CN105315433A - Low-free high-compatibility toluene diisocyanate trimer curing agent and preparation method thereof - Google Patents
Low-free high-compatibility toluene diisocyanate trimer curing agent and preparation method thereof Download PDFInfo
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- 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
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- 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
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Abstract
The invention discloses a low-free high-compatibility toluene diisocyanate trimer curing agent and a preparation method thereof. The preparation method comprises the following steps: under nitrogen protection, putting a toluene diisocyanate monomer, a solvent and an antioxidant into a reaction vessel; controlling the reaction temperature to be 10-50 DEG C at an earlier stage; adding a catalyst in batches when NCO% is 12-14wt% and 10-11wt% and reaction is started; when NCO is 9.3-10wt%, adding the residual catalyst and controlling the temperature to be 50-100 DEG C; when NCO% is 8.0-9.3wt%, adding a polymerization inhibitor, reacting for 0.5-1 h, adding a component A, reacting for 2-4 h, adding a component B, reacting for 1-2 h, stopping reaction, cooling to room temperature and discharging materials so as to obtain the toluene diisocyanate trimer curing agent with free TDI less than 0.5%, xylene tolerance larger than 3, light color, quick drying and stable performance finally.
Description
Technical field
The present invention relates to polyurethane curing agent, particularly relate to a kind of low-free toluene diisocyanate trimer with high compatibility solidifying agent and preparation method thereof.
Background technology
Polyurethane curing agent, as the important component of in double-component polyurethane paint, containing polyisocyanates group, can solidify to form Polyurethane lacquer with other polyether polyatomic alcohol component at room-temperature rapid coupling.TDI tripolymer is a class special in polyurethane curing agent, has dumb light, quick-drying, high, the resistant to elevated temperatures feature of hardness.As a kind of very useful solidifying agent, TDI trimer curing agent is not only applicable to polyurethane system, and be applicable to diversified formulation for coating material system, system such as containing other types resins such as epoxy resin, poly-(methyl) acrylate, polyacrylamide, resol, is also widely used in fields such as foam material, elastomerics, seal gum, sizing agents simultaneously.
TDI is the raw material of synthesis of polyurethane solidifying agent in polyurethane industrial.TDI saturated vapor pressure is higher, and simultaneous reactions activity is high, and toxicity is comparatively large, to environment and harm larger.Simultaneously because TDI has two kinds of isomer 2,4 ?TDI and 2,6 ?TDI, wherein 2,6 ?TDI are due to reason sterically hindered in molecule, and active do not have clear superiority, under making general condition compared with the NCO base on tripolymer, TDI raw material cannot change into isocyanuric acid ester in 100% ground, so still containing certain free TDI monomer in obtained solidifying agent product.TDI monomer residual in polyurethane curing agent is poisonous and waste resource not only, and can affect many performances of Polyurethane lacquer, such as storage characteristics, fragility etc.So the free TDI reduced in free solidifying agent product is imperative.Standard GB/T 18581 ?free TDI content in 2009 pairs of polyurethane coatings made restriction, after regulation dual-component coating has been joined according to construction ratio, free vulcabond (TDI, HDI) content summation must be less than 0.4%, usual solidifying agent accounts for about 30% of formulation for coating material, so the free TDI content of solidifying agent must be less than 1.2% could meet national standard.If hardener dose strengthens, its free TDI requires lower.
The important indicator of evaluate cure agent, except the content of free TDI monomer, also comprises: (1) look number, requires that look shallow is transparent, reaches " water white ", and number requirement of platinum cobalt look best is below 40, and this just requires that side reaction is few; (2) dimethylbenzene tolerance, require with the compatibility of resin Composition good, reacted polarity and the molecular weight distribution of system, dimethylbenzene tolerance is higher, then the obtained paint film transparency is better; (3) NCO group content, NCO group content back has answered the content of effective group in solidifying agent, and content is higher, and quality product is better; (4) viscosity, general requirement viscosity can not be too high, and this just requires that three pentamer content increase as far as possible, and high polymer content more than nine aggressiveness reduces as far as possible.
The method reducing trimer curing agent Free TDI at present both at home and abroad comprises physical partition method and chemical synthesis.
Physical partition method, comprises solvent extration, supercritical fluid extraction, decompression co-boiling distiling method, molecular sieve adsorption and film evaporation method.Solvent extration such as notification number is Chinese invention patent, the US Patent No. 3883577 of CN100439414C, supercritical fluid extraction is as US Patent No. 4871460, decompression co-boiling distiling method is as US Patent No. 4385171, molecular sieve adsorption is as US Patent No. 4061662, and film evaporation method is as European patent EP 0105242, US Patent No. 4888442, US5051152, US5202001 etc.These physical partition method separating effects are all relatively good, can reach less than 0.5%.But have that cost is high, the shortcoming of complex process.First such as solvent extraction needs to consume a large amount of extraction agent, and extraction simultaneously needs to carry out multi-pass operations, and extraction agent reclaims difficulty.Decompression co-boiling distiling method needs to consume azeotropic mixture, and azeotropic mixture reclaims difficulty, and residual azeotropic mixture affects product performance.Molecular sieve adsorption separation efficiency is low, molecular sieve desorption reclaims difficulty.Supercritical fluid extraction and film evaporation method equipment are accurate expensive, operating cost and energy consumption high, thus with high costs.
Chemical synthesis is the method adopting formulating of recipe and process optimization, adopts efficient high-selectivity catalyst and optimised process by chemical reaction, the isocyanate-monomer remained in solidifying agent fully to be reacted, and reaches the object reducing free TDI.Because its equipment is simple, cost is lower, is the primary position of domestic and international technological development.Notification number is that the Bayer Chinese patent of CN1307164C adopts Mannich alkaline catalysts, under relatively-high temperature under the condition not containing any alcohol or carbamate, the surprising selectivity adding Mannich alkaline catalysts, makes the content of free TDI in product very low, can reach 0.1%.But the defect of the method is long pyroreaction, cause that product look is number higher, molecular weight distribution broadens, product viscosity is comparatively large, poor compatibility.Notification number is that the Bayer Chinese invention patent of CN1319951C have employed Mannich alkaline catalysts, and adding in three collecting process other 2,4 ?TDI, be equivalent to change general T DI ?80 isomer ratios, the product Free TDI of synthesis is lower, can reach less than 0.5%, but the defect of the method be introduce other TDI ?100 raw materials, raw materials cost is higher, is difficult to obtain, and the consistency of product is poor.Publication number is the Chinese invention patent application of CN104059215A, adds solvent in batches, constantly measures and regulation system viscosity and solid content in building-up process, employ monohydroxy-alcohol modification, product free TDI is lower simultaneously, can reach less than 1%, dimethylbenzene tolerance is better, is greater than 1.4.But the open defect of the method is repeatedly adjusting viscosity and solid content, cause the stability between different batches inadequate, free TDI still needs to continue to reduce simultaneously, and dimethylbenzene tolerance needs to continue to improve.Publication number is that the Chinese invention patent application of CN104403085A only adopts the method in batches adding catalyzer to reduce free TDI, but its level of response is comparatively dark, and dimethylbenzene tolerance is poor.US Patent No. 3384624, US6664414 adopt phenylcarbinol etc. to come to reduce free TDI by reaction, can less than 0.5 be reduced to, but only to 2,4 ?TDI effect better, to 2,6 ?TDI impact little, and due to consumption increasings such as phenylcarbinols, consume many NCO, make the NCO of the finished product too low, and do not consider the problem of tolerance.
Improve the method for the tolerance of trimer curing agent product at present both at home and abroad mainly by monohydroxy-alcohol modification.Notification number be the Chinese invention patent of CN1186405C adopt be add before trimerization reaction molecular weight 60 ?200 fatty alcohol to improve tolerance.Notification number is the Chinese invention patent employing of CN102911343B is the polar solvent solution dripping monohydroxy-alcohol after trimerization reaction.But the defect of these two kinds of methods is the middle short chain monocarbon alcohols being all confined to normal temperature liquid state, only can limited raising dimethylbenzene tolerance.
On the current technology, also do not prepare in prior art that cost while of simultaneously meeting that free TDI content is low, tolerance is high, viscosity is suitable, nco value is high is low, the simple toluene diisocyanate trimer solidifying agent of technique.
Summary of the invention
The object of the invention is to for the deficiencies in the prior art, there is provided a kind of free TDI content little by 0.5%, dimethylbenzene tolerance is greater than 3.0, NCO content be 7.0 ?8.0%, solid content is 50 ± 2%, platinum cobalt look number is less than 20, and cost is low, the simple low-free toluene diisocyanate trimer with high compatibility solidifying agent of technique and preparation method thereof.
In order to realize above object, the present invention adopts following technical scheme:
The preparation method of low-free toluene diisocyanate trimer with high compatibility solidifying agent, comprises the steps:
1) under nitrogen protection, isocyanate-monomer, solvent composition and antioxidant component are stirred, holding temperature 10 ?50 DEG C; Drip catalyst component 30% ?60wt%, time for adding 0.5 ?2h, continue 10 ?50 DEG C of stirring reactions 3 ?8 hours; Described isocyanate-monomer is selected from 2,4 ?tolylene diisocyanate and 2,6 ?tolylene diisocyanate, wherein 2,4 ?tolylene diisocyanate and 2,6 ?the mass ratio of tolylene diisocyanate be 60:40 to 100:0; The consumption of isocyanate-monomer account for raw material gross weight 35 ?55%;
2) when NCO% be 12 ?14wt% time, add catalyst component 15 ?30wt%, continue 10 ?50 DEG C of stirring reactions 3 ?8 hours;
3) when NCO% be 10 ?11wt% time, add catalyst component 15 ?30wt%, continue 10 ?15 DEG C of stirring reactions 3 ?15 hours;
4) when NCO% be 9.3 ?10wt% time, add the catalyzer of residual content, be heated to 50 ?100 DEG C, stirring reaction 2 ?10 hours; When NCO% be 8.5 ?9.3% time, add stopper, temperature remain on 50 ?100 DEG C, stirring reaction 0.5 ?1 hour; Add component A, continue stirring reaction 2 ?4 hours; Add B component again, continue stirring reaction 1 ?2 hours, cooling discharge; Described component A is the mixture of alcohol and solvent; Described alcohol be selected from unitary secondary alcohol or unitary tertiary alcohol one or more; B component be selected from molecular weight be 180 ?400 monohydroxy-alcohol in one or more mixture;
Described catalyst component is selected from the Mannich base compounds with di alkylamino group methyl and phenolic hydroxyl group in same a part; Catalyst component uses with the form of pure compound or solution; Total consumption of the effective constituent of catalyst component account for raw material gross weight 0.1 ?0.5wt%.
For realizing the object of the invention further, preferably, described solvent composition is toluene, dimethylbenzene, hexanaphthene, chlorobenzene, pimelinketone, mibk, N, N ?dimethyl formamide, N, N ?N,N-DIMETHYLACETAMIDE, dimethyl sulfoxide (DMSO), n-propyl acetate, ethyl acetate, butylacetate, isopropyl acetate, isobutyl acetate, N ?one or more mixture in methyl-2-pyrrolidone, tetrahydrofuran (THF) and sherwood oil; The consumption of solvent composition account for raw material gross weight 40 ?60wt%.
Preferably, described antioxidant component be selected from sodium phosphite, ortho phosphorous acid, four [β ?(3,5 ?bis-tertiary Ding Ji ?4 ?hydroxy phenyl) propionic acid] one or more mixture in pentaerythritol ester, ditertbutylparacresol, triphenyl phosphite, tricresyl phosphite monooctyl ester and tridecyl phosphite and three [2,4 ?di-tert-butyl-phenyl] phosphorous acid ester (irgasfos 168); The consumption of antioxidant component account for raw material gross weight 0.1 ?1wt%.
Preferably, described stopper is selected from one or more the mixture in phosphoric acid, Benzoyl chloride, methyl tosylate, methyl-sulfate, phosphoric acid di-n-butyl and anhydrous hydrogen chloride; The consumption of polymerization inhibitor component account for raw material gross weight 0.1 ?2wt%.
Preferably, step 4) described in component A in institute's hydroxyl and step 1) mol ratio that adds the isocyanate group of isocyanate-monomer is: OH:NCO=1:50 ?1:100.
Preferably, step 4) described in B component in institute's hydroxyl and step 1) mol ratio that adds the isocyanate group of isocyanate-monomer is: OH:NCO=1:20 ?1:40.
Preferably, contained in component A solvent and step 1) the solvent quality sum that adds be raw material gross weight 49 ?51wt%.
Preferably, step 1) ?step 3) temperature of reaction control 20 ?40 DEG C; Step 4) temperature of reaction control 60 ?80 DEG C.
Preferably, described unitary secondary alcohol be Virahol, sec-butyl alcohol, 2 ?amylalcohol or 2 ?hexanol; Described unitary tertiary alcohol is the trimethyl carbinol and tertiary amyl alcohol; Described Mannich base compounds is 2,4,6 ?three (dimethylamino methyl) phenol, 2,2 ’ ?two [2,6 ?two (dimethylamino methyl) ?4 ?hydroxy phenyl] propane, 4 ?Jia Ji ?2,6 ?two (dimethylamino methyl) phenol, 2,5 ?two (dimethylamino methyl) Resorcinol, 2,4 ?two (dimethylamino methyl) ?6 ?one or more mixture in methylphenol.The catalyst component of preferred use is 2,2 ’ ?two [2,6 ?two (dimethylamino methyl) ?4 ?hydroxy phenyl] propane, be based on dihydroxyphenyl propane, dimethylamine and formaldehyde by the obtained catalyst component of the method for US Patent No. 4255569 synthesis.
B component described in step (4) can molecular weight be 180 ?400, fusing point more than 25 DEG C long chain monohydric alcohols, preferably n-dodecanol, hexadecanol, stearyl alcohol or behenyl alcohol (behenyl alcohol).
A kind of low-free toluene diisocyanate trimer with high compatibility solidifying agent, it is obtained by above-mentioned preparation method, and its free TDI content is little by 0.5%, its dimethylbenzene tolerance is greater than 3.0, NCO content be 7.0 ?8.0%, solid content is 50 ± 2%, and platinum cobalt look number is less than 20.
Isocyanate-monomer component of the present invention with using any desired mixt of organic diisocyanate monomer, can comprise: the monoisocyanates of aliphatics, alicyclic, araliphatic or fragrant branching isocyanate groups, as phenyl isocyanate, octyl group isocyanic ester; The vulcabond of aliphatics, alicyclic, araliphatic or fragrant branching isocyanate groups, as hexamethylene diisocyanate (HDI), isoflurane chalcone diisocyanate (IPDI), diphenylmethanediisocyanate (MDI), xylylene diisocyanate (XDI), tetramethylxylylene diisocyanate (TMXDI), 2,2,4 ?trimethylhexane diisocyanate (TMHDI), Methylcyclohexyl diisocyanate (HTDI), dicyclohexylmethylene vulcabond (H
12mDI), tolylene diisocyanate (TDI), PPDI (PPDI), naphthalene diisocyanate (NDI); Triisocyanate and/or higher order isocyanate, as nonane triisocyanate, 1,6,11 ?undecane triisocyanate, poly methylene poly phenyl poly isocyanate (PAPI).Preferred use 2,4 ?tolylene diisocyanate and 2,6 ?the mixture of tolylene diisocyanate, in the mixture 2,4 ?TDI and 2,6 ?the mass ratio of TDI be 60:40 ?100:0.
Major advantage and the beneficial effect of hinge structure of the present invention are:
1, have employed two sections of temperature hierarchy of high temperature after first low temperature.Mannich alkali catalyst, have obvious selective advantage than reaction under high temperature at relatively low temperature, side reaction is few and three pentamer ratios are high, and the look of product is number lower, but low temperature will cause the reaction times to extend, and particularly reacts the later stage, low temperature viscosity is larger, reacts slower.The present invention finds, the later stage adopts relatively-high temperature, can accelerate speed of reaction, reduces viscosity, is conducive to free monomer and diffuses out from the parcel of oligopolymer and participate in reaction, thus surprisingly further reduces free monomer content.Under the suitable low temperature in early stage, the highly selective of Mannich base and later stage relatively-high temperature promote that free monomer reduces, and what both synergy was surprising has synthesized low free product.Make the reaction times be unlikely long simultaneously.
2, have employed the mode in batches adding catalyzer.Will keep certain speed of reaction at relatively low temperature, need more catalyzer, but once add a large amount of catalyzer, reaction very exothermic is difficult to control, and adds catalyzer in batches and can make going on of reacting balance.The present invention simultaneously finds, adding catalyzer can also improve Mannich base catalyst reaction selectivity in batches further, and under same NCO group transformation efficiency, free monomer is lower.
3, a small amount of secondary alcohol or tertiary alcohol is adopted to reduce free monomer further.Secondary alcohol or tertiary alcohol sterically hindered due to it, have higher reaction preference to free monomer, the present invention find, a small amount of adding just can reduce free monomer content, and avoids a large amount of consumption of NCO group.With under the synergy of preceding step, synthesize the product that free monomer is less than 0.5wt%.
4, the solid-state long chain monohydric alcohols modification of normal temperature is adopted effectively to improve tolerance.Improve on tolerance basis in known monohydroxy-alcohol modification, invention has been improvement.The present invention finds, relative to traditional molecular weight 60 ?200 the monohydroxy-alcohol of normal temperature liquid state, molecular weight 180 ?400 the solid-state monohydroxy-alcohol of normal temperature, in raising dimethylbenzene tolerance, there is significant advantage.Because later stage of the present invention adopts relatively-high temperature, can very fast thawing and dissolve solid-state monohydroxy-alcohol, avoid inhomogeneous reaction.The present invention's highly selective reaction in earlier stage in addition, the product assay making trimerization product middle-molecular-weihydroxyethyl relatively low is higher, thus makes the polarity of product entirety lower, acts synergistically with long chain monohydric alcohols modification, makes the tolerance of product of the present invention higher.
5, the toluene diisocyanate trimer solidifying agent product of the present invention's synthesis have that look shallow, the content of free TDI monomer is low, dimethylbenzene tolerance is high, the advantage of quick-drying and stable performance, the present invention simultaneously adopts chemical synthesis, with employing physical separation method separated free TDI, compare and have that cost is low, the simple advantage of technique.
6, the toluene diisocyanate trimer solidifying agent product that the present invention obtains has following index: free TDI content is little by 0.5%, is preferably less than 0.3%, and dimethylbenzene tolerance is greater than 3.0, be preferably greater than 4.0, NCO content be 7.0 ?8.0%, Gu containing being 50 ± 2%, platinum cobalt look number is less than 20.
Embodiment
In order to better set forth the present invention; below in conjunction with embodiment, the present invention will be further described; but embodiments of the present invention are not limited thereto, content according to the present invention, to some immaterial improvement and the adjustment at place of the present invention, still belongs to scope.
The product property testing method of each embodiment and comparative example is as follows: look number uses number test of a platinum cobalt look, according to GB/T3143 ?1982 to test; Viscosity is 25 DEG C of tests, adopt rotary viscometer according to GB/T2794 ?1995 to test; Solid content according to GB/T2793 ?1995 to test; Nco value according to GB/T12009.4 ?1989 to test; Free TDI content according to GB/T18446 ?2009 to test; Dimethylbenzene tolerance adopts dimethylbenzene titration test, is the quality of dimethylbenzene and the ratio of sample mass when there is muddy insolubles.
Embodiment 1
To with agitator, thermometer and logical N
2add in the 500mL four-hole boiling flask of protection 100gTDI ?80 and 100g N-BUTYL ACETATE and 1gBHT (ditertbutylparacresol); heating in water bath is to 40 DEG C; add 0.3g catalyzer (2 again; 4; 6 ?three (dimethylamino methyl) phenol; be called for short DMP ?30), continue at 40 DEG C of stirring reactions, every 0.5h sampling and measuring nco value.After 4h, nco value is 13.4wt%, second time add 0.15gDMP ?30, continue insulation reaction.After 8h, nco value is 10.6wt%, third time add 0.15gDMP ?30, continue insulation reaction.After 12h, nco value is 9.5wt%, add for the 4th time 0.1gDMP ?30, heat to 70 DEG C, stir insulation reaction.After 10h, nco value is 8.9wt%, adds 0.6g stopper methyl tosylate, continues after insulation reaction 0.5h, adds 0.7g Virahol and 7g N-BUTYL ACETATE, continues stirring reaction 3h, adds 7g lauryl alcohol and continues stopped reaction after reaction 1h, cooling discharging.
Embodiment 2
To with agitator, thermometer and logical N
2add in the 500mL four-hole boiling flask of protection 200gTDI ?80 and 200g N-BUTYL ACETATE and 1g inferior sodium phosphate; water-bath temperature control is to 20 DEG C; add 1.0g catalyst solution (2 again; 2 ’ ?two [2; 6 ?two (dimethylamino methyl) ?4 ?hydroxy phenyl] propane; be made into the DMF solution of 25wt%), continue at 20 DEG C of stirring reactions, every 0.5h sampling and measuring nco value.After 6h, nco value is 12.2wt%, and second time adds 0.4g catalyst solution, continues insulation reaction.After 8h, nco value is 10.3wt%, and third time adds 0.4g catalyst solution, continues insulation reaction.After 10h, nco value is 9.4wt%, adds 0.5g catalyst solution, heats to 60 DEG C for the 4th time, stirs insulation reaction.After 6h, nco value is 9.0wt%, adds 1g stopper phosphoric acid di-n-butyl, continues after insulation reaction 1h, adds 1.4g Virahol and 16g N-BUTYL ACETATE, continues stirring reaction 2h, adds 15g hexadecanol and continues stopped reaction after reaction 2h, cooling discharging.
Embodiment 3
To with agitator, thermometer and logical N
2add in the 1000mL four-hole boiling flask of protection 300gTDI ?80 and 300g N-BUTYL ACETATE and 2g antioxidant 1010 (four [β ?(3; 5 ?bis-tertiary Ding Ji ?4 ?hydroxy phenyl) propionic acid] pentaerythritol ester); water-bath temperature control is to 35 DEG C; add again 0.6g catalyzer (4 ?Jia Ji ?2; 6 ?two (dimethylamino methyl) phenol); continue at 30 DEG C of stirring reactions, each 0.5h sampling and measuring nco value.After 6h, nco value is 12.5wt%, and second time adds 0.3g catalyzer, continues insulation reaction.After 4h, nco value is 10.6wt%, and third time adds 0.4g catalyst solution, continues insulation reaction.After 15h, nco value is 9.4wt%, adds 0.4g catalyst solution, heats to 75 DEG C for the 4th time, stirs insulation reaction.After 3h, nco value is 9.1wt%, adds 1.5g stopper methyl tosylate, continues after insulation reaction 0.5h, adds 2.5g sec-butyl alcohol and 35g N-BUTYL ACETATE, continues stirring reaction 3h, adds 32g stearyl alcohol and continues stopped reaction after reaction 2h, cooling discharging.
Embodiment 4
To with agitator, thermometer and logical N
2add in the 1000mL four-hole boiling flask of protection 300gTDI ?80 and 300g N-BUTYL ACETATE and 2g antioxidant 1010 (four [β ?(3; 5 ?bis-tertiary Ding Ji ?4 ?hydroxy phenyl) propionic acid] pentaerythritol ester); water-bath temperature control is to 30 DEG C; add 1g catalyst solution (2 again; 2 ’ ?two [2; 6 ?two (dimethylamino methyl) ?4 ?hydroxy phenyl] propane; be made into the DMF solution of 20wt%); continue at 30 DEG C of stirring reactions, each 0.5h sampling and measuring nco value.After 6h, nco value is 12.9wt%, and second time adds 0.4g catalyst solution, continues insulation reaction.After 8h, nco value is 10.7wt%, and third time adds 0.7g catalyst solution, continues insulation reaction.After 12h, nco value is 9.5wt%, adds 0.5g catalyst solution, heats to 80 DEG C for the 4th time, stirs insulation reaction.After 4h, nco value is 8.8wt%, adds 1.0g stopper Benzoyl chloride, continues after insulation reaction 1h, adds the 2.5g trimethyl carbinol and 31g N-BUTYL ACETATE, continues stirring reaction 3h, adds 28g behenyl alcohol and continues stopped reaction after reaction 2h, cooling discharging.
Embodiment 5
To with agitator, thermometer and logical N
2add in the 1000mL four-hole boiling flask of protection 300gTDI ?80 and 300g N-BUTYL ACETATE and 2g antioxidant BHT (ditertbutylparacresol); water-bath temperature control is to 30 DEG C; add again 1.5g catalyst solution (DMP ?30 and 2; 2 ’ ?two [2; 6 ?two (dimethylamino methyl) ?4 ?hydroxy phenyl] mixing solutions of mass ratio 1:1 of propane; be made into the N-BUTYL ACETATE solution of 20wt% together); continue at 30 DEG C of stirring reactions, each 0.5h sampling and measuring nco value.After 5h, nco value is 12.5wt%, and second time adds 0.9g catalyst solution, continues insulation reaction.After 6h, nco value is 10.3wt%, and third time adds 0.75g catalyst solution, continues insulation reaction.After 10h, nco value is 9.5wt%, adds 0.9g catalyst solution, heats to 70 DEG C for the 4th time, stirs insulation reaction.After 5h, nco value is 9.3wt%, adds 1.0g stopper phosphoric acid, continues after insulation reaction 1h, adds 1.5g Virahol and 30g N-BUTYL ACETATE, continues stirring reaction 2h, adds 28g behenyl alcohol and continues stopped reaction after reaction 2h, cooling discharging.
Comparative example
To with agitator, thermometer and logical N
2protection 500mL four-hole boiling flask in add 100gTDI ?80 (2,4 ?TDI massfraction be 80wt%, 2; 6 ?TDI massfraction be 20wt%) and 100g N-BUTYL ACETATE and 1g inferior sodium phosphate; stir, heating in water bath to 60 DEG C, then by 0.5gDMP ?30 disposablely join in reaction vessel; continue stirring reaction; every 0.5h sampling and measuring nco value, after 10h, nco value is 8.9wt%; add 0.5g stopper Benzoyl chloride, continue insulation reaction 1h.Drip the mixing solutions of 7.5g n-Octanol and 9g N-BUTYL ACETATE, continue stirring reaction 1h.Stopped reaction, after cooling, discharging obtains finished product.
Table 1 comparative example and embodiment properties of sample test result
What comparative example adopted is conventional known synthesis technique, adopt traditional DMP ?30 catalyzer, once adding, trimerization reaction at suitable temperature, is finally the liquid monohydroxy-alcohol modification raising tolerance of representative with n-Octanol.
As can be seen from the results, for same DMP ?30 catalyzer, embodiment 1 have employed and adds that catalyzer steadily controls to react in batches, significantly reduces free monomer content than comparative example under the synergy of two sections of temperature hierarchy and a small amount of secondary alcohol, reaches less than 0.5%.Under the effect of the semi-solid lauryl alcohol of normal temperature, tolerance is brought up to more than 3.0 in addition.Embodiment 2,4,5, have employed preferably more high reactivity and optionally catalyzer, free TDI has been reduced to less than 0.3%.Embodiment 3,4,5, have employed solid-state stearyl alcohol or behenyl alcohol, significantly tolerance has been brought up to more than 4.0 further.In addition, each embodiment all adopts relative low temperature early stage, and number all comparatively comparative example is low, lower than 20 for look.
Present invention employs two sections of temperature hierarchy of high temperature after first low temperature, the later stage adopts relatively-high temperature, accelerates speed of reaction, reduces viscosity, is conducive to free monomer and diffuses out from the parcel of oligopolymer and participate in reaction, thus significantly reduce free monomer content further.Under the suitable low temperature in early stage, the highly selective of Mannich base and later stage relatively-high temperature promote that free monomer reduces, and both collaborative has synthesized low free product, makes the reaction times be unlikely long simultaneously.Present invention employs the mode in batches adding catalyzer.Will keep certain speed of reaction at relatively low temperature, need more catalyzer, but once add a large amount of catalyzer, reaction very exothermic is difficult to control, and adds catalyzer in batches and can make going on of reacting balance.The present invention simultaneously finds, adding catalyzer can also improve Mannich base catalyst reaction selectivity in batches further, and under same NCO group transformation efficiency, free monomer is lower.The present invention adopts a small amount of secondary alcohol or tertiary alcohol to reduce free monomer further.Secondary alcohol or tertiary alcohol sterically hindered due to it, have higher reaction preference to free monomer, the present invention find, a small amount of adding just can reduce free monomer content, and avoids a large amount of consumption of NCO group.With under the synergy of preceding step, synthesize the product that free monomer is less than 0.5wt%.
Claims (10)
1. the preparation method of low-free toluene diisocyanate trimer with high compatibility solidifying agent, is characterized in that comprising the steps:
1) under nitrogen protection, isocyanate-monomer, solvent composition and antioxidant component are stirred, holding temperature 10 ?50 DEG C; Drip catalyst component 30% ?60wt%, time for adding 0.5 ?2h, continue 10 ?50 DEG C of stirring reactions 3 ?8 hours; Described isocyanate-monomer is selected from 2,4 ?tolylene diisocyanate and 2,6 ?tolylene diisocyanate, wherein 2,4 ?tolylene diisocyanate and 2,6 ?the mass ratio of tolylene diisocyanate be 60:40 to 100:0; The consumption of isocyanate-monomer account for raw material gross weight 35 ?55%;
2) when NCO% be 12 ?14wt% time, add catalyst component 15 ?30wt%, continue 10 ?50 DEG C of stirring reactions 3 ?8 hours;
3) when NCO% be 10 ?11wt% time, add catalyst component 15 ?30wt%, continue 10 ?15 DEG C of stirring reactions 3 ?15 hours;
4) when NCO% be 9.3 ?10wt% time, add the catalyzer of residual content, be heated to 50 ?100 DEG C, stirring reaction 2 ?10 hours; When NCO% be 8.5 ?9.3% time, add stopper, temperature remain on 50 ?100 DEG C, stirring reaction 0.5 ?1 hour; Add component A, continue stirring reaction 2 ?4 hours; Add B component again, continue stirring reaction 1 ?2 hours, cooling discharge; Described component A is the mixture of alcohol and solvent; Described alcohol be selected from unitary secondary alcohol or unitary tertiary alcohol one or more; B component be selected from molecular weight be 180 ?400 monohydroxy-alcohol in one or more mixture;
Described catalyst component is selected from the Mannich base compounds with di alkylamino group methyl and phenolic hydroxyl group in same a part; Catalyst component uses with the form of pure compound or solution; Total consumption of the effective constituent of catalyst component account for raw material gross weight 0.1 ?0.5wt%.
2. the preparation method of low-free toluene diisocyanate trimer with high compatibility solidifying agent according to claim 1, it is characterized in that, described solvent composition is toluene, dimethylbenzene, hexanaphthene, chlorobenzene, pimelinketone, mibk, N, N ?dimethyl formamide, N, N ?N,N-DIMETHYLACETAMIDE, dimethyl sulfoxide (DMSO), n-propyl acetate, ethyl acetate, butylacetate, isopropyl acetate, isobutyl acetate, N ?one or more mixture in methyl-2-pyrrolidone, tetrahydrofuran (THF) and sherwood oil; The consumption of solvent composition account for raw material gross weight 40 ?60wt%.
3. the preparation method of low-free toluene diisocyanate trimer with high compatibility solidifying agent according to claim 1, it is characterized in that, described antioxidant component be selected from sodium phosphite, ortho phosphorous acid, four [β ?(3,5 ?bis-tertiary Ding Ji ?4 ?hydroxy phenyl) propionic acid] one or more mixture in pentaerythritol ester, ditertbutylparacresol, triphenyl phosphite, tricresyl phosphite monooctyl ester and tridecyl phosphite and three [2,4 ?di-tert-butyl-phenyl] phosphorous acid ester; The consumption of antioxidant component account for raw material gross weight 0.1 ?1wt%.
4. the preparation method of low-free toluene diisocyanate trimer with high compatibility solidifying agent according to claim 1, it is characterized in that, described stopper is selected from one or more the mixture in phosphoric acid, Benzoyl chloride, methyl tosylate, methyl-sulfate, phosphoric acid di-n-butyl and anhydrous hydrogen chloride; The consumption of polymerization inhibitor component account for raw material gross weight 0.1 ?2wt%.
5. the preparation method of low-free toluene diisocyanate trimer with high compatibility solidifying agent according to claim 1, it is characterized in that, step 4) described in component A in institute's hydroxyl and step 1) mol ratio that adds the isocyanate group of isocyanate-monomer is: OH:NCO=1:50 ?1:100.
6. the preparation method of low-free toluene diisocyanate trimer with high compatibility solidifying agent according to claim 1, it is characterized in that, step 4) described in B component in institute's hydroxyl and step 1) mol ratio that adds the isocyanate group of isocyanate-monomer is: OH:NCO=1:20 ?1:40.
7. the preparation method of low-free toluene diisocyanate trimer with high compatibility solidifying agent according to claim 1, is characterized in that, solvent contained in component A and step 1) the solvent quality sum that adds be raw material gross weight 49 ?51wt%.
8. according to claim 1 ?the preparation method of low-free toluene diisocyanate trimer with high compatibility solidifying agent described in 7 any one, it is characterized in that: step 1) ?step 3) temperature of reaction control 20 ?40 DEG C; Step 4) temperature of reaction control 60 ?80 DEG C.
9. according to claim 1 ?the preparation method of low-free toluene diisocyanate trimer with high compatibility solidifying agent described in 7 any one, it is characterized in that: described unitary secondary alcohol be Virahol, sec-butyl alcohol, 2 ?amylalcohol or 2 ?hexanol; Described unitary tertiary alcohol is the trimethyl carbinol and tertiary amyl alcohol; Described Mannich base compounds is 2,4,6 ?three (dimethylamino methyl) phenol, 2,2 ’ ?two [2,6 ?two (dimethylamino methyl) ?4 ?hydroxy phenyl] propane, 4 ?Jia Ji ?2,6 ?two (dimethylamino methyl) phenol, 2,5 ?two (dimethylamino methyl) Resorcinol and 2,4 ?two (dimethylamino methyl) ?6 ?one or more mixture in methylphenol.
10. low-free toluene diisocyanate trimer with high compatibility solidifying agent, it is characterized in that its by claim 1 ?preparation method described in 7 any one obtain, its free TDI content is little by 0.5%, its dimethylbenzene tolerance is greater than 3.0, NCO content be 7.0 ?8.0%, solid content is 50 ± 2%, and platinum cobalt look number is less than 20.
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