CN108047428B - Low-viscosity biuret polyisocyanate and preparation method and application thereof - Google Patents
Low-viscosity biuret polyisocyanate and preparation method and application thereof Download PDFInfo
- Publication number
- CN108047428B CN108047428B CN201711186891.4A CN201711186891A CN108047428B CN 108047428 B CN108047428 B CN 108047428B CN 201711186891 A CN201711186891 A CN 201711186891A CN 108047428 B CN108047428 B CN 108047428B
- Authority
- CN
- China
- Prior art keywords
- diisocyanate
- reaction
- biuret
- catalyst
- phosphine
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/78—Nitrogen
- C08G18/7806—Nitrogen containing -N-C=0 groups
- C08G18/7818—Nitrogen containing -N-C=0 groups containing ureum or ureum derivative groups
- C08G18/7831—Nitrogen containing -N-C=0 groups containing ureum or ureum derivative groups containing biuret groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C275/00—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
- C07C275/46—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups containing any of the groups, X being a hetero atom, Y being any atom, e.g. acylureas
- C07C275/58—Y being a hetero atom
- C07C275/62—Y being a nitrogen atom, e.g. biuret
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/78—Nitrogen
- C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
- C08G18/798—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing urethdione groups
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
Abstract
The present invention relates to a low viscosity biuret polyisocyanate and a process for the preparation thereof, said low viscosity biuret polyisocyanate comprising urea diketones and biuret groups in a molar ratio of the urea diketones to the biuret groups of from 0.01 to 0.80. The preparation method comprises the steps of catalyzing the dimerization reaction of diisocyanate by using phosphine compounds to obtain isocyanate oligomer partially containing uretdione groups, and then adding a catalyst and water into a reaction system to continuously react to obtain the biuret polyisocyanate. The biuret polyisocyanate prepared by the method has low viscosity and chroma lower than 20Hazen, and the conversion rate of diisocyanate raw materials is obviously improved.
Description
Technical Field
The invention relates to low-viscosity biuret polyisocyanate and a preparation method thereof, and the low-viscosity biuret polyisocyanate can be used as a curing agent for polyurethane coating.
Background
The polyurethane coating has wide application in the fields of automobile original factory paint, automobile refinishing paint, plastic paint, industrial paint, wood paint, leather paint and the like due to the excellent performances of wide construction temperature range, good flexibility, strong adhesive force and the like. Industrial diisocyanate products for polyurethane coatings mainly comprise HDI, IPDI, TDI, XDI and the like, and are divided into aliphatic isocyanates and aromatic isocyanates. The aliphatic isocyanate curing agent has good yellowing resistance, the HDI-based isocyanate curing agent in the current market mainly comprises two products, namely HDI tripolymer and HDI biuret, and the flexibility and the adhesive force of the HDI-based biuret coating film are particularly excellent.
In recent years, there has been a trend toward reducing the emission of volatile organic compounds from coatings, and high-solids coatings are an important development for reducing the emission of volatile organic compounds from coatings, and the viscosity of polyisocyanates and polyols can be reduced to produce high-solids two-component polyurethane coatings.
Biuret polyisocyanates can be prepared by reacting polyisocyanates with water, amines or reagents that generate water in situ, but the biurets prepared by conventional processes are highly viscous and require dilution for use. The viscosity of HDI biuret at 25 deg.C is more than 8000cP, and it is usually diluted with organic solvent such as xylene, ethylene glycol ethyl ether acetate, propylene glycol methyl ether acetate, ethyl acetate, isopropyl acetate, n-propyl acetate, butyl acetate, isobutyl acetate, etc. when used, which obviously does not contribute to the reduction of organic compound emissions.
The patent CN106084182A discloses that water reacts with polyisocyanate to prepare biuret, and N heterocyclic carbene metal complex is added in the reaction process, so that the decomposition of biuret structure can be inhibited to generate free monomer, the prepared HDI biuret product has good stability, but the viscosity of the product is very high, and the product needs to be diluted to 75% of solid content by adopting solvents such as esters, ketones and aromatic hydrocarbons, and the volatilization of organic solvent during use is not beneficial to the health of human body and environmental protection.
Bayer US 39766622 prepares low viscosity biuret polyisocyanates by adjusting the molar ratio of diisocyanate to biuretizing agent, which requires controlling the molar ratio of diisocyanate to monofunctional biuretizing agent to be at least 11: 1. The essence of the method is to control the conversion rate of diisocyanate, under the condition that the molar ratio of diisocyanate to the monofunctional biuretizing agent is at least 11:1, a large amount of diisocyanate monomers do not participate in the reaction, and need to be separated and recycled, thus inevitably causing additional energy consumption.
Patent US4388245 of Asahi company discloses a process for preparing low-viscosity biuret polyisocyanate by a high-temperature heating method, based on the heat sensitivity of a biuret structure, diisocyanate and high-viscosity biuret are mixed according to the mass ratio of 1:2 and heated at 100-200 ℃, the molecular weight distribution of the high-viscosity biuret moves towards the direction favorable for generating oligomer, and after unreacted diisocyanate monomer is separated, a low-viscosity biuret product is obtained. However, the high-viscosity biuret polyisocyanate is synthesized at high temperature and then decomposed into low-viscosity biuret by high-temperature heating, which is obviously uneconomical, and the color number of the low-viscosity biuret polyisocyanate product after high-temperature heating is higher.
Bayer patent US4837359 reports that reacting diisocyanates with diamines at temperatures above 250 ℃ produces biuret polyisocyanates which produce biuret polyisocyanates with lower viscosity and lower product color numbers. However, a large flow rate of gaseous diamine is difficult to achieve in the actual production process, and the reactivity of diamine with isocyanate is very high, and it is difficult to control the reaction from a technological point of view.
The existing conventional process for preparing the low-viscosity biuret polyisocyanate has certain defects, and the product with lower viscosity can be prepared by controlling the large excess of the diisocyanate, but the method relates to the problems of separation and reuse of a large amount of diisocyanate monomers which do not participate in the reaction, and has very high energy consumption; the preparation of low-viscosity biuret polyisocyanates by high-temperature heating leads to a relatively high color number of the final product.
Disclosure of Invention
The invention aims to make up the defects of the prior art and provide a preparation method of low-viscosity biuret polyisocyanate. The biuret polyisocyanate obtained by the method has low viscosity and chroma lower than 20Hazen, and meanwhile, the conversion rate of diisocyanate raw materials is obviously improved, and the energy consumption is low.
Another object of the present invention is to provide a low viscosity biuret polyisocyanate having a viscosity in the range of 1500-5000cP (25 ℃), which can be used as a curing agent for polyurethane coatings.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a low viscosity biuret polyisocyanate comprising uretdione groups and biuret groups in a molar ratio of the uretdione groups to the biuret groups of from 0.01 to 0.80, preferably from 0.02 to 0.60. The viscosity is 1500-5000cP (25 deg.C).
A process for preparing low-viscosity biuret polyisocyanate includes such steps as catalytic dimerization reaction of diisocyanate with phosphine compound, adding carboxylic acid catalyst to intermediate product, heating, and introducing water for continuous reaction.
As a specific scheme, the method of the invention comprises the following steps:
(1) under the protection of nitrogen, adding diisocyanate into a reaction vessel, heating to 20-130 ℃, adding a certain amount of catalyst under the stirring condition, and carrying out dimerization reaction;
(2) after the reaction is carried out for 0.5 to 6 hours, adding a certain amount of carboxylic acid, heating to 80 to 220 ℃, and slowly adding water to carry out biuretization reaction for 0.5 to 7 hours (the adding time of the water is the reaction time of the stage) to obtain biuret reaction liquid;
(3) and (3) feeding the biuret reaction liquid obtained in the step (2) into a separation device to remove monomers, so as to obtain a biuret polyisocyanate product with low viscosity.
In the process of the present invention, the biuret polyisocyanates contain uretdione groups and biuret groups in a molar ratio of uretdione groups to biuret groups of from 0.01 to 0.80, preferably from 0.02 to 0.60.
In the process of the invention, the conversion of the diisocyanate monomer in the dimerization stage is from 3 to 30%, preferably from 5 to 25%. The temperature in the diisocyanate dimerization stage is 20 to 130 ℃, preferably 40 to 110 ℃; the reaction time is from 0.5 to 6 hours, preferably from 1 to 5 hours. The conversion rate of the diisocyanate monomer in the reaction stage is controlled within the range, the viscosity of the final product is low, and the comprehensive performance is optimal.
In the process of the present invention, the dimerization reaction of the diisocyanate is carried out in the presence of a phosphine-based catalyst selected from the group consisting of amino-substituted phosphines, trialkylphosphines, cycloalkylphosphines, preferably amino-substituted phosphines, such as tris (dimethylamino) phosphine, tris (diethylamino) phosphine, most preferably tris (dimethylamino) phosphine; the phosphine catalyst is used in an amount of 0.02 to 4% by weight, preferably 0.05 to 3% by weight, based on the mass of the diisocyanate monomer.
In the method of the invention, the reaction of the isocyanate oligomer and the water is carried out under the catalysis of carboxylic acid, and the carboxylic acid is preferably one or more of formic acid, acetic acid, propionic acid, pivalic acid, oxalic acid and malonic acid; the carboxylic acid catalyst is used in an amount of 0.05 to 5% by weight, preferably 0.08 to 4% by weight, based on the mass of diisocyanate monomer. The inventor finds that the carboxylic acid compound added in the reaction stage can not only terminate the dimerization reaction of diisocyanate monomers, but also catalyze the reaction of isocyanate and water, and the generated uretdione group can not be decomposed in the high-temperature reaction stage by researching the reaction mechanism.
In the method of the invention, the molar ratio of the diisocyanate monomer to the water is 4:1-19:1, preferably 6:1-18: 1; the biuretizing reaction temperature is 80-220 ℃, and preferably 100-200 ℃; the reaction time is from 0.5 to 7 hours, preferably from 0.8 to 6 hours.
In the method of the present invention, the diisocyanate is aliphatic diisocyanate and/or alicyclic diisocyanate, preferably one or more of hexamethylene diisocyanate, 1, 4-cyclohexane diisocyanate, 4' -dicyclohexylmethane diisocyanate and isophorone diisocyanate, and more preferably isophorone diisocyanate.
In the process of the present invention, the conversion of the diisocyanate monomer is 32 to 80%, preferably 35 to 70%, throughout the reaction.
In the method, the separation device is a thin film evaporator, the separation temperature of the thin film evaporator is controlled to be 95-220 ℃, and the absolute separation pressure is controlled to be 1-500 Pa.
In the method, the film evaporator is a roller type film wiping system film evaporator or a scraper type film wiping system film evaporator.
The low-viscosity biuret polyisocyanate can be used as a curing agent for preparing two-component polyurethane coating.
The invention has the positive effects that: the conventional biuret polyisocyanate product has high viscosity, and is usually diluted by organic solvents such as xylene, ethylene glycol ethyl ether acetate, propylene glycol methyl ether acetate, ethyl acetate, isopropyl acetate, n-propyl acetate, butyl acetate, isobutyl acetate and the like when in use, and the volatilization of the organic solvents is not beneficial to the health and environmental protection of human bodies. The conversion rate of the diisocyanate monomer in the prior art is low, and a large amount of unreacted diisocyanate monomer needs to be separated and recycled, so that the energy consumption is very high. Before the reaction of water and isocyanate to prepare the biuret polyisocyanate, the invention uses a phosphine compound to catalyze the dimerization reaction of diisocyanate to obtain partial isocyanate oligomer containing uretdione groups, the viscosity of the biuret polyisocyanate can be reduced by the isocyanate oligomer containing the uretdione groups, the conversion rate of the diisocyanate in the reaction stage of the water and the isocyanate is improved, and the prepared biuret polyisocyanate has low viscosity and the chroma lower than 20 Hazen. The biuret polyisocyanates prepared by the process according to the invention are particularly suitable for direct use by downstream customers as curing agents in the coating industry without the need for dilution with organic solvents.
Detailed Description
The present invention will be described in further detail with reference to specific examples, but the present invention is not limited thereto.
The color number of the biuret polyisocyanate is measured by a BYK LCS IV color number instrument and measured by a Hazen color scale. The isocyanate starting material was quantified using Gel chromatography (column MZ-Gel SDplus10E3A 5 μm, 35 ℃, mobile phase tetrahydrofuran, 1.0mL/min) as a monitoring means to determine the conversion of the reaction (calculated on the basis of the isocyanate mass). The viscosity is measured with a Brookfield viscometer (model RVDV-II + P, 25 ℃).
The molar ratio of uretdione groups to biuret groups in the biuret polyisocyanates obtained in the examples and comparative examples is indicated by U/B and the test method employed13C-NMR Nuclear magnetic resonance method using a Bruker400MHz instrument with a sample concentration of 50% (CDCl)3Solution), test conditions were 100MHz, relaxation time: 4sec, min2000 scans, at 77.0ppm CDCl3As a reference for displacement.
Under the condition of not specially describing, the reaction system is always under the protection of dry nitrogen gas before the reaction and during the whole reaction process when the catalyst is added.
Example 1
1) Adding 2223g (10mol) of isophorone diisocyanate into a four-neck flask, heating to 40 ℃, adding 1.1g of tris (dimethylamino) phosphine under the stirring condition, and starting timing reaction;
2) after 1 hour of reaction, a specified conversion was reached, 4 wt% of pivalic acid based on the amount of isophorone diisocyanate was added, the temperature was raised to 110 ℃, 12.9g of water was slowly added, and the reaction was stirred for 2 hours;
3) and (3) separating the biuret reaction liquid obtained in the step (2) by using a roller type film scraping system film evaporator to obtain a low-viscosity biuret polyisocyanate product, wherein the separation temperature is 170 ℃, and the absolute separation pressure is 400 Pa.
Examples 2-4 the process conditions were the same as in example 1, except for the amount of tris (dimethylamino) phosphine added and the reaction time in the dimerization stage, and the specific information is given in table 1.
Comparative example 1
1) Adding 2223g (10mol) of isophorone diisocyanate into a four-neck flask, adding 4 wt% of pivalic acid based on the amount of isophorone diisocyanate, heating to 110 ℃, slowly adding 15.8g of water, and stirring for reaction for 2 hours;
2) and (2) separating the biuret reaction liquid obtained in the step (1) by using a roller type film scraping system film evaporator to obtain a low-viscosity biuret polyisocyanate product, wherein the separation temperature is 170 ℃, and the absolute separation pressure is 400 Pa.
TABLE 1 detailed information of examples 1-4 and comparative example 1
Example 5
1) Adding 1680g (10mol) of hexamethylene diisocyanate into a four-neck flask, heating to 70 ℃, adding 16.8g of tri (dimethylamino) phosphine under the stirring condition, and starting timing reaction;
2) after 4 hours of reaction, propionic acid with 2 wt% of hexamethylene diisocyanate was added to reach a predetermined conversion rate, the temperature was raised to 190 ℃, 36g of water was slowly added, and the reaction was stirred for 6 hours;
3) and (3) separating the biuret reaction liquid obtained in the step (2) by using a wiped film system film evaporator to obtain a low-viscosity biuret polyisocyanate product, wherein the separation temperature is 100 ℃, and the absolute separation pressure is 100 Pa.
Examples 6-8 the process conditions were the same as in example 5, except for the amount of propionic acid added and the amount of water added, for information shown in table 2.
Comparative example 2 is similar to example 5 except for the amount of water added, and the specific information is shown in table 2.
TABLE 2 detailed information of examples 5-8 and comparative example 2
The results show that: the phosphine compound is used to catalyze the dimerization reaction of diisocyanate, and the added amount of water is controlled to prepare biuret polyisocyanate product with low viscosity and color number lower than 20 Hazen.
Claims (18)
1. A process for the preparation of a low viscosity biuret polyisocyanate, comprising the steps of: carrying out dimerization reaction on diisocyanate to obtain a part of isocyanate oligomer containing uretdione groups, and then adding a catalyst and water into a reaction system to carry out biuretization reaction to generate biuret polyisocyanate; carrying out dimerization reaction of diisocyanate in the presence of a phosphine catalyst, wherein the molar ratio of diisocyanate monomer to water is 4:1-19: 1;
wherein, in the dimerization reaction stage, the conversion rate of the diisocyanate monomer is 3-30%; in the whole reaction process, the conversion rate of the diisocyanate monomer is 32-80%;
the low viscosity biuret polyisocyanates prepared by the process comprise uretdione groups and biuret groups, and the molar ratio of the uretdione groups to the biuret groups is from 0.01 to 0.80.
2. The process according to claim 1, wherein in the dimerization stage, the conversion of the diisocyanate monomer is 5 to 25%; in the whole reaction process, the conversion rate of the diisocyanate monomer is 35-70%.
3. The method according to claim 1, wherein the phosphine catalyst is selected from the group consisting of amino-substituted phosphines, trialkylphosphines, cycloalkylphosphines; the phosphine catalyst is used in an amount of 0.02 to 4 wt% based on the mass of the diisocyanate monomer.
4. The process according to claim 3, wherein the phosphine catalyst is selected from the group consisting of an amino-substituted phosphine; the phosphine catalyst is used in an amount of 0.05 to 3 wt% based on the mass of the diisocyanate monomer.
5. The process according to claim 4, wherein the phosphine catalyst is tris (dimethylamino) phosphine and/or tris (diethylamino) phosphine.
6. The production method according to claim 5, wherein the phosphine catalyst is tris (dimethylamino) phosphine.
7. The process according to claim 1, wherein the temperature in the diisocyanate dimerization stage is 20 to 130 ℃; the reaction time is 0.5-6 hours.
8. The process according to claim 7, characterized in that the temperature in the diisocyanate dimerization stage is 40-110 ℃; the reaction time is 1-5 hours.
9. The process according to claim 1, wherein the catalyst for biuretization is a carboxylic acid; the catalyst is used in an amount of 0.05 to 5 wt.%, based on the mass of diisocyanate monomer.
10. The method of claim 9, wherein the biuretizing catalyst is one or more of formic acid, acetic acid, propionic acid, pivalic acid, oxalic acid and malonic acid; the catalyst is used in an amount of 0.08 to 4% by weight, based on the mass of diisocyanate monomer.
11. The method of claim 1, wherein the molar ratio of diisocyanate monomer to water is from 6:1 to 18: 1.
12. The method according to claim 1, wherein the biuretization reaction is carried out at a reaction temperature of 80 to 220 ℃; the reaction time is 0.5-7 hours.
13. The method according to claim 12, wherein the biuretization reaction is carried out at a reaction temperature of 100 to 200 ℃; the reaction time is 0.8-6 hours.
14. The process according to claim 1, wherein the diisocyanate is an aliphatic diisocyanate and/or an alicyclic diisocyanate.
15. The method of claim 14, wherein the diisocyanate is one or more of hexamethylene diisocyanate, 1, 4-cyclohexane diisocyanate, 4' -dicyclohexylmethane diisocyanate, and isophorone diisocyanate.
16. The method of claim 15, wherein the diisocyanate is isophorone diisocyanate.
17. The method according to claim 1, wherein the molar ratio of the uretdione groups to the biuret groups is 0.02 to 0.60.
18. Use of the low-viscosity biuret polyisocyanates obtained by the process according to any of claims 1 to 17 as curing agents for the preparation of two-component polyurethane coatings.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711186891.4A CN108047428B (en) | 2017-11-24 | 2017-11-24 | Low-viscosity biuret polyisocyanate and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711186891.4A CN108047428B (en) | 2017-11-24 | 2017-11-24 | Low-viscosity biuret polyisocyanate and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108047428A CN108047428A (en) | 2018-05-18 |
| CN108047428B true CN108047428B (en) | 2020-11-20 |
Family
ID=62120104
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711186891.4A Active CN108047428B (en) | 2017-11-24 | 2017-11-24 | Low-viscosity biuret polyisocyanate and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108047428B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109761903B (en) * | 2018-12-26 | 2020-07-28 | 万华化学集团股份有限公司 | Preparation method of 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 |
| CN111217972B (en) * | 2020-01-13 | 2022-02-15 | 万华化学集团股份有限公司 | Preparation method of biuret polyisocyanate with storage stability |
| CN114507332B (en) * | 2020-11-16 | 2024-02-27 | 万华化学（宁波）有限公司 | Polyisocyanate containing biuret structure and preparation method thereof |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5859163A (en) * | 1997-08-22 | 1999-01-12 | Bayer Corporation | Allophanate group-containing polyisocyanates improved compatibility with aldimines |
| DE10336184A1 (en) * | 2003-08-07 | 2005-02-24 | Bayer Materialscience Ag | New catalysts for selective isocyanate dimerization |
| DE102005013329A1 (en) * | 2005-03-23 | 2006-11-16 | Degussa Ag | Low-viscosity uretdione group-containing polyaddition compounds, process for their preparation and use |
| CN101506264A (en) * | 2006-08-14 | 2009-08-12 | 拜尔材料科学有限公司 | Low surface energy polyisocyanates and their use in two-component coating compositions |
| US9550857B2 (en) * | 2010-07-13 | 2017-01-24 | Basf Se | High-functionality polyisocyanates containing urethane groups |
| JP6595234B2 (en) * | 2014-07-11 | 2019-10-23 | 旭化成株式会社 | Polyisocyanate composition, block polyisocyanate composition and method for producing them |
-
2017
- 2017-11-24 CN CN201711186891.4A patent/CN108047428B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN108047428A (en) | 2018-05-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108047428B (en) | Low-viscosity biuret polyisocyanate and preparation method and application thereof | |
| EP2174967B1 (en) | Polyisocyanates suitable for the formulation of paints and varnishes with a low solvent content, and process for the preparation thereof | |
| CN1502605B (en) | Preparation of polyisocyanates containing uretidione groups | |
| JP4642328B2 (en) | Method for producing TDI trimer with low monomer content | |
| CN103897130B (en) | Hyperbranched polyisocyanates of a kind of aqueous dispersion type and preparation method thereof | |
| JP2507415B2 (en) | Process for producing polyisocyanate containing isocyanurate group | |
| CN101289427B (en) | Preparation of polyisocyanates containing uretdione groups using phosphine catalysts | |
| JP2004250662A (en) | Process for producing low-monomer-content tdi trimer | |
| CA2162832A1 (en) | Polyisocyanates containing allophanate groups | |
| CN109761903B (en) | Preparation method of polyisocyanate containing uretdione group | |
| CN102050836A (en) | Phosphorus-containing polyisocyanate and preparation method thereof | |
| CN109651279B (en) | Preparation method of low-chroma and storage-stable aliphatic polyisocyanate | |
| CN107304244B (en) | Modified polyisocyanate composition and preparation method thereof | |
| CN105026454A (en) | Method for producing TDI-trimerisates with high purity | |
| JPH04306218A (en) | Low-viscosity polyisocyanate | |
| CN104479103B (en) | Polyurethane curing agent having high functionality, preparation method and use thereof | |
| Wang et al. | Synthesis of HDI/IPDI hybrid isocyanurate and its application in polyurethane coating | |
| EP4056618A1 (en) | Aliphatic polyisocyanate composition, prepararion method therefor, and coating composition | |
| CN113637140B (en) | Hydrophilic isocyanate crosslinking agent and preparation method thereof | |
| CN105585690A (en) | Method for preparing polydimethyl siloxane/hydroxyl-terminated polybutadiene modified UV curing hyperbranched polyurethane | |
| CN114507332A (en) | Polyisocyanate containing biuret structure and preparation method thereof | |
| CN111793003A (en) | Preparation method of polyaspartic acid ester resin | |
| JP5546385B2 (en) | Process for producing polyisocyanate containing biuret structure | |
| CN107200828B (en) | Polyurethane for single-component coating and preparation method thereof | |
| US20060287462A1 (en) | Process for preparing polyamines having primary amino groups |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |