CN109912775A - A kind of double stimuli responsive Water-based polyurethane elastomer and preparation method thereof - Google Patents
A kind of double stimuli responsive Water-based polyurethane elastomer and preparation method thereof Download PDFInfo
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- CN109912775A CN109912775A CN201910269833.0A CN201910269833A CN109912775A CN 109912775 A CN109912775 A CN 109912775A CN 201910269833 A CN201910269833 A CN 201910269833A CN 109912775 A CN109912775 A CN 109912775A
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- stimuli responsive
- polyurethane elastomer
- double stimuli
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Abstract
The invention discloses a kind of double stimuli responsive Water-based polyurethane elastomers and preparation method thereof.Double stimuli responsive Water-based polyurethane elastomer is on the basis of non-aqueous in aqueous polyurethane and non-solvent constituent mass, including 30-70% macromolecule dihydric alcohol, 15-50% diisocyanate, 4-8% hydrophilic chain extender, 0.1-11% glycol chain extender, the agent of 0.1-2.2% polyol crosslink, 0.01-0.08% catalyst, 3-6% triethylamine, 0-5% diamine chain extenders, 0.1-11% sensitive dyes and the 0.1-11% photoresponse factor.The present invention adds sensitive dyes and the photoresponse factor in preparation process, and the polyurethane elastomer of preparation has shape memory function, and has stimulating responsive to light and/or pH.
Description
Technical field
The invention belongs to polyurethane elastomer preparation technical fields, more particularly to a kind of aqueous poly- ammonia of double stimuli responsive
Ester elastomer and preparation method thereof.
Background technique
Aqueous polyurethane replaces the organic solvent in conventional urethane by decentralized medium of water, is a kind of novel green, ring
It protects, safe and healthy polyurethane material.In recent years, with the increasing of state treatment environmental protection dynamics, there is good mechanics and machinery
The water-base polyurethane material of performance be widely used in coating, ink, adhesive, fabric coating and finishing agent, leather finishing agent,
The fields such as sheet surface treating agent and fiber surface treatment agent.
Summary of the invention
The purpose of the present invention is to provide a kind of double stimuli responsive Water-based polyurethane elastomers and preparation method thereof, pass through
Sensitive dyes and the photoresponse factor are added in preparation process, the polyurethane elastomer of preparation has shape memory function, and right
Light and/or pH have stimulating responsive.
In order to solve the above technical problems, the present invention is achieved by the following technical solutions:
The present invention is a kind of double stimuli responsive Water-based polyurethane elastomer, with non-aqueous and non-solvent in aqueous polyurethane
On the basis of property constituent mass, comprising: 30-70% macromolecule dihydric alcohol, 15-50% diisocyanate, 4-8% hydrophilic chain extender,
0.1-11% glycol chain extender, the agent of 0.1-2.2% polyol crosslink, 0.01-0.08% catalyst, 3-6% triethylamine, 0-
5% diamine chain extenders, 0.1-11% sensitive dyes and the 0.1-11% photoresponse factor.
Further, the sensitive dyes are selected from one of flowering structure A~F or several combinations, structural formula
Are as follows:
Further, the diisocyanate is selected from toluene di-isocyanate(TDI) (TDI), methyl diphenylene diisocyanate
(MDI), one of isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI) or any a variety of mixing；
The macromolecule dihydric alcohol is selected from the polymer polyatomic alcohol with 2000~8000g/mol number-average molecular weight, described
Polymer polyatomic alcohol includes polyadipate -1,4- butyl glycol ester diol (PBA), polycaprolactone diols (PCL), polycarbonate two
First alcohol (PCDL) and polylactide dihydric alcohol (PCL)；
The hydrophilic chain extender is selected from dihydromethyl propionic acid (DMPA) or dimethylolpropionic acid (DMBA)；
The glycol chain extender is selected from 1,4- butanediol (BDO) or 1,6-HD (HDO)；
The diamine chain extenders are selected from ethylenediamine (EDA) or isophorone diamine (IPDA)；
The catalyst is selected from one of dibutyl tin dilaurate (DBTDL), organo-bismuth (DY-20) and BACT-20C
Or it is a variety of
The polyol crosslink agent is selected from one of TMP, PCL-3057, BY-3095 or a variety of.
Further, the photoresponse factor is 2- cinnamoyl amido -1,3-PD.
A kind of preparation method of double stimuli responsive Water-based polyurethane elastomer, comprising:
The preparation of step 1, aqueous polyurethane emulsion:
It takes macromolecule dihydric alcohol vacuum dehydration 0.5-1.5 hours at 110-120 DEG C, adds the diisocyanate of metering
Ester, sensitive dyes, be added after reaction 2-4 hours at 70-100 DEG C hydrophilic chain extender, glycol chain extender, the photoresponse factor,
Polyol crosslink agent, catalysts and solvents, 60-90 DEG C reaction 1-4 hours, then under conditions of high speed shear and 0-40 DEG C
Triethylamine is added, water and diamine chain extenders are added after reaction 0.5-5 minutes, after emulsification 5-30 minutes, reaction product is in 40-50
DEG C, slough solvent under 0.01MPa vacuum condition, obtain double stimuli responsive aqueous polyurethane emulsion；
Step 2, the preparation of double stimuli responsive Water-based polyurethane elastomer:
Step 1 gained double stimuli responsive aqueous polyurethane emulsion is poured into the mold for being coated with release agent, it is certainly dry to it
After a period of time, then it is placed in 40 DEG C of baking ovens and double stimuli responsive Water-based polyurethane elastomer can be obtained at glue film.
Further, on the basis of non-aqueous in aqueous polyurethane and non-solvent constituent mass, the addition of the solvent
Amount is 20-50%, and the additive amount of the water is 150%-300%；
The solvent is selected from one of acetone or butanone.
The invention has the following advantages:
1, the present invention is by adding sensitive dyes and the photoresponse factor, the polyurethane elastomer tool of preparation in preparation process
There is shape memory function, and there is stimulating responsive to light and/or pH；
2, the present invention prepares aqueous polyurethane and takes water as a solvent, and has pollution-free, safe and reliable, good mechanical performance, phase
The advantages that capacitive is good, easily modified；
3, stimulating factor is introduced high molecular main chain or side chain by certain chemical reaction by preparation method of the present invention
A kind of stimulus responsive polymer polymer of formation, this combination impart high molecular material multi-functional.
Certainly, it implements any of the products of the present invention and does not necessarily require achieving all the advantages described above at the same time.
Specific embodiment
Embodiment 1
60 DEG C are cooled to after the number-average molecular weight Mn PBA for being 3000 is dehydrated 1 hour at 110 DEG C, takes 4.10 grams of additions
Into the three-necked flask of 100mL, 4.32 grams of IPDI, 0.2 gram of sensitive dyes A are added, stir and is warming up to 90 DEG C of reactions 2 is small
When after 0.56 gram of DMPA, 0.1 gram of TMP, 038 gram of BDO, 0.13g photoresponse factor, 0.01 gram of DBTDL and 10 gram of acetone is added, it is permanent
Temperature is cooled to 30 DEG C after being stirred to react 4 hours at 70 DEG C；Then 0.4 gram of TEA and 10 gram of acetone is added, after reaction 30 seconds, in height
20 grams of water are added under speed stirring (3000 revs/min), reaction product was transferred to Rotary Evaporators after 30 minutes by 0.21 gram of IPDA,
Acetone is sloughed under 45 DEG C, 0.01MPa vacuum condition, obtains double stimuli responsive aqueous polyurethane emulsion.
Lotion is poured into mold, from after dry 4h, being placed in 40 DEG C of baking ovens can be obtained double stimuli responsive at glue film
Water-based polyurethane elastomer.
Embodiment 2
By number-average molecular weight Mn be 2000 PTMG at 120 DEG C vacuum dehydration 50 DEG C are cooled to after 1 hour, take 4.0 grams
It is added in the three-necked flask of 100mL, adds 4.1 grams of TDI, 0.3 gram of sensitive dyes B, 0.16 gram of photoresponse factor, stirring
And 0.8 gram of DMPA, 0.22 gram of TMP, 0.22 gram of BDO, 0.4g photoresponse factor, 0.01 is added after being warming up to 80 DEG C of reactions 3 hours
Gram DBTDL and 8 gram of acetone, constant temperature are cooled to 20 DEG C after being stirred to react 3 hours at 80 DEG C；Then it is added 0.6 gram TEA and 10 gram third
After five minutes, 18 grams of water are added, 0.21 gram of IPDA will reaction after 30 minutes in ketone, reaction under high-speed stirred (3000 revs/min)
Product is transferred to Rotary Evaporators, sloughs acetone under 40 DEG C, 0.01MPa vacuum condition, obtains the aqueous poly- ammonia of double stimuli responsive
Ester lotion.
Lotion is poured into mold, from after dry 4h, being placed in 40 DEG C of baking ovens can be obtained double stimuli responsive at glue film
Water-based polyurethane elastomer.
Embodiment 3
50 DEG C are cooled to after the number-average molecular weight Mn PCL for being 2000 is dehydrated 1 hour at 120 DEG C, takes 4.6 grams to be added to
In the three-necked flask of 250mL, 4.06 grams of MDI, 0.2 gram of sensitive dyes E are added, stirs and is warming up to 80 DEG C and react 3 hours
0.42 gram of DMPA, 0.16 gram of BY-3095,0.22 gram of HDO, 0.13 gram of photoresponse factor, 0.01 gram DY-20 and 12 gram third are added afterwards
Ketone, constant temperature are cooled to 20 DEG C after being stirred to react 3 hours at 80 DEG C；Then 0.3 gram of TEA and 10 gram of acetone is added, reacts 5 minutes
Afterwards, 30 grams of water are added under high-speed stirred (3000 revs/min), reaction product is transferred to rotation after 30 minutes and steamed by 0.2 gram of EDA
Instrument is sent out, acetone is sloughed under 50 DEG C, 0.01MPa vacuum condition, obtains double stimuli responsive aqueous polyurethane emulsion.
Lotion is poured into mold, from after dry 4h, being placed in 40 DEG C of baking ovens can be obtained double stimuli responsive at glue film
Water-based polyurethane elastomer.
In the description of this specification, the description of reference term " one embodiment ", " example ", " specific example " etc. means
Particular features, structures, materials, or characteristics described in conjunction with this embodiment or example are contained at least one implementation of the invention
In example or example.In the present specification, schematic expression of the above terms may not refer to the same embodiment or example.
Moreover, particular features, structures, materials, or characteristics described can be in any one or more of the embodiments or examples to close
Suitable mode combines.
Present invention disclosed above preferred embodiment is only intended to help to illustrate the present invention.There is no detailed for preferred embodiment
All details are described, are not limited the invention to the specific embodiments described.Obviously, according to the content of this specification,
It can make many modifications and variations.These embodiments are chosen and specifically described to this specification, is in order to better explain the present invention
Principle and practical application, so that skilled artisan be enable to better understand and utilize the present invention.The present invention is only
It is limited by claims and its full scope and equivalent.
Claims (6)
1. a kind of double stimuli responsive Water-based polyurethane elastomer, which is characterized in that with non-aqueous in aqueous polyurethane and non-molten
On the basis of agent constituent mass, comprising: 30-70% macromolecule dihydric alcohol, 15-50% diisocyanate, the hydrophilic chain extension of 4-8%
Agent, 0.1-11% glycol chain extender, the agent of 0.1-2.2% polyol crosslink, 0.01-0.08% catalyst, 3-6% triethylamine,
0-5% diamine chain extenders further include 0.1-11% sensitive dyes and the 0.1-11% photoresponse factor.
2. a kind of double stimuli responsive Water-based polyurethane elastomer according to claim 1, which is characterized in that described two is different
Cyanate is selected from toluene di-isocyanate(TDI) (TDI), methyl diphenylene diisocyanate (MDI), isophorone diisocyanate
(IPDI), one of hexamethylene diisocyanate (HDI) or any a variety of mixing；
The macromolecule dihydric alcohol is selected from the polymer polyatomic alcohol with 2000~8000g/mol number-average molecular weight, the polymerization
Object polyalcohol includes polyadipate -1,4- butyl glycol ester diol (PBA), polycaprolactone diols (PCL), polycarbonate glycol
(PCDL) and polylactide dihydric alcohol (PCL)；
The hydrophilic chain extender is selected from dihydromethyl propionic acid (DMPA) or dimethylolpropionic acid (DMBA)；
The glycol chain extender is selected from 1,4- butanediol (BDO) or 1,6-HD (HDO)；
The diamine chain extenders are selected from ethylenediamine (EDA) or isophorone diamine (IPDA)；
The catalyst is selected from one of dibutyl tin dilaurate (DBTDL), organo-bismuth (DY-20) and BACT-20C or more
Kind；
The polyol crosslink agent is selected from one of TMP, PCL-3057, BY-3095 or a variety of.
3. a kind of double stimuli responsive Water-based polyurethane elastomer according to claim 1, which is characterized in that the sensitivity
Property dyestuff be selected from one of flowering structure A~F or several combinations, structural formula are as follows:
4. a kind of double stimuli responsive Water-based polyurethane elastomer according to claim 1, which is characterized in that the light is rung
Answering the factor is 2- cinnamoyl amido -1,3- propylene glycol.
5. a kind of a kind of preparation side of double stimuli responsive Water-based polyurethane elastomer as described in claim 1-4 is any one
Method characterized by comprising
The preparation of step 1, aqueous polyurethane emulsion:
It takes macromolecule dihydric alcohol vacuum dehydration 0.5-1.5 hours at 110-120 DEG C, adds the diisocyanate, quick of metering
Hydrophilic chain extender, glycol chain extender, the photoresponse factor, polyalcohol are added after reaction 2-4 hours at 70-100 DEG C for perceptual dyestuff
Crosslinking agent, catalysts and solvents, 60-90 DEG C reaction 1-4 hours, be then added three under conditions of high speed shear and 0-40 DEG C
Water and diamine chain extenders are added after reaction 0.5-5 minute in ethamine, after emulsifying 5-30 minutes, reaction product 40-50 DEG C,
Solvent is sloughed under 0.01MPa vacuum condition, obtains double stimuli responsive aqueous polyurethane emulsion；
Step 2, the preparation of double stimuli responsive Water-based polyurethane elastomer:
Step 1 gained double stimuli responsive aqueous polyurethane emulsion is poured into and is coated in release agent mold, when it from when doing one section
Between after, then be placed in 40 DEG C of baking ovens and double stimuli responsive Water-based polyurethane elastomer can be obtained at glue film.
6. a kind of preparation method of double stimuli responsive Water-based polyurethane elastomer according to claim 5, feature exist
In on the basis of non-aqueous in aqueous polyurethane and non-solvent constituent mass, the additive amount of the solvent is 20-50%, institute
The additive amount for stating water is 150%-300%；
The solvent is selected from one of acetone or butanone.
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Cited By (4)
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| CN110551273A (en) * | 2019-09-17 | 2019-12-10 | 齐鲁工业大学 | Preparation method of dual-stimulus-response polyurethane micelle |
| CN111978507A (en) * | 2020-07-20 | 2020-11-24 | 温州大学 | Preparation method of pH-responsive color-changing polyurethane hydrogel |
| CN112662247A (en) * | 2020-12-31 | 2021-04-16 | 常州市天盾涂料有限公司 | High-toughness water-based acrylic coating and preparation method thereof |
| CN114395129A (en) * | 2021-12-22 | 2022-04-26 | 山东一诺威新材料有限公司 | Preparation method of polyether polyol with photodegradation characteristic |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111978507A (en) * | 2020-07-20 | 2020-11-24 | 温州大学 | Preparation method of pH-responsive color-changing polyurethane hydrogel |
| CN112662247A (en) * | 2020-12-31 | 2021-04-16 | 常州市天盾涂料有限公司 | High-toughness water-based acrylic coating and preparation method thereof |
| CN112662247B (en) * | 2020-12-31 | 2022-02-18 | 常州市天盾涂料有限公司 | High-toughness water-based acrylic coating and preparation method thereof |
| CN114395129A (en) * | 2021-12-22 | 2022-04-26 | 山东一诺威新材料有限公司 | Preparation method of polyether polyol with photodegradation characteristic |
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