CN117701130A - Wear-resistant antiknock waterborne modified polyurethane matt oil and preparation method thereof - Google Patents
Wear-resistant antiknock waterborne modified polyurethane matt oil and preparation method thereof Download PDFInfo
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- CN117701130A CN117701130A CN202311751805.5A CN202311751805A CN117701130A CN 117701130 A CN117701130 A CN 117701130A CN 202311751805 A CN202311751805 A CN 202311751805A CN 117701130 A CN117701130 A CN 117701130A
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- 229920002635 polyurethane Polymers 0.000 title claims abstract description 92
- 239000004814 polyurethane Substances 0.000 title claims abstract description 92
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000003921 oil Substances 0.000 claims abstract description 48
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 40
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 40
- 239000010703 silicon Substances 0.000 claims abstract description 40
- 239000000839 emulsion Substances 0.000 claims abstract description 37
- 238000003756 stirring Methods 0.000 claims abstract description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229920002396 Polyurea Polymers 0.000 claims abstract description 27
- 239000012948 isocyanate Substances 0.000 claims abstract description 19
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 19
- 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
- 239000003085 diluting agent Substances 0.000 claims abstract description 12
- 108010064470 polyaspartate Proteins 0.000 claims abstract description 11
- 229920001610 polycaprolactone Polymers 0.000 claims abstract description 11
- 239000004632 polycaprolactone Substances 0.000 claims abstract description 11
- 229920000805 Polyaspartic acid Polymers 0.000 claims abstract description 10
- 150000002148 esters Chemical class 0.000 claims abstract description 10
- 239000002518 antifoaming agent Substances 0.000 claims abstract description 8
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 42
- 238000006243 chemical reaction Methods 0.000 claims description 42
- 239000000203 mixture Substances 0.000 claims description 42
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 30
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 30
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 28
- 229910052698 phosphorus Inorganic materials 0.000 claims description 22
- 239000011574 phosphorus Substances 0.000 claims description 22
- -1 phosphorus polyol Chemical class 0.000 claims description 21
- 239000002904 solvent Substances 0.000 claims description 21
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 20
- 229920005862 polyol Polymers 0.000 claims description 19
- 235000012239 silicon dioxide Nutrition 0.000 claims description 15
- 239000000377 silicon dioxide Substances 0.000 claims description 15
- 230000018044 dehydration Effects 0.000 claims description 13
- 238000006297 dehydration reaction Methods 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 12
- 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 11
- 239000003795 chemical substances by application Substances 0.000 claims description 11
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 11
- 239000002270 dispersing agent Substances 0.000 claims description 11
- 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 11
- 238000009736 wetting Methods 0.000 claims description 11
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- 239000004094 surface-active agent Substances 0.000 claims description 10
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 claims description 10
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 238000006386 neutralization reaction Methods 0.000 claims description 8
- 238000002390 rotary evaporation Methods 0.000 claims description 7
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 6
- 239000005977 Ethylene Substances 0.000 claims description 6
- 239000013530 defoamer Substances 0.000 claims description 5
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 238000000034 method Methods 0.000 claims 6
- 239000000463 material Substances 0.000 description 10
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 6
- 239000003063 flame retardant Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000002966 varnish Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- MTEZSDOQASFMDI-UHFFFAOYSA-N 1-trimethoxysilylpropan-1-ol Chemical compound CCC(O)[Si](OC)(OC)OC MTEZSDOQASFMDI-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-N Metaphosphoric acid Chemical compound OP(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- CLWRFNUKIFTVHQ-UHFFFAOYSA-N [N].C1=CC=NC=C1 Chemical compound [N].C1=CC=NC=C1 CLWRFNUKIFTVHQ-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 239000006224 matting agent Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
Landscapes
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention relates to the technical field of matt oil, and discloses wear-resistant antiknock waterborne modified polyurethane matt oil and a preparation method thereof. Firstly, reacting polycaprolactone, dimethylolpropionic acid and the like with a silicon-containing phosphorus-terminated isocyanate prepolymer to obtain a polyurethane oligomer, then reacting the polyurethane oligomer with polyaspartic acid ester to obtain a water-based polyurethane polyurea emulsion, and finally adding a linear water-based polyurethane emulsion, a water-based polyurethane polyurea emulsion and the like into a defoaming agent, a diluting agent and the like, stirring and dispersing to obtain polyurethane matt oil. The polyurethane matt oil prepared by the invention has excellent wear resistance, antiknock performance and flame retardance.
Description
Technical Field
The invention relates to the technical field of matt oil, in particular to wear-resistant antiknock waterborne modified polyurethane matt oil and a preparation method thereof.
Background
With the improvement of the living standard and aesthetic consciousness of people, the water-based matte paint is popular with people due to the characteristics of being simple, elegant and attractive. Therefore, the research on the water-based matte paint is one of hot spots of research by researchers. The polyurethane material has the characteristics of excellent mechanical property, wear resistance, chemical resistance and the like, and is widely applied to the fields of national defense, textile, medical treatment, traffic and the like.
For example, patent publication No. CN105176365B discloses a high-resistance water-based matt surface oil for plastic films and a preparation method thereof, and the high-resistance water-based matt surface oil is prepared from water-based matt resin, a defoaming agent, a leveling agent, a crosslinking agent and the like, has the advantages of environmental protection, friction resistance, high viscosity and the like, but does not improve the flame retardant property and the antiknock property of the water-based matt surface oil.
The invention discloses a weather-resistant water-based polyurethane matt varnish, which is prepared from PUA emulsion, a flame retardant, a wetting dispersant and the like, and the prepared polyurethane matt varnish has the characteristics of flame retardance, wear resistance, good flexibility and the like, but the antiknock performance of the polyurethane matt varnish is not improved.
Disclosure of Invention
(one) solving the technical problems
Aiming at the defects of the prior art, the invention provides the wear-resistant antiknock waterborne modified polyurethane matt oil and the preparation method thereof, and the prepared polyurethane matt oil has excellent wear-resistant, antiknock and flame-retardant effects.
(II) technical scheme
The wear-resistant antiknock waterborne modified polyurethane matt oil is prepared from the following raw materials in parts by weight: 3-6 parts of defoamer, 3-8 parts of wetting dispersant, 2-6 parts of surfactant, 1-2 parts of flatting agent, 8-15 parts of diluent, 100 parts of linear aqueous polyurethane emulsion and 60-100 parts of aqueous polyurethane polyurea emulsion.
Preferably, the preparation method comprises the following steps: adding a defoaming agent, a wetting dispersant, a surfactant, a leveling agent and a diluent into deionized water, stirring and dispersing, adding linear aqueous polyurethane emulsion and aqueous polyurethane polyurea emulsion into the mixture, and stirring and dispersing to obtain polyurethane matt oil.
Preferably, the preparation method of the aqueous polyurethane polyurea emulsion comprises the following steps:
(1) Adding silicon dioxide into a flask filled with an ethyl acetate solvent, stirring and dispersing, adding gamma-glycidoxypropyl trimethoxysilane into the flask, heating to 60-80 ℃, stirring and reacting for 8-15h, filtering, washing with ethyl acetate after the reaction is finished, and drying to obtain an intermediate 1.
(2) Adding tributyl phosphate and phosphoric acid into a flask, controlling the temperature to be 80-90 ℃, stirring uniformly, adding the intermediate 1 into the flask, heating to 95-120 ℃, stirring and reacting for 4-10h, cooling to room temperature after the reaction is finished, washing with acetone, and drying to obtain the silicon-containing phosphorus polyol.
(3) Toluene-2, 4-diisocyanate, silicon-containing phosphorus polyol and dibutyl tin dilaurate are added into a flask filled with an acetone solvent, the temperature is raised to 60-80 ℃, the mixture is stirred and reacted for 5-10 hours, the mixture is cooled to room temperature after the reaction is finished, and the solvent is removed by rotary evaporation, so that the silicon-containing phosphorus-terminated isocyanate prepolymer is obtained.
(4) Adding polycaprolactone, dimethylolpropionic acid and 1, 4-cyclohexanedimethanol into a flask, dehydrating in vacuum, adding silicon-containing phosphorus-terminated isocyanate prepolymer into the flask, stirring and reacting for 2-6 hours at 50-80 ℃, adding polyaspartic acid ester into the flask, continuing to react for 30-80 minutes, adding triethylamine into the flask for neutralization for 30-60 minutes, and expanding the chain of the polydiene triamine for 20-50 minutes, thus obtaining the aqueous polyurethane polyurea emulsion after the reaction is finished.
Preferably, in the step (1), the mass ratio of the silicon dioxide to the gamma-glycidoxypropyl trimethoxysilane is 1:8-10.
Preferably, in the step (2), the mass ratio of tributyl phosphate, phosphoric acid and the intermediate 1 is 1:0.2-0.25:0.3-0.42.
Preferably, in the step (3), the ratio of toluene-2, 4-diisocyanate, silicon-containing phosphorus polyol and dibutyltin dilaurate is 0.5-0.8:1:0.003-0.005.
Preferably, in the step (4), the mass ratio of polycaprolactone, dimethylolpropionic acid, 1, 4-cyclohexanedimethanol, silicon-containing phosphorus-terminated isocyanate prepolymer, polyaspartic acid ester, triethylamine and ethylene diamine is 1:0.1-0.18:0.08-0.14:1.2-3.4:0.8-1.6:0.1-0.15:0.02-0.1.
Preferably, in the step (4), the vacuum dehydration temperature is 100-110 ℃, the pressure is-0.08 to-0.05 MPa, and the time is 1-3h.
(III) beneficial technical effects
The invention uses gamma-glycidol ether oxypropyl trimethoxy silane to react with silicon dioxide and tributyl phosphate in sequence to obtain silicon-containing phosphorus polyol, and then the silicon-containing phosphorus polyol reacts with toluene-2, 4-diisocyanate under the catalysis of dibutyl tin dilaurate to obtain silicon-containing phosphorus terminal isocyanate prepolymer. Firstly, reacting polycaprolactone, dimethylolpropionic acid and the like with a silicon-containing phosphorus-terminated isocyanate prepolymer to obtain a polyurethane oligomer, then reacting the polyurethane oligomer with polyaspartic acid ester to obtain a water-based polyurethane polyurea emulsion, and finally adding a linear water-based polyurethane emulsion, a water-based polyurethane polyurea emulsion and the like into a defoaming agent, a diluting agent and the like, stirring and dispersing to obtain polyurethane matt oil.
The polyurethane matt oil prepared by the invention contains silicon dioxide, the silicon dioxide can be used as a matting agent to reduce the gloss of the polyurethane matt oil, but the silicon dioxide has larger surface energy and is extremely easy to agglomerate, and the polyurethane matt oil can react with organic matters, so that the purpose of dispersing the silicon dioxide can be achieved, and the matting and matt effects can be improved.
The polyurethane matt oil prepared by the invention contains a polyurethane polyurea structure, the polyurethane matt oil has better compatibility with linear polyurethane, urea bonds with stronger acting force exist among polyurea molecules contained in the polyurethane matt oil to form a hard segment chain, the urea bonds are formed by hydrogen bonds, the polyurea molecule chain segments move under the action of external high-frequency impact load, the hydrogen bonds are broken to absorb a large amount of energy, when the impact wave is counteracted, the action among the molecule chain segments stops, new groups of hydrogen bonds are reformed in the polyurethane matt oil, and the polyurea structure can continuously release and absorb energy through the continuous movement, breaking and recombination of the hydrogen bonds, so that the antiknock aim is achieved.
The polyurethane matt oil prepared by the invention contains a polyurethane polyurea structure, wherein the polyurethane structure is a wear-resistant structure, and the siloxane structure and silicon dioxide contained in the polyurethane matt oil have silicon-oxygen bonds with higher bond energy, so that more energy can be absorbed when the polyurethane matt oil is impacted by the outside, and the wear resistance of the polyurethane matt oil is further improved.
The polyurethane matt oil prepared by the invention contains phosphorus element and silicon element, when the material is heated, the phosphorus element contained in the polyurethane matt oil can generate acidic substances such as phosphoric acid, metaphosphoric acid and the like, and the substances have strong dehydration property, can promote the material to dehydrate into carbon, and form a compact carbon layer on the surface of the substrate. When the silicon element contained in the material is heated, a glassy substance can be formed on the surface of the material, and the material is isolated from external substance transmission and energy transmission, so that the flame retardant property of the material is further improved. The polyurethane matt oil prepared by the invention has excellent wear resistance, antiknock performance and flame retardance.
Drawings
FIG. 1 is a route to silicon-containing phosphorus polyol.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described in the following in conjunction with the embodiments of the present invention, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which are derived by a person skilled in the art based on the embodiments of the invention, fall within the scope of protection of the invention.
The preparation method of the linear aqueous polyurethane emulsion comprises the following steps: 5.9g of polycarbonate diol is taken in a flask, dehydrated in vacuum at 120 ℃, 1.7g of toluene-2, 4-diisocyanate and 0.007g of dibutyltin dilaurate are added into the flask, stirred and reacted for 30min at 80 ℃, then a mixed solution of dimethylolpropionic acid/N-methylpyrrolidone is added into the flask, the reaction is continued for 3h, the solution is cooled to room temperature, and 1g of triethylamine is added into the solution for neutralization for 30min, thus obtaining the linear aqueous polyurethane emulsion. The preparation route is referred to in fig. 1.
Example 1
(1) 3g of silicon dioxide is added into a flask filled with ethyl acetate solvent, stirred and dispersed, 30g of gamma-glycidoxypropyl trimethoxysilane is added into the flask, the temperature is raised to 70 ℃, the reaction is stirred for 12 hours, and after the reaction is finished, the mixture is filtered, washed with ethyl acetate and dried to obtain an intermediate 1.
(2) Adding 20g of tributyl phosphate and 4.2g of phosphoric acid into a flask, controlling the temperature to be 85 ℃, stirring uniformly, adding 8.4g of intermediate 1 into the flask, heating to 110 ℃, stirring for reaction for 8 hours, cooling to room temperature after the reaction is finished, washing with acetone, and drying to obtain the silicon-containing phosphorus polyol.
(3) 15g of toluene-2, 4-diisocyanate, 30g of silicon-containing phosphorus polyol and 0.25g of dibutyltin dilaurate are added into a flask filled with an acetone solvent, the temperature is raised to 70 ℃, the mixture is stirred and reacted for 8 hours, the mixture is cooled to room temperature after the reaction is finished, and the solvent is removed by rotary evaporation, so that the silicon-containing phosphorus-terminated isocyanate prepolymer is obtained.
(4) Adding 40g of polycaprolactone, 5g of dimethylolpropionic acid and 4g of 2-1, 4-cyclohexanedimethanol into a flask, carrying out vacuum dehydration, wherein the vacuum dehydration temperature is 110 ℃, the pressure is-0.05 MPa, the time is 2 hours, then adding 50g of silicon-containing phosphorus-terminated isocyanate prepolymer into the mixture, stirring the mixture at 70 ℃ for reaction for 6 hours, then adding 60g of polyaspartic acid ester into the mixture, continuing the reaction for 60 minutes, then adding 5g of triethylamine into the mixture for neutralization for 40 minutes, and carrying out chain extension for 30 minutes by 3.2g of ethylene triamine, thus obtaining the aqueous polyurethane polyurea emulsion after the reaction is finished.
(5) Adding 4g of defoamer W0506, 5g of wetting dispersant YF-98, 4g of surfactant F-105, 1.5g of flatting agent BYK358 and 12g of 692 active diluent into deionized water, stirring and dispersing, and then adding 100g of linear aqueous polyurethane emulsion and 60g of aqueous polyurethane polyurea emulsion into the mixture, stirring and dispersing to obtain polyurethane matt oil.
Example 2
(1) 3g of silicon dioxide is added into a flask filled with ethyl acetate solvent, stirred and dispersed, 25g of gamma-glycidoxypropyl trimethoxysilane is added into the flask, the temperature is raised to 70 ℃, the reaction is stirred for 10 hours, and after the reaction is finished, the mixture is filtered, washed by ethyl acetate and dried to obtain an intermediate 1.
(2) Adding 20g of tributyl phosphate and 4g of phosphoric acid into a flask, controlling the temperature to be 90 ℃, stirring uniformly, adding 8g of intermediate 1 into the flask, heating to 120 ℃, stirring and reacting for 8 hours, cooling to room temperature after the reaction is finished, washing with acetone, and drying to obtain the silicon-containing phosphorus polyol.
(3) 15g of toluene-2, 4-diisocyanate, 30g of silicon-containing phosphorus polyol and 0.15g of dibutyltin dilaurate are added into a flask filled with an acetone solvent, the temperature is raised to 70 ℃, the mixture is stirred and reacted for 5 hours, the mixture is cooled to room temperature after the reaction is finished, and the solvent is removed by rotary evaporation, so that the silicon-containing phosphorus-terminated isocyanate prepolymer is obtained.
(4) Adding 40g of polycaprolactone, 6g of dimethylolpropionic acid and 4g of 2-1, 4-cyclohexanedimethanol into a flask, carrying out vacuum dehydration, wherein the vacuum dehydration temperature is 110 ℃, the pressure is-0.06 MPa, the time is 3h, then adding 120g of silicon-containing phosphorus-terminated isocyanate prepolymer into the flask, stirring the mixture at 60 ℃ for reaction for 5h, then adding 60g of polyaspartic acid ester into the flask, continuing to react for 40min, then adding 5g of triethylamine into the flask for neutralization for 60min, and carrying out chain extension on 3g of ethylene triamine for 50min, thus obtaining the aqueous polyurethane polyurea emulsion after the reaction is finished.
(5) 6g of defoaming agent W0506, 7g of wetting dispersant YF-98, 4g of surfactant F-105, 1.4g of flatting agent BYK358 and 10g of 692 active diluent are added into deionized water, stirred and dispersed, and then 100g of linear aqueous polyurethane emulsion and 70g of aqueous polyurethane polyurea emulsion are added into the mixture, stirred and dispersed, and polyurethane matt oil is obtained.
Example 3
(1) 3g of silicon dioxide is added into a flask filled with ethyl acetate solvent, stirred and dispersed, 28g of gamma-glycidoxypropyl trimethoxysilane is added into the flask, the temperature is raised to 70 ℃, the reaction is stirred for 12 hours, and after the reaction is finished, the mixture is filtered, washed with ethyl acetate and dried to obtain an intermediate 1.
(2) Adding 20g of tributyl phosphate and 4.5g of phosphoric acid into a flask, controlling the temperature to be 80 ℃, stirring uniformly, adding 7g of intermediate 1 into the flask, heating to 100 ℃, stirring and reacting for 10 hours, cooling to room temperature after the reaction is finished, washing with acetone, and drying to obtain the silicon-containing phosphorus polyol.
(3) 15g of toluene-2, 4-diisocyanate, 30g of silicon-containing phosphorus polyol and 0.2g of dibutyltin dilaurate are added into a flask filled with an acetone solvent, the temperature is raised to 70 ℃, the mixture is stirred and reacted for 10 hours, the mixture is cooled to room temperature after the reaction is finished, and the solvent is removed by rotary evaporation, so that the silicon-containing phosphorus-terminated isocyanate prepolymer is obtained.
(4) Adding 40g of polycaprolactone, 6g of dimethylolpropionic acid and 4g of 2-1, 4-cyclohexanedimethanol into a flask, carrying out vacuum dehydration, wherein the vacuum dehydration temperature is 110 ℃, the pressure is-0.05 MPa, the time is 2 hours, then adding 100g of silicon-containing phosphorus-terminated isocyanate prepolymer into the mixture, stirring the mixture at 60 ℃ for reaction for 6 hours, then adding 50g of polyaspartic acid ester into the mixture, continuing the reaction for 80 minutes, then adding 4g of triethylamine into the mixture for neutralization for 60 minutes, and carrying out chain extension for 40 minutes by 0.8g of ethylene triamine, thus obtaining the aqueous polyurethane polyurea emulsion after the reaction is finished.
(5) 3g of defoamer W0506, 7g of wetting dispersant YF-98, 5g of surfactant F-105, 1.5g of flatting agent BYK358 and 12g of 692 active diluent are added into deionized water, stirred and dispersed, and then 100g of linear aqueous polyurethane emulsion and 80g of aqueous polyurethane polyurea emulsion are added into the mixture, stirred and dispersed, and polyurethane matt oil is obtained.
Example 4
(1) 3g of silicon dioxide is added into a flask filled with ethyl acetate solvent, stirred and dispersed, 30g of gamma-glycidoxypropyl trimethoxysilane is added into the flask, the temperature is raised to 70 ℃, the reaction is stirred for 12 hours, and after the reaction is finished, the mixture is filtered, washed with ethyl acetate and dried to obtain an intermediate 1.
(2) Adding 20g of tributyl phosphate and 4.5g of phosphoric acid into a flask, controlling the temperature to be 80 ℃, stirring uniformly, adding 8g of intermediate 1 into the flask, heating to 100 ℃, stirring and reacting for 10 hours, cooling to room temperature after the reaction is finished, washing with acetone, and drying to obtain the silicon-containing phosphorus polyol.
(3) 24g of toluene-2, 4-diisocyanate, 30g of silicon-containing phosphorus polyol and 0.13g of dibutyltin dilaurate are added into a flask filled with an acetone solvent, the temperature is raised to 80 ℃, the mixture is stirred and reacted for 7 hours, the mixture is cooled to room temperature after the reaction is finished, and the solvent is removed by rotary evaporation, so that the silicon-containing phosphorus-terminated isocyanate prepolymer is obtained.
(4) Adding 40g of polycaprolactone, 4g of dimethylolpropionic acid and 5g of 2-1, 4-cyclohexanedimethanol into a flask, carrying out vacuum dehydration, wherein the vacuum dehydration temperature is 100 ℃, the pressure is-0.07 MPa, the time is 2h, adding 120g of silicon-containing phosphorus-terminated isocyanate prepolymer into the mixture, stirring the mixture at 70 ℃ for reaction for 5h, adding 50g of polyaspartic acid ester into the mixture, continuing the reaction for 80min, adding 4g of triethylamine into the mixture for neutralization for 40min, and carrying out chain extension on 2g of ethylene triamine for 40min, thus obtaining the aqueous polyurethane polyurea emulsion after the reaction is finished.
(5) 5g of defoaming agent W0506, 7g of wetting dispersant YF-98, g of surfactant F-105, 2g of flatting agent BYK358 and 12g of 692 active diluent are added into deionized water, stirred and dispersed, and then 100g of linear aqueous polyurethane emulsion and 90g of aqueous polyurethane polyurea emulsion are added into the mixture, stirred and dispersed, thus obtaining polyurethane matt oil.
Example 5
(1) 3g of silicon dioxide is added into a flask filled with ethyl acetate solvent, stirred and dispersed, 25g of gamma-glycidoxypropyl trimethoxysilane is added into the flask, the temperature is raised to 70 ℃, the reaction is stirred for 14h, and after the reaction is finished, the mixture is filtered, washed with ethyl acetate and dried to obtain an intermediate 1.
(2) Adding 20g of tributyl phosphate and 4.2g of phosphoric acid into a flask, controlling the temperature to be 80 ℃, stirring uniformly, adding 7g of intermediate 1 into the flask, heating to 110 ℃, stirring and reacting for 8 hours, cooling to room temperature after the reaction is finished, washing with acetone, and drying to obtain the silicon-containing phosphorus polyol.
(3) 20g of toluene-2, 4-diisocyanate, 30g of silicon-containing phosphorus polyol and 0.15g of dibutyltin dilaurate are added into a flask filled with an acetone solvent, the temperature is raised to 70 ℃, the mixture is stirred and reacted for 8 hours, the mixture is cooled to room temperature after the reaction is finished, and the solvent is removed by rotary evaporation, so that the silicon-containing phosphorus-terminated isocyanate prepolymer is obtained.
(4) Adding 40g of polycaprolactone, 7g of dimethylolpropionic acid and 4g of 2-1, 4-cyclohexanedimethanol into a flask, carrying out vacuum dehydration, wherein the vacuum dehydration temperature is 110 ℃, the pressure is-0.08 MPa, the time is 2.4h, then adding 120g of silicon-containing phosphorus-terminated isocyanate prepolymer into the flask, stirring the mixture at 50 ℃ for 3h, then adding 60g of polyaspartic acid ester into the flask, continuing to react for 80min, then adding 4g of triethylamine into the flask for neutralization 40min, and carrying out chain extension on 3g of ethylene triamine for 20-50min, thus obtaining the aqueous polyurethane polyurea emulsion after the reaction is finished.
(5) 6g of defoaming agent W0506, 3g of wetting dispersant YF-98, 5g of surfactant F-105, 1.5g of flatting agent BYK358 and 10g of 692 active diluent are added into deionized water, stirred and dispersed, and then 100g of linear aqueous polyurethane emulsion and 100g of aqueous polyurethane polyurea emulsion are added into the mixture, stirred and dispersed, and polyurethane matt oil is obtained.
Comparative example 1
Adding 4g of defoamer W0506, 5g of wetting dispersant YF-98, 4g of surfactant F-105, 1.5g of flatting agent BYK358 and 12g of 692 active diluent into deionized water, stirring and dispersing, and then adding 100g of linear aqueous polyurethane emulsion into the mixture, stirring and dispersing to obtain polyurethane matt oil.
Adding a nitrogen-pyridine cross-linking agent into the polyurethane matt oil, uniformly mixing, coating the mixture on the surface of black paint leather, sequentially drying the mixture at room temperature for 24 hours, and drying the mixture in a drying oven at 100 ℃ for 10 hours, and testing.
Low temperature deflection test: the material was placed at-20℃and repeatedly flexed 30000 times to see if the coating cracked.
Scratch resistance test: the surface of the coating was rubbed with cotton cloth for 30 times, and the change of the coating was observed.
As can be seen from the table, the low temperature flexibility and scratch resistance of examples 1 to 5 are better than those of comparative example 1, and therefore, the polyurethane matt oil prepared by the invention has excellent wear resistance.
The limiting oxygen index of the material was tested using a limiting oxygen index tester.
The hardness of the material was tested using a shore durometer.
As shown in the table, the oxygen index of examples 1-5 is larger than that of comparative example 1, and the flame retardant effect is better than that of comparative example 1, so that the polyurethane matt oil prepared by the invention has better flame retardant property. The higher the hardness is, the stronger the deformation resistance caused by external pressure is, and the higher the antiknock capability is, so that the polyurethane matt oil prepared by the invention has better antiknock capability.
The foregoing description illustrates the major features, principles, and advantages of the invention. It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments or examples, and that the present invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. The foregoing implementations or examples should be regarded as illustrative rather than limiting. The scope of the invention is indicated by the appended claims rather than by the foregoing description, and all changes that come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any reference sign in a claim should not be construed as limiting the claim concerned.
Furthermore, it should be understood that although the present disclosure describes embodiments, not every embodiment is provided with a separate embodiment, and that this description is provided for clarity only, and that the disclosure is not limited to the embodiments described in detail below, and that the embodiments described in the examples may be combined as appropriate to form other embodiments that will be apparent to those skilled in the art.
Claims (8)
1. The wear-resistant antiknock waterborne modified polyurethane matt oil is characterized by being prepared from the following raw materials in parts by weight: 3-6 parts of defoamer, 3-8 parts of wetting dispersant, 2-6 parts of surfactant, 1-2 parts of flatting agent, 8-15 parts of diluent, 100 parts of linear aqueous polyurethane emulsion and 60-100 parts of aqueous polyurethane polyurea emulsion.
2. A method for preparing the wear-resistant antiknock line water-based modified polyurethane matt oil according to claim 1, which is characterized in that the preparation method comprises the following steps: adding a defoaming agent, a wetting dispersant, a surfactant, a leveling agent and a diluent into deionized water, stirring and dispersing, adding linear aqueous polyurethane emulsion and aqueous polyurethane polyurea emulsion into the mixture, and stirring and dispersing to obtain polyurethane matt oil.
3. The preparation method of the wear-resistant antiknock line water-based modified polyurethane matt oil according to claim 2, characterized in that the preparation method of the water-based polyurethane polyurea emulsion is as follows:
(1) Adding silicon dioxide into a flask filled with an ethyl acetate solvent, stirring and dispersing, adding gamma-glycidoxypropyl trimethoxysilane into the flask, heating to 60-80 ℃, stirring and reacting for 8-15h, after the reaction is finished, filtering, washing with ethyl acetate, and drying to obtain an intermediate 1;
(2) Adding tributyl phosphate and phosphoric acid into a flask, controlling the temperature to be 80-90 ℃, stirring uniformly, adding an intermediate 1 into the flask, heating to 95-120 ℃, stirring and reacting for 4-10 hours, cooling to room temperature after the reaction is finished, washing with acetone, and drying to obtain silicon-containing phosphorus polyol;
(3) Adding toluene-2, 4-diisocyanate, silicon-containing phosphorus polyol and dibutyltin dilaurate into a flask filled with an acetone solvent, heating to 60-80 ℃, stirring for reacting for 5-10h, cooling to room temperature after the reaction is finished, and removing the solvent by rotary evaporation to obtain a silicon-containing phosphorus-terminated isocyanate prepolymer;
(4) Adding polycaprolactone, dimethylolpropionic acid and 1, 4-cyclohexanedimethanol into a flask, dehydrating in vacuum, adding silicon-containing phosphorus-terminated isocyanate prepolymer into the flask, stirring and reacting for 2-6 hours at 50-80 ℃, adding polyaspartic acid ester into the flask, continuing to react for 30-80 minutes, adding triethylamine into the flask for neutralization for 30-60 minutes, and expanding the chain of the polydiene triamine for 20-50 minutes, thus obtaining the aqueous polyurethane polyurea emulsion after the reaction is finished.
4. The method for preparing the water-based modified polyurethane matt oil for the wear-resistant and antiknock wires, according to claim 3, wherein in the step (1), the mass ratio of silicon dioxide to gamma-glycidoxypropyl trimethoxysilane is 1:8-10.
5. The method for preparing the water-based modified polyurethane matt oil for the wear-resistant and antiknock line according to claim 3, wherein in the step (2), the mass ratio of tributyl phosphate to phosphoric acid to the intermediate 1 is 1:0.2-0.25:0.3-0.42.
6. The method for preparing the water-based modified polyurethane matt oil for the wear-resistant and antiknock line according to claim 3, wherein in the step (3), the ratio of toluene-2, 4-diisocyanate, silicon-containing phosphorus polyol and dibutyltin dilaurate is 0.5-0.8:1:0.003-0.005.
7. The method for preparing the water-based modified polyurethane matt oil for the wear-resistant and antiknock line according to claim 3, wherein in the step (4), the mass ratio of polycaprolactone, dimethylolpropionic acid, 1, 4-cyclohexanedimethanol, silicon-containing phosphorus-terminated isocyanate prepolymer, polyaspartate, triethylamine and ethylene triamine is 1:0.1-0.18:0.08-0.14:1.2-3.4:0.8-1.6:0.1-0.15:0.02-0.1.
8. The method for preparing the water-based modified polyurethane matt oil for the wear-resistant and antiknock line according to claim 3, wherein in the step (4), the vacuum dehydration temperature is 100-110 ℃, the pressure is-0.08 to-0.05 MPa, and the time is 1-3h.
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