CN109851747A - A kind of aqueous polyurethane heat-barrier material and preparation method thereof - Google Patents
A kind of aqueous polyurethane heat-barrier material and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to fine polymer field of material technology more particularly to a kind of aqueous polyurethane heat-barrier material and preparation method thereof.The present invention provides a kind of preparation methods of aqueous polyurethane heat-barrier material, comprising the following steps: a) poly (propylene carbonate) polyalcohol, diisocyanate and hydrophilic chain extender is carried out the first reaction under the action of catalyst, obtains the first product；B) neutralizer is added in first product and carries out neutralization reaction, deionized water is added and is emulsified, add non-hydrophilic chain extender and carry out the second reaction, obtain the second product；C) aerosil, foam stabiliser and thickener are added in second product, is stirred foaming, it is dry, obtain aqueous polyurethane heat-barrier material.The experimental results showed that aqueous polyurethane heat-barrier material made from preparation method of the present invention has good flexibility, lower thermal conductivity and thermal diffusivity.
Description
Technical field
The invention belongs to fine polymer field of material technology more particularly to a kind of aqueous polyurethane heat-barrier material and its systems
Preparation Method.
Background technique
Aqueous polyurethane is they Yu Shuizhong and a kind of polyurethane resin formed, due to being that dispersion is situated between with water
Matter, have many advantages, such as compared to traditional solvent-borne polyurethane material it is nontoxic, pollution-free, non-ignitable, at low cost, be a kind of pair of human body without
Harmful, environmental-friendly new material.Aqueous polyurethane has excellent film forming, flexibility, and mechanical strength is high, and adhesive property is excellent
It is good, at present coating, adhesive, leather, in terms of be widely used.In general, many fabrics, leather products need
Certain heat-proof quality, such as apron for kitchen use, gloves needs are heat-insulated to protect wearer not to be burned, and outdoor sports are needed with fabric
It comfortably to be experienced every amount of solar heat to user, however aqueous polyurethane thermal conductivity itself is high, product heat-proof quality is very poor.
Summary of the invention
In view of this, the present invention provides a kind of aqueous polyurethane heat-barrier material and preparation method thereof, it is existing for solving
The very poor problem of aqueous polyurethane heat-proof quality.
The specific technical solution of the present invention is as follows:
A kind of preparation method of aqueous polyurethane heat-barrier material, comprising the following steps:
A) poly (propylene carbonate) polyalcohol, diisocyanate and hydrophilic chain extender are carried out to first under the action of catalyst anti-
It answers, obtains the first product；
B) neutralizer is added in first product and carries out neutralization reaction, deionized water is added and is emulsified, adds
Non-hydrophilic chain extender carries out the second reaction, obtains the second product；
C) aerosil, foam stabiliser and thickener are added in second product, is stirred foaming,
It is dry, obtain aqueous polyurethane heat-barrier material.
In the present invention, using poly (propylene carbonate) polyalcohol as the first product of Material synthesis, then that the first product is neutralized,
Emulsification and the second reaction, obtain the second product, aerosil are added in the second product and foam stabiliser is sent out
Bubble, obtain aqueous polyurethane heat-barrier material, the experimental results showed that the aqueous polyurethane heat-barrier material have good flexibility, compared with
Low thermal conductivity and thermal diffusivity.Also, the aqueous polyurethane heat-barrier material that preparation method of the present invention obtains is based on aqueous poly- ammonia
Ester, it is environmentally friendly using water as decentralized medium, it is not detrimental to health, is a kind of green material.
Aerosil is a kind of porous functional material, and inner void and solid phase particulates are nanoscales, tool
There are high porosity, lower thermal conductivity, there is huge applications prospect in ultra heat insulating material.But the material is brittle solid, it can not
It is used separately as heat-barrier material, using limited.Preparation method of the present invention is compound by aqueous polyurethane and aerosil,
Aqueous polyurethane flexibility is good, has complementary advantages, it is heat-insulated that the aqueous polyurethane with good flexibility and heat insulation is prepared
Material has potential great market application prospect.
Preferably, the temperature of first reaction is 70 DEG C~90 DEG C；
The time of first reaction is 2h~6h.
Preferably, the temperature of second reaction is -10 DEG C~25 DEG C；
The time of second reaction is 10min~60min.
Preferably, after step a), before step b), further includes: diluent is added.Diluent is acetone or carbonic acid diformazan
The low boiling point solvents such as ester.The viscosity for being added to reduce reaction mass of diluent, conducive to the progress of reaction.
Preferably, step b) is described adds after the second reaction of non-hydrophilic chain extender progress, described to obtain the second product
Before, further includes: remove diluent.Removing diluent is specially that diluent is removed under reduced pressure.
Preferably, the poly (propylene carbonate) polyalcohol, the diisocyanate, the hydrophilic chain extender, the non-parent
Water chain extender, the aerosil, the foam stabiliser and the thickener mass ratio be 60:(18~63):
(2~10): (0.1~3) (0.1~10): (0.1~4): (0.1-4).
In the present invention, poly (propylene carbonate) polyalcohol is initiator to be added, with epoxy third using carbon dioxide as starting material
Alkane carries out catalysis reaction copolymerization, and the structure with carbonate group and ether, intensity is high, and hydrolysis is at low cost, comprehensive performance
It is excellent, and consumption carbon dioxide gas can alleviate section greenhouse effects, while save the energy such as petroleum, to environmental protection, energy conservation
Emission reduction has a very big significance.
In the present invention, the temperature of neutralization reaction is -10 DEG C~40 DEG C, and the time of neutralization reaction is 3min~5min.Emulsification
Temperature be -10 DEG C~25 DEG C, time of emulsion reaction is 10min~60min.
In the present invention, aerosil, foam stabiliser and thickener is added in step c) in second product
It is stirred after foaming, before dry, further includes:
Foamed product is coated in silicone oil paper.
Dry temperature is 60 DEG C~80 DEG C；After drying, further includes: separated.
In the present invention, poly (propylene carbonate) polyalcohol, catalyst, diluent, neutralizer and thickener mass ratio be 60:
0.06~0.36:5~20:2~10:0.1~10.
The total amount of deionized water and the mass ratio of poly (propylene carbonate) polyalcohol are 100~300:60.
Preferably, the molecular weight of the poly (propylene carbonate) polyalcohol is 1000~3000；
The hydroxy functionality of the poly (propylene carbonate) polyalcohol is 2~3；
The mole fraction of carbonate group is 0.3~0.4 in the poly (propylene carbonate) polyol molecule.
In the present invention, diisocyanate is aromatic diisocyanate.
Preferably, the diisocyanate is toluene di-isocyanate(TDI) and/or methyl diphenylene diisocyanate.
Preferably, the hydrophilic chain extender is selected from ethylenediamine base ethanesulfonic acid sodium, dihydromethyl propionic acid or dimethylolpropionic acid；
The non-hydrophilic chain extender is selected from ethylenediamine or triethylene diamine.
It is furthermore preferred that hydrophilic chain extender is dihydromethyl propionic acid, non-hydrophilic chain extender is ethylenediamine.
Preferably, the neutralizer is selected from triethylamine, tripropyl amine (TPA), tri-n-butylamine, sodium hydroxide or ammonium hydroxide.
Foam stabiliser is organosilicone surfactants.
In the present invention, organosilicone surfactants are selected from DC193, DC197 or DC198, more preferably DC193.
In the present invention, catalyst is selected from stannous octoate, di-n-butyltin dilaurate or tin acetate.
In the present invention, aerosil is carbon/aerosil of hydridization method preparation, specifically by hydridization gas
Then hybrid gel is made by sol-gel in the raw material mixing of each constituent element of gel, re-dry, heat treatment obtain the carbon of hydridization/
Aerosil.
In the present invention, thickener be polyurethane-type thickener, polyurethane-type thickener be selected from Coatex company 830W,
2025 or 3025, polyurethane-type thickener is more preferably the 830W of Coatex company.
In conclusion the present invention provides a kind of preparation methods of aqueous polyurethane heat-barrier material, comprising the following steps: a)
Poly (propylene carbonate) polyalcohol, diisocyanate and hydrophilic chain extender are subjected to the first reaction under the action of catalyst, obtain
One product；B) acetone is added in first product and neutralizer carries out neutralization reaction, deionized water is added and is emulsified, then
Non-hydrophilic chain extender is added and carries out the second reaction, obtains the second product；C) silica airsetting is added in second product
Glue, foam stabiliser and thickener are stirred foaming, dry, obtain aqueous polyurethane heat-barrier material.In the present invention, with poly-
Polypropylene carbonate ester polyol is the first product of Material synthesis, and then that the first product is neutralized, emulsification and the second reaction obtain the
Two products are added aerosil, foam stabiliser and thickener in the second product and are stirred foaming, dry, obtain
To aqueous polyurethane heat-barrier material.The experimental results showed that the aqueous polyurethane heat-barrier material has good flexibility, lower
Thermal conductivity and thermal diffusivity.Also, the aqueous polyurethane heat-barrier material that preparation method of the present invention obtains is based on aqueous polyurethane, with
Water is decentralized medium, environmentally friendly, is not detrimental to health, and is a kind of green material.
Specific embodiment
The present invention provides a kind of aqueous polyurethane heat-barrier materials and preparation method thereof, for solving existing aqueous polyurethane
The very poor problem of heat-proof quality.
The technical scheme in the embodiments of the invention will be clearly and completely described below, it is clear that described implementation
Example is only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, this field is common
Technical staff's every other embodiment obtained without making creative work belongs to the model that the present invention protects
It encloses.
Embodiment 1
In terms of mass parts, taking 60 parts of molecular weight is 3000, and the poly (propylene carbonate) dihydric alcohol that hydroxy functionality is 2 is added
14.76 parts of toluene di-isocyanate(TDI)s and 3 parts of dihydromethyl propionic acids carry out 3h first at 80 DEG C and react, obtain the first product, drop
For temperature to 40 DEG C, 10 parts of acetone, which are added, in the first product reduces viscosity, and 2.26 parts of triethylamines are added and carry out 3min neutralization reaction, add
Enter 150 parts of deionized water 2000rpm emulsification 15min, 0.85 part of ethylenediamine be added and carries out the reaction of 30min second (chain extending reaction),
Removed under reduced pressure acetone obtains the second product.Take 80 part of second product, be added 3 part of 200 mesh aerosil and 0.24 part
DC193, is added 10 parts of deionized waters and 3.04 parts of thickeners, and 2000rpm carries out 10min stirring foaming, obtains aqueous polyurethane
Waterborne PU Composite is applied in silicone oil paper by composite material, and it is for 24 hours, isolated aqueous to be placed on drying in 80 DEG C of baking ovens
Polyurethane heat-barrier material.
Embodiment 2
In terms of mass parts, taking 60 parts of molecular weight is 3000, and the poly (propylene carbonate) dihydric alcohol that hydroxy functionality is 2 is added
14.76 parts of toluene di-isocyanate(TDI)s and 3 parts of dihydromethyl propionic acids carry out 3h first at 80 DEG C and react, obtain the first product, drop
For temperature to 40 DEG C, 10 parts of acetone, which are added, in the first product reduces viscosity, and 2.26 parts of triethylamines are added and carry out 3min neutralization reaction, add
Enter 150 parts of deionized water 2000rpm emulsification 15min, 0.85 part of ethylenediamine be added and carries out the reaction of 30min second (chain extending reaction),
Removed under reduced pressure acetone obtains the second product.Take 80 part of second product, be added 4 part of 200 mesh aerosil and 0.24 part
DC193, is added 10 parts of deionized waters and 2.76 parts of thickeners, and 2000rpm carries out 10min stirring foaming, obtains aqueous polyurethane
Waterborne PU Composite is applied in silicone oil paper by composite material, and it is for 24 hours, isolated aqueous to be placed on drying in 80 DEG C of baking ovens
Polyurethane heat-barrier material.
Embodiment 3
In terms of mass parts, taking 60 parts of molecular weight is 3000, and the poly (propylene carbonate) dihydric alcohol that hydroxy functionality is 2 is added
14.76 parts of toluene di-isocyanate(TDI)s and 3 parts of dihydromethyl propionic acids carry out 3h first at 80 DEG C and react, obtain the first product, drop
For temperature to 40 DEG C, 10 parts of acetone, which are added, in the first product reduces viscosity, and 2.26 parts of triethylamines are added and carry out 3min neutralization reaction, add
Enter 150 parts of deionized water 2000rpm emulsification 15min, 0.85 part of ethylenediamine be added and carries out the reaction of 30min second (chain extending reaction),
Removed under reduced pressure acetone obtains the second product.Take 80 part of second product, be added 6 part of 200 mesh aerosil and 0.24 part
DC193, is added 10 parts of deionized waters and 1.83 parts of thickeners, and 2000rpm carries out 10min stirring foaming, obtains aqueous polyurethane
Waterborne PU Composite is applied in silicone oil paper by composite material, and it is for 24 hours, isolated aqueous to be placed on drying in 80 DEG C of baking ovens
Polyurethane heat-barrier material.
Embodiment 4
In terms of mass parts, taking 60 parts of molecular weight is 3000, and the poly (propylene carbonate) dihydric alcohol that hydroxy functionality is 2 is added
14.76 parts of toluene di-isocyanate(TDI)s and 3 parts of dihydromethyl propionic acids carry out 3h first at 80 DEG C and react, obtain the first product, drop
For temperature to 40 DEG C, 10 parts of acetone, which are added, in the first product reduces viscosity, and 2.26 parts of triethylamines are added and carry out 3min neutralization reaction, add
Enter 150 parts of deionized water 2000rpm emulsification 15min, 0.85 part of ethylenediamine be added and carries out the reaction of 30min second (chain extending reaction),
Removed under reduced pressure acetone obtains the second product.Take 80 part of second product, be added 8 part of 200 mesh aerosil and 0.24 part
DC193, is added 10 parts of deionized waters and 1.28 parts of thickeners, and 2000rpm carries out 10min stirring foaming, obtains aqueous polyurethane
Waterborne PU Composite is applied in silicone oil paper by composite material, and it is for 24 hours, isolated aqueous to be placed on drying in 80 DEG C of baking ovens
Polyurethane heat-barrier material.
Comparative example 1
In terms of mass parts, taking 60 parts of molecular weight is 3000, and the poly (propylene carbonate) dihydric alcohol that hydroxy functionality is 2 is added
14.76 parts of toluene di-isocyanate(TDI)s and 3 parts of dihydromethyl propionic acids carry out 3h first at 80 DEG C and react, obtain the first product, drop
For temperature to 40 DEG C, 10 parts of acetone, which are added, in the first product reduces viscosity, and 2.26 parts of triethylamines are added and carry out 3min neutralization reaction, add
Enter 150 parts of deionized water 2000rpm emulsification 15min, 0.85 part of ethylenediamine be added and carries out the reaction of 30min second (chain extending reaction),
Removed under reduced pressure acetone obtains the second product.Second product is applied in silicone oil paper, drying in 80 DEG C of baking ovens is placed on and for 24 hours, separates
To aqueous polyurethane heat-barrier material.
Embodiment 5
Aqueous polyurethane heat-barrier material made from Example 1~4 and comparative example 1 is cut into 4cm*4cm square sheet,
Its thermal conductivity and thermal diffusivity are tested using Hot Disk thermal constant analyzer, experimental result is as shown in table 1.Table 1 the result shows that,
Using aerosil and the aqueous polyurethane heat-barrier material (embodiment 1-4) of the compound preparation of aqueous polyurethane relative to list
Pure water-base polyurethane material (comparative example 1) has lower thermal conductivity and thermal diffusivity, and flexibility is good.
The heating conduction of 1 aqueous polyurethane heat-barrier material of 1 Examples 1 to 4 of table and comparative example is tested
| Thermal conductivity (W/mK) | Thermal diffusivity (m2/s) | |
| Embodiment 1 | 0.0680 | 0.1016 |
| Embodiment 2 | 0.0660 | 0.1231 |
| Embodiment 3 | 0.0589 | 0.0956 |
| Embodiment 4 | 0.0573 | 0.1032 |
| Comparative example 1 | 0.2040 | 0.1651 |
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of preparation method of aqueous polyurethane heat-barrier material, which comprises the following steps:
A) poly (propylene carbonate) polyalcohol, diisocyanate and hydrophilic chain extender are subjected to the first reaction under the action of catalyst,
Obtain the first product；
B) neutralizer is added in first product and carries out neutralization reaction, deionized water is added and is emulsified, non-parent is added
Water chain extender carries out the second reaction, obtains the second product；
C) aerosil, foam stabiliser and thickener are added in second product, is stirred foaming, does
It is dry, obtain aqueous polyurethane heat-barrier material.
2. preparation method according to claim 1, which is characterized in that the temperature of first reaction is 70 DEG C~90 DEG C；
The time of first reaction is 2h~6h.
3. preparation method according to claim 1, which is characterized in that the temperature of second reaction is -10 DEG C~25 DEG C；
The time of second reaction is 10min~60min.
4. preparation method according to claim 1, which is characterized in that after step a), before step b), further includes: add
Enter diluent.
5. the preparation method according to claim 4, which is characterized in that step b) is described to add non-hydrophilic chain extender progress
After second reaction, it is described obtain the second product before, further includes: remove the diluent.
6. preparation method according to claim 1, which is characterized in that the poly (propylene carbonate) polyalcohol, described two different
Cyanate, the hydrophilic chain extender, the non-hydrophilic chain extender, the aerosil, the foam stabiliser and institute
The mass ratio for stating thickener is 60:(18~63): (2~10): (0.1~3) (0.1~10): (0.1~4): (0.1~4).
7. preparation method according to claim 1, which is characterized in that the molecular weight of the poly (propylene carbonate) polyalcohol is
1000~3000；
The hydroxy functionality of the poly (propylene carbonate) polyalcohol is 2~3；
The mole fraction of carbonate group is 0.3~0.4 in the poly (propylene carbonate) polyol molecule.
8. preparation method according to claim 1, which is characterized in that the diisocyanate is toluene di-isocyanate(TDI)
And/or methyl diphenylene diisocyanate.
9. preparation method according to claim 1, which is characterized in that the hydrophilic chain extender is selected from ethylenediamine base ethanesulfonic acid
Sodium, dihydromethyl propionic acid or dimethylolpropionic acid；
The non-hydrophilic chain extender is selected from ethylenediamine or triethylene diamine.
10. preparation method according to claim 1, which is characterized in that the neutralizer is selected from triethylamine, tripropyl amine (TPA), three
Butylamine, sodium hydroxide or ammonium hydroxide.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113999411A (en) * | 2021-09-29 | 2022-02-01 | 上海工程技术大学 | Water-based polyurethane acrylate/silicon dioxide aerogel composite membrane and preparation method and application thereof |
| CN114410207A (en) * | 2022-03-16 | 2022-04-29 | 太原理工大学 | Preparation method of silicon dioxide aerogel modified polyurethane heat insulation material |
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| CN108129628A (en) * | 2017-12-20 | 2018-06-08 | 福建师范大学泉港石化研究院 | From fire-retardant heat insulation aqueous polyurethane composition, foaming body and preparation method thereof |
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| EP1442069A1 (en) * | 2001-10-31 | 2004-08-04 | Bayer MaterialScience AG | Low apparent density water blown foamed plastics containing polyurethane groups |
| CN108129628A (en) * | 2017-12-20 | 2018-06-08 | 福建师范大学泉港石化研究院 | From fire-retardant heat insulation aqueous polyurethane composition, foaming body and preparation method thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113999411A (en) * | 2021-09-29 | 2022-02-01 | 上海工程技术大学 | Water-based polyurethane acrylate/silicon dioxide aerogel composite membrane and preparation method and application thereof |
| CN114410207A (en) * | 2022-03-16 | 2022-04-29 | 太原理工大学 | Preparation method of silicon dioxide aerogel modified polyurethane heat insulation material |
| CN114410207B (en) * | 2022-03-16 | 2023-02-28 | 太原理工大学 | Preparation method of silicon dioxide aerogel modified polyurethane heat insulation material |
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