CN109761903B - Preparation method of polyisocyanate containing uretdione group - Google Patents
Preparation method of polyisocyanate containing uretdione group Download PDFInfo
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Abstract
The invention discloses a preparation method of polyisocyanate with uretdione groups, wherein diisocyanate monomers with the total mass M in a reaction system are subjected to polymerization reaction under the catalysis of tertiary phosphine to prepare polyisocyanate containing the uretdione groups, the reaction is terminated when the ratio of the consumed mass M1 of the diisocyanate monomers in the system to the total mass M of the diisocyanate monomers reaches a required ratio, unreacted diisocyanate monomers in the system are removed and reused in the system, and the content of phosphine oxide in the unreacted diisocyanate monomers is controlled not to exceed 1wt%, preferably not to exceed 0.5wt% before the unreacted diisocyanate monomers removed from the system are reused in the system. The uretdione isocyanate homopolymer prepared by the method has low color number and good storage stability.
Description
Technical Field
The invention belongs to the technical field of isocyanate preparation, and particularly relates to a preparation method of uretdione polyisocyanate.
Background
Isocyanate homopolymers containing uretdione groups have a very low viscosity and are therefore excellent for use as crosslinker components in low solvent, high solids coating compositions.
At present, processes for preparing polyisocyanates having uretdione groups from aliphatic or cycloaliphatic diisocyanate monomers in the presence of catalysts are known, the advantages and disadvantages of various dimerization catalysts or catalyst systems being thoroughly discussed in the literature (cf., for example, J.Prakt. chem.336(1994)185-200, EP-A569804, EP-A572995, EP-A645411, EP-A780377, U.S. Pat. No. 3,973,403, WO 97/45399 and WO 99/07765).
US 8134014 discloses a process for preparing polyisocyanates containing uretdione groups using fused ring substituted aminopyridines as catalysts, which produces isocyanate homopolymers having a high content of uretdione groups and no particular limitation on the isocyanates to be used, but pyridine compounds are liable to cause coloration of the products.
DE-A3030513 discloses the preparation of tris (dialkylamino) phosphines with polyisocyanates having a high uretdione content as oligomerization catalysts, alone or in combination with cocatalysts (DE-A-3437635). However, their technical use is threatened by phosphorus oxides with a high potential carcinogenic risk, such as, for example, hexamethylphosphoric triamide.
At present, uretdione polyisocyanate prepared by catalysis of tertiary phosphine has the defects of high product color number and easy turbidity phenomenon when the product is stored at low temperature (less than 0 ℃).
Disclosure of Invention
In view of the above, the present invention provides a method for preparing a polyisocyanate containing uretdione groups, which can obtain a polyisocyanate having high long-term low-temperature storage stability by controlling the content of phosphine oxide.
In order to realize the purpose of the invention, the invention adopts the following technical scheme:
the invention provides a preparation method of polyisocyanate containing uretdione groups, wherein diisocyanate monomers with the total mass M in a reaction system are subjected to polymerization reaction under the catalysis of tertiary phosphine to prepare the polyisocyanate containing the uretdione groups, the reaction is terminated when the ratio of the consumed mass M1 of the diisocyanate monomers in the system to the total mass M of the diisocyanate monomers reaches a required ratio, unreacted diisocyanate monomers in the system are removed and reused in the system, and the content of phosphine oxide in the unreacted diisocyanate monomers is controlled not to exceed 1wt%, preferably not to exceed 0.5wt% before the unreacted diisocyanate monomers removed from the system are reused in the system.
Compared with the polyisocyanate containing the uretdione group prepared by the dimerization method in the prior art, the preparation method provided by the invention has the advantage that the storage stability of the prepared product is greatly improved by controlling the content of phosphine oxide in the recycling part not to exceed 1wt% of the unreacted diisocyanate monomer in the recycling part.
In some embodiments, the reaction is terminated when the mass M1 consumed by the diisocyanate monomers in the system reaches a value of 10% to 80%, preferably 30% to 70%, of the total mass M of the diisocyanate monomers in the system (i.e., M1/M).
In the invention, the tertiary phosphine has the following structure:
wherein R is1、R2、R3Independently of one another, are selected from aliphatic substituents or aromatic substituents. In some embodiments, the aliphatic substituent is selected from the group consisting of a straight chain alkyl, branched chain alkyl, or cyclic alkyl, and the aromatic substituent is preferably C7-C10Aromatic substituents of (a), such as benzyl; said aliphatic substituent is preferably C1-C10Straight chain alkyl group of (1), C3-C10Branched alkyl of C3-C10Cycloalkyl groups of (a); the aromatic substituent is preferably benzyl. In some preferred embodiments, the tertiary phosphine is selected from trimethyl phosphine, triethyl phosphine, tripropyl phosphine, triisopropyl phosphine, tri-n-butyl phosphine, tri-tert-butyl phosphine, dicyclopentyl butyl phosphine, tripentyl phosphine, tricyclopentyl phosphine, trihexyl phosphine, tribenzyl phosphine, benzyl dimethyl phosphine, tricyclohexyl phosphine, tri-n-octyl phosphine. In some preferred embodiments, the tertiary phosphine is used in an amount of 0.01 to 5wt%, preferably 0.1 to 3wt%, such as 0.3 wt%, 0.5wt% of the diisocyanate monomer.
The catalyst tertiary phosphine used in the invention is a nucleophilic reagent, for example, trioctylphosphine is a relatively weak base, the solvent must be strictly deoxidized when in use, the solvent needs to be protected by inert gas, and severe oxidation reaction can occur to generate trioctylphosphine oxide if exposed to air. The inventor researches and discovers that the tertiary phosphine serving as a catalyst can cause the phosphine oxide content in a system to increase when the tertiary phosphine is used, and the phosphine oxide content can even be more than 1 percent, if the tertiary phosphine is not removed, the phosphine oxide content in the product is high, and further the stability of the product in long-term low-temperature storage is influenced.
In the preparation process of the present invention, a catalyst poison may be added to the system to terminate the reaction. In some embodiments, the catalyst poison used is dimethyl sulfate, phosphate, acid chloride, sulfur or peroxide, the amount of catalyst poison required for reaction termination depends on the amount of catalyst used in the system, and generally the amount of terminator is equimolar to the amount of catalyst used in the system, and 60 to 90% equivalent of catalyst poison to the amount of catalyst used in the system is sufficient to terminate the reaction in view of various losses of catalyst during the reaction.
In the present invention, unreacted diisocyanate monomer in the reaction system is removed after termination of the reaction and the phosphine oxide content in the portion of the removed system is determined, and the phosphine oxide content in the portion of the removed system can be detected by gas chromatography, as is well known to those skilled in the art. When the content of the phosphine oxide is measured to be not more than 1wt percent (namely less than or equal to), the phosphine oxide can be directly recycled to the system to supplement the monomer and the catalyst and then the reaction is continued; when the phosphine oxide content in the part of the removal system is more than 1wt%, the phosphine oxide can be subjected to vacuum distillation, extraction and/or rectification treatment to remove phosphine oxide components contained in the phosphine oxide, and then the phosphine oxide is recycled to the system for subsequent reaction. In some preferred embodiments, the reduced pressure distillation or rectification to remove the phosphine oxide content of the removed portion may be carried out at a temperature of 130-150 ℃ and an absolute pressure of 0.5-3 kPa.
In the preparation process of the present invention, the polymerization temperature is 0 to 150 ℃ and preferably 25 to 80 ℃.
In the preparation process, the diisocyanate monomer is selected from one or more of Hexamethylene Diisocyanate (HDI), 2-methylpentane-1, 5-diisocyanate, isophorone diisocyanate (IPDI), 1, 3-bis (isocyanatomethyl) cyclohexane, 1, 4-bis (isocyanatomethyl) cyclohexane, norbornane dimethylene isocyanate, 2, 4-trimethylhexamethylene diisocyanate, 2,4, 4-trimethylhexamethylene diisocyanate and 4,4' -dicyclohexylmethane diisocyanate.
In the preparation process of the present invention, a suitable cocatalyst may be used in the process of the present invention together with the catalyst. Suitable cocatalysts include in particular low molecular weight monovalent or polyvalent fatty alcohols, preferably alcohols having a relative molecular weight of from 32 to 200. The alcohol compound includes one or more of methanol, ethanol, n-propanol, isopropanol, n-butanol, n-hexanol, 2-ethyl-1-hexanol, 1-methoxy-2-propanol, ethylene glycol, propylene glycol, isomeric butanediol, hexanediol or octanediols, diethylene glycol, dipropylene glycol, 2-ethyl-1, 3-hexanediol, 2, 4-trimethylpentanediol, glycerol, or trimethylolpropane, and the cocatalyst is used in an amount of 0 to 5wt%, preferably 0.01 to 3wt%, based on the total mass M of the diisocyanate monomer in the reaction system.
In addition, stabilizers and additives which are customary in polyisocyanate chemistry, such as antioxidants, for example, sterically hindered phenols (2, 6-di-tert-butylphenol, 4-methyl-2, 6-di-tert-butylphenol), light stabilizers, for example, HA L S amine, triazoles, etc., may be added at any desired point in the process of the present invention.
Compared with the prior art, the invention has the following advantages:
according to the preparation method disclosed by the invention, on the basis of the prior art, the content of phosphine oxide in the unreacted monomer recycled to the system is controlled to be not more than 1wt%, so that the obtained polyisocyanate containing the uretdione group is not easy to generate a turbid phenomenon during low-temperature storage, and the stability of the polyisocyanate during low-temperature storage is improved.
Detailed Description
The technical solution and the effects of the present invention are further described by the following specific examples. It should be understood that the following examples are only illustrative of the present invention and are not intended to limit the scope of the present invention. Simple modifications of the invention applying the inventive concept are within the scope of the invention as claimed.
The following test methods were used in the examples of the invention:
(1) determination of reaction conversion:
isocyanate raw material was quantified by using a Gel chromatography (L C-20AD/RID-10A, column MZ-Gel SD plus10E3A,5 μm (8.0 × 300mm), MZ-Gel SDplus 500A 5 μm (8.0 × 300mm), MZ-Gel SDplus 100A5 μm (8.0 × 300mm) in series, a mobile phase tetrahydrofuran, a flow rate of 1.0m L/min, an analysis time of 40min, a column temperature of 35 ℃ C.), and the areas of the polymer and the monomer in the system were measured by an area normalization method, and a reaction conversion (%) < S (monomer peak area)/S (sum of component peak areas) < 100%.
(2) Method for measuring content of uretdione group and NCO group in isocyanate: the sample concentration was 50% (CDCl) using 13C-NMR and Bruker 400MHz instrument3Solution) at a frequency of 100MHz, to 77.0ppm dcl3As a reference for displacement.
(3) The phosphine oxide content is determined by gas chromatography, using gas chromatography conditions known in the art as follows:
chromatographic column Rxi-17+ (30m 0.25mm 0.25 μm), sample introduction amount of 1 μ L, split ratio of 30:1, injection port temperature of 240 deg.C, carrier gas (N)2) The flow rate is 1.0m L/min, the temperature is programmed to be increased to 80 ℃ for 2min and increased to 260 ℃ at the rate of 10 ℃/min for 10min, the temperature of the FID detector is 280 ℃, the hydrogen flow rate is 40m L/min, and the air flow rate is 400m L/min.
(4) The viscosity measurement method comprises the following steps: dynamic mechanical viscosity was measured using a Brookfield DV-I Prime viscometer using a spindle S21 at 25 ℃.
In the following examples, the raw material information used is as follows:
hexamethylene diisocyanate: wanhua chemistry, purity > 99%;
2-ethyl-1, 3-hexanediol: the purity of the Aladdin reagent is more than 99 percent;
tri-n-octylphosphine: sigma reagent with purity > 95%;
tricyclohexylphosphine: the purity of the Aladdin reagent is 96 percent;
t-butyl hydroperoxide: an aladine reagent, with a purity of 50%;
dimethyl sulfate: aladdin reagent, purity 98.5%.
In the case where no specific description is given in the following examples and comparative examples, the reaction solution is kept under a dry nitrogen atmosphere until the catalyst is added and the whole reaction is carried out.
Example 1
Hexamethylene diisocyanate (HDI for short) with the total mass M of 1000g is stirred at 50 ℃, 2-ethyl-1, 3-hexanediol and 3g tri-n-octylphosphine are sequentially added, and the proportion of the consumption mass M1 of HDI in the reaction system to the total mass M of the added HDI is quantitatively monitored through gel chromatography;
when the mass M1 of HDI consumed in the system accounted for 50% of the total mass M of HDI added, 1.46g of t-butyl hydroperoxide was added and heated for 1 hour to 80 ℃ to terminate the reaction, unreacted HDI in the reaction system was removed by two-stage thin-layer distillation at a temperature of 150 ℃ and a pressure of 1mbar, and it was determined that the content of phosphine oxide in the removed portion accounted for 0.15% by weight of the content of unreacted HDI therein; then, recycling the removed part into the system, and supplementing fresh 500g of HDI and 3g of tri-n-octylphosphine for continuous reaction;
when the above step was repeated 18 times, the phosphine oxide content in the removed portion was detected to be 0.98 wt% based on the unreacted HDI content therein; when the above was repeated 19 times, the content of phosphine oxide in the removed portion was detected to be 1.2 wt% based on the content of unreacted HDI therein;
subjecting a part of the unreacted monomers removed for the 19 th time to reduced pressure distillation treatment at a temperature of 130 ℃ and a pressure of 0.5kPa for 1h to remove phosphine oxides contained therein, and when the content of the phosphine oxides therein was measured to be 0.3 wt%, recycling the treated part to the system, and supplementing 550g (distillation loss 50g) of HDI and 3g of tri-n-octylphosphine to continue the reaction;
when the mass of HDI consumed was 50% of the total mass M of HDI in the system, 1.46g of t-butyl hydroperoxide was added and heated for 1 hour to 80 ℃ to terminate the reaction, and unreacted HDI in the reaction system was removed by two-stage thin-layer distillation at a temperature of 150 ℃ and a pressure of 1mbar to obtain a polyisocyanate product containing uretdione groups.
The properties and the radical content of the polyisocyanate product obtained in example 1 were determined as follows:
viscosity: 162mPas/25 ℃;
content of NCO groups: 21.8 percent;
uretdione: 40mol percent.
Example 2
Hexamethylene diisocyanate (HDI for short) with the total mass M of 1000g is stirred at 50 ℃, 2-ethyl-1, 3-hexanediol and 3g tri-n-octylphosphine are sequentially added, and the proportion of the consumption mass M1 of HDI in the reaction system to the total mass M of the added HDI is quantitatively monitored through gel chromatography;
when the mass M1 of HDI consumed in the system accounted for 50% of the total mass M of HDI added, the reaction was terminated by adding 1.02g of dimethyl sulfate and heating for 1 hour to 80 ℃, unreacted HDI in the reaction system was removed by two-stage thin-layer distillation at a temperature of 150 ℃ and a pressure of 1mbar, and the content of phosphine oxide in the removed portion was measured to account for 0.08% by weight of the content of unreacted HDI therein; then, recycling the removed part into the system, and supplementing fresh 500g of HDI and 3g of tri-n-octylphosphine for continuous reaction;
repeating the steps for 20 times, tracking and evaluating the content of phosphine oxide in the recycled monomer for each time, and when the recycled monomer is recycled for 20 times, the content of phosphine oxide in the recycled HDI is 0.87 wt%, thus preparing the polyisocyanate product containing the uretdione group.
The properties and the radical content of the polyisocyanate product obtained in example 2 were determined as follows:
viscosity: 168mPas/25 ℃;
content of NCO groups: 21.75 percent;
uretdione: 41mol percent.
Example 3
Hexamethylene diisocyanate (HDI for short) with the total mass M of 1000g is stirred at 50 ℃, 2-ethyl-1, 3-hexanediol and 3g of tricyclohexylphosphine are added in sequence, and the proportion of the mass M1 consumed by HDI in the reaction system in the total mass M of the added HDI is quantitatively monitored through gel chromatography;
when the mass M1 of HDI consumed in the system accounted for 50% of the total mass M of HDI added, 1.93g of t-butyl hydroperoxide was added and heated for 1 hour to 80 ℃ to terminate the reaction, unreacted HDI in the reaction system was removed by two-stage thin-layer distillation at a temperature of 150 ℃ and a pressure of 1mbar, and it was determined that the content of phosphine oxide in the removed portion accounted for 0.18% by weight of the content of unreacted HDI therein; then, recycling the removed part into the system, and supplementing fresh 500g of HDI and 3g of tricyclohexyl phosphine for continuous reaction;
when the above step was repeated 19 times, the phosphine oxide content in the removed portion was detected to be 0.98 wt% based on the unreacted HDI content therein; when the waste water is recycled for 20 times, the phosphine oxide content in the removal part is 1.5 wt%;
subjecting the 20 th-time removed part of the unreacted monomers to reduced pressure distillation treatment at the temperature of 130 ℃ and the pressure of 0.5kPa for 1h to remove phosphine oxide contained in the unreacted monomers, and when the content of the phosphine oxide is measured to be 0.38 wt%, recycling the treated part into the system, and supplementing fresh 542g (distillation loss 42g) of HDI and 3g of tricyclohexylphosphine to continue the reaction;
when the mass of HDI consumed was 50% of the total mass M of HDI in the system, 1.46g of t-butyl hydroperoxide was added and heated for 1 hour to 80 ℃ to terminate the reaction, and unreacted HDI in the reaction system was removed by two-stage thin-layer distillation at a temperature of 150 ℃ and a pressure of 1mbar to obtain a polyisocyanate product containing uretdione groups.
The properties and the radical content of the polyisocyanate product obtained in example 3 were determined as follows:
viscosity: 165mPas/25 ℃;
content of NCO groups: 21.78 percent;
uretdione: 40mol percent.
Comparative example 1
Stirring hexamethylene diisocyanate (HDI for short) with the total mass M of 1000g at the temperature of 50 ℃, sequentially adding 20g of 2-ethyl-1, 3-hexanediol and 3g of tri-n-octylphosphine for reaction, and quantitatively monitoring the proportion of the consumed mass M1 of the HDI in the reaction system in the total mass M of the HDI by gel chromatography;
when the mass M1 of HDI consumed in the system accounted for 50% of the total mass M of HDI added, 1.46g of t-butyl hydroperoxide was added and heated for 1 hour to 80 ℃ to terminate the reaction, unreacted HDI in the reaction system was removed by two-stage thin-layer distillation at a temperature of 150 ℃ and a pressure of 1mbar, and it was determined that the content of phosphine oxide in the removed portion accounted for 0.15% by weight of the content of unreacted HDI therein; then, recycling the removed part into a system, and supplementing fresh 500g of HDI and 3g of tri-n-octylphosphine for continuous reaction; and repeating the steps for 20 times, tracking and evaluating the content of phosphine oxide in the recycled monomer for each time, wherein the content of phosphine oxide in the recycled unreacted HDI is finally stabilized at 1.2 wt%, and obtaining a polyisocyanate product containing a uretdione group for the 21 st time.
The properties and the radical content of the polyisocyanate product obtained in comparative example 1 were determined as follows:
viscosity: 178mPas/25 ℃;
content of NCO groups: 21.8 percent;
uretdione: 38mol percent.
The polyisocyanate products containing uretdione groups obtained in the above examples 1 and 2 and comparative example 1 were stored in an environment of-10 ℃ and observed with follow-up observation every other week (12 weeks for follow-up observation), and the results are shown in the following Table 1:
TABLE 1
| Serial number | Phosphine oxide content in monomer (wt%) | Turbid time (week) |
| Example 1 | 0.3 | No turbidity |
| Example 2 | 0.87 | No turbidity |
| Example 3 | 0.38 | No turbidity |
| Comparative example 1 | 1.2 | 5 |
In the above embodiment, the content of phosphine oxide in the removed unreacted monomer is controlled to be less than 1wt%, so that the obtained polyisocyanate product containing uretdione groups does not generate turbidity when stored in an environment at-10 ℃, and the low-temperature stability of the uretdione polyisocyanate product prepared by catalysis of tertiary phosphine is improved.
Claims (18)
1. A preparation method of polyisocyanate containing uretdione groups is characterized in that diisocyanate monomers with the total mass M in a reaction system are subjected to polymerization reaction under the catalysis of tertiary phosphine to prepare polyisocyanate containing the uretdione groups, the reaction is terminated when the ratio of the consumed mass M1 of the diisocyanate monomers in the system to the total mass M of the diisocyanate monomers reaches a required ratio, unreacted diisocyanate monomers in the system are removed and are reused in the system, and the content of phosphine oxide in the unreacted diisocyanate monomers is controlled to be not more than 1wt% before the unreacted diisocyanate monomers removed from the system are reused in the system.
2. The method of claim 1, wherein the content of phosphine oxide in the unreacted diisocyanate monomer is not more than 0.5 wt%.
3. The process according to claim 1, wherein the reaction is terminated when the mass M1 of the diisocyanate monomer consumed in the system is 10 to 80% of the total mass M of the diisocyanate monomer in the system.
4. The process according to claim 1, wherein the reaction is terminated when the mass M1 of the diisocyanate monomer consumed in the system is 30 to 70% of the total mass M of the diisocyanate monomer in the system.
5. The method of claim 1, wherein said tertiary phosphine has the structure:
wherein R is1、R2、R3Independently of one another, are selected from aliphatic substituents or aromatic substituents.
6. The method according to claim 5, wherein the aliphatic substituent is selected from the group consisting of a linear alkyl group, a branched alkyl group and a cyclic alkyl group, and the aromatic substituent is selected from the group consisting of C7-C10The aromatic substituent(s) of (1).
7. The method of claim 5, wherein the aliphatic substituent is selected from C1-C10Straight chain alkyl group of (1), C3-C10Branched alkyl of C3-C10Cycloalkyl groups of (a);
the aromatic substituent is selected from benzyl.
8. The process according to claim 5, wherein the aliphatic substituent is selected from the group consisting of n-butyl, tert-butyl, n-octyl and cyclohexyl.
9. The method according to claim 1, wherein the tertiary phosphine is used in an amount of 0.01 to 5wt% based on the amount of the diisocyanate monomer.
10. The method according to claim 1, wherein the tertiary phosphine is used in an amount of 0.1 to 3wt% based on the amount of the diisocyanate monomer.
11. The production method according to claim 1, wherein before the unreacted diisocyanate monomer is recycled to the system, it is subjected to distillation under reduced pressure, extraction and/or rectification to remove phosphine oxide contained therein and control the content of phosphine oxide to not more than 1% by weight.
12. The production process according to claim 11, wherein the temperature of the vacuum distillation or the rectification is 130 ℃ to 150 ℃ and the absolute pressure is 0.5 to 3 kPa.
13. The method according to claim 1, wherein the polymerization temperature is 0 to 150 ℃.
14. The method according to claim 1, wherein the polymerization temperature is 25 to 80 ℃.
15. The method of claim 1, wherein the diisocyanate monomer is selected from one or more of hexamethylene diisocyanate, 2-methylpentane-1, 5-diisocyanate, isophorone diisocyanate, 1, 3-bis (isocyanatomethyl) cyclohexane, 1, 4-bis (isocyanatomethyl) cyclohexane, norbornane dimethylene isocyanate, 2, 4-trimethylhexamethylene diisocyanate, 2,4, 4-trimethylhexamethylene diisocyanate or 4,4' -dicyclohexylmethane diisocyanate.
16. The preparation method of claim 1, wherein the system further comprises a co-catalyst, wherein the co-catalyst is selected from alcohol compounds, and the amount of the co-catalyst is 0-5wt% of the total mass M of the diisocyanate monomer in the reaction system.
17. The preparation method according to claim 1, characterized in that the system further comprises a cocatalyst, wherein the cocatalyst is selected from alcohol compounds with a relative molecular weight of 32-200, and the amount of the cocatalyst is 0.01-3wt% of the total mass M of the diisocyanate monomer in the reaction system.
18. The method of claim 17, wherein the alcohol compound comprises one or more of methanol, ethanol, n-propanol, isopropanol, n-butanol, n-hexanol, 2-ethyl-1-hexanol, 1-methoxy-2-propanol, ethylene glycol, propylene glycol, isomeric butylene glycols, diethylene glycol, dipropylene glycol, 2-ethyl-1, 3-hexanediol, 2, 4-trimethylpentanediol, glycerol, or trimethylolpropane.
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| CN110305294B (en) * | 2019-07-15 | 2021-04-20 | 万华化学集团股份有限公司 | Preparation method of storage-stable polyisocyanate containing uretdione group |
| CN111040101B (en) * | 2019-12-23 | 2021-09-07 | 万华化学集团股份有限公司 | Polyisocyanate having stable color number and containing uretdione group and preparation method thereof |
| CN111072917B (en) * | 2020-01-02 | 2021-06-29 | 万华化学集团股份有限公司 | Polyisocyanate composition with stable storage and preparation method thereof |
| CN111303373B (en) * | 2020-02-25 | 2022-07-12 | 万华化学集团股份有限公司 | Low-chroma allophanate composition and preparation method and application thereof |
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| DE3432081A1 (en) * | 1984-08-31 | 1986-03-06 | Bayer Ag, 5090 Leverkusen | METHOD FOR THE PRODUCTION OF OLIGOMER POLYISOCYANATES AND THEIR USE IN THE PRODUCTION OF POLYURETHANE PLASTICS |
| DE3900053A1 (en) * | 1989-01-03 | 1990-07-12 | Bayer Ag | PROCESS FOR THE PREPARATION OF POLYISOCYANATES USING URETDION AND ISOCYANATE GROUPS, THE POLYISOCYANATES AVAILABLE FOR THIS PROCESS, AND THEIR USE IN TWO-COMPONENT POLYURETHANE VARNISHES |
| DE10035013A1 (en) * | 2000-07-19 | 2002-01-31 | Bayer Ag | Process for the preparation of uretdione polyisocyanates with improved monomer stability |
| EP1426393A3 (en) * | 2002-12-05 | 2009-11-04 | Bayer MaterialScience AG | Low monomer urethdione-groups containing polyisocyanates |
| JP4143825B2 (en) * | 2003-01-28 | 2008-09-03 | 三菱瓦斯化学株式会社 | Polyisocyanate compound, production method thereof, polyaddition composition, and powder coating |
| DE102006061536A1 (en) * | 2006-12-27 | 2008-07-03 | Bayer Materialscience Ag | Process for the conditioning of isocyanates |
| DE102007018015A1 (en) * | 2007-04-17 | 2008-10-23 | Bayer Materialscience Ag | Preparation of uretdione group-containing polyisocyanates |
| CN105061709B (en) * | 2015-08-26 | 2018-02-27 | 华南理工大学 | A kind of polyurethane curing agent and its preparation method based on toluene diisocyanate dimer |
| CN109642015B (en) * | 2016-09-02 | 2022-09-23 | 科思创德国股份有限公司 | Method for producing polyisocyanurate plastics by means of phosphine catalysis |
| CN108047428B (en) * | 2017-11-24 | 2020-11-20 | 万华化学集团股份有限公司 | Low-viscosity biuret polyisocyanate and preparation method and application thereof |
-
2018
- 2018-12-26 CN CN201811597900.3A patent/CN109761903B/en active Active
- 2018-12-27 WO PCT/CN2018/124363 patent/WO2020133067A1/en active Application Filing
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| CN109761903A (en) | 2019-05-17 |
| WO2020133067A1 (en) | 2020-07-02 |
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