CN116836620B - 一种高弹性高阻燃的改性聚氨酯涂料及其制备方法 - Google Patents
一种高弹性高阻燃的改性聚氨酯涂料及其制备方法 Download PDFInfo
- Publication number
- CN116836620B CN116836620B CN202311004848.7A CN202311004848A CN116836620B CN 116836620 B CN116836620 B CN 116836620B CN 202311004848 A CN202311004848 A CN 202311004848A CN 116836620 B CN116836620 B CN 116836620B
- Authority
- CN
- China
- Prior art keywords
- stirring
- flame retardant
- glycol
- liquid
- polyurethane coating
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000011527 polyurethane coating Substances 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 34
- 239000003063 flame retardant Substances 0.000 claims abstract description 56
- 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 claims abstract description 54
- -1 polysiloxane Polymers 0.000 claims abstract description 47
- 239000007788 liquid Substances 0.000 claims abstract description 41
- 238000006243 chemical reaction Methods 0.000 claims abstract description 34
- 239000004814 polyurethane Substances 0.000 claims abstract description 32
- 229920002635 polyurethane Polymers 0.000 claims abstract description 32
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 21
- 239000004970 Chain extender Substances 0.000 claims abstract description 16
- 239000011248 coating agent Substances 0.000 claims abstract description 15
- 238000000576 coating method Methods 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 62
- 238000003756 stirring Methods 0.000 claims description 36
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 30
- 239000000203 mixture Substances 0.000 claims description 29
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 28
- 239000003795 chemical substances by application Substances 0.000 claims description 28
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 22
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 22
- 239000000347 magnesium hydroxide Substances 0.000 claims description 22
- RGPUVZXXZFNFBF-UHFFFAOYSA-K diphosphonooxyalumanyl dihydrogen phosphate Chemical compound [Al+3].OP(O)([O-])=O.OP(O)([O-])=O.OP(O)([O-])=O RGPUVZXXZFNFBF-UHFFFAOYSA-K 0.000 claims description 16
- 239000012948 isocyanate Substances 0.000 claims description 16
- 229920000515 polycarbonate Polymers 0.000 claims description 15
- 239000004417 polycarbonate Substances 0.000 claims description 15
- 239000004254 Ammonium phosphate Substances 0.000 claims description 14
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 14
- 235000019289 ammonium phosphates Nutrition 0.000 claims description 14
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 14
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 13
- 239000003054 catalyst Substances 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 13
- 229920000728 polyester Polymers 0.000 claims description 13
- 229920000570 polyether Polymers 0.000 claims description 13
- 238000010992 reflux Methods 0.000 claims description 13
- 125000003277 amino group Chemical group 0.000 claims description 12
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 claims description 11
- 235000011187 glycerol Nutrition 0.000 claims description 11
- 230000003472 neutralizing effect Effects 0.000 claims description 11
- 238000012360 testing method Methods 0.000 claims description 11
- 150000002009 diols Chemical class 0.000 claims description 10
- 239000002244 precipitate Substances 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 8
- 239000000049 pigment Substances 0.000 claims description 8
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 7
- WERYXYBDKMZEQL-UHFFFAOYSA-N 1,4-butanediol Substances OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- 230000003712 anti-aging effect Effects 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 238000000465 moulding Methods 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 238000007789 sealing Methods 0.000 claims description 5
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 4
- 239000000047 product Substances 0.000 claims description 4
- 244000043261 Hevea brasiliensis Species 0.000 claims description 3
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical group CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 3
- 150000001298 alcohols Chemical class 0.000 claims description 3
- 239000002274 desiccant Substances 0.000 claims description 3
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 3
- 238000007865 diluting Methods 0.000 claims description 3
- 239000012153 distilled water Substances 0.000 claims description 3
- 239000008131 herbal destillate Substances 0.000 claims description 3
- 239000004816 latex Substances 0.000 claims description 3
- 229920000126 latex Polymers 0.000 claims description 3
- 229920003052 natural elastomer Polymers 0.000 claims description 3
- 229920001194 natural rubber Polymers 0.000 claims description 3
- 230000009965 odorless effect Effects 0.000 claims description 3
- 229920001451 polypropylene glycol Polymers 0.000 claims description 3
- 239000001361 adipic acid Substances 0.000 claims description 2
- 235000011037 adipic acid Nutrition 0.000 claims description 2
- 125000003342 alkenyl group Chemical group 0.000 claims description 2
- 229920001577 copolymer Polymers 0.000 claims description 2
- 238000006068 polycondensation reaction Methods 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims 1
- 239000002245 particle Substances 0.000 abstract description 12
- 238000004132 cross linking Methods 0.000 abstract description 7
- 230000008859 change Effects 0.000 abstract description 5
- 230000018044 dehydration Effects 0.000 abstract description 3
- 238000006297 dehydration reaction Methods 0.000 abstract description 3
- 230000008569 process Effects 0.000 abstract description 3
- 230000035699 permeability Effects 0.000 abstract description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 10
- 238000009472 formulation Methods 0.000 description 7
- VVJKKWFAADXIJK-UHFFFAOYSA-N Allylamine Chemical compound NCC=C VVJKKWFAADXIJK-UHFFFAOYSA-N 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 239000003973 paint Substances 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 4
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 4
- 235000019837 monoammonium phosphate Nutrition 0.000 description 4
- 239000006012 monoammonium phosphate Substances 0.000 description 4
- 229910019440 Mg(OH) Inorganic materials 0.000 description 3
- 238000003763 carbonization Methods 0.000 description 3
- XYXJKPCGSGVSBO-UHFFFAOYSA-N 1,3,5-tris[(4-tert-butyl-3-hydroxy-2,6-dimethylphenyl)methyl]-1,3,5-triazinane-2,4,6-trione Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C)=C1CN1C(=O)N(CC=2C(=C(O)C(=CC=2C)C(C)(C)C)C)C(=O)N(CC=2C(=C(O)C(=CC=2C)C(C)(C)C)C)C1=O XYXJKPCGSGVSBO-UHFFFAOYSA-N 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 239000004595 color masterbatch Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- 239000004289 sodium hydrogen sulphite Substances 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000002981 blocking agent Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000005489 elastic deformation Effects 0.000 description 1
- 239000013013 elastic material Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920003225 polyurethane elastomer Polymers 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000008093 supporting effect Effects 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
- 238000005303 weighing Methods 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
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
- C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/44—Polycarbonates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4825—Polyethers containing two hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/18—Fireproof paints including high temperature resistant paints
-
- 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
- C08K2003/2217—Oxides; Hydroxides of metals of magnesium
- C08K2003/2224—Magnesium hydroxide
-
- 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
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
- C08K2003/322—Ammonium phosphate
- C08K2003/323—Ammonium polyphosphate
-
- 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
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
- C08K2003/327—Aluminium phosphate
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Polyurethanes Or Polyureas (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Paints Or Removers (AREA)
Abstract
本发明公开了一种高弹性高阻燃的改性聚氨酯涂料及其制备方法,所述改性聚氨酯涂料主要采用醇类化合物、异氰酸酯化合物、催化剂、中和剂、扩链剂及阻燃剂等组分进行反应生产,制备方法包括聚氨酯硬段反应、预聚体制备、扩链反应及溶胶反应。本发明首次利用pH变化及脱水过程中的溶胶反应,使液态阻燃剂缓慢结晶呈微米颗粒并均匀分布在聚氨酯网络中;还加入软段长链的聚硅氧烷作为扩链剂所用胺基的载体作为扩链交联的网络节点;还采用无溶剂法制备聚氨酯,无反应污水,所得聚氨酯涂料在涂覆后兼具较高的阻燃性能、回弹性能以及防颗粒脱落性能,涂覆所得薄膜还具有较佳防渗透性和耐候性。
Description
技术领域
本发明涉及阻燃聚合物弹性体技术领域,尤其涉及一种高弹性高阻燃的改性聚氨酯涂料及其制备方法。
背景技术
弹性涂料是以合成树脂乳液为基料,与颜料、填料及助剂配制而成,施涂一定厚度(干膜厚度大于等于150μm)后,具有弥盖因基材伸缩(运动)产生细小裂纹的有弹性的功能性涂料,目前使用较多的弹性涂料主要有聚氨酯涂料和环氧涂料。
现有的聚氨酯类弹性涂料多为双组分常温固化涂料,由聚氨酯弹性预聚物甲组分和由含羟基树脂组分与颜料、助剂等混合组成的乙组分所组成,施工时将甲、乙组分按比例混合,涂装后涂料交联固化成膜,形成具有弹性的彩色地面涂膜。但现场配制反应的常温固化聚氨酯涂料具有反应不均匀、局面力学性能偏低以及耐热和阻燃性能较差的特点。
因此也有一些厂家采用封闭剂将单组分聚氨酯的异氰酸酯端基进行封端,而后进行热处理(端基解封)固化成型,同时加入一些阻燃剂,但如此制作的弹性涂料阻燃剂颗粒与聚氨酯交联体系分布较不均匀,在成型后易成块脱落或形成力学缺陷,且造成聚氨酯网络的回弹性能大幅度降低,且形变后不具有可恢复性。因此最重要的问题是在添加阻燃剂后如何保持聚氨酯弹性体本身的高回弹性,此问题亟待解决。
发明内容
本发明的目的是为了解决现有技术中存在的缺点,而提出的一种高弹性高阻燃的改性聚氨酯涂料及其制备方法。
为了实现上述目的,本发明采用了如下技术方案:
一种高弹性高阻燃的改性聚氨酯涂料,采用以下重量百分比的组分进行反应生产:
醇类化合物,58-60%;
异氰酸酯化合物,18-20%;(由于醇类化合物分子量较大,故异氰酸酯化合物的摩尔量约为醇类化合物的1.5-1.9倍)
催化剂,0.1-0.2%;
中和剂,0.4-1%;
扩链剂,0.2-0.3%;
阻燃剂,15-18%;
其余为颜料、抗老化剂、固化剂以及封闭剂。
优选地,醇类化合物包括聚酯二醇、聚醚二醇、聚碳酸酯二醇、甘油和丁二醇,且聚酯二醇、聚醚二醇、聚碳酸酯二醇、甘油(用来增加支化链,形成交联网络,提高弹性)和丁二醇的重量比为1:0.6-0.8:0.4-0.5:0.6-0.8:0.1-0.15;
聚酯二醇为聚已二酸-1,4-丁二醇酯二醇(PBA,分子量为2000),由己二酸、1,4一丁二醇缩聚反应而成,常温下为白色蜡状固体,40℃开始成为液体,75℃下粘度为275cps,羟值为68-85mgKOH/g;聚醚二醇为聚环氧丙烷二元醇(PPG,分子量为1000),具体选择为PPG1000,羟值为107-117mgKOH/g,粘度为110-150cps(25℃);聚碳酸酯二醇为1,6-乙二醇/1,5-戊二醇-聚碳酸酯二醇共聚物,分子量为1000,羟值为95-110mgKOH/g,酸值小于0.1mgKOH/g,粘度为550cPs的粘稠液体。
优选地,异氰酸酯化合物包括甲苯二异氰酸酯(TDI,液体)和二苯基甲烷二异氰酸酯(MDI,常温为固体,35℃熔化为液体),甲苯二异氰酸酯(TDI,液体)和二苯基甲烷二异氰酸酯的重量比为1:0.8-1.2。
本发明采用芳香族二异氰酸酯,使聚氨酯硬段内聚强度增大,材料强度、耐热及阻燃性能均比脂肪族异氰酸酯型聚氨酯高,由于硬段(芳香族二异氰酸酯或与扩链剂反应所得)的刚性芳环含量高,支撑性较高使其受弹性变形后的回弹性较高。
优选地,催化剂为二丁基锡二月桂酸(DBTDL),常温下为液体.
优选地,扩链剂为胺基取代聚硅氧烷,用于降低硬度,提高回弹性(由于改性氨基聚硅氧烷的分子链较软,提高聚氨酯涂料硬度的同时可提高聚氨酯涂料的柔韧度,从而可提高聚氨酯的弹性,聚氨酯涂料形变时不易出现裂纹,具有较佳的防渗透性);
胺基取代聚硅氧烷的制备过程为:端基或侧链含活性氢的聚硅氧烷(分子量为5000-8000,含氢量为2.6mmol/g),与含端烯基的伯胺化合物(如烯丙基胺)在Pt催化剂下回流反应2h(伯胺化合物的沸点以上,如烯丙基胺采用55℃回流),得到胺基取代聚硅氧烷;
本发明采用软段长链的聚硅氧烷作为扩链剂所用胺基的载体,以软段作为各聚氨酯硬段的网络节点,形成交联网络,还可以起到交联的作用,大幅提高弹性且聚硅氧烷在燃烧时易形成硬化层且与其他阻燃剂一起促进碳化层的生成。
优选地,中和剂包括三乙胺、氢氧化镁和氢氧化钠,三乙胺、氢氧化镁和氢氧化钠的重量比为1:3-4:0.1-0.5,将三乙胺和氢氧化钠进行溶解而后加入氢氧化镁得浑浊液的中和剂,现配现用,氢氧化镁可用于体系除水,还可以作为阻燃剂的一部分,中和剂用于降低酸值,可以避免铵盐离子的产生造成意外结晶,从而促使异氰酸根与扩链剂的伯胺键进行扩链反应。
优选地,阻燃剂包括液体磷酸二氢铝、磷酸铵、氢氧化镁;磷酸二氢铝、磷酸铵、氢氧化镁的重量比为1:0.4-0.7:1.2-1.6。
进一步地,液体磷酸二氢铝(即铝胶溶液)是通过Al(OH)3和H3PO4反应来制得的,Al(OH)3和H3PO4的摩尔比为1:3.5,用少量蒸馏水将Al(OH)3调匀,再慢慢将混合均匀的Al(OH)3水溶胶加到装有H3PO4(85%水溶液)的烧杯中,边加边搅拌,在水浴锅中加热至60℃,持续搅拌2h至无沉淀,即得到透明、无色及无嗅的磷酸二氢铝[Al(H2PO4)3]粘性液体,pH为2.3;
更进一步地,阻燃剂的配制过程如下:在密闭容器中,将磷酸铵缓慢加入到60℃的铝胶溶液中,均质搅拌5min后,pH逐渐转变至6.7(磷酸铵部分转化为磷酸一氢铵和磷酸二氢铵),并产生絮状沉淀(氢氧化铝);投入氢氧化镁,至pH为12.5,絮状沉淀完全溶解,呈现透明溶液状,即为液态阻燃剂。
本发明首次采用液体磷酸二氢铝(铝胶)与传统阻燃剂磷酸铵(氮磷复合阻燃剂)、氢氧化镁(碱性阻燃剂)进行组合,利用pH的骤变得到透明稳定的液态阻燃剂,而随着与聚氨酯反应体系混合后,其中水可起到聚氨酯终止剂的作用,后采用真空挥发除去水,随着水分挥发,阻燃剂中各组分如Al(OH)3、Mg(OH)3和NH4H2PO4逐渐沉积为溶胶,待体系水分含量小于0.05%,阻燃剂各组分成细微颗粒(粒径小于100μm)状均匀分布在聚氨酯网络中,并成为聚氨酯涂料的次级结构支撑物,从而提高聚氨酯的变形回弹性。
本发明首次利用液态阻燃剂与聚氨酯反应体系进行直接混合,并利用pH变化(混匀后pH降低)及脱水过程中的溶胶反应使其中阻燃组分缓慢结晶呈微米颗粒,均匀分布在聚氨酯网络中,从而兼具
本发明还提出对应的一种高弹性高阻燃的改性聚氨酯涂料的制备方法,包括以下步骤:
S1、聚氨酯硬段反应:
将醇类化合物进行脱水,聚酯二醇、聚醚二醇和聚碳酸酯二醇采用110℃真空挥发脱水,甘油和丁二醇采用干燥剂脱水;将甘油和丁二醇温度控制在75-77℃,加入占总量一半的异氰酸酯化合物和催化剂,搅拌回流(装有冷凝回流器)反应1.5-2.5h;
S2、预聚体制备:
同时快速投入聚酯二醇、聚醚二醇、聚碳酸酯二醇以及占总量一半的异氰酸酯化合物和催化剂,搅拌回流(装有冷凝回流器)反应2-3h,即得预聚体,测定pH为5.9-6.3;
S3、扩链反应:
在预聚体中加入中和剂,搅拌为低剪切搅拌(小于100r/min),调整pH为7.6-8.2后,调整投入扩链剂,搅拌转为高剪切搅拌(>1000r/min),降温至70-73℃,反应20-30min,控制体系粘度小于5000cps(当粘度高于5000cps,立即冷却降温,并投入水或丙酮终止反应);
S4、溶胶反应:
将液态的阻燃剂滴加到S3的反应体系中,加完后高剪切搅拌3min,至体系呈完全澄清的粘稠液状态,测量pH为10.6,低剪切搅拌5min左右开始出现乳白色溶胶;
70℃下,采用真空减压蒸馏去除水分及易挥发组分,得到粘稠液体,检测固含量大于95%,搅拌冷却后无明显沉淀,呈透明白色溶胶状,外观类似天然橡胶的稀释乳胶液,投入颜料、抗老化剂、固化剂以及封闭剂(亚硫酸氢钠)相关组分,混匀后即为改性聚氨酯涂料成品,涂覆后加热至70℃以上(根据固化剂温度而定),解封固化成型,测试阻燃性能和回弹性。
与现有技术相比,本发明的有益效果是:
1.本发明首次利用液态阻燃剂与聚氨酯反应体系进行直接混合,并利用pH变化(混匀后pH降低)及脱水过程中的溶胶反应使其中阻燃组分缓慢结晶呈微米颗粒,均匀分布在聚氨酯网络中,从而兼具高阻燃性和高回弹性,同时由于均匀性好可适当减少阻燃剂的实际用量,进一步保证回弹性;
2.为了进一步保证回弹性和阻燃性能,本发明还加入软段长链的聚硅氧烷作为扩链剂所用胺基的载体,以软段作为各聚氨酯硬段的网络节点,形成交联网络,还可以起到交联的作用,大幅提高弹性且聚硅氧烷在燃烧时易形成硬化层且与其他阻燃剂一起促进碳化层的生成;
3.本发明采用无溶剂法制备聚氨酯,无反应污水,所得聚氨酯涂料在涂覆后兼具较高的阻燃性能、回弹性能以及防颗粒脱落性能,涂覆所得薄膜还具有较佳防渗透性和耐候性。
具体实施方式
下面对本发明实施例中的技术方案进行清楚、完整地描述,显然,所描述的实施例仅仅是本发明一部分实施例,而不是全部的实施例。
制备例A:
中和剂的配制:中和剂包括三乙胺、氢氧化镁和氢氧化钠,三乙胺、氢氧化镁和氢氧化钠的重量比为1:3-4:0.1-0.5,将三乙胺和氢氧化钠进行溶解而后加入氢氧化镁得浑浊液的中和剂,现配现用,氢氧化镁可用于体系除水,还可以作为阻燃剂的一部分,中和剂用于降低酸值,可以避免铵盐离子的产生造成意外结晶,从而促使异氰酸根与扩链剂的伯胺键进行扩链反应。
表1.中和剂的配方表
制备例B:
阻燃剂的制备:
液体磷酸二氢铝(即铝胶溶液)是通过Al(OH)3和H3PO4反应来制得的,Al(OH)3和H3PO4的摩尔比为1:3.5,用少量蒸馏水将Al(OH)3调匀,再慢慢将混合均匀的Al(OH)3水溶胶加到装有H3PO4(85%水溶液)的烧杯中,边加边搅拌,在水浴锅中加热至60℃,持续搅拌2h至无沉淀,即得到透明、无色及无嗅的磷酸二氢铝[Al(H2PO4)3]粘性液体,pH为2.3;
阻燃剂包括液体磷酸二氢铝、磷酸铵、氢氧化镁;磷酸二氢铝、磷酸铵、氢氧化镁的重量比为1:0.4-0.7:1.2-1.6。
更进一步地,阻燃剂的配制过程如下:在密闭容器中,将磷酸铵缓慢加入到60℃的铝胶溶液中,均质搅拌5min后,pH逐渐转变至6.7(磷酸铵部分转化为磷酸一氢铵和磷酸二氢铵),并产生絮状沉淀(氢氧化铝);投入氢氧化镁,至pH为12.5,絮状沉淀完全溶解,呈现透明溶液状,即为液态阻燃剂。
表2.阻燃剂的配方表
制备例B | 磷酸二氢铝/kg | 磷酸铵/kg | 氢氧化镁/kg |
制备例B1 | 1 | 0.4 | 1.6 |
制备例B2 | 1 | 0.55 | 1.4 |
制备例B3 | 1 | 0.7 | 1.2 |
本发明首次采用液体磷酸二氢铝(铝胶)与传统阻燃剂磷酸铵(氮磷复合阻燃剂)、氢氧化镁(碱性阻燃剂)进行组合,利用pH的骤变得到透明稳定的液态阻燃剂,而随着与聚氨酯反应体系混合后,其中水可起到聚氨酯终止剂的作用,后采用真空挥发除去水,随着水分挥发,阻燃剂中各组分如Al(OH)3、Mg(OH)3和NH4H2PO4逐渐沉积为溶胶,待体系水分含量小于0.05%,阻燃剂各组分成细微颗粒(粒径小于100μm)状均匀分布在聚氨酯网络中,并成为聚氨酯涂料的次级结构支撑物,从而提高聚氨酯的变形回弹性。
制备例C:
扩链剂的制备:扩链剂为胺基取代聚硅氧烷,用于降低硬度,提高回弹性(由于改性氨基聚硅氧烷的分子链较软,提高聚氨酯涂料硬度的同时可提高聚氨酯涂料的柔韧度,从而可提高聚氨酯的弹性,聚氨酯涂料形变时不易出现裂纹,具有较佳的防渗透性);
胺基取代聚硅氧烷的制备过程为:端基或侧链含活性氢的聚硅氧烷(分子量为5000-8000,含氢量为2.6mmol/g),与烯丙基胺在Pt催化剂下55℃回流反应2h,得到胺基取代聚硅氧烷;
本发明采用软段长链的聚硅氧烷作为扩链剂所用胺基的载体,以软段作为各聚氨酯硬段的网络节点,形成交联网络,还可以起到交联的作用,大幅提高弹性且聚硅氧烷在燃烧时易形成硬化层且与其他阻燃剂一起促进碳化层的生成。
制备例D:
醇类化合物的配方:聚酯二醇、聚醚二醇、聚碳酸酯二醇、甘油和丁二醇的重量比为1:0.6-0.8:0.4-0.5:0.6-0.8:0.1-0.15;
表3.醇类化合物的配方表
制备例E:
异氰酸酯化合物的配方:甲苯二异氰酸酯和二苯基甲烷二异氰酸酯的重量比为1:0.8-1.2。
表4.异氰酸酯化合物的配方表
制备例E | TDI/kg | MDI/kg |
制备例E1 | 1 | 0.8 |
制备例E2 | 1 | 1 |
制备例E3 | 1 | 1.2 |
实施例:
本发明还提出如权利要求1-9任一的一种高弹性高阻燃的改性聚氨酯涂料的制备方法,包括以下步骤:
S1、聚氨酯硬段反应:
将醇类化合物进行脱水,聚酯二醇、聚醚二醇和聚碳酸酯二醇采用110℃真空挥发脱水,甘油和丁二醇采用干燥剂脱水;将甘油和丁二醇温度控制在75-77℃,加入占总量一半的异氰酸酯化合物和催化剂,搅拌回流(装有冷凝回流器)反应1.5-2.5h;
S2、预聚体制备:
同时快速投入聚酯二醇、聚醚二醇、聚碳酸酯二醇以及占总量一半的异氰酸酯化合物和催化剂,搅拌回流(装有冷凝回流器)反应2-3h,即得预聚体,测定pH为5.9-6.3;
S3、扩链反应:
在预聚体中加入中和剂,搅拌为低剪切搅拌(小于100r/min),调整pH为7.6-8.2后,调整投入扩链剂,搅拌转为高剪切搅拌(>1000r/min),降温至70-73℃,反应20-30min,控制体系粘度小于5000cps(当粘度高于5000cps,立即冷却降温,并投入水或丙酮终止反应);
S4、溶胶反应:
将液态的阻燃剂滴加到S3的反应体系中,加完后高剪切搅拌3min,至体系呈完全澄清的粘稠液状态,测量pH为10.6,低剪切搅拌5min左右开始出现乳白色溶胶;
70℃下,采用真空减压蒸馏去除水分及易挥发组分,得到粘稠液体,检测固含量大于95%,搅拌冷却后无明显沉淀,呈透明白色溶胶状,外观类似天然橡胶的稀释乳胶液,投入颜料(炭黑及色母)、抗老化剂(采用盖德生产的聚氨酯海绵抗氧化剂1790)、固化剂(乙二胺)以及封闭剂——亚硫酸氢钠,混匀后即为改性聚氨酯涂料成品,涂覆后加热至70℃以上,解封固化成型,测试阻燃性能和回弹性。
以上表格中各实施例的配方组分,通过计算辅助称量以及取样控制R值(-NCO与-OH的摩尔比)为1.5-1.9,并进行交叉试验,测试聚氨酯涂料成品涂覆成膜后的阻燃性能及回弹性能,并设置空白试验进行对比,即——
对比制备例B4:采用制备例B所得当量的Al(OH)3、Mg(OH)3和NH4H2PO4颗粒,研磨成阻燃剂粉末;
对比例1:
将对比制备例B4的阻燃剂粉末直接与实施例S3所得的反应体系进行混合,投入颜料(炭黑及色母)、抗老化剂(采用盖德生产的聚氨酯海绵抗氧化剂1790)、固化剂(乙二胺)以及封闭剂——亚硫酸氢钠,高剪切搅拌混匀后即为得到聚氨酯涂料对比料,涂覆后加热至70℃以上,解封固化成型,测试阻燃性能和回弹性。
各实施例及对比例的配方用量如下表5所示:
表5.改性聚氨酯涂料的配方表
将各实施例性能进行测试,包括以下方面:
回弹率测试:参照《GB/T 1681硫化橡胶回弹性的测定》对实施例1-9和对比例1的聚氨酯涂料涂覆200μm厚的薄膜进行回弹性测试;
拉伸强度测试:参照《GB/T 10654高分子多孔弹性材料拉伸强度和断裂伸长率的测定》对实施例1-9和对比例1的聚氨酯涂料涂覆200μm厚的薄膜进行拉伸强度测试;
阻燃性能测试:参《GB/T8626—88建筑材料可燃性试验方法》对实施例1-9和对比例1的聚氨酯涂料涂覆200μm厚的薄膜进行燃烧性能测试,所得级别从高到低分别为A(不燃)、B1(难燃)、B2(可燃)和B3(易燃);
颗粒脱落率测试:采用100kg的砝码对实施例1-9和对比例1的聚氨酯涂料涂覆200μm厚的薄膜进行压缩形变1h后,将砝码来回摩擦移动10min左右,测试薄膜表面颗粒含量,单位mg/cm2。
各实施例性能比较如下表6所示:
表中B1-A表明,局部为不燃,局部为难燃,可能与涂布厚度及其他试剂混匀后产生的影响,但整体均为难燃,高于对比例1直接混合,而且回弹性能及防颗粒脱落性能均大幅提高,表明本发明的改进为有效改进。
以上所述,仅为本发明较佳的具体实施方式,但本发明的保护范围并不局限于此,任何熟悉本技术领域的技术人员在本发明揭露的技术范围内,根据本发明的技术方案及其发明构思加以等同替换或改变,都应涵盖在本发明的保护范围之内。
Claims (4)
1.一种高弹性高阻燃的改性聚氨酯涂料,其特征在于,采用以下重量百分比的组分进行反应生产:
醇类化合物,58-60%;
异氰酸酯化合物,18-20%;
催化剂,0.1-0.2%;
中和剂,0.4-1%;
扩链剂,0.2-0.3%;
阻燃剂,15-18%;
其余为颜料、抗老化剂、固化剂以及封闭剂;
所述醇类化合物包括聚酯二醇、聚醚二醇、聚碳酸酯二醇、甘油和丁二醇,且聚酯二醇、聚醚二醇、聚碳酸酯二醇、甘油和丁二醇的重量比为1:0.6-0.8:0.4-0.5:0.6-0.8:0.1-0.15;所述聚酯二醇为聚已二酸-1,4-丁二醇酯二醇,由己二酸、1,4一丁二醇缩聚反应而成,常温下为白色蜡状固体,40℃开始成为液体,75℃下粘度为275cps,羟值为68-85mgKOH/g;所述聚醚二醇为聚环氧丙烷二元醇,具体选择为PPG1000,羟值为107-117mgKOH/g,粘度为110-150cps;所述聚碳酸酯二醇为1,6-乙二醇/1,5-戊二醇-聚碳酸酯二醇共聚物,分子量为1000,羟值为95-110mgKOH/g,酸值小于0.1mgKOH/g,粘度为550cPs的粘稠液体;
所述异氰酸酯化合物包括甲苯二异氰酸酯和二苯基甲烷二异氰酸酯,甲苯二异氰酸酯和二苯基甲烷二异氰酸酯的重量比为1:0.8-1.2;
所述扩链剂为胺基取代聚硅氧烷,所述胺基取代聚硅氧烷的制备过程为:端基或侧链含活性氢的聚硅氧烷,与含端烯基的伯胺化合物在Pt催化剂下回流反应2h,得到胺基取代聚硅氧烷;
所述阻燃剂包括液体磷酸二氢铝、磷酸铵、氢氧化镁;液体磷酸二氢铝、磷酸铵、氢氧化镁的重量比为1:0.4-0.7:1.2-1.6;
所述液体磷酸二氢铝是通过Al(OH)3和H3PO4反应来制得的,Al(OH)3和H3PO4的摩尔比为1:3.5,用少量蒸馏水将Al(OH)3调匀,再慢慢将混合均匀的Al(OH)3水溶胶加到装有H3PO4的烧杯中,边加边搅拌,在水浴锅中加热至60℃,持续搅拌2h至无沉淀,即得到透明、无色及无嗅的磷酸二氢铝粘性液体,pH为2.3;
所述阻燃剂的配制过程如下:在密闭容器中,将磷酸铵缓慢加入到60℃的液体磷酸二氢铝中,均质搅拌5min后,pH逐渐转变至6.7,并产生絮状沉淀;投入氢氧化镁,至pH为12.5,絮状沉淀完全溶解,呈现透明溶液状,即为液态阻燃剂。
2.根据权利要求1所述的一种高弹性高阻燃的改性聚氨酯涂料,其特征在于,所述催化剂为二丁基锡二月桂酸。
3.根据权利要求1所述的一种高弹性高阻燃的改性聚氨酯涂料,其特征在于,所述中和剂包括三乙胺、氢氧化镁和氢氧化钠,三乙胺、氢氧化镁和氢氧化钠的重量比为1:3-4:0.1-0.5,将三乙胺和氢氧化钠进行溶解而后加入氢氧化镁得浑浊液的中和剂,现配现用。
4.如权利要求1所述的一种高弹性高阻燃的改性聚氨酯涂料的制备方法,其特征在于,包括以下步骤:
S1、聚氨酯硬段反应:
将醇类化合物进行脱水,聚酯二醇、聚醚二醇和聚碳酸酯二醇采用110℃真空挥发脱水,甘油和丁二醇采用干燥剂脱水;将甘油和丁二醇温度控制在75-77℃,加入占总量一半的异氰酸酯化合物和催化剂,搅拌回流反应1.5-2.5h;
S2、预聚体制备:
同时快速投入聚酯二醇、聚醚二醇、聚碳酸酯二醇以及占总量一半的异氰酸酯化合物和催化剂,搅拌回流反应2-3h,即得预聚体,测定pH为5.9-6.3;
S3、扩链反应:
在预聚体中加入中和剂,搅拌为低剪切搅拌,调整pH为7.6-8.2后,投入扩链剂,搅拌转为高剪切搅拌,降温至70-73℃,反应20-30min,控制体系粘度小于5000cps;
S4、溶胶反应:
将液态的阻燃剂滴加到S3的反应体系中,加完后高剪切搅拌3min,至体系呈完全澄清的粘稠液状态,测量pH为10.6,低剪切搅拌5min左右开始出现乳白色溶胶;
70℃下,采用真空减压蒸馏去除水分及易挥发组分,得到粘稠液体,检测固含量大于95%,搅拌冷却后无明显沉淀,呈透明白色溶胶状,外观类似天然橡胶的稀释乳胶液,投入颜料、抗老化剂、固化剂以及封闭剂,混匀后即为改性聚氨酯涂料成品,涂覆后加热至解封固化成型,测试阻燃性能和回弹性。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202311004848.7A CN116836620B (zh) | 2023-08-10 | 2023-08-10 | 一种高弹性高阻燃的改性聚氨酯涂料及其制备方法 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202311004848.7A CN116836620B (zh) | 2023-08-10 | 2023-08-10 | 一种高弹性高阻燃的改性聚氨酯涂料及其制备方法 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN116836620A CN116836620A (zh) | 2023-10-03 |
CN116836620B true CN116836620B (zh) | 2024-03-29 |
Family
ID=88174521
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202311004848.7A Active CN116836620B (zh) | 2023-08-10 | 2023-08-10 | 一种高弹性高阻燃的改性聚氨酯涂料及其制备方法 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN116836620B (zh) |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1371382A (zh) * | 1999-08-30 | 2002-09-25 | 联合化学技术公司 | 氨丙基或氨烷基官能聚烷基或聚芳基硅氧烷的制备方法 |
CN104211878A (zh) * | 2014-09-26 | 2014-12-17 | 合肥工业大学 | 一种聚氨酯环氧树脂丙烯酸酯三元共聚树脂纳米水分散液的制备方法 |
CN108774306A (zh) * | 2018-06-29 | 2018-11-09 | 南京红宝丽新材料有限公司 | 一种匀质的不燃型聚氨酯泡沫隔热保温材料及其制备方法 |
CN111793352A (zh) * | 2020-07-07 | 2020-10-20 | 惠州大亚湾达志精细化工有限公司 | 水性聚氨酯粉体粘合剂、弹性材料及其制备方法 |
CN115160911A (zh) * | 2022-08-17 | 2022-10-11 | 漳州市恩扬工艺品有限公司 | 一种聚氨酯面漆组合物及其制备方法 |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
TWI394765B (zh) * | 2008-12-12 | 2013-05-01 | Ind Tech Res Inst | 難燃水性聚胺基甲酸酯分散液 |
-
2023
- 2023-08-10 CN CN202311004848.7A patent/CN116836620B/zh active Active
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1371382A (zh) * | 1999-08-30 | 2002-09-25 | 联合化学技术公司 | 氨丙基或氨烷基官能聚烷基或聚芳基硅氧烷的制备方法 |
CN104211878A (zh) * | 2014-09-26 | 2014-12-17 | 合肥工业大学 | 一种聚氨酯环氧树脂丙烯酸酯三元共聚树脂纳米水分散液的制备方法 |
CN108774306A (zh) * | 2018-06-29 | 2018-11-09 | 南京红宝丽新材料有限公司 | 一种匀质的不燃型聚氨酯泡沫隔热保温材料及其制备方法 |
CN111793352A (zh) * | 2020-07-07 | 2020-10-20 | 惠州大亚湾达志精细化工有限公司 | 水性聚氨酯粉体粘合剂、弹性材料及其制备方法 |
CN115160911A (zh) * | 2022-08-17 | 2022-10-11 | 漳州市恩扬工艺品有限公司 | 一种聚氨酯面漆组合物及其制备方法 |
Non-Patent Citations (1)
Title |
---|
PA阻燃剂的合成及应用研究;杨锦飞等;南京师大学报(自然科学版);第17卷(第1期);第42-44页 * |
Also Published As
Publication number | Publication date |
---|---|
CN116836620A (zh) | 2023-10-03 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US6794445B2 (en) | Aqueous polysiloxane-polyurethane dispersion, its preparation and use in coating compositions | |
JP5170499B2 (ja) | ブロックイソシアネート含有エマルジョン組成物及びその製造方法並びに焼付け型塗料用又は接着剤用組成物 | |
US3770703A (en) | Heat hardenable mixtures of epsilon-caprolactam blocked polyisocyanates and cycloaliphatic polyamines | |
TW321660B (zh) | ||
CN108864399B (zh) | 一种有机硅改性阻燃聚氨酯及其制备 | |
KR102247683B1 (ko) | 난연성 폴리우레탄 폼 조성물 및 이의 경화물을 포함하는 난연성 폴리우레탄 폼 | |
JP5299420B2 (ja) | ブロックイソシアネート含有エマルジョン組成物及びその製造方法並びに多孔質基材用水性下地処理剤及び水性焼付け型塗料組成物 | |
KR20070101149A (ko) | 개선된 저장 안정성을 갖는 수성 폴리우레탄 분산액 | |
CN112225878A (zh) | 一种高耐碱水性双组分异氰酸酯固化剂及其制备方法 | |
CN113698567B (zh) | 一种亲水硅氧烷改性的聚氨酯或聚氨酯-脲水分散体、制备方法及应用 | |
JP5154804B2 (ja) | 熱硬化性樹脂組成物、当該硬化物、およびこれらから誘導される各種物品 | |
JP2004231931A (ja) | ポリイソシアネート溶液並びにこれを用いた接着剤および塗料 | |
CN116836620B (zh) | 一种高弹性高阻燃的改性聚氨酯涂料及其制备方法 | |
CN114805734B (zh) | 一种水性聚氨酯分散体及其制备方法,一种自交联型水性聚氨酯防水涂料 | |
CN114716910A (zh) | 一种合成革用有机硅耐刮擦防污涂层及其制备方法 | |
CN112778493B (zh) | 一种聚碳酸亚丙酯多元醇型水性聚氨酯防水乳液及其制备方法与应用 | |
CN102532475A (zh) | 聚脲树脂组合物和固化剂 | |
CN115141595A (zh) | 一种高耐水洗阻燃型聚氨酯热熔胶黏剂及其制备方法 | |
JP6135669B2 (ja) | コーティング剤、ならびにこれを用いた塗膜およびフィルム | |
JP2006316127A (ja) | 無溶剤型硬化性ウレタン樹脂組成物及び該組成物を用いて得られるシート状物。 | |
JP3197130B2 (ja) | 熱架橋性ポリウレタンエマルジョン組成物 | |
KR102092532B1 (ko) | 스웨이드의 함침 코팅용 난연성 수분산 폴리우레탄 수지조성물 및 그 제조방법 | |
JP4030230B2 (ja) | 難燃性ポリウレタン発泡シートおよび該シートを用いた合成皮革 | |
JP5482892B2 (ja) | ポリウレタン樹脂形成性組成物 | |
KR102255391B1 (ko) | 난연성 폴리우레탄 폼 조성물 및 이의 경화물을 포함하는 난연성 폴리우레탄 폼 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |