CN109134813A - A kind of carbamide resin synthesis technology - Google Patents
A kind of carbamide resin synthesis technology Download PDFInfo
- Publication number
- CN109134813A CN109134813A CN201810806559.1A CN201810806559A CN109134813A CN 109134813 A CN109134813 A CN 109134813A CN 201810806559 A CN201810806559 A CN 201810806559A CN 109134813 A CN109134813 A CN 109134813A
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- China
- Prior art keywords
- component
- aminophenyl
- ethyl carbonate
- added
- carbamide
- Prior art date
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- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 title claims abstract description 117
- 238000005516 engineering process Methods 0.000 title claims abstract description 14
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 10
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 10
- -1 polypropylene Polymers 0.000 claims abstract description 51
- 229920002396 Polyurea Polymers 0.000 claims abstract description 44
- 239000004202 carbamide Substances 0.000 claims abstract description 44
- 235000013877 carbamide Nutrition 0.000 claims abstract description 44
- 239000003973 paint Substances 0.000 claims abstract description 42
- 239000011248 coating agent Substances 0.000 claims abstract description 41
- 238000000576 coating method Methods 0.000 claims abstract description 41
- CQDGTJPVBWZJAZ-UHFFFAOYSA-N monoethyl carbonate Chemical compound CCOC(O)=O CQDGTJPVBWZJAZ-UHFFFAOYSA-N 0.000 claims abstract description 38
- UKJLNMAFNRKWGR-UHFFFAOYSA-N cyclohexatrienamine Chemical group NC1=CC=C=C[CH]1 UKJLNMAFNRKWGR-UHFFFAOYSA-N 0.000 claims abstract description 32
- PVNHYDDCQMHWAL-UHFFFAOYSA-N 2-phenyl-1h-benzimidazol-4-amine Chemical compound N=1C=2C(N)=CC=CC=2NC=1C1=CC=CC=C1 PVNHYDDCQMHWAL-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000000203 mixture Substances 0.000 claims abstract description 31
- 229920000642 polymer Polymers 0.000 claims abstract description 29
- 239000004970 Chain extender Substances 0.000 claims abstract description 27
- 239000004743 Polypropylene Substances 0.000 claims abstract description 27
- 230000000694 effects Effects 0.000 claims abstract description 27
- 229920001155 polypropylene Polymers 0.000 claims abstract description 27
- 239000002270 dispersing agent Substances 0.000 claims abstract description 26
- 239000000463 material Substances 0.000 claims abstract description 25
- 150000005846 sugar alcohols Polymers 0.000 claims abstract description 25
- 238000005507 spraying Methods 0.000 claims abstract description 21
- 125000006840 diphenylmethane group Chemical class 0.000 claims abstract description 16
- ONIKNECPXCLUHT-UHFFFAOYSA-N 2-chlorobenzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1Cl ONIKNECPXCLUHT-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000004886 process control Methods 0.000 claims abstract description 10
- 239000000049 pigment Substances 0.000 claims abstract description 4
- 238000002360 preparation method Methods 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 50
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 40
- 238000000034 method Methods 0.000 claims description 26
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 22
- 229930195729 fatty acid Natural products 0.000 claims description 22
- 239000000194 fatty acid Substances 0.000 claims description 22
- 229910052757 nitrogen Inorganic materials 0.000 claims description 20
- 230000008569 process Effects 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 16
- 239000000178 monomer Substances 0.000 claims description 15
- JTPLPDIKCDKODU-UHFFFAOYSA-N acetic acid;2-(2-aminoethylamino)ethanol Chemical compound CC(O)=O.CC(O)=O.CC(O)=O.NCCNCCO JTPLPDIKCDKODU-UHFFFAOYSA-N 0.000 claims description 10
- 238000006073 displacement reaction Methods 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 9
- OTEKOJQFKOIXMU-UHFFFAOYSA-N 1,4-bis(trichloromethyl)benzene Chemical compound ClC(Cl)(Cl)C1=CC=C(C(Cl)(Cl)Cl)C=C1 OTEKOJQFKOIXMU-UHFFFAOYSA-N 0.000 claims description 8
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 8
- 150000003384 small molecules Chemical class 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 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- 239000007921 spray Substances 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 2
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- BHRZNVHARXXAHW-UHFFFAOYSA-N sec-butylamine Chemical compound CCC(C)N BHRZNVHARXXAHW-UHFFFAOYSA-N 0.000 claims description 2
- 238000010422 painting Methods 0.000 claims 2
- LJPCNSSTRWGCMZ-UHFFFAOYSA-N 3-methyloxolane Chemical compound CC1CCOC1 LJPCNSSTRWGCMZ-UHFFFAOYSA-N 0.000 claims 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 claims 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims 1
- 238000009775 high-speed stirring Methods 0.000 claims 1
- 238000010992 reflux Methods 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 13
- 238000004925 denaturation Methods 0.000 abstract description 2
- 230000036425 denaturation Effects 0.000 abstract description 2
- 238000010292 electrical insulation Methods 0.000 abstract description 2
- 239000011810 insulating material Substances 0.000 abstract description 2
- 239000002585 base Substances 0.000 description 25
- 238000010276 construction Methods 0.000 description 15
- 238000003860 storage Methods 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 230000008901 benefit Effects 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 8
- 238000005260 corrosion Methods 0.000 description 8
- 238000007254 oxidation reaction Methods 0.000 description 8
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 7
- 239000005977 Ethylene Substances 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 229910000831 Steel Inorganic materials 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 239000010959 steel Substances 0.000 description 6
- 238000013019 agitation Methods 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- 239000004567 concrete Substances 0.000 description 5
- 229920001971 elastomer Polymers 0.000 description 5
- 229920003023 plastic Polymers 0.000 description 5
- 239000004033 plastic Substances 0.000 description 5
- 229920002635 polyurethane Polymers 0.000 description 5
- 239000004814 polyurethane Substances 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 4
- 239000011083 cement mortar Substances 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 229910052801 chlorine Inorganic materials 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 239000005060 rubber Substances 0.000 description 3
- 239000002689 soil Substances 0.000 description 3
- 229910001018 Cast iron Inorganic materials 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229920005830 Polyurethane Foam Polymers 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 230000002421 anti-septic effect Effects 0.000 description 2
- 239000002518 antifoaming agent Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 239000000806 elastomer Substances 0.000 description 2
- 239000011152 fibreglass Substances 0.000 description 2
- GFAUNYMRSKVDJL-UHFFFAOYSA-N formyl chloride Chemical compound ClC=O GFAUNYMRSKVDJL-UHFFFAOYSA-N 0.000 description 2
- 125000002883 imidazolyl group Chemical group 0.000 description 2
- 239000003317 industrial substance Substances 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical group OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 238000009527 percussion Methods 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000011496 polyurethane foam Substances 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- 230000035939 shock Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 230000035882 stress Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- YXRKNIZYMIXSAD-UHFFFAOYSA-N 1,6-diisocyanatohexane Chemical compound O=C=NCCCCCCN=C=O.O=C=NCCCCCCN=C=O.O=C=NCCCCCCN=C=O YXRKNIZYMIXSAD-UHFFFAOYSA-N 0.000 description 1
- DWYHDSLIWMUSOO-UHFFFAOYSA-N 2-phenyl-1h-benzimidazole Chemical compound C1=CC=CC=C1C1=NC2=CC=CC=C2N1 DWYHDSLIWMUSOO-UHFFFAOYSA-N 0.000 description 1
- 235000001674 Agaricus brunnescens Nutrition 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910001141 Ductile iron Inorganic materials 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- 241000220324 Pyrus Species 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000007824 aliphatic compounds Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 150000003851 azoles Chemical class 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000004210 cathodic protection Methods 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- JXCHMDATRWUOAP-UHFFFAOYSA-N diisocyanatomethylbenzene Chemical compound O=C=NC(N=C=O)C1=CC=CC=C1 JXCHMDATRWUOAP-UHFFFAOYSA-N 0.000 description 1
- 125000005982 diphenylmethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000010410 dusting Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 235000021017 pears Nutrition 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920003226 polyurethane urea Polymers 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000005488 sandblasting Methods 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 239000009671 shengli Substances 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 238000004162 soil erosion Methods 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Classifications
-
- 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
-
- 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
- C08G18/4833—Polyethers containing oxyethylene units
- C08G18/4837—Polyethers containing oxyethylene units and other oxyalkylene units
-
- 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
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6681—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38
- C08G18/6685—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3225 or polyamines of C08G18/38
-
- 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
- C09D175/02—Polyureas
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Polyurethanes Or Polyureas (AREA)
- Paints Or Removers (AREA)
Abstract
The invention discloses a kind of carbamide resin synthesis technologies, the carbamide paint component A is by 4, 4 '-'-diphenylmethane diisocyanates, high activity polypropylene oxide-ethylene oxide ethoxylated polyhydric alcohol, chlorobenzoyl chloride, dispersing agent, ethyl carbonate composition, under certain process control condition, synthesis 4, the performed polymer of 4 '-'-diphenylmethane diisocyanates, B component is by 4, 4 '-bis- sec-butylamine base diphenyl methanes, -5 (6) aminophenyl benzimidazole of 2- (4- aminophenyl), pigment, ethyl carbonate composition, under certain process control condition, it is mixed to form the B component containing chain extender;Under the process control condition of the preparation process of coating, A, B component form polyurea coating after spraying.Carbamide paint of the invention has high stabile against thermal denaturation, tensile strength and high tenacity, chemicals-resistant corrosivity height, excellent electrical insulation capability, it is used as the insulating materials or encapsulating material of electronics, appliance device, also can be widely used to machinery, chemical industry, oil field.
Description
Technical field
The invention belongs to the preparations of polymer composite, the especially production field of carbamide resin modified coating.
Background technique
Spray Polyurea Elastomer Technology experienced three polyurethane, polyurethane-urea and polyureas developing stage.In three kinds of systems
Middle component A is essentially identical, is aromatic series or aliphatic prepolymer and semi-prepolymer, and difference is B component.Spraying is poly-
The B component of urethane is made of terminal hydroxy group resin and terminal hydroxy group chain extender, and contains the catalyst for improving reactivity.
Spraying polyurethane/urea B component is also possible to hold amine resin and amine chainextender group either terminal hydroxy group resin
At typically containing the catalyst for improving reactivity.And the B component of spray polyurea must be by Amino End Group resin and end ammonia
Base chain extender composition, and any hydroxyl moieties and catalyst are free of, a certain amount of dispersing agent and neutral ash 2BL can be contained.
Since the reactivity of Amino End Group compound and isocyanate component is high, it is not necessarily to any catalyst, it can be in room
Temperature or low temperature lower moment complete reaction, thus effectively overcome polyurethane and polyurethane/urea elastomer in the construction process, because
The influence of environment temperature and humidity and the fatal defects for foaming, material property being caused sharply to decline.
Polyurea Spraying integrates the plurality of advantages of the anti-corrosion materials such as coating, rubber and plastics, be at present in the world
One of state-of-the-art aseptic technic.Its technical advantage is mainly manifested in rapid curing, can be in any curved surface spraying without generating stream
Phenomenon is dropped down, gel time is as short as 10s or hereinafter, 10min can reach walking intensity;It is insensitive to temperature, moisture, when construction
It is not influenced by environment temperature, humidity.Polyureas can construct under -28 DEG C of low temperature environment, can also be under moist rainy environment
Construction;100% solid content, meets environmental requirement, does not have smell in construction and use process, is especially suitable for the storage of improper ventilation
The anticorrosive construction of top tank structure and inner wall of the pipe;Primary construction can reach thickness requirement, and overcoming traditional anticorrosive paint must be more
The disadvantage of secondary construction;Coating is fine and close, seamless, can tolerate the long-term corrosion of the media such as water, seawater, acid, alkali, salt, oil, chemically-resistant
Medium and soil erosion ability are very prominent;High mechanical strength, elongation is good, and shock resistance is good, in temperature alternating and external force
Not cracky under percussion;Adhesive force is good, and adhesive force is greater than 10MPa on the steel of sandblasting to Sa2.5 grades, is used for a long time not
It falls off;Breakdown voltage resistant up to 20kv/mm or more is good with cathodic protection matching;Without catalyst, resistance to UV aging
Can be good, not dusting is used for a long time outdoors, does not crack;It is wide using temperature, it can be used for a long time at -50~+121 DEG C, modification is resistance to
High temperature polyureas can be 150 DEG C or less the long-time services the advantages that.
Polyurea Spraying has brilliant physical property and workability, is a kind of novel application techniques.It can be with
Substitute traditional polyurethane, epoxy resin, glass reinforced plastic, FBE and polyolefins compound completely or partially, chemical anticorrosion,
The industries such as pipeline, building, ship, water conservancy, traffic, machinery, mine be wear-resisting have broad application prospects.
Lining and coating two major classes are generally divided into for chemical metallization storage tank anti-corrosion material.Common lining has rubber lining
In, plastic lining and glass reinforced plastic lining etc..Rubber lining generally uses natural rubber or synthetic rubber, can make at normal temperatures and pressures
With.The disadvantage is that need scene heating vulcanization, construction technology is sufficiently complex, quality it is difficult to ensure that.Plastic lining is generally prefabricated section
Shape material applies the special barbola work of man-hour requirement, and seam crossing easily causes to leak, so as to cause global failure.Glass steel lining
In use hand paste technique, smell is big, pollution environment, and multiple tracks is needed to construct, and construction quality is difficult to ensure.
Traditional anticorrosive paint has the advantages that easy for construction, can use in inner wall or outer wall.But these coating systems one
As there is hardness have a surplus toughness deficiency, easily crack under thermal stress or percussion, premature cracking may cause storage
Liquid leakage, repairing and maintenance cause expense to increase;System contains organic solvent, is harmful to the human body, pollutes environment, solvent volatilization
The pin hole of generation will cause the infiltration of corrosive medium;It must be constructed using multiple tracks, the disadvantages of period is long, low efficiency.
Polyureas spraying technology efficiently solves above-mentioned problem, and applying in the inside and outside wall antiseptic project of steel storage tank has
Apparent technical advantage, Daqing oil field, Shengli Oil Field, Xinjiang Oilfield, Qilu Petrochemical, Lanzhou Petrochemical, Yueyang petrochemical industry original
It is applied successfully in the projects such as oil tank, heavy oil tank, Water Tank and hydrochloric acid tank car.
In addition, SPUA technology can also be used in the chemical storage tank for having thermal requirements, the protective layer as insulating layer.Traditional side
Method is galvanized iron sheet to be wrapped up outside polyurethane foam, but existing seam is easy to cause into water, and foam is corroded aging quickly.
And anti-corrosion and waterproof can be played a dual role of using SPUA technology, and it is seamless, it is both artistic and practical.
To prevent industrial chemicals from revealing, storage tank cofferdam is had around certain chemical storage tanks.The storage tank cofferdam of early stage is very
It is simple and crude, it is usually enclosed and is made by concrete or cob wall, rubble is spread in bottom.Once a large amount of leakages occur for raw material, cofferdam can
Interim storage, but the industrial chemicals revealed on a small quantity can penetrate into soil, cause serious pollution to soil.With developed country pair
Environmental protection is increasingly paid attention to, it is desirable that storage tank cofferdam must be completely enclosed with soil protection.Plastic lining is once in storage tank cofferdam
Using, have the advantages that antiseptic property is good, but complicated construction technique, it is especially non-in complex-shaped, more than pipe fitting place construction
It is often difficult.In addition, the plastic lining after construction there are a large amount of seams, leakage is often resulted in, however polyureas can be resistant to water and most
Number chemical mediators erosion, and have the characteristics that it is pollution-free, do not trickle, construct it is fast.More importantly polyureas bullet after spraying
Property body is seamless, flexibility is good, and elongation is up to 300% or more, the hair cracks on concrete substrate can be connected to one
It rises, antiseep excellent.Currently, polyureas widely applied on external concrete storage tank cofferdam Pacific Northwest with
And the application of Alaska Sector shows that polyureas can be subjected to harsh weather test.In addition to storage tank cofferdam, similar application neck
There are also the protection on the surfaces such as chemical industry trench, power plant gutter and ground impervious barrier in domain.
Polyureas represents the trend of international newest aseptic technic.Many famous pipeline engineering all make in the world at present
With polyureas or/in conjunction with polyurethane foam for the oil-gas pipeline that needs to keep the temperature.
With the Popularization And Development of polyureas technology, the superiority of polyureas technology, which has, has obtained the common recognition of people.Soon
In the future, polyureas will become together one of the main anti-corrosion material of pipeline outer wall with clinkery epoxy powder, 3PE.
SPUA material is also widely used as the inner wall anti-corrosive of ductile iron pipe, steel pipe and pipe of cement.Reaching 50 years makes
With the service life, cast iron pipe or steel pipe inner wall must carry out preservative treatment, and common method was lining cement mortar in the past.Cement mortar
Pipe lining with the longest history, but there are stress shrink after it is easy to crack, surface defect (such as pitted skin, sand cave, hollowing) is more;
Cement-mortar lining will cause the raising of dissolved matter content, and hardness changes, NH3It is precipitated, water quality is caused to alkalize;Water
Unstability also will affect the disadvantages of cement mortar.
As CO in water2Superequilibrium quantity concentration, which reaches 7mg/L, will lead to that mortar is impaired, and sand grains is lost, and influence water quality.SPUA material
Material, which is used as cast iron pipe inner wall anti-corrosion material, has adhesive force good, does not crack, corrosion resistance is strong, long service life;Surface is smooth, water
The power coefficient of friction resistance is fewer than concrete pipe and steel pipe, can improve emptying effectiveness.Under conditions of identical caliber, the power and energy of pump are saved
20% or more source, substantially reduces operating cost;Non-scaling, water quality will not be stain by the mushroom microorganism in water or oxidation and rusting,
The advantages that not generating secondary pollution, being able to maintain permanent carrying capacity and constant clean water quality degree.
A kind of manufacturing method of water-soluble poly carbamide resin, this method are introduced in China Patent No. ZL201110101576.3
The carbamide resin of acquisition is mainly used as the plated film of object.So that part of it carbamide resin is penetrated into inner, is conducive to improve poly-
Adherency between carbamide resin and object, the carbamide resin are mainly used as fiber plated film and concrete plated film waterproof etc..It is water-soluble at this
In the application process of property polyureas, there are the limitations of application field.
A kind of polyurea resin compound and curing agent, the combination are described in China Patent No. ZL201110403185.7
Object satisfaction does not need to solidify for a long time, and when solidification is not influenced by environmental conditions, and exposure for a long time is not in air for carbamide resin
Turn yellow, still, the curing time of the polyurea resin compound is relatively long in fact.
A kind of manufacturing process of nano material carbamide resin is described in China Patent No. ZL201210198415.5, it should
Carbamide paint is the carbamide resin synthesized using two component of A, B, while being blended into zinc oxide or the titanium dioxide of 20~50nm
As the inorganic modified packing material of carbamide resin, however, in the technical process of the invention, the zinc oxide and titanium dioxide of use
Granularity seem and become larger.
It is strong for the shock resistance for further increasing carbamide resin in view of deficiency, the present invention present on the above patented technology
Degree, in the process of the present invention, is suitably added inorganic carbon sources packing material, and the purpose is to not reduce carbamide paint using the longevity
Under the premise of life, the manufacturing cost of carbamide paint is improved, is conducive to the application field for expanding polyurea modified composite material.
Summary of the invention:
The purpose of the present invention is studying a kind of manufacturing process of carbamide paint, under the premise of not increasing manufacturing cost, fill
The characteristics of dividing using synthesis carbamide resin, the performance for improving carbamide paint by reasonably selecting process control condition, raw material is special
Sign, reaches the final purpose of optimization performance, while reducing the industrial production cost of carbamide paint.
The purpose of the present invention is be realized in that
A kind of carbamide resin synthesis technology, the carbamide paint component A are living by 4,4 '-'-diphenylmethane diisocyanates, height
Property polypropylene oxide-ethylene oxide ethoxylated polyhydric alcohol, chlorobenzoyl chloride, dispersing agent, ethyl carbonate composition, in certain process control condition
Under, the performed polymer of 4,4 '-'-diphenylmethane diisocyanates is synthesized, B component is by 4,4 '-bis- sec-butylamine base diphenyl methanes, 2-
(4- aminophenyl) -5 (6) aminophenyl benzimidazole, pigment, ethyl carbonate composition, under certain process control condition, mixing
Form the B component containing chain extender;Under the process control condition of the preparation process of coating, A, B component are formed after spraying
Polyurea coating.Itself the specific process is as follows:
1, it is added in a kettle and accounts for twice of component A total weight of ethyl carbonate, high activity polypropylene oxide-ethylene oxide
Ethoxylated polyhydric alcohol, sorbitan fatty acid ester dispersing agent are high first with closed reactor after air 10min in nitrogen displacement bottle
4,4 '-'-diphenylmethane diisocyanates are gradually added drop-wise to high activity under vigorous stirring by speed stirring premix 18~26min of bottom material
In the system of polypropylene oxide-ethylene oxide ethoxylated polyhydric alcohol and ethyl carbonate.Reaction temperature is 66~88 DEG C, is continued after adding anti-
It answers 4.5~6.0h and then chlorobenzoyl chloride is added, the reaction was continued 0.6~1.0h, immediately in -0.088~-0.096MPa, temperature
Under conditions of 123~136 DEG C, 3.5~4.5h is vacuumized, small molecule and residual monomer is removed, is cooled to room temperature, obtains polyureas
Component A performed polymer needed for coating;Wherein, high activity polypropylene oxide-ethylene oxide ethoxylated polyhydric alcohol accounts for the 33 of component A total weight
~38%wt, sorbitan fatty acid ester are 0.3~0.6%wt, and 4,4 '-'-diphenylmethane diisocyanates are 62~67%;
Chlorobenzoyl chloride is 0.3~0.6%wt;Dispersing agent hydroxyethyl ethylenediamine triacetate is 3~6%wt.
2, under the protection of nitrogen, it is added twice of B component total weight of ethyl carbonate into reaction kettle, it is added 0.3~
The sorbitan fatty acid ester of 0.6%wt adds and 4,4 '-diphenylmethane diisocyanates under conditions of being stirred continuously
The molar ratio of ester is -5 (6) aminophenyl benzo miaow of 4,4 '-bis- sec-butylamine base diphenyl methanes and 2- (4- aminophenyl) of 1:1
The mixture of azoles heats mixture, temperature is made to rise to 68~86 DEG C under conditions of control stirring rate is 200~300rpm,
Flow back 38~48min, with the mixture of B component is cooled to room temperature, chain extender B component needed for obtaining carbamide paint;Its
In the molar ratio of -5 (6) aminophenyl benzimidazole of 4,4 '-bis- sec-butylamine base diphenyl methanes and 2- (4- aminophenyl) be
0.68~0.86:0.32~0.14.
3, the chain extender B component obtained by component A performed polymer needed for the carbamide paint 1) obtained and 2), by spraying
Afterwards, setting time is 3~8s.
In the process of the present invention, in order to improve the rigidity and wearability of carbamide resin coating, in synthesis carbamide resin
In component, it is suitably added -5 (6) aminophenyl benzimidazole of 2- (4- aminophenyl), the purpose is to make full use of 2- (4- amino
Phenyl) -5 (6) aminophenyl benzimidazoles molecular structure in, containing there are two the rigid structure of phenyl ring and an imidazole ring, warp
It crosses and tests repeatedly, discovery is after being added a certain amount of -5 (6) aminophenyl benzimidazole of 2- (4- aminophenyl), carbamide resin
The rigidity and wearability of coating are able to a degree of raising, and in order to adapt to the application of carbamide resin coating, 2- (4- amino is added
Phenyl) -5 (6) aminophenyl benzimidazoles amount it is relatively large.By the way that -5 (6) of relatively great amount of 2- (4- aminophenyl) are added
After the monomer of aminophenyl benzimidazole, it is found that the impact strength of polyurea coating is greatly improved, tested discovery repeatedly
The impact strength of carbamide resin coating is related with the rigid structure of its phenyl ring and imidazole ring, while suitably increasing 2- (4-
Aminophenyl) -5 (6) aminophenyl benzimidazoles monomer dosage after, impact strength increase it is fairly obvious, still, when
- 5 (6) aminophenyl benzimidazole monomer dosage of 2- (4- aminophenyl) increases to 0.38mol/mol 4,4 '-bis- sec-butylamine bases
When diphenyl methane, the increase of obtained carbamide resin coating impact strength at double but sacrifices its of carbamide resin coating
His characteristic, such formula is out of season.
When -5 (6) aminophenyl benzimidazole monomer dosage of 2- (4- aminophenyl) is reduced to 0.03mol/mol 4,4 ' -
When double sec-butylamine base diphenyl methanes, the reduction of obtained carbamide resin coating impact strength at double, it is such formula be also
It is out of season.
In addition the present invention is control appropriate using the purpose of 2- (4- aminophenyl) -5 (6) aminophenyl benzimidazole monomer
Make 4,4 '-'-diphenylmethane diisocyanate performed polymers and 4,4 '-bis- sec-butylamine base diphenyl methanes reaction rate, simultaneously
The internal stress of polyurea coating is reduced, and then improves the adhesive force of polyurea coating, be conducive to raising carbamide resin coating uses the longevity
Life.
In the process of the present invention, it in order to improve the flexibility of carbamide resin coating, is added in the structure of polyurea coating
Certain high activity polypropylene oxide-ethylene oxide ethoxylated polyhydric alcohol containing epoxy construction, the purpose is to apply improving polyureas
The flexibility of layer.
In the process of the present invention, it either during the pre-polymerization of component A or in the forming process of B component, is intended to
Deaeration is carried out to component materials or removes the processing of volatile substances, the purpose is to reduce the generation of polyurea coating forming process
Stomata, to shorten the service life of polyurea coating.
In the process of the present invention, quickly due to 4,4 '-'-diphenylmethane diisocyanates and aminated compounds reaction rate,
In order to reduce the reaction rate of MDI and aminated compounds, MDI compound is subjected to a degree of modification, is converted it into
MDI tripolymer compound, and 4 are made full use of, 4 '-'-diphenylmethane diisocyanates (MDI) can occur three under catalytic action
Poly- reaction, is limited by reaction condition, usually mainly obtains tripolymer, pentamer, heptamer etc. containing isocyanurate ring
Mixture.But in order to synthesis process again through may more than obtain 4,4 '-'-diphenylmethane diisocyanate tripolymer compounds,
When reaction carries out to a certain extent, addition chlorobenzoyl chloride makes 4,4 '-'-diphenylmethane diisocyanates terminate reaction, due to HDI tri-
Aggressiveness belongs to aliphatic compound, the characteristics of according to carbamide resin coating, is free of this kind of oxidizable group of phenyl ring, therefore have
There is good anti-yellowing property.Meanwhile the stable structure of the isocyanurate ring of HDI trimer, not legibility at high temperature, therefore
It has many advantages, such as that thermal stability is good, wearability is good, good corrosion resistance.
The present invention fits in two active principles of A, B as needed in order to improve the mobility of carbamide resin figure layer component
When the certain ethyl carbonate of addition, purpose improves the mobility of A, B component in spraying process, reduces polyurea coating because instead
It answers rate too fast, causes the phenomenon that coating is uneven, be on the one hand conducive to construct in this way, in addition improve the matter of polyurea coating
Amount.
Certainly the present invention appropriate can select to increase the aesthetics of polyurea coating according to the color of coated article part
A certain amount of organic or inorganic pigment is added, the purpose is to can also improve while improving the aesthetic measure of coated article part
The simulation quality of coated article part.
Discoloration occurs because of ultraviolet irradiation in order to reduce polyurea coating, antioxidant can be properly added in B component.
Meanwhile according to the application of polyurea coating, certain fire retardant can also be added, or is added centainly in its component
Defoaming agent, to improve the anti-flammability and compactness of polyurea coating.
The defoaming agent and pigment that can be added in the present invention are in order to according to poly- not within claim of the invention
The actual needs of urea coating is properly added.
Process description of the invention:
In the manufacturing process of carbamide paint of the present invention, under certain process control condition, 4,4 '-two are added into reaction kettle
Phenylmethane diisocyanate, high activity polypropylene oxide-ethylene oxide ethoxylated polyhydric alcohol, chlorobenzoyl chloride, dispersing agent are closed by reaction
At containing 4,4 '-'-diphenylmethane diisocyanates and high activity polypropylene oxide-ethylene oxide ethoxylated polyhydric alcohol performed polymer A group
Point, performed polymer becomes a kind of solids, is convenient for construction application after the substance processing of deaeration or removing volatilization.
Under certain process control condition, a certain amount of ethyl carbonate is added into reaction kettle, in the condition being sufficiently stirred
Under, dispersing agent, which is dissolved in ethyl carbonate solvent, adds 4,4 '-bis- sec-butylamine base diphenyl methanes, 2- (4- aminophenyl) -5
(6) aminophenyl benzimidazole, so that these mixture of substances are uniform, forms the B group containing chain extender by being sufficiently stirred
Point.
The carbamide paint forms polyurea coating by spraying.
The beneficial effects of the present invention are:
Carbamide paint of the invention has high stabile against thermal denaturation, tensile strength and high tenacity, chemicals-resistant corrosivity high, excellent
Different electrical insulation capability is used as the insulating materials or encapsulating material of electronics, appliance device, also can be widely used to machinery, chemical industry,
Petroleum, military project, field of aerospace.
Detailed description of the invention:
Fig. 1 is 1 polyurea coating performance characteristic table of comparative example of the invention.
Fig. 2 is 2 polyurea coating performance characteristic table of comparative example of the invention.
Specific embodiment
Technique of the invention is described in further detail below with reference to embodiment.
Embodiment 1:
Addition accounts for twice of component A total weight of ethyl carbonate, 33%wt high activity polypropylene oxide-oxidation in a kettle
Ethylene ethoxylated polyhydric alcohol, 0.3%wt sorbitan fatty acid ester dispersing agent, dispersing agent hydroxyethyl ethylenediamine triacetate are 3%
Wt, first with closed reactor after air 10min in nitrogen displacement bottle, high-speed stirred premixes bottom material 18min, in high degree of agitation
It is lower by 67%wt4,4 '-'-diphenylmethane diisocyanates are gradually added drop-wise to high activity polypropylene oxide-ethylene oxide ethoxylated polyhydric alcohol
In the system of ethyl carbonate.Reaction temperature is 66 DEG C, the reaction was continued 6.0h and then 0.3%wt benzoyl is added after adding
Chlorine, the reaction was continued 0.6h vacuumize 3.5h immediately under conditions of -0.088MPa, temperature are 136 DEG C, remove small molecule and residual
Remaining monomer, is cooled to room temperature, component A performed polymer needed for obtaining carbamide paint.
Under the protection of nitrogen, twice of B component total weight of ethyl carbonate is added into reaction kettle, is added 0.3%wt's
Sorbitan fatty acid ester adds and mole of 4,4 '-'-diphenylmethane diisocyanates under conditions of being stirred continuously
Than 4 for 1:1, the mixing of -5 (6) aminophenyl benzimidazole of 4 '-bis- sec-butylamine base diphenyl methanes and 2- (4- aminophenyl)
Object heats mixture under conditions of control stirring rate is 200rpm, and temperature is made to rise to 86 DEG C, and flow back 38min, with i.e. by B
The mixture of component is cooled to room temperature, chain extender B component needed for obtaining carbamide paint;Wherein 4,4 '-bis- sec-butylamine base hexichol
The molar ratio of -5 (6) aminophenyl benzimidazole of methylmethane and 2- (4- aminophenyl) is 0.68:0.32.
Component A performed polymer needed for carbamide paint derived above and 2 are contained into chain extender B component, after spraying, coagulated
Gu the time is 8s.
Embodiment 2:
Addition accounts for twice of component A total weight of ethyl carbonate, 38%wt high activity polypropylene oxide-oxidation in a kettle
Ethylene ethoxylated polyhydric alcohol, 0.6%wt sorbitan fatty acid ester dispersing agent, dispersing agent hydroxyethyl ethylenediamine triacetate are 6%
Wt, first with closed reactor after air 10min in nitrogen displacement bottle, high-speed stirred premixes bottom material 26min, in high degree of agitation
It is lower by 62%wt4,4 '-'-diphenylmethane diisocyanates are gradually added drop-wise to high activity polypropylene oxide-ethylene oxide ethoxylated polyhydric alcohol
In the system of ethyl carbonate.Reaction temperature is 88 DEG C, the reaction was continued 4.5h and then 0.6%wt benzoyl is added after adding
Chlorine, the reaction was continued 1.0h vacuumize 4.5h immediately under conditions of -0.096MPa, temperature are 123 DEG C, remove small molecule and residual
Remaining monomer, is cooled to room temperature, component A performed polymer needed for obtaining carbamide paint.
Under the protection of nitrogen, twice of B component total weight of ethyl carbonate is added into reaction kettle, is added 0.6%wt's
Sorbitan fatty acid ester adds and mole of 4,4 '-'-diphenylmethane diisocyanates under conditions of being stirred continuously
Than 4 for 1:1, the mixing of -5 (6) aminophenyl benzimidazole of 4 '-bis- sec-butylamine base diphenyl methanes and 2- (4- aminophenyl)
Object heats mixture under conditions of control stirring rate is 300rpm, and temperature is made to rise to 68 DEG C, and flow back 48min, with i.e. by B
The mixture of component is cooled to room temperature, chain extender B component needed for obtaining carbamide paint;Wherein 4,4 '-bis- sec-butylamine base hexichol
The molar ratio of -5 (6) aminophenyl benzimidazole of methylmethane and 2- (4- aminophenyl) is 0.86:0.14.
Component A performed polymer needed for carbamide paint derived above and 2 are contained into chain extender B component, after spraying, coagulated
Gu the time is 3s.
Embodiment 3:
Addition accounts for twice of component A total weight of ethyl carbonate, 34%wt high activity polypropylene oxide-oxidation in a kettle
Ethylene ethoxylated polyhydric alcohol, 0.4%wt sorbitan fatty acid ester dispersing agent, dispersing agent hydroxyethyl ethylenediamine triacetate are 4%
Wt, first with closed reactor after air 10min in nitrogen displacement bottle, high-speed stirred premixes bottom material 21min, in high degree of agitation
It is lower by 66%wt4,4 '-'-diphenylmethane diisocyanates are gradually added drop-wise to high activity polypropylene oxide-ethylene oxide ethoxylated polyhydric alcohol
In the system of ethyl carbonate.Reaction temperature is 72 DEG C, the reaction was continued 5.3h and then 0.4%wt benzoyl is added after adding
Chlorine, the reaction was continued 0.8h vacuumize 4.1h immediately under conditions of -0.090MPa, temperature are 126 DEG C, remove small molecule and residual
Remaining monomer, is cooled to room temperature, component A performed polymer needed for obtaining carbamide paint.
Under the protection of nitrogen, twice of B component total weight of ethyl carbonate is added into reaction kettle, is added 0.4%wt's
Sorbitan fatty acid ester adds and mole of 4,4 '-'-diphenylmethane diisocyanates under conditions of being stirred continuously
Than 4 for 1:1, the mixing of -5 (6) aminophenyl benzimidazole of 4 '-bis- sec-butylamine base diphenyl methanes and 2- (4- aminophenyl)
Object heats mixture under conditions of control stirring rate is 220pm, and temperature is made to rise to 71 DEG C, and flow back 41min, with i.e. by B
The mixture of component is cooled to room temperature, chain extender B component needed for obtaining carbamide paint;Wherein 4,4 '-bis- sec-butylamine base hexichol
The molar ratio of -5 (6) aminophenyl benzimidazole of methylmethane and 2- (4- aminophenyl) is 0.73:0.27.
Component A performed polymer needed for carbamide paint derived above and 2 are contained into chain extender B component, after spraying, coagulated
Gu the time is 4s.
Comparative example 1:
33%wt high activity polypropylene oxide-ethylene oxide ethoxylated polyhydric alcohol, 0.3%wt dehydration mountain are added in a kettle
Pears alcohol fatty acid ester dispersing agent, dispersing agent hydroxyethyl ethylenediamine triacetate is 3%wt, first with air in nitrogen displacement bottle
Closed reactor after 10min, high-speed stirred premixes bottom material 18min, under vigorous stirring by 67%wt4,4 '-diphenyl-methanes two
Isocyanates is gradually added drop-wise in the system of high activity polypropylene oxide-ethylene oxide ethoxylated polyhydric alcohol and ethyl carbonate.Reaction temperature
Degree is 86 DEG C, the reaction was continued 4.5h and then 0.3%wt chlorobenzoyl chloride is added after adding, the reaction was continued 0.6h, immediately-
Under conditions of 0.088MPa, temperature are 136 DEG C, 4.5h is vacuumized, small molecule and residual monomer is removed, is cooled to room temperature, obtains
A component performed polymer needed for carbamide paint.
Under the protection of nitrogen, the sorbitan fatty acid ester of 0.3%wt is added into reaction kettle, what is be stirred continuously
Under the conditions of, add 4, the 4 '-bis- sec-butylamine base diphenylmethyls for being 1:1 with the molar ratio of 4,4 '-'-diphenylmethane diisocyanates
The mixture of -5 (6) aminophenyl benzimidazole of alkane and 2- (4- aminophenyl), the condition that control stirring rate is 200rpm
Under, mixture is heated, temperature is made to rise to 86 DEG C, flow back 38min, with the mixture of B component is cooled to room temperature, is gathered
Chain extender B component needed for urea coating;Wherein -5 (6) ammonia of 4,4 '-bis- sec-butylamine base diphenyl methanes and 2- (4- aminophenyl)
The molar ratio of base phenylbenzimidazol is 0.68:0.32.
Component A performed polymer needed for carbamide paint derived above and 2 are contained into chain extender B component, after spraying, coagulated
Gu the time is 3s.
This example compares with example 1, is added without ethyl carbonate in a kettle, is found that while the basic phase of setting time
Together, but there is certain rough place in obtained polyurea coating surface.
Embodiment 4:
Addition accounts for twice of component A total weight of ethyl carbonate, 35%wt high activity polypropylene oxide-oxidation in a kettle
Ethylene ethoxylated polyhydric alcohol, 0.5%wt sorbitan fatty acid ester dispersing agent, dispersing agent hydroxyethyl ethylenediamine triacetate are 5%
Wt, first with closed reactor after air 10min in nitrogen displacement bottle, high-speed stirred premixes bottom material 23min, in high degree of agitation
It is lower by 65%wt4,4 '-'-diphenylmethane diisocyanates are gradually added drop-wise to high activity polypropylene oxide-ethylene oxide ethoxylated polyhydric alcohol
In the system of ethyl carbonate.Reaction temperature is 81 DEG C, the reaction was continued 5.8h and then 0.5%wt benzoyl is added after adding
Chlorine, the reaction was continued 0.8h vacuumize 4.5h immediately under conditions of -0.093MPa, temperature are 135 DEG C, remove small molecule and residual
Remaining monomer, is cooled to room temperature, component A performed polymer needed for obtaining carbamide paint.
Under the protection of nitrogen, twice of B component total weight of ethyl carbonate is added into reaction kettle, is added 0.5%wt's
Sorbitan fatty acid ester adds and mole of 4,4 '-'-diphenylmethane diisocyanates under conditions of being stirred continuously
Than 4 for 1:1, the mixing of -5 (6) aminophenyl benzimidazole of 4 '-bis- sec-butylamine base diphenyl methanes and 2- (4- aminophenyl)
Object heats mixture under conditions of control stirring rate is 246rpm, and temperature is made to rise to 81 DEG C, and flow back 44min, with i.e. by B
The mixture of component is cooled to room temperature, chain extender B component needed for obtaining carbamide paint;Wherein 4,4 '-bis- sec-butylamine base hexichol
The molar ratio of -5 (6) aminophenyl benzimidazole of methylmethane and 2- (4- aminophenyl) is 0.81:0.19.
Component A performed polymer needed for carbamide paint derived above and 2 are contained into chain extender B component, after spraying, coagulated
Gu the time is 6s.
Embodiment 5:
Addition accounts for twice of component A total weight of ethyl carbonate, 36%wt high activity polypropylene oxide-oxidation in a kettle
Ethylene ethoxylated polyhydric alcohol, 0.3%wt sorbitan fatty acid ester dispersing agent, dispersing agent hydroxyethyl ethylenediamine triacetate are
3.8%wt, first with closed reactor after 10 min of air in nitrogen displacement bottle, high-speed stirred premixes bottom material 26min, in fierceness
By 64%wt4 under stirring, it is more that 4 '-'-diphenylmethane diisocyanates are gradually added drop-wise to high activity polypropylene oxide-ethylene oxide ether
In the system of the pure and mild ethyl carbonate of member.Reaction temperature is 88 DEG C, the reaction was continued 6.0h and then 0.4%wt benzene is added after adding
Formyl chloride, the reaction was continued, and 1.0h vacuumizes 4.5h, removes small point immediately under conditions of -0.096 MPa, temperature are 136 DEG C
Son and residual monomer, are cooled to room temperature, component A performed polymer needed for obtaining carbamide paint.
Under the protection of nitrogen, twice of B component total weight of ethyl carbonate is added into reaction kettle, is added 0.3%wt's
Sorbitan fatty acid ester adds and mole of 4,4 '-'-diphenylmethane diisocyanates under conditions of being stirred continuously
Than 4 for 1:1, the mixing of -5 (6) aminophenyl benzimidazole of 4 '-bis- sec-butylamine base diphenyl methanes and 2- (4- aminophenyl)
Object heats mixture under conditions of control stirring rate is 300rpm, and temperature is made to rise to 86 DEG C, and flow back 48min, with i.e. by B
The mixture of component is cooled to room temperature, chain extender B component needed for obtaining carbamide paint;Wherein 4,4 '-bis- sec-butylamine base hexichol
The molar ratio of -5 (6) aminophenyl benzimidazole of methylmethane and 2- (4- aminophenyl) is 0.84:0.16.
Component A performed polymer needed for carbamide paint derived above and 2 are contained into chain extender B component, after spraying, coagulated
Gu the time is 5s.
Embodiment 6:
Addition accounts for twice of component A total weight of ethyl carbonate, 37%wt high activity polypropylene oxide-oxidation in a kettle
Ethylene ethoxylated polyhydric alcohol, 0.6%wt sorbitan fatty acid ester dispersing agent, dispersing agent hydroxyethyl ethylenediamine triacetate are
4.8%wt, first with closed reactor after 10 min of air in nitrogen displacement bottle, high-speed stirred premixes bottom material 18min, in fierceness
By 63%wt4 under stirring, it is more that 4 '-'-diphenylmethane diisocyanates are gradually added drop-wise to high activity polypropylene oxide-ethylene oxide ether
In the system of the pure and mild ethyl carbonate of member.Reaction temperature is 66 DEG C, the reaction was continued 4.5h and then 0.6%wt benzene is added after adding
Formyl chloride, the reaction was continued, and 0.6h vacuumizes 3.5h, removes small point immediately under conditions of -0.088MPa, temperature are 123 DEG C
Son and residual monomer, are cooled to room temperature, component A performed polymer needed for obtaining carbamide paint.
Under the protection of nitrogen, twice of B component total weight of ethyl carbonate is added into reaction kettle, is added 0.6%wt's
Sorbitan fatty acid ester adds and mole of 4,4 '-'-diphenylmethane diisocyanates under conditions of being stirred continuously
Than 4 for 1:1, the mixing of -5 (6) aminophenyl benzimidazole of 4 '-bis- sec-butylamine base diphenyl methanes and 2- (4- aminophenyl)
Object heats mixture under conditions of control stirring rate is 200rpm, and temperature is made to rise to 68 DEG C, and flow back 38min, with i.e. by B
The mixture of component is cooled to room temperature, chain extender B component needed for obtaining carbamide paint;Wherein 4,4 '-bis- sec-butylamine base hexichol
The molar ratio of -5 (6) aminophenyl benzimidazole of methylmethane and 2- (4- aminophenyl) is 0.78:0.22.
Component A performed polymer needed for carbamide paint derived above and 2 are contained into chain extender B component, after spraying, coagulated
Gu the time is 7s.
Comparative example 2:
Addition accounts for twice of component A total weight of ethyl carbonate, 38%wt high activity polypropylene oxide-oxidation in a kettle
Ethylene ethoxylated polyhydric alcohol, 0.6%wt sorbitan fatty acid ester dispersing agent, dispersing agent hydroxyethyl ethylenediamine triacetate are 6%
Wt, first with closed reactor after air 10min in nitrogen displacement bottle, high-speed stirred premixes bottom material 26min, in high degree of agitation
It is lower by 62%wt4,4 '-'-diphenylmethane diisocyanates are gradually added drop-wise to high activity polypropylene oxide-ethylene oxide ethoxylated polyhydric alcohol
In the system of ethyl carbonate.Reaction temperature is 88 DEG C, after adding after the reaction was continued 6.0h, immediately -0.088~-
Under conditions of 0.096MPa, temperature are 123 DEG C, 4.5h is vacuumized, small molecule and residual monomer is removed, is cooled to room temperature, obtains
A component performed polymer needed for carbamide paint.
Under the protection of nitrogen, twice of B component total weight of ethyl carbonate is added into reaction kettle, is added 0.6%wt's
Sorbitan fatty acid ester adds and mole of 4,4 '-'-diphenylmethane diisocyanates under conditions of being stirred continuously
Than 4 for 1:1, the mixing of -5 (6) aminophenyl benzimidazole of 4 '-bis- sec-butylamine base diphenyl methanes and 2- (4- aminophenyl)
Object heats mixture under conditions of control stirring rate is 300rpm, and temperature is made to rise to 68 DEG C, and flow back 48min, with i.e. by B
The mixture of component is cooled to room temperature, chain extender B component needed for obtaining carbamide paint;Wherein 4,4 '-bis- sec-butylamine base hexichol
The molar ratio of -5 (6) aminophenyl benzimidazole of methylmethane and 2- (4- aminophenyl) is 0.86:0.14.
Component A performed polymer needed for carbamide paint derived above and 2 are contained into chain extender B component, after spraying, coagulated
Gu the time is 18s.
This example compares with example 2, it is found that the setting time of polyureas is opposite and extend, tracing it to its cause is in MDI performed polymer
Synthesis process in, since reaction rate is too fast, the degree of polymerization of MDI performed polymer is caused to increase.
Claims (1)
1. a kind of carbamide resin synthesis technology, which is characterized in that the carbamide paint component A is by 4,4 '-diphenyl-methane, two isocyanide
Acid esters, high activity polypropylene oxide-ethylene oxide ethoxylated polyhydric alcohol, chlorobenzoyl chloride, dispersing agent, ethyl carbonate composition, in certain work
Under skill control condition, the performed polymer of 4,4 '-'-diphenylmethane diisocyanates is synthesized, B component is by 4,4 '-bis- sec-butylamine base hexichol
Methylmethane, -5 (6) aminophenyl benzimidazole of 2- (4- aminophenyl), pigment, ethyl carbonate composition, in certain technology controlling and process item
Under part, it is mixed to form the B component containing chain extender;Under the process control condition of the preparation process of coating, A, B component are by spray
Polyurea coating is formed after painting;Itself the specific process is as follows:
1) in a kettle be added account for twice of component A total weight ethyl carbonate, high activity polypropylene oxide-ethylene oxide ether it is more
First alcohol, sorbitan fatty acid ester dispersing agent, first with closed reactor after air 10min in nitrogen displacement bottle, high-speed stirring
Premix 18~26min of bottom material is mixed, 4,4 '-'-diphenylmethane diisocyanates are gradually added drop-wise to high activity polyoxy under vigorous stirring
In the system for changing propylene-ethylene oxide ethoxylated polyhydric alcohol and ethyl carbonate.Reaction temperature is 66~88 DEG C, and the reaction was continued after adding
4.5~6.0h and then chlorobenzoyl chloride is added, the reaction was continued 0.6~1.0h is in -0.088~-0.096MPa, temperature immediately
Under conditions of 123~136 DEG C, 3.5~4.5h is vacuumized, small molecule and residual monomer is removed, is cooled to room temperature, obtains polyureas painting
Component A performed polymer needed for material;Wherein, high activity polypropylene oxide-ethylene oxide ethoxylated polyhydric alcohol account for component A total weight 33~
38%wt, sorbitan fatty acid ester are 0.3~0.6%wt, and 4,4 '-'-diphenylmethane diisocyanates are 62~67%;Point
Powder chlorobenzoyl chloride is 0.3~0.6%wt;Dispersing agent hydroxyethyl ethylenediamine triacetate is 3~6%wt;
2) under the protection of nitrogen, twice of B component total weight of ethyl carbonate is added into reaction kettle, 0.3~0.6%wt is added
Sorbitan fatty acid ester, under conditions of being stirred continuously, add with mole of 4,4 '-'-diphenylmethane diisocyanates
Than 4 for 1:1, the mixing of -5 (6) aminophenyl benzimidazole of 4 '-bis- sec-butylamine base diphenyl methanes and 2- (4- aminophenyl)
Object heats mixture under conditions of control stirring rate is 200~300rpm, and temperature is made to rise to 68~86 DEG C, and reflux 38~
48min, with the mixture of B component is cooled to room temperature, chain extender B component needed for obtaining carbamide paint;Wherein 4,4 '-is bis-
The molar ratio of -5 (6) aminophenyl benzimidazole of sec-butylamine base diphenyl methane and 2- (4- aminophenyl) is 0.68~0.86:
0.32~0.14;
3) the chain extender B component obtained by component A performed polymer needed for carbamide paint that step 1) obtains and 2), by spraying
Afterwards, setting time is 3~8s.
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CN113480840A (en) * | 2021-07-09 | 2021-10-08 | 成都上泰科技有限公司 | Method for manufacturing high-performance polyurea composite material containing reinforced fiber cloth |
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