CN114015016B - TDI trimer and preparation method thereof - Google Patents
TDI trimer and preparation method thereof Download PDFInfo
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- CN114015016B CN114015016B CN202111401698.4A CN202111401698A CN114015016B CN 114015016 B CN114015016 B CN 114015016B CN 202111401698 A CN202111401698 A CN 202111401698A CN 114015016 B CN114015016 B CN 114015016B
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- 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
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3271—Hydroxyamines
- C08G18/3275—Hydroxyamines containing two hydroxy groups
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
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Abstract
The invention provides a preparation method of TDI trimer. The TDI trimer is synthesized by taking polymeric toluene diisocyanate, a polar solvent, an acidic auxiliary agent, alcohol amine, a trimerization catalyst, a polymerization inhibitor and monohydric phenols as raw materials. After premixing, acid-base adjustment, prepolymerization, trimerization and termination, the TDI trimer is obtained. The TDI trimer has the advantages of low cost of raw materials, available performance, simple preparation method and process, mild reaction conditions and industrial application value.
Description
Technical Field
The invention belongs to the field of polyurethane, and particularly relates to a low-cost TDI trimer and a preparation method thereof.
Technical Field
Compared with other types of isocyanate curing agents, the Toluene Diisocyanate (TDI) trimer curing agent has the advantages of high functionality, low viscosity, high thermal stability and good corrosion resistance due to the existence of isocyanurate rings, and meanwhile, has high reactivity of-NCO groups and high reaction speed due to the strong electron withdrawing effect of the isocyanurate rings, so that the TDI trimer curing agent has the characteristics of quick curing, high hardness, easiness in polishing and the like when being matched with hydroxyl resin, and is widely applied to furniture wood lacquer, such as quick-drying wood matt lacquer and gloss lacquer. The synthesis scheme of TDI trimer is reported in many documents, such as patent document CN 101239987A,CN 102816293B,CN 110790880A,CN 105131249A,CN 101307128B.
At present, one of the preparation processes of TDI trimer is to carry out trimerization polymerization reaction on TDI monomer under the action of trimerization catalyst to form a trimer, and after the reaction is carried out to a certain extent, unreacted free monomer is separated out by a scraper evaporation or solvent extraction process. And secondly, directly carrying out trimerization reaction on TDI monomer under the action of a trimerization catalyst, and adding a polymerization inhibitor to terminate the reaction after the reaction is carried out until the free monomer meets the requirements.
In the two processes, the raw materials which must be used are Toluene Diisocyanate (TDI) monomers, namely TDI-80, TDI-65, TDI-100 or a mixture of the TDI-80, TDI-65 and TDI-100, wherein the raw material cost is about 60% or more of the cost of the TDI trimer product, and particularly under the condition of high TDI price, the expensive toluene diisocyanate raw material is always the cost burden of producing the TDI trimer.
Therefore, the development of low cost toluene diisocyanate monomer substitutes is an urgent need in the curative industry.
Disclosure of Invention
The invention aims to provide a TDI trimer with low cost and a preparation method thereof, wherein the TDI trimer has the advantages of low cost of raw materials for production, available performance, simple preparation method and process, mild reaction conditions and industrial application value.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
a TDI trimer and a preparation method thereof are prepared by the following steps:
s1, a premixing stage: dissolving polymeric toluene diisocyanate in a polar solvent at room temperature to form a mixed solution;
s2, adjusting the acid and alkali: at room temperature, adding an acidic auxiliary agent into the mixed solution formed in the step S1, and adjusting the pH to 5-6;
s3, a prepolymerization reaction stage: adding di/tri-alcohol amine into the mixed solution after the acid and alkali adjustment of S2 at a certain temperature to perform prepolymerization to obtain a solution of a prepolymer;
s4, trimerization reaction: adding a trimerization catalyst into the prepolymer solution, and adding monohydric phenols after tracking the change of NCO content to 10.5-11.5 wt%;
s5, reaction termination stage: tracking the change of NCO content to 7.5-9.0wt%, adding polymerization inhibitor, cooling to room temperature, and discharging.
The low-cost toluene diisocyanate monomer substitute in the scheme is polymeric toluene diisocyanate, is not a standard product, is tar generated in the process of producing toluene diisocyanate, still contains toluene diisocyanate monomer, but is difficult to extract the monomer and has high extraction cost, so that the toluene diisocyanate monomer substitute is generally incinerated in the existing production process. The invention surprisingly discovers that the TDI trimer prepared by polymerizing toluene diisocyanate can obviously reduce the raw material cost of the trimer under the premise of available performance, simple preparation method and process and mild reaction conditions, and has industrial application value. Toluene diisocyanate is generally synthesized by a phosgenation process, and a part of the monomers of toluene diisocyanate are polymerized into toluene diisocyanate, i.e., TDI tar, during a high temperature process. After separation in the refining unit, toluene diisocyanate monomer is taken out from the top of the tower, and TDI tar is obtained from the tower bottom. It should be noted that, as mentioned above, in the present production of TDI trimer, the trimerization catalyst is directly added into the TDI monomer raw material, and polymerization inhibitor is added to complete the reaction after polymerization, while the polymeric toluene diisocyanate is used to produce TDI trimer, and the process and the conventional TDI monomer are used as raw materials, so that the technical difficulties of three aspects need to be overcome: firstly, because polymeric toluene diisocyanate is produced in the tower kettle of a refining tower and contains a large amount of iron impurities, the direct use can cause uncontrollable reaction due to high iron impurities, and explosion polymerization and a large amount of heat release are generated; secondly, as the polymeric toluene diisocyanate contains 75-55% of multi-benzene ring polymeric structure, the chemical structure determines that the rigidity of molecules is stronger than that of TDI monomers, and therefore, the molecular flexibility needs to be adjusted to be proper. Thirdly, the molecular weight of the polymeric toluene diisocyanate is larger than that of TDI monomer, the molecular weight of the product needs to be regulated during trimerization reaction, and the curing performance of the trimeric product is seriously damaged due to the too large molecular weight.
In the preparation method, the mass ratio of each component is as follows, based on the total mass of TDI trimer finished products: polymerization of toluene diisocyanate: 40-70%; polar solvent: 20-50%; acid auxiliary agent: 0.05-0.2%; di/tri alcohol amine: 5-15%; monohydric phenols: 4.75-20%; trimerization catalyst: 0.1-0.3%, polymerization inhibitor: 0.1-0.3%.
. In the present invention, the polymeric toluene diisocyanate comprises 25% to 45% toluene diisocyanate monomer, preferably 30% to 40%, more preferably 30% to 35%; and/or, the polymeric toluene diisocyanate has an NCO content of 30% to 34%; preferably 31% -33%, more preferably 31.5% -32.5%.
In the invention, the polar solvent is one or more of ethyl acetate, butyl acetate, toluene and xylene, preferably one or two of ethyl acetate and butyl acetate, more preferably butyl acetate; and/or the acidic auxiliary is dry hydrogen chloride or anhydrous phosphoric acid, preferably dry hydrogen chloride; and/or the trimerization catalyst is one or more of lithium acetate, triethylene diamine, DMP-30 and tri-n-butyl phosphorus, preferably one or two of tri-n-butyl phosphorus and DMP-30, and more preferably DMP-30.
In the present invention, the di/tri alcohol amine is one or more of diethanolamine, triethanolamine, triisopropanolamine, N' -bis (2 hydroxypropyl) aniline, preferably at least one of diethanolamine and triethanolamine, more preferably triethanolamine.
In the present invention, the monohydric phenol is one or more of phenol, cresol and chlorophenol, preferably one or two of phenol, cresol and cresol, more preferably cresol.
In the invention, the polymerization inhibitor is one or more of dibutyl phosphate, benzoyl chloride and methyl p-toluenesulfonate, preferably one or two of dibutyl phosphate and benzoyl chloride, and more preferably benzoyl chloride.
In the present invention, the temperature in the prepolymerization stage is 50 to 80℃and preferably 60 to 75℃and the reaction time is 1 to 3 hours and preferably 2 to 3 hours.
In the present invention, the temperature of the trimerization and reaction termination stage is 50 to 70 ℃, preferably 55 to 65 ℃, and the reaction time is 0.5 to 2 hours, preferably 1 to 1.5 hours.
In the present invention, the solids content of the trimer preparation is 50 to 80%, preferably 50 to 70%, more preferably 55 to 60%; the NCO content of the trimeric articles is 7.0 to 8.5%, preferably 7.4 to 8.2%, more preferably 8.0 to 8.1%.
The invention has the beneficial effects that:
(1) A low cost polymeric toluene diisocyanate is selected to replace the traditional toluene diisocyanate monomer for the production of TDI trimer and provides a method of preparation.
(2) The prepared TDI trimer has the advantages of available performance, simple production method and process, mild reaction conditions and industrial application value.
(3) The original traditional incineration treatment way of the polymerized toluene diisocyanate is changed, the waste is recycled, the pollutant emission is reduced, and the benefit is increased.
Detailed Description
The present invention will be described in detail by way of the following specific examples of the present invention, which should not be construed as limiting the present invention in any sense.
The raw material sources are as follows:
the polymerized toluene diisocyanate is derived from tar produced by a Wanhua chemical smoke table industrial garden Toluene Diisocyanate (TDI) device, contains 45% -55% of toluene diisocyanate monomer, and has an NCO content of 33.0% -35.5%, and the TDI monomer needs to be added to adjust the monomer content and the NCO content before use. Polar solvent, di/ternary alcohol amine, trimerization catalyst, polymerization inhibitor, monohydroxyphenols are all reagent grade, and suppliers are Komio Europe
Drying equipment: drying is carried out by adopting a general blast drying oven.
And (3) solid content testing: the test was performed using mass differential method.
NCO content test: the test was performed by di-n-butylamine titration.
Example 1
S1, a premixing stage: firstly, toluene diisocyanate monomer (TDI-80) is added into original polymerized toluene diisocyanate until the monomer content is 25% and the NCO content is 30%; and then respectively weighing 3.3 kg of toluene and 3 kg of xylene to prepare a solvent for later use. Then, 5.5 kg of the above-mentioned polymeric toluene diisocyanate was weighed out at room temperature, and a mixed solution of polymeric toluene diisocyanate was prepared by dissolving in the above-mentioned 6.3 kg of solvent.
S2, adjusting the acid and alkali: 11.8 kg of the mixed solution of the polymeric toluene diisocyanate prepared in the step S1 is poured into a reaction kettle, and 0.025 kg of dry hydrogen chloride is introduced at room temperature to adjust the pH value to 5.3.
S3, a prepolymerization reaction stage: the mixed solution of the polymerized toluene diisocyanate prepared in the step S2 is preheated to 50 ℃ and kept at the temperature for 0.5 hour, stirring is started, 0.25 kg of diethanolamine and 0.45 kg of triethanolamine are added at one time, the temperature is raised to 80 ℃ and reacted for 1.0 hour, and the temperature is reduced to 70 ℃ to obtain a prepolymer solution.
S4, trimerization reaction: the reaction temperature was controlled at 70℃continuously while maintaining stirring conditions, 0.008 kg of DMP-30 and 0.008 kg of triethylenediamine catalyst were added to the prepolymer solution prepared in S3 at a time for 0.5 hours, and samples were taken every 10 minutes during the reaction to analyze NCO content, and 0.45 kg of phenol and 0.35 kg of cresol were added when the NCO content was 11.5%, and the reaction was continued for 0.5 hours to prepare a trimer solution.
S5, reaction termination stage: the reaction temperature was controlled at 50℃and stirring was continued, and when the NCO content was 9.0%, 0.008 kg of phosphoric acid and 0.008 kg of benzoyl chloride were added to the trimer solution prepared in S3 at one time, and after reacting at 70℃for 0.5 hours, the mixture was cooled to room temperature and discharged, and the NCO content was analyzed to be 8.5% and the solid content was 52.8%.
Example 2
S1, a premixing stage: firstly, toluene diisocyanate monomer (TDI-80) is added into original polymerized toluene diisocyanate until the monomer content is 30 percent and the NCO content is 31 percent; then, 1 kg of ethyl acetate and 1.5 kg of butyl acetate are respectively weighed to prepare solvents for standby. Then, 5 kg of the above-mentioned polymeric toluene diisocyanate was weighed at room temperature, and a mixed solution of polymeric toluene diisocyanate was prepared by dissolving in the above-mentioned 2.5 kg of solvent.
S2, adjusting the acid and alkali: the mixed solution of 7.5 kg of polymeric toluene diisocyanate prepared in the step S1 is poured into a reaction kettle, and 0.015 kg of dry hydrogen chloride is introduced at room temperature to adjust the pH value to 5.3.
S3, a prepolymerization reaction stage: the mixed solution of the polymerized toluene diisocyanate prepared in the step S2 is preheated to 50 ℃ and kept at the temperature for 0.5 hour, stirring is started, 0.33 kg of diethanolamine and 0.34 kg of triisopropanolamine are added at one time, the temperature is raised to 5 ℃ and reacted for 2 hours, and the temperature is reduced to 55 ℃ to obtain a prepolymer solution.
S4, trimerization reaction: the reaction temperature was continuously controlled at 55℃and stirring conditions were maintained, and 0.008 kg of DMP-30 and 0.008 kg of lithium acetate catalyst were added to the prepolymer solution prepared in S3 at a time to react at 55℃for 0.5 hours, during which the NCO content was analyzed by sampling every 10 minutes, and when the NCO content was 11.3%, 0.65 kg of phenol was added to continue the reaction for 1 hour to prepare a trimer solution.
S5, reaction termination stage: continuously controlling the reaction temperature to 55 ℃ and maintaining stirring conditions, when the NCO content is 8.7%, adding 0.025 kg of dibutyl phosphate into the trimer solution prepared in S4 at one time, reacting for 1.5 hours at the temperature of 55 ℃, cooling to room temperature, discharging, and analyzing that the NCO content is 7.10% and the solid content is 71.8%.
Example 3
S1, a premixing stage: firstly, toluene diisocyanate monomer (TDI-80) is added into original polymerized toluene diisocyanate until the monomer content is 35 percent and the NCO content is 32 percent; and then weighing 6.25 kg of ethyl acetate solvent for later use. Then, 7.6 kg of the above-mentioned polymeric toluene diisocyanate was weighed out at room temperature, and a mixed solution of polymeric toluene diisocyanate was prepared by dissolving in the above-mentioned 6.25 kg of solvent.
S2, adjusting the acid and alkali: 13.85 kg of the mixed solution of the polymeric toluene diisocyanate prepared in the step S1 is poured into a reaction kettle, and 0.025 kg of dry hydrogen chloride is introduced at room temperature to adjust the pH value to 5.3.
S3, a prepolymerization reaction stage: the mixed solution of the polymerized toluene diisocyanate prepared in the step S2 is preheated to 50 ℃ and kept at the temperature for 0.5 hour, stirring is started, 0.95 kg of triethanolamine is added at one time, and the temperature is raised to 60 ℃ for 2 hours to obtain a prepolymer solution.
S4, trimerization reaction: continuously controlling the reaction temperature at 60 ℃ and maintaining stirring conditions, adding 0.02 kg of DMP-30 catalyst into the prepolymer solution prepared in the step S3 at one time, reacting for 0.5 hour at 60 ℃, sampling and analyzing the NCO content every 10 minutes during the reaction, adding 1.25 kg of cresol when the NCO content is 11.1%, and continuously reacting for 1 hour to prepare the trimer solution.
S5, reaction termination stage: continuously controlling the reaction temperature at 60 ℃ and maintaining stirring conditions, when the NCO content is 8.75%, adding 0.020 kg of benzoyl chloride into the trimer solution prepared in S4 at one time, reacting for 1.5 hours at 60 ℃, cooling to room temperature, discharging, and analyzing that the NCO content is 8.05% and the solid content is 61.22%.
Example 4
S1, a premixing stage: firstly, toluene diisocyanate monomer (TDI-80) is added into original polymerized toluene diisocyanate until the monomer content is 40% and the NCO content is 33%; and then 1.95 kg of ethyl acetate is weighed for standby. Then, 5 kg of the above-mentioned polymeric toluene diisocyanate was weighed at room temperature, and a mixed solution of polymeric toluene diisocyanate was prepared by dissolving in the above-mentioned 1.95 kg of solvent.
S2, adjusting the acid and alkali: the mixed solution of 6.95 kg of polymeric toluene diisocyanate prepared in the step S1 is poured into a reaction kettle, and 0.012 kg of anhydrous phosphoric acid is introduced at room temperature to adjust the pH value to 5.0.
S3, a prepolymerization reaction stage: the mixed solution of the polymerized toluene diisocyanate prepared in the step S2 is preheated to 50 ℃ and kept at the temperature for 0.5 hour, stirring is started, 0.35 kg of diethanolamine and 0.95 kg of N, N' -bis (2-hydroxypropyl) aniline are added at a time, the temperature is raised to 70 ℃ for 2.5 hours, and then the temperature is reduced to 60 ℃ to obtain a prepolymer solution.
S4, trimerization reaction: continuously controlling the reaction temperature at 60 ℃ and maintaining the stirring condition, adding 0.02 kg of n-butyl phosphorus catalyst into the prepolymer solution prepared in the step S3 at one time, reacting for 0.5 hour at 60 ℃, sampling and analyzing the NCO content every 10 minutes during the reaction, adding 0.46 kg of cresol and 0.35 kg of chlorophenol when the NCO content is 10.5%, and continuously reacting for 0.5 hour to prepare the trimer solution.
S5, reaction termination stage: continuously controlling the reaction temperature at 60 ℃ and maintaining stirring conditions, when the NCO content is 7.5%, adding 0.015 kg of p-toluenesulfonate and 0.001 kg of benzoyl chloride into the trimer solution prepared in S4 at one time, reacting for 1.0 hour at 60 ℃, cooling to room temperature, discharging, and analyzing that the NCO content is 7.43% and the solid content is 80%.
Example 5
S1, a premixing stage: firstly, toluene diisocyanate monomer (TDI-80) is added into original polymerized toluene diisocyanate until the monomer content is 45% and the NCO content is 34%; then 2.46 kg of butyl acetate is weighed for standby. Then, 5 kg of the above-mentioned polymeric toluene diisocyanate was weighed out at room temperature, and a mixed solution of polymeric toluene diisocyanate was prepared by dissolving in the above-mentioned 2.46 kg of solvent.
S2, adjusting the acid and alkali: the mixed solution of 7.46 kg of polymeric toluene diisocyanate prepared in the step S1 is poured into a reaction kettle, and 0.015 kg of dry hydrogen chloride is introduced at room temperature to adjust the pH value to 5.5.
S3, a prepolymerization reaction stage: the mixed solution of the polymeric toluene diisocyanate prepared in the step S1 is preheated to 50 ℃ and kept at the temperature for 0.5 hour, stirring is started, and 0.65 kg of triethanolamine is added at one time to react for 2.5 hours at 50 ℃ to obtain a prepolymer solution.
S4, trimerization reaction: continuously controlling the reaction temperature to 50 ℃ and maintaining the stirring condition, adding 0.015 kg of DMP-30 catalyst into the prepolymer solution prepared in the step S3 at one time, reacting for 0.5 hour at 50 ℃, sampling and analyzing the NCO content every 10 minutes during the reaction, adding 1.0 kg of cresol when the NCO content is 10.9%, and continuously reacting for 1 hour to prepare the trimer solution.
S5, reaction termination stage: continuously controlling the reaction temperature at 50 ℃ and maintaining stirring conditions, adding 0.018 kg of benzoyl chloride into the trimer solution prepared in S4 at one time when the NCO content is 8.25%, reacting for 1.5 hours at 50 ℃, cooling to room temperature, discharging, and analyzing that the NCO content is 7.87% and the solid content is 74.1%.
Example 6
S1, a premixing stage: firstly, toluene diisocyanate monomer (TDI-80) is added into original polymerized toluene diisocyanate until the monomer content is 30 percent and the NCO content is 31 percent; and then weighing 3.9 kg of butyl acetate for standby. Then, 9.5 kg of the above-mentioned polymeric toluene diisocyanate was weighed out at room temperature, and a mixed solution of polymeric toluene diisocyanate was prepared by dissolving in the above-mentioned 3.9 kg of solvent.
S2, adjusting the acid and alkali: the mixed solution of 14.4 kg of polymeric toluene diisocyanate prepared in the step S1 was poured into a reaction vessel, and 0.018 kg of dry hydrogen chloride was introduced at room temperature to adjust the pH to 5.5.
S3, a prepolymerization reaction stage: the mixed solution of the polymerized toluene diisocyanate prepared in the step S2 is preheated to 50 ℃ and kept at the temperature for 0.5 hour, stirring is started, 0.95 kg of N, N' -bis (2-hydroxypropyl) aniline is added at one time, the temperature is raised to 70 ℃ for reaction for 3.0 hours, and then the temperature is reduced to 60 ℃ to obtain a prepolymer solution.
S4, trimerization reaction: the reaction temperature was continuously controlled at 60℃with stirring, 0.01 kg of DMP-30 and 0.01 kg of n-butyl phosphorus catalyst were added to the prepolymer solution prepared in S3 at a time, and reacted at 60℃for 0.5 hours, during which the NCO content was analyzed by sampling every 10 minutes, and when the NCO content was 10.8%, 1.2 kg of cresol was added, and the reaction was continued for 1 hour, to prepare a trimer solution.
S5, reaction termination stage: continuously controlling the reaction temperature at 60 ℃ and maintaining stirring conditions, when the NCO content is 8.15%, adding 0.020 kg of benzoyl chloride into the trimer solution prepared in S4 at one time, reacting for 2.0 hours at 60 ℃, cooling to room temperature, discharging, and analyzing that the NCO content is 7.50% and the solid content is 75.41%.
Comparative example 1
S1, a premixing stage: firstly, toluene diisocyanate monomer (TDI-80) is added into original polymerized toluene diisocyanate until the monomer content is 35 percent and the NCO content is 32 percent; and then weighing 6.25 kg of ethyl acetate solvent for later use. Then, 7.6 kg of the above-mentioned polymeric toluene diisocyanate was weighed out at room temperature, and a mixed solution of polymeric toluene diisocyanate was prepared by dissolving in the above-mentioned 6.25 kg of solvent.
S2, adjusting the acid and alkali: 13.85 kg of the mixed solution of the polymeric toluene diisocyanate prepared in the step S1 is poured into a reaction kettle, and 0.045 kg of dry hydrogen chloride is introduced at room temperature to adjust the pH value to 5.3.
S3, a trimerization reaction stage: the mixed solution of the polymeric toluene diisocyanate prepared in the step S2 was preheated to 50 ℃ and kept at the temperature for 0.5 hour, stirring was started, 0.02 kg of DMP-30 catalyst was stirred, and the temperature was raised to 60 ℃ to react for 1.5 hours to prepare a trimer solution.
S4, reaction termination stage: to the trimer solution prepared in S4, 0.020 kg of benzoyl chloride was added at a time, and after 1.5 hours of reaction at 60℃the mixture was cooled to room temperature and discharged, and the NCO content was found to be 10.05% and the solid content was found to be 55.1%.
Those skilled in the art will appreciate that certain modifications and adaptations of the invention are possible and can be made under the teaching of the present specification. Such modifications and adaptations are intended to be within the scope of the present invention as defined in the appended claims.
Claims (11)
1. A method for preparing a TDI trimer, comprising the steps of:
s1, a premixing stage: dissolving polymeric toluene diisocyanate in a polar solvent at room temperature to form a mixed solution;
s2, adjusting the acid and alkali: at room temperature, adding an acidic auxiliary agent into the mixed solution formed in the step S1, and adjusting the pH to 5-6;
s3, a prepolymerization reaction stage: adding di/tri-alcohol amine into the mixed solution after the acid and alkali adjustment of S2 at a certain temperature to perform prepolymerization to obtain a solution of a prepolymer;
s4, trimerization reaction: adding a trimerization catalyst into the prepolymer solution, and adding monohydric phenols after tracking the change of NCO content to 10.5-11.5 wt%;
s5, reaction termination stage: tracking the change of NCO content to 7.5-9.0wt%, adding polymerization inhibitor, cooling to room temperature, and discharging;
the polymerized toluene diisocyanate contains 25% -45% of toluene diisocyanate monomers; the NCO content of the polymeric toluene diisocyanate is 30% -34%.
2. The method according to claim 1, wherein the mass proportions of the components, based on the total mass of the product, are as follows:
polymerization of toluene diisocyanate: 40-70%; polar solvent: 20-50%; acid auxiliary agent: 0.05-0.2%; di/tri alcohol amine: 5-15%; monohydric phenols: 4.75-20%; trimerization catalyst: 0.1-0.3%, polymerization inhibitor: 0.1-0.3%.
3. The process of claim 1 wherein said polymeric toluene diisocyanate comprises 30% to 40% toluene diisocyanate monomer; and/or, the polymeric toluene diisocyanate has an NCO content of 31% to 33%.
4. The process according to claim 1 or 2, wherein the polymeric toluene diisocyanate comprises 30% to 35% toluene diisocyanate monomer; and/or, the polymeric toluene diisocyanate has an NCO content of 31.5% to 32.5%.
5. A process according to any one of claims 1 to 3, wherein the polar solvent is one or more of ethyl acetate, butyl acetate, toluene, xylene; and/or the acid auxiliary is dry hydrogen chloride or anhydrous phosphoric acid; and/or the trimerization catalyst is one or more of lithium acetate, triethylene diamine, DMP-30 and tri-n-butyl phosphorus.
6. A method according to any one of claims 1-3, wherein the di/tri-alkanolamine is one or more of diethanolamine, triethanolamine, triisopropanolamine, N-bis (2-hydroxypropyl) aniline.
7. A method according to any one of claims 1 to 3, wherein the monohydric phenol is one or more of phenol, cresol and chlorophenol.
8. A process according to any one of claims 1 to 3, wherein the polymerization inhibitor is one or more of dibutyl phosphate, benzoyl chloride, methyl p-toluenesulfonate.
9. A process according to any one of claims 1 to 3, characterized in that the temperature of the prepolymerization stage is 50 to 80 ℃ and the reaction time is 1 to 3 hours.
10. A process according to any one of claims 1 to 3, characterized in that the temperature of the trimerization and reaction termination stage is 50-70 ℃ and the reaction time is 0.5-2 hours.
11. TDI trimer prepared by the process according to any one of claims 1 to 10, characterised in that the solids content of the trimer preparation is 50 to 80%; the NCO content of the trimeric articles is 7.0-8.5%.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| GB1235733A (en) * | 1967-10-19 | 1971-06-16 | Du Pont | Improvements in and relating to aromatic polyisocyanates |
| JPS5029464B2 (en) * | 1972-11-15 | 1975-09-23 | Sumitomo Chemical Co | |
| BR8800728A (en) * | 1988-02-18 | 1989-09-19 | Sanko Ind Quimica Ltda | FOAM COMPOSITION OF CELLULAR STRUCTURE POLYURETHANE WITH ABSORBENT CHARACTERISTICS |
| US7378543B2 (en) * | 2003-07-24 | 2008-05-27 | Bayer Materialscience Llc | Stable liquid biuret modified and biuret allophanate modified toluene diisocyanates, prepolymers thereof, and processes for their preparation |
| US20050159495A1 (en) * | 2004-01-20 | 2005-07-21 | Jennings William J. | Toluene diisocyanate tar fluidizer and method of use |
| CN105026454A (en) * | 2013-03-12 | 2015-11-04 | 拜耳材料科技股份有限公司 | Method for producing TDI-trimerisates with high purity |
| CN106753180B (en) * | 2017-01-06 | 2020-12-22 | 沧州大化股份有限公司 | Method for processing crude TDI |
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