CN112110869B - Preparation method of HDI trimer with low free monomer content - Google Patents
Preparation method of HDI trimer with low free monomer content Download PDFInfo
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- 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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- 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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- 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 relates to the technical field of fine chemical synthesis, in particular to a preparation method of an HDI trimer with low free monomer content. The preparation method provided by the invention adopts two-stage reaction to synthesize the HDI trimer product, firstly, a crude product is preliminarily synthesized by the first catalyst, then, the second catalyst is added to further synthesize the product, and finally, the HDI trimer with low free monomer content can be obtained by simple post-treatment. Compared with the conventional HDI trimer production method, the preparation method has the following obvious advantages: 1) by adding the pH regulator, the synthesis of HDI tripolymer can be accurately controlled, the generation of high polymer is reduced, the content of HDI monomer in the product is low, the generation amount of high polymer is less, the main body content of HDI tripolymer is high, and the product quality is good; 2) the post-treatment mode is simple, the cost is low, the industrialization is easy, the product is colorless and transparent, and the service life is long.
Description
Technical Field
The invention relates to the technical field of fine chemical synthesis, in particular to a preparation method of an HDI trimer with low free monomer content.
Background
The isocyanate trimer mainly comprises TDI trimer and HDI trimer, wherein the TDI trimer influences the application range due to poor yellowing resistance, and the HDI trimer has more excellent application characteristics. The HDI trimer has a six-membered ring structure, and the stability of the structure allows the HDI trimer to have excellent thermal stability, weather resistance and color retention, and simultaneously has an-NCO group in the HDI trimer, thereby having excellent properties of general polyurethanes, such as physical and mechanical properties of water resistance, wear resistance, corrosion resistance and high strength.
Chinese patent publication No. CN104447413A discloses a method for preparing HDI trimer, which proposes to add a terminator and then continue heating, and then separate the HDI trimer with a molecular still to solve the problem of high HDI monomer content. However, this method is too costly for the work-up of the crude product after the reaction.
Disclosure of Invention
The invention aims to provide a preparation method with low free monomer content, which has low cost and low free monomer content in the HDI trimer.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of an HDI trimer with low free monomer content, which comprises the following steps:
mixing 1, 6-hexamethylene diisocyanate with a first catalyst, adjusting the pH value to 7-10, and carrying out a first-stage polymerization reaction to obtain a first product system;
mixing the first product system, a second catalyst and a polymerization inhibitor, adjusting the pH value to 3-6.5, and sequentially carrying out second-stage polymerization reaction and post-treatment to obtain the HDI trimer with the low free monomer content;
the post-treatment comprises the following steps:
and adding an adsorbent and a filter aid into a second product system obtained by the second-stage polymerization reaction, and sequentially heating and filtering.
Preferably, the first catalyst is one or more of triethanolamine, 1, 2-dimethylpropylamine, N-dimethylallylamine, N-dimethylbenzylamine, acrylamide, iodoacemethylamine, tris (hydroxymethyl) aminomethane, aniline, sodium carbonate, disodium hydrogen phosphate, sodium phosphate and borax;
the mass ratio of the first catalyst to the 1, 6-hexamethylene diisocyanate is (0.3-5): 100.
preferably, the first-stage polymerization reaction is carried out under stirring conditions;
the rotating speed of the stirring is more than or equal to 150 r/min.
Preferably, the temperature of the first-stage polymerization reaction is 40-80 ℃, and the time of the first-stage polymerization reaction is 1-8 h.
Preferably, the second catalyst is one or more of glycine, N-tris (hydroxymethyl) methylglycine, phthalic acid, disodium hydrogen phosphate, citric acid, acetic acid, salicylic acid, 2-morpholine ethanesulfonic acid, bis (2-ethylhexyl) terephthalic acid, hydroxyethylpiperazine ethanethiosulfonic acid, 1, 4-piperazine diethylsulfonic acid, 3-morpholine propanesulfonic acid, chloroacetic acid, phenoxy isobutyric acid, p-hydroxybiphenyl-4-carboxylic acid and phthalic anhydride;
the ratio of the mass of the second catalyst to the total mass of the 1, 6-hexamethylene diisocyanate and the first catalyst is (1.5-7): 100.
preferably, the polymerization inhibitor is one or more of hydroquinone, p-tert-butylcatechol, 2, 6-di-tert-butyl-p-methylphenol, 4' -dinitrile biphenyl, bisphenol A, p-benzoquinone, phenothiazine, diphenylamine, benzidine, p-phenylenediamine and N-nitrosodiphenylamine;
the ratio (0.1-1) of the mass of the polymerization inhibitor to the total mass of the 1, 6-hexamethylene diisocyanate and the first catalyst is: 1000.
preferably, the temperature of the second-stage polymerization reaction is 120-180 ℃, and the time of the second-stage polymerization reaction is 1-4 h.
Preferably, the adsorbent is one or more of activated alumina, polymeric alumina and polyacrylamide;
the filter aid is one or more of calcined kaolin, calcium bentonite, light calcium carbonate and calcined diatomite.
Preferably, the mass ratio of the adsorbent to the total mass of the 1, 6-hexamethylene diisocyanate, the first catalyst, the second catalyst and the polymerization inhibitor is (0.3-2.5): 100, respectively;
the mass ratio of the filter aid to the total mass of the 1, 6-hexamethylene diisocyanate, the first catalyst, the second catalyst and the polymerization inhibitor is (3-15): 100.
the invention provides a preparation method of an HDI trimer with low free monomer content, which comprises the following steps: mixing 1, 6-hexamethylene diisocyanate with a first catalyst, adjusting the pH value to 7-10, and carrying out a first-stage polymerization reaction to obtain a first product system; mixing the first product system, a second catalyst and a polymerization inhibitor, adjusting the pH value to 3-6.5, and sequentially carrying out second-stage polymerization reaction and post-treatment to obtain the HDI trimer with the low free monomer content; the post-treatment comprises the following steps: and adding an adsorbent and a filter aid into a second product system obtained by the second-stage polymerization reaction, and sequentially heating and filtering. The HDI trimer product is synthesized by adopting two-stage reaction, firstly, a crude product is preliminarily synthesized by a first catalyst, then, a second catalyst is added to further synthesize the product, and finally, the HDI trimer with low free monomer content can be obtained by simple post-treatment. Compared with the conventional HDI trimer production method, the preparation method has the following obvious advantages: 1) by adding the pH regulator, the synthesis of HDI tripolymer can be accurately controlled, the generation of high polymer is reduced, the content of HDI monomer in the product is low, the generation amount of high polymer is less, the main body content of HDI tripolymer is high, the yield is high, and the product quality is good; 2) the post-treatment mode is simple, the cost is low, the industrialization is easy, the product is colorless and transparent, and the service life is long.
Detailed Description
The invention provides a preparation method of HDI tripolymer with low free monomer content, which comprises the following steps:
mixing 1, 6-hexamethylene diisocyanate with a first catalyst, adjusting the pH value to 7-10, and carrying out a first-stage polymerization reaction to obtain a first product system;
mixing the first product system, a second catalyst and a polymerization inhibitor, adjusting the pH value to 3-6.5, and sequentially carrying out second-stage polymerization reaction and post-treatment to obtain the HDI trimer with the low free monomer content;
the post-treatment comprises the following steps:
and adding an adsorbent and a filter aid into a second product system obtained by the second-stage polymerization reaction, and sequentially heating and filtering.
In the present invention, all the raw material components are commercially available products well known to those skilled in the art unless otherwise specified.
The method comprises the steps of mixing 1, 6-hexamethylene diisocyanate with a first catalyst, adjusting the pH value to 7-10, and carrying out a first-stage polymerization reaction to obtain a first product system. In the invention, the first catalyst is preferably one or more of triethanolamine, 1, 2-dimethylpropylamine, N-dimethylallylamine, N-dimethylbenzylamine, acrylamide, iodoacemethylamine, tris (hydroxymethyl) aminomethane, aniline, sodium carbonate, disodium hydrogen phosphate, sodium phosphate and borax; when the first catalyst is more than two of the specific choices, the proportion of the specific substances is not limited in any way, and the specific substances can be mixed according to any proportion. In the present invention, the mass ratio of the first catalyst to the 1, 6-hexamethylene isocyanate is preferably (0.3 to 5): 100, more preferably (1.5 to 3): 100.
the process for adjusting the pH value is not limited in any way, and the process well known to a person skilled in the art can ensure that the pH value of the mixed solution obtained by mixing is within the range of 7-10; the pH value of the mixed solution is more preferably 7-8.9, and most preferably 7.5-8.
In the present invention, the mixing is preferably carried out under stirring conditions, and the stirring speed is not particularly limited in the present invention, and may be carried out by a process known to those skilled in the art.
In the present invention, the mixing is preferably performed by uniformly mixing the 1, 6-hexamethylene diisocyanate and the first catalyst, and then adding the pH adjuster. The addition manner of the pH regulator is not particularly limited, and the pH regulator can be added in a manner known to those skilled in the art.
In the present invention, after the completion of the mixing, the present invention preferably further includes replacing the atmosphere of the mixed liquid obtained by the mixing with vacuum and nitrogen gas. The process of the present invention for the substitution is not particularly limited, and may be carried out by a process known to those skilled in the art. In the present invention, the number of the substitution is preferably not less than 3, and most preferably 3.
In the present invention, the first-stage polymerization reaction is preferably carried out under a nitrogen atmosphere.
In the invention, the first-stage polymerization reaction is preferably carried out under the condition of stirring, and the rotating speed of the stirring is preferably not less than 150r/min, and more preferably 200-500 r/min. In the invention, the temperature of the first-stage polymerization reaction is preferably 40-80 ℃, and more preferably 60-70 ℃; the time of the first-stage polymerization reaction is preferably 1-8 h, and more preferably 3-4 h.
In the present invention, the first stage polymerization reaction can rapidly form a polymer from a monomer, including a dimer, a trimer and a multimer, wherein the trimer is the main component.
After the first product system is obtained, the first product system, the second catalyst and the polymerization inhibitor are mixed, the pH value is adjusted to 3-6.5, and second-stage polymerization reaction and post-treatment are sequentially carried out to obtain the HDI trimer with the low free monomer content. In the invention, the second catalyst is preferably one or more of glycine, N-tris (hydroxymethyl) methylglycine, phthalic acid, disodium hydrogen phosphate, citric acid, acetic acid, salicylic acid, 2-morpholine ethanesulfonic acid, bis (2-ethylhexyl) terephthalic acid, hydroxyethylpiperazine ethanethiosulfonic acid, 1, 4-piperazine diethylsulfonic acid, 3-morpholine propanesulfonic acid, chloroacetic acid, phenoxy isobutyric acid, p-hydroxybiphenyl-4-carboxylic acid and phthalic anhydride; when the second catalyst is more than two of the specific choices, the proportion of the specific substances is not limited in any way, and the specific substances can be mixed according to any proportion. In the present invention, the ratio of the mass of the second catalyst to the total mass of the 1, 6-hexamethylene diisocyanate and the first catalyst is preferably (1.5 to 7): 100, more preferably (3-6.5): 100.
in the invention, the polymerization inhibitor is preferably one or more of hydroquinone, p-tert-butyl catechol, 2, 6-di-tert-butyl-p-methylphenol, 4' -dinitryl biphenyl, bisphenol A, p-benzoquinone, phenothiazine, diphenylamine, benzidine, p-phenylenediamine and N-nitrosodiphenylamine; when the polymerization inhibitor is more than two of the above specific choices, the invention does not have any special limitation on the proportion of the specific substances, and the specific substances are mixed according to any proportion. In the present invention, the ratio of the mass of the polymerization inhibitor to the total mass of the 1, 6-hexamethylene diisocyanate and the first catalyst is preferably (0.1 to 1): 1000, more preferably (0.2 to 0.8): 1000, most preferably (0.4 to 0.6): 1000.
the process for adjusting the pH value is not limited in any way, and the process well known to a person skilled in the art can ensure that the pH value of the mixed solution obtained by mixing is within the range of 3-6.5; the pH value of the mixed solution is more preferably 4.5-5.5.
In the present invention, the mixing is preferably performed under stirring conditions, and the rotation speed of the stirring is not particularly limited in the present invention, and may be performed by a process known to those skilled in the art.
In the present invention, the mixing is preferably performed by adding a catalyst and a polymerization inhibitor to the first product system. The catalyst and the polymerization inhibitor are preferably added simultaneously.
In the invention, the second-stage polymerization reaction is preferably carried out in a nitrogen atmosphere, and the temperature of the second-stage polymerization reaction is preferably 120-180 ℃, and more preferably 150-160 ℃; the time of the second-stage polymerization reaction is preferably 1-4 h, and more preferably 2-3 h.
In the present invention, the second stage polymerization reaction can be carried out in order to further reduce the monomer content, and the remaining monomers can be slowly converted into dimers and then into trimers, while reducing the formation of multimers, i.e., while reducing the content of free monomers, the formation of multimers can be minimized.
After the second-stage polymerization reaction is completed, the temperature reduction is preferably included in the present invention, and the temperature reduction is performed by using a temperature reduction method well known to those skilled in the art without any particular limitation in the present invention.
In the present invention, the post-treatment preferably comprises the steps of: and adding an adsorbent and a filter aid into a second product system obtained by the second-stage polymerization reaction, and sequentially heating and filtering. In the invention, the adsorbent is preferably one or more of activated alumina, polymeric alumina and polyacrylamide; the ratio of the mass of the adsorbent to the total mass of the 1, 6-hexamethylene diisocyanate, the first catalyst, the second catalyst and the polymerization inhibitor is preferably (0.3-2.5): 100, more preferably (1 to 1.5): 100; the filter aid is preferably one or more of calcined kaolin, calcium bentonite, light calcium carbonate and calcined diatomite; when the filter aid is more than two of the above specific choices, the invention has no special limitation on the proportion of the specific substances, and the specific substances can be mixed according to any proportion. In the invention, the mass ratio of the filter aid to the total mass of the 1, 6-hexamethylene diisocyanate, the first catalyst, the second catalyst and the polymerization inhibitor is preferably (3-15): 100, more preferably (10-13): 100.
in the present invention, the heating is preferably performed in a nitrogen atmosphere. In the invention, the heating temperature is preferably 60-80 ℃, and more preferably 65-75 ℃. In the invention, after the temperature is raised to the heating temperature, the stirring is preferably carried out for 0.5-1 h at the temperature; the stirring rate is not particularly limited in the present invention, and may be carried out at a rate known to those skilled in the art.
In the present invention, the heating process can accelerate the reaction.
In the present invention, the suction filtration is preferably a negative pressure suction filtration, and the negative pressure suction filtration is performed by a process well known to those skilled in the art without any particular limitation.
The preparation of the HDI trimer with a low free monomer content according to the invention is described in detail below with reference to the examples, which should not be construed as limiting the scope of the invention.
Examples 1 to 11
Adding disodium hydrogen phosphate into 2000g of HDI monomer until the mixture is uniformly mixed, adjusting the pH value to 8.0, performing vacuum nitrogen replacement for 3 times, and performing a first-stage polymerization reaction under the conditions of nitrogen atmosphere and stirring (150r/min) to obtain a first product system;
adding 81.6g of glycine and 0.6g of 4,4' -dicyanobiphenyl into the first product system in a nitrogen atmosphere, adjusting the pH value to 4.0, introducing nitrogen, heating to 160 ℃, keeping the temperature for 2h, cooling, adding 42g of polyacrylamide and 212g of light calcium carbonate, stirring for 1h at 60 ℃ in the nitrogen atmosphere at the rotating speed of 90r/min, and performing vacuum filtration to obtain the HDI trimer with the low free monomer content.
The amount of disodium hydrogen phosphate added, the temperature and the time of the first polymerization stage are shown in table 1, and the monomer content, dimer content, trimer content, multimer content and — NCO content of the low free monomer content HDI trimer prepared in examples 1 to 11 were measured by di-n-butylamine titration, and the results are shown in table 1:
TABLE 1 amount of disodium hydrogen phosphate added, temperature and time of the first stage of polymerization, and monomer content, dimer content, in the HDI trimer with low free monomer content obtained in examples 1 to 11,
Trimer content, polymer content and-NCO content
Examples 12 to 22
Adding 40g of disodium hydrogen phosphate into 2000g of HDI monomer until the mixture is uniformly mixed, adjusting the pH value to 8.0, performing vacuum nitrogen replacement for 3 times, and performing a first-stage polymerization reaction (at 60 ℃ for 3 hours) under the conditions of nitrogen atmosphere and stirring (150r/min) to obtain a first product system;
and (2) adding glycine and 0.6g of 4,4' -dicyanobiphenyl into the first product system in a nitrogen atmosphere, adjusting the pH value to 4.0, introducing nitrogen, heating to 160 ℃, keeping the temperature for 2 hours, cooling, adding 42g of polyacrylamide and 212g of light calcium carbonate, carrying out second-stage polymerization reaction in the nitrogen atmosphere at the rotating speed of 90r/min, and carrying out vacuum filtration to obtain the HDI trimer with the low free monomer content.
The addition amount of glycine, the temperature and the time of the second-stage polymerization reaction are shown in table 2, the monomer content, dimer content, trimer content, multimer content and-NCO content of the HDI trimer with low free monomer content prepared in examples 12 to 22 were measured by di-n-butylamine titration, and the measurement results are shown in table 2:
TABLE 2 Glycine addition amount, temperature and time of second-stage polymerization, and monomer content, dimer content, trimer content, multimer content and-NCO content of the HDI trimer with low free monomer content obtained in examples 12 to 22
Example 23
Adding 40g of a first catalyst (the mass ratio of N, N-dimethylbenzylamine to iodoacetyl methylamine to disodium hydrogen phosphate is 3:3:4) into 2000g of HDI monomer until the mixture is uniformly mixed, adjusting the pH value to 8.0, performing vacuum nitrogen replacement for 3 times, and performing a first-stage polymerization reaction (at 60 ℃ for 3 hours) under the conditions of nitrogen atmosphere and stirring (150r/min) to obtain a first product system;
adding 81.6g of a second catalyst (the mass ratio of glycine to N-tris (hydroxymethyl) methylglycine to citric acid is 2:1:1) and 0.6g of 4,4' -dicyanobiphenyl into the first product system under a nitrogen atmosphere, adjusting the pH value to 4.0, introducing nitrogen, heating to 160 ℃, keeping the temperature for 2 hours, cooling, adding 42g of polyacrylamide and 212g of light calcium carbonate, carrying out a second-stage polymerization reaction in the nitrogen atmosphere at the rotating speed of 90r/min, and carrying out reduced pressure suction filtration to obtain the HDI trimer with the low free monomer content, wherein the HDI trimer with the low free monomer content is 0.1-0.5%, the dimer content is 1-2%, the trimer content is 73-80%, the polymer content is 18-26% and the NCO mass fraction is 23-24%.
Examples 24 to 26
Adding 40g of a first catalyst (the mass ratio of N, N-dimethylbenzylamine to iodoacetyl methylamine to disodium hydrogen phosphate is 3:3:4) into 2000g of HDI monomer until the mixture is uniformly mixed, adjusting the pH value (shown in table 3), performing vacuum nitrogen replacement for 3 times, and performing a first-stage polymerization reaction (at 60 ℃ for 3 hours) under the conditions of nitrogen atmosphere and stirring (150r/min) to obtain a first product system;
adding 81.6g of a second catalyst (the mass ratio of glycine to N-tris (hydroxymethyl) methylglycine to citric acid is 2:1:1) and 0.6g of 4,4' -dicyanobiphenyl into the first product system in a nitrogen atmosphere, adjusting the pH value to 4.0, introducing nitrogen, heating to 160 ℃, keeping the temperature for 2 hours, cooling, adding 42g of polyacrylamide and 212g of light calcium carbonate, carrying out a second-stage polymerization reaction in the nitrogen atmosphere at the rotating speed of 90r/min, and carrying out reduced pressure suction filtration to obtain the HDI trimer with the low free monomer content;
the monomer content, dimer content, trimer content, multimer content and-NCO content of the HDI trimers with low free monomer contents prepared in examples 24 to 26 were measured by di-n-butylamine titration, and the results are shown in table 3:
TABLE 3 pH values in examples 24 to 26 and monomer content, dimer content, trimer content, multimer content and-NCO content in the HDI trimers with low free monomer contents obtained
Examples 27 to 29
Adding 40g of a first catalyst (the mass ratio of N, N-dimethylbenzylamine to iodoacetyl methylamine to disodium hydrogen phosphate is 3:3:4) into 2000g of HDI monomer until the mixture is uniformly mixed, adjusting the pH value to 8.0, performing vacuum nitrogen replacement for 3 times, and performing a first-stage polymerization reaction (at 60 ℃ for 3 hours) under the conditions of nitrogen atmosphere and stirring (150r/min) to obtain a first product system;
adding 81.6g of a second catalyst (the mass ratio of glycine to N-tris (hydroxymethyl) methylglycine to citric acid is 2:1:1) and 0.6g of 4,4' -dicyanobiphenyl into the first product system in a nitrogen atmosphere, adjusting the pH value (shown in table 4), introducing nitrogen, heating to 160 ℃, keeping the temperature for 2 hours, cooling, adding 42g of polyacrylamide and 212g of light calcium carbonate, carrying out a second-stage polymerization reaction in the nitrogen atmosphere at the rotating speed of 90r/min, and carrying out reduced pressure suction filtration to obtain the HDI trimer with the low free monomer content;
the monomer content, dimer content, trimer content, multimer content and-NCO content of the HDI trimers with low free monomer content prepared in examples 27 to 29 were measured by di-n-butylamine titration, and the results are shown in table 4:
TABLE 4 pH values in examples 27 to 29 and monomer content, dimer content, trimer content, multimer content and-NCO content in the HDI trimers with low free monomer contents obtained
Examples 30 to 32
Adding 40g of a first catalyst (the mass ratio of N, N-dimethylbenzylamine to iodoacetyl methylamine to disodium hydrogen phosphate is 3:3:4) into 2000g of HDI monomer until the mixture is uniformly mixed, adjusting the pH value to 8.0, performing vacuum nitrogen replacement for 3 times, and performing a first-stage polymerization reaction (at 60 ℃ for 3 hours) under the conditions of nitrogen atmosphere and stirring (150r/min) to obtain a first product system;
adding 81.6g of a second catalyst (the mass ratio of glycine to N-tris (hydroxymethyl) methylglycine to citric acid is 2:1:1) and 4,4' -dicyanobenzene into the first product system in a nitrogen atmosphere, adjusting the pH value to 4.0, introducing nitrogen, heating to 160 ℃, keeping the temperature for 2 hours, cooling, adding 42g of polyacrylamide and 212g of light calcium carbonate, carrying out a second-stage polymerization reaction in the nitrogen atmosphere at the rotating speed of 90r/min, and carrying out reduced pressure suction filtration to obtain the HDI trimer with the low free monomer content;
the amount of 4,4' -dicyanobiphenyl used is shown in table 5, the monomer content, dimer content, trimer content, multimer content and-NCO content of the HDI trimer with low free monomer content prepared in examples 30 to 32 were measured by di-n-butylamine titration, and the results are shown in table 5:
TABLE 5 pH values in examples 30 to 32 and monomer content, dimer content, trimer content, multimer content and-NCO content in the prepared HDI trimers with a low free monomer content
As can be seen from tables 1-5, multiple experiments show that the two-stage reaction control method can effectively obtain the HDI trimer product with low free monomer content.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (3)
1. A method for preparing HDI trimer with low free monomer content is characterized by comprising the following steps:
mixing 1, 6-hexamethylene diisocyanate with a first catalyst, adjusting the pH value to 7-10, and carrying out a first-stage polymerization reaction to obtain a first product system; the first catalyst is disodium hydrogen phosphate or a catalyst with the mass ratio of 3:3:4 a mixture of N, N-dimethylbenzylamine, iodoacetyl methylamine, and disodium hydrogen phosphate; the mass ratio of the first catalyst to the 1, 6-hexamethylene diisocyanate is (0.3-5): 100, respectively; the first-stage polymerization reaction is carried out under the condition of stirring; the rotating speed of the stirring is more than or equal to 150 r/min; the temperature of the first-stage polymerization reaction is 40-80 ℃, and the time of the first-stage polymerization reaction is 1-8 h;
mixing the first product system, a second catalyst and a polymerization inhibitor, adjusting the pH value to 3-6.5, and sequentially carrying out second-stage polymerization reaction and post-treatment to obtain the HDI trimer with the low free monomer content; the second catalyst is glycine or a mixture of glycine, N-tris (hydroxymethyl) methylglycine and citric acid in a mass ratio of 2:1: 1; the ratio of the mass of the second catalyst to the total mass of the 1, 6-hexamethylene diisocyanate and the first catalyst is (1.5-7): 100, respectively; the polymerization inhibitor is 4,4' -dicyanobiphenyl; the ratio of the mass of the polymerization inhibitor to the total mass of the 1, 6-hexamethylene diisocyanate and the first catalyst (0.1-1): 1000, parts by weight; the temperature of the second-stage polymerization reaction is 120-180 ℃, and the time of the second-stage polymerization reaction is 1-4 hours;
the post-treatment comprises the following steps:
and adding an adsorbent and a filter aid into a second product system obtained by the second-stage polymerization reaction, and sequentially heating and filtering.
2. The preparation method of claim 1, wherein the adsorbent is one or more of activated alumina, polymeric alumina and polyacrylamide;
the filter aid is one or more of calcined kaolin, calcium bentonite, light calcium carbonate and calcined diatomite.
3. The production method according to claim 1, wherein the ratio of the mass of the adsorbent to the total mass of the 1, 6-hexamethylene diisocyanate, the first catalyst, the second catalyst and the polymerization inhibitor is (0.3 to 2.5): 100, respectively;
the mass ratio of the filter aid to the total mass of the 1, 6-hexamethylene diisocyanate, the first catalyst, the second catalyst and the polymerization inhibitor is (3-15): 100.
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| CN114315652B (en) * | 2022-01-13 | 2023-11-14 | 甘肃智仑新材料科技有限公司 | Aromatic ring tracing type tectorial membrane propping agent for fracturing and preparation method and application thereof |
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