CN113004492A - Preparation method of toluene diisocyanate trimer curing agent - Google Patents
Preparation method of toluene diisocyanate trimer curing agent Download PDFInfo
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- CN113004492A CN113004492A CN201911321400.1A CN201911321400A CN113004492A CN 113004492 A CN113004492 A CN 113004492A CN 201911321400 A CN201911321400 A CN 201911321400A CN 113004492 A CN113004492 A CN 113004492A
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- toluene diisocyanate
- curing agent
- diisocyanate trimer
- trimer curing
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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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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention provides a preparation method of a toluene diisocyanate trimer curing agent, wherein toluene diisocyanate and a modifier are added into a reaction kettle, heated to 50-60 ℃, uniformly stirred and subjected to heat preservation reaction for 1-6 hours; adding a trimerization catalyst, and continuing the heat preservation reaction at 50-60 ℃; detecting the NCO content in the third step every half an hour; when the NCO content is less than 36 percent, adding a polymerization inhibitor to terminate the trimerization reaction; continuing heating, and distilling out unreacted toluene diisocyanate; and finally, adding an organic solvent, and uniformly stirring to obtain the toluene diisocyanate trimer curing agent. The preparation method is simple in preparation process, the raw materials are properly added in excess, then polymerization inhibition is carried out, redundant raw materials are distilled out, and finally the raw materials are mixed with the organic solvent according to a certain proportion, so that the obtained toluene diisocyanate trimer curing agent does not contain other redundant impurities, is good in curing effect, and is suitable for large-scale industrial production.
Description
Technical Field
The invention relates to the technical field of curing agent preparation, in particular to a preparation method of a toluene diisocyanate trimer curing agent.
Background
The toluene diisocyanate trimer is formed by self-polymerization of toluene diisocyanate under the action of a catalyst, has an isocyanurate six-membered ring structure, and has more excellent performance. The polymers have high thermal stability, typically with isocyanurate rings above 200 ℃, which is mainly related to the absence of labile hydrogen atoms in their six-membered rings and the thermal stability of the CONR structure itself. Secondly, the introduction of the ring can improve the electricity-saving performance, the mechanical performance, the strength, the hardness and the like of the polyurethane material. In addition, the presence of nitrogen atoms in the heterocyclic ring also provides some improvement in flame retardancy.
For example, Chinese patent "CN 1186405C" discloses a preparation method of a toluene diisocyanate trimer curing agent with good solubility, which comprises the following raw materials of (A) 40-66 parts of toluene diisocyanate or a mixture of two toluene diisocyanates, (B) 25-55 parts of ester solvent with the boiling point less than or equal to 200 ℃ (C) 3-10 parts of aliphatic alcohol containing 1-2 hydroxyl groups and having the molecular weight of 60-200, (D) 0.009-0.014 part of isocyanate trimerization catalyst, and the parts are parts by weight; firstly, putting A, B, C raw material into a reaction kettle, stirring and introducing N2 for protection reaction, stirring and reacting for 1-6 hours at the temperature of 30-80 ℃, then adding D raw material for continuous reaction, cooling, keeping the reaction at the temperature of 50-100 ℃, detecting the weight percentage content of free NCO groups every 1 hour, immediately adding isocyanate trimerization polymerization inhibitor when the relative solid content is 50% and the weight percentage content of NCO is 7.4-8.4%, cooling to the temperature below 40 ℃ and discharging. The technical scheme has the advantages of complex reaction process, high reaction temperature, unsuitability for industrial large-scale production and low preparation efficiency.
Disclosure of Invention
In order to solve the problems of complicated reaction process, high reaction temperature, unsuitability for industrial large-scale production and low preparation efficiency in the prior art, the invention provides a preparation method of a toluene diisocyanate trimer curing agent.
The invention realizes the aim through the following technical scheme: a preparation method of a toluene diisocyanate trimer curing agent comprises the following steps:
the method comprises the following steps: adding toluene diisocyanate and a modifier into a reaction kettle, heating to 50-60 ℃, and uniformly stirring;
step two: keeping the temperature of the solution in the step one for reacting for 1-6 hours;
step three: adding a trimerization catalyst into the reaction product obtained in the second step, and continuing the heat preservation reaction at 50-60 ℃;
step four: detecting the NCO content in the third step every half an hour;
step five: when the NCO content is less than 36 percent, adding a polymerization inhibitor to terminate the trimerization reaction;
step six: heating the reactant in the fifth step, and distilling unreacted toluene diisocyanate;
step seven: and (5) adding an organic solvent into the product obtained in the sixth step, and uniformly stirring to obtain the toluene diisocyanate trimer curing agent.
On the basis, the modifier in the first step is dehydrated polyol, and the ratio of the polyol to the toluene diisocyanate is 1: 4.
On the basis, the trimerization catalyst in the third step is at least one of alkaline salts of lithium acetate and potassium acetate, tertiary phosphines of tri-N-butyl phosphine and triethyl phosphine, and tertiary amines of trivinyl diamine and N, N-dimethyl benzylamine.
On this basis, the weight of the trimerization catalyst is 0.1-0.3% of the total weight of the polyol and the toluene diisocyanate.
On the basis, the polymerization inhibitor in the fifth step is at least one of benzoyl chloride, phosphoric acid, methyl p-toluenesulfonate and dimethyl sulfate.
On the basis, the weight of the polymerization inhibitor is 0.01-0.2% of the total weight of the polyalcohol and the toluene diisocyanate.
On the basis, the organic solvent in the seventh step is ethyl acetate.
On the basis, the ratio of the organic solvent to the toluene diisocyanate trimer in the seventh step is 1: 3 to 1: 4.
Compared with the prior art, the invention has the beneficial effects that: the preparation method is simple in preparation process, the raw materials are properly added in excess, then polymerization inhibition is carried out, redundant raw materials are distilled out, and finally the raw materials are mixed with the organic solvent according to a certain proportion, so that the obtained toluene diisocyanate trimer curing agent does not contain other redundant impurities, is good in curing effect, and is suitable for large-scale industrial production.
Detailed Description
The present invention will be described in further detail with reference to examples. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The invention schematically shows a preparation method of a toluene diisocyanate trimer curing agent.
Adding 4 parts of toluene diisocyanate and 1 part of polyol into a reaction kettle, heating to 50-60 ℃, and uniformly stirring; then keeping the temperature and reacting for 1-6 hours; then adding 0.2 part of trimerization catalyst, and continuing the heat preservation reaction at 50-60 ℃; detecting the NCO content in the third step every half an hour; when the NCO content is less than 36 percent, adding 0.2 part of polymerization inhibitor to terminate the trimerization reaction; then heating, distilling out unreacted toluene diisocyanate, and obtaining toluene diisocyanate tripolymer; and finally adding ethyl acetate, and uniformly stirring to obtain the toluene diisocyanate trimer curing agent. Wherein the polyol is at least one of polyester polyol, polyether polyol, polyol containing two or more hydroxyl groups and micromolecular polyol. Wherein the trimerization catalyst is at least one of alkaline salts of lithium acetate and potassium acetate, tertiary phosphines of tri-N-butylphosphine and triethylphosphine, and tertiary amines of trivinyldiamine and N, N-dimethylbenzylamine. Wherein the polymerization inhibitor is at least one of benzoyl chloride, phosphoric acid, methyl p-toluenesulfonate and dimethyl sulfate. Wherein the ratio of ethyl acetate to toluene diisocyanate trimer is 1: 3 to 1: 4.
The invention has the beneficial effects that: the preparation method is simple in preparation process, the raw materials are properly added in excess, then polymerization inhibition is carried out, redundant raw materials are distilled out, and finally the raw materials are mixed with the organic solvent according to a certain proportion, so that the obtained toluene diisocyanate trimer curing agent does not contain other redundant impurities, is good in curing effect, and is suitable for large-scale industrial production.
While the foregoing description shows and describes the preferred embodiments of the present invention, it is to be understood that the invention is not limited to the forms disclosed herein, but is not to be construed as excluding other embodiments and is capable of use in various other combinations, modifications, and environments and is capable of changes within the scope of the inventive concept as described herein, commensurate with the above teachings, or the skill or knowledge of the relevant art. And that modifications and variations may be effected by those skilled in the art without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (8)
1. A preparation method of a toluene diisocyanate trimer curing agent is characterized by comprising the following steps:
the method comprises the following steps: adding toluene diisocyanate and a modifier into a reaction kettle, heating to 50-60 ℃, and uniformly stirring;
step two: keeping the temperature of the solution in the step one for reacting for 1-6 hours;
step three: adding a trimerization catalyst into the reaction product obtained in the second step, and continuing the heat preservation reaction at 50-60 ℃;
step four: detecting the NCO content in the third step every half an hour;
step five: when the NCO content is less than 36 percent, adding a polymerization inhibitor to terminate the trimerization reaction;
step six: heating the reactant in the fifth step, and distilling unreacted toluene diisocyanate;
step seven: and (5) adding an organic solvent into the product obtained in the sixth step, and uniformly stirring to obtain the toluene diisocyanate trimer curing agent.
2. The method for preparing a tolylene diisocyanate trimer curing agent according to claim 1, characterized in that: the modifier in the first step is dehydrated polyol, and the ratio of the polyol to toluene diisocyanate is 1: 4.
3. The method for preparing a tolylene diisocyanate trimer curing agent according to claim 1, characterized in that: the trimerization catalyst in the third step is at least one of alkaline salts of lithium acetate and potassium acetate, tertiary phosphines of tri-N-butylphosphine and triethylphosphine, and tertiary amines of triethylenediamine and N, N-dimethylbenzylamine.
4. The method for preparing a tolylene diisocyanate trimer curing agent according to claim 1, characterized in that: the weight of the trimerization catalyst is 0.1-0.3% of the total weight of the polyalcohol and the toluene diisocyanate.
5. The method for preparing a tolylene diisocyanate trimer curing agent according to claim 1, characterized in that: and in the fifth step, the polymerization inhibitor is at least one of benzoyl chloride, phosphoric acid, methyl p-toluenesulfonate and dimethyl sulfate.
6. The method for preparing a tolylene diisocyanate trimer curing agent according to claim 1, characterized in that: the weight of the polymerization inhibitor is 0.01-0.2% of the total weight of the polyalcohol and the toluene diisocyanate.
7. The method for preparing a tolylene diisocyanate trimer curing agent according to claim 1, characterized in that: and the organic solvent in the seventh step is ethyl acetate.
8. The method for preparing a tolylene diisocyanate trimer curing agent according to claim 1, characterized in that: in the seventh step, the ratio of the organic solvent to the toluene diisocyanate trimer is 1: 3 to 1: 4.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911321400.1A CN113004492A (en) | 2019-12-19 | 2019-12-19 | Preparation method of toluene diisocyanate trimer curing agent |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201911321400.1A CN113004492A (en) | 2019-12-19 | 2019-12-19 | Preparation method of toluene diisocyanate trimer curing agent |
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| CN113004492A true CN113004492A (en) | 2021-06-22 |
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| CN201911321400.1A Pending CN113004492A (en) | 2019-12-19 | 2019-12-19 | Preparation method of toluene diisocyanate trimer curing agent |
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Application publication date: 20210622 |