UV-curable coatings applications | |
| de Vasconcelos Vieira Lopes et al. | Synthesis of polyols and polyurethanes from vegetable oils–kinetic and characterization | |
| Wang et al. | Making alkyd greener: Modified cardanol as bio-based reactive diluents for alkyd coating | |
| Wang et al. | Corrosion-resistant polyurethane coatings from structure-homogenized biorefinery lignin through fractionation and oxypropylation | |
| CN110951041A (en) | Waterborne polyurethane-acrylate hybrid copolymer and preparation method thereof | |
| Baghban et al. | A facile method to synthesis of a highly acrylated epoxidized soybean oil with low viscosity: Combined experimental and computational approach | |
| Villada et al. | Alkyd-urethane resins based on castor oil: Synthesis, characterization and coating properties | |
| CN112028801A (en) | Chain extender and preparation method and application thereof | |
| Etxaniz et al. | Dispersion characteristics and curing behaviour of waterborne UV crosslinkable polyurethanes based on renewable dimer fatty acid polyesters | |
| CN117757032B (en) | Self-catalytic bio-based aqueous polyurethane emulsion and preparation method and application thereof | |
| Su et al. | Synthesis and membrane performance characterization of self-emulsified waterborne nitrocellulose dispersion modified with castor oil | |
| Bakare et al. | Synthesis and characterization of rubber‐seed‐oil‐based polyurethanes |
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 |