CN104927615B - A kind of preparation method of the TDI tripolymer dumb light curing agent of low free monomer content - Google Patents
A kind of preparation method of the TDI tripolymer dumb light curing agent of low free monomer content Download PDFInfo
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- CN104927615B CN104927615B CN201510337036.3A CN201510337036A CN104927615B CN 104927615 B CN104927615 B CN 104927615B CN 201510337036 A CN201510337036 A CN 201510337036A CN 104927615 B CN104927615 B CN 104927615B
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- butyl acetate
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- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 40
- 239000000178 monomer Substances 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title abstract description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 61
- 239000003054 catalyst Substances 0.000 claims abstract description 35
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000012948 isocyanate Substances 0.000 claims abstract description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000007787 solid Substances 0.000 claims abstract description 12
- -1 woodenware Substances 0.000 claims abstract description 10
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 9
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 9
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 27
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 25
- 239000000203 mixture Substances 0.000 claims description 23
- 238000001514 detection method Methods 0.000 claims description 17
- 238000010792 warming Methods 0.000 claims description 13
- 239000002253 acid Substances 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 10
- ADJMNWKZSCQHPS-UHFFFAOYSA-L zinc;6-methylheptanoate Chemical compound [Zn+2].CC(C)CCCCC([O-])=O.CC(C)CCCCC([O-])=O ADJMNWKZSCQHPS-UHFFFAOYSA-L 0.000 claims description 10
- WSFQLUVWDKCYSW-UHFFFAOYSA-M sodium;2-hydroxy-3-morpholin-4-ylpropane-1-sulfonate Chemical compound [Na+].[O-]S(=O)(=O)CC(O)CN1CCOCC1 WSFQLUVWDKCYSW-UHFFFAOYSA-M 0.000 claims description 9
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 8
- 230000015572 biosynthetic process Effects 0.000 claims description 8
- 229910052700 potassium Inorganic materials 0.000 claims description 8
- 239000011591 potassium Substances 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- AHDSRXYHVZECER-UHFFFAOYSA-N 2,4,6-tris[(dimethylamino)methyl]phenol Chemical compound CN(C)CC1=CC(CN(C)C)=C(O)C(CN(C)C)=C1 AHDSRXYHVZECER-UHFFFAOYSA-N 0.000 claims description 7
- 238000003786 synthesis reaction Methods 0.000 claims description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- 238000009472 formulation Methods 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- ONIKNECPXCLUHT-UHFFFAOYSA-N 2-chlorobenzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1Cl ONIKNECPXCLUHT-UHFFFAOYSA-N 0.000 claims description 5
- 229910017061 Fe Co Inorganic materials 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 238000005070 sampling Methods 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- QQGISFDJEJMKIL-JAIQZWGSSA-N (5z)-5-[[3-(hydroxymethyl)thiophen-2-yl]methylidene]-10-methoxy-2,2,4-trimethyl-1h-chromeno[3,4-f]quinolin-9-ol Chemical group C1=CC=2NC(C)(C)C=C(C)C=2C2=C1C=1C(OC)=C(O)C=CC=1O\C2=C/C=1SC=CC=1CO QQGISFDJEJMKIL-JAIQZWGSSA-N 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 claims description 2
- 238000013329 compounding Methods 0.000 claims 3
- 238000007689 inspection Methods 0.000 claims 1
- 239000003973 paint Substances 0.000 abstract description 25
- 239000002904 solvent Substances 0.000 abstract description 21
- 239000004814 polyurethane Substances 0.000 abstract description 14
- 229920002635 polyurethane Polymers 0.000 abstract description 14
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 4
- 239000003112 inhibitor Substances 0.000 abstract description 4
- 229920003023 plastic Polymers 0.000 abstract description 4
- 239000004033 plastic Substances 0.000 abstract description 4
- 238000006116 polymerization reaction Methods 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 229920000728 polyester Polymers 0.000 abstract description 3
- 229910052751 metal Inorganic materials 0.000 abstract description 2
- 239000002184 metal Substances 0.000 abstract description 2
- 230000037452 priming Effects 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 17
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 15
- 238000000034 method Methods 0.000 description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 8
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 8
- 150000002513 isocyanates Chemical class 0.000 description 7
- 238000001704 evaporation Methods 0.000 description 6
- 239000010408 film Substances 0.000 description 6
- 239000004215 Carbon black (E152) Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 229930195733 hydrocarbon Natural products 0.000 description 5
- 150000002430 hydrocarbons Chemical class 0.000 description 5
- 238000009413 insulation Methods 0.000 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 description 5
- 239000011248 coating agent Substances 0.000 description 4
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 4
- 235000011056 potassium acetate Nutrition 0.000 description 4
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 4
- 239000013638 trimer Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 2
- GTEXIOINCJRBIO-UHFFFAOYSA-N 2-[2-(dimethylamino)ethoxy]-n,n-dimethylethanamine Chemical class CN(C)CCOCCN(C)C GTEXIOINCJRBIO-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical group COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000011527 polyurethane coating Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000005292 vacuum distillation Methods 0.000 description 2
- MTZUIIAIAKMWLI-UHFFFAOYSA-N 1,2-diisocyanatobenzene Chemical compound O=C=NC1=CC=CC=C1N=C=O MTZUIIAIAKMWLI-UHFFFAOYSA-N 0.000 description 1
- OVSKIKFHRZPJSS-UHFFFAOYSA-N 2,4-D Chemical compound OC(=O)COC1=CC=C(Cl)C=C1Cl OVSKIKFHRZPJSS-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 206010011224 Cough Diseases 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 206010019233 Headaches Diseases 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- 206010023644 Lacrimation increased Diseases 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- YPWFISCTZQNZAU-UHFFFAOYSA-N Thiane Chemical compound C1CCSCC1 YPWFISCTZQNZAU-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 208000006673 asthma Diseases 0.000 description 1
- CMCJNODIWQEOAI-UHFFFAOYSA-N bis(2-butoxyethyl)phthalate Chemical compound CCCCOCCOC(=O)C1=CC=CC=C1C(=O)OCCOCCCC CMCJNODIWQEOAI-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 206010006451 bronchitis Diseases 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 230000007850 degeneration Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- MCPKSFINULVDNX-UHFFFAOYSA-N drometrizole Chemical compound CC1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 MCPKSFINULVDNX-UHFFFAOYSA-N 0.000 description 1
- 208000017574 dry cough Diseases 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 231100000869 headache Toxicity 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- 150000002440 hydroxy compounds Chemical class 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 230000004317 lacrimation Effects 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000001473 noxious effect Effects 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000029058 respiratory gaseous exchange Effects 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- ANOBYBYXJXCGBS-UHFFFAOYSA-L stannous fluoride Chemical compound F[Sn]F ANOBYBYXJXCGBS-UHFFFAOYSA-L 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 description 1
- 239000000052 vinegar Substances 0.000 description 1
- 235000021419 vinegar Nutrition 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- 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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/78—Nitrogen
- C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
- C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
- C08G18/794—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aromatic isocyanates or isothiocyanates
Abstract
The present invention relates to a kind of preparation method of the TDI tripolymer dumb light curing agent of low free monomer content, its formula components is：2,4 toluene di-isocyanate(TDI)s, PPG, long-chain alcohol, catalyst A, n-butanol, catalyst B, polymerization inhibitor, antioxidant and solvent；The TDI tripolymer dumb light curing agent of low free monomer content produced by the present invention, solid content is that 50 ± 2%, nco value is 8.0 ± 0.3%, viscosity (apply 4 glasss) 15~25s, free TDI≤0.5%, toluene tolerance >=1, aromatic-free, with environmental protection, scratch resistance it is good, it is transparent good the features such as；The polyurethane paint prepared with hydroxy component has high rigidity, high transparency, paint film resistance to marring is good, levelability is good, the features such as richness is high, intermiscibility is wide, is to be used for the environment-friendlycuring curing agents such as various bi-component polyester paints, polyurethane paint, decorative paint, floor paint, the priming paint such as woodenware, metal, plastics.
Description
Technical field
The present invention relates to a kind of preparation method of polyurethane curing agent, more particularly to a kind of low free monomer content
TDI tripolymer dumb light curing agent.
Background technology
Bicomponent polyurethane coating is usually to be made up of isocyanate prepolymer and hydroxy-containing resin two parts, commonly referred to as
Curing agent component and host component, can be divided into acroleic acid polyurethane, alcohol acid and polyurethane, polyester according to the difference of hydroxy-containing component and gather
The kinds such as urethane, polyether-polyurethane, epoxy polyurethane, typically all with film-forming temperature is low, adhesive force is strong, hardness is big, wearability
The superior functions such as good and chemicals-resistant, good weatherability, are a kind of coating most widely used at present, are mainly used in original factory of vehicle
The side such as paint, plastic paint, woodcare paint, industrial paint, anticorrosive paint floor paint, electronic paint, fabric leather coating, printing-ink industry
Face.In China, polyurethane coating accounts for 75% or so the market share in woodwork coating, 40% is accounted in car refinishing paint left
The right market share, also increasingly wider in the application of other field such as anticorrosive paint, plastic paint etc., the market share is about
10%.
The TDI curing agent commonly used on the market at present has TDI tripolymers, TDI-TMP addition products, and produces the main of curing agent
Raw material is exactly toluene di-isocyanate(TDI) (abbreviation TDI), and TDI is a kind of volatilizable noxious material, the protein that it can be with human body
Reaction makes albuminous degeneration, therefore the maximum of human body is endangered.TDI steam has strong lacrimation, and breathing is stimulated after suction
System, causes dry cough, laryngalgia, headache, bronchitis and asthma, and serious meeting causes death.In order to avoid isocyanate-monomer
Harm to human body, each state all works out the limitation of polyurethane products free monomers；The European Community provide, containing TDI, HDI, IPDI,
The container outer wall of the chemicals such as HMDI must put up mark：Diisocyanate free monomer mass fraction person below 0.5%, outside
Wall indicates " containing isocyanates ", is environment-friendly products；Free monomer content indicates " harmful " caution sign 0.5%~2.0%
And " containing isocyanates "；Free monomer content person more than 2%, except " containing isocyanates " is indicated, must also indicate " poisonous " and attached
There is human skeleton bones of the dead mark.
Country has formulated mandatory standard in terms of coating environmental protection in recent years, in standard GB/T 18581-2009《It is indoor
Limits of harmful substances in decorating and renovating material solvent wood coatings》In define VOC in polyurethane paint
(VOC) content≤670g/L, benzene content≤0.3%, toluene, dimethylbenzene, ethylene total content≤30%, free TDI, | HDI contents
Summation≤0.4%.
Reducing polyurethane curing agent free TDI content of monomer turns into the direction of domestic coated sand intensifier industry emphasis tackling key problem, from
From the point of view of technical principle, the technological approaches of reduction free TDI can be divided into chemical method and physical method, including：It is direct synthesis technique, molten
Agent extraction, high vacuum film evaporation method, molecularly distilled and chemical catalysis method for refining etc..Current large-scale industrial production
It is mostly offshore company, such as Bayer companies, Rhodia companies, Nippon Polyurethane Industry Co., Ltd., minimizing technology is Gao Zhen
Empty film evaporation method.But high vacuum film evaporation method, invests excessive, process control needs are high, domestic at present to remove work to the method
Skill and plant issue are never solved well, and the free isocyanate monomer content in most of domestic TDI curing agent is tight
Weight is exceeded, and TDI content is difficult to accomplish within 0.5%, mostly 1% or so.
A kind of film evaporation method processing solidification is all disclosed in Chinese patent literature CN1793194A, CN101717571A
The method of free toluene diisocyanate in agent addition product, it is by the way of multiple-effect thin film evaporation, at high temperature by true
Empty mode evaporates free toluene di-isocyanate(TDI), and the content of free TDI is between 0.15~0.5%.
Chinese patent literature CN 101456940A disclose a kind of solvent-borne type of low free toluene diisocyanate content
The synthetic method of polyurethane curing agent, is carried out in two stages：First stage, by toluene di-isocyanate(TDI) and polyalcohol in a solvent
Reacted, detect that NCO content reacts the degree carried out to monitor by being sampled in the mixture of reaction in course of reaction,
When NCO stable content, the as reaction end of first stage；Second stage, second is added in the mixture of above-mentioned reaction
Ethyl sodio acetoacetic ester, continues to react, in course of reaction by sampled in the mixture of reaction detect NCO content monitor react into
Capable degree, after NCO content is stablized again, the as reaction end of second stage is also the terminal of total overall reaction, second
The reaction in stage is carried out at low temperature；Product is TDI-TMP addition products, 50% ＜ containing free TDI content 0.5% admittedly.Should
Method utilizes the difference of acetoacetic ester at low temperature with the reactivity of the NCO group on toluene di-isocyanate(TDI) diverse location,
By low-temp reaction, the purpose of reduction free toluene diisocyanate is reached；It is theoretically feasible, but TDI-80/20 has 2,
Two kinds of isomers of 4- toluene di-isocyanate(TDI)s and 2,6- toluene di-isocyanate(TDI), the NCO reactivities on 4 are high, at low temperature
Can be reacted with acetoacetic ester, but the NCO on 2,6 due to steric hindrance be difficult and acetoacetic ester react, although 2,4-
Toluene diisocyanate monomer take part in reaction, but 2,6- toluene diisocyanate monomer are also present, therefore be difficult to accomplish 50%
Admittedly free TDI content ＜ 0.5% in the TDI-TMP curing agent contained；Other curing agent is long in period of storage, variation of ambient temperature
Under can cause reaction, nco value reduction, viscosity increase, easy gel.
Chinese patent literature CN 100439414C disclose a kind of preparation method of low-free TDI trimer curing agent,
It includes：By in TDI, solvent S, catalyst A input reactors, antioxidant and long-chain alcohol are added, heating and thermal insulation detects nco value；
When nco value reaches 20~40%, Phase transfer solvent X and catalyst B is added, when nco value reaches 10~15%, resistance is added
Poly- agent stopped reaction；Supplementing solvent S, vacuum distillation removes Phase transfer solvent X.Wherein solvent S be ethyl acetate, butyl acetate,
And its mixture；Phase transfer solvent X is petroleum ether, dimethyl carbonate, normal hexane, thiacyclohexane or its any mixture；Catalyst
A, catalyst B are all lithium acetate, KOH, NaOH, tributylphosphine, triethylenediamine and its any mixture；Obtained product
For TDI tripolymers, 45% ＜ containing free TDI content 0.5% admittedly.The method is the improved process of solvent extraction, unreacted trip
Free isocyanate monomer-soluble solution in hydrocarbon mixture (such as petroleum ether, dimethyl carbonate, n-hexane, hexamethylene benzene or its mixture),
And curing agent polymer is then unable to solution modeling in bottom, then continue plus catalyst reaction in upper strata mixing hydrocarbon solvent, still
It is difficult to which its reaction of control, easily produces high polymer, or even gel in the case of stirring in a kettle；It is lower free without stirring
Isocyanate-monomer is difficult that reaction is complete.And ethyl acetate, butyl acetate low boiling point, easily with hydrocarbon mixture formation azeotropic mixture,
Conventional vacuum distillation is difficult to remove hydrocarbon mixture, then constantly adds and waste substantial amounts of ethyl acetate, butyl acetate；And decompression is steamed
Temperature will be improved when evaporating, the time is long, the curing agent in kettle is not just known whether or curing agent under catalyst, high temperature；Separately
Contain ester, free monomer in the solvent distilled outside, can neither use, can not discharge, storage is all a problem, therefore how
Recycling design is difficult.Both made method feasible, it is also not possible to eliminate the mixing hydrocarbon solvent remained in curing agent, eventually influence
Properties of product.
The content of the invention
The present invention is intended to provide a kind of preparation method of the TDI tripolymer dumb light curing agent of low free monomer content.
The present invention uses 2,4- toluene di-isocyanate(TDI)s to be that TDI trimer curing agents are raw material, it is to avoid 2,6- toluene two
NCO on isocyanates 2,6 is because steric hindrance is difficult to react and left behind；Conventional TDI trimer curing agents one
As it is all more crisp, pliability, glossiness and resistance to marring are all poor, and tolerance of the curing agent to toluene can be improved using long-chain alcohol
Degree and the pliability for improving film.
TDI trimer catalysts use DMP-30, triazine (PC-41), double (dimethylaminoethyl) ethers, triethylene two
Amine, isooctyl acid potassium, zinc Isoocatanoate, potassium acetate, zinc naphthenate or its mixture.
Later stage, the present invention used the hydroxy compounds n-butanol of small molecule free TDI to be converted into nontoxic material
The free TDI content of monomer in curing agent can be effectively reduced in the presence of catalyst；Reduce the catalyst of free TDI content
For isooctyl acid potassium, zinc Isoocatanoate, potassium acetate, zinc naphthenate one kind.
Because benzene kind solvent toxicity is big, the present invention is using the ethyl acetate, butyl acetate, dimethyl carbonate of low toxicity as anti-
The solvent and diluted solvent answered.
In order to solve the problems, such as techniques as described above, the present invention takes following technical scheme：The present invention relates to the low trip of one kind
From the TDI tripolymer dumb light curing agent of content of monomer, it is characterised in that：By weight percentage, its formula composition is：2,4- first
Phenylene diisocyanate 48.0~52.0%, long-chain alcohol 1.5~4.0%, catalyst A 0.1~0.3%, n-butanol 1.6~
3.0%th, catalyst B 0.04~0.1%, polymerization inhibitor 0.16~0.30%, antioxidant 0.2~0.4%, solvent 40~50%；Institute
The long-chain alcohol stated is laruyl alcohol, 16 carbon alcohol, one or more of combinations of octadecanol；Described catalyst A be DMP-30,
One kind and isooctyl acid potassium, zinc Isoocatanoate, potassium acetate of triazine (PC-41), double (dimethylaminoethyl) ethers or triethylenediamine
Or a kind of composition of the and solvent of zinc naphthenate；Described catalyst B is isooctyl acid potassium, zinc Isoocatanoate, potassium acetate, aphthenic acids
One or more of combinations of zinc；Described polymerization inhibitor is one kind of phosphoric acid, hypophosphorous acid or chlorobenzoyl chloride；Described antioxidant is
BHT, BHEB, DBEP, 1331,1010,1098 or UV-P one or more of combinations；Described solvent is ethyl acetate, vinegar
One or more of combinations of acid butyl ester, dimethyl carbonate；Described long-chain alcohol, n-butanol or solvent is beforehand with dewater treatment.
The present invention proposes a kind of preparation method of the TDI tripolymer dumb light curing agent of low free monomer content, and its feature exists
In：Comprise the following steps：
1), 2,4- toluene di-isocyanate(TDI)s, long-chain alcohol, solvent are put into reactor respectively by weight percentage, led to
N2Protection, is warming up to after 75~80 DEG C, 0.5~1h of insulation, cools to 55 DEG C, then adds the catalyst A compounded, control temperature
Degree starts to detect NCO, detects a nco value every 0.5h afterwards after 55~65 DEG C are reacted 4h；
2), when the NCO of detection is 10 ± 0.5%, n-butanol and catalyst B are added, control temperature is at 55~60 DEG C；When
The NCO of detection adds polymerization inhibitor, antioxidant and diluted solvent at 8.0 ± 0.3%, stirs 0.5h, cools to 40 DEG C, sampling
Color (Fe-Co colorimetrics), solid content, viscosity, toluene tolerance, nco value and free TDI value are determined, reaches and was discharged after requirement
Filter packaging.
The TDI tripolymer dumb light curing agent of low free monomer content produced by the present invention, technical target of the product is：Color
(Fe-Co)≤1, solid content be 50 ± 2%, nco value be 8.0 ± 0.3%, viscosity (apply -4 glasss) 15~25s, free TDI≤
0.5%th, toluene tolerance >=1, aromatic-free, with environmental protection, scratch resistance is good, richness is high, it is transparent good the features such as；With hydroxyl
The polyurethane paint that component is prepared has high rigidity, high transparency, and paint film resistance to marring is good, levelability is good, and richness is high, intermiscibility
Wide the features such as, be to be used for various bi-component polyester dumb light paints, polyurethane matte paint, decorative paint, the floors such as woodenware, metal, plastics
The environment-friendlycuring curing agents such as paint, priming paint.
Embodiment
With reference to embodiment, the present invention is further illustrated.
Embodiment 1：
In synthesis reactor, based on formulation weight ratio, 25 parts of laruyl alcohol, 462 parts of butyl acetate are sequentially added, 108 are warming up to
DEG C or so have a backflow, 2~3h of backflow is dehydrated, if in water knockout drum without globule appearance if cooling down；When cool to 40 DEG C with
When lower, 486 parts of 2,4- toluene di-isocyanate(TDI)s are added, lead to N2Protection, is warming up to after 75~80 DEG C, 0.5~1h of insulation, cools to
55 DEG C, 1.8 parts of the catalyst A compounded by DMP-30, isooctyl acid potassium and butyl acetate is added, control temperature is anti-at 55~65 DEG C
Answer after 4h, start to detect NCO, detect a nco value every 0.5h afterwards；When the NCO of detection is 10 ± 0.5%, add just
0.5 part of 20 parts of butanol and isooctyl acid potassium catalyst, control temperature is at 55~60 DEG C；When the NCO of detection is 8.0 ± 0.3%, stop
Only it is passed through N2, add 2.0 parts of chlorobenzoyl chloride, 2.7 parts of antioxidant BHEB and add butyl acetate latting drown to 50 ± 2% solid contents,
0.5h is stirred, 40 DEG C is cooled to, filters and packages.
Embodiment 2：
In synthesis reactor, based on formulation weight ratio, 32 parts of laruyl alcohol, 436 parts of butyl acetate are sequentially added, 108 are warming up to
DEG C or so have a backflow, 2~3h of backflow is dehydrated, if in water knockout drum without globule appearance if cooling down；When cool to 40 DEG C with
When lower, 502 parts of 2,4- toluene di-isocyanate(TDI)s are added, lead to N2Protection, is warming up to after 75~80 DEG C, 0.5~1h of insulation, cools to
55 DEG C, 1.8 parts of the catalyst A compounded by DMP-30, zinc naphthenate and butyl acetate is added, control temperature is anti-at 55~65 DEG C
Answer after 4h, start to detect NCO, detect a nco value every 0.5h afterwards；When the NCO of detection is 10 ± 0.5%, add just
0.6 part of 22 parts of butanol and zinc naphthenate catalyst, control temperature is at 55~60 DEG C；When the NCO of detection is 8.0 ± 0.3%, stop
Only it is passed through N2, add 2.4 parts of phosphoric acid, 3.2 parts of antioxidant BHT and add butyl acetate latting drown to 50 ± 2% solid contents, stirring
0.5h, cools to 40 DEG C, filters and packages.
Embodiment 3：
In synthesis reactor, based on formulation weight ratio, 20 parts of laruyl alcohol, 8 parts of 16 carbon alcohol, butyl acetate 448 are sequentially added
Part, being warming up to 108 DEG C or so has backflow, and 2~3h of backflow is dehydrated, the cooling down if occurring in water knockout drum without the globule；When
When cooling to less than 40 DEG C, 496 parts of 2,4- toluene di-isocyanate(TDI)s are added, lead to N2Protection, is warming up to 75~80 DEG C, insulation 0.5
After~1h, 55 DEG C are cooled to, 1.7 parts of the catalyst A compounded by PC-41, zinc Isoocatanoate and butyl acetate is added, temperature is controlled
After 55~65 DEG C are reacted 4h, start to detect NCO, detect a nco value every 0.5h afterwards；When detection NCO 10 ±
When 0.5%, 0.5 part of 21 parts of n-butanol and zinc Isoocatanoate catalyst are added, control temperature is at 55~60 DEG C；When the NCO of detection exists
When 8.0 ± 0.3%, stopping is passed through N2, add 2.0 parts of chlorobenzoyl chloride, 2.8 parts of antioxidant 1010 and add butyl acetate latting drown and arrive
50 ± 2% solid contents, stir 0.5h, cool to 40 DEG C, filter and package.
According to relevant national standard, the TDI tripolymers dumb light to low free monomer content made from present example solidifies
The technical indicator of agent is detected that test result is as shown in table 1.
The TDI tripolymer dumb light curing agent technical indicators of the low free monomer content of table 1
Although the present invention has been explained in detail and has been cited embodiment, for one of ordinary skill in the art, show
So can as specified above and make various schemes, modification and change, should be construed as being included within the scope of claim.
Claims (3)
1. a kind of TDI tripolymer dumb light curing agent of low free monomer content, it is characterised in that：Described low free monomer content
TDI tripolymer dumb light curing agent, be made up of following steps：
A) is in synthesis reactor, based on formulation weight ratio, sequentially adds 25 parts of laruyl alcohol, 462 parts of butyl acetate, is warming up to 108 DEG C
There is backflow left and right, and 2~3h of backflow is dehydrated, the cooling down if occurring in water knockout drum without the globule；
B) adds 486 parts of 2,4- toluene di-isocyanate(TDI)s when cooling to below 40 DEG C, leads to N2Protection, is warming up to 75~80 DEG C,
It is incubated after 0.5~1h, cools to 55 DEG C, add 1.8 parts of catalyst A, control temperature starts inspection after 55~65 DEG C are reacted 4h
NCO is surveyed, a nco value is detected every 0.5h afterwards；
C) is when the NCO of detection is 10 ± 0.5%, adds 0.5 part of 20 parts of n-butanol and catalyst B, control temperature 55~
60℃；When the NCO of detection is 8.0 ± 0.3%, stopping is passed through N2, add 2.0 parts of chlorobenzoyl chloride, 2.7 parts of antioxidant BHEB
With addition butyl acetate latting drown to 50 ± 2% solid contents, 0.5h is stirred, 40 DEG C are cooled to；
D) samplings detection product physical and chemical index：Outward appearance is water-white to micro- yellow liquor body, color (Fe-Co colorimetrics)≤1, solid content
50.2%th, viscosity (applying -4,25 DEG C) 18 ± 2s, toluene tolerance >=1, nco value 7.9% and free TDI value≤0.26%, is closed
Lattice, are filtered and packaged；
Wherein, described catalyst A is DMP-30, isooctyl acid potassium and butyl acetate compounding mixture；Described catalyst B is
Isooctyl acid potassium；Described laruyl alcohol, n-butanol and butyl acetate is beforehand with dewater treatment.
2. a kind of TDI tripolymer dumb light curing agent of low free monomer content, it is characterised in that：Described low free monomer content
TDI tripolymer dumb light curing agent, be made up of following steps：
A) is in synthesis reactor, based on formulation weight ratio, sequentially adds 32 parts of laruyl alcohol, 436 parts of butyl acetate, is warming up to 108 DEG C
There is backflow left and right, and 2~3h of backflow is dehydrated, the cooling down if occurring in water knockout drum without the globule；
B) adds 502 parts of 2,4- toluene di-isocyanate(TDI)s when cooling to below 40 DEG C, leads to N2Protection, is warming up to 75~80 DEG C,
It is incubated after 0.5~1h, cools to 55 DEG C, adds 1.8 parts of the catalyst A compounded by DMP-30, zinc naphthenate and butyl acetate,
Temperature is controlled after 55~65 DEG C are reacted 4h, starts to detect NCO, detects a nco value every 0.5h afterwards；
C) adds 0.6 part of 22 parts of n-butanol and zinc naphthenate catalyst, controls temperature when the NCO of detection is 10 ± 0.5%
At 55~60 DEG C；When the NCO of detection is 8.0 ± 0.3%, stopping is passed through N2, add 2.4 parts of phosphoric acid, 3.2 parts of antioxidant BHT
With addition butyl acetate latting drown to 50 ± 2% solid contents, 0.5h is stirred, 40 DEG C are cooled to；
D) samplings detection product physical and chemical index：Outward appearance is water-white to micro- yellow liquor body, color (Fe-Co colorimetrics)≤1, solid content
51.1%th, viscosity (applying -4,25 DEG C) 20 ± 2s, toluene tolerance >=1, nco value 8.2% and free TDI value≤0.36%, is closed
Lattice, are filtered and packaged；
Wherein, described catalyst A is DMP-30, zinc naphthenate and butyl acetate compounding mixture；Described catalyst B is
Zinc naphthenate；Described laruyl alcohol, n-butanol and butyl acetate is beforehand with dewater treatment.
3. a kind of TDI tripolymer dumb light curing agent of low free monomer content, it is characterised in that：Described low free monomer content
TDI tripolymer dumb light curing agent, be made up of following steps：
A) is in synthesis reactor, based on formulation weight ratio, sequentially adds 20 parts of laruyl alcohol, 8 parts of 16 carbon alcohol, butyl acetate 448
Part, being warming up to 108 DEG C or so has backflow, and 2~3h of backflow is dehydrated, the cooling down if occurring in water knockout drum without the globule；
B) adds 496 parts of 2,4- toluene di-isocyanate(TDI)s when cooling to below 40 DEG C, leads to N2Protection, is warming up to 75~80 DEG C,
It is incubated after 0.5~1h, cools to 55 DEG C, adds A1.7 parts of the catalyst compounded by PC-41, zinc Isoocatanoate and butyl acetate, control
Temperature processed starts to detect NCO, detects a nco value every 0.5h afterwards after 55~65 DEG C are reacted 4h；
C) adds 0.5 part of 21 parts of n-butanol and zinc Isoocatanoate catalyst, controls temperature when the NCO of detection is 10 ± 0.5%
At 55~60 DEG C；When the NCO of detection is 8.0 ± 0.3%, stopping is passed through N2, add 2.0 parts of chlorobenzoyl chloride, antioxidant 1010
2.8 parts cool to 40 DEG C with addition butyl acetate latting drown to 50 ± 2% solid contents, stirring 0.5h；
D) samplings detection product physical and chemical index：Outward appearance is water-white to micro- yellow liquor body, color (Fe-Co colorimetrics)≤1, solid content
50.6%th, viscosity (applying -4,25 DEG C) 21 ± 2s, toluene tolerance >=1, nco value 8.0% and free TDI value≤0.32%, is closed
Lattice, are filtered and packaged；
Wherein, described catalyst A is PC-41, zinc Isoocatanoate and butyl acetate compounding mixture；Described catalyst B is
Zinc Isoocatanoate；Described laruyl alcohol, 16 carbon alcohol, n-butanol and butyl acetate is beforehand with dewater treatment.
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