CN108148171B - Hydrolysis-resistant aqueous polyurethane dispersion and preparation method thereof - Google Patents
Hydrolysis-resistant aqueous polyurethane dispersion and preparation method thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title abstract description 6
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- 239000000243 solution Substances 0.000 claims abstract description 35
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- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims abstract description 24
- GGJRAQULURVTAJ-PDBXOOCHSA-N rac-1-alpha-linolenoylglycerol Chemical compound CC\C=C/C\C=C/C\C=C/CCCCCCCC(=O)OCC(O)CO GGJRAQULURVTAJ-PDBXOOCHSA-N 0.000 claims abstract description 21
- 229920002635 polyurethane Polymers 0.000 claims abstract description 20
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 18
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229920000909 polytetrahydrofuran Polymers 0.000 claims abstract description 16
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000010438 heat treatment Methods 0.000 claims abstract description 12
- 239000011259 mixed solution Substances 0.000 claims abstract description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 9
- 239000003054 catalyst Substances 0.000 claims abstract description 8
- 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 abstract description 8
- 238000003756 stirring Methods 0.000 claims abstract description 8
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 6
- 238000001816 cooling Methods 0.000 claims abstract description 6
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 6
- 238000002390 rotary evaporation Methods 0.000 claims abstract description 6
- 239000005058 Isophorone diisocyanate Substances 0.000 claims abstract description 5
- 150000001875 compounds Chemical class 0.000 claims abstract description 5
- 238000004945 emulsification Methods 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 3
- GGJRAQULURVTAJ-UHFFFAOYSA-N glyceryl monolinolenate Natural products CCC=CCC=CCC=CCCCCCCCC(=O)OCC(O)CO GGJRAQULURVTAJ-UHFFFAOYSA-N 0.000 claims abstract 5
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 16
- 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 8
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 238000009833 condensation Methods 0.000 claims description 5
- 230000005494 condensation Effects 0.000 claims description 5
- -1 ethyl orthosilicate compound Chemical class 0.000 claims description 5
- 238000010992 reflux Methods 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 239000012456 homogeneous solution Substances 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000002086 nanomaterial Substances 0.000 abstract description 5
- RZRNAYUHWVFMIP-KTKRTIGZSA-N 1-oleoylglycerol Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCC(O)CO RZRNAYUHWVFMIP-KTKRTIGZSA-N 0.000 abstract description 2
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 239000002131 composite material Substances 0.000 abstract description 2
- RZRNAYUHWVFMIP-HXUWFJFHSA-N glycerol monolinoleate Natural products CCCCCCCCC=CCCCCCCCC(=O)OC[C@H](O)CO RZRNAYUHWVFMIP-HXUWFJFHSA-N 0.000 abstract description 2
- 239000002904 solvent Substances 0.000 description 8
- 229920006264 polyurethane film Polymers 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229910002808 Si–O–Si Inorganic materials 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000002329 infrared spectrum Methods 0.000 description 3
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- 239000002243 precursor Substances 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229940085633 glyceryl linolenate Drugs 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000003780 insertion Methods 0.000 description 2
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- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
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- 238000006297 dehydration reaction Methods 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
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- 125000003010 ionic group Chemical group 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000000825 pharmaceutical preparation Substances 0.000 description 1
- 229940127557 pharmaceutical product Drugs 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/6692—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/34
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- 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
- C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
- C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
- C08G18/0823—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing carboxylate salt groups or groups forming them
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
- C08G18/348—Hydroxycarboxylic acids
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/101—Esters; Ether-esters of monocarboxylic acids
- C08K5/103—Esters; Ether-esters of monocarboxylic acids with polyalcohols
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- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
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Abstract
The invention relates to a preparation method of a hydrolysis-resistant aqueous polyurethane dispersion, which comprises the following steps: s1, adjusting a methyl ethyl ketone solution of glyceryl monolinolenate to be alkalescent by using ammonia water, then dripping the methyl ethyl ketone solution of ethyl orthosilicate, and stirring to react for 3-4h to obtain a mixed solution containing a compound of the glyceryl monolinolenate and the ethyl orthosilicate; s2, under the protection of nitrogen, mixing dry polytetrahydrofuran, a catalyst and acetone, heating to obtain a uniform solution, adding isophorone diisocyanate, reacting for 1-2h, adding an N-methylpyrrolidone solution of 2, 2-dimethylolpropionic acid, reacting for 3-4h, cooling to room temperature, adding the mixed solution in S1, heating to react for 2-4h, adding triethylamine for neutralization, adding water for emulsification, and removing acetone and methyl ethyl ketone by rotary evaporation to obtain the catalyst. The water-based polyurethane has the beneficial effects that the water-based polyurethane is modified by the composite nano material of the glycerol monooleate and the tetraethoxysilane, so that the hydrolysis resistance of the water-based polyurethane is obviously improved.
Description
Technical Field
The invention belongs to the field of waterborne polyurethane, and particularly relates to a hydrolysis-resistant waterborne polyurethane dispersion and a preparation method thereof.
Background
Aqueous polyurethane dispersions (PUDs) have attracted much attention because of their zero or very low Volatile Organic Compound (VOC) content. Waterborne Polyurethanes (WPUs) have many excellent properties such as adhesion, flexibility, gloss, weatherability, etc.; therefore, WPU is one of the most rapidly developing fields in the field of polyurethane chemistry, and is widely used as an adhesive, a coating material, and a printing ink. However, WPUs have an inherent disadvantage of poor water resistance, limiting their applications, which may be attributed to insertion of hydrophilic ionic groups in the structure, thus exhibiting high hydrophilicity as compared to solvent-borne polyurethanes. Meanwhile, due to the insertion of a hydrophilic ion substrate, ester bonds in a molecular chain can be hydrolyzed more quickly in an aqueous environment, so that the molecular weight is reduced and the physical and mechanical properties are reduced. Furthermore, WPU films generally have a low average molecular weight and poor resistance to organic solvents.
The nano particles have surface and small size effects and good interaction with a matrix interface, so that the WPU is modified by the nano material, and the heat resistance, the mechanical property, the water resistance and the like of the WPU material can be improved. The hydrolysis resistance of the polyurethane dispersion can be improved by the nano materials such as silicon dioxide, montmorillonite and graphene, but the nano materials cannot be uniformly dispersed into the matrix of the waterborne polyurethane, so that the improvement of the WPU hydrolysis resistance is limited. In addition, the organic fluorine can also be used for modifying waterborne polyurethane, so that the hydrolysis resistance of the WPU can be improved, but the WPU modified by the organic fluorine polymer has the defect of poor exposed flexibility and high modification cost, so that the application of the WPU is limited.
Disclosure of Invention
The invention aims to solve the technical problem of providing a hydrolysis-resistant aqueous polyurethane dispersion and a preparation method thereof, aiming at overcoming the defect of poor water resistance of the polyurethane dispersion in the prior art.
The technical scheme for solving the technical problems is as follows: a method for preparing hydrolysis-resistant aqueous polyurethane dispersion comprises the following steps:
s1, adjusting the pH of a methyl ethyl ketone solution of glycerol monolinolenate to 7-9 by using ammonia water
Fully stirring at 40-60 ℃ to obtain a reaction solution, then dropwise adding a methyl ethyl ketone solution of ethyl orthosilicate into the reaction solution, wherein the mass of the ethyl orthosilicate dropwise added into the reaction solution is 0.8-1.2% of the mass of the mono-glyceryl linolenate in the reaction solution, and after the dropwise adding is finished, stirring and reacting at 40-60 ℃ for 3-4h to obtain a mixed solution containing the mono-glyceryl linolenate and the ethyl orthosilicate compound;
s2, mixing dry polytetrahydrofuran, a catalyst and acetone in a reaction container provided with a condensation reflux device under the protection of nitrogen, heating to 75-85 ℃ to obtain a uniform solution, adding isophorone diisocyanate, reacting for 1-2h, then adding an N-methyl pyrrolidone solution of 2, 2-dimethylolpropionic acid, and reacting for 3-4h, wherein the molar ratio of the polytetrahydrofuran to the isophorone diisocyanate to the catalyst to the 2, 2-dimethylolpropionic acid is 1: 5.5-6.5: 0.1-0.2: 1.2-1.5, cooling to room temperature, adding the mixed solution in S1, heating to 65-75 ℃, reacting for 2-4h, wherein the mass ratio of the compound of the glycerol mono-linolenate and the tetraethoxysilane in the added mixed solution to the polytetrahydrofuran in the uniform solution is 0.5-0.7: and 3, adding triethylamine for neutralization, adding water for emulsification, and finally performing rotary evaporation to remove acetone and methyl ethyl ketone to obtain the hydrolysis-resistant aqueous polyurethane dispersion.
On the basis of the technical scheme, the invention can also make the following further specific selection.
Specifically, the dosage ratio of the glycerol monolinolenate to the methyl ethyl ketone in the methyl ethyl ketone solution of the glycerol monolinolenate in S1 is 0.5-0.6g to 15 mL.
Specifically, the dosage ratio of the ethyl orthosilicate to the methyl ethyl ketone in the ethyl orthosilicate methyl ketone solution in S1 is 0.05-0.06g:5 mL. Specifically, the dosage ratio of the polytetrahydrofuran to the acetone in the S2 is 3g to 25-30 mL.
Specifically, the dosage ratio of the 2, 2-dimethylolpropionic acid to the N-methylpyrrolidone in the N-methylpyrrolidone solution of the 2, 2-dimethylolpropionic acid in S2 is 0.2-0.3g:5 mL.
Specifically, the catalyst in S2 is dibutyltin dilaurate.
Specifically, the step of adding triethylamine to S2 for neutralization is to add triethylamine dropwise to the reaction product to adjust the pH value to 7-8.
Specifically, the step of adding water for emulsification in the step S2 is to add deionized water, wherein the mass ratio of the added deionized water to the polytetrahydrofuran in the uniform solution is 8-15: 3, the solid content of the obtained hydrolysis-resistant aqueous polyurethane dispersoid is 25-35 wt%.
In addition, the invention also provides a hydrolysis-resistant aqueous polyurethane dispersion which is prepared by the method.
Compared with the prior art, the invention has the following beneficial effects:
(1) according to the invention, the aqueous polyurethane is modified by the composite nano material of the glycerol monooleate and the tetraethoxysilane, organic-inorganic components are combined together through a silicon-oxygen bond, a long fat side chain is introduced into a molecular chain of the aqueous polyurethane, the lipophilicity of the aqueous polyurethane is improved, meanwhile, an oxygen atom in an introduced Si-O-Si group can form a hydrogen bond with water, and the aqueous polyurethane dispersion with good hydrolysis resistance can be obtained under the combined action of the long fat side chain and the oxygen atom;
(2) the method has the advantages that the glycerol mono-linolenate is used as an organic precursor, the ethyl orthosilicate is used as an inorganic precursor, both the glycerol mono-linolenate and the ethyl orthosilicate are relatively environment-friendly and safe, no harmful substances are introduced into a waterborne polyurethane dispersion system, the inherent advantages of the waterborne polyurethane are kept, and the waterborne polyurethane has potential application in the aspects of being used as a regeneration material and preparing an environment-friendly film; the two precursors are compounded into a nano particle, and the modification of the nano particle on the waterborne polyurethane can improve the hydrolysis resistance and the mechanical property and the heat resistance;
(3) the preparation method is simple, the reaction condition is mild, the requirement on reaction equipment is not high, and the large-scale production is easy.
Drawings
FIG. 1 is a reaction scheme of S1 for preparing a complex containing glycerol monolinolenate and ethyl orthosilicate in example 1 of the present invention;
FIG. 2 is a reaction scheme of S2 in example 1 of the present invention for preparing a hydrolysis-resistant aqueous polyurethane dispersion;
FIG. 3 is an infrared spectrum of the hydrolysis-resistant aqueous polyurethane dispersion prepared in example 1 of the present invention.
Detailed Description
The principles and features of this invention are described in connection with the drawings and the detailed description of the invention, which are set forth below as examples to illustrate the invention and not to limit the scope of the invention.
The pharmaceutical products used in the following examples are commercially available products unless otherwise specified, and the methods used are conventional methods used by those skilled in the art without further specification. For the sake of avoiding redundancy, the polytetrahydrofuran used in the following examples is commercially available PTMG2000, and is dried before use, and the specific method of drying is: adding commercial polytetrahydrofuran (PTMG2000) into a four-mouth bottle, and placing the bottle into a drying tower for storage after vacuum dehydration for 2h under the conditions that the vacuum degree is-0.095 MPa and the temperature is 130 ℃ for later use.
Example 1
A hydrolysis-resistant aqueous polyurethane dispersion, which is prepared by the following method:
s1, introducing nitrogen into a 100mL three-neck flask, dissolving 0.5227g of glycerol mono-Linolenate (LMG) in 15mL of methyl ethyl ketone solvent, adjusting the solution to be alkalescent (pH 8) by using ammonia water, stirring for one hour at 60 ℃, dissolving 0.0528g of Tetraethoxysilane (TEOS) in 5mL of methyl ethyl ketone solvent, dropwise adding the mixture into the three-neck flask, and reacting for 3 hours to obtain a compound containing the glycerol mono-linolenate and the tetraethoxysilane
The specific reaction equation of the mixed solution of (LMG-TEOS nanocomposite), S1, is shown in FIG. 1;
s2, adding 3g of dried polytetrahydrofuran (PTMG2000), 25mL of acetone and 0.3g of dibutyltin dilaurate (DBTDL) into a 250mL four-mouth bottle which is provided with a condensation reflux device and a mechanical stirrer and is protected by nitrogen, heating to 80 ℃, adding 0.0089mol (2g) of isophorone diisocyanate (IPDI) after the system becomes a uniform stable solution, reacting at 80 ℃ for 1h, adding 0.0021mol (0.275g) of 2, 2-dimethylolpropionic acid (DMPA) and 5mL of 1-methyl-2 pyrrolidone (NMP), reacting at 80 ℃ for 3h, cooling to room temperature, adding all mixed liquid obtained in S1, heating to 72 ℃ for reacting for 2h, adding 0.0025mol (0.2550g) of triethylamine for neutralizing reaction for 10min, adding 10mL of deionized water, and performing rotary evaporation to remove acetone and methyl ethyl ketone solvents to obtain the hydrolysis-resistant aqueous polyurethane dispersion, the solids content was about 30% by weight, and the specific reaction scheme for S2 is shown in FIG. 2.
Example 2
A hydrolysis-resistant aqueous polyurethane dispersion, which is prepared by the following method:
s1, introducing nitrogen into a 100mL three-neck flask, dissolving 0.60g of glycerol mono-Linolenate (LMG) in 15mL of methyl ethyl ketone solvent, adjusting the solution to be alkalescent (pH is 9) by using ammonia water, stirring for one hour at 40 ℃, dissolving 0.06g of Tetraethoxysilane (TEOS) in 5mL of methyl ethyl ketone solvent, dropwise adding the mixture into the three-neck flask, and reacting for 4 hours to obtain a compound containing glycerol mono-linolenate and tetraethoxysilane
(LMG-TEOS nanocomposite);
s2, adding 3g (0.0015mol) of dried polytetrahydrofuran (PTMG2000), 30mL of acetone and 0.4g of dibutyltin dilaurate (DBTDL) into a 250mL four-mouth bottle provided with a condensation reflux device and a mechanical stirrer and protected by nitrogen, heating to 75 ℃, adding 0.0082mol of isophorone diisocyanate (IPDI) after the system becomes a uniform stable solution, reacting for 1h at 75 ℃, adding 0.0018mol of 2, 2-dimethylolpropionic acid (DMPA) and 5mL of 1-methyl-2 pyrrolidone (NMP), reacting for 3h at 75 ℃, cooling to room temperature, adding all mixed liquid obtained in S1, heating to 65 ℃ for reacting for 4h, adding 0.0030mol of triethylamine for neutralization for 15min, adding 15mL of deionized water, removing acetone and methyl ethyl ketone by rotary evaporation, and finally obtaining hydrolysis-resistant aqueous polyurethane, the solids content was about 25% by weight.
Example 3
A hydrolysis-resistant aqueous polyurethane dispersion, which is prepared by the following method:
s1, introducing nitrogen into a 100mL three-neck flask, dissolving 0.50g of glycerol mono-Linolenate (LMG) in 15mL of methyl ethyl ketone solvent, adjusting the solution to be alkalescent (pH is 7) by using ammonia water, stirring for one hour at 40 ℃, dissolving 0.05g of Tetraethoxysilane (TEOS) in 5mL of methyl ethyl ketone solvent, dropwise adding the mixture into the three-neck flask, and reacting for 3 hours to obtain a mixed solution containing glycerol mono-linolenate and tetraethoxysilane compound (LMG-TEOS nano composite material);
s2, adding 3g (0.0015mol) of dried polytetrahydrofuran (PTMG2000), 28mL of acetone and 0.6g of dibutyltin dilaurate (DBTDL) into a 250mL four-neck bottle provided with a condensation reflux device and a mechanical stirrer and protected by nitrogen, heating to 85 ℃, adding 0.0098mol of isophorone diisocyanate (IPDI) after the system becomes a uniform stable solution, reacting at 85 ℃ for 1h, adding 0.0023mol of 2, 2-dimethylolpropionic acid (DMPA) and 5mL of 1-methyl-2 pyrrolidone (NMP), reacting at 85 ℃ for 3h, cooling to room temperature, adding all mixed liquid obtained in S1, heating to 75 ℃ for 3h, adding 0.0025mol (0.2550g) of triethylamine, neutralizing for 12min, adding 8mL of deionized water, removing acetone and a solvent by rotary evaporation, and finally obtaining the hydrolysis-resistant aqueous polyurethane dispersion, the solids content was about 34% by weight.
Hydrolysis-resistant aqueous polyurethane dispersions prepared in example 1 were testedThe infrared spectrum of the sample obtained by infrared spectrum test is shown in FIG. 3, in FIG. 3 3320cm-1is-N-H stretching vibration peak, 2940cm-1And 2875cm-1Near by the stretching vibration peak of methyl methylene, 1720cm-1Is the stretching vibration peak of C ═ O, 1550 is-NH, -CN stretching vibration peak, 779cm-1Is a Si-O-Si symmetric stretching vibration peak, 1050cm-1The water-based polyurethane dispersion with a target structure is successfully synthesized for an asymmetric stretching vibration peak of Si-O-Si through infrared indication.
Respectively taking the aqueous polyurethane dispersions obtained in the embodiments 1 to 3 as samples, casting and naturally drying the samples on the surface of smooth glass to obtain polyurethane films, then respectively putting the obtained polyurethane films into water, taking out the samples every 24 hours, and sucking surface moisture by using filter paper, observing that the polyurethane films soaked for 96 hours are almost not different from the polyurethane films not put into the water by naked eyes, and basically maintaining the mechanical properties of the polyurethane films unchanged through a mechanical test, which shows that the aqueous polyurethane obtained by the invention has better hydrolysis resistance, and the water absorption of the polyurethane films soaked is also tested, and the specific results are shown in the following table:
from the table, the water absorption rate of the hydrolysis-resistant aqueous polyurethane dispersion prepared by the invention is low, the maximum water absorption rate is only 3% after the aqueous polyurethane dispersion is soaked for 96 hours, and the water absorption data also shows that the aqueous polyurethane dispersion has better hydrolysis resistance.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (9)
1. A method for preparing hydrolysis-resistant aqueous polyurethane dispersoid is characterized by comprising the following steps:
s1, adjusting the pH value of a methyl ethyl ketone solution of glyceryl monolinolenate to 7-9 by using ammonia water, fully stirring at 40-60 ℃ to obtain a reaction solution, then dropwise adding the methyl ethyl ketone solution of ethyl orthosilicate into the reaction solution, wherein the mass of the ethyl orthosilicate dropwise added into the reaction solution is 0.8-1.2% of the mass of the glyceryl monolinolenate in the reaction solution, and after dropwise adding, stirring and reacting at 40-60 ℃ for 3-4h to obtain a mixed solution containing the glyceryl monolinolenate and an ethyl orthosilicate compound;
s2, mixing dry polytetrahydrofuran, a catalyst and acetone in a reaction container provided with a condensation reflux device under the protection of nitrogen, heating to 75-85 ℃ to obtain a uniform solution, adding isophorone diisocyanate, reacting for 1-2h, then adding an N-methyl pyrrolidone solution of 2, 2-dimethylolpropionic acid, and reacting for 3-4h, wherein the molar ratio of the polytetrahydrofuran to the isophorone diisocyanate to the catalyst to the 2, 2-dimethylolpropionic acid is 1: 5.5-6.5: 0.1-0.2: 1.2-1.5, cooling to room temperature, adding the mixed solution in S1, heating to 65-75 ℃, reacting for 2-4h, wherein the mass ratio of the compound of the glycerol mono-linolenate and the tetraethoxysilane in the added mixed solution to the polytetrahydrofuran in the uniform solution is 0.5-0.7: and 3, adding triethylamine for neutralization, adding water for emulsification, and finally performing rotary evaporation to remove acetone and methyl ethyl ketone to obtain the hydrolysis-resistant aqueous polyurethane dispersion.
2. The method for preparing the aqueous polyurethane dispersion against hydrolysis according to claim 1, wherein the ratio of the amount of the glycerol monolinolenate to the amount of the methyl ethyl ketone in the methyl ethyl ketone solution of the glycerol monolinolenate in S1 is 0.5-0.6g:15 mL.
3. The method of claim 1, wherein the amount of ethyl orthosilicate and methyl ethyl ketone in the ethyl orthosilicate solution in S1 is 0.05-0.06g:5 mL.
4. The method for preparing the hydrolysis-resistant aqueous polyurethane dispersion according to claim 1, wherein the amount ratio of polytetrahydrofuran to acetone in S2 is 3g:25-30 mL.
5. The method of claim 1, wherein the ratio of the amount of 2, 2-dimethylolpropionic acid to N-methylpyrrolidone in the solution of 2, 2-dimethylolpropionic acid in N-methylpyrrolidone in S2 is 0.2-0.3 g/5 mL.
6. The method of claim 1, wherein the catalyst in S2 is dibutyltin dilaurate.
7. The method for preparing the aqueous polyurethane dispersion against hydrolysis according to claim 1, wherein the step of adding triethylamine to the reaction product for neutralization in S2 is to add triethylamine dropwise to adjust the pH value to 7-8.
8. The method for preparing the hydrolysis-resistant aqueous polyurethane dispersion according to claim 1, wherein the step of adding water for emulsification in S2 is to add deionized water, and the mass ratio of the added deionized water to the polytetrahydrofuran in the homogeneous solution is 8-15: 3, the solid content of the obtained hydrolysis-resistant aqueous polyurethane dispersoid is 25-35 wt%.
9. A hydrolysis-resistant aqueous polyurethane dispersion, which is obtained by the production method according to any one of claims 1 to 8.
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