CN116970361A - Waterborne polyurethane colloid, preparation method thereof and application of waterborne polyurethane colloid - Google Patents
Waterborne polyurethane colloid, preparation method thereof and application of waterborne polyurethane colloid Download PDFInfo
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- CN116970361A CN116970361A CN202310978543.XA CN202310978543A CN116970361A CN 116970361 A CN116970361 A CN 116970361A CN 202310978543 A CN202310978543 A CN 202310978543A CN 116970361 A CN116970361 A CN 116970361A
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- component
- epoxy resin
- aqueous polyurethane
- colloid
- ultra
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- 239000004814 polyurethane Substances 0.000 title claims abstract description 187
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 186
- 239000000084 colloidal system Substances 0.000 title claims abstract description 146
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000004699 Ultra-high molecular weight polyethylene Substances 0.000 claims abstract description 78
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 78
- 229920000785 ultra high molecular weight polyethylene Polymers 0.000 claims abstract description 78
- 239000004745 nonwoven fabric Substances 0.000 claims abstract description 75
- 239000003822 epoxy resin Substances 0.000 claims abstract description 70
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 70
- -1 silane hydrocarbon Chemical class 0.000 claims abstract description 43
- 239000012948 isocyanate Substances 0.000 claims abstract description 27
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 27
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims abstract description 25
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 25
- 239000004359 castor oil Substances 0.000 claims abstract description 25
- 235000019438 castor oil Nutrition 0.000 claims abstract description 25
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 25
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 claims abstract description 25
- 239000002904 solvent Substances 0.000 claims abstract description 23
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 11
- 239000003054 catalyst Substances 0.000 claims abstract description 11
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 11
- 229910000077 silane Inorganic materials 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000004593 Epoxy Substances 0.000 claims description 67
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 30
- 239000000203 mixture Substances 0.000 claims description 25
- 238000003756 stirring Methods 0.000 claims description 21
- 239000000835 fiber Substances 0.000 claims description 19
- 239000004848 polyfunctional curative Substances 0.000 claims description 16
- 239000004642 Polyimide Substances 0.000 claims description 15
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 15
- 229920001721 polyimide Polymers 0.000 claims description 15
- 239000004944 Liquid Silicone Rubber Substances 0.000 claims description 14
- 229920002379 silicone rubber Polymers 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 13
- 239000003292 glue Substances 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 239000004698 Polyethylene Substances 0.000 claims description 5
- 239000000416 hydrocolloid Substances 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 229920000573 polyethylene Polymers 0.000 claims description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- 229910021485 fumed silica Inorganic materials 0.000 claims description 4
- 238000005520 cutting process Methods 0.000 claims description 3
- 239000004744 fabric Substances 0.000 claims description 3
- 238000004804 winding Methods 0.000 claims description 3
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 2
- UWFRVQVNYNPBEF-UHFFFAOYSA-N 1-(2,4-dimethylphenyl)propan-1-one Chemical compound CCC(=O)C1=CC=C(C)C=C1C UWFRVQVNYNPBEF-UHFFFAOYSA-N 0.000 claims description 2
- SYEWHONLFGZGLK-UHFFFAOYSA-N 2-[1,3-bis(oxiran-2-ylmethoxy)propan-2-yloxymethyl]oxirane Chemical compound C1OC1COCC(OCC1OC1)COCC1CO1 SYEWHONLFGZGLK-UHFFFAOYSA-N 0.000 claims description 2
- HPILSDOMLLYBQF-UHFFFAOYSA-N 2-[1-(oxiran-2-ylmethoxy)butoxymethyl]oxirane Chemical compound C1OC1COC(CCC)OCC1CO1 HPILSDOMLLYBQF-UHFFFAOYSA-N 0.000 claims description 2
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 2
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 claims description 2
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 claims description 2
- 239000013522 chelant Substances 0.000 claims description 2
- 238000013329 compounding Methods 0.000 claims description 2
- GLTDLAUASUFHNK-UHFFFAOYSA-N n-silylaniline Chemical compound [SiH3]NC1=CC=CC=C1 GLTDLAUASUFHNK-UHFFFAOYSA-N 0.000 claims description 2
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000003208 petroleum Substances 0.000 claims description 2
- 239000012974 tin catalyst Substances 0.000 claims description 2
- 229920001296 polysiloxane Polymers 0.000 claims 1
- VEDJZFSRVVQBIL-UHFFFAOYSA-N trisilane Chemical compound [SiH3][SiH2][SiH3] VEDJZFSRVVQBIL-UHFFFAOYSA-N 0.000 claims 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 21
- 230000035939 shock Effects 0.000 abstract description 19
- 239000010410 layer Substances 0.000 description 38
- 230000000052 comparative effect Effects 0.000 description 27
- 238000012360 testing method Methods 0.000 description 20
- 239000002994 raw material Substances 0.000 description 15
- 239000000499 gel Substances 0.000 description 13
- ORTUYCUWCKNIND-UHFFFAOYSA-N 3-[2-(2-aminoethylamino)ethylamino]propanenitrile Chemical compound NCCNCCNCCC#N ORTUYCUWCKNIND-UHFFFAOYSA-N 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 12
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 12
- 239000004952 Polyamide Substances 0.000 description 11
- 229920002647 polyamide Polymers 0.000 description 11
- 230000000694 effects Effects 0.000 description 10
- 239000011259 mixed solution Substances 0.000 description 10
- 238000007599 discharging Methods 0.000 description 8
- 230000035515 penetration Effects 0.000 description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 238000004132 cross linking Methods 0.000 description 5
- 229910021389 graphene Inorganic materials 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 239000012286 potassium permanganate Substances 0.000 description 5
- 238000010008 shearing Methods 0.000 description 5
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 4
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 4
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 4
- 229920000768 polyamine Polymers 0.000 description 4
- 230000003014 reinforcing effect Effects 0.000 description 4
- 239000002356 single layer Substances 0.000 description 4
- 230000002195 synergetic effect Effects 0.000 description 4
- 230000008685 targeting Effects 0.000 description 4
- 230000008719 thickening Effects 0.000 description 4
- 108010010803 Gelatin Proteins 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000008273 gelatin Substances 0.000 description 3
- 229920000159 gelatin Polymers 0.000 description 3
- 235000019322 gelatine Nutrition 0.000 description 3
- 235000011852 gelatine desserts Nutrition 0.000 description 3
- 229910052901 montmorillonite Inorganic materials 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 239000005995 Aluminium silicate Substances 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- 235000012211 aluminium silicate Nutrition 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 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
- 238000010030 laminating Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000003892 spreading Methods 0.000 description 2
- 230000007480 spreading Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- IBVAQQYNSHJXBV-UHFFFAOYSA-N adipic acid dihydrazide Chemical compound NNC(=O)CCCCC(=O)NN IBVAQQYNSHJXBV-UHFFFAOYSA-N 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001409 amidines Chemical class 0.000 description 1
- 229920003180 amino resin Polymers 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- DDSWIYVVHBOISO-UHFFFAOYSA-N ctk0i1982 Chemical compound N[SiH](N)N DDSWIYVVHBOISO-UHFFFAOYSA-N 0.000 description 1
- 230000004069 differentiation Effects 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 229920006158 high molecular weight polymer Polymers 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229920003987 resole Polymers 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 230000009974 thixotropic effect Effects 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- 239000012745 toughening agent Substances 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/12—Layered products comprising a layer of synthetic resin next to a fibrous or filamentary layer
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
- B32B5/022—Non-woven fabric
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
- B32B2262/02—Synthetic macromolecular fibres
- B32B2262/0253—Polyolefin fibres
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/558—Impact strength, toughness
-
- 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
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
-
- 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
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
The application relates to the technical field of ultra-high molecular weight polyethylene non-woven fabrics, in particular to a waterborne polyurethane colloid, a preparation method thereof and application of the waterborne polyurethane colloid; the waterborne polyurethane colloid comprises a component A and a component B, wherein the component A comprises closed isocyanate, a silane hydrocarbon solvent, an epoxy resin curing agent and an auxiliary agent: the component B comprises waterborne polyurethane, epoxy resin, an organosilicon cross-linking agent, a catalyst, an epoxy resin solvent and the balance of water; the auxiliary agent comprises the following components in percentage by mass (2-3): 1:1, polyoxyethylene hydrogenated castor oil and an auxiliary agent A. The waterborne polyurethane colloid has better shear strength and the ultra-high molecular weight polyethylene non-woven fabric prepared by adopting the waterborne polyurethane colloid has excellent shock resistance through the compatibility of the blocked isocyanate, the epoxy resin curing agent, the organosilicon crosslinking agent, the waterborne polyurethane, the epoxy resin, the modified graphene and the polyoxyethylene hydrogenated castor oil.
Description
Technical Field
The application relates to the technical field of ultra-high molecular weight polyethylene non-woven fabrics, in particular to a waterborne polyurethane colloid, a preparation method thereof and application of the waterborne polyurethane colloid.
Background
The ultra-high molecular weight polyethylene non-woven fabric is prepared by uniformly spreading silk by using ultra-high molecular weight polyethylene as a base material through a textile production line, coating glue solution to prepare single-layer non-woven fabric, and then laminating the single-layer non-woven fabric in a single-layer 0 DEG/90 DEG orthogonal arrangement manner or laminating the single-layer non-woven fabric in a multi-layer structure in a composite manner according to the fiber direction to prepare the composite non-woven fabric. The ultra-high molecular weight polyethylene non-woven fabric has high strength and high modulus, and the breaking of the ultra-high molecular weight polyethylene non-woven fabric can absorb the energy of bullets well, and is mainly used for producing bulletproof and explosion-proof equipment such as bulletproof clothes, bulletproof helmets, bulletproof boards, explosion-proof carpets and the like.
In the current ultra-high molecular weight polyethylene non-woven fabric manufacturing industry, the main stream of colloid is water-based polyurethane, and chemical components including epoxy, modified phenolic aldehyde, dispersing agent, wetting agent and the like are matched, wherein the mass ratio of polyurethane is 25-30%, and the rest is solvent and water; in the current production process, the actual conditions of poor colloid dispersibility, effective substance reduction caused by easy precipitation, uneven sizing and the like exist, so that the adhesiveness between the prepared ultra-high molecular weight polyethylene non-woven fabrics and the film forming property on the surfaces of the non-woven fabrics are poor, and the shock resistance is poor.
Disclosure of Invention
In order to solve the problem that the ultra-high molecular weight polyethylene non-woven fabric prepared by the existing aqueous polyurethane colloid is poor in shock resistance, the application provides the aqueous polyurethane colloid, a preparation method thereof and application of the aqueous polyurethane colloid.
In a first aspect, the present application provides a waterborne polyurethane colloid.
A waterborne polyurethane colloid comprises a component A and a component B, wherein, the percentage of the total weight of the component A and the component B is calculated,
the component A comprises 1.5 to 2.5 percent of closed isocyanate, 6 to 10 percent of auxiliary agent, 2 to 4 percent of epoxy resin curing agent and 0.5 to 1.5 percent of silane hydrocarbon solvent:
the component B comprises 28-20% of waterborne polyurethane, 3-5% of epoxy resin, 3-8% of organosilicon cross-linking agent, 0.1-0.3% of catalyst, 3-5% of epoxy resin solvent and the balance of water;
the auxiliary agent comprises the following components in percentage by mass (2-3): 1:1, polyoxyethylene hydrogenated castor oil and an auxiliary agent A.
Through adopting above-mentioned technical scheme, adopt closure isocyanate, epoxy resin curing agent, organosilicon cross-linking agent, waterborne polyurethane, epoxy, modified graphene and polyoxyethylene hydrogenated castor oil to match and use for the rete that waterborne polyurethane colloid formed has excellent toughness, intensity, has promoted the bonding strength between the ultra-high molecular weight polyethylene non-woven fabrics layer and the layer, and then makes the ultra-high molecular weight polyethylene non-woven fabrics that adopts the preparation of waterborne polyurethane colloid have excellent shock resistance.
On the one hand, the polyoxyethylene hydrogenated castor oil has better thixotropic and thickening effects, and the organic silicon cross-linking agent and the polyoxyethylene hydrogenated castor oil can improve the dispersion effect of raw materials in the aqueous polyurethane colloid, so that the components in a film layer formed by the aqueous polyurethane colloid are more uniformly supplemented.
On the other hand, the thickening effect of the polyoxyethylene hydrogenated castor oil is cooperated with the epoxy resin and the epoxy resin curing agent, so that the attaching effect of the waterborne polyurethane colloid on the fiber is improved; the aqueous polyurethane colloid is uniformly adhered to the ultra-high molecular weight polyethylene, so that a film layer formed by the aqueous polyurethane colloid has excellent toughness and strength.
Further, under the condition of high temperature, the closed isocyanate and the epoxy resin curing agent cooperate with each other, the modified graphene, the organosilicon crosslinking agent, the epoxy resin and the improved aqueous polyurethane colloid form a film layer with a network structure with good elasticity, and the film layer has excellent elasticity, toughness and strength and good bonding strength between the ultra-high molecular weight polyethylene non-woven fabrics, so that the impact resistance of the ultra-high molecular weight polyethylene non-woven fabrics prepared by adopting the aqueous polyurethane colloid is improved.
Preferably, the epoxy resin curing agent is a combination of a room temperature epoxy curing agent, a medium temperature epoxy curing agent and a high temperature epoxy curing agent.
Preferably, the room temperature epoxy hardener is aliphatic polyamine, alicyclic polyamine; one of low molecular polyamides and modified aromatic amines;
the medium-temperature epoxy curing agent is one of partial alicyclic polyamine, tertiary amine, amidine and boron trifluoride complex which belong to medium-temperature curing;
the high-temperature epoxy curing agent is one of aromatic polyamine, anhydride, resol, amino resin, dicyandiamide and hydrazide.
By adopting the technical scheme, the room temperature epoxy curing agent (the curing temperature is 20-50 ℃), the medium temperature epoxy curing agent (the curing temperature is 50-100 ℃) and the high temperature epoxy curing agent (the curing temperature is more than 100 ℃) are adopted in the waterborne polyurethane colloid, so that the waterborne polyurethane colloid has certain viscosity and certain fluidity before curing; the epoxy resin curing agent reacts with active groups of other raw materials in a gradient manner, so that a film layer formed by the waterborne polyurethane colloid is uniform and has toughness, strength and bonding strength, and further the impact resistance of the ultra-high molecular weight polyethylene non-woven fabric prepared by the waterborne polyurethane colloid is improved.
Preferably, the epoxy resin curing agent is prepared from the following components in percentage by mass: 2: (0.5-4) a room temperature epoxy hardener, a medium temperature epoxy hardener, and a high temperature epoxy hardener.
By adopting the technical scheme, the impact resistance of the ultra-high molecular weight polyethylene non-woven fabric prepared by adopting the waterborne polyurethane colloid is further improved by optimizing the dosages of the room temperature epoxy curing agent, the medium temperature epoxy curing agent and the high temperature epoxy curing agent.
Preferably, the auxiliary agent A comprises at least one of fumed silica, calcium carbonate, liquid silicone rubber, polyimide and nano titanium dioxide.
By adopting the technical scheme, the auxiliary agent A is adopted in the waterborne polyurethane colloid, so that the toughness and strength of a film layer formed by the waterborne polyurethane colloid and the bonding strength between the layers of the ultra-high molecular weight polyethylene non-woven fabric are improved, and the shock resistance of the ultra-high molecular weight polyethylene non-woven fabric prepared by the waterborne polyurethane colloid is further improved.
Preferably, the auxiliary agent A is prepared from the following components in percentage by mass (2-3): 1:2, a polyimide, and a calcium carbonate.
By adopting the technical scheme, the auxiliary agent A adopts the following components in mass ratio (2-3): 1:2, the composition of the liquid silicone rubber, polyimide and calcium carbonate further improves the toughness and strength of a film layer formed by the aqueous polyurethane colloid and the bonding strength between the ultra-high molecular weight polyethylene non-woven fabrics layers.
The liquid silicone rubber can react with an organosilicon cross-linking agent, aqueous polyurethane and epoxy resin under certain conditions to form a cross-linked network structure; the polyimide and the calcium carbonate are better used for reinforcing a network structure formed by the liquid silicone rubber, so that the toughness and strength of a film layer formed by the aqueous polyurethane colloid and the bonding strength between the film layer and the ultra-high molecular weight polyethylene non-woven fabric are further improved, and the shock resistance of the ultra-high molecular weight polyethylene non-woven fabric prepared by the aqueous polyurethane colloid is further improved.
Preferably, the epoxy resin solvent is one of butanediol diglycidyl ether, glycerol triglycidyl ether and ethylene glycol diglycidyl ether; the silane hydrocarbon solvent is one of benzene, toluene and petroleum ether.
Through adopting above-mentioned technical scheme, adopt epoxy solvent and silane hydrocarbon solvent to make have good compatibility between each raw materials in the aqueous polyurethane colloid, and then make the rete that aqueous polyurethane colloid formed more even, and then promote the shock resistance of the ultra-high molecular weight polyethylene non-woven fabrics that adopts aqueous polyurethane colloid to prepare.
Preferably, the catalyst is a chelate tin catalyst.
By adopting the technical scheme, the catalyst promotes the organosilicon cross-linking agent, the closed isocyanate and the liquid silicone rubber to carry out cross-linking reaction, so that the cross-linking density and strength of a film layer formed by the waterborne polyurethane are improved, and further, the shock resistance of the ultra-high molecular weight polyethylene non-woven fabric prepared by adopting the waterborne polyurethane colloid is improved.
Preferably, the organosilicon cross-linking agent is one of gamma-aminopropyl trimethoxysilane, gamma-aminopropyl triethoxysilane, N-beta- (aminoethyl) -gamma-aminopropyl trimethoxysilane, phenylamino-silane, triamino silane, gamma-mercaptopropyl trimethoxysilane, gamma-ureido propyl trihexyloxy silane and gamma-methacryloxypropyl trimethoxysilane.
By adopting the technical scheme, the organosilicon cross-linking agent is optimized, so that the cross-linking strength and toughness of a film layer formed by the waterborne polyurethane are improved, and the shock resistance of the ultra-high molecular weight polyethylene non-woven fabric prepared by adopting the waterborne polyurethane colloid is further improved.
In one aspect, the application provides a method for preparing a waterborne polyurethane colloid.
The preparation method of the waterborne polyurethane colloid comprises the following specific preparation steps:
preparation of component A: mixing the blocked isocyanate, the auxiliary agent, the epoxy resin curing agent and the silane hydrocarbon solvent, and stirring for 20-30min under the conditions of 20-30 ℃ and 200-400rpm/min to obtain a component A;
preparing a component B; firstly, mixing epoxy resin, an organosilicon cross-linking agent, a catalyst and an epoxy resin solvent, and stirring for 10-20min under the conditions of 20-30 ℃ and 200-400rpm/min to form a first mixture; adding water into the aqueous polyurethane and mixing to form a second mixture; then adding the first mixture into the second mixture at 20-30deg.C under 2000-4000rpm/min, and stirring for 30-40min to obtain component B.
By adopting the technical scheme, the A component and the B component of the prepared aqueous polyurethane colloid have better dispersibility and stability.
In another aspect, the present application provides an application of the aqueous polyurethane colloid.
The method for preparing the ultra-high molecular weight polyethylene non-woven fabric by adopting the aqueous polyurethane colloid provided by the application comprises the following steps:
(1) The mass ratio is 1: mixing the component A and the component B of (1-1.3), stirring for 10-20min at the temperature of 20-25 ℃ and the rotating speed of 200-400rpm/min to prepare aqueous polyurethane colloid, and placing the prepared aqueous polyurethane colloid in an environment of 18-22 ℃ for later use; (2) paving ultra-high molecular weight polyethylene fibers; (3) Drawing the paved ultra-high molecular weight polyethylene fibers through a glue groove, simultaneously conveying the aqueous polyurethane colloid to the glue groove to be compounded with the ultra-high molecular weight polyethylene fibers, and then compounding the ultra-high molecular weight polyethylene after the glue is attached with a low-melting-point polyethylene film to prepare unidirectional non-woven fabrics; (4) drying and winding the unidirectional laid cloth; (5) Cutting the unidirectional non-woven fabric, performing secondary cross stacking by adopting a method of 0 degree/90 degrees, and heating and pressurizing to prepare the ultra-high molecular weight polyethylene non-woven fabric;
the temperature of the glue tank is 30-50 ℃; the drying condition is that the temperature is 80-110 ℃ and the drying time is 20-40min; the temperature of heating and pressurizing is 80-110 ℃.
By adopting the technical scheme, the temperature of the glue tank, the drying temperature and the composite temperature of the unidirectional non-woven fabric are set to be suitable for the room temperature epoxy curing agent, the medium temperature epoxy curing agent and the high temperature epoxy curing agent, and the room temperature epoxy curing agent reacts under the action of the temperature of the glue tank, so that the adhesion of the waterborne polyurethane colloid on the ultra-high molecular weight polyethylene non-woven fabric is improved; under the action of the drying temperature, the medium-temperature epoxy curing agent and the high-temperature epoxy curing agent sequentially react to form a network structure in cooperation with the activated closed isocyanate, and the network structure is formed by the reaction of the closed isocyanate, the epoxy resin and/or the aqueous polyurethane, the modified graphene, the organosilicon crosslinking agent and/or the liquid silicone rubber, so that the toughness and the strength of a film layer formed by the aqueous polyurethane colloid and the bonding strength between the ultra-high molecular weight polyethylene non-woven fabrics are improved, and the shock resistance of the ultra-high molecular weight polyethylene non-woven fabrics prepared by the aqueous polyurethane colloid is further improved.
In summary, the application has the following beneficial effects:
1. according to the application, the sealing isocyanate, the epoxy resin curing agent, the organosilicon crosslinking agent, the waterborne polyurethane, the epoxy resin, the modified graphene and the polyoxyethylene hydrogenated castor oil are adopted for compatibility, so that the film layer formed by the waterborne polyurethane colloid has excellent toughness and strength; on one hand, the organosilicon cross-linking agent and polyoxyethylene hydrogenated castor oil can improve the dispersion effect of raw materials in the aqueous polyurethane colloid; on the other hand, the thickening effect of the polyoxyethylene hydrogenated castor oil is cooperated with the epoxy resin and the epoxy resin curing agent, so that the attaching effect of the waterborne polyurethane colloid on the fiber is improved; further, under the condition of high temperature, the closed isocyanate and the epoxy resin curing agent cooperate with each other, and the modified graphene, the organosilicon crosslinking agent, the epoxy resin and the improved aqueous polyurethane colloid form a film layer with a network structure with good elasticity, so that the aqueous polyurethane colloid has good shear strength and the ultra-high molecular weight polyethylene non-woven fabric prepared by adopting the aqueous polyurethane colloid has excellent shock resistance.
2. The epoxy resin curing agent adopts a composition of a room-temperature epoxy curing agent, a medium-temperature epoxy curing agent and a high-temperature epoxy curing agent, and the epoxy resin curing agent reacts with active groups of other raw materials in a gradient manner, so that a film layer formed by the waterborne polyurethane colloid is uniform and has toughness and strength, and the shock resistance of the ultra-high molecular weight polyethylene non-woven fabric prepared by the waterborne polyurethane colloid is improved.
3. Adopting the auxiliary agent A as the mass ratio of (2-3): 1:2, the toughness and strength of a film layer formed by the aqueous polyurethane colloid and the bonding strength between the ultra-high molecular weight polyethylene non-woven fabrics layers are further improved, and further the shock resistance of the ultra-high molecular weight polyethylene non-woven fabrics prepared by the aqueous polyurethane colloid is improved.
Detailed Description
Raw materials
Calcium carbonate (average particle size 15 μm), titanium dioxide (average particle size 50 nm), kaolin (particle size: 10 μm), montmorillonite (particle size: 10 μm), gelatin (food grade, executive standard national standard), polyimide (brand: TS2400W/TS1450, supplier: ganzhen chemical Co., ltd.), blocked isocyanate (model: PT-1080Y; supplier: guangzhou green and St. Limited), graphene (particle size: 10 μm), polyoxyethylene hydrogenated castor oil (model: HEL-40), hydroxyethyl cellulose (model: 250HBR, manufacturer: sub-cross-dragon), waterborne polyurethane (supplier: deep-field chemical Co., ltd., model: FO 401), epoxy resin (brand: bisphenol A epoxy resin E-44), polyamide (viscosity PA S/25 ℃ C.: 7000), N-cyanoethyl diethylenetriamine (viscosity: 700-1000mPa. S), liquid silicone rubber (model: GJ-3, supplier: north China solid technology Co., ltd.), silica (HL-300, supplier: ultra-high molecular weight polyethylene (ultra-high molecular weight: 3, hem. Co., ltd.)), polyethylene (model: 3, ultra-high molecular weight polymer: 0.0.98/0 g.m.)), polyethylene film (model: ultra-0..
Examples
Example 1, a waterborne polyurethane colloid, which is prepared by adopting the following raw materials in table 1, comprises the following specific preparation steps:
preparation of component A: adding the blocked isocyanate, the silane hydrocarbon solvent, the epoxy resin curing agent and the auxiliary agent into a reaction kettle, stirring for 20min at the temperature of 20 ℃ and the rotating speed of 400rpm/min to prepare a component A, and discharging for later use.
Preparing a component B; firstly, adding epoxy resin, an organosilicon cross-linking agent, a catalyst and an epoxy resin solvent into a reaction kettle, stirring for 10min at the temperature of 20 ℃ and the rotating speed of 200rpm/min to form a first mixture, and discharging for standby.
Then adding water and aqueous polyurethane into a reaction kettle, stirring to form a second mixture, and heating to 20 ℃; and adding the first mixture into the second mixture at the rotating speed of 4000rpm/min, continuously stirring for 30min to prepare the component B, and discharging for later use.
The modified graphene is prepared by adding graphene into a mixed solution of concentrated sulfuric acid and potassium permanganate, continuously treating the mixed solution with ultrasonic waves for 2 hours at the temperature of 30 ℃, and then washing, filtering and drying the treated mixed solution.
Wherein, the mixed solution of the concentrated sulfuric acid and the potassium permanganate is obtained by mixing 100ml of concentrated sulfuric acid and 10g of potassium permanganate; the ratio of the mass (g) of the graphene to the volume (ml) of the concentrated sulfuric acid is 1:10.
Example 2, a waterborne polyurethane colloid, is different from example 1 in the weight and types of raw materials adopted in the waterborne polyurethane, and specifically, as shown in table 1, the preparation process parameter settings of the waterborne polyurethane colloid are different, and specifically, the following steps are adopted:
preparation of component A: adding the blocked isocyanate, the silane hydrocarbon solvent, the epoxy resin curing agent and the auxiliary agent into a reaction kettle, stirring for 25min at the temperature of 25 ℃ and the rotating speed of 300rpm/min to prepare a component A, and discharging for later use.
Preparing a component B; firstly, adding epoxy resin, an organosilicon cross-linking agent, a catalyst and an epoxy resin solvent into a reaction kettle, stirring for 15min at the temperature of 25 ℃ and the rotating speed of 300rpm/min to form a first mixture, and discharging for standby.
Then adding water and aqueous polyurethane into a reaction kettle, stirring to form a second mixture, and heating to 25 ℃; the first mixture was added to the second mixture at 3000rpm/min and stirring was continued for 35min to prepare component B, which was discharged for further use.
The modified graphene is prepared by adding graphene into a mixed solution of concentrated sulfuric acid and potassium permanganate, continuously treating the mixed solution with ultrasonic waves for 3 hours at the temperature of 40 ℃, and then washing, filtering and drying the mixed solution.
Example 3, a waterborne polyurethane colloid, is different from example 1 in the weight and variety of the raw materials adopted in the waterborne polyurethane, and specifically, as shown in table 1, the preparation process parameter settings of the waterborne polyurethane colloid are different, and specifically, the following steps are adopted: preparation of component A: adding the blocked isocyanate, the silane hydrocarbon solvent, the epoxy resin curing agent and the auxiliary agent into a reaction kettle, stirring for 20-30min at the temperature of 30 ℃ and the rotating speed of 200rpm/min to prepare a component A, and discharging for later use.
Preparing a component B; firstly, adding epoxy resin, an organosilicon cross-linking agent, a catalyst and an epoxy resin solvent into a reaction kettle, stirring for 20min at the temperature of 30 ℃ and the rotating speed of 400rpm/min to form a first mixture, and discharging for standby.
Then adding water and aqueous polyurethane into a reaction kettle, stirring to form a second mixture, heating to 30 ℃, adding the first mixture into the second mixture at the rotating speed of 2000rpm/min, continuously stirring for 40min to prepare a component B, and discharging for later use.
The modified graphene is prepared by adding graphene into a mixed solution of concentrated sulfuric acid and potassium permanganate, continuously treating the mixed solution with ultrasonic waves for 4 hours at 50 ℃, and then washing, filtering and drying the treated mixed solution.
Example 4, a waterborne polyurethane gel, was different from example 1 in the weight and types of raw materials used in the waterborne polyurethane, and is shown in table 1.
TABLE 1 list of the types and amounts of raw materials in the aqueous polyurethane colloids of examples 1 to 4
Example 5, a waterborne polyurethane colloid, differs from example 1 in that the epoxy resin curing agent adopts a mass ratio of 1:2:0.5 polyamide, N-cyanoethyldiethylenetriamine and dicyandiamide.
Example 6, a waterborne polyurethane colloid, differs from example 1 in that the epoxy resin curing agent adopts a mass ratio of 1:2:1 polyamide, N-cyanoethyldiethylenetriamine and dicyandiamide.
Example 7, a waterborne polyurethane colloid, differs from example 1 in that the epoxy resin curing agent adopts a mass ratio of 1:2: 1-hexamethylenediamine, 2-methylimidazole and adipic acid dihydrazide.
Example 8, a waterborne polyurethane colloid, differs from example 1 in that the epoxy resin curing agent adopts a mass ratio of 1:2:3 polyamide, N-cyanoethyldiethylenetriamine and dicyandiamide.
Example 9, a waterborne polyurethane colloid, differs from example 1 in that the epoxy resin curing agent adopts a mass ratio of 1:2:4 polyamide, N-cyanoethyldiethylenetriamine and dicyandiamide.
Example 10, a waterborne polyurethane gel, differs from example 1 in that a polyamide (room temperature epoxy curative) was substituted in equal amounts for N-cyanoethyldiethylenetriamine (medium temperature epoxy curative).
Example 11, a waterborne polyurethane gel, differs from example 1 in that N-cyanoethyldiethylenetriamine (medium temperature epoxy hardener) was used to replace the polyamide (room temperature epoxy hardener) and dicyandiamide (high temperature epoxy hardener) in equal amounts.
Example 12, a waterborne polyurethane gel, differs from example 1 in that dicyandiamide (high temperature epoxy hardener) is used to replace the polyamide (room temperature epoxy hardener) and N-cyanoethyl diethylenetriamine (medium temperature epoxy hardener) in equal amounts.
Example 13, a waterborne polyurethane colloid, differs from example 1 in that the auxiliary agent A is used in a mass ratio of 2:1:2, a polyimide, and a calcium carbonate.
Example 14, a waterborne polyurethane colloid, differs from example 1 in that the auxiliary agent A has a mass ratio of 3:1:2, a polyimide, and a calcium carbonate.
Example 15, a waterborne polyurethane gel, differs from example 1 in that; adopting fumed silica to replace liquid silicone rubber in equal quantity; the epoxy resin curing agent is dicyandiamide only.
Example 16, a waterborne polyurethane gel, differs from example 1 in that liquid silicone rubber is used to replace the polyimide and calcium carbonate in equal amounts; the epoxy resin curing agent is dicyandiamide only.
Example 17, an application of a waterborne polyurethane colloid, a method for preparing an ultra-high molecular weight polyethylene non-woven fabric by adopting the waterborne polyurethane colloid, comprises the following preparation steps:
(1) And stirring the component A and the component B of the aqueous polyurethane colloid for 10min at the temperature of 20 ℃ and the rotating speed of 300rmp/min to prepare the aqueous polyurethane colloid.
(2) And placing the cylindrical ultrahigh molecular weight polyethylene fibers in a yarn-removing frame for yarn laying.
(3) Uniformly spreading the ultra-high molecular weight polyethylene fibers by a traction roller and a yarn dividing device.
(4) Transporting the uniformly spread ultra-high molecular weight polyethylene through a glue groove by using a tractor; and (3) conveying the aqueous polyurethane colloid (adopting the embodiment 1) to a colloid tank with the temperature of 30 ℃, enabling the ultra-high molecular weight polyethylene fiber to be adhered by rotating an adhesive applying roller, and then compositing the ultra-high molecular weight polyethylene uniformly paved after adhering with a low-melting-point polyethylene film to prepare the unidirectional non-woven fabric.
(5) And the unidirectional non-woven fabric is dried for 20min by a dryer with the temperature of 80 ℃ under the action of a tractor, and then is wound by a winding machine.
(6) Cutting unidirectional non-woven fabric, performing secondary cross stacking by 0/90 deg. method, and heating and pressurizing (110 deg.C, 60 t/m) 2 ) An ultra-high molecular weight polyethylene nonwoven fabric (density: 120+ -10 g/m 2 )。
Examples 18-19, an aqueous polyurethane gel, were used with the differences from example 17 in the process parameters and aqueous polyurethane gel settings used, as shown in Table 2.
Table 2 list of process parameters and settings of the aqueous polyurethane colloids used in the method for preparing ultra-high molecular weight polyethylene nonwoven fabrics using the aqueous polyurethane colloids of examples 17 to 19
| Differentiation of | Example 17 | Example 18 | Example 19 |
| Glue groove temperature/DEGC | 30 | 40 | 50 |
| Drying temperature/. Degree.C | 80 | 100 | 110 |
| Drying time/min | 20 | 30 | 40 |
| Pressure temperature/. Degree.C | 110 | 100 | 80 |
| Aqueous polyurethane colloid | Example 1 | Example 2 | Example 3 |
| Mass ratio of component A to component B | 1：1 | 1：1.2 | 1：1.3 |
Examples 20-32, the use of a hydrocolloid, differs from example 17 in that the hydrocolloid is used in examples 4-16 in sequence.
Comparative example
Comparative example 1, a waterborne polyurethane colloid, differs from example 1 in that the epoxy resin is substituted for the blocked isocyanate in equal amounts; the modified graphene is replaced by kaolin in an equivalent way, and the polyoxyethylene hydrogenated castor oil is replaced by hydroxyethyl cellulose in an equivalent way.
Comparative example 2, a waterborne polyurethane colloid, differs from example 1 in that the epoxy curative N-cyanoethyldiethylenetriamine is equivalent to the blocked isocyanate; montmorillonite is adopted to substitute modified graphene in an equivalent way, and hydroxyethyl cellulose is adopted to substitute polyoxyethylene hydrogenated castor oil in an equivalent way.
Comparative example 3, a waterborne polyurethane colloid, differs from example 1 in that the epoxy curative N-cyanoethyldiethylenetriamine is equivalent to the blocked isocyanate; montmorillonite equivalent replaced modified graphene and gelatin equivalent replaced polyoxyethylene hydrogenated castor oil.
Comparative example 4, a waterborne polyurethane gel, differs from example 1 in that the blocked isocyanate is substituted for the medium temperature epoxy hardener and the high temperature epoxy hardener in equal amounts; and the polyoxyethylene hydrogenated castor oil is adopted to equivalently replace the room-temperature epoxy curing agent.
Comparative example 5, a waterborne polyurethane gel, differs from example 1 in that no blocked isocyanate is used.
Comparative example 6, a waterborne polyurethane gel, differs from example 1 in that no epoxy curing agent was used.
Comparative example 7, a waterborne polyurethane gel, differs from example 1 in that no epoxy curing agent and no blocked isocyanate are used.
Comparative example 8, a waterborne polyurethane gel, differs from example 1 in that the composition of component A and component B is as follows:
the raw materials of the component A comprise the following components in parts by weight: 70g of poly adipic acid-1, 4-butanediol ester diol, 20g of a toughening agent, 3g of 1, 4-butanediol, 1.05g of organotin DBTDL, 5.5g of dicyandiamide, 5602g of a silane coupling agent KH, 2.5g of fumed silica and 2.0g of modified graphene;
the raw materials of the component B comprise the following components in parts by weight: 44g of toluene diisocyanate, 55g of epoxy resin and 10g of diglycidyl ether.
Comparative examples 9 to 16, the use of a hydrocolloid, which differs from example 17 in that the hydrocolloid is used in comparative examples 1 to 8 at a time.
Performance test
Test 1: shear strength
Reference is made to GB/T7124-2008 "determination of tensile shear Strength of Adhesives".
Test sample: taking the aqueous polyurethane colloid of the examples 1-16 as an example sample; the aqueous polyurethane colloids of comparative examples 1 to 8 were used as comparative examples.
Test results: the results of the test of the shear strength of the aqueous polyurethane colloids of examples 1 to 16 and comparative examples 1 to 8 are shown in Table 3.
Test 2: stability of
And fully mixing the component A and the component B of the aqueous polyurethane colloid according to the mass ratio of 1:1 at 20 ℃, standing for 48 hours at 20 ℃ after preparation, and observing layering condition of the aqueous polyurethane colloid.
Test 3: target test
The ultra-high molecular weight polyethylene nonwoven fabrics prepared in examples 17 to 32 and comparative examples 9 to 16 were cut into 40cm by 40cm size and formulated into a total areal density of 6kg/m by orthogonal lamination 2 The left and right test target pieces (75 layers of weftless fabric of each target piece) are used for manufacturing 2 samples of each test sample, each target piece is used for testing 6 guns, the number of layers penetrated by 6 bullets is tested, and the average value of the number of layers penetrated by the bullets of 12 guns of each test sample is taken; wherein the firearm is 54 pistol and bulletThe lead core bullet is 51 type lead core bullet with the diameter of 7.62mm and the bullet speed of 455 soil is 5m/s.
Test sample: the ultra-high molecular weight polyethylene non-woven fabrics prepared in examples 17-32 are used as example samples; the ultra-high molecular weight polyethylene nonwoven fabrics prepared in comparative examples 9 to 16 were used as comparative examples.
Test results: the test results of the number of penetration layers in the targeting test of the ultra high molecular weight polyethylene nonwoven fabrics prepared in examples 17 to 32 and comparative examples 8 to 15 are shown in Table 3.
TABLE 3 test results of shear strengths of the aqueous polyurethane colloids of examples 1 to 16 and comparative examples 1 to 8 and test results list of number of penetration layers of the targeting test of the ultra high molecular weight polyethylene nonwoven fabrics prepared in examples 17 to 32 and comparative examples 9 to 16
It can be seen in combination with examples 1-32 and comparative examples 1-16 and with Table 3 that:
the shear strength of the aqueous polyurethane colloid of examples 1-16 is higher than that of comparative examples 1-8, and the average number of penetration layers of the ultra-high molecular weight polyethylene non-woven fabrics prepared in examples 17-32 is lower than that of comparative examples 9-16, which shows that the aqueous polyurethane colloid has excellent toughness and strength due to the compatibility of the blocked isocyanate, the epoxy resin curing agent, the organosilicon crosslinking agent, the aqueous polyurethane, the epoxy resin, the modified graphene and the polyoxyethylene hydrogenated castor oil; on one hand, the organosilicon cross-linking agent and polyoxyethylene hydrogenated castor oil can improve the dispersion effect of raw materials in the aqueous polyurethane colloid; on the other hand, the thickening effect of the polyoxyethylene hydrogenated castor oil is cooperated with the epoxy resin and the epoxy resin curing agent, so that the attaching effect of the waterborne polyurethane colloid on the fiber is improved; further, under the condition of high temperature, the closed isocyanate and the epoxy resin curing agent cooperate with each other, and the modified graphene, the organosilicon crosslinking agent, the epoxy resin and the improved aqueous polyurethane colloid form a film layer with a network structure with better elasticity, so that the aqueous polyurethane colloid has higher shear strength and the ultra-high molecular weight polyethylene non-woven fabric prepared by adopting the aqueous polyurethane colloid has excellent shock resistance.
The aqueous polyurethane colloid of example 1 has higher shear strength than that of comparative examples 5-8, and the ultra-high molecular weight polyethylene nonwoven fabric prepared in example 17 has lower average penetration layer number than that of comparative examples 13-16, which indicates that the aqueous polyurethane colloid prepared by the combination of aqueous polyurethane, epoxy resin curing agent and blocked isocyanate has higher shear strength and the ultra-high molecular weight polyethylene nonwoven fabric prepared by the aqueous polyurethane colloid has excellent impact resistance compared with the aqueous polyurethane colloid by adopting the mixture of synthetic aqueous polyurethane monomer and epoxy resin. The molecular weight of the reacted aqueous polyurethane colloid is larger after the reaction, so that the formed network structure film layer is more crosslinked, and the film layer has higher strength and toughness.
The aqueous polyurethane colloid of example 1 has better shear strength and stability than those of comparative examples 1 to 4, and the ultra-high molecular weight polyethylene nonwoven fabric prepared in example 17 has a lower average number of penetration layers than those of comparative examples 9 to 12, possibly because the polyoxyethylene hydrogenated castor oil promotes the compatibility of the epoxy resin and the aqueous polyurethane compared with the hydroxyethyl cellulose and the gelatin, so that the aqueous polyurethane colloid containing the epoxy resin and the aqueous polyurethane is more stable; in contrast 4, the polyoxyethylene hydrogenated castor oil is used to replace the room temperature epoxy hardener in an equal amount, and the concentration of the aqueous polyurethane colloid is increased and the stability is reduced probably because the content of the polyoxyethylene hydrogenated castor oil is increased.
The polyoxyethylene hydrogenated castor oil and the room temperature epoxy curing agent are adopted in the aqueous polyurethane colloid for compatibility, so that the aqueous polyurethane colloid has better initial viscosity, and the adhesion of the aqueous polyurethane colloid on the ultra-high molecular weight polyethylene fiber is improved; the intermediate temperature epoxy curing agent, the high temperature epoxy curing agent and the closed isocyanate are used together, so that the aqueous polyurethane colloid reacts at different temperatures, and the shearing strength of the aqueous polyurethane colloid and the shock resistance of the ultra-high molecular weight polyethylene non-woven fabric prepared by the aqueous polyurethane colloid are improved.
The shearing strength of the aqueous polyurethane colloid of examples 1-9 is higher than that of examples 10-12, and the average number of penetration layers of the ultra-high molecular weight polyethylene non-woven fabrics prepared in examples 17-25 in a targeting test is lower than that of examples 26-28, which shows that in the aqueous polyurethane colloid, the epoxy curing agent adopts a room temperature epoxy curing agent, a medium temperature epoxy curing agent and a high temperature epoxy curing agent for compatibility, so that the shearing strength of the aqueous polyurethane colloid and the impact resistance of the ultra-high molecular weight polyethylene non-woven fabrics prepared by the aqueous polyurethane colloid are improved.
The possible reason for obtaining the beneficial effects is that the waterborne polyurethane colloid adopts the epoxy curing agent to form a film, the waterborne polyurethane colloid can better wrap the ultra-high molecular weight polyethylene fiber and react with the organosilicon cross-linking agent, the waterborne polyurethane, the epoxy resin, the modified graphene, the polyoxyethylene hydrogenated castor oil and the liquid silicone rubber to form a network structure, so that an integral body is formed between the ultra-high molecular weight polyethylene fiber, a better synergistic effect is generated, the waterborne polyurethane colloid has better shearing strength, and the prepared ultra-high molecular weight polyethylene non-woven fabric has excellent shock resistance.
The epoxy curing agent is prepared from a room temperature epoxy curing agent, a medium temperature epoxy curing agent and a high temperature epoxy curing agent, wherein the room temperature epoxy curing agent reacts when the waterborne polyurethane colloid is compounded with the ultra-high molecular weight polyethylene fiber, so that the viscosity of the waterborne polyurethane colloid is improved, and the room temperature epoxy curing agent is cooperated with polyoxyethylene hydrogenated castor oil, so that the adhesive quantity of the ultra-high molecular weight polyethylene fiber is improved; the medium-temperature epoxy curing agent and the high-temperature epoxy curing agent react respectively when the unidirectional non-woven fabric is dried and the unidirectional non-woven fabric is compounded with the unidirectional non-woven fabric, so that the curing time is prolonged, and the crosslinking degree of a network structure formed by the waterborne polyurethane colloid is further improved.
The waterborne polyurethane colloids of examples 6-8 have higher shear strength than those of examples 1, 5 and 9, and the ultra-high molecular weight polyethylene non-woven fabrics prepared in examples 22-24 have lower average penetration layer number than those of examples 17, 21 and 25, indicating that the epoxy resin curing agent adopts the following components in mass ratio of 1:2: (1-3) polyamide, N-cyanoethyl diethylenetriamine and dicyandiamide are used together, so that the shearing strength of the aqueous polyurethane colloid can be improved, and the shock resistance of the ultra-high molecular weight polyethylene non-woven fabric prepared by adopting the aqueous polyurethane colloid can be improved.
The possible reasons for obtaining the above-mentioned beneficial effects are that the mass ratio of polyamide, N-cyanoethyldiethylenetriamine and dicyandiamide is 1:2: in the step (1-3), the adhesive-attaching amount of the aqueous polyurethane colloid is proper, and the intermediate-temperature epoxy curing agent and the high-temperature epoxy curing agent react stepwise, so that the prepared ultra-high molecular weight polyethylene non-woven fabric not only forms a whole among the fibers of the unidirectional non-woven fabric, but also forms a whole among the layers of the unidirectional non-woven fabric, has a better synergistic effect, and improves the shock resistance of the ultra-high molecular weight polyethylene non-woven fabric prepared by adopting the aqueous polyurethane colloid.
The aqueous polyurethane colloids of examples 13 to 14 had higher shear strength than examples 15 to 16 and example 1, and the ultra-high molecular weight polyethylene nonwoven fabrics prepared in examples 29 to 30 had lower average number of penetration layers than examples 31 to 32 and example 17 in the targeting test, indicating that when the auxiliary agent A was used in a mass ratio of (2 to 3): 1:2, and the auxiliary agent A and other raw materials in the aqueous polyurethane colloid are better in synergistic effect, possibly because the liquid silicone rubber increases the crosslinking density of a network structure formed by the aqueous polyurethane colloid, and the polyimide and the calcium carbonate reinforce the strength and the toughness of the network structure formed by the aqueous polyurethane colloid.
When the content of the liquid silicone rubber is small, the formed network structure is less, the synergistic effect of the formed network structure and the reinforcing of polyimide and calcium carbonate is poor, and the reinforcing effect of the composition of polyimide and calcium carbonate on the film layer formed by the aqueous polyurethane colloid is poor.
When the content of the liquid silicone rubber is continuously increased, the content of polyimide and calcium carbonate is reduced, and the reinforcing effect of polyimide and calcium carbonate on a network structure formed by the aqueous polyurethane colloid is weakened, so that the shock resistance of the ultra-high molecular weight polyethylene non-woven fabric prepared by adopting the aqueous polyurethane colloid is reduced.
The present embodiment is only for explanation of the present application and is not to be construed as limiting the present application, and modifications to the present embodiment, which may not creatively contribute to the present application as required by those skilled in the art after reading the present specification, are all protected by patent laws within the scope of claims of the present application.
Claims (10)
1. A waterborne polyurethane colloid is characterized by comprising a component A and a component B, wherein the component A and the component B are calculated according to the total weight percentage of the component A and the component B,
the component A comprises 1.5 to 2.5 percent of closed isocyanate, 6 to 10 percent of auxiliary agent, 2 to 4 percent of epoxy resin curing agent and 0.5 to 1.5 percent of silane hydrocarbon solvent:
the component B comprises 28-20% of waterborne polyurethane, 3-5% of epoxy resin, 3-8% of organosilicon cross-linking agent, 0.1-0.3% of catalyst, 3-5% of epoxy resin solvent and the balance of water;
the auxiliary agent comprises the following components in percentage by mass (2-3): 1:1, polyoxyethylene hydrogenated castor oil and an auxiliary agent A.
2. The aqueous polyurethane gel of claim 1, wherein the epoxy resin curing agent is a combination of a room temperature epoxy curing agent, a medium temperature epoxy curing agent, and a high temperature epoxy curing agent.
3. The aqueous polyurethane colloid of claim 2, wherein the epoxy resin curing agent is in mass ratio of 1:2: (0.5-4) a room temperature epoxy hardener, a medium temperature epoxy hardener, and a high temperature epoxy hardener.
4. The aqueous polyurethane colloid according to claim 1, wherein the auxiliary agent A comprises at least one of fumed silica, calcium carbonate, liquid silicone rubber, polyimide and nano titanium dioxide.
5. The aqueous polyurethane colloid according to claim 4, wherein the auxiliary agent A is (2-3): 1:2, a polyimide, and a calcium carbonate.
6. The aqueous polyurethane gel according to claim 1, wherein the epoxy resin solvent is one of butanediol diglycidyl ether, glycerol triglycidyl ether and ethylene glycol diglycidyl ether; the silane hydrocarbon solvent is one of benzene, toluene and petroleum ether.
7. A waterborne polyurethane gel according to claim 1, wherein the catalyst is a chelate tin catalyst.
8. The aqueous polyurethane gel of claim 1, wherein the silicone cross-linking agent is one of gamma-aminopropyl trimethoxysilane, gamma-aminopropyl triethoxysilane, N-beta- (aminoethyl) -gamma-aminopropyl trimethoxysilane, anilino-silane, trisilane, gamma-mercaptopropyl trimethoxysilane, gamma-ureido propyl trihexyloxy silane, gamma-methacryloxypropyl trimethoxysilane.
9. A process for preparing a hydrocolloid as claimed in any one of claims 1 to 8, wherein,
preparation of component A: mixing the blocked isocyanate, the auxiliary agent, the epoxy resin curing agent and the silane hydrocarbon solvent, and stirring for 20-30min under the conditions of 20-30 ℃ and 200-400rpm/min to obtain a component A;
preparing a component B; firstly, mixing epoxy resin, an organosilicon cross-linking agent, a catalyst and an epoxy resin solvent, and stirring for 10-20min under the conditions of 20-30 ℃ and 200-400rpm/min to form a first mixture; adding water into the aqueous polyurethane and mixing to form a second mixture; then adding the first mixture into the second mixture at 20-30deg.C under 2000-4000rpm/min, and stirring for 30-40min to obtain component B.
10. Use of the aqueous polyurethane colloid according to any of claims 1-8 for the preparation of ultra high molecular weight polyethylene nonwoven fabrics, comprising the following steps: (1) the mass ratio is 1: mixing the component A and the component B of (1-1.3), stirring for 10-20min at the temperature of 20-25 ℃ and the rotating speed of 200-400rpm/min to prepare aqueous polyurethane colloid, and placing the prepared aqueous polyurethane colloid in an environment of 18-22 ℃ for later use; (2) paving ultra-high molecular weight polyethylene fibers; (3) Drawing the paved ultra-high molecular weight polyethylene fibers through a glue groove, simultaneously conveying the aqueous polyurethane colloid to the glue groove to be compounded with the ultra-high molecular weight polyethylene fibers, and then compounding the ultra-high molecular weight polyethylene after the glue is attached with a low-melting-point polyethylene film to prepare unidirectional non-woven fabrics; (4) drying and winding the unidirectional laid cloth; (5) Cutting the unidirectional non-woven fabric, performing secondary cross stacking by adopting a method of 0 degree/90 degrees, and heating and pressurizing to prepare the ultra-high molecular weight polyethylene non-woven fabric;
the temperature of the glue tank is 30-50 ℃; the drying condition is that the temperature is 80-110 ℃ and the drying time is 20-40min; the temperature of heating and pressurizing is 80-110 ℃.
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| CN102618202A (en) * | 2012-04-01 | 2012-08-01 | 江阴市诺科科技有限公司 | Water-based polyurethane composite adhesive for tanning and preparation method and application of composite adhesive |
| CN106189988A (en) * | 2016-07-14 | 2016-12-07 | 江苏必康制药股份有限公司 | A kind of Graphene modification glue and its production and use |
| KR20170135273A (en) * | 2016-05-31 | 2017-12-08 | (주)흥일폴리켐 | Method for manufacturing water-soluble polyurethane/epoxy hybrid resin for speaker damper |
| CN110358490A (en) * | 2019-06-12 | 2019-10-22 | 刘培军 | A kind of preparation method of footwear material adhesive |
| CN112662165A (en) * | 2020-12-21 | 2021-04-16 | 安徽凯沃科技有限公司 | Polyurethane mountain rock bulletproof radiation-proof wallboard |
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| CN102618202A (en) * | 2012-04-01 | 2012-08-01 | 江阴市诺科科技有限公司 | Water-based polyurethane composite adhesive for tanning and preparation method and application of composite adhesive |
| KR20170135273A (en) * | 2016-05-31 | 2017-12-08 | (주)흥일폴리켐 | Method for manufacturing water-soluble polyurethane/epoxy hybrid resin for speaker damper |
| CN106189988A (en) * | 2016-07-14 | 2016-12-07 | 江苏必康制药股份有限公司 | A kind of Graphene modification glue and its production and use |
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| CN112662165A (en) * | 2020-12-21 | 2021-04-16 | 安徽凯沃科技有限公司 | Polyurethane mountain rock bulletproof radiation-proof wallboard |
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