CN116135926A - Nano modified waterborne polyurethane composite material and preparation method thereof - Google Patents
Nano modified waterborne polyurethane composite material and preparation method thereof Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 114
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 95
- 239000004814 polyurethane Substances 0.000 title claims abstract description 95
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- 239000006185 dispersion Substances 0.000 claims abstract description 97
- 239000007788 liquid Substances 0.000 claims abstract description 73
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 69
- 239000002114 nanocomposite Substances 0.000 claims abstract description 63
- 239000003054 catalyst Substances 0.000 claims abstract description 52
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 49
- 239000003607 modifier Substances 0.000 claims abstract description 49
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 47
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 46
- 239000004970 Chain extender Substances 0.000 claims abstract description 40
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 40
- 229920000570 polyether Polymers 0.000 claims abstract description 40
- 229920005862 polyol Polymers 0.000 claims abstract description 40
- 150000003077 polyols Chemical class 0.000 claims abstract description 40
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 36
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 34
- 239000002994 raw material Substances 0.000 claims abstract description 32
- 239000002135 nanosheet Substances 0.000 claims abstract description 28
- 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 abstract description 27
- 239000000203 mixture Substances 0.000 claims description 68
- 238000003756 stirring Methods 0.000 claims description 67
- 239000002270 dispersing agent Substances 0.000 claims description 40
- 238000002156 mixing Methods 0.000 claims description 38
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 30
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical group OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 26
- 238000010438 heat treatment Methods 0.000 claims description 26
- 230000003472 neutralizing effect Effects 0.000 claims description 25
- 239000011259 mixed solution Substances 0.000 claims description 22
- 229920006374 copolyamide PA6I/6T Polymers 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 238000001816 cooling Methods 0.000 claims description 13
- 239000011261 inert gas Substances 0.000 claims description 13
- 229920005646 polycarboxylate Polymers 0.000 claims description 12
- 238000009210 therapy by ultrasound Methods 0.000 claims description 11
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 10
- 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 10
- 239000003513 alkali Substances 0.000 claims description 10
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 10
- 229920001451 polypropylene glycol Polymers 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 150000001413 amino acids Chemical class 0.000 claims description 8
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 claims description 6
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 claims description 6
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 4
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 claims description 4
- OCZBPNBIXHLBFM-UHFFFAOYSA-N n,n-di(propan-2-yl)cyclohexanamine Chemical compound CC(C)N(C(C)C)C1CCCCC1 OCZBPNBIXHLBFM-UHFFFAOYSA-N 0.000 claims description 4
- 229920000909 polytetrahydrofuran Polymers 0.000 claims description 4
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 4
- JCIIKRHCWVHVFF-UHFFFAOYSA-N 1,2,4-thiadiazol-5-amine;hydrochloride Chemical compound Cl.NC1=NC=NS1 JCIIKRHCWVHVFF-UHFFFAOYSA-N 0.000 claims description 3
- 229940058020 2-amino-2-methyl-1-propanol Drugs 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 3
- CBTVGIZVANVGBH-UHFFFAOYSA-N aminomethyl propanol Chemical compound CC(C)(N)CO CBTVGIZVANVGBH-UHFFFAOYSA-N 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 229940096826 phenylmercuric acetate Drugs 0.000 claims description 3
- 235000011056 potassium acetate Nutrition 0.000 claims description 3
- KMBMQZQZBOLJHN-UHFFFAOYSA-N 2-methyloxirane;oxolane Chemical compound CC1CO1.C1CCOC1 KMBMQZQZBOLJHN-UHFFFAOYSA-N 0.000 claims description 2
- UEEJHVSXFDXPFK-UHFFFAOYSA-O N-dimethylethanolamine Chemical compound C[NH+](C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-O 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 claims description 2
- 125000002524 organometallic group Chemical group 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 229960004109 potassium acetate Drugs 0.000 claims description 2
- 229940096992 potassium oleate Drugs 0.000 claims description 2
- MLICVSDCCDDWMD-KVVVOXFISA-M potassium;(z)-octadec-9-enoate Chemical compound [K+].CCCCCCCC\C=C/CCCCCCCC([O-])=O MLICVSDCCDDWMD-KVVVOXFISA-M 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 9
- 230000004888 barrier function Effects 0.000 abstract description 6
- 238000001179 sorption measurement Methods 0.000 abstract description 4
- 239000003063 flame retardant Substances 0.000 description 25
- 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 24
- 230000000052 comparative effect Effects 0.000 description 21
- 229910052751 metal Inorganic materials 0.000 description 11
- 239000002184 metal Substances 0.000 description 11
- 235000013339 cereals Nutrition 0.000 description 9
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- -1 tetrahydrofuran-oxypropylene glycol Chemical compound 0.000 description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000000839 emulsion Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 229920005749 polyurethane resin Polymers 0.000 description 3
- 239000005995 Aluminium silicate Substances 0.000 description 2
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical group CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 235000012211 aluminium silicate Nutrition 0.000 description 2
- 239000003242 anti bacterial agent Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 239000007822 coupling agent Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000013530 defoamer Substances 0.000 description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 2
- 239000010985 leather Substances 0.000 description 2
- 239000010445 mica Substances 0.000 description 2
- 229910052618 mica group Inorganic materials 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 239000002064 nanoplatelet Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002562 thickening agent Substances 0.000 description 2
- 239000012855 volatile organic compound Substances 0.000 description 2
- 108010068370 Glutens Proteins 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 241000209140 Triticum Species 0.000 description 1
- 235000021307 Triticum Nutrition 0.000 description 1
- 239000004964 aerogel Substances 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229920006020 amorphous polyamide Polymers 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000000567 combustion gas Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 230000003670 easy-to-clean Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 239000006221 furniture coating Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 235000021312 gluten Nutrition 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- SXWZSWLBMCNOPC-UHFFFAOYSA-M potassium;6-methylheptanoate Chemical compound [K+].CC(C)CCCCC([O-])=O SXWZSWLBMCNOPC-UHFFFAOYSA-M 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000009988 textile finishing Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- ADJMNWKZSCQHPS-UHFFFAOYSA-L zinc;6-methylheptanoate Chemical compound [Zn+2].CC(C)CCCCC([O-])=O.CC(C)CCCCC([O-])=O ADJMNWKZSCQHPS-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
- C08L75/08—Polyurethanes from polyethers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/005—Additives being defined by their particle size in general
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/006—Additives being defined by their surface area
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses a nano modified waterborne polyurethane composite material and a preparation method thereof, wherein the nano modified waterborne polyurethane composite material is prepared from the following raw materials in parts by weight: 25-45 parts of toluene-2, 4-diisocyanate, 20-35 parts of polyether polyol, 5-10 parts of modified nano composite dispersion liquid, 5-10 parts of temperature resistant modifier, 1-5 parts of catalyst, 1-5 parts of hydrophilic chain extender and 5-15 parts of neutralizer. The modified nano composite dispersion liquid is prepared from the following raw materials in parts by weight: 25-35 parts of graphene oxide nano-sheets, 20-30 parts of nano-alumina, 10-20 parts of water reducer and 15-30 parts of dispersing aid agent. According to the invention, through the matching use of the temperature resistant modifier and the modified nano composite dispersion liquid and the adsorption effect of the graphene oxide nano sheets in the modified nano composite dispersion liquid on the temperature resistant modifier, the temperature resistant modifier and the graphene oxide nano sheets can be uniformly dispersed in the polyurethane composite material, so that the temperature resistance and the barrier property of the composite material are improved.
Description
Technical Field
The invention relates to the technical field of polyurethane, in particular to a nano modified waterborne polyurethane composite material and a preparation method thereof.
Background
Polyurethane has the advantages of wear resistance, chemical resistance, high hardness, strong adhesive force, room temperature curing and the like, and is widely applied to the fields of paint, adhesives, leather and the like. However, the conventional solvent-based polyurethane requires a large amount of organic solvent in the preparation process, which results in a large emission of Volatile Organic Compounds (VOCs) and is very unfavorable to the environment and human health. And with the enhancement of environmental awareness, the common polyurethane material cannot meet the increasing demands of people, so that the Waterborne Polyurethane (WPU) is generated. The water-based polyurethane takes water as a dispersion medium, is nontoxic, pollution-free, low in cost, convenient to prepare and easy to clean, is an environment-friendly material, and is widely applied to various fields of building decoration, leather coating, plastic chemical industry, textile finishing, automobile coating and the like. However, the use field of the waterborne polyurethane has the risk of inflammability, and if the waterborne polyurethane is not subjected to flame retardant treatment, the hidden danger of fire disaster can be caused, so that the personal and property safety is threatened. Therefore, the flame retardant treatment of polyurethane has become a technical problem to be solved.
At present, most of flame-retardant WPU is of an additive type, but the additive is usually added in a large amount to obtain better flame-retardant performance, and the flame-retardant components added in a blending way are extremely easy to cause instability of polyurethane emulsion to cause demulsification or precipitation in the WPU. The key problems of the existing water-based polyurethane flame retardance are as follows: the flame retardant is difficult to uniformly and stably disperse in the polyurethane matrix, and the flame retardant effect is not obvious, and the reason is that: (1) The characteristics of WPU make the flame retardant component added by blending extremely easy to cause instability of polyurethane emulsion and cause demulsification, even the flame retardant is difficult to stably disperse and produce precipitation in WPU, and the emulsion has the defects of poor film forming property and the like; (2) Flame retardants are generally added in large amounts to achieve good flame retardant properties.
CN109161322a discloses a water-based polyurethane flame retardant coating for building furniture coating and a preparation method thereof. According to the method, the microporous internal network wheat gluten and the silicon dioxide aerogel of melamine are used as the carbon-forming flame retardant, and are further uniformly mixed with mica powder, kaolin powder, titanate coupling agent, aqueous polyurethane, thickener, defoamer, antibacterial agent and a proper amount of water to prepare the aqueous polyurethane flame retardant coating. In the water-based polyurethane flame-retardant coating, the carbon-forming flame retardant is 4-8 parts by weight, the mica powder is 4-8 parts by weight, the kaolin powder is 7-10 parts by weight, the titanate coupling agent is 1-2 parts by weight, the water-based polyurethane is 48-68 parts by weight, the thickener is 2-4 parts by weight, the defoamer is 1-2 parts by weight, the antibacterial agent is 1-3 parts by weight, and the water is 40-60 parts by weight.
While graphene has shown its excellent properties in many respects as a novel nanofiller, including flame retardant modification in polymers, excellent flame retardant results can be obtained with only a very small addition. The flame retardant polyurethane is characterized in that the flame retardant polyurethane is a special lamellar structure, namely, in the combustion process of the graphene composite material, a porous protective carbon layer can be generated on the surface of the polymer, and the carbon layer plays roles of barrier, oxygen isolation, heat insulation, smoke release inhibition, combustible gas entering combustion gas phase prevention and the like, so that the flame retardant effect is achieved, but the dispersibility of the graphene in the polyurethane is poor, so that the graphene is uniformly dispersed in the polyurethane, and the preparation of the waterborne polyurethane with good flame retardant property has become the key point of the current research.
Accordingly, the inventor has the problem of providing a nano modified aqueous polyurethane composite material capable of improving the mechanical property, thermal stability and flame retardance and a preparation method thereof, which aims to achieve the purpose of having more practical value, by keeping the experience of abundant design development and actual manufacturing in the related industry for many years and researching and improving the prior art and the defects.
Disclosure of Invention
In order to solve the problems of poor stability, poor tensile strength, poor elongation at break and other mechanical properties in the prior art, the invention provides a nano modified waterborne polyurethane composite material and a preparation method thereof.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
the nano modified waterborne polyurethane composite material is prepared from the following raw materials in parts by weight:
25-45 parts of toluene-2, 4-diisocyanate, 20-35 parts of polyether polyol, 5-10 parts of modified nano composite dispersion liquid, 5-10 parts of temperature resistant modifier, 1-5 parts of catalyst, 1-5 parts of hydrophilic chain extender and 5-15 parts of neutralizer.
Preferably, the modified nano composite dispersion liquid is prepared from the following raw materials in parts by weight:
25-35 parts of graphene oxide nano-sheets, 20-30 parts of nano-alumina, 10-20 parts of water reducer and 15-30 parts of dispersing aid agent.
Preferably, the preparation method of the modified nano composite dispersion liquid comprises the following steps:
s1, mixing and stirring a water reducer and an auxiliary dispersing agent uniformly according to parts by weight to obtain a composite high-performance dispersing agent;
s2, adding graphene oxide nano-sheets into water at 50-60 ℃, stirring to be uniformly dispersed, adding the composite high-performance dispersing agent obtained in the step S1, uniformly stirring, and finally adding the nano-alumina, and uniformly stirring to obtain a mixed solution;
s3, mixing the mixed solution obtained in the step S2 at a concentration of 100-150W/cm 2 And carrying out ultrasonic treatment for 3-5h under the condition to obtain the composite modified nano dispersion liquid.
Preferably, the nano alumina is rod-shaped gamma-Al 2 O 3 The diameter grain in the nano alumina is less than or equal to 20-50nm, and the specific surface area is more than or equal to 50 square meters per gram;
the nano alumina treatment comprises aggregation, separation and deacidification treatment at one time to obtain powdery nano alumina; the nano aluminum oxide can play a role in coordination and crosslinking among molecular chains in the polyurethane resin material.
Preferably, the water reducer is a polycarboxylate water reducer, and the alkali content is less than or equal to 0.2%; after the polycarboxylate water reducer is added, the polycarboxylate water reducer molecules can be directionally adsorbed on the surface of the dispersion aid agent, so that the surface of the dispersion aid agent has the same charge (usually negative charge), an electrostatic repulsive effect is formed, the mutual dispersion of the dispersion aid agent and the disintegration of a flocculation structure are promoted, and the water in the wrapped part is released to participate in flowing, so that the fluidity of the modified nano composite dispersion liquid in the polyurethane composite material is effectively increased; and the performance of the obtained polyurethane composite material is more excellent, and the polyurethane composite material can be widely applied.
The dispersion aid agent is selected from one or more of water-soluble alcohol, amino acid or sulfamic acid.
Preferably, the polyether polyol is one or more of polyoxypropylene glycol, polytetrahydrofuran glycol and tetrahydrofuran-propylene oxide copolyglycol.
Preferably, the catalyst is an organometallic catalyst selected from one or more of dibutyltin dilaurate, stannous octoate, potassium iso-octoate, potassium acetate, potassium oleate, phenylmercuric acetate and zinc iso-octoate.
Preferably, the temperature resistant modifier is PA6I/6T, the PA6I/6T is an amorphous polyamide with a low melting point (about 130 ℃), and the temperature resistance and the barrier property of the composite material can be obviously improved under the condition that other properties are not influenced by introducing the PA6I/6T and blending the PA6I/6T with PLA.
The hydrophilic chain extender is 1, 4-butanediol.
Preferably, the neutralizing agent is one or more of triethylamine, N-dimethylethanolamine, triethanolamine, methyldiethanolamine, diisopropylcyclohexylamine, N-methylmorpholine, 2-amino-2-methyl-1-propanol and ammonia water.
The preparation process of the nano modified waterborne polyurethane composite material further comprises the following steps:
s1, mixing toluene-2, 4-diisocyanate, polyether polyol and a hydrophilic chain extender, heating to 100-120 ℃ and stirring for reaction to obtain a mixture A;
s2, under the protection of inert gas, cooling the mixture A in the step S1 to 40-50 ℃, adding the modified nano composite dispersion liquid, the temperature-resistant modifier and the catalyst, heating to 80-90 ℃, and preserving heat for 2-3 hours to obtain a mixture B;
and S3, adding a neutralizing agent into the mixture B in the step S2, and uniformly stirring to obtain the nano modified waterborne polyurethane composite material.
According to the invention, through the matched use of the temperature resistant modifier and the modified nano composite dispersion liquid and through the adsorption effect of the graphene oxide nano sheets in the modified nano composite dispersion liquid on the temperature resistant modifier, the temperature resistant modifier and the graphene oxide nano sheets can be uniformly dispersed in the polyurethane composite material, so that the temperature resistance and the barrier property of the composite material are improved.
Compared with the prior art, the invention has the beneficial effects that:
1. in the preparation of the modified nano composite dispersion liquid, a small amount of water reducer and a dispersing aid agent are mixed and stirred to prepare the composite high-performance dispersing agent, so that the dispersing effect of the nano material in the composite solution is obviously improved; the polycarboxylic acid water reducer is utilized to reduce the water consumption of the standard consistence of the mixture, increase the fluidity of the mixture, and simultaneously form a polymer molecule adsorption layer through a large number of active groups carried by the polycarboxylic acid water reducer, so that a steric hindrance effect is generated, and a double dispersion effect is further generated on the nano material and the polyurethane composite material, so that the performance of the obtained polyurethane composite material is more excellent, and the polyurethane composite material can be widely applied.
2. According to the invention, through the matching use of the temperature resistant modifier and the modified nano composite dispersion liquid and the adsorption effect of the graphene oxide nano sheets in the modified nano composite dispersion liquid on the temperature resistant modifier, the temperature resistant modifier and the graphene oxide nano sheets can be uniformly dispersed in the polyurethane composite material, so that the temperature resistance and the barrier property of the composite material are improved.
Detailed Description
The technical solutions of the present invention will be clearly and completely described in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
The nano modified waterborne polyurethane composite material is prepared from the following raw materials in parts by weight:
25 parts of toluene-2, 4-diisocyanate, 20 parts of polyether polyol, 5 parts of modified nano composite dispersion liquid, 5 parts of temperature resistant modifier, 1 part of catalyst, 1 part of hydrophilic chain extender and 5 parts of neutralizer.
The modified nano composite dispersion liquid is prepared from the following raw materials in parts by weight:
25 parts of graphene oxide nano-sheets, 20 parts of nano-alumina, 10 parts of water reducer and 15 parts of auxiliary dispersing agent.
The preparation method of the modified nano composite dispersion liquid comprises the following steps:
s1, mixing and stirring a water reducer and an auxiliary dispersing agent uniformly according to parts by weight to obtain a composite high-performance dispersing agent;
s2, adding graphene oxide nano-sheets into water at 50-60 ℃, stirring to be uniformly dispersed, adding the composite high-performance dispersing agent obtained in the step S1, uniformly stirring, and finally adding the nano-alumina, and uniformly stirring to obtain a mixed solution;
s3, mixing the mixed solution obtained in the step S2 at a concentration of 100-150W/cm 2 And carrying out ultrasonic treatment for 3-5h under the condition to obtain the composite modified nano dispersion liquid.
The nano aluminum oxide is rod-shaped gamma-Al 2 O 3 The diameter grain in the nano alumina is less than or equal to 20-50nm, and the specific surface area is more than or equal to 50 square meters per gram.
The water reducer is a polycarboxylate water reducer, and the alkali content is less than or equal to 0.2%;
the dispersion aid agent is selected from the group consisting of water-soluble alcohol and amino acid mixtures.
The polyether polyol is polyoxypropylene glycol.
The catalyst is an organic metal catalyst dibutyl tin dilaurate.
The temperature resistant modifier is PA6I/6T;
the hydrophilic chain extender is 1, 4-butanediol.
The neutralizing agent is triethylamine.
The preparation process of the nano modified waterborne polyurethane composite material further comprises the following steps:
s1, mixing toluene-2, 4-diisocyanate, polyether polyol and a hydrophilic chain extender, heating to 100-120 ℃ and stirring for reaction to obtain a mixture A;
s2, under the protection of inert gas, cooling the mixture A in the step S1 to 40-50 ℃, adding the modified nano composite dispersion liquid, the temperature-resistant modifier and the catalyst, heating to 80-90 ℃, and preserving heat for 2-3 hours to obtain a mixture B;
and S3, adding a neutralizing agent into the mixture B in the step S2, and uniformly stirring to obtain the nano modified waterborne polyurethane composite material.
Example 2
The nano modified waterborne polyurethane composite material is prepared from the following raw materials in parts by weight:
30 parts of toluene-2, 4-diisocyanate, 25 parts of polyether polyol, 6 parts of modified nano composite dispersion liquid, 6 parts of temperature resistant modifier, 2 parts of catalyst, 2 parts of hydrophilic chain extender and 7 parts of neutralizer.
The modified nano composite dispersion liquid is prepared from the following raw materials in parts by weight:
27 parts of graphene oxide nano-sheets, 22 parts of nano-alumina, 12 parts of a water reducer and 20 parts of a dispersion aid agent.
The preparation method of the modified nano composite dispersion liquid comprises the following steps:
s1, mixing and stirring a water reducer and an auxiliary dispersing agent uniformly according to parts by weight to obtain a composite high-performance dispersing agent;
s2, adding graphene oxide nano-sheets into water at 50-60 ℃, stirring to be uniformly dispersed, adding the composite high-performance dispersing agent obtained in the step S1, uniformly stirring, and finally adding the nano-alumina, and uniformly stirring to obtain a mixed solution;
s3, mixing the mixed solution obtained in the step S2 at a concentration of 100-150W/cm 2 And carrying out ultrasonic treatment for 3-5h under the condition to obtain the composite modified nano dispersion liquid.
The nano aluminum oxide is rod-shaped gamma-Al 2 O 3 The diameter grain in the nano alumina is less than or equal to 20-50nm, and the specific surface area is more than or equal to 50 square meters per gram.
The water reducer is a polycarboxylate water reducer, and the alkali content is less than or equal to 0.2%;
the dispersion aid agent is selected from the group consisting of water-soluble alcohol and sulfamic acid mixtures.
The polyether polyol is polytetrahydrofuran diol.
The catalyst is an organic metal catalyst stannous octoate.
The temperature resistant modifier is PA6I/6T;
the hydrophilic chain extender is 1, 4-butanediol.
The neutralizing agent is N, N-dimethylethanolamine.
The preparation process of the nano modified waterborne polyurethane composite material further comprises the following steps:
s1, mixing toluene-2, 4-diisocyanate, polyether polyol and a hydrophilic chain extender, heating to 100-120 ℃ and stirring for reaction to obtain a mixture A;
s2, under the protection of inert gas, cooling the mixture A in the step S1 to 40-50 ℃, adding the modified nano composite dispersion liquid, the temperature-resistant modifier and the catalyst, heating to 80-90 ℃, and preserving heat for 2-3 hours to obtain a mixture B;
and S3, adding a neutralizing agent into the mixture B in the step S2, and uniformly stirring to obtain the nano modified waterborne polyurethane composite material.
Example 3
The nano modified waterborne polyurethane composite material is prepared from the following raw materials in parts by weight:
35 parts of toluene-2, 4-diisocyanate, 27 parts of polyether polyol, 7 parts of modified nano composite dispersion liquid, 7 parts of temperature resistant modifier, 3 parts of catalyst, 3 parts of hydrophilic chain extender and 10 parts of neutralizer.
The modified nano composite dispersion liquid is prepared from the following raw materials in parts by weight:
30 parts of graphene oxide nano-sheets, 25 parts of nano-alumina, 15 parts of water reducer and 22 parts of auxiliary dispersing agent.
The preparation method of the modified nano composite dispersion liquid comprises the following steps:
s1, mixing and stirring a water reducer and an auxiliary dispersing agent uniformly according to parts by weight to obtain a composite high-performance dispersing agent;
s2, adding graphene oxide nano-sheets into water at 50-60 ℃, stirring to be uniformly dispersed, adding the composite high-performance dispersing agent obtained in the step S1, uniformly stirring, and finally adding the nano-alumina, and uniformly stirring to obtain a mixed solution;
s3, mixing the mixed solution obtained in the step S2 at a concentration of 100-150W/cm 2 And carrying out ultrasonic treatment for 3-5h under the condition to obtain the composite modified nano dispersion liquid.
The nano aluminum oxide is rod-shaped gamma-Al 2 O 3 The diameter grain in the nano alumina is less than or equal to 20-50nm, and the specific surface area is more than or equal to 50 square meters per gram.
The water reducer is a polycarboxylate water reducer, and the alkali content is less than or equal to 0.2%;
the dispersion aid agent is selected from water-soluble alcohols.
The polyether polyol is a mixture of polyoxypropylene glycol and tetrahydrofuran-oxypropylene glycol.
The catalyst is an organic metal catalyst and is selected from a mixture of dibutyl tin dilaurate and stannous octoate.
The temperature resistant modifier is PA6I/6T;
the hydrophilic chain extender is 1, 4-butanediol.
The neutralizing agent is a mixture of triethylamine and N, N-dimethylethanolamine.
The preparation process of the nano modified waterborne polyurethane composite material further comprises the following steps:
s1, mixing toluene-2, 4-diisocyanate, polyether polyol and a hydrophilic chain extender, heating to 100-120 ℃ and stirring for reaction to obtain a mixture A;
s2, under the protection of inert gas, cooling the mixture A in the step S1 to 40-50 ℃, adding the modified nano composite dispersion liquid, the temperature-resistant modifier and the catalyst, heating to 80-90 ℃, and preserving heat for 2-3 hours to obtain a mixture B;
and S3, adding a neutralizing agent into the mixture B in the step S2, and uniformly stirring to obtain the nano modified waterborne polyurethane composite material.
Example 4
The nano modified waterborne polyurethane composite material is prepared from the following raw materials in parts by weight:
40 parts of toluene-2, 4-diisocyanate, 30 parts of polyether polyol, 8 parts of modified nano composite dispersion liquid, 8 parts of temperature resistant modifier, 4 parts of catalyst, 4 parts of hydrophilic chain extender and 12 parts of neutralizer.
The modified nano composite dispersion liquid is prepared from the following raw materials in parts by weight:
32 parts of graphene oxide nano-sheets, 27 parts of nano-alumina, 17 parts of water reducer and 26 parts of dispersing aid agent.
The preparation method of the modified nano composite dispersion liquid comprises the following steps:
s1, mixing and stirring a water reducer and an auxiliary dispersing agent uniformly according to parts by weight to obtain a composite high-performance dispersing agent;
s2, adding graphene oxide nano-sheets into water at 50-60 ℃, stirring to be uniformly dispersed, adding the composite high-performance dispersing agent obtained in the step S1, uniformly stirring, and finally adding the nano-alumina, and uniformly stirring to obtain a mixed solution;
s3, mixing the mixed solution obtained in the step S2 at a concentration of 100-150W/cm 2 And carrying out ultrasonic treatment for 3-5h under the condition to obtain the composite modified nano dispersion liquid.
The nano aluminum oxide is rod-shaped gamma-Al 2 O 3 The diameter grain in the nano alumina is less than or equal to 20-50nm, and the specific surface area is more than or equal to 50 square meters per gram.
The water reducer is a polycarboxylate water reducer, and the alkali content is less than or equal to 0.2%;
the auxiliary dispersing agent is selected from water-soluble sulfamic acid.
The polyether polyol is a mixture of polytetrahydrofuran glycol and tetrahydrofuran-propylene oxide copolymer glycol.
The catalyst is a mixture of organic metal catalyst potassium isooctanoate and potassium acetate.
The temperature resistant modifier is PA6I/6T;
the hydrophilic chain extender is 1, 4-butanediol.
The neutralizing agent is a mixture of triethanolamine and diisopropylcyclohexylamine.
The preparation process of the nano modified waterborne polyurethane composite material further comprises the following steps:
s1, mixing toluene-2, 4-diisocyanate, polyether polyol and a hydrophilic chain extender, heating to 100-120 ℃ and stirring for reaction to obtain a mixture A;
s2, under the protection of inert gas, cooling the mixture A in the step S1 to 40-50 ℃, adding the modified nano composite dispersion liquid, the temperature-resistant modifier and the catalyst, heating to 80-90 ℃, and preserving heat for 2-3 hours to obtain a mixture B;
and S3, adding a neutralizing agent into the mixture B in the step S2, and uniformly stirring to obtain the nano modified waterborne polyurethane composite material.
Example 5
The nano modified waterborne polyurethane composite material is prepared from the following raw materials in parts by weight:
45 parts of toluene-2, 4-diisocyanate, 35 parts of polyether polyol, 10 parts of modified nano composite dispersion liquid, 10 parts of temperature resistant modifier, 5 parts of catalyst, 5 parts of hydrophilic chain extender and 15 parts of neutralizer.
The modified nano composite dispersion liquid is prepared from the following raw materials in parts by weight:
35 parts of graphene oxide nano-sheets, 30 parts of nano-alumina, 20 parts of water reducer and 30 parts of auxiliary dispersing agent.
The preparation method of the modified nano composite dispersion liquid comprises the following steps:
s1, mixing and stirring a water reducer and an auxiliary dispersing agent uniformly according to parts by weight to obtain a composite high-performance dispersing agent;
s2, adding graphene oxide nano-sheets into water at 50-60 ℃, stirring to be uniformly dispersed, adding the composite high-performance dispersing agent obtained in the step S1, uniformly stirring, and finally adding the nano-alumina, and uniformly stirring to obtain a mixed solution;
s3, mixing the mixed solution obtained in the step S2 at a concentration of 100-150W/cm 2 And carrying out ultrasonic treatment for 3-5h under the condition to obtain the composite modified nano dispersion liquid.
The nano aluminum oxide is rod-shaped gamma-Al 2 O 3 The diameter grain in the nano alumina is less than or equal to 20-50nm, and the specific surface area is more than or equal to 50 square meters per gram.
The water reducer is a polycarboxylate water reducer, and the alkali content is less than or equal to 0.2%;
the auxiliary dispersing agent is selected from water-soluble amino acids.
The polyether polyol is tetrahydrofuran-propylene oxide copolymer glycol.
The catalyst is a mixture of organic metal catalyst phenylmercuric acetate and zinc isooctanoate.
The temperature resistant modifier is PA6I/6T;
the hydrophilic chain extender is 1, 4-butanediol.
The neutralizer is a mixture of diisopropyl cyclohexylamine, 2-amino-2-methyl-1-propanol and ammonia water.
The preparation process of the nano modified waterborne polyurethane composite material further comprises the following steps:
s1, mixing toluene-2, 4-diisocyanate, polyether polyol and a hydrophilic chain extender, heating to 100-120 ℃ and stirring for reaction to obtain a mixture A;
s2, under the protection of inert gas, cooling the mixture A in the step S1 to 40-50 ℃, adding the modified nano composite dispersion liquid, the temperature-resistant modifier and the catalyst, heating to 80-90 ℃, and preserving heat for 2-3 hours to obtain a mixture B;
and S3, adding a neutralizing agent into the mixture B in the step S2, and uniformly stirring to obtain the nano modified waterborne polyurethane composite material.
Comparative example 1
The nano modified waterborne polyurethane composite material is prepared from the following raw materials in parts by weight:
25 parts of toluene-2, 4-diisocyanate, 20 parts of polyether polyol, 5 parts of temperature resistant modifier, 1 part of catalyst, 1 part of hydrophilic chain extender and 5 parts of neutralizer.
The polyether polyol is polyoxypropylene glycol.
The catalyst is an organic metal catalyst dibutyl tin dilaurate.
The temperature resistant modifier is PA6I/6T;
the hydrophilic chain extender is 1, 4-butanediol.
The neutralizing agent is triethylamine.
The preparation process of the nano modified waterborne polyurethane composite material further comprises the following steps:
s1, mixing toluene-2, 4-diisocyanate, polyether polyol and a hydrophilic chain extender, heating to 100-120 ℃ and stirring for reaction to obtain a mixture A;
s2, under the protection of inert gas, cooling the mixture A in the step S1 to 40-50 ℃, adding a temperature-resistant modifier and a catalyst, heating to 80-90 ℃, and preserving heat for 2-3 hours to obtain a mixture B;
and S3, adding a neutralizing agent into the mixture B in the step S2, and uniformly stirring to obtain the nano modified waterborne polyurethane composite material.
Comparative example 2
The nano modified waterborne polyurethane composite material is prepared from the following raw materials in parts by weight:
25 parts of toluene-2, 4-diisocyanate, 20 parts of polyether polyol, 5 parts of dispersion liquid, 5 parts of temperature resistant modifier, 1 part of catalyst, 1 part of hydrophilic chain extender and 5 parts of neutralizer.
The dispersion liquid is polytetrafluoroethylene concentrated dispersion liquid.
The polyether polyol is polyoxypropylene glycol.
The catalyst is an organic metal catalyst dibutyl tin dilaurate.
The temperature resistant modifier is PA6I/6T;
the hydrophilic chain extender is 1, 4-butanediol.
The neutralizing agent is triethylamine.
The preparation process of the nano modified waterborne polyurethane composite material further comprises the following steps:
s1, mixing toluene-2, 4-diisocyanate, polyether polyol and a hydrophilic chain extender, heating to 100-120 ℃ and stirring for reaction to obtain a mixture A;
s2, under the protection of inert gas, cooling the mixture A in the step S1 to 40-50 ℃, adding polytetrafluoroethylene concentrated dispersion, a temperature-resistant modifier and a catalyst, heating to 80-90 ℃, and preserving heat for 2-3 hours to obtain a mixture B;
and S3, adding a neutralizing agent into the mixture B in the step S2, and uniformly stirring to obtain the nano modified waterborne polyurethane composite material.
Comparative example 3
The nano modified waterborne polyurethane composite material is prepared from the following raw materials in parts by weight:
25 parts of toluene-2, 4-diisocyanate, 20 parts of polyether polyol, 5 parts of modified nano composite dispersion liquid, 5 parts of temperature resistant modifier, 1 part of catalyst, 1 part of hydrophilic chain extender and 5 parts of neutralizer.
The modified nano composite dispersion liquid is prepared from the following raw materials in parts by weight:
20 parts of nano aluminum oxide, 10 parts of water reducer and 15 parts of dispersing aid agent.
The preparation method of the modified nano composite dispersion liquid comprises the following steps:
s1, mixing and stirring a water reducer and an auxiliary dispersing agent uniformly according to parts by weight to obtain a composite high-performance dispersing agent;
s2, adding the nano aluminum oxide into the composite high-performance dispersing agent obtained in the step S1, and uniformly stirring to obtain a mixed solution;
s3, mixing the mixed solution obtained in the step S2 at a concentration of 100-150W/cm 2 And carrying out ultrasonic treatment for 3-5h under the condition to obtain the composite modified nano dispersion liquid.
The nano aluminum oxide is rod-shaped gamma-Al 2 O 3 The diameter grain in the nano alumina is less than or equal to 20-50nm, and the specific surface area is more than or equal to 50 square meters per gram.
The water reducer is a polycarboxylate water reducer, and the alkali content is less than or equal to 0.2%;
the dispersion aid agent is selected from the group consisting of water-soluble alcohol and amino acid mixtures.
The polyether polyol is polyoxypropylene glycol.
The catalyst is an organic metal catalyst dibutyl tin dilaurate.
The temperature resistant modifier is PA6I/6T;
the hydrophilic chain extender is 1, 4-butanediol.
The neutralizing agent is triethylamine.
The preparation process of the nano modified waterborne polyurethane composite material further comprises the following steps:
s1, mixing toluene-2, 4-diisocyanate, polyether polyol and a hydrophilic chain extender, heating to 100-120 ℃ and stirring for reaction to obtain a mixture A;
s2, under the protection of inert gas, cooling the mixture A in the step S1 to 40-50 ℃, adding the modified nano composite dispersion liquid, the temperature-resistant modifier and the catalyst, heating to 80-90 ℃, and preserving heat for 2-3 hours to obtain a mixture B;
and S3, adding a neutralizing agent into the mixture B in the step S2, and uniformly stirring to obtain the nano modified waterborne polyurethane composite material.
Comparative example 4
The nano modified waterborne polyurethane composite material is prepared from the following raw materials in parts by weight:
25 parts of toluene-2, 4-diisocyanate, 20 parts of polyether polyol, 5 parts of modified nano composite dispersion liquid, 5 parts of temperature resistant modifier, 1 part of catalyst, 1 part of hydrophilic chain extender and 5 parts of neutralizer.
The modified nano composite dispersion liquid is prepared from the following raw materials in parts by weight:
25 parts of graphene oxide nano-sheets, 10 parts of a water reducer and 15 parts of a dispersing aid agent.
The preparation method of the modified nano composite dispersion liquid comprises the following steps:
s1, mixing and stirring a water reducer and an auxiliary dispersing agent uniformly according to parts by weight to obtain a composite high-performance dispersing agent;
s2, adding graphene oxide nano-sheets into water at 50-60 ℃, stirring to be uniformly dispersed, adding the composite high-performance dispersing agent obtained in the S1, and uniformly stirring to obtain a mixed solution;
s3, mixing the mixed solution obtained in the step S2 at a concentration of 100-150W/cm 2 And carrying out ultrasonic treatment for 3-5h under the condition to obtain the composite modified nano dispersion liquid.
The water reducer is a polycarboxylate water reducer, and the alkali content is less than or equal to 0.2%;
the dispersion aid agent is selected from the group consisting of water-soluble alcohol and amino acid mixtures.
The polyether polyol is polyoxypropylene glycol.
The catalyst is an organic metal catalyst dibutyl tin dilaurate.
The temperature resistant modifier is PA6I/6T;
the hydrophilic chain extender is 1, 4-butanediol.
The neutralizing agent is triethylamine.
The preparation process of the nano modified waterborne polyurethane composite material further comprises the following steps:
s1, mixing toluene-2, 4-diisocyanate, polyether polyol and a hydrophilic chain extender, heating to 100-120 ℃ and stirring for reaction to obtain a mixture A;
s2, under the protection of inert gas, cooling the mixture A in the step S1 to 40-50 ℃, adding the modified nano composite dispersion liquid, the temperature-resistant modifier and the catalyst, heating to 80-90 ℃, and preserving heat for 2-3 hours to obtain a mixture B;
and S3, adding a neutralizing agent into the mixture B in the step S2, and uniformly stirring to obtain the nano modified waterborne polyurethane composite material.
Comparative example 5
The nano modified waterborne polyurethane composite material is prepared from the following raw materials in parts by weight:
25 parts of toluene-2, 4-diisocyanate, 20 parts of polyether polyol, 5 parts of modified nano composite dispersion liquid, 5 parts of temperature resistant modifier, 1 part of catalyst, 1 part of hydrophilic chain extender and 5 parts of neutralizer.
The modified nano composite dispersion liquid is prepared from the following raw materials in parts by weight:
25 parts of graphene oxide nano-sheets, 20 parts of nano-alumina and 15 parts of dispersing aid agents.
The preparation method of the modified nano composite dispersion liquid comprises the following steps:
s1, uniformly mixing and stirring the auxiliary dispersing agent according to parts by weight to obtain a composite high-performance dispersing agent;
s2, adding graphene oxide nano-sheets into water at 50-60 ℃, stirring to be uniformly dispersed, adding the composite high-performance dispersing agent obtained in the step S1, uniformly stirring, and finally adding the nano-alumina, and uniformly stirring to obtain a mixed solution;
s3, mixing the mixed solution obtained in the step S2 at a concentration of 100-150W/cm 2 And carrying out ultrasonic treatment for 3-5h under the condition to obtain the composite modified nano dispersion liquid.
The nano aluminum oxide is rod-shaped gamma-Al 2 O 3 The diameter grain in the nano alumina is less than or equal to 20-50nm, and the specific surface area is more than or equal to 50 square meters per gram.
The dispersion aid agent is selected from the group consisting of water-soluble alcohol and amino acid mixtures.
The polyether polyol is polyoxypropylene glycol.
The catalyst is an organic metal catalyst dibutyl tin dilaurate.
The temperature resistant modifier is PA6I/6T;
the hydrophilic chain extender is 1, 4-butanediol.
The neutralizing agent is triethylamine.
The preparation process of the nano modified waterborne polyurethane composite material further comprises the following steps:
s1, mixing toluene-2, 4-diisocyanate, polyether polyol and a hydrophilic chain extender, heating to 100-120 ℃ and stirring for reaction to obtain a mixture A;
s2, under the protection of inert gas, cooling the mixture A in the step S1 to 40-50 ℃, adding the modified nano composite dispersion liquid, the temperature-resistant modifier and the catalyst, heating to 80-90 ℃, and preserving heat for 2-3 hours to obtain a mixture B;
and S3, adding a neutralizing agent into the mixture B in the step S2, and uniformly stirring to obtain the nano modified waterborne polyurethane composite material.
Comparative example 6
The nano modified waterborne polyurethane composite material is prepared from the following raw materials in parts by weight:
25 parts of toluene-2, 4-diisocyanate, 20 parts of polyether polyol, 5 parts of modified nano composite dispersion liquid, 1 part of catalyst, 1 part of hydrophilic chain extender and 5 parts of neutralizer.
The modified nano composite dispersion liquid is prepared from the following raw materials in parts by weight:
25 parts of graphene oxide nano-sheets, 20 parts of nano-alumina, 10 parts of water reducer and 15 parts of auxiliary dispersing agent.
The preparation method of the modified nano composite dispersion liquid comprises the following steps:
s1, mixing and stirring a water reducer and an auxiliary dispersing agent uniformly according to parts by weight to obtain a composite high-performance dispersing agent;
s2, adding graphene oxide nano-sheets into water at 50-60 ℃, stirring to be uniformly dispersed, adding the composite high-performance dispersing agent obtained in the step S1, uniformly stirring, and finally adding the nano-alumina, and uniformly stirring to obtain a mixed solution;
s3, mixing the mixed solution obtained in the step S2 at a concentration of 100-150W/cm 2 And carrying out ultrasonic treatment for 3-5h under the condition to obtain the composite modified nano dispersion liquid.
The nano aluminum oxide is rod-shaped gamma-Al 2 O 3 The diameter grain in the nano alumina is less than or equal to 20-50nm, and the specific surface area is more than or equal to 50 square meters per gram.
The water reducer is a polycarboxylate water reducer, and the alkali content is less than or equal to 0.2%;
the dispersion aid agent is selected from the group consisting of water-soluble alcohol and amino acid mixtures.
The polyether polyol is polyoxypropylene glycol.
The catalyst is an organic metal catalyst dibutyl tin dilaurate.
The hydrophilic chain extender is 1, 4-butanediol.
The neutralizing agent is triethylamine.
The preparation process of the nano modified waterborne polyurethane composite material further comprises the following steps:
s1, mixing toluene-2, 4-diisocyanate, polyether polyol and a hydrophilic chain extender, heating to 100-120 ℃ and stirring for reaction to obtain a mixture A;
s2, under the protection of inert gas, cooling the mixture A in the S1 to 40-50 ℃, adding the modified nano composite dispersion liquid and the catalyst, heating to 80-90 ℃, and preserving heat for 2-3 hours to obtain a mixture B;
and S3, adding a neutralizing agent into the mixture B in the step S2, and uniformly stirring to obtain the nano modified waterborne polyurethane composite material.
The nano modified aqueous polyurethane composite materials prepared in examples 1 to 5 and comparative examples 1 to 6 were subjected to performance test.
Wherein, the tensile strength and the elongation at break are tested according to the specification of GB/T528-2009;
the flame retardant performance is tested according to the UL-94 standard, and a TG-DSC comprehensive thermal analyzer is used for testing the thermal decomposition temperature of the polyurethane composite material, wherein the test standard is GB/T13464-2008;
stability: the polyurethane composites provided in the above examples and comparative examples were allowed to stand for 48 hours, and observed for uniformity and sedimentation.
The test results are shown in Table 1 below:
TABLE 1
In comparison with example 1, the modified nanocomposite dispersion was not added in comparative example 1; the dispersion in comparative example 2 is a general commercially available polytetrafluoroethylene concentrated dispersion; the raw material for preparing the modified nanocomposite dispersion in comparative example 3 was free of graphene oxide nanoplatelets; the raw material for preparing the modified nanocomposite dispersion in comparative example 4 was free of added nano alumina; the raw material for preparing the modified nanocomposite dispersion in comparative example 5 was free of water reducer; comparative example 6 was free of addition of temperature resistant modifier.
The test results show that: the tensile strength, elongation at break, flame retardant property and thermal stability of the nano modified waterborne polyurethane composite material prepared in the comparative example are all reduced to a certain extent, wherein the comprehensive performance of the prepared polyurethane composite material is greatly reduced due to the fact that the modified nano composite dispersion liquid is not added in the comparative example 1, and compared with the examples, the composite material has larger difference and the performance is far less than the examples;
wherein the dispersion liquid in the comparative example 2 is a common commercial polytetrafluoroethylene concentrated dispersion liquid, and the performance of the prepared polyurethane composite material is reduced to a certain extent;
wherein the graphene oxide nanoplatelets are not added due to the raw materials for preparing the modified nanocomposite dispersion in comparative example 3; in comparative example 4, nano alumina was not added due to the raw material for preparing the modified nanocomposite dispersion; in the comparative example 5, the raw materials for preparing the modified nano composite dispersion liquid are not added with the water reducer, so that the performances of the prepared polyurethane composite material are reduced to a certain extent, and the comprehensive performances of the polyurethane resin material are improved by fully showing that the graphene oxide nano sheets, the nano alumina and the water reducer are beneficial to the improvement of the comprehensive performances of the polyurethane resin material;
the comparative example 6 is free from adding the temperature-resistant modifier, so that the flame retardant property and the thermal stability of the polyurethane composite material are greatly reduced, and the combination of the temperature-resistant modifier and the modified nano composite dispersion liquid can be effectively proved to improve the temperature resistance and the barrier property of the composite material.
The foregoing is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art, who is within the scope of the present invention, should make equivalent substitutions or modifications according to the technical scheme of the present invention and the inventive concept thereof, and should be covered by the scope of the present invention.
Claims (10)
1. The nano modified waterborne polyurethane composite material is characterized by being prepared from the following raw materials in parts by weight:
25-45 parts of toluene-2, 4-diisocyanate, 20-35 parts of polyether polyol, 5-10 parts of modified nano composite dispersion liquid, 5-10 parts of temperature resistant modifier, 1-5 parts of catalyst, 1-5 parts of hydrophilic chain extender and 5-15 parts of neutralizer.
2. The nano-modified waterborne polyurethane composite material according to claim 1, wherein the modified nano-composite dispersion liquid is prepared from the following raw materials in parts by weight:
25-35 parts of graphene oxide nano-sheets, 20-30 parts of nano-alumina, 10-20 parts of water reducer and 15-30 parts of dispersing aid agent.
3. The nano-modified waterborne polyurethane composite according to claim 2, wherein the preparation method of the modified nano-composite dispersion liquid comprises the following steps:
s1, mixing and stirring a water reducer and an auxiliary dispersing agent uniformly according to parts by weight to obtain a composite high-performance dispersing agent;
s2, adding graphene oxide nano-sheets into water at 50-60 ℃, stirring to be uniformly dispersed, adding the composite high-performance dispersing agent obtained in the step S1, uniformly stirring, and finally adding the nano-alumina, and uniformly stirring to obtain a mixed solution;
s3, mixing the mixed solution obtained in the step S2 at a concentration of 100-150W/cm 2 And carrying out ultrasonic treatment for 3-5h under the condition to obtain the composite modified nano dispersion liquid.
4. The nano modified waterborne polyurethane composite material according to claim 2, wherein the nano aluminum oxide is rod-shaped gamma-Al 2 O 3 The diameter grain in the nano alumina is less than or equal to 20-50nm, and the specific surface area is more than or equal to 50 square meters per gram.
5. The nano modified waterborne polyurethane composite material according to claim 2, wherein the water reducer is a polycarboxylate water reducer, and the alkali content is less than or equal to 0.2%;
the dispersion aid agent is selected from one or more of water-soluble alcohol, amino acid or sulfamic acid.
6. The nano-modified waterborne polyurethane composite material according to claim 1, wherein the polyether polyol is one or more of polyoxypropylene glycol, polytetrahydrofuran glycol and tetrahydrofuran-propylene oxide copolyglycol.
7. The nano-modified waterborne polyurethane composite material according to claim 1, wherein the catalyst is an organometallic catalyst and is selected from one or more of dibutyltin dilaurate, stannous octoate, potassium iso-octoate, potassium acetate, potassium oleate, phenylmercuric acetate and zinc iso-octoate.
8. The nano-modified waterborne polyurethane composite material according to claim 1, wherein the temperature resistant modifier is PA6I/6T;
the hydrophilic chain extender is 1, 4-butanediol.
9. The nano-modified waterborne polyurethane composite material according to claim 1, wherein the neutralizing agent is one or more of triethylamine, N-dimethylethanolamine, triethanolamine, methyldiethanolamine, diisopropylcyclohexylamine, N-methylmorpholine, 2-amino-2-methyl-1-propanol and ammonia water.
10. A process for preparing a nano modified aqueous polyurethane composite material, which is used for preparing the nano modified aqueous polyurethane composite material as claimed in any one of claims 1 to 9, and further comprises the following steps:
s1, mixing toluene-2, 4-diisocyanate, polyether polyol and a hydrophilic chain extender, heating to 100-120 ℃ and stirring for reaction to obtain a mixture A;
s2, under the protection of inert gas, cooling the mixture A in the step S1 to 40-50 ℃, adding the modified nano composite dispersion liquid, the temperature-resistant modifier and the catalyst, heating to 80-90 ℃, and preserving heat for 2-3 hours to obtain a mixture B;
and S3, adding a neutralizing agent into the mixture B in the step S2, and uniformly stirring to obtain the nano modified waterborne polyurethane composite material.
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