CN115873494B - Organosilicon modified waterborne polyurethane antifouling coating and preparation method thereof - Google Patents
Organosilicon modified waterborne polyurethane antifouling coating and preparation method thereof Download PDFInfo
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- CN115873494B CN115873494B CN202211576809.XA CN202211576809A CN115873494B CN 115873494 B CN115873494 B CN 115873494B CN 202211576809 A CN202211576809 A CN 202211576809A CN 115873494 B CN115873494 B CN 115873494B
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- 239000011248 coating agent Substances 0.000 title claims abstract description 30
- 238000000576 coating method Methods 0.000 title claims abstract description 30
- 230000003373 anti-fouling effect Effects 0.000 title claims abstract description 24
- 239000004814 polyurethane Substances 0.000 title claims abstract description 17
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims description 8
- 229920001610 polycaprolactone Polymers 0.000 claims abstract description 28
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000004632 polycaprolactone Substances 0.000 claims abstract description 26
- 239000000463 material Substances 0.000 claims abstract description 23
- 150000002009 diols Chemical class 0.000 claims abstract description 17
- 239000011527 polyurethane coating Substances 0.000 claims abstract description 17
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 125000005442 diisocyanate group Chemical group 0.000 claims abstract description 11
- 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 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000003054 catalyst Substances 0.000 claims abstract description 7
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims abstract description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 36
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 13
- 238000010790 dilution Methods 0.000 claims description 12
- 239000012895 dilution Substances 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 10
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 238000004945 emulsification Methods 0.000 claims description 8
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 6
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical group CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 6
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 238000010992 reflux Methods 0.000 claims description 6
- 238000002390 rotary evaporation Methods 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- -1 3- [ [ (tert-butyl) silyl ] oxy ] -5-hydroxy-benzyl Chemical group 0.000 claims description 5
- WVDDGKGOMKODPV-UHFFFAOYSA-N benzyl alcohol Substances OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 5
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 239000001384 succinic acid Substances 0.000 claims description 4
- UWJJYHHHVWZFEP-UHFFFAOYSA-N pentane-1,1-diol Chemical compound CCCCC(O)O UWJJYHHHVWZFEP-UHFFFAOYSA-N 0.000 claims description 2
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical group CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 2
- 239000000314 lubricant Substances 0.000 claims 7
- 238000006068 polycondensation reaction Methods 0.000 claims 1
- 239000002994 raw material Substances 0.000 claims 1
- 230000000655 anti-hydrolysis Effects 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 238000006116 polymerization reaction Methods 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 16
- 238000012360 testing method Methods 0.000 description 15
- 230000007062 hydrolysis Effects 0.000 description 10
- 238000006460 hydrolysis reaction Methods 0.000 description 10
- IZSHZLKNFQAAKX-UHFFFAOYSA-N 5-cyclopenta-2,4-dien-1-ylcyclopenta-1,3-diene Chemical group C1=CC=CC1C1C=CC=C1 IZSHZLKNFQAAKX-UHFFFAOYSA-N 0.000 description 6
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 6
- 230000006872 improvement Effects 0.000 description 6
- 239000010985 leather Substances 0.000 description 6
- 239000002649 leather substitute Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000010410 layer Substances 0.000 description 5
- YVXYOKIVVJYKGS-UHFFFAOYSA-N cyclopenta-2,4-diene-1,1-dicarboxylic acid Chemical compound OC(=O)C1(C(O)=O)C=CC=C1 YVXYOKIVVJYKGS-UHFFFAOYSA-N 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 4
- 238000007334 copolymerization reaction Methods 0.000 description 3
- OLLFKUHHDPMQFR-UHFFFAOYSA-N dihydroxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](O)(O)C1=CC=CC=C1 OLLFKUHHDPMQFR-UHFFFAOYSA-N 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 229920002545 silicone oil Polymers 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 235000011089 carbon dioxide Nutrition 0.000 description 2
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 2
- 150000004756 silanes Chemical class 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- HECLRDQVFMWTQS-UHFFFAOYSA-N Dicyclopentadiene Chemical group C1C2C3CC=CC3C1C=C2 HECLRDQVFMWTQS-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- FQINETJTVSEXPE-UHFFFAOYSA-N butanedioic acid;butane-1,4-diol Chemical compound OCCCCO.OC(=O)CCC(O)=O FQINETJTVSEXPE-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000006471 dimerization reaction Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses an organosilicon modified waterborne polyurethane antifouling coating, which comprises the following components in parts by weight: a diisocyanate: 70-100 parts; modified polycaprolactone diol: 200-400 parts; hydroxysilane: 20-50 parts; catalyst: 0.1 to 0.5 part; 2, 2-dimethylolpropionic acid: 10-15 parts; a dihydric alcohol: 10-20 parts; triethylamine: 10-15 parts; diethylamine: 4-8 parts. The invention has the beneficial effects that the modified polycaprolactone diol, the hydroxy silane and the diisocyanate are mainly adopted for polymerization to prepare the coating material, so that the anti-fouling capability of the polyurethane coating material is improved, the mechanical property of the polyurethane coating material is improved, and the anti-hydrolysis capability of the polyurethane coating material is enhanced.
Description
Technical Field
The invention relates to the field of polymers, in particular to an organosilicon modified waterborne polyurethane antifouling coating.
Background
Synthetic leather is a plastic product that mimics the composition and structure of natural leather and can be used as a substitute for natural leather. The porous polyurethane layer is usually produced by using an impregnated nonwoven fabric as a mesh layer and a microporous polyurethane layer as a grain layer. The front and back sides of the leather are very similar to leather, and the leather has certain air permeability and is more similar to natural leather than common artificial leather. Is widely used for manufacturing shoes, boots, bags, balls and the like.
Because synthetic leather is a polyester product, the surface of the synthetic leather is easy to adhere to granular stains, and an antifouling coating layer is needed to protect the synthetic leather.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention aims to provide an organosilicon modified waterborne polyurethane antifouling coating.
In order to achieve the above purpose, the present invention provides the following technical solutions:
an organosilicon modified waterborne polyurethane antifouling coating,
comprises the following components in parts by weight:
a diisocyanate: 70-100 parts;
modified polycaprolactone diol: 200-400 parts;
hydroxysilane: 20-50 parts;
catalyst: 0.1 to 0.5 part;
2, 2-dimethylolpropionic acid: 10-15 parts;
a dihydric alcohol: 10-20 parts;
triethylamine: 10-15 parts;
diethylamine: 4-8 parts.
The preparation method of the modified polycaprolactone diol comprises the steps of mixing epsilon-caprolactone, 1, 4-butanediol, 1, 4-succinic acid, dicyclopentadiene dicarboxylic acid and n-butyl titanate, heating to 160 ℃ under the protection of nitrogen in a flask with a condenser tube, stirring for 30min in an oil bath under the stirring state, keeping the heating rate at 15 ℃/h, heating to 210 ℃, reacting for 3h, rapidly heating to 230 ℃, polycondensing at 60Pa for 3h, and cooling to room temperature to obtain the modified polycaprolactone diol.
As a further improvement of the invention:
the catalyst is dibutyl tin dilaurate.
As a further improvement of the invention:
the diisocyanate is toluene diisocyanate.
As a further improvement of the invention:
the mole ratio of epsilon-caprolactone to 1, 4-butanediol to 1, 4-succinic acid to dicyclopentadiene dicarboxylic acid is 1:1-4:1-4:0.1-0.5.
As a further improvement of the invention:
the n-butyl titanate is used for 3-5% of the mass of epsilon-caprolactone.
As a further improvement of the invention:
the dihydric alcohol is propylene glycol, butanediol or pentanediol.
As a further improvement of the invention:
the hydroxy silane is as follows: diphenylsilanediol, 3- [ [ (tert-butyl) silyl ] oxy ] -5-hydroxy-benzyl alcohol. As another object of the invention, a method for preparing an organosilicon modified waterborne polyurethane antifouling coating is provided,
step one:
the diisocyanate, the modified polycaprolactone dihydric alcohol, the hydroxysilane and the catalyst are put into a flask with a reflux condenser, and are reacted for 2 hours at 75 ℃ under the stirring state;
step two:
adding 2, 2-dimethylolpropionic acid and dihydric alcohol, adding acetone for dilution, and reacting for 1h at 80-120 ℃;
step three:
cooling to 40 ℃, and continuously adding acetone for dilution;
step four:
adding triethylamine to neutralize and form salt for 10min;
step five:
adding water for emulsification for 5min, adding mixed solution of ethylenediamine and water, and continuing emulsification for 20min;
step six:
and removing acetone by rotary evaporation to obtain the aqueous polyurethane coating material.
The invention has the beneficial effects that the modified polycaprolactone diol, the hydroxy silane and the diisocyanate are mainly adopted for polymerization to prepare the coating material, so that the anti-fouling capability of the polyurethane coating material is improved, the mechanical property of the polyurethane coating material is improved, and the anti-hydrolysis capability of the polyurethane coating material is enhanced.
Among them, hydroxysilane is preferably diphenylsilanediol, 3- [ [ (tert-butyl) silyl ] oxy ] -5-hydroxy-benzyl alcohol, which is mainly because these two silanes carry rigid groups, thus further improving mechanical properties. In the modification process of polycaprolactone, epsilon-caprolactone, butanediol, succinic acid and cyclopentadiene dicarboxylic acid are mainly adopted for copolymerization, and the applicant has unexpectedly found that polycaprolactone diol after cyclopentadiene dicarboxylic acid is copolymerized has stronger hydrolysis resistance after being introduced into a coating material, so that the hydrolysis problem of the aqueous polyurethane coating is solved. Meanwhile, at low temperature, the cyclopentadienyl group also has stronger intermolecular acting force, so that the mechanical property is improved.
Drawings
FIG. 1 is a photograph of an anti-fouling test of test 1 of the second embodiment;
FIG. 2 is a photograph of a test 1 anti-fouling test of comparative example one;
FIG. 3 is a photograph of a test 1 anti-soil test of comparative example two;
FIG. 4 is a photograph of a test 1 anti-fouling test of comparative example three.
Detailed Description
The invention will be further described in detail with reference to examples of embodiments shown in the drawings.
Embodiment one:
preparation of modified polycaprolactone diol:
mixing epsilon-caprolactone, 1, 4-butanediol, 1, 4-succinic acid, dicyclopentadiene dicarboxylic acid and n-butyl titanate with the mass of epsilon-caprolactone being 3% in a molar ratio of 1:1.8:1.5:0.1, heating to 160 ℃ under the oil bath under the protection of nitrogen in a flask with a condenser tube, blending and stirring for 30min, keeping the heating rate at 15 ℃/h, heating to 210 ℃, reacting for 3h, rapidly heating to 230 ℃ and polycondensing for 3h under the pressure of 60Pa, and cooling to room temperature to obtain the modified polycaprolactone diol.
Wherein dicyclopentadiene dicarboxylic acid is a compound which can be easily synthesized in the prior art, the dicyclopentadiene dicarboxylic acid used in the examples is self-made, and the specific preparation process is as follows:
preparation of dicyclopentadiene dicarboxylic acid:
adding dicyclopentadiene (DCPD) into a flask with a fractionating column, charging nitrogen, removing air, heating to 170 ℃, collecting fractions with a boiling range of 41-42 ℃ to obtain Cyclopentadiene (CPD), adding anhydrous magnesium sulfate into a collecting bottle, and placing into an ice bath to prevent dimerization;
adding the obtained cyclopentadiene into tetrahydrofuran to react with sodium to obtain CPDNa, continuously injecting the CPDNa into excessive dry ice water under stirring, naturally recovering the dry ice, mixing for 20 hours, adding deionized water dissolved products, removing an oil layer to obtain pale yellow solution, neutralizing the pale yellow solution with dilute hydrochloric acid to a pH value of 3, carrying out suction filtration, washing with water to neutrality, and drying the filtrate to obtain dicyclopentadiene dicarboxylic acid. Wherein the mass ratio of sodium to dicyclopentadiene is 5:1.
Embodiment two:
preparation of an antifouling coating:
step one:
80g of TDI, 280g of the modified polycaprolactone diol prepared in example one, 30g of 3- [ [ (tert-butyl) silyl ] oxy ] -5-hydroxy-benzyl alcohol, 0.1g of dibutyltin dilaurate were placed in a flask with reflux condenser and reacted for 2h at 75℃with stirring;
step two:
12g of 2, 2-dimethylolpropionic acid and 13g of 1, 4-butanediol are added, 70g of acetone is added for dilution, and the mixture is reacted for 1h at 110 ℃;
step three:
cooling to 40 ℃, and continuously adding 120g of acetone for dilution;
step four:
adding 10.2g of triethylamine to neutralize and form salt for 10min;
step five:
adding 950g of water for emulsification for 5min, adding a mixed solution of 4.05g of ethylenediamine and 20g of water, and continuing to emulsify for 20min;
step six:
and removing acetone by rotary evaporation to obtain the aqueous polyurethane coating material.
Comparative example one:
step one:
80g of TDI, 280g of poly (1, 4-butanediol succinate) (PBS) and 0.1g of dibutyltin dilaurate are put into a flask with a reflux condenser and reacted for 2h at 75 ℃ under stirring;
step two:
12g of 2, 2-dimethylolpropionic acid and 13g of 1, 4-butanediol are added, 70g of acetone is added for dilution, and the mixture is reacted for 1h at 110 ℃;
step three:
cooling to 40 ℃, and continuously adding 120g of acetone for dilution;
step four:
adding 10.2g of triethylamine to neutralize and form salt for 10min;
step five:
adding 950g of water for emulsification for 5min, adding a mixed solution of 4.05g of ethylenediamine and 20g of water, and continuing to emulsify for 20min;
step six:
and removing acetone by rotary evaporation to obtain the aqueous polyurethane coating material.
Comparative example two:
step one:
80g of TDI, 280g of polycaprolactone diol (PCL 2000), 30g of hydroxy silicone oil and 0.1g of dibutyltin dilaurate are put into a flask with a reflux condenser and reacted for 2 hours at 75 ℃ under stirring;
step two:
12g of 2, 2-dimethylolpropionic acid and 13g of 1, 4-butanediol are added, 70g of acetone is added for dilution, and the mixture is reacted for 1h at 110 ℃;
step three:
cooling to 40 ℃, and continuously adding 120g of acetone for dilution;
step four:
adding 10.2g of triethylamine to neutralize and form salt for 10min;
step five:
adding 950g of water for emulsification for 5min, adding a mixed solution of 4.05g of ethylenediamine and 20g of water, and continuing to emulsify for 20min;
step six:
and removing acetone by rotary evaporation to obtain the aqueous polyurethane coating material.
Comparative example three:
step one:
80g of TDI, 260g of polycaprolactone diol (PCL 2000), 30g of hydroxy silicone oil and 0.1g of dibutyltin dilaurate are put into a flask with a reflux condenser and reacted for 2 hours at 75 ℃ under stirring;
step two:
12g of 2, 2-dimethylolpropionic acid, 13g of 1, 4-butanediol and 20g of dicyclopentadiene dicarboxylic acid are added, 70g of acetone is added for dilution, and the mixture is reacted for 1h at 110 ℃;
step three:
cooling to 40 ℃, and continuously adding 120g of acetone for dilution;
step four:
adding 10.2g of triethylamine to neutralize and form salt for 10min;
step five:
adding 950g of water for emulsification for 5min, adding a mixed solution of 4.05g of ethylenediamine and 20g of water, and continuing to emulsify for 20min;
step six:
and removing acetone by rotary evaporation to obtain the aqueous polyurethane coating material.
And (3) testing:
test 1: coating the coating materials of the second embodiment and the first to third embodiments on PU synthetic leather to form a coating; placing the mixture in river sewage for 7 days, and observing the adhesion condition of pollutants.
Test 2: the coating materials of the second embodiment and the first to third embodiments are smeared on release paper by a smearing rod, then placed in an oven at 135 ℃ for 1min, taken out, the coating is peeled off, and the tensile strength of the peeled coating is tested. (GB/T13022-1991)
Test 3: the coating materials of the second and the third examples are coated on release paper by a coating rod, then the release paper is placed in an oven at 135 ℃ for 1min, taken out, the coating is peeled off, and the sample is hung in a constant temperature and humidity device for hot and humid ageing, constant temperature and humidity, and the temperature is 70 ℃ and the relative humidity is 95%. After 7 days of hot-air treatment, the surface change was observed.
In test 1, it is evident that the surface of the example was less stained than that of the comparative example one, and that the comparative example two and the comparative example three also had better anti-fouling ability after the addition of the hydroxy silicone oil, but the example two had better anti-fouling effect than the example two.
In the tensile strength, the examples are greatly improved compared with the comparative examples one, two and three, mainly because of the addition of dicyclopentadienyl groups and rigid silane, and the mechanical strength is improved. Meanwhile, the dicyclopentadienyl group is also added in the third comparative example, but the dicyclopentadienyl group is added in the diisocyanate copolymerization step, and the polycaprolactone has larger molecular weight, wherein the dicyclopentadienyl group is not contained, and the dicyclopentadienyl group is broken in a chain segment of the polycaprolactone in the breaking process, so that the mechanical property of the third comparative example is improved to a small extent, but the mechanical property of the third comparative example is weaker than that of the third comparative example.
In the hydrolysis capability test of test 3, the hydrolysis capability of the embodiment is greatly improved compared with the first, second and third comparative examples, because the dicyclopentadienyl groups act on the polycaprolactone segments of the macromolecular segments, and hydrolysis mainly occurs on the polycaprolactone groups in the hydrolysis process of the coating, and the dicyclopentadiene in the second embodiment plays a good role in resisting hydrolysis at key positions. Thus, in comparison of the second example and the third comparative example, it was found that the biscyclopentadiene group was bonded to the polycaprolactone segment to have a better hydrolysis resistance.
The invention has the beneficial effects that the modified polycaprolactone diol, the hydroxy silane and the diisocyanate are mainly adopted for polymerization to prepare the coating material, so that the anti-fouling capability of the polyurethane coating material is improved, the mechanical property of the polyurethane coating material is improved, and the anti-hydrolysis capability of the polyurethane coating material is enhanced.
Among them, hydroxysilane is preferably diphenylsilanediol, 3- [ [ (tert-butyl) silyl ] oxy ] -5-hydroxy-benzyl alcohol, which is mainly because these two silanes carry rigid groups, thus further improving mechanical properties. In the modification process of polycaprolactone, epsilon-caprolactone, butanediol, succinic acid and cyclopentadiene dicarboxylic acid are mainly adopted for copolymerization, and the applicant has unexpectedly found that polycaprolactone diol after cyclopentadiene dicarboxylic acid is copolymerized has stronger hydrolysis resistance after being introduced into a coating material, so that the hydrolysis problem of the aqueous polyurethane coating is solved. Meanwhile, at low temperature, the cyclopentadienyl group also has stronger intermolecular acting force, so that the mechanical property is improved.
The above description is only a preferred embodiment of the present invention, and the protection scope of the present invention is not limited to the above examples, and all technical solutions belonging to the concept of the present invention belong to the protection scope of the present invention. It should be noted that modifications and adaptations to the present invention may occur to one skilled in the art without departing from the principles of the present invention and are intended to be within the scope of the present invention.
Claims (7)
1. An organosilicon modified waterborne polyurethane antifouling coating, which is characterized in that:
comprises the following raw materials in parts by weight:
a diisocyanate: 70-100 parts of a lubricant;
modified polycaprolactone diol: 200-400 parts of a lubricant;
hydroxysilane: 20-50 parts of a lubricant;
catalyst: 0.1-0.5 parts;
2, 2-dimethylolpropionic acid: 10-15 parts of a lubricant;
a dihydric alcohol: 10-20 parts of a lubricant;
triethylamine: 10-15 parts of a lubricant;
diethylamine: 4-8 parts of a lubricant;
the preparation method of the modified polycaprolactone diol comprises the steps of mixing epsilon-caprolactone, 1, 4-butanediol, 1, 4-succinic acid, dicyclopentadiene dicarboxylic acid and n-butyl titanate, heating to 160 ℃ under the protection of nitrogen in a flask with a condenser tube, stirring for 30min in an oil bath under the stirring state, keeping the heating rate at 15 ℃/h, heating to 210 ℃, reacting for 3h, heating to 230 ℃, performing polycondensation reaction for 3h under the pressure of 60Pa, and cooling to room temperature to obtain the modified polycaprolactone diol;
the hydroxysilane is 3- [ [ (tert-butyl) silyl ] oxy ] -5-hydroxy-benzyl alcohol.
2. The silicone-modified waterborne polyurethane antifouling coating according to claim 1, wherein:
the catalyst is dibutyl tin dilaurate.
3. The silicone-modified waterborne polyurethane antifouling coating according to claim 1, wherein:
the diisocyanate is toluene diisocyanate.
4. The silicone-modified waterborne polyurethane antifouling coating according to claim 1, wherein:
the mole ratio of epsilon-caprolactone to 1, 4-butanediol to 1, 4-succinic acid to dicyclopentadiene dicarboxylic acid is 1:1-4: 1-4:0.1-0.5.
5. The silicone-modified waterborne polyurethane antifouling coating according to claim 1, wherein:
the dosage of the n-butyl titanate is 3% -5% of the mass of epsilon-caprolactone.
6. The silicone-modified waterborne polyurethane antifouling coating according to claim 1, wherein:
the dihydric alcohol is propylene glycol, butanediol or pentanediol.
7. A method for preparing an organosilicon modified aqueous polyurethane antifouling coating as claimed in any one of claims 1 to 6, wherein:
step one:
the diisocyanate, the modified polycaprolactone dihydric alcohol, the hydroxysilane and the catalyst are put into a flask with a reflux condenser, and are reacted for 2 hours at 75 ℃ under the stirring state;
step two:
adding 2, 2-dimethylolpropionic acid and dihydric alcohol, adding acetone for dilution, and reacting for 1h at 80-120 ℃;
step three:
cooling to 40 ℃, and continuously adding acetone for dilution;
step four:
adding triethylamine to neutralize and form salt for 10min;
step five:
adding water for emulsification for 5min, adding mixed solution of ethylenediamine and water, and continuing emulsification for 20min;
step six:
and removing acetone by rotary evaporation to obtain the aqueous polyurethane coating material.
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