CN108864402B - Modified isocyanate and preparation method thereof - Google Patents
Modified isocyanate and preparation method thereof Download PDFInfo
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- CN108864402B CN108864402B CN201710315749.9A CN201710315749A CN108864402B CN 108864402 B CN108864402 B CN 108864402B CN 201710315749 A CN201710315749 A CN 201710315749A CN 108864402 B CN108864402 B CN 108864402B
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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
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
- C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
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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
- C08G18/797—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing carbodiimide and/or uretone-imine groups
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Abstract
The invention relates to a modified isocyanate and a preparation method thereof, wherein the modified isocyanate has excellent storage stability and low color number, the color number is less than or equal to 100APHA, preferably less than or equal to 90APHA, more preferably less than or equal to 70APHA, the viscosity is 5-500 mPa & s, preferably 20-200 mPa & s at 25 ℃, the modified isocyanate can be stored for more than 100 days at-15 ℃ without crystallization, the modified isocyanate does not have obvious flatulence when stored for more than 100 days at normal temperature (20-35 ℃), and the modified isocyanate does not have obvious flatulence even if stored for more than 72 hours at high temperature of 60-80 ℃. The preparation method is simple and easy to implement, and can improve the storage stability of the product.
Description
Technical Field
The invention relates to modified isocyanate and a preparation method thereof, in particular to modified isocyanate with excellent storage stability and low color number.
Background
As a main raw material in polyurethane chemistry, diphenylmethane diisocyanate is widely applied in the industries of foams, adhesives and the like. However, diphenylmethane diisocyanate is easy to crystallize, is not favorable for storage and other factors, so that processes such as heat preservation, drying and the like are required in the processes of storage, transportation and use, the use is very inconvenient, and the expensive transportation, processing and other costs are increased.
In the prior art, the modification of diphenylmethane diisocyanate by using carbodiimide modification method to improve the storage stability of diphenylmethane diisocyanate has become a common recognition in the industry. The method adopts 4, 4-diphenylmethane diisocyanate as a raw material to modify carbodiimide, so that the storage stability of the carbodiimide is improved to a certain extent, and the carbodiimide is not crystallized at about 0 ℃, for example, the carbodiimide modified isocyanate prepared by CN200680050633.7 can be liquid at 0 ℃, but the technical scheme does not specifically provide a solution for improving the storage stability under the extremely cold condition and does not provide corresponding revelation for the situation that the product can be applied to different regions and the region under the extremely cold condition (such as-15 ℃ or lower), so that how to improve the low-temperature storage stability is one of the problems to be solved at present.
In addition, because the problem of yellowing of color occurs during the process of terminating the carbodiimide modification reaction, the color number of the product is often controlled by adding hindered amine (also called hindered amine) auxiliaries, such as CN201510149042.6, CN200680050633.7 and the like, which are mentioned in the specification of adding hindered amine (also called hindered amine) auxiliaries in the process of carrying out the carbodiimide modification reaction. The yellow color generated when the carbodiimide reaction is stopped can be controlled to a certain extent by adding the hindered amine auxiliary agent, but the amine substance has a certain catalytic action on the diphenylmethane diisocyanate, and can be catalyzed to react when being stored for a long time, particularly at a high temperature, so that the adverse conditions of high viscosity, flatulence and the like are generated, and the storage stability and the safety of the product are relatively high.
Therefore, there is a need to develop an isocyanate product that has good storage stability at both higher and lower temperatures, while having a lower color number.
Disclosure of Invention
In view of the problems of the prior art, it is an object of the present invention to provide a modified isocyanate. The modified isocyanate has excellent storage stability and low color number; can be stably stored at normal temperature for a long time and at high temperature for a short time, particularly can be stably stored and used at-15 ℃, and preferably has a color number of 70APHA or less.
Another object of the present invention is to provide a process for preparing the modified isocyanate.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a modified isocyanate comprising an organic isocyanate, a carbodiimide group-containing modified isocyanate and optionally a uretonimine group-containing modified isocyanate;
the total mass of the modified isocyanate containing carbodiimide groups and the optional modified isocyanate containing uretonimine groups accounts for 2.9-53%, preferably 5.9-44%, and more preferably 8.9-33% of the total mass of the modified isocyanate;
the color number of the modified isocyanate is less than or equal to 100APHA, preferably less than or equal to 90APHA, more preferably less than or equal to 70APHA, the viscosity at 25 ℃ is 5-500 mPa & s, preferably 20-200 mPa & s, and the isocyanate group content of the modified isocyanate is 25-33 wt%, preferably 26.5-32.5 wt%, more preferably 28-32 wt%;
the reaction raw materials of the modified isocyanate comprise an isocyanate monomer, a catalyst, an antioxidant, a micromolecular alcohol and a terminator.
In the modified isocyanate, the content of the organic isocyanate accounts for 47-97.1%, preferably 56-94.1%, and more preferably 67-91.1% of the total mass of the modified isocyanate.
The effective component and the main component of the modified isocyanate are the organic isocyanate, the modified isocyanate containing carbodiimide groups and the optional modified isocyanate containing uretonimine groups. The modified isocyanate further contains trace additives and/or impurities, and the content of the trace additives and/or impurities is not counted in the calculation of the content of the organic isocyanate, the modified isocyanate containing carbodiimide groups and the optional modified isocyanate containing uretonimine groups in the modified isocyanate.
Isocyanate monomers which can be used as the reaction raw material of the present invention include isocyanates, modified products of isocyanates, prepolymers of isocyanates, etc. which are commonly used in the art. Examples of the above-mentioned isocyanates include, but are not limited to, Tolylene Diisocyanate (TDI), diphenylmethane diisocyanate (MDI), 1, 5-Naphthalene Diisocyanate (NDI), Hexamethylene Diisocyanate (HDI), methylcyclohexyl diisocyanate, 4' -dicyclohexylmethane diisocyanate, isophorone diisocyanate (IPDI), p-phenylene diisocyanate (PPDI), p-phenylene diisocyanate (XDI), tetramethyldimethylene diisocyanate (TMXDI), and polymers thereof, and the like; examples of the modified product of the above-mentioned isocyanate include, but are not limited to, isocyanates containing groups such as ester groups, urea groups, biuret groups, allophanate groups, uretonimine groups, carbodiimide groups, isocyanurate groups, iminooxadiazinedione groups, uretdione groups, urethane groups and the like; examples of the above-mentioned prepolymer of isocyanate include, but are not limited to, products of reaction of isocyanate monomers with hydroxyl compounds and/or amino compounds; these isocyanates, modified products of isocyanates, prepolymers of isocyanates may be used alone or in combination.
According to the preferable technical scheme of the invention, the isocyanate monomer in the reaction raw materials is diphenylmethane diisocyanate, and comprises 30-80% of 2, 4-diphenylmethane diisocyanate, 20-70% of 4, 4-diphenylmethane diisocyanate and 0-10% of 2, 2-diphenylmethane diisocyanate, based on the total mass of the diphenylmethane diisocyanate; preferably, the composition comprises 40-75% of 2, 4-diphenylmethane diisocyanate, 25-60% of 4, 4-diphenylmethane diisocyanate and 0-8% of 2, 2-diphenylmethane diisocyanate; more preferably, the composition comprises 45-70% of 2, 4-diphenylmethane diisocyanate, 30-55% of 4, 4-diphenylmethane diisocyanate and 0-5% of 2, 2-diphenylmethane diisocyanate.
As a preferable technical scheme of the invention, the color number of the diphenylmethane diisocyanate is less than or equal to 50 APHA. The high color number diphenylmethane diisocyanate can still be used as the raw material of the present invention, and when the high color number diphenylmethane diisocyanate is used, according to the technical scheme of the present invention, the color number of the final product can still be controlled within the color number range required by the present invention, and the excellent storage stability is maintained, but the color number is slightly higher than that of the preferred technical scheme.
In the present invention, the catalyst is a catalyst having an accelerating effect on the generation of carbodiimide groups, and is used in an amount of 0.5 to 20ppm, preferably 1 to 10ppm, more preferably 2.5 to 6ppm, based on the total mass of the isocyanate monomer. The catalyst may be a catalyst commonly used in the art, for example, a five-membered heterocyclic phospholene compound and the like, and such catalysts may be used alone or in combination.
In the present invention, the terminator is a chemical substance that is catalytically toxic to the catalyst, i.e., a chemical substance that can deactivate the catalyst and terminate the reaction for producing carbodiimide. Preferably, the terminator of the present invention is one or more selected from an acyl chloride terminator, an organic strong acid terminator and an organic weak acid terminator, preferably an organic strong acid terminator, or a mixture of an organic strong acid terminator and an acyl chloride terminator, and the amount of the terminator is 5 to 200ppm, preferably 20 to 150ppm, more preferably 30 to 80ppm, based on the total mass of the isocyanate monomer. In addition, other terminating agents commonly used in the art may also be used in the present invention.
In the invention, the antioxidant is selected from one or more of hindered phenol antioxidants, hindered amine antioxidants and phosphite antioxidants, preferably hindered phenol antioxidants and/or phosphite antioxidants, more preferably hindered phenol antioxidants and phosphite antioxidants, the phosphite antioxidants account for 10% -50% of the total mass of the antioxidant, and the antioxidant is 50-500 ppm, preferably 100-400 ppm, calculated on the total mass of the isocyanate monomer.
The hindered phenol type antioxidant, hindered amine type antioxidant and phosphite type antioxidant may be selected from antioxidants commonly used in the art, and examples thereof include, but are not limited to, 2, 6-di-tert-butyl-4-methylphenol, n-octadecyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, diisodecyl pentaerythritol diphosphite, triphenyl phosphite, 4-diisoidenebisphenol alkyl phosphite, and the like.
The antioxidant of the present invention is selected in consideration of the following advantageous effects: on one hand, the hindered phenol antioxidant is one of the most effective antioxidants, and can avoid the high color number caused by thermo-oxidative aging and free radical oxidation of unsaturated bonds of benzene rings in a diphenylmethane diisocyanate structure; on the other hand, because the hindered phenol antioxidant is weakly acidic and has a large amount of active hydrogen in a large using amount, in the later-stage storage process, the active hydrogen in the hindered phenol antioxidant can react with a catalyst which is not completely poisoned and inactivated by a terminator to prevent the color number from increasing, so that the long-term storage stability of the hindered phenol antioxidant is greatly improved while the low color number is controlled, and the hindered phenol antioxidant can be stably stored for a short time even at the high temperature of 70-80 ℃; in addition, when the optimized phosphite antioxidant and the hindered phenol antioxidant are used simultaneously, the synergistic effect is good, under the condition of achieving the same antioxidant effect, if the hindered phenol antioxidant or the phosphite antioxidant is independently added, the using amount of the hindered phenol antioxidant or the phosphite antioxidant is larger, and the total using amount of the antioxidants is reduced by simultaneously adding the phosphite antioxidant and the hindered phenol antioxidant.
In the invention, the small molecular alcohol is a mono-alcohol and/or diol with a relative molecular mass of 32-400, a liquid state at normal temperature and a viscosity of less than 100mPa & s, preferably a mono-alcohol or a mixture of the mono-alcohol and the diol, more preferably a mixture of the mono-alcohol and the diol, and the amount of the small molecular alcohol is 0.01-5%, preferably 0.05-1%, based on the total mass of the isocyanate monomer; the mono-alcohol is selected from one or more of ethanol, propanol, isopropanol, n-butanol, isobutanol, sec-butanol and n-pentanol, preferably isopropanol and/or isobutanol; the diol is selected from one or more of 1, 2-butanediol, methyl propanediol, 1, 2-propanediol, 1, 3-butanediol, diethylene glycol, dipropylene glycol, diethylene glycol monobutyl ether, dipropylene glycol monomethyl ether and dipropylene glycol monobutyl ether, preferably one or more of methyl propanediol, diethylene glycol, dipropylene glycol and 1,2 propanediol.
According to the invention, the isocyanate monomer is subjected to modified grafting by adding a small amount of micromolecular alcohol, so that the crystallization temperature of the product can be effectively reduced, and the low-temperature storage stability of the product is improved. When a mono-alcohol or a mixture of a mono-alcohol and a diol is used, the low-temperature storage stability of the product can be further improved, and particularly when a mixture of a mono-alcohol and a diol is used, the low-temperature storage stability of the product is better.
The preparation method of the modified isocyanate comprises the following steps of:
(1) under the protection of inert gas, mixing an isocyanate monomer, a catalyst, an antioxidant and micromolecular alcohol;
(2) performing carbodiimide modification reaction at 70-140 ℃, preferably 90-120 ℃, and more preferably 95-110 ℃;
(3) when the content of isocyanate groups in the reaction mixture reaches 25 to 33% by weight, preferably 26.5 to 32.5% by weight, more preferably 28 to 32% by weight, a terminator is added to terminate the carbodiimide-modification reaction.
The preferable technical scheme of the preparation method comprises the following steps according to the types and the proportions of the components:
(1) under the protection of inert gas, respectively dissolving or dispersing a catalyst, an antioxidant and a terminator in small molecular alcohol to form a catalyst and small molecular alcohol mixture, an antioxidant and small molecular alcohol mixture, a terminator and small molecular alcohol mixture, and then mixing an isocyanate monomer, the catalyst and small molecular alcohol mixture, the antioxidant and the small molecular alcohol mixture;
preferably, the mass proportion of the catalyst, the antioxidant and the terminator in the small molecular alcohol is not more than 50 percent, based on the total mass of the mixture of each component and the small molecular alcohol respectively;
(2) performing carbodiimide modification reaction at 70-140 ℃, preferably 90-120 ℃, and more preferably 95-110 ℃;
(3) when the content of isocyanate groups in the reaction mixture reaches 25 to 33% by weight, preferably 26.5 to 32.5% by weight, more preferably 28 to 32% by weight, a terminator and a small molecule alcohol mixture are added to terminate the carbodiimide modification reaction.
The catalyst, the antioxidant and the terminator are respectively dissolved or dispersed in low-viscosity micromolecule alcohol, so that the components can fully participate in the reaction in the subsequent reaction process, and the performance of the final product is improved. The concentration of each of the different components in the small molecule alcohol is based on the fact that the different components can be sufficiently dissolved or dispersed, in which case the higher or lower concentration does not affect the implementation of the technical scheme of the invention, but in the preferred technical scheme of the invention, the mass proportion of the different components in the small molecule alcohol does not exceed 50%.
As a method for dissolving or dispersing each component in a small molecule alcohol in the present invention, there can be exemplified: when two or more small molecular alcohols are adopted, different small molecular alcohols are mixed, and then the mixture is divided into different parts to dissolve different components (catalyst, antioxidant and terminator);
another example is: when two or more than two kinds of small molecular alcohols are adopted, different small molecular alcohols are respectively combined into different parts before different steps of the preparation method are carried out, and then the small molecular alcohols are respectively mixed with the catalyst, the antioxidant and the terminator to be fully dissolved or dispersed in different components; wherein, when different kinds of small molecular alcohols are used in each small molecular alcohol mixture, the mutual proportion of the different small molecular alcohols does not influence the implementation of the invention;
yet another example is: when a small molecule alcohol is used, the small molecule alcohol is divided into different parts to dissolve or disperse different components (catalyst, antioxidant and terminator);
the above-listed examples are only for illustration and are not intended to limit the mutual ratio of different small molecule alcohols, the mutual ratio of different small molecule alcohol mixtures, etc., but it is necessary to control the different components (catalyst, antioxidant, terminating agent) to be sufficiently dissolved or dispersed in the small molecule alcohol, respectively, so that the different components can sufficiently participate in the reaction and the quality of the final product can be improved.
As a preferred technical solution of the present invention, the preparation method further comprises the steps of:
(4) and (3) reducing the temperature of the mixture to 30-65 ℃, preferably 30-45 ℃, stirring for 2-10 hours, preferably 3-5 hours, and finishing the reaction.
The step (4) is beneficial to further reacting the catalyst and the terminator in the mixture to further poison and inactivate the catalyst, and can generate modified isocyanate containing uretonimine groups in the mixture, improve the storage stability of the product and reduce the barrel expansion and flatulence phenomenon in the product storage process.
It should be noted that, after step (3) of the preparation method of the present invention is finished, the obtained product is the modified isocyanate required by the present invention; step (4) of the preparation method is a preferable technical scheme, after step (4) is finished, the obtained product is also the modified isocyanate required by the invention, and the storage stability of the product obtained in step (4) is higher than that of the product obtained in step (3).
In the present invention, the test standard for the content of isocyanate groups is GB 12009.4-1989, and the test standard for the color number is GB 3143-1982.
The invention has the beneficial effects that:
1. the content range of the modified isocyanate containing carbodiimide groups and the optional modified isocyanate containing uretonimine groups in the modified isocyanate is controlled, and the following properties of the modified isocyanate product are greatly facilitated: does not crystallize at low temperature (0 ℃) or even under extremely cold conditions (-15 ℃), does not expand during sealed storage at normal temperature, and has small volume change during high-temperature storage;
2. by adding specific micromolecular alcohol or combination thereof to modify and graft the isocyanate monomer, the crystallization temperature of the product can be effectively reduced, and the storage stability of the modified isocyanate product is improved;
3. by screening the types and the proportion of the reaction raw materials, particularly controlling the content of 2,4 isomers in diphenylmethane diisocyanate, the crystallization temperature of the product is reduced, the storage stability is improved, and the color number is reduced;
4. by screening the types and the proportion of the antioxidant, on one hand, the antioxidant effect of the product can be greatly improved, the color number is reduced, the storage stability is improved, and on the other hand, the using amount of the antioxidant is reduced, and the cost is reduced;
5. on the basis of a large number of experiments, the process of the preparation method is optimized, and particularly, different components are respectively mixed with the small molecular alcohol to be fully dissolved or dispersed and then participate in the reaction, so that the reaction is more sufficient and the reaction process is more stable; the preparation method is optimized on the whole, so that the preparation method is simple, convenient and efficient, the reaction process is stable, the product quality is improved, and the qualification rate is improved.
Examples
The examples of the invention and the comparative examples used the following raw materials:
isocyanate monomer:
MDI-30、
MDI-50、
MDI-60、
MDI-100, all of which are Wanhua chemical products;
the amounts of the respective raw materials used in the examples and comparative examples are shown in Table 1.
TABLE 1 raw materials (g) for examples and comparative examples
The preparation methods of the examples and comparative examples are as follows:
example 1
Nitrogen was introduced into the reactor, and 20kg of nitrogen was added
MDI-30, heated to 90 ℃; uniformly mixing 31.08g of diethylene glycol and 31.08g of methyl propylene glycol to obtain micromolecular alcohol; adding 0.04g of 1-phenyl-3-methyl-2-phosphole-1-oxide into 0.16g of small molecular alcohol, uniformly mixing and adding into a reactor;
adding 8g of 2, 6-di-tert-butyl-4-methylphenol and 2g of diisodecyl diphosphite pentaerythritol ester into 50g of small molecular alcohol, uniformly mixing and adding into a reactor;
raising the temperature of the mixture in the reactor to 120 ℃ and reacting for 2 hours; adding 1.2g of p-toluenesulfonic acid into 12g of small molecular alcohol, uniformly mixing, adding into a reactor, and inactivating catalyst poisoning in the mixture;
the temperature of the mixture in the reactor was lowered to 45 ℃ and stirred for 3.5 hours to obtain a sample.
The color number of the obtained sample is 60APHA, and the content of isocyanate group is 29.3%; the total mass of the carbodiimide group-containing modified isocyanate and the uretonimine group-containing modified isocyanate accounted for 14.33% of the total mass of the modified isocyanate.
Example 2
Nitrogen was introduced into the reactor, and 20kg of nitrogen was added
MDI-50, heating to 90 ℃;
adding 0.1g of 1-methyl-3-methyl-2-phosphole-1-oxide into 0.4g of isopropanol, uniformly mixing and adding into a reactor;
adding 4g of n-octadecyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate and 2g of triphenyl phosphite into 20g of isopropanol, uniformly mixing and adding into a reactor;
the temperature of the mixture in the reactor is raised to 110 ℃ and the reaction lasts for 2.5 hours; adding 1.6g of trifluoromethanesulfonic acid and 0.2g of benzoyl chloride to 2.7g of isopropanol, uniformly mixing, adding into a reactor, and deactivating the catalyst in the mixture by poisoning;
the temperature of the mixture in the reactor was lowered to 40 ℃ and stirred for 4 hours to obtain a sample.
The color number of the obtained sample is 50APHA, and the content of isocyanate group is 31.7%; the total mass of the carbodiimide group-containing modified isocyanate and the uretonimine group-containing modified isocyanate accounted for 5.68% of the total mass of the modified isocyanate.
Example 3
Nitrogen was introduced into the reactor, and 20kg of nitrogen was added
MDI-100, heating to 90 ℃;
adding 0.16g of 1-methyl-3-phenyl-2-phosphole-1-oxide into 0.64g of 1, 2-propylene glycol, uniformly mixing and adding into a reactor;
adding 2g of n-octadecyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate and 1g of 4, 4-diisoidenebisphenol alkyl phosphite into 60g of 1, 2-propylene glycol, uniformly mixing and adding into a reactor;
the temperature of the mixture in the reactor is raised to 95 ℃ and the reaction is carried out for 4 hours; adding 0.8g of trifluoromethanesulfonic anhydride and 0.8g of adipoyl chloride to 2.4g of 1, 2-propanediol, mixing them uniformly, adding them into a reactor, and deactivating the catalyst in the mixture by "poisoning";
the temperature of the mixture in the reactor was lowered to 35 ℃ and stirred for 4 hours to obtain a sample.
The color number of the obtained sample is 50APHA, and the content of isocyanate group is 27.3%; the total mass of the carbodiimide group-containing modified isocyanate and the uretonimine group-containing modified isocyanate accounted for 22.7% of the total mass of the modified isocyanate.
Example 4
Nitrogen was introduced into the reactor, and 20kg of nitrogen was added
MDI-60, heating to 100 ℃;
adding 0.24g of 1-phenyl-3-methyl-2-phosphole-1-oxide to a small molecule alcohol mixture prepared from 4g of 1, 2-propanediol and 12g of isopropanol, uniformly mixing and adding to a reactor;
adding 1.5g of 2, 6-di-tert-butyl-4-methylphenol and 0.5g of 4, 4-diiso-idenebisphenol C-alkyl phosphite to a small molecular alcohol mixture prepared from 40g of 1, 2-propanediol and 20g of isopropanol, uniformly mixing and adding into a reactor;
raising the temperature of the mixture in the reactor to 100 ℃ and reacting for 3 hours; adding 0.8g of trifluoromethanesulfonic anhydride and 0.2g of benzoyl chloride to a mixture of small molecule alcohols prepared from 50g of 1, 2-propanediol and 50g of isopropanol, mixing homogeneously and adding to the reactor to deactivate the catalyst "poisoning" in the mixture;
the temperature of the mixture in the reactor was lowered to 35 ℃ and stirred for 4 hours to obtain a sample.
The color number of the obtained sample is 60APHA, and the content of isocyanate group is 30%; the total mass of the carbodiimide group-containing modified isocyanate and the uretonimine group-containing modified isocyanate accounted for 11.7% of the total mass of the modified isocyanate.
Comparative example 1
Nitrogen was introduced into the reactor, and 2kg of nitrogen was added
MDI-100, heating to 90 ℃, adding 1.5g of 3, 5-di-tert-butyl-4-hydroxytoluene and 0.4g of bis (1,2,2,6, 6-pentamethyl-4-piperidine) sebacate, and uniformly stirring;
0.005g of 1-methyl-1-oxo-1-phospholane-2-ene is prepared into a toluene solution with the concentration of 1 percent and added into a reactor to be stirred uniformly;
the mixture was heated to 95 ℃ and reacted for 240 minutes, 0.1g of ethyl trifluoromethanesulfonate was added, and the mixture was stirred for 1 hour to terminate the reaction, whereby a sample was obtained.
The color number of the obtained sample was 60 APHA.
Comparative example 2
Nitrogen was introduced into the reactor, and 2kg of nitrogen was added
MDI-50, 0.04g 1-methyl-8- (1,2,2,6,6, -pentamethyl-4-piperidine) sebacate, 2g tricresyl phosphite, 0.02g 1-methyl-1-oxo-1-phosphocyclopent-2-ene, stirred well and heated to 110 ℃ with continuous stirring;
and when the NCO content of the mixture reaches 31%, adding 0.2g of p-toluenesulfonic acid, uniformly stirring, cooling to normal temperature, preserving heat for 20 hours, and discharging to obtain a sample.
The color number of the obtained sample was 100 APHA.
The color number test standards of the examples and comparative examples are GB 3143-1982;
1.5kg of each of the samples of examples and comparative examples was sealed in an aluminum foil bag, stored at-15 ℃ for 100 days, and the crystallization was observed;
respectively taking the samples of the examples and the comparative examples, hermetically packaging the samples by adopting a 2L tinplate square barrel, storing the samples for 100 days at normal temperature, and observing whether the samples have flatulence or not; in the results of the storage conditions at normal temperature, "no" indicates that no macroscopic drum or deformation occurs, "flatulence" indicates that macroscopic significant drum or deformation occurs, and "slight flatulence" indicates that macroscopic slight drum or deformation occurs;
1.5kg of each of the samples of examples and comparative examples was sealed in an aluminum foil bag, stored at 75 ℃ for 72 hours, and the storage stability was observed; the high-temperature storage stability test is judged according to the volume change of the aluminum foil before and after the high-temperature storage test, and the higher the volume increase percentage is, the more serious the bag expansion condition is, and the worse the storage stability is;
the properties and test results of the examples and comparative examples are shown in Table 2.
Table 2 storage stability test results of examples and comparative examples
Claims (27)
1. A modified isocyanate, characterized in that the modified isocyanate consists of an organic isocyanate, a modified isocyanate containing carbodiimide groups and optionally a modified isocyanate containing uretonimine groups;
the reaction raw materials of the modified isocyanate comprise an isocyanate monomer, a catalyst, an antioxidant, micromolecular alcohol and a terminator;
the antioxidant is selected from one or more of hindered phenol antioxidants, hindered amine antioxidants and phosphite antioxidants;
the small molecular alcohol is diol or a mixture of mono-alcohol and diol, the relative molecular mass of the small molecular alcohol is 32-400, the small molecular alcohol is liquid at normal temperature, and the viscosity of the small molecular alcohol is lower than 100mPa & s;
the total mass of the modified isocyanate containing carbodiimide groups and the optional modified isocyanate containing uretonimine groups accounts for 2.9 to 53 percent of the total mass of the modified isocyanate;
the isocyanate group content of the modified isocyanate is 25 to 33 weight percent.
2. The modified isocyanate according to claim 1, wherein the total mass of the carbodiimide group-containing modified isocyanate and the optional uretonimine group-containing modified isocyanate is from 5.9% to 44% of the total mass of the modified isocyanate;
the content of isocyanate group of the modified isocyanate is 26.5-32.5 wt%.
3. The modified isocyanate according to claim 2, wherein the total mass of the carbodiimide group-containing modified isocyanate and the optional uretonimine group-containing modified isocyanate is 8.9 to 33% of the total mass of the modified isocyanate;
the isocyanate group content of the modified isocyanate is 28-32 wt%.
4. The modified isocyanate according to claim 1,2 or 3, wherein the modified isocyanate has a color number of 100APHA or less and a viscosity of 5 to 500mPa s at 25 ℃.
5. The modified isocyanate according to claim 4, wherein the modified isocyanate has a color number of 70APHA or less and a viscosity of 20 to 200 mPa-s at 25 ℃.
6. The modified isocyanate according to claim 1,2 or 3, wherein the small molecular alcohol is used in an amount of 0.01 to 5% based on the total mass of the isocyanate monomer; the mono-alcohol is selected from one or more of ethanol, propanol, isopropanol, n-butanol, isobutanol, sec-butanol and n-pentanol; the diol is selected from one or more of 1, 2-butanediol, methyl propylene glycol, 1, 2-propanediol, 1, 3-butanediol, diethylene glycol, dipropylene glycol, diethylene glycol monobutyl ether, dipropylene glycol monomethyl ether and dipropylene glycol monobutyl ether.
7. The modified isocyanate according to claim 6, wherein the small molecular alcohol is used in an amount of 0.05 to 1% based on the total mass of the isocyanate monomer; the mono-alcohol is selected from isopropanol and/or isobutanol; the diol is selected from one or more of methyl propylene glycol, diethylene glycol, dipropylene glycol and 1, 2-propylene glycol.
8. The modified isocyanate according to claim 1,2 or 3, wherein the isocyanate monomer is diphenylmethane diisocyanate having a color number of 50APHA or less.
9. The modified isocyanate according to claim 8, wherein the isocyanate monomer comprises 30 to 80% of 2, 4-diphenylmethane diisocyanate, 20 to 70% of 4, 4-diphenylmethane diisocyanate and 0 to 10% of 2, 2-diphenylmethane diisocyanate based on the total mass of the diphenylmethane diisocyanates.
10. The modified isocyanate according to claim 9, wherein the isocyanate monomer comprises 40 to 75% of 2, 4-diphenylmethane diisocyanate, 25 to 60% of 4, 4-diphenylmethane diisocyanate and 0 to 8% of 2, 2-diphenylmethane diisocyanate.
11. The modified isocyanate according to claim 10, wherein the isocyanate monomer comprises 45 to 70% of 2, 4-diphenylmethane diisocyanate, 30 to 55% of 4, 4-diphenylmethane diisocyanate and 0 to 5% of 2, 2-diphenylmethane diisocyanate.
12. The modified isocyanate according to claim 1,2 or 3, wherein the amount of the catalyst is 0.5 to 20ppm based on the total mass of the isocyanate monomer.
13. The modified isocyanate according to claim 12, wherein the amount of the catalyst is 1 to 10ppm based on the total mass of the isocyanate monomer.
14. The modified isocyanate according to claim 13, wherein the amount of the catalyst is 2.5 to 6ppm based on the total mass of the isocyanate monomer.
15. The modified isocyanate according to claim 1,2 or 3, wherein the terminator is one or more selected from the group consisting of an acid chloride terminator, a strong organic acid terminator and a weak organic acid terminator, and is used in an amount of 5 to 200ppm based on the total mass of the isocyanate monomer.
16. The modified isocyanate according to claim 15, wherein the terminator is selected from an organic strong acid terminator or a mixture of an organic strong acid terminator and an acyl chloride terminator, and the amount of the terminator is 20 to 150ppm based on the total mass of the isocyanate monomer.
17. The modified isocyanate according to claim 1,2 or 3, wherein the antioxidant is used in an amount of 50 to 500ppm based on the total mass of the isocyanate monomer.
18. The modified isocyanate according to claim 17, wherein the antioxidant is selected from hindered phenol antioxidants and/or phosphite antioxidants, and the antioxidant is used in an amount of 100 to 400ppm based on the total mass of the isocyanate monomer.
19. The modified isocyanate according to claim 18, wherein the antioxidant is selected from hindered phenol antioxidants and phosphite antioxidants, and the phosphite antioxidants account for 10 to 50 percent of the total mass of the antioxidants.
20. A process for preparing a modified isocyanate according to any one of claims 1 to 19, comprising the steps of, in proportions:
(1) under the protection of inert gas, mixing an isocyanate monomer, a catalyst, an antioxidant and micromolecular alcohol;
(2) performing carbodiimide modification reaction at 70-140 ℃;
(3) when the content of the isocyanate group in the reaction mixture reaches 25 to 33 weight percent, adding a terminating agent to terminate the carbodiimide modification reaction.
21. The method of claim 20,
performing carbodiimide modification reaction at 90-120 ℃;
and (3) adding a terminating agent to terminate the carbodiimide modification reaction when the content of the isocyanate groups in the reaction mixture reaches 26.5-32.5 wt%.
22. The method of claim 21,
performing carbodiimide modification reaction at 95-110 ℃;
and (3) adding a terminating agent to terminate the carbodiimide modification reaction when the content of the isocyanate group in the reaction mixture reaches 28 to 32 weight percent.
23. The method of claim 20, comprising the steps of, in proportions:
(1) under the protection of inert gas, respectively dissolving or dispersing a catalyst, an antioxidant and a terminator in small molecular alcohol to form a catalyst and small molecular alcohol mixture, an antioxidant and small molecular alcohol mixture, a terminator and small molecular alcohol mixture, and then mixing an isocyanate monomer, the catalyst and small molecular alcohol mixture, the antioxidant and the small molecular alcohol mixture;
(2) performing carbodiimide modification reaction at 70-140 ℃;
(3) when the content of the isocyanate group in the reaction mixture reaches 25 to 33 weight percent, adding a terminator and a small molecular alcohol mixture to terminate the carbodiimide modification reaction.
24. The method of claim 23,
the mass proportion of the catalyst, the antioxidant and the terminating agent in the micromolecular alcohol in the step (1) is not more than 50 percent, and the mass proportions are respectively calculated by the total mass of the mixture of each component and the micromolecular alcohol;
performing carbodiimide modification reaction at 90-120 ℃;
and (3) when the content of the isocyanate group in the reaction mixture reaches 26.5-32.5 wt%, adding a terminator and a small molecular alcohol mixture to terminate the carbodiimide modification reaction.
25. The method of claim 24,
performing carbodiimide modification reaction at 95-110 ℃;
and (3) when the content of the isocyanate group in the reaction mixture reaches 28 to 32 weight percent, adding a terminator and a small molecular alcohol mixture to terminate the carbodiimide modification reaction.
26. The method of manufacturing of claim 20 or 23, further comprising the steps of:
(4) and (3) reducing the temperature of the mixture to 30-65 ℃, stirring for 2-10 hours, and finishing the reaction.
27. The preparation method according to claim 26, wherein the reaction is terminated by cooling the mixture to 30 to 45 ℃ in step (4) and stirring for 3 to 5 hours.
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| CN110878033B (en) * | 2019-12-05 | 2022-04-22 | 万华化学集团股份有限公司 | Functional color reducing agent and method for stabilizing color number of diisocyanate product |
| CN111171773B (en) * | 2020-01-20 | 2022-03-11 | 万华化学集团股份有限公司 | Adhesive, ecological plate prepared from adhesive and preparation method of ecological plate |
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| CN114605287B (en) * | 2022-03-31 | 2023-05-30 | 中国科学院过程工程研究所 | Compound stabilizer for improving stability of non-phosgene XDI, and preparation method and application thereof |
| CN115417971B (en) * | 2022-09-16 | 2023-09-19 | 万华化学集团股份有限公司 | Flame-retardant isocyanate composite material prepared by using TDI rectifying tower kettle liquid and preparation method thereof |
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| CN101356153A (en) * | 2006-01-05 | 2009-01-28 | 拜尔材料科学股份公司 | Process for preparing liquid, storage-stable organic isocyanates containing carbodiimide and/or uretonimine groups |
| CN102015814A (en) * | 2007-12-17 | 2011-04-13 | 拜尔材料科学有限公司 | Freeze-stable aromatic diisocyanates and processes for the preparation of these freeze-stable products |
| CN104945585A (en) * | 2014-03-31 | 2015-09-30 | 东曹株式会社 | Low-temperature storage stability polyisocyanate composition and method for preparing same |
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| CN101356153A (en) * | 2006-01-05 | 2009-01-28 | 拜尔材料科学股份公司 | Process for preparing liquid, storage-stable organic isocyanates containing carbodiimide and/or uretonimine groups |
| CN102015814A (en) * | 2007-12-17 | 2011-04-13 | 拜尔材料科学有限公司 | Freeze-stable aromatic diisocyanates and processes for the preparation of these freeze-stable products |
| CN104945585A (en) * | 2014-03-31 | 2015-09-30 | 东曹株式会社 | Low-temperature storage stability polyisocyanate composition and method for preparing same |
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