CN104927615A - Preparation method for TDI trimer matt curing agent low in free monomer content - Google Patents
Preparation method for TDI trimer matt curing agent low in free monomer content Download PDFInfo
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- CN104927615A CN104927615A CN201510337036.3A CN201510337036A CN104927615A CN 104927615 A CN104927615 A CN 104927615A CN 201510337036 A CN201510337036 A CN 201510337036A CN 104927615 A CN104927615 A CN 104927615A
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- catalyst
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- tdi
- curing agent
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- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 37
- 239000000178 monomer Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 239000013638 trimer Substances 0.000 title abstract description 7
- 239000002904 solvent Substances 0.000 claims abstract description 29
- 239000003054 catalyst Substances 0.000 claims abstract description 24
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims abstract description 19
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000003112 inhibitor Substances 0.000 claims abstract description 9
- 239000007787 solid Substances 0.000 claims abstract description 7
- 229920000570 polyether Polymers 0.000 claims abstract 6
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract 4
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 30
- 238000006243 chemical reaction Methods 0.000 claims description 23
- 239000000203 mixture Substances 0.000 claims description 18
- OEOIWYCWCDBOPA-UHFFFAOYSA-N 6-methyl-heptanoic acid Chemical compound CC(C)CCCCC(O)=O OEOIWYCWCDBOPA-UHFFFAOYSA-N 0.000 claims description 16
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 8
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 8
- 230000003647 oxidation Effects 0.000 claims description 8
- 238000007254 oxidation reaction Methods 0.000 claims description 8
- 229910052700 potassium Inorganic materials 0.000 claims description 8
- 239000011591 potassium Substances 0.000 claims description 8
- 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 8
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims description 8
- 229910052725 zinc Inorganic materials 0.000 claims description 8
- 239000011701 zinc Substances 0.000 claims description 8
- 238000003756 stirring 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
- 238000009413 insulation Methods 0.000 claims description 6
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 claims description 6
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 6
- 229920002554 vinyl polymer Polymers 0.000 claims description 6
- 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 5
- 239000002131 composite material Substances 0.000 claims description 5
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 claims description 5
- CXHHBNMLPJOKQD-UHFFFAOYSA-M methyl carbonate Chemical compound COC([O-])=O CXHHBNMLPJOKQD-UHFFFAOYSA-M 0.000 claims description 5
- PASDCCFISLVPSO-UHFFFAOYSA-N benzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1 PASDCCFISLVPSO-UHFFFAOYSA-N 0.000 claims description 4
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 claims description 4
- 238000005070 sampling Methods 0.000 claims description 4
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 claims description 3
- GTEXIOINCJRBIO-UHFFFAOYSA-N 2-[2-(dimethylamino)ethoxy]-n,n-dimethylethanamine Chemical compound CN(C)CCOCCN(C)C GTEXIOINCJRBIO-UHFFFAOYSA-N 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 229910017061 Fe Co Inorganic materials 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- CMCJNODIWQEOAI-UHFFFAOYSA-N bis(2-butoxyethyl)phthalate Chemical compound CCCCOCCOC(=O)C1=CC=CC=C1C(=O)OCCOCCCC CMCJNODIWQEOAI-UHFFFAOYSA-N 0.000 claims description 2
- 238000007599 discharging Methods 0.000 claims description 2
- MCPKSFINULVDNX-UHFFFAOYSA-N drometrizole Chemical compound CC1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 MCPKSFINULVDNX-UHFFFAOYSA-N 0.000 claims description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Natural products OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical group CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims 6
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims 3
- 239000003973 paint Substances 0.000 abstract description 21
- 239000004814 polyurethane Substances 0.000 abstract description 15
- 229920002635 polyurethane Polymers 0.000 abstract description 15
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 4
- 229920003023 plastic Polymers 0.000 abstract description 4
- 239000004033 plastic Substances 0.000 abstract description 4
- 239000003963 antioxidant agent Substances 0.000 abstract description 2
- 230000003078 antioxidant effect Effects 0.000 abstract description 2
- 229910052751 metal Inorganic materials 0.000 abstract description 2
- 239000002184 metal Substances 0.000 abstract description 2
- 229920000728 polyester Polymers 0.000 abstract description 2
- 230000037452 priming Effects 0.000 abstract description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 abstract 1
- 238000006116 polymerization reaction Methods 0.000 abstract 1
- 229920005862 polyol Polymers 0.000 abstract 1
- 150000003077 polyols Chemical class 0.000 abstract 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 150000002148 esters Chemical class 0.000 description 8
- 238000001816 cooling 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
- 238000001704 evaporation Methods 0.000 description 5
- 229930195733 hydrocarbon Natural products 0.000 description 5
- 150000002430 hydrocarbons Chemical class 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000012948 isocyanate Substances 0.000 description 4
- 150000002513 isocyanates Chemical class 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 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 3
- 238000012546 transfer Methods 0.000 description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-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
- 238000001514 detection method Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 239000011527 polyurethane coating Substances 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 102000004169 proteins and genes Human genes 0.000 description 2
- 108090000623 proteins and genes Proteins 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000012855 volatile organic compound Substances 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- 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
- 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
- -1 TDI Substances 0.000 description 1
- 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 description 1
- 238000013459 approach Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 208000006673 asthma Diseases 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
- 238000001311 chemical methods and process Methods 0.000 description 1
- 238000004925 denaturation Methods 0.000 description 1
- 230000036425 denaturation Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 208000017574 dry cough Diseases 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000008020 evaporation Effects 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
- 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
- 239000004922 lacquer Substances 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
- 238000000199 molecular distillation Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 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
- 238000004886 process control Methods 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
- 210000002345 respiratory system Anatomy 0.000 description 1
- ANOBYBYXJXCGBS-UHFFFAOYSA-L stannous fluoride Chemical compound F[Sn]F ANOBYBYXJXCGBS-UHFFFAOYSA-L 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
- 231100000167 toxic agent Toxicity 0.000 description 1
- 239000003440 toxic substance Substances 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
- 239000002699 waste material 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 invention relates to a preparation method for a TDI trimer matt curing agent low in free monomer content. According to the formula, the curing agent comprises 2,4-toluene diisocyanate, polyether polyol, long-chain alcohol, a catalyst A, n-butanol, a catalyst B, polymerization inhibitor, antioxidant and a solvent. According to the prepared TDI trimer matt curing agent low in free monomer content, the solid content is 50+/-2%, the NCO value is 8.0+/-0.3%, the viscosity (Tu-4 cup) is 15-25 s, the free TDI is smaller than or equal to 0.5%, the toluene tolerance is larger than or equal to 1, and the curing agent does not contain arene and is characterized by being environmentally friendly, good in scratch resistance, good in transparency and the like. Polyurethane paint manufactured through hydroxyl group components is characterized by being high in hardness, high in transparency, good in film scratch resistance, good in leveling property, high in fullness, high in solubility and the like. The environment-friendly curing agent is used for various two-component polyester paint, polyurethane paint, decorative paint, floor paint, priming paint and the like of woodware, metal, plastics and the like.
Description
Technical field
The present invention relates to a kind of preparation method of polyurethane curing agent, refer more particularly to a kind of TDI tripolymer dumb light solidifying agent of low free monomer content.
Background technology
Bicomponent polyurethane coating is generally made up of isocyanate prepolymer and hydroxy-containing resin two portions, be commonly referred to curing agent component and host component, difference according to hydroxy-containing component can be divided into acroleic acid polyurethane, alcohol acid and polyurethane, polyester-polyurethane, polyether-polyurethane, the kinds such as epoxy polyurethane, generally all there is film-forming temperature low, strong adhesion, hardness is large, good and the chemicals-resistant of wear resistance, the high-performances such as good weatherability, a kind of coating most widely used at present, be mainly used in original factory of vehicle paint, plastic paint, wood lacquer, industrial paint, protective system floor paint, electronic paint, fabric leather coating, the aspects such as printing-ink industry.In China, polyurethane coating accounts for the market share of about 75% in woodwork coating, accounts for the market share of about 40% in car refinishing paint, and at other field as the application of protective system, plastic paint etc. is also more and more wider, the market share is about 10%.
TDI solidifying agent conventional on the market at present has TDI tripolymer, TDI-TMP affixture, and the main raw material producing solidifying agent is exactly tolylene diisocyanate (being called for short TDI), TDI is a kind of volatilizable toxic substance, it can make protein denaturation with the proteins react of human body, therefore to the maximum harm of human body.The steam of TDI has strong lacrimation, stimulates respiratory system after suction, and cause dry cough, laryngalgia, headache, bronchitis and asthma, serious meeting causes death.In order to avoid isocyanate-monomer is to the harm of human body, each state all works out the limitation of polyurethane products free monomers; The European Community specifies, the container outer wall containing chemical such as TDI, HDI, IPDI, HMDI must put up mark: vulcabond free monomer massfraction person below 0.5%, and outer wall is indicated " containing isocyanic ester ", is environmentfriendly products; Free monomer content, 0.5% ~ 2.0%, indicates " being harmful to " warning sign and " containing isocyanic ester "; Free monomer content is person more than 2%, except indicating " containing isocyanic ester ", also must indicate " poisonous " and having human skeleton bones of the dead mark.
Country has formulated compulsory standard in coating environmental protection in recent years, volatile organic compounds in polyurethane paint (VOC) content≤670g/L is defined in standard GB/T 18581-2009 " in indoor decorating and refurnishing materials solvent wood coatings limits of harmful substances ", benzene content≤0.3%, toluene, dimethylbenzene, ethylene total content≤30%, free TDI, | HDI content summation≤0.4%.
Reduce the direction that polyurethane curing agent free TDI monomer content becomes the tackling key problem of domestic and international solidifying agent industry emphasis, from know-why, the technological approaches reducing free TDI can be divided into chemical process and physical method, comprising: direct synthesis technique, solvent extration, high vacuum film evaporation method, molecular distillation method and chemical catalysis method for refining etc.What current large-scale industrialization was produced is mostly offshore company, and as Bayer company, Rhodia company, Nippon Polyurethane Industry Co., Ltd. etc., minimizing technology is high vacuum film evaporation method.But high vacuum film evaporation method, invest excessive, process control needs is high, domesticly at present technology and equipment problem is removed to this method never solve well, free isocyanate monomer content severe overweight in the domestic TDI solidifying agent of major part, the content of TDI is difficult to accomplish within 0.5%, mostly about 1%.
The method of the free toluene diisocyanate in a kind of film evaporation method process solidifying agent affixture is all disclosed in Chinese patent literature CN1793194A, CN101717571A, its Bian mode of multiple-effect thin film evaporation, at high temperature evaporate free tolylene diisocyanate by the mode of vacuum, the content of free TDI is between 0.15 ~ 0.5%.
Chinese patent literature CN 101456940A discloses a kind of synthetic method of dissolvant type polyurethane curing agent of low free toluene diisocyanate content, carry out in two stages: the first stage, tolylene diisocyanate and polyvalent alcohol are reacted in a solvent, the degree of reacting and carrying out is monitored by the content of sampling detection NCO in the mixture of reaction in reaction process, when the stable content of NCO, be the reaction end of first stage; Subordinate phase, acetylacetic ester is added in the mixture of above-mentioned reaction, continue reaction, the degree of reacting and carrying out is monitored by the content of sampling detection NCO in the mixture of reaction in reaction process, after the content of NCO is stablized again, being the reaction end of subordinate phase, is also the terminal of total overall reaction, and the reaction of subordinate phase is carried out at low temperatures; Product is TDI-TMP affixture, and 50% admittedly containing free TDI content < 0.5%.This method utilize acetylacetic ester at low temperatures with the difference of the reactive behavior of the NCO group on tolylene diisocyanate different positions, by low-temp reaction, reach the object reducing free toluene diisocyanate; Feasible in theory, but TDI-80/20 has 2,4-tolylene diisocyanate and 2,6-tolylene diisocyanate two kinds of isomer, NCO reactive behavior on 4 is high, can react with acetylacetic ester at low temperatures, but the NCO on 2,6 reacts with acetylacetic ester due to sterically hindered being difficult to, although 2,4-toluene diisocyanate monomer take part in reaction, but 2,6-toluene diisocyanate monomer also exists, be therefore difficult to accomplish the 50% TDI-TMP solidifying agent Free TDI < 0.5% admittedly contained; Solidifying agent is long in period of storage in addition, can induce reaction under variation of ambient temperature, and nco value reduces, viscosity increases, easy gel.
Chinese patent literature CN 100439414C discloses a kind of preparation method of low-free TDI trimer curing agent, and it comprises: TDI, solvent S, catalyst A are dropped in reactor, add oxidation inhibitor and long-chain alcohol, heating and thermal insulation, detect nco value; When nco value reaches 20 ~ 40%, add Phase transfer solvent X and catalyst B, until when nco value reaches 10 ~ 15%, add stopper stopped reaction; Supplementing solvent S, underpressure distillation removing Phase transfer solvent X.Wherein solvent S be vinyl acetic monomer, N-BUTYL ACETATE, and composition thereof; Phase transfer solvent X is sherwood oil, methylcarbonate, normal hexane, cyclohexane or its any mixture; Catalyst A, catalyst B are all Lithium Acetate, KOH, NaOH, tributylphosphine, triethylenediamine and any mixture thereof; Obtained product is TDI tripolymer, and 45% admittedly containing free TDI content < 0.5%.This method is the improved technology of solvent extration, unreacted free isocyanate monomer is dissolvable in water hydrocarbon mixture (as sherwood oil, methylcarbonate, normal hexane, hexanaphthene benzene or its mixture), solidifying agent polymkeric substance then can not solution modeling in bottom, then continue to add catalyst reaction at upper strata hydrocarbon mixture solvent, but be difficult to when stirring control its reaction in a still, easy generation superpolymer, even gel; And do not stir lower free isocyanate monomer and be difficult to react completely.And vinyl acetic monomer, N-BUTYL ACETATE boiling point are low, very easily form azeotrope with hydrocarbon mixture, conventional underpressure distillation is difficult to remove hydrocarbon mixture, then constantly add and waste a large amount of vinyl acetic monomers, N-BUTYL ACETATE; And will temperature be improved during underpressure distillation, the time is long, and whether the solidifying agent in still does not just know or solidifying agent under catalyzer, high temperature; Containing ester, free monomer in the solvent distilled in addition, can not use, can not discharge, storage is all a problem, and therefore how recycling design is difficult.Both made method feasible, and also can not eliminate hydrocarbon mixture solvent residual in solidifying agent, finally can affect product performance.
Summary of the invention
The present invention aims to provide a kind of preparation method of TDI tripolymer dumb light solidifying agent of low free monomer content.
It is raw material that the present invention adopts 2,4 toluene diisocyanate to be TDI trimer curing agent, avoids NCO on 2,6-tolylene diisocyanate 2,6 and is difficult to reaction due to sterically hindered and left behind; Conventional TDI trimer curing agent is general all more crisp, and snappiness, glossiness and resistance to marring are all poor, adopts long-chain alcohol can improve solidifying agent to the tolerance of toluene and the snappiness improving film.
TDI trimer catalyst adopts DMP-30, triazine (PC-41), two (dimethylaminoethyl) ether, triethylenediamine, isocaprylic acid potassium, isocaprylic acid zinc, Potassium ethanoate, zinc naphthenate or its mixture.
Later stage is that free TDI is converted into nontoxic material, and the present invention adopts micromolecular oxy-compound propyl carbinol effectively can reduce free TDI monomer content in solidifying agent under the effect of catalyzer; The catalyzer reducing free TDI content is the one of isocaprylic acid potassium, isocaprylic acid zinc, Potassium ethanoate, zinc naphthenate.
Because benzene kind solvent toxicity is large, the present invention adopts the vinyl acetic monomer of low toxicity, N-BUTYL ACETATE, methylcarbonate as the solvent of reaction and letdown solvent dun.
In order to solve technical problem recited above, the present invention takes following technical scheme: the TDI tripolymer dumb light solidifying agent that the present invention relates to a kind of low free monomer content, it is characterized in that: by weight percentage, its formula consists of: 2,4 toluene diisocyanate 48.0 ~ 52.0%, long-chain alcohol 1.5 ~ 4.0%, catalyst A 0.1 ~ 0.3%, propyl carbinol 1.6 ~ 3.0%, catalyst B 0.04 ~ 0.1%, stopper 0.16 ~ 0.30%, oxidation inhibitor 0.2 ~ 0.4%, solvent 40 ~ 50%; Described long-chain alcohol is the combination of one or more of lauryl alcohol, 16 carbon alcohol, octadecanol; Described catalyst A is the composition of a kind of and solvent of a kind of and isocaprylic acid potassium of DMP-30, triazine (PC-41), two (dimethylaminoethyl) ether or triethylenediamine, isocaprylic acid zinc, Potassium ethanoate or zinc naphthenate; Described catalyst B is the combination of one or more of isocaprylic acid potassium, isocaprylic acid zinc, Potassium ethanoate, zinc naphthenate; Described stopper is the one of phosphoric acid, Hypophosporous Acid, 50 or Benzoyl chloride; Described oxidation inhibitor is BHT, BHEB, DBEP, 1331,1010,1098 or the combination of one or more of UV-P; Described solvent is the combination of one or more of vinyl acetic monomer, N-BUTYL ACETATE, methylcarbonate; Described long-chain alcohol, propyl carbinol or solvent are beforehand with processed.
The present invention proposes a kind of preparation method of TDI tripolymer dumb light solidifying agent of low free monomer content, it is characterized in that: comprise the following steps:
1), by weight percentage respectively 2,4 toluene diisocyanate, long-chain alcohol, solvent are put in reactor, logical N
2protection, is warmed up to 75 ~ 80 DEG C, after insulation 0.5 ~ 1h, cools to 55 DEG C, then adds composite good catalyst A, and control temperature, after 55 ~ 65 DEG C of reaction 4h, starts to detect NCO, detects a nco value afterwards every 0.5h;
2), when the NCO detected is 10 ± 0.5% time, add propyl carbinol and catalyst B, control temperature is at 55 ~ 60 DEG C; When the NCO detected is 8.0 ± 0.3% time, add stopper, oxidation inhibitor and letdown solvent dun, stir 0.5h, cool to 40 DEG C, sampling and measuring color (Fe-Co colorimetric), solid content, viscosity, toluene tolerance, nco value and free TDI value, after reaching requirement, discharging filters and packages.
The TDI tripolymer dumb light solidifying agent of the low free monomer content that the present invention obtains, technical target of the product is: color (Fe-Co)≤1, solid content are 50 ± 2%, nco value is 8.0 ± 0.3%, viscosity (being coated with-4 glasss) 15 ~ 25s, free TDI≤0.5%, toluene tolerance >=1, aromatic free, features such as there is environmental protection, scratch resistance is good, fullness ratio is high, the transparency is good; The polyurethane paint prepared with hydroxy component has high rigidity, high transparent, paint film resistance to marring is good, levelling property is good, the features such as fullness ratio is high, intermiscibility is wide are for environment-friendly type fixed agents such as the various bi-component polyester dumb light such as woodenware, metal, plastics paint, polyurethane matte paint, fancy paint, hard floor paint, priming paint.
Embodiment
Below in conjunction with embodiment, the present invention is further illustrated.
Embodiment 1:
In synthesis reactor, by formulation weight ratio, add lauryl alcohol 25 parts, N-BUTYL ACETATE 462 parts successively, being warmed up to about 108 DEG C has backflow, and backflow 2 ~ 3h dewaters, if occur without the globule in water trap, and cooling down; When cooling to below 40 DEG C, add 2,4 toluene diisocyanate 486 parts, logical N
2protection, is warmed up to 75 ~ 80 DEG C, after insulation 0.5 ~ 1h, cool to 55 DEG C, add by the composite catalyst A 1.8 parts of DMP-30, isocaprylic acid potassium and N-BUTYL ACETATE, control temperature is after 55 ~ 65 DEG C of reaction 4h, start to detect NCO, detect a nco value every 0.5h afterwards; When the NCO detected is 10 ± 0.5% time, add propyl carbinol 20 parts and isocaprylic acid potassium catalyzer 0.5 part, control temperature is at 55 ~ 60 DEG C; When the NCO detected is 8.0 ± 0.3% time, stop passing into N
2, add Benzoyl chloride 2.0 parts, oxidation inhibitor BHEB 2.7 parts and add N-BUTYL ACETATE latting drown to 50 ± 2% solid contents, stirring 0.5h, cool to 40 DEG C, filter and package.
Embodiment 2:
In synthesis reactor, by formulation weight ratio, add lauryl alcohol 32 parts, N-BUTYL ACETATE 436 parts successively, being warmed up to about 108 DEG C has backflow, and backflow 2 ~ 3h dewaters, if occur without the globule in water trap, and cooling down; When cooling to below 40 DEG C, add 2,4 toluene diisocyanate 502 parts, logical N
2protection, is warmed up to 75 ~ 80 DEG C, after insulation 0.5 ~ 1h, cool to 55 DEG C, add by the composite catalyst A 1.8 parts of DMP-30, zinc naphthenate and N-BUTYL ACETATE, control temperature is after 55 ~ 65 DEG C of reaction 4h, start to detect NCO, detect a nco value every 0.5h afterwards; When the NCO detected is 10 ± 0.5% time, add propyl carbinol 22 parts and zinc naphthenate catalyzer 0.6 part, control temperature is at 55 ~ 60 DEG C; When the NCO detected is 8.0 ± 0.3% time, stop passing into N
2, add phosphoric acid 2.4 parts, antioxidant BHT 3.2 parts and add N-BUTYL ACETATE latting drown to 50 ± 2% solid contents, stirring 0.5h, cool to 40 DEG C, filter and package.
Embodiment 3:
In synthesis reactor, by formulation weight ratio, add lauryl alcohol 20 parts, 16 carbon alcohol 8 parts, N-BUTYL ACETATE 448 parts successively, being warmed up to about 108 DEG C has backflow, and backflow 2 ~ 3h dewaters, if occur without the globule in water trap, and cooling down; When cooling to below 40 DEG C, add 2,4 toluene diisocyanate 496 parts, logical N
2protection, is warmed up to 75 ~ 80 DEG C, after insulation 0.5 ~ 1h, cool to 55 DEG C, add by the composite catalyst A 1.7 parts of PC-41, isocaprylic acid zinc and N-BUTYL ACETATE, control temperature is after 55 ~ 65 DEG C of reaction 4h, start to detect NCO, detect a nco value every 0.5h afterwards; When the NCO detected is 10 ± 0.5% time, add propyl carbinol 21 parts and isocaprylic acid zinc catalyst 0.5 part, control temperature is at 55 ~ 60 DEG C; When the NCO detected is 8.0 ± 0.3% time, stop passing into N
2, add Benzoyl chloride 2.0 parts, antioxidant 1010 2.8 parts and add N-BUTYL ACETATE latting drown to 50 ± 2% solid contents, stirring 0.5h, cool to 40 DEG C, filter and package.
According to relevant national standard, detect the technical indicator of the TDI tripolymer dumb light solidifying agent of the low free monomer content that example of the present invention obtains, test result is as shown in table 1.
The TDI tripolymer dumb light solidifying agent technical indicator of table 1 low free monomer content
Although the present invention has been explained in detail and has quoted embodiment as proof, for those of ordinary skill in the art, the various schemes obviously can made according to above-mentioned explanation, amendment and change, within the scope that all should be included in claim.
Claims (2)
1. the TDI tripolymer dumb light solidifying agent of a low free monomer content, it is characterized in that: by weight percentage, its formula consists of: 2,4 toluene diisocyanate 48.0 ~ 52.0%, long-chain alcohol 1.5 ~ 4.0%, catalyst A 0.1 ~ 0.3%, propyl carbinol 1.6 ~ 3.0%, catalyst B 0.04 ~ 0.1%, stopper 0.16 ~ 0.30%, oxidation inhibitor 0.2 ~ 0.4%, solvent 40 ~ 50%; Described polyether glycol is the one of 210 polyethers, 220 polyethers; Described long-chain alcohol is the combination of one or more of lauryl alcohol, 16 carbon alcohol, octadecanol; Described catalyst A is the composition of a kind of and solvent of a kind of and isocaprylic acid potassium of DMP-30, triazine (PC-41), two (dimethylaminoethyl) ether or triethylenediamine, isocaprylic acid zinc, Potassium ethanoate or zinc naphthenate; Described catalyst B is isocaprylic acid potassium, isocaprylic acid zinc, Potassium ethanoate, one or more combination of zinc naphthenate; Described stopper is the one of phosphoric acid, Hypophosporous Acid, 50 or Benzoyl chloride; Described oxidation inhibitor is BHT, BHEB, DBEP, 1331,1010,1098 or the combination of one or more of UV-P; Described solvent is the combination of one or more of vinyl acetic monomer, N-BUTYL ACETATE, methylcarbonate; Described polyether glycol, long-chain alcohol, propyl carbinol or solvent are beforehand with processed.
2. the preparation method of the TDI tripolymer dumb light solidifying agent of a kind of low free monomer content as claimed in claim 1, is characterized in that: described preparation method, comprises the following steps:
1), by weight percentage respectively 2,4 toluene diisocyanate, polyether glycol, long-chain alcohol, solvent are put in reactor, logical N
2protection, is warmed up to 75 ~ 80 DEG C, after insulation 0.5 ~ 1h, cools to 55 DEG C, then adds composite good catalyst A, and control temperature, after 55 ~ 65 DEG C of reaction 4h, starts to detect NCO, detects a nco value afterwards every 0.5h;
2), when the NCO detected is 10 ± 0.5% time, add propyl carbinol and catalyst B, control temperature is at 55 ~ 60 DEG C; When the NCO detected is 8.0 ± 0.3% time, add stopper, oxidation inhibitor and letdown solvent dun, stir 0.5h, cool to 40 DEG C, sampling and measuring color (Fe-Co colorimetric), solid content, viscosity, toluene tolerance, nco value and free TDI value, after reaching requirement, discharging filters and packages.
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| CN110982045A (en) * | 2019-11-21 | 2020-04-10 | 万华化学集团股份有限公司 | Low-viscosity and low-color-number isocyanate curing agent, and preparation method and application thereof |
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