Bio-based pentamethylene diisocyanate curing agent as well as preparation method and application thereof

A pentamethylene diisocyanate, bio-based technology, applied in organic chemistry, chemical recycling, polyurea/polyurethane coatings, etc., can solve problems such as affecting product appearance and performance, increasing catalyst usage, and unsatisfactory catalyst dispersion, etc. To achieve the effect of good appearance and chemical resistance, optimized synthesis and separation process, and stable and controllable reaction process

Active Publication Date: 2020-12-15
CNOOC CHANGZHOU PAINT & COATINGS IND RES INST +2
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, since the bio-based pentamethylene diisocyanate PDI is prepared from the bio-based raw material 1,5-pentamethylenediamine PDA through the phosgene method, its PDI monomer usually contains a lot of trace bio-based impurities, resulting in its There are also the following problems in the process of synthesizing isocyanate polymers: 1) trace impurities remaining in the bio-based pentamethylene diisocyanate PDI monomer affect the physical and chemical properties such as chromaticity, viscosity and transparency of PDI isocyanate polymers, and then Affect the appearance and performance of subsequent products; 2) Since the reactivity of bio-based pentamethylene diisocyanate PDI is higher than that of hexamethylene diisocyanate HDI, in the process of synthesizing isocyanate polymer, bio-based pentamethylene diisocyanate Isocyanate PDI is more sensitive to the catalyst, resulting in unsatisfactory dispersion of the catalyst, which is likely to cause the generation of gel particles and cause trouble for subsequent separation; due to the unsatisfactory dispersion of the catalyst, it is necessary to increase the amount of catalyst used, which will easily lead to an increase in the viscosity of the PDI isocyanate polymer , the chroma increases, and even the phenomenon of bursting occurs, which seriously affects the appearance and performance of subsequent products

Method used

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  • Bio-based pentamethylene diisocyanate curing agent as well as preparation method and application thereof
  • Bio-based pentamethylene diisocyanate curing agent as well as preparation method and application thereof
  • Bio-based pentamethylene diisocyanate curing agent as well as preparation method and application thereof

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preparation example Construction

[0037] The embodiment of the present invention provides a preparation method of bio-based pentamethylene diisocyanate curing agent, comprising the following steps:

[0038] Step 1): under nitrogen protection, add pentamethylene diisocyanate PDI to the reaction flask;

[0039] Step 2): adding catalyst A to the reaction bottle, and performing a pre-reaction at 50-150° C. for 0-5 hours;

[0040] Step 3): Add the PDI trimer catalyst dropwise to the reaction bottle, heat and stir the reaction at 50-100°C for 1h-10h, and test the NCO content every 15min;

[0041] Step 4): When the NCO content reaches the preset content value, add a polymerization inhibitor to the reaction bottle, and keep it warm for 1h-5h at 50-100°C;

[0042] Step 5): Adding antioxidant D into the reaction bottle, incubating and reacting at 50-100°C for 0.5h-1h, and discharging to obtain PDI isocyanate composition E;

[0043] Step 6): Use a thin film evaporator to pre-separate the PDI monomers of the product PDI...

Embodiment 1

[0058] Take 500 parts by mass of PDI (silver silver light), add 0.5 parts by mass of catalyst A pentaerythritol diisodecyl diphosphite, heat to 100°C under the protection of nitrogen, pre-react for 2h, and control the flow rate of nitrogen to 50ml / min, then Cool down to 50°C, add the diluted PDI trimer catalyst dropwise, raise the temperature to 60°C, test the -NCO content every 15 minutes, the NCO drops to 42.7%, add 1 mass part of the polymerization inhibitor o-toluenesulfonamide, at 60°C 0.5h at a temperature of Base] ethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane 0.5 parts by mass, react for 1h, stop the reaction, and discharge to obtain PDI isocyanate composition E.

[0059]The preparation process of the diluted PDI trimer catalyst is as follows: add 2 mass parts of butyl acetate to 0.1 mass part of catalyst trioctylphosphine, and stir at low temperature for 1 hour. The diluted PDI trimer catalyst was added to the reaction bottle in a dropwise distribution manner, and the dr...

Embodiment 2

[0062] Take 500 parts by mass of PDI (silver and silver light), add 0.5 parts by mass of the catalyst pentaerythritol diisodecyl diphosphite, heat to 100°C under the protection of nitrogen, pre-react for 2 hours, the flow rate of nitrogen is 50ml / min, and then cool down to 50 ℃, add the diluted PDI trimer catalyst dropwise, raise the temperature to 60 ℃, test the -NCO content every 15 minutes, and the NCO drops to 41.8%, add 1 mass part of polymerization inhibitor o-toluenesulfonamide, at a temperature of 60 ℃ Insulated for 0.5h, the antioxidant D was 3,9-bis[1,1-dimethyl-2-[(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]ethyl Base]-2,4,8,0.5 parts by mass of 10-tetraoxaspiro[5.5]undecane, reacted for 1h, stopped the reaction, and discharged to obtain PDI isocyanate composition E;

[0063] The preparation process of the diluted PDI trimer catalyst is as follows: adding 1 mass part of butyl acetate and 1 mass part of methanol to 0.1 mass part of catalyst trioctylphosphine,...

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Abstract

The invention relates to a method for preparing polyisocyanate containing allophanate and isocyanurate groups, in particular to a bio-based pentamethylene diisocyanate curing agent as well as a preparation method and application thereof. The preparation method of the bio-based pentamethylene diisocyanate curing agent provided by the invention can be used for preparing a polyisocyanate curing agentcontaining allophanate and isocyanurate groups, and comprises the following steps: mixing a PDI monomer with a hydrolytic chlorine concentration of 0-50ppm with a catalyst A, carrying out pre-reaction for 0-5h, diluting a PDI tripolymer catalyst with a mixed solvent (a solvent B and a solvent C), dropwise adding the PDI tripolymer catalyst at a constant speed section by sections, carrying out polymerization reaction, adding a polymerization inhibitor to terminate the reaction when the conversion rate reaches 30%-40%, adding an antioxidant D, and carrying out two-stage separation by virtue ofa film evaporator and a molecular distiller to obtain a PDI-type polyisocyanate composition.The residual PDI monomer in the product is 0.5% or below, viscosity is low, and color is light. Meanwhile, the curing agent has good compatibility with hydroxyl resin, and has the advantages of being high in reaction activity, high in glossiness, good in chemical medium resistance and the like.

Description

technical field [0001] The invention belongs to the technical field of polyisocyanate curing agents, and in particular relates to a bio-based pentamethylene diisocyanate curing agent and its preparation method and application. Background technique [0002] In recent years, in my country's high-performance polyurethane coatings industry, research on bio-based polyisocyanate polymers has attracted more and more attention and research from relevant scientific and technical personnel at home and abroad. Polyisocyanate is an essential component of polyurethane resin, which is directly related to the comprehensive physical and chemical properties of the material. Aromatic polyisocyanates such as TDI and MDI have a rigid benzene ring structure and have certain limitations in weather resistance. Therefore, aliphatic polyisoesters with excellent performance such as IPDI and HDI (hexamethylene diisoate) are becoming more and more popular, especially straight-chain aliphatic structure...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C08G18/09C08G18/79C09D175/04C07D251/34
CPCC08G18/09C08G18/792C09D175/04C07D251/34Y02P20/584
Inventor 谭伟民王黎狄志刚史立平雒新亮王亚鑫郁飞刘仲阳何毅
Owner CNOOC CHANGZHOU PAINT & COATINGS IND RES INST
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