CN110790880B - Preparation method of TDI tripolymer, TDI tripolymer containing solvent and application thereof - Google Patents
Preparation method of TDI tripolymer, TDI tripolymer containing solvent and application thereof Download PDFInfo
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- CN110790880B CN110790880B CN201911119333.5A CN201911119333A CN110790880B CN 110790880 B CN110790880 B CN 110790880B CN 201911119333 A CN201911119333 A CN 201911119333A CN 110790880 B CN110790880 B CN 110790880B
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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
- C08G18/02—Polymeric products of isocyanates or isothiocyanates of isocyanates or isothiocyanates only
- C08G18/022—Polymeric products of isocyanates or isothiocyanates of isocyanates or isothiocyanates only the polymeric products containing isocyanurate groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
- C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
- C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
- C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
- C07D251/30—Only oxygen atoms
- C07D251/34—Cyanuric or isocyanuric esters
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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
- C08G18/792—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
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Abstract
The invention provides a preparation method of TDI trimer, which is prepared by taking toluene diisocyanate as a monomer raw material and carrying out self-polymerization in a solvent under the action of a Mannich base catalyst, wherein the content of secondary amine structural impurities in the Mannich base catalyst is less than or equal to 1000 ppm. The preparation method of the TDI trimer provided by the invention has the advantages that the TDI trimer product with lighter color, better yellowing resistance and more stable storage is prepared by controlling the content of impurities, the preparation method is simple and convenient in process, mild in reaction condition, free from excessive economic cost and very high in industrial application value.
Description
Technical Field
The invention relates to the field of polyisocyanates, in particular to a preparation method of TDI tripolymer, the TDI tripolymer containing solvent prepared by the preparation method and application thereof.
Background
The preparation of polyisocyanate compositions based on the self-polymerization of isocyanates has been known for a long time in the art and is reported in numerous publications and patent documents, such as patent document DE 4428107 a1, US 2993870A, DE 1201992B, DE 2452532 a1 and journal document j.prakt.chem.336,185-200,1994.
The preparation method of the TDI trimer curing agent product which is common in commerce at present mainly comprises the following steps: the desired product is finally obtained by self-polymerizing the commercially available toluene diisocyanate starting material with a suitable organic solvent under the catalysis of a phenol catalyst containing dialkylaminomethyl groups (i.e.a Mannich base) until almost complete conversion, and then deactivating the catalyst by addition of an acidic substance or by means of an alkylating agent.
The preparation process of the TDI trimer curing agent needs to face an important problem, namely, the TDI belongs to aromatic isocyanate and has poor self yellowing resistance, so that a paint film or a glue film formed by the prepared TDI trimer curing agent in downstream application has poor aging resistance. Around the technical problem of improving the quality of the TDI trimer curing agent, a great deal of literature and patent reports related research work, wherein most of the research work is carried out around the quality of the TDI raw material. For example, in patent CN 105026454A a process is described for preparing light-colored TDI-polyisocyanates by limiting the 2-chloro-6-isocyanato-methyl-cyclohexadiene content of TDI.
In order to further improve the performance of the TDI trimer curing agent and improve the product quality, other influencing factors influencing the performance of the TDI trimer curing agent need to be continuously and deeply researched.
Disclosure of Invention
In order to overcome the above-mentioned defects in the prior art and further improve the properties of TDI trimer, it is an object of the present invention to provide a method for preparing TDI trimer.
It is another object of the present invention to provide a TDI trimer composition containing a solvent and its use.
The preparation method of the TDI trimer provided by the invention is characterized in that toluene diisocyanate is used as a monomer raw material and is prepared through a self-polymerization reaction in a solvent under the action of a Mannich base catalyst, wherein the Mannich base catalyst is prepared from a phenolic compound, formaldehyde and dialkylamine through a Mannich reaction, and the content of secondary amine structural impurities is less than or equal to 1000ppm (mass ratio).
The Mannich base catalyst is used for initiating and accelerating the trimerization reaction of toluene diisocyanate, and the structure of the Mannich base catalyst is provided with N, N-dialkylaminomethyl and phenolic OH-groups which are bonded to aromatic compounds, wherein the N, N-dialkylaminomethyl and phenolic OH-groups can be positioned on one or more benzene aromatic compounds. In some preferred embodiments, the Mannich base catalysts of the present invention have the N, N-dialkylaminomethyl group and the phenolic OH-group on the same benzene aromatic compound. In some more preferred embodiments, the Mannich base catalysts of the present invention, wherein the N, N-dialkylaminomethyl groups are located in the ortho position relative to the phenolic hydroxyl group, an exemplary structure is shown in formula 1, but is not limited thereto.
Mannich base catalysts are generally prepared from a phenolic compound, formaldehyde and a dialkylamine by a Mannich reaction. However, the compound generally contains a large amount of secondary amine structural impurities, and an exemplary structure is shown in formula 2, but the compound is not limited thereto.
The secondary amine structure impurities are generally present in an amount of > 1500ppm by mass, depending on the type of phenolic compound, dialkylamine and the usual variations in the process parameters. The existing preparation process is not specially researched for the impurities, and is not subjected to purification treatment.
The inventor finds that: secondary amine structure impurities are easily oxidized into azo substances to form a large aromatic system for color development, in addition, secondary amine is easy to generate a color-generating group under the action of isocyanic acid radical in a monomer raw material, and then the secondary amine is dehydrogenated under the action of oxygen to generate a large aromatic system for color development, so that secondary amine structure impurities are one of important factors for causing the yellowing of TDI tripolymer. Therefore, secondary amine structure impurities in the Mannich base catalyst are reduced to a certain level, and the catalyst has a remarkable improvement effect on the yellowing resistance of a TDI trimer.
In some preferred embodiments, the level of secondary amine structure impurities in the Mannich base catalyst can be 500ppm or less, thereby better improving the yellowing resistance of the TDI trimer.
In the preparation method, secondary amine structure impurities in the Mannich base catalyst can be purified by corresponding selection of a purification method by a person skilled in the art according to different types of catalysts, so that the reduction of the impurity content can be controlled, and the catalytic performance of the catalyst is not influenced. In some preferred embodiments, the purification method may be, but is not limited to, recrystallization, distillation, rectification, and the like.
In some more preferred embodiments, when the mannich base catalyst is in a solid form, the purification method can be recrystallization, for example, the mannich base catalyst can be obtained by forming a saturated solution of a crude catalyst in a good solvent at 75-90 ℃, then placing the solution at-15 to-30 ℃ for crystallization for 10-20 hours, filtering and drying the precipitated crystals, wherein the good solvent comprises but is not limited to butyl acetate, ethyl acetate, chlorobenzene, 1, 2-dichloroethane, tetrahydrofuran and the like.
In other more preferred embodiments, when the Mannich base catalyst is in liquid form, the purification process may be a short path distillation, and the particular distillation conditions may be selected or adjusted by one skilled in the art depending on the boiling point of the catalyst.
In the preparation method of the present invention, the phenolic compound for preparing the mannich base catalyst may be any kind known in the art. In some preferred embodiments, the phenolic compound may be selected from phenol, p-isononyl phenol, bisphenol a, and the like, but is not limited thereto; in some more preferred embodiments, the phenolic compound may be selected from phenol or bisphenol a.
In the preparation method of the present invention, the dialkylamine used to prepare the mannich base catalyst may be any known in the art. In some preferred embodiments, the "alkyl" of the dialkylamine may be a linear or branched C1-C18 alkyl group, and the alkyl chain may optionally include one or more heteroatoms such as O, S. In some more preferred embodiments, the "alkyl" group in the dialkylamine can be a C1-C3 alkyl group, including but not limited to methyl, ethyl, propyl, isopropyl, and the like. In some most preferred embodiments, the dialkylamine is dimethylamine.
In some most preferred embodiments, mannich base-based catalysts for use in the preparation process of the present invention may be prepared by reference to patent documents US 3996223 and US 4115373, starting with phenol or bisphenol a, dimethylamine and formaldehyde.
The Mannich base catalyst may be used in any amount known in the art for the preparation of the present invention. In some preferred embodiments, the Mannich base catalyst may be used in an amount of 0.05 to 0.8 wt% based on the mass of toluene diisocyanate, including but not limited to 0.05 wt%, 0.06 wt%, 0.08 wt%, 0.12 wt%, 0.15 wt%, 0.2 wt%, 0.25 wt%, 0.35 wt%, 0.45 wt%, 0.5 wt%, 0.6 wt%, 0.7 wt%, 0.8 wt%, and the like or any combination of ranges. In some more preferred embodiments, the Mannich base catalyst can be used in an amount of 0.1 to 0.4 wt% of the mass of toluene diisocyanate, including but not limited to 0.1 wt%, 0.2 wt%, 0.3 wt%, 0.4 wt%, etc., or any combination of ranges.
In the preparation method of the present invention, the ratio of the amount of the monomeric toluene diisocyanate to the solvent may be any ratio known in the art. In some preferred embodiments, the ratio of the amount of the monomeric toluene diisocyanate to the solvent may be 2 to 8: 8-2, including but not limited to 2: 8. 3: 7. 4: 6. 5: 5. 6: 4. 7: 3. 8: 2, etc. or any combination of the ratio intervals.
In the preparation method of the invention, the monomer raw material toluene diisocyanate can be a mixture of 2, 4-toluene diisocyanate and 2, 6-toluene diisocyanate in any proportion. In some preferred embodiments, the amount of 2, 4-toluene diisocyanate in the monomer feed may be 65 to 95 wt%, including but not limited to 65 wt%, 70 wt%, 75 wt%, 80 wt%, 85 wt%, 90 wt%, 95 wt%, etc., or any combination of ranges of amounts. In other preferred embodiments, the amount of 2, 6-toluene diisocyanate in the monomer feed may be 5 to 35 wt%, including but not limited to 5 wt%, 10 wt%, 15 wt%, 20 wt%, 25 wt%, 30 wt%, 35 wt%, etc., or any combination of amounts.
In the preparation process of the present invention, the monomeric toluene diisocyanate may be of any origin, for example, synthesized by itself or purchased commercially. In some preferred embodiments, the monomeric starting material toluene diisocyanate may be derived from
TDI (Wanhua chemical),
TDI (basf),
TDI (Kestechuang) and the like.
In the preparation method of the present invention, the kind of the solvent may be any kind known in the art. In some preferred embodiments, the solvent includes, but is not limited to, toluene, xylene, cyclohexane, chlorobenzene, butyl acetate, ethyl glycol acetate, amyl acetate, hexyl acetate, methoxypropyl acetate, tetrahydrofuran, dioxane, acetone, N-methylpyrrolidone, methyl ethyl ketone, mineral spirits, highly substituted aromatic compounds, plasticizers, and the like, wherein the highly substituted aromatic compounds, for example, may be selected from one or more of heavy benzene, tetrahydronaphthalene, and decahydronaphthalene; the plasticizer may be, for example, a phthalate, benzoate, sulfonate or phosphate ester.
In the preparation method of the present invention, the process conditions of the self-polymerization reaction may be any process conditions known in the art, or may be appropriately adjusted by those skilled in the art according to the actual reaction conditions. In some preferred embodiments, the reaction temperature of the self-polymerization reaction may be 40 to 120 ℃, including but not limited to 40 ℃, 45 ℃, 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃, 85 ℃, 90 ℃, 95 ℃, 100 ℃, 110 ℃, 120 ℃ or any combination of temperature ranges. In some more preferred embodiments, the reaction temperature for the self-polymerization reaction may be 50 to 80 ℃. In other preferred embodiments, the reaction time of the self-polymerization reaction may be 5 to 48 hours, including but not limited to 8 hours, 15 hours, 20 hours, 25 hours, 40 hours, etc., or any combination of time intervals. In some more preferred embodiments, the reaction time for the self-polymerization reaction may be 10 to 30 hours.
In the preparation method of the present invention, the reaction degree of the self-polymerization reaction can be any degree known in the art to meet the requirements of the TDI trimer product, or can be adjusted by those skilled in the art according to the actual reaction condition. In some preferred embodiments, the degree of reaction of the self-polymerization reaction may be such that the content of unreacted monomeric starting material toluene diisocyanate in the reaction system is less than 0.5% by weight.
In the preparation method of the present invention, the reaction termination mode of the self-polymerization reaction may be any mode known in the art, or may be appropriately adjusted by those skilled in the art according to the actual reaction conditions. In some preferred embodiments, a Mannich base catalyst poison is added to terminate the self-polymerization reaction when the level of unreacted monomeric toluene diisocyanate in the self-polymerization reaction system is low to a certain level. In some more preferred embodiments, a catalyst poison is added to terminate the self-polymerization reaction when the content of the unreacted monomer starting material toluene diisocyanate in the self-polymerization reaction system is less than 0.5 wt.%.
In the preparation process of the present invention, the catalyst poison may be of any kind known in the art, for example, an acidic reactive substance such as a protic acid (e.g., dibutyl phosphate), or an acylating agent and an alkylating agent (e.g., diacid isophthalate or methyl tosylate). In some preferred embodiments, the catalyst poison may be dibutyl phosphate and/or methyl tosylate. As will be appreciated by those skilled in the art, different types of catalysts used in the reaction system and different types of selected catalyst poisons will result in different amounts of catalyst poisons, and in the preparation process of the present invention, the amount of catalyst poisons added is based on the deactivation of the Mannich base catalyst in the reaction system.
In the preparation method of the present invention, before the catalyst poison is added to terminate the self-polymerization reaction, or when the content of the unreacted monomer raw material toluene diisocyanate in the self-polymerization reaction system is less than 0.5 wt%, solid acid may be added to the reaction system and stirred for reaction, and then the solid acid is removed by filtration. The solid acid used in the preparation method contains a large number of atom empty orbitals on the surface, can selectively identify and coordinate the Mannich base catalyst, particularly has strong adsorption effect on secondary amine structure impurities, and can be separated from a reaction system through the adsorption effect of the solid acid, so that the content of the catalyst remaining in a TDI trimer product, particularly the content of the secondary amine structure impurities, is greatly reduced, and the improvement of the properties of the TDI trimer product is facilitated.
In some preferred embodiments, the solid acid includes, but is not limited to, immobilized liquid acids, oxides, sulfides, metal salts, zeolite molecular sieves, heteropolyacids, cation exchange resins, natural clay minerals, solid superacids, and the like, as long as they have good adsorption capacity for the mannich base type catalysts, particularly for secondary amine structural impurities. In some more preferred embodiments, the solid acid may be selected from metal oxide solid acids, wherein the metal oxide component may be one, two or more, supported, or unsupported. In some most preferred embodiments, the solid acid includes, but is not limited to, WO3/ZrO2Solid acid, supported on SiO2Inorganic acids (e.g. phosphoric acid, sulfuric acid) on diatomaceous earthOr boric acid), SiO2-Al2O3Solid acid, ZrO2-SiO2Solid acids, polystyrene sulfonic acid type resins, and the like. In other preferred embodiments, the solid acid may be added in an amount of 0.1 to 1.0 wt% based on the total mass of the monomer raw material toluene diisocyanate and the solvent, including but not limited to 0.1 wt%, 0.2 wt%, 0.5 wt%, 0.8 wt%, 1.0 wt%, and the like or any combination of content intervals. In other preferred embodiments, the stirring reaction time after the solid acid is added may be 5 to 20min, including but not limited to 5min, 8min, 10min, 15min, 20min, and other time values or any combination of time intervals.
The preparation method can prepare TDI tripolymer products in a form of solvent-containing products, and can also remove the solvent according to a conventional solvent removal method to obtain solvent-free products. In some preferred embodiments, the TDI trimer product produced by the preparation process of the present invention is a solvent-containing product.
Therefore, the invention also provides a TDI trimer containing a solvent, which is prepared by the preparation method of any one of the technical schemes. The solvent-containing TDI trimer according to the invention is prepared by the preparation method according to the invention without further processing steps, and mainly comprises a solvent and the prepared TDI trimer, and also comprises a trace amount of unreacted monomer raw material toluene diisocyanate (generally, the content is less than 0.5 wt%).
The solvent-containing TDI trimers provided by the invention have an APHA-color value of less than or equal to 25 Hazen (Hazen), preferably less than or equal to 20 Hazen.
The TDI trimer product prepared by the preparation method can be used in any known downstream field, such as paint, coating, adhesive and the like, and is especially used as a curing agent in the paint.
The invention thus also provides the use of the abovementioned solvent-containing TDI trimers as curing agent components in polyurethane paints.
Based on the color number and yellowing resistance of the product of the TDI trimer containing the solvent, the TDI trimer containing the solvent is particularly suitable for being used as a curing agent component in polyurethane paint, and a formed polyurethane paint film also has excellent yellowing resistance and can obviously improve the ultraviolet aging resistance of the paint film.
The solvent-containing TDI trimers of the invention are suitable for single-component and two-component polyurethane paints. In some preferred embodiments, it is particularly suitable for two-component polyurethane paints.
The TDI trimer containing the solvent can be independently used as a curing agent in polyurethane paint, and can also be combined with any other curing agent known in the field of polyurethane paint in any proportion.
The invention also provides a polyurethane paint which comprises a curing agent component, wherein the curing agent component is the TDI trimer containing the solvent provided by the invention. In some preferred embodiments, the present invention also provides a two-component polyurethane paint comprising a curative component, wherein the curative component is the solvent-containing TDI trimer provided herein.
The polyurethane paints to which the present invention relates may comprise, in addition to the solvent-containing TDI trimers described herein, any component known in the art including, but not limited to, polyhydroxy polyesters, polyhydroxy polyethers, polyhydroxy polyacrylates, optionally low molecular weight polyols, and the like, as are well known in the polyurethane paint art. The polyurethane paint of the present invention may also contain any of the adjuvants known in the art, including but not limited to wetting agents, leveling agents, antiskinning agents, defoamers, matting agents, and the like, depending on the performance requirements.
The polyurethane paint can be prepared by the existing process and the existing equipment.
The preparation method of the TDI trimer provided by the invention is based on the Mannich base catalyst for the first time, the relation between secondary amine structure impurities in the catalyst and the properties of the TDI trimer product is found, the TDI trimer product with lighter color, better yellowing resistance and more stable storage is prepared by controlling the content of the impurities, and when the product is used in the downstream field (such as polyurethane paint), a formed paint film or a formed adhesive film also has excellent yellowing resistance and ageing resistance. The preparation method has the advantages of simple process, mild reaction conditions, no need of consuming excessive economic cost and great industrial application value.
Detailed Description
The technical solution of the present invention is further described in detail with reference to the following specific examples.
< sources of raw materials >
(1) Toluene diisocyanate (I) is added to the reaction mixture,
TDI series, wanhua chemistry;
(2) butyl acetate, science of west longas;
(3) dibutyl phosphate, sigma aldrich;
(4) methyl tosylate, sigma aldrich;
(5) mannich bases based on bisphenol a/formalin (Fomalin)/dimethylamine, cf synthesis in US 4115373, pages six, lines 5-10;
(6) mannich bases based on phenol/formalin (Fomalin)/dimethylamine, cf synthesis on page eight, lines 5-40 in US 4115373;
(7)WO3/ZrO2solid acids, see M.Hino, K.Arata.Synthesis of crude oxide supported on zirconia and its catalytic action for reactions of butanol and pentanone [ J]Synthesized in Journal of the Chemical society, Chemical communications, 1988,18, 1259-;
(8) polyol (matte varnish), HS-129, SAPICI;
(9)
TL75E (colloquially referred to in the art as the "TDI-TMP adduct"), Van der Waals chemical.
< detection method >
All percentages mentioned in the examples according to the invention and in the comparative examples are percentages by mass, unless otherwise stated.
The NCO content was determined according to GB/T12009.4-1989.
The color number was measured in 50mm disposable rectangular cuvettes using LICO 400 from HACH Lange, based on the method of GB/T3143-1982.
Based on the method of GB/T18583-2008, the content of the residual monomer in the reaction system is determined by gas chromatography.
The solid content was determined based on the method of GB/T1725-1979.
The kinetic viscosity was measured at 25 ℃ using a Brookfield DV-I Prime viscometer with S21 spindle.
Ultraviolet aging resistance test: GB/T1865.
Drying (tack-free) test: GB/T1728.
Matte glossiness test: GB/T9754.
And (3) testing pencil hardness: GB/T1730.
And (4) testing the adhesive force grade: GB/T9286.
And (3) leveling property testing: a paint film is prepared on the surface of the tinplate, the sample plate is placed under the conditions of constant temperature and constant humidity (30 ℃, 35-40% relative humidity), and the time required for the painted surface to reach a uniform, smooth and wrinkle-free state (no orange peel or goose skin) is observed.
Example 1
1. Purification of mannich bases
Reference is made to US 4115373 for the synthesis of a solid mannich base catalyst based on bisphenol a/formalin/dimethylamine.
Gradually adding a catalyst into butyl acetate at 90 ℃ until the catalyst is saturated, quickly transferring the saturated solution of the catalyst to-20 ℃, standing for 12 hours, separating out the catalyst, filtering the solution to obtain a purified solid catalyst, and drying at 30 ℃/0.6 mbar.
The dried catalyst (secondary amine impurity content about 1000ppm) was dissolved in xylene to form a xylene solution for use.
2. Preparation of TDI trimer
500g of
TDI-80 as a starting diisocyanate and 500g of butyl acetate were placed in a 2L reaction vessel purged with nitrogen in advance and mixed to obtain a reaction mixture(ii) a The reaction mixture was heated to the desired reaction temperature of 75 ℃. 1.5g of a solution of the polymerization catalyst in xylene of Mannich base, with a catalyst concentration of 40% by weight, are added dropwise to initiate the trimerization reaction. After the reaction was carried out for 4, 8 and 12 hours, 0.75g of each polymerization catalyst solution was additionally added, and the reaction was continued at a reaction temperature of 75 ℃ until the desired NCO content was reached (NCO content ═ 8.03 wt%).
To the reaction mixture was added 2.25g of methyl tosylate to terminate the polymerization. Thereafter, the reaction product was stirred at 80 ℃ for 1 hour. The solvent-containing product thus obtained, designated "TDI trimer curing agent 1", had the following properties:
the NCO content was 8.03% by weight,
viscosity 1290 mPas/25 ℃,
the residual monomer content is 0.02 wt%,
the solid content is 50.1 wt%,
color number 25 hasen.
Example 2
1. Purification of mannich bases
Reference is made to US 4115373 for the synthesis of a solid mannich base catalyst based on bisphenol a/formalin/dimethylamine.
Gradually adding a catalyst into butyl acetate at 75 ℃ until the catalyst is saturated, quickly transferring a saturated solution of the catalyst to-20 ℃, standing for 12 hours, separating out the catalyst, filtering the solution to obtain a purified solid catalyst, and drying at 30 ℃/0.6 mbar.
The dried catalyst (secondary amine impurity level about 500ppm) was dissolved in xylene to form a xylene solution for use.
2. Preparation of TDI trimer
500g of
TDI-80 as a starting diisocyanate and 500g of butyl acetate were placed in advance in a 2L reaction vessel purged with nitrogen and mixed to obtain a reaction mixture; the reaction mixture is heated to the desired reaction temperature 75 ℃ is adopted. 1.5g of a solution of the polymerization catalyst in xylene of Mannich base, with a catalyst concentration of 40% by weight, are added dropwise to initiate the trimerization reaction. After the reaction was carried out for 4, 8 and 12 hours, 0.75g of each polymerization catalyst solution was additionally added, and the reaction was continued at a reaction temperature of 75 ℃ until the desired NCO content was reached (NCO content ═ 8.02 wt%).
To the reaction mixture was added 2.25g of methyl tosylate to terminate the polymerization. Thereafter, the reaction product was stirred at 80 ℃ for 1 hour. The solvent-containing product thus obtained, designated "TDI trimer curing agent 2", had the following properties:
the NCO content was 8.02% by weight,
the viscosity was 1300mPa s/25 c,
the residual monomer content is 0.03 wt%,
the solid content is 50 wt%,
color number 20 hasen.
Example 3
1. Purification of mannich bases
Reference is made to US 4115373 for the synthesis of phenol/formalin/dimethylamine based liquid mannich base catalysts.
Carrying out short-range distillation treatment on the Mannich base catalyst obtained by synthesis to obtain a purified Mannich base catalyst, wherein the conditions are as follows: 180 ℃/0.1mbar, 0.5Kg of feed per hour, 0.05m of evaporation area2。
The catalyst collected by distillation (secondary amine impurity content about 500ppm) was dissolved in butyl acetate to form a butyl acetate solution, which was then used.
2. Preparation of TDI trimer
500g of
TDI-80 as a starting diisocyanate and 500g of butyl acetate were placed in advance in a 2L reaction vessel purged with nitrogen and mixed to obtain a reaction mixture; the reaction mixture was heated to the desired reaction temperature of 75 ℃. 1.5g of a solution of the polymerization catalyst in butyl acetate as Mannich base at a catalyst concentration of 40% by weight are added dropwiseThe trimerization reaction is initiated. After the reaction was carried out for 4, 8 and 12 hours, 0.75g of each polymerization catalyst solution was additionally added, and the reaction was continued at a reaction temperature of 75 ℃ until the desired NCO content was reached (NCO content ═ 8.01 wt%).
To the reaction mixture was added 2.25g of dibutyl phosphate to terminate the polymerization. Thereafter, the reaction product was stirred at 75 ℃ for 1 hour. The solvent-containing product thus obtained, designated "TDI trimer curing agent 3", had the following properties:
the NCO content was 8.01% by weight,
viscosity 1280 mPas/25 ℃,
the residual monomer content is 0.02 wt%,
the solid content is 51.4 wt%,
color number 21 hasen.
Example 4
500g of
TDI-80 as a starting diisocyanate and 500g of butyl acetate were placed in advance in a 2L reaction vessel purged with nitrogen and mixed to obtain a reaction mixture; the reaction mixture was heated to the desired reaction temperature of 75 ℃. 1.5g of the polymerization catalyst solution (same as in example 2) was added dropwise to initiate trimerization. After the reaction was carried out for 4, 8 and 12 hours, 0.75g of each polymerization catalyst solution was additionally added, and the reaction was continued at a reaction temperature of 75 ℃ until the desired NCO content was reached (NCO content ═ 8.01 wt%).
5g of WO was added to the system3/ZrO2The solid acid was stirred for 10min, and after filtration, 2.25g of methyl tosylate was added to the reaction mixture to terminate the polymerization. Thereafter, the reaction product was stirred at 75 ℃ for 1.0 hour. The solvent-containing product thus obtained, designated "TDI trimer curing agent 4", had the following properties:
the NCO content was 8.01% by weight,
viscosity 1295 mPas/25 ℃,
the residual monomer content is 0.03 wt%,
the solid content is 50.1 wt%,
color number 20 hasen.
Comparative example 1
500g of
TDI-80 as a starting diisocyanate and 500g of butyl acetate were placed in advance in a 2L reaction vessel purged with nitrogen and mixed to obtain a reaction mixture; the reaction mixture was heated to the desired reaction temperature of 75 ℃. 1.5g of a solution of the polymerization catalyst, which is a solution of Mannich base in butyl acetate with a concentration of 40% by weight of Mannich base based on bisphenol A/formalin/dimethylamine and which, without purification, has a secondary amine impurity content of about 2000ppm, is added dropwise, initiates the trimerization reaction. After the reaction was carried out for 4, 8 and 12 hours, 0.75g of each polymerization catalyst solution was additionally added, and the reaction was continued at a reaction temperature of 75 ℃ until the desired NCO content was reached (NCO content ═ 7.99 wt%).
To the reaction mixture was added 2.25g of methyl tosylate to terminate the polymerization. Thereafter, the reaction product was stirred at 75 ℃ for 1 hour. The solvent-containing product thus obtained, designated "TDI trimer curing agent 1'", had the following properties:
NCO content 7.99 wt%,
viscosity 1330 mPas/25 ℃,
the residual monomer content is 0.02 wt%,
the solid content is 50.1 wt%,
color number 38 hasen.
Examples of the use
The TDI trimer curing agents 2, 3, 4 and 1 'prepared in examples 2 to 4 and comparative example 1 were mixed with TDI trimer curing agent 1' and TDI trimer curing agent 3, respectively
TL75E was mixed at a mass ratio of 1:2 to make a curing agent mixture, and the resulting mixture was mixed with a commercially available polyol (matte varnish, HS-129) at a 1:1 NCO/OH molar ratio, respectively, and butyl acetate/xylene (etc.) was addedMass mixing) was diluted with the mixed solvent (wherein the curing agent content in the solution of the curing agent and butyl acetate/xylene was 40 wt%), and finally a paint was prepared. The paint vehicle prepared by adding the TDI trimer curing agent 2, the TDI trimer curing agent 3 and the TDI trimer curing agent 4 is labeled as paint vehicle 2, paint vehicle 3 and paint vehicle 4, and the paint vehicle prepared by adding the TDI trimer curing agent 1 'is labeled as paint vehicle 1'. The results of the performance tests on the paint in terms of uv aging resistance, adhesion and the like are shown in table 1.
Table 1 results of performance testing
As can be seen from the performance test results in Table 1, the paint prepared by using the TDI trimer as the curing agent can obviously improve the ultraviolet aging resistance, and particularly, the ultraviolet aging resistance can be further improved after the TDI trimer curing agent is treated by using a solid acid. Moreover, other properties of the paint film can be kept at a high level without being affected.
Storage stability test
Respectively placing 800g of the TDI trimer curing agent 2, the TDI trimer curing agent 3, the TDI trimer curing agent 4 and the TDI trimer curing agent 1' prepared in the examples 2-4 and the comparative example 1 in a 1L aluminum bottle, sealing after charging nitrogen gas for protection, placing the sample in an explosion-proof oven under the environment condition of 50 ℃ for 6 months, and testing the chromaticity and the viscosity of the sample.
TABLE 250 ℃/6 month storage stability test results
| Item | Curing agent 2 | Curing agent 3 | Curing agent 4 | Curing agent 1' |
| viscosity/mPas/25 deg.C | 1300 | 1295 | 1280 | 3000 |
| Chroma/hasen | 30 | 29 | 20 | 201 |
The stability test results in table 2 show that the TDI trimer curing agent of the present invention has good storage stability, and particularly, after the TDI trimer curing agent is treated with a solid acid, the storage stability can be further improved, and yellowing does not easily occur even after long-term storage.
Unless otherwise defined, all terms used herein have the meanings commonly understood by those skilled in the art.
The described embodiments of the present invention are for illustrative purposes only and are not intended to limit the scope of the present invention, and those skilled in the art may make various other substitutions, alterations, and modifications within the scope of the present invention, and thus, the present invention is not limited to the above-described embodiments but only by the claims.
Claims (14)
1. A preparation method of TDI trimer is characterized in that toluene diisocyanate is used as a monomer raw material, and the TDI trimer is prepared through a self-polymerization reaction in a solvent under the action of a Mannich base catalyst, wherein the Mannich base catalyst is prepared through a Mannich reaction of a phenolic compound, formaldehyde and dialkyl amine, and the content of secondary amine structural impurities is less than or equal to 1000 ppm.
2. The method according to claim 1, wherein the Mannich base catalyst is used in an amount of 0.05 to 0.8 wt% based on the toluene diisocyanate.
3. The method according to claim 2, wherein the Mannich base catalyst is used in an amount of 0.1 to 0.4 wt% based on the toluene diisocyanate.
4. The method according to any one of claims 1 to 3, wherein the phenolic compound is selected from one or more of phenol, p-isononyl phenol, bisphenol A; the dialkylamine is selected from dimethylamine.
5. The method according to any one of claims 1 to 3, wherein the mass ratio of the toluene diisocyanate to the solvent is 2 to 8: 8 to 2.
6. The method according to any one of claims 1 to 3, wherein the toluene diisocyanate is a mixture of 2, 4-toluene diisocyanate and 2, 6-toluene diisocyanate in any ratio.
7. The method according to claim 6, wherein the toluene diisocyanate contains 65 to 95 wt% of the 2, 4-toluene diisocyanate and 5 to 35 wt% of the 2, 6-toluene diisocyanate.
8. The method of any one of claims 1-3, wherein the method of preparing the TDI trimer further comprises: when the content of unreacted toluene diisocyanate in the self-polymerization reaction system was less than 0.5% by weight, a solid acid was added and the reaction was stirred, and then the solid acid was removed by filtration.
9. The preparation method according to claim 8, wherein the solid acid is added in an amount of 0.1 to 1.0 wt% based on the total mass of the toluene diisocyanate and the solvent, and the stirring reaction is carried out for 5 to 20 min.
10. The method according to claim 9, wherein the solid acid is a metal oxide solid acid.
11. The method of any one of claims 1 to 3, wherein the self-polymerization reaction is terminated by the addition of a catalyst poison of the Mannich base catalyst, which is selected from dibutyl phosphate and/or methyl tosylate.
12. A solvent-containing TDI trimer produced by the production process according to any one of claims 1 to 11.
13. Use of the solvent-containing TDI trimer of claim 12 as a curative component in a polyurethane paint.
14. Use according to claim 13, characterised in that the polyurethane paint is a two-component polyurethane paint.
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| CN112898889B (en) * | 2021-01-26 | 2022-04-01 | 江苏凯伦建材股份有限公司 | Polyurethane waterproof coating and application thereof |
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Denomination of invention: The invention relates to a preparation method of TDI Trimer, TDI Trimer containing solvent and its application Effective date of registration: 20211123 Granted publication date: 20210723 Pledgee: Bank of China Limited by Share Ltd. Yantai branch Pledgor: Wanhua Chemical Group Co.,Ltd. Registration number: Y2021980013026 |
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