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Preparation method of aqueous polyurethane based on anionic azo hydrophilic chain extender

A technology of hydrophilic chain extender and water-based polyurethane, which is applied in the preparation of water-based polyurethane, and in the field of water-based polyurethane preparation based on anionic azo hydrophilic chain extender, which can solve the problems affecting the cis-trans isomerization efficiency of azo groups, Poor material migration resistance, limited doping concentration and other problems, to achieve the effect of long-term maintenance of azo functional properties, good acid and alkali resistance, and reduced procedures

Active Publication Date: 2015-08-26
UNIV OF SCI & TECH OF CHINA +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Although the host-guest doping method has a simple process, it only needs to mix some azo small molecule compounds into the polyurethane matrix, but in fact, a mixture is obtained by this method, and the small molecule azo compounds are mixed with the matrix. Not only the doping concentration is limited, but also problems such as migration in the mixture material and oozing out of the material often occur during use, resulting in a decrease in material performance; the reactive method is to use azo small molecule compounds as polymers The reacted monomer, through the active functional group of the azo compound, participates in the polymerization to obtain the polyurethane containing the azo chromophore structure
[0003] Chinese patent 201310573640.7 discloses a method for preparing azo-type water-based polyurethane through azodiols. This method uses azodiols instead of small-molecule diol chain extenders to prepare target materials, and solves the problem of blending azo compounds It causes problems such as poor material migration resistance, but the amount of azodiol added is affected by the ratio of raw materials (the molar ratio of isocyanate to hydroxyl in polyurethane synthesis is generally between 0.8-1.2, and the addition of azodiol will rapidly increase the polyurethane The content of hydroxyl groups in the proportion) is very limited. In this patent, azodiol only partially or completely replaces the small molecule diol used in polyurethane synthesis. Azodiol is used in non-aqueous and non-solvent substances in water-based polyurethane Content up to 15wt%
After the water-resistant azodiol is added, the water-resistant azo component enters the interior of the electric double layer structure of the water-based polyurethane emulsion ball after the self-emulsification process, and it is difficult for the weakly penetrating ultraviolet light to irradiate the inner surface of the emulsion ball. Azo groups, which affect the cis-trans isomerization efficiency of azo groups (under the irradiation of ultraviolet light of a specific wavelength, the percentage of trans-configuration of azobenzene converted to cis-configuration), it is difficult to reach 100%
In short, this method has certain limitations for the synthesis of azo-type anionic waterborne polyurethanes.

Method used

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  • Preparation method of aqueous polyurethane based on anionic azo hydrophilic chain extender
  • Preparation method of aqueous polyurethane based on anionic azo hydrophilic chain extender
  • Preparation method of aqueous polyurethane based on anionic azo hydrophilic chain extender

Examples

Experimental program
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Effect test

Embodiment 1

[0039] 50.00g PBA (M n =3200) into a 500mL three-necked flask, dehydrated at 110°C for 1 hour, then cooled to 55°C, took 11.10g of TDI and added it to the three-necked flask, stirred and reacted at 80°C for 3 hours, then added 9.60g of sulfonic acid type azophile Water chain extender, 1.50g DEG, 0.01g DBTDL and 45.00g methyl ethyl ketone, stirred and reacted at a constant temperature of 70°C for 3 hours, then cooled to 30°C, transferred the reaction solution into a high-speed shear disperser, at 3000 rpm Add 4.36g TEA under low pressure, add 150g water after reacting for 5 minutes, add 0.35g EDA to react for 30 minutes after stirring for 1 minute, transfer the reaction solution to a rotary evaporator, remove butanone under 45°C and 0.01MPa vacuum conditions, A sulfonic acid type azo aqueous polyurethane emulsion is obtained.

[0040] If other conditions of the present embodiment remain unchanged, and PBA is replaced by PCL, PCDL, PTMG or PPG respectively, a stable colored wat...

Embodiment 2

[0042] 160.00g PPG (M n =2000) into a 1000mL three-necked flask, dehydrated at 120°C for 1 hour, then cooled to 60°C, took 62.10g of IPDI and added it to the three-necked flask, stirred and reacted at 90°C for 3 hours, then added 17.20g of carboxylic acid type azophile Water chain extender, 6.90g BDO, 0.01g DBTDL and 120.00g acetone, stirred and reacted at a constant temperature of 75°C for 3 hours, then cooled down to 30°C, transferred the reaction solution into a high-speed shear disperser, under the condition of 3000 rpm Add 14.66g TEA, add 580g water after reacting for 5 minutes, add 0.90g IPDA to react for 30 minutes after stirring for 1 minute, transfer the reaction solution to a rotary evaporator, remove acetone under 40°C and 0.01MPa vacuum conditions to obtain carboxyl Acid type azo water-based polyurethane emulsion.

[0043] If other conditions of this embodiment remain unchanged, and BDO is replaced by HDO, EG or DEG, a stable colored water-based polyurethane emuls...

Embodiment 3

[0046] 80.00g PTMG (M n =2000) into a 500mL three-necked flask, dehydrated at 120°C for 1 hour, then cooled to 60°C, took 35.10g of IPDI and added it to the three-necked flask, stirred and reacted at 90°C for 3 hours, then added 2.30g of carboxylic acid type azophile Water chain extender, 5.5g dimethylolpropionic acid, 6.90g HDO, 0.01g DBTDL and 70.00g methyl ethyl ketone, stirred and reacted at 75°C for 3 hours at a constant temperature, then cooled to 30°C, and the reaction solution was transferred to high-speed shear dispersion machine, add 5.39g TEA under the condition of 3000 rev / min, add 290g water after reacting for 5 minutes, and then transfer to rotary evaporator after stirring for 1 minute, remove methyl ethyl ketone under 45°C and 0.01MPa vacuum condition to obtain carboxy Acid / sulfonic acid hybrid pigmented aqueous polyurethane emulsion.

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Abstract

The invention discloses a preparation method of aqueous polyurethane based on an anionic azo hydrophilic chain extender. According to the preparation method, the anionic azo hydrophilic chain extender containing azo color radicals is utilized for partially or completely replacing a normal hydrophilic chain extender, so as to prepare azo anionic aqueous polyurethane; the problem that the content of hydrophilic groups in a polyurethane system is greatly limited or reduced by a traditional copolymerization method cannot be caused by the addition of the color radicals. According to the azo anionic aqueous polyurethane prepared by virtue of the preparation method, the azo color radicals are located at side chains of polyurethane molecular chains, the azo hydrophilic chain extender with strong hydrophily is distributed on the surfaces of emulsified sphere particles to form a stable double electric layer structure in a self-emulsifying process, the reversible cis-trans isomerism change can be caused by virtue of relatively low energy excitation, the quantity of the azo groups linked into aqueous polyurethane is large, and the change of polyurethane emulsion particle size caused by ultraviolet irradiation shows that functional materials can be used as ultraviolet light responsive nano carriers.

Description

1. Technical field [0001] The invention relates to a method for preparing water-based polyurethane, in particular to a method for preparing water-based polyurethane based on an anionic azo hydrophilic chain extender, and belongs to the technical field of water-based polyurethane materials. 2. Background technology [0002] At present, non-functional hydrophilic chain extenders such as dihydroxymethylpropionic acid and diaminoalkyl sulfonate are often used in the production of water-based polyurethane. The production of functional water-based polyurethane also requires blending or copolymerization to add other functional substances or monomers. body. For example, the existing methods for making polyurethane have azo characteristics can be divided into two types: host-guest doping type and reactive type. Although the host-guest doping method has a simple process, it only needs to mix some azo small molecule compounds into the polyurethane matrix, but in fact, a mixture is obt...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C08G18/66C08G18/32C08G18/34C08G18/08C09D175/06C09D175/08
CPCC08G18/0823C08G18/3836C08G18/3857C08G18/6651C08G18/6685C08G18/6692C09D175/06C09D175/08
Inventor 张兴元李军配李发萍彭腾杨劲松
Owner UNIV OF SCI & TECH OF CHINA
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