CN113856751A - Catalyst, preparation method thereof and polymerization method of isocyanate - Google Patents
Catalyst, preparation method thereof and polymerization method of isocyanate Download PDFInfo
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- CN113856751A CN113856751A CN202111004543.7A CN202111004543A CN113856751A CN 113856751 A CN113856751 A CN 113856751A CN 202111004543 A CN202111004543 A CN 202111004543A CN 113856751 A CN113856751 A CN 113856751A
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- 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
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- C07D251/34—Cyanuric or isocyanuric esters
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- C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
- C07D295/04—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms
- C07D295/08—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly bound oxygen or sulfur atoms
- C07D295/084—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly bound oxygen or sulfur atoms with the ring nitrogen atoms and the oxygen or sulfur atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings
- C07D295/088—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly bound oxygen or sulfur atoms with the ring nitrogen atoms and the oxygen or sulfur atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings to an acyclic saturated chain
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Abstract
The invention relates to the field of polyisocyanate polymerization, and in particular relates to a catalyst, a preparation method thereof and a polymerization method of isocyanate. The catalyst is piperazine quaternary ammonium base compound, and the preparation method of the catalyst comprises the following steps: under the protection of Ar atmosphere, dripping propylene oxide into an aqueous solution of the aliphatic substituted derivative of piperazine; stirring at room temperature, and reacting for 4-9 h; and after the reaction is finished, taking the lower layer solution, and performing rotary evaporation to obtain the piperazine quaternary ammonium base compound, namely the catalyst. The method for polymerizing the isocyanate comprises the following steps: under the protection of inert gas, carrying out polymerization reaction on isocyanate raw materials under the catalytic action of the catalyst; when the-NCO content in the reaction liquid reached 5 to 80% by weight based on the weight of the reaction liquid, the polymerization reaction was terminated. According to the invention, the cyclic piperazine skeleton is introduced into the catalyst, so that the reaction between small molecules is promoted, and the reaction between macromolecules and the small molecules is inhibited, thereby improving the conversion rate of a substrate and ensuring the purity of a product.
Description
Technical Field
The invention relates to the field of polyisocyanate polymerization, and in particular relates to a catalyst, a preparation method thereof and a polymerization method of isocyanate.
Background
Diisocyanate polymers have unique advantages in various polyurethane coatings and adhesives and are widely used. However, monomers are volatile and toxic, and therefore, they are often prepared as multimers for use. Since the polyisocyanurate of aliphatic diisocyanate has excellent thermal stability, weather resistance and medium resistance, its self-polymerization reaction has been widely studied. The difficulty in the preparation process lies in the selection of the catalyst, and the types of the currently used catalysts are various and comprise: quaternary ammonium bases, quaternary ammonium salts, metal salts, hydrides, oxides, and the like. Therefore, how to prepare a novel catalyst by utilizing green and mild reaction conditions and ensure that the isocyanurate polymerization reaction catalyzed by the catalyst has higher monomer conversion rate and the trimer content in the product is a problem to be solved urgently.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: the cyclic piperazine skeleton is introduced into the catalyst, so that the monomer conversion rate of the reaction is high, and the trimer in the product accounts for the main component.
The technical scheme adopted by the invention for solving the technical problems is as follows: in a first aspect, the catalyst has the general structural formula:
further, R in the structural general formula of the catalyst1Is an alkyl group having 1 to 20 carbon atoms.
Further, R in the structural general formula of the catalyst2Is hydroxyalkyl having 1 to 20 carbon atoms.
Further, the raw materials of the catalyst comprise aliphatic substituted derivatives of piperazine, water and alkylene oxide;
further, the aliphatic substituted derivatives of piperazine include 1, 4-dimethylpiperazine; the alkylene oxide comprises propylene oxide.
In a second aspect, a method of preparing the catalyst comprises: under the protection of Ar, dropwise adding a certain amount of propylene oxide into an aqueous solution of 1, 4-dimethylpiperazine, wherein the amount of water is 1.5-4 times of the molar amount of the 1, 4-dimethylpiperazine, and the amount of propylene oxide is 1.0-2.5 times of the molar amount of the 1, 4-dimethylpiperazine; then stirring at room temperature, and reacting for 4-9 h; taking the lower layer solution after the reaction is finished; and (4) performing rotary evaporation to obtain the piperazine quaternary ammonium base.
The main reaction equation is as follows:
in a third aspect, the isocyanate polymerization process comprises: under the protection of inert gas, taking isocyanate as a substrate and carrying out polymerization reaction under the catalysis of a catalyst, wherein the reaction temperature is 10-100 ℃ (preferably 30-80 ℃), and the dosage of the catalyst is 10-800ppm (preferably 200-800ppm) based on the mass of the substrate; the catalyst used in the present invention may be used in the form of a solution without a solvent or dissolved in a catalyst solvent, and when the catalyst is used in the form of a solution, the amount of the catalyst solution is 5 to 50 wt% (preferably 10 to 30 wt%) based on the amount of the reaction solution; when the-NCO content of the reaction liquid is 5 to 80 wt% (preferably 10 to 70 wt% or 20 to 50 wt%) based on the amount of the reaction liquid as the reaction proceeds, the reaction is terminated by a high-temperature treatment or by adding a catalyst poison in an amount of twice the molar amount or twice a slight excess amount of the catalyst.
Further, the catalyst solvent suitable for the present invention includes a straight or branched chain monohydric alcohol and dihydric alcohol having 1 to 20 carbon atoms, and includes one or more hydroxyl groups in the whole molecule; optional catalyst solvents include methanol, ethanol, 1-or 2-propanol, n-butanol, isobutanol, sec-butanol, tert-butanol, n-octanol, isooctanol, heptanol, 2-ethyl-1, 3-hexanediol, 1, 3-butanediol or 1, 4-butanediol, 1-methoxy-2-propanol, preferably methanol, n-butanol, hexanol, heptanol and isooctanol.
Further, suitable substrates for the present invention include all aliphatic isocyanates, wherein the substrate can be a single aliphatic isocyanate or a mixture of a plurality of aliphatic isocyanates; all structural or configurational isomers of the isocyanates listed below are optional examples: bis (isocyanatoalkyl) ethers, propane diisocyanate, butane diisocyanate, pentane diisocyanate (pentamethylene diisocyanate, PDI), hexane diisocyanate (hexamethylene diisocyanate, HDI), heptane diisocyanate, octane diisocyanate (e.g., octamethylene diisocyanate), nonane diisocyanate (e.g., trimethyl-HDI, TMDI, typically present as a mixture of the 2, 4, 4-and 2, 2, 4-isomers), triisocyanates (e.g., 4-isocyanatomethyl-1, 8-octane diisocyanate), decane diisocyanate (e.g., decamethylene diisocyanate) and triisocyanates, undecane diisocyanate and triisocyanates, dodecane diisocyanate (e.g., dodecamethylene diisocyanate) and triisocyanates, mixtures of these, and mixtures of these, Tetradecane diisocyanate (e.g., tetradecylene diisocyanate), 1, 4-cyclohexane diisocyanate (CHDI), 3-isocyanatomethyl-3, 5, 5-trimethylcyclohexyl isocyanate (isophorone diisocyanate, IPDI), 4' -dicyclohexylmethane diisocyanate (H12MDI), and Pentamethylene Diisocyanate (PDI) is preferably used.
Further, catalyst poisons suitable for the present invention include acids or acid derivatives; alternative catalyst poisons include one or more of phosphoric acid, benzoyl chloride, phenylmethanesulfonate, phosphate esters, phosphite esters, methanesulfonic acid, p-toluenesulfonic acid and the like, with dibutyl phosphate being preferred.
The invention has the beneficial effects that:
according to the invention, a cyclic piperazine skeleton is introduced into a catalyst, so that the reaction among small molecules is promoted, the small molecule reaction comprises the dimerization reaction and the trimerization reaction of an isocyanate substrate, the reaction of an isocyanate substrate monomer and a small amount of alcohol in a system, and the reaction between a large molecule and the small molecule or the large molecule is inhibited, and the reaction of a generated polymer and the small amount of alcohol in the system and the polymerization reaction of the isocyanate substrate are inhibited, so that the purposes of high monomer conversion rate and the tripolymer in a product accounting for main components are achieved.
Drawings
The invention is further illustrated by the following figures and examples.
FIG. 1 is a GPC measurement result graph.
In the figure: a-a commercially available PDI trimer, B-a PDI trimer produced according to the present invention.
Detailed Description
The process provided by the present invention is further illustrated by the following examples, but the invention is not limited thereto. All percentages referred to in the present invention are mass percentages unless otherwise specified.
Example 1
The molar ratio of the 1, 4-dimethylpiperazine to the water to the propylene oxide is adjusted to 1:1.5: 1. Under Ar protection, propylene oxide (3.5ml) was added dropwise to 1, 4-dimethylpiperazine (6.8ml) and water (1.4ml) over 0.5 h. And then continuously stirring for 4 hours at room temperature to obtain a reaction product 1 #. And qualitatively analyzing the synthesized reaction product by adopting nuclear magnetism. The nuclear magnetic results are shown below:
monosubstituted quaternary ammonium bases1H NMR(400M，TMS):δ1.18(m，3H)，1.89(s，3H)，2.22-2.50(m，10H)，2.31(s，3H)，3.15-3.61(m，1H)，5.6(s，1H)。
Disubstituted quaternary ammonium bases1H NMR(400M，TMS):δ1.06(m，6H)，2.25-2.31(m，8H)，2.69(s，6H)，3.36-4.30(m，6H)，5.6(s，2H)。
Then, the reaction product is subjected to quantitative analysis by reverse phase liquid chromatography, and the result shows that: the mass content of the mono-substituted quaternary ammonium base is 35.1 percent, the mass content of the di-substituted quaternary ammonium base is 31.1 percent, and the mass content of the byproduct is 33.8 percent.
Example 2
The molar ratio of the 1, 4-dimethylpiperazine to the water to the propylene oxide is adjusted to 1:2: 1.4. Under Ar protection, propylene oxide (4.9ml) was added dropwise to 1, 4-dimethylpiperazine (6.8ml) and water (1.9ml) over 0.5 h. And then continuously stirring for 4 hours at room temperature to obtain a reaction product No. 2. And qualitatively analyzing the synthesized reaction product by adopting nuclear magnetism. The nuclear magnetic results are shown below:
monosubstituted quaternary ammonium bases1H NMR(400M，TMS):δ1.18(m，3H)，1.89(s，3H)，2.22-2.50(m，10H)，2.31(s，3H)，3.15-3.61(m，1H)，5.6(s，1H)。
Disubstituted quaternary ammonium bases1H NMR(400M，TMS):δ1.06(m，6H)，2.25-2.31(m，8H)，2.69(s，6H)，3.36-4.30(m，6H)，5.6(s，2H)。
Then, the reaction product is subjected to quantitative analysis by reverse phase liquid chromatography, and the result shows that: the mass content of the mono-substituted quaternary ammonium base is 19.1 percent, the mass content of the di-substituted quaternary ammonium base is 78.5 percent, and the mass content of a byproduct is 2.4 percent.
Example 3
The molar ratio of the 1, 4-dimethylpiperazine to the water to the propylene oxide is adjusted to 1:2: 1.4. Under Ar protection, propylene oxide (4.9ml) was added dropwise to 1, 4-dimethylpiperazine (6.8ml) and water (1.9ml) over 0.5 h. And then continuously stirring for 6 hours at room temperature to obtain a reaction product No. 3. And qualitatively analyzing the synthesized reaction product by adopting nuclear magnetism. The nuclear magnetic results are shown below:
monosubstituted quaternary ammonium bases1H NMR(400M，TMS):δ1.18(m，3H)，1.89(s，3H)，2.22-2.50(m，10H)，2.31(s，3H)，3.15-3.61(m，1H)，5.6(s，1H)。
Disubstituted quaternary ammonium bases1H NMR(400M，TMS):δ1.06(m，6H)，2.25-2.31(m，8H)，2.69(s，6H)，3.36-4.30(m，6H)，5.6(s，2H)。
Then, the reaction product is subjected to quantitative analysis by reverse phase liquid chromatography, and the result shows that: the mass content of the mono-substituted quaternary ammonium base is 7.7 percent, the mass content of the di-substituted quaternary ammonium base is 91.6 percent, and the mass content of the byproduct is 0.7 percent.
Example 4
The molar ratio of the 1, 4-dimethylpiperazine to the water to the propylene oxide is adjusted to 1:2: 1.4. Under Ar protection, propylene oxide (4.9ml) was added dropwise to 1, 4-dimethylpiperazine (6.8ml) and water (1.9ml) over 0.5 h. Then continuously stirring for 9h at room temperature to obtain a reaction product No. 4. And qualitatively analyzing the synthesized reaction product by adopting nuclear magnetism. The nuclear magnetic results are shown below:
monosubstituted quaternary ammonium bases1H NMR(400M，TMS):δ1.18(m，3H)，1.89(s，3H)，2.22-2.50(m，10H)，2.31(s，3H)，3.15-3.61(m，1H)，5.6(s，1H)。
Disubstituted quaternary ammonium bases1H NMR(400M，TMS):δ1.06(m，6H)，2.25-2.31(m，8H)，2.69(s，6H)，3.36-4.30(m，6H)，5.6(s，2H)。
Then, the reaction product is subjected to quantitative analysis by reverse phase liquid chromatography, and the result shows that: the mass content of the mono-substituted quaternary ammonium base is 9.2 percent, the mass content of the di-substituted quaternary ammonium base is 44.7 percent, and the mass content of the byproduct is 46.1 percent.
Example 5
The molar ratio of the 1, 4-dimethyl piperazine to the water to the propylene oxide is adjusted to be 1:2:2. Under Ar protection, propylene oxide (7.0ml) was added dropwise to 1, 4-dimethylpiperazine (6.8ml) and water (1.8ml) over 0.5 h. And then continuously stirring for 4 hours at room temperature to obtain a reaction product No. 5. And qualitatively analyzing the synthesized reaction product by adopting nuclear magnetism. The nuclear magnetic results are shown below:
monosubstituted quaternary ammonium bases1H NMR(400M，TMS):δ1.18(m，3H)，1.89(s，3H)，2.22-2.50(m，10H)，2.31(s，3H)，3.15-3.61(m，1H)，5.6(s，1H)。
Disubstituted quaternary ammonium bases1H NMR(400M，TMS):δ1.06(m，6H)，2.25-2.31(m，8H)，2.69(s，6H)，3.36-4.30(m，6H)，5.6(s，2H)。
Then, the reaction product is subjected to quantitative analysis by reverse phase liquid chromatography, and the result shows that: the mass content of the mono-substituted quaternary ammonium base is 19.6 percent, the mass content of the di-substituted quaternary ammonium base is 78.3 percent, and the mass content of a byproduct is 2.1 percent.
Example 6
The molar ratio of the 1, 4-dimethyl piperazine to the water to the propylene oxide is adjusted to be 1:2: 2.5. Under Ar protection, propylene oxide (8.8ml) was added dropwise over 0.5h to 1, 4-dimethylpiperazine (6.8ml) and water (0.1mol, 1.8 ml). And then continuously stirring for 4 hours at room temperature to obtain a reaction product No. 6. And qualitatively analyzing the synthesized reaction product by adopting nuclear magnetism. The nuclear magnetic results are shown below:
monosubstituted quaternary ammonium bases1H NMR(400M，TMS):δ1.18(m，3H)，1.89(s，3H)，2.22-2.50(m，10H)，2.31(s，3H)，3.15-3.61(m，1H)，5.6(s，1H)。
Disubstituted quaternary ammonium bases1H NMR(400M，TMS):δ1.06(m，6H)，2.25-2.31(m，8H)，2.69(s，6H)，3.36-4.30(m，6H)，5.6(s，2H)。
Then, the reaction product is subjected to quantitative analysis by reverse phase liquid chromatography, and the result shows that: the mass content of the mono-substituted quaternary ammonium base is 3.7 percent, the mass content of the di-substituted quaternary ammonium base is 93.4 percent, and the mass content of a byproduct is 2.9 percent.
Example 7
The molar ratio of 1, 4-diethylpiperazine, water and propylene oxide is adjusted to 1:2.5: 2.5. Under Ar protection, propylene oxide (8.8ml) was added dropwise over 0.5h to 1, 4-diethylpiperazine (6.8ml) and water (2.3 ml). And then continuously stirring for 4 hours at room temperature to obtain a reaction product No. 7. And qualitatively analyzing the synthesized reaction product by adopting nuclear magnetism. The nuclear magnetic results are shown below:
monosubstituted quaternary ammonium bases1H NMR(400M，TMS):δ1.18(m，3H)，1.89(s，3H)，2.22-2.50(m，10H)，2.31(s，3H)，3.15-3.61(m，1H)，5.6(s，1H)。
Disubstituted quaternary ammonium bases1H NMR(400M，TMS):δ1.06(m，6H)，2.25-2.31(m，8H)，2.69(s，6H)，3.36-4.30(m，6H)，5.6(s，2H)。
Then, the reaction product is subjected to quantitative analysis by reverse phase liquid chromatography, and the result shows that: the mass content of the mono-substituted quaternary ammonium base is 9.1 percent, the mass content of the di-substituted quaternary ammonium base is 88.6 percent, and the mass content of the byproduct is 2.3 percent.
Example 8
The molar ratio of the 1, 4-dimethylpiperazine to the water to the propylene oxide is adjusted to 1:4: 2.5. Under Ar protection, propylene oxide (8.8ml) was added dropwise to 1, 4-dimethylpiperazine (6.8ml) and water (3.6ml) over 0.5 h. And then continuously stirring for 4 hours at room temperature to obtain a reaction product 8 #. And qualitatively analyzing the synthesized reaction product by adopting nuclear magnetism. The nuclear magnetic results are shown below:
disubstituted quaternary ammonium bases1H NMR(400M，TMS):δ1.06(m，6H)，2.25-2.31(m，8H)，2.69(s，6H)，3.36-4.30(m，6H)，5.6(s，2H)。
Then, the reaction product is subjected to quantitative analysis by reverse phase liquid chromatography, and the result shows that: the mass content of the mono-substituted quaternary ammonium base is 0 percent, the mass content of the di-substituted quaternary ammonium base is 98.3 percent, and the mass content of a byproduct is 1.7 percent.
Trimers of PDI were prepared using the reaction products obtained in examples 1 to 8 above as catalysts, respectively, using PDI as a substrate, as shown in examples 9 to 12 below:
example 9
Weighing PDI (20g) monomer, adding the monomer into a reaction bottle, heating to 90 ℃ under the protection of Ar, preheating for one hour, controlling the temperature to be 80 ℃, dropwise adding 600ppm of uniformly mixed 1# catalyst solution (diluted by methanol with the dilution degree of 10%), controlling the dropwise adding speed to be 1 drop/15 s, and controlling the floating range of the reaction temperature to be not more than +/-1 ℃. When the-NCO value in the reaction liquid reaches about 40 wt%, dibutyl phosphate twice the molar amount of the initial catalyst is added immediately to terminate the reaction.
Example 10
Weighing PDI (20g) monomer, adding the monomer into a reaction bottle, heating to 90 ℃ under the protection of Ar, preheating for one hour, controlling the temperature to be 80 ℃, dropwise adding 600ppm of uniformly mixed 2# catalyst solution (diluted by methanol with the dilution degree of 10%), controlling the dropwise adding speed to be 1 drop/15 s, and controlling the floating range of the reaction temperature to be not more than +/-1 ℃. When the-NCO value in the reaction liquid reaches about 40 wt%, dibutyl phosphate twice the molar amount of the initial catalyst is added immediately to terminate the reaction.
Example 11
Weighing PDI (20g) monomer, adding the monomer into a reaction bottle, heating to 90 ℃ under the protection of Ar, preheating for one hour, controlling the temperature to be 80 ℃, dropwise adding 600ppm of uniformly mixed 3# catalyst solution (diluted by methanol with the dilution degree of 10%), controlling the dropwise adding speed to be 1 drop/15 s, and controlling the floating range of the reaction temperature to be not more than +/-1 ℃. When the-NCO value in the reaction liquid reaches about 40 wt%, dibutyl phosphate with twice molar weight of the initial catalyst is added immediately to terminate the reaction
Example 12
Weighing PDI (20g) monomer, adding the monomer into a reaction bottle, heating to 90 ℃ under the protection of Ar, preheating for one hour, controlling the temperature to be 80 ℃, dropwise adding 600ppm of uniformly mixed 4# catalyst solution (diluted by methanol with the dilution degree of 10%), controlling the dropwise adding speed to be 1 drop/15 s, and controlling the floating range of the reaction temperature to be not more than +/-1 ℃. When the-NCO value in the reaction liquid reaches about 40 wt%, dibutyl phosphate twice the molar amount of the initial catalyst is added immediately to terminate the reaction.
Example 13
Weighing PDI (20g) monomer, adding the monomer into a reaction bottle, heating to 90 ℃ under the protection of Ar, preheating for one hour, controlling the temperature to be 80 ℃, dropwise adding 600ppm of 5# catalyst solution which is uniformly mixed, (diluting with methanol, the dilution is 10%), the dropwise adding speed is 1 drop/15 s, and the floating range of the reaction temperature is controlled not to exceed +/-1 ℃. When the-NCO value in the reaction liquid reaches about 40 wt%, dibutyl phosphate twice the molar amount of the initial catalyst is added immediately to terminate the reaction.
Example 14
Weighing PDI (20g) monomer, adding the monomer into a reaction bottle, heating to 90 ℃ under the protection of Ar, preheating for one hour, controlling the temperature to be 80 ℃, dropwise adding 600ppm of uniformly mixed 6# catalyst solution (diluted by methanol with the dilution degree of 10%), controlling the dropwise adding speed to be 1 drop/15 s, and controlling the floating range of the reaction temperature to be not more than +/-1 ℃. When the-NCO value in the reaction liquid reaches about 40 wt%, dibutyl phosphate twice the molar amount of the initial catalyst is added immediately to terminate the reaction.
Example 15
Weighing PDI (20g) monomer, adding the monomer into a reaction bottle, heating to 90 ℃ under the protection of Ar, preheating for one hour, controlling the temperature to be 80 ℃, dropwise adding 600ppm of the uniformly mixed 7# catalyst solution (diluted by methanol with the dilution degree of 10%), controlling the dropwise adding speed to be 1 drop/15 s, and controlling the floating range of the reaction temperature to be not more than +/-1 ℃. When the-NCO value in the reaction liquid reaches about 40 wt%, dibutyl phosphate twice the molar amount of the initial catalyst is added immediately to terminate the reaction.
Example 16
Weighing PDI (20g) monomer, adding the monomer into a reaction bottle, heating to 90 ℃ under the protection of Ar, preheating for one hour, controlling the temperature to be 80 ℃, dropwise adding 600ppm of uniformly mixed 8# catalyst solution (diluted by methanol with the dilution degree of 10%), controlling the dropwise adding speed to be 1 drop/15 s, and controlling the floating range of the reaction temperature to be not more than +/-1 ℃. When the-NCO value in the reaction liquid reaches about 40 wt%, dibutyl phosphate twice the molar amount of the initial catalyst is added immediately to terminate the reaction.
Comparative example
Weighing PDI (20g) monomer, adding the monomer into a reaction bottle, heating to 90 ℃ under the protection of Ar, preheating for one hour, controlling the temperature to be stable at 80 ℃, dropwise adding 600ppm of uniformly mixed 2-hydroxypropyl trimethyl ammonium caprylate (9#) solution, (diluting with methanol, the dilution degree is 10%), the dropwise adding speed is 1 drop/15 s, and the floating range of the reaction temperature is controlled not to exceed +/-1 ℃. When the-NCO value in the reaction liquid reaches about 40 wt%, dibutyl phosphate twice the molar amount of the initial catalyst is added immediately to terminate the reaction.
The invention determines the-NCO content according to a hydrochloric acid-di-n-butylamine titration method. The invention tests the color number of the product according to the method of GB/T3143-1982. The present invention uses gel permeation chromatography (Agilent-1260, column Plgel MIXED-C, mobile phase tetrahydrofuran) to determine the polymer content. The reagents used in the synthesis of the catalysts of the present invention were purchased from aladdin and, if not specifically indicated, were all analytical grade. The amounts of 1, 4-dimethylpiperazine, water and propylene oxide used in examples 1 to 8 are shown in Table 1; the polymerization products obtained in examples 9 to 16 and comparative example were subjected to NCO content and color measurement, and the results are shown in Table 2.
TABLE 1 Experimental data Table for examples 1-8
TABLE 2 Experimental data Table for examples 9-16 and comparative examples
From tables 1, 2, examples 2-4 the catalysts were prepared using 1, 4-dimethylpiperazine to water and propylene oxide ratios for each of the 1:2:1.4, the reaction time is respectively 4, 6 and 9, the catalysts 2#, 3# and 4# prepared in the examples 2-4 are respectively used in the examples 9-11 to participate in PDI polymerization reaction, when the specific gravity of-NCO in the reaction solution reaches about 40 wt%, the content of the generated tripolymer is higher, and catalyst poison is added into the reaction system to quench the catalyst and terminate the polymerization reaction. The time for completing the polymerization reaction in examples 9-11 was 1h, 1.7h, and 1h, and the color numbers of the PDI trimers were 85, 40, and 90, respectively, and the above data indicate that when the catalyst was prepared in the same substrate ratio, the catalyst activity was higher at the preparation times of 4h and 9h, but the color number of the PDI trimer was higher, i.e., the PDI trimer was yellow, the product quality was lower, and the catalyst preparation time of 6h had a much higher quality than the catalysts preparation times of 4h and 9h, although the activity was lower.
The time taken for preparing the catalysts from table 1, table 2, example 2, and examples 5 to 6 was 4 hours and the specific gravities of 1, 4-dimethylpiperazine and water in the reaction solutions were also the same, the specific gravities of the propylene oxide in the reaction solutions were sequentially increased, and when the prepared catalysts 2#, 5#, and 6# were applied to PDI polymerization reactions, the time taken for completing the polymerization reactions in examples 9, 12, and 13 were 1 hour, 1.5 hours, and 4.2 hours, respectively, and the activity of the prepared catalysts was decreased as the ratio of propylene oxide in the reaction system of the catalyst preparation was increased. In example 7, the ratio of water in the reaction solution was increased to make 7# compared to example 6, and by applying 7# to example 14, the data showed that the time for completion of the polymerization reaction in example 14 was much less than 4.2 hours in example 13, and further showed that the increase of specific gravity of water in the reaction system during the preparation of the catalyst increased the activity of the catalyst.
By contrast, the catalyst 3# produced by the reaction under the conditions of example 3 has the best catalytic reaction effect when applied to the reaction of example 10; the time for completing the polymerization reaction in example 10 was 1.7h, and the color number was 40; the polymerization reaction in the comparative example was completed for 4 hours, and the color number was 40; compared with the comparative example, the time for completing the polymerization reaction of the example 10 is far shorter than that of the comparative example under the premise of ensuring the quality of the polymerization product. In addition, gel permeation chromatography experiments were also performed on the PDI trimer produced under the conditions of this example 10 and the PDI trimer on the market, as shown in fig. 1, in which the highest peak of the two curves is the peak of the PDI trimer, and the remaining peaks are the peaks of the multimer, and the areas of the peaks correspond to the content of the substance; from the GPC results, it can be seen that the trimer content in the present invention (69.1%) was similar to the commercial PDI trimer content (75.9%). In conclusion, the cyclic piperazine skeleton is introduced into the catalyst, so that the reaction between small molecules, such as dimerization and trimerization of the isocyanate substrate, and the reaction between the isocyanate substrate monomer and a small amount of alcohol in the system are promoted, and the reaction between macromolecules and the small molecules or the macromolecules, such as the reaction between the generated polymer and the small amount of alcohol in the system and the polymerization of the isocyanate substrate, are inhibited, so that the purposes of high monomer conversion rate and the tripolymer accounting for the main component are achieved.
In light of the foregoing description of preferred embodiments in accordance with the invention, it is to be understood that numerous changes and modifications may be made by those skilled in the art without departing from the scope of the invention. The technical scope of the present invention is not limited to the contents of the specification, and must be determined according to the scope of the claims.
Claims (10)
1. A catalyst, characterized in that the structural formula of the catalyst is as follows:
2. the catalyst of claim 1 wherein R is represented by the general structural formula1Is an alkyl group having 1 to 20 carbon atoms.
3. The catalyst of claim 1 wherein R is represented by the general structural formula2Is hydroxyalkyl having 1 to 20 carbon atoms.
4. The catalyst of claim 1, wherein the starting materials for the catalyst comprise an aliphatic substituted derivative of piperazine, water, and an alkylene oxide.
5. A catalyst as claimed in claim 4, wherein the molar ratio of the aliphatic substituted derivative of piperazine, water and alkylene oxide is 1 (1.5-4) to (1.0-2.5).
6. A catalyst as claimed in claim 4, wherein said aliphatic substituted derivative of piperazine comprises 1, 4-dimethylpiperazine; the alkylene oxide comprises propylene oxide.
7. A method of preparing a catalyst, comprising:
under the protection of Ar atmosphere, dripping propylene oxide into an aqueous solution of the aliphatic substituted derivative of piperazine;
stirring at room temperature, and reacting for 4-9 h;
and after the reaction is finished, taking the lower layer solution, and performing rotary evaporation to obtain the piperazine quaternary ammonium base compound, namely the catalyst.
8. The method of claim 7, wherein the catalyst is prepared according to the reaction equation
9. A method for polymerizing isocyanates, comprising:
under the protection of inert gas, carrying out polymerization reaction on isocyanate raw materials under the catalysis of the catalyst of any one of claims 1 to 6; when the-NCO content in the reaction liquid reached 5 to 80% by weight based on the weight of the reaction liquid, the polymerization reaction was terminated.
10. The method of claim 9, wherein the polymerization temperature is 10-100 ℃; the amount of the catalyst is 10-800ppm of the amount of isocyanate.
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| CN115246793A (en) * | 2022-07-28 | 2022-10-28 | 山东新和成精化科技有限公司 | Preparation method of diisocyanate trimer, catalyst and preparation method thereof |
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