CN106589373B - A kind of super-hydrophobic polyimide foam and preparation method thereof - Google Patents
A kind of super-hydrophobic polyimide foam and preparation method thereof Download PDFInfo
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- CN106589373B CN106589373B CN201611126780.XA CN201611126780A CN106589373B CN 106589373 B CN106589373 B CN 106589373B CN 201611126780 A CN201611126780 A CN 201611126780A CN 106589373 B CN106589373 B CN 106589373B
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- 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
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1057—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain
- C08G73/106—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain containing silicon
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- 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
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1003—Preparatory processes
- C08G73/1035—Preparatory processes from tetracarboxylic acids or derivatives and diisocyanates
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- Chemical Kinetics & Catalysis (AREA)
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Abstract
The present invention relates to a kind of super-hydrophobic polyimide foams and preparation method thereof, belong to technical field of polymer materials.Super-hydrophobic polyimide foam in the present invention includes the component of following mass fraction: 80-120 parts of aromatic dianhydride, 20-90 parts of polar solvent, 5-100 parts of containing hydrogen silicone oil, 5-20 parts of low mass molecule alcohol, 5-20 parts of polyether modified silicon oil, 5-10 parts of catalyst, 150-300 parts of polyisocyanates.Compared with the prior art, hydrophobic performance of the present invention is excellent, and heat resistance, stability, anti-flammability are all preferable, while process flow is simple, is conducive to industrialized production and popularization.
Description
Technical field
The present invention relates to a kind of super-hydrophobic polyimide foams and preparation method thereof, belong to technical field of polymer materials.
Background technique
Polyimide foam is because of its excellent flame retardant property, heat-insulating property, sound insulation value, low-smoke low-toxicity performance, in the world
On be widely used for naval vessel, aircraft carrier, submarine, aircraft as exhausted heat-insulated and acoustic material.
Isocyanate group polyimide foam is sent out in the presence of a catalyst by aromatic dianhydride or aromatic esters
Raw polycondensation reaction is steeped using the low-molecular material of generation, such as carbon dioxide as a kind of Thermocurable polyimide made from foaming agent
Foam plastics.Due in technical process use room temperature free foaming, and it is lower to the purity requirement of raw material thus have very
Apparent industrialized production advantage.
As heat-barrier material, if it absorbs water, thermal coefficient can be greatly improved, heat insulation is reduced, loses heat-insulated material
The effect of material.The water absorption rate of isocyanate group polyimide foam is very low, but water can also penetrate into foam, one
Its using effect is also influenced to a certain extent under a little particular surroundings.So improving popularization and use of its hydrophobicity for the material
It is of great significance.
Summary of the invention
In order to solve foregoing problems, the present invention provides a kind of super-hydrophobic polyimide foam and preparation method thereof.
Super-hydrophobic polyimide foam in the present invention includes the component of following mass fraction: 80-120 parts of aromatic dianhydride,
20-90 parts of polar solvent, 5-100 parts of containing hydrogen silicone oil, 5-20 parts of low mass molecule alcohol, 5-20 parts of polyether modified silicon oil, catalyst 5-10
Part, 150-300 parts of polyisocyanates.
The aromatic dianhydride is pyromellitic acid dianhydride, 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydrides, 3,3 ', 4,4 '-biphenyl
Base tetracarboxylic dianhydride, 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydrides, 3,3 ', 4,4 '-diphenyl sulphone (DPS) tetracarboxylic dianhydrides, 3,3 ', 4,
One or more of 4 '-diphenyl ether tetracid dianhydrides.
The polar solvent be N, N '-dimethyl formamide, N, N '-dimethyl acetamide, n-methyl-2-pyrrolidone,
It is one or more of in dimethyl sulfoxide, tetrahydrofuran.
The containing hydrogen silicone oil, hydrogen content 0.01-1.6%.In the Si -- H bond of containing hydrogen silicone oil active hydrogen can and isocyanates
In-NCO group reacts under the effect of the catalyst, forms Si-C key, poly dimethyl silicon is introduced in polyimide molecule chain
Oxygen alkane side chain, assigns the ultra-hydrophobicity of product.
The polyether modified silicon oil is one or both of SiOC type silicone oil or SiC type silicone oil as foam stabiliser
Combination, play the role of it is even bubble and stable foam, allow product abscess more evenly with it is fine and closely woven.
The catalyst is one of triethanolamine, triethylenediamine, stannous octoate, two fourth tin of dilaurate or several
Kind.
The polyisocyanates is polyphenyl polymethylene polyisocyanates, xylene diisocyanate or toluene
The one or more of diisocyanate.
The preparation step of super-hydrophobic polyimide foam in the present invention is as follows: (1) aromatic dianhydride is molten in reaction kettle
In polar solvent, it is then proportionally added into low mass molecule alcohol, 80-120 DEG C of reaction 1-2 hours is heated to, is then cooled to room temperature,
It is successively proportionally added into containing hydrogen silicone oil, catalyst, polyether modified silicon oil again, stirs evenly, obtains foam precursors；(2) by foam
Precursor is uniform by stirring or high-pressure atomization collisional mixing with polyisocyanates, pours into foaming in mold and obtains among foam
Body；(3) foam intermediate is placed in micro-wave oven, with microwave heating 0.5-2 hours, solidifies it further, then by foam
It is placed in infrared baking oven and is heated to 150-300 DEG C, obtain finished product after 0.5-2 hours.
The present invention provides a kind of super-hydrophobic polyimide foams and preparation method thereof, compared with the prior art, this hair
The bright innovative containing hydrogen silicone oil that introduces in formula participates in chemical reaction, because the Si-H in containing hydrogen silicone oil strand contains vivaciously
Hydrogen, can under the effect of the catalyst in isocyanates-NCO group reacted, thus in polyimide foam molecule
The side chain that longer polydimethylsiloxane is introduced in chain forms super-hydrophobic group, assigns the super-hydrophobicity of product, absorbs water at room temperature
Rate can be lower than 0.30%.Hydrophobic performance of the present invention is excellent, and heat resistance, stability, anti-flammability are all preferable, while process flow is simple,
Be conducive to industrialized production and popularization.
Specific embodiment
Below with reference to the embodiment technical solution that the present invention will be described in detail.
Embodiment 1.
(1) mass fraction is pressed, 100 parts of pyromellitic acid dianhydrides are dissolved in 80 parts of polar solvent N, N- dimethyl in reaction kettle
In formamide, then be added 10 parts of ethylene glycol, be heated to 110 DEG C react 1.5 hours, be then cooled to room temperature, then successively by than
Containing hydrogen silicone oil, 10 parts of triethylenediamine catalyst, the 5 parts of SiC type polyether modified silicon oils of 5 parts of hydrogen contents 0.2% are added in example, stir
It mixes uniformly, obtains foam precursors.
(2) foam precursors obtained and the more methyl polyisocyanates of phenyl more than 160 parts are stirred by paddle mixer
It is uniformly mixed, pours into foaming in mold and obtain foam intermediate.
(3) foam intermediate is placed in micro-wave oven, with microwave heating 1 hour, solidifies it further.Then by foam
It is placed in infrared baking oven and is heated to 250 DEG C, obtain finished product after 2 hours.
Obtained foam density is 10kg/m3, there is super-hydrophobicity, water absorption rate is less than 0.30% at room temperature.
Embodiment 2.
(1) mass fraction is pressed, 100 parts of pyromellitic acid dianhydrides are dissolved in 80 parts of polar solvent N, N- dimethyl in reaction kettle
In formamide, then be added 10 parts of ethylene glycol, be heated to 110 DEG C react 1.5 hours, be then cooled to room temperature, then successively by than
Containing hydrogen silicone oil, 10 parts of triethylenediamine catalyst, the 5 parts of SiC type polyether modified silicon oils of 30 parts of hydrogen contents 0.2% are added in example, stir
It mixes uniformly, obtains foam precursors.
(2) foam precursors obtained and the more methyl polyisocyanates of phenyl more than 160 parts are stirred by paddle mixer
It is uniformly mixed, pours into foaming in mold and obtain foam intermediate.
(3) foam intermediate is placed in micro-wave oven, with microwave heating 1 hour, solidifies it further.Then by foam
It is placed in infrared baking oven and is heated to 250 DEG C, obtain finished product after 2 hours.
Obtained foam density is 10kg/m3, there is super-hydrophobicity, water absorption rate is less than 0.25% at room temperature.
Embodiment 3.
(1) mass fraction is pressed, by 80 part 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydrides are dissolved in 20 parts of polarity in reaction kettle
In Solvents N-methyl -2-Pyrrolidone, 5 parts of ethylene glycol are then added, is heated to 110 DEG C and reacts 1.5 hours, be then cooled to room
Temperature, then be successively proportionally added into the containing hydrogen silicone oil of 40 parts of hydrogen contents 0.8%, 5 parts of triethylenediamine catalyst, 5 parts of SiC types and gather
Ether modified silicon oil, stirs evenly, and obtains foam precursors.
(2) foam precursors obtained and the more methyl polyisocyanates of phenyl more than 150 parts are stirred by paddle mixer
It is uniformly mixed, pours into foaming in mold and obtain foam intermediate.
(3) foam intermediate is placed in micro-wave oven, with microwave heating 1 hour, solidifies it further.Then by foam
It is placed in infrared baking oven and is heated to 250 DEG C, obtain finished product after 2 hours.Obtained foam density is 15kg/m3, have super thin
Aqueous, water absorption rate is less than 0.16% at room temperature.
Embodiment 4.
(1) mass fraction is pressed, 120 parts of equal 3,3 ', 4,4 '-diphenyl ether tetracid dianhydrides are dissolved in 90 parts of polarity in reaction kettle
In solvent n,N-Dimethylformamide, 20 parts of ethylene glycol are then added, is heated to 110 DEG C and reacts 1.5 hours, be then cooled to room
Temperature, then successively it is proportionally added into the containing hydrogen silicone oil of 20 parts of hydrogen contents 1.6%, 10 parts of triethylenediamine catalyst, 20 parts of SiOC types
Polyether modified silicon oil stirs evenly, and obtains foam precursors.
(2) foam precursors obtained and the more methyl polyisocyanates of phenyl more than 300 parts are stirred by paddle mixer
It is uniformly mixed, pours into foaming in mold and obtain foam intermediate.
(3) foam intermediate is placed in micro-wave oven, with microwave heating 1 hour, solidifies it further.Then by foam
It is placed in infrared baking oven and is heated to 250 DEG C, obtain finished product after 2 hours.Obtained foam density is 8kg/m3, have super-hydrophobic
Property, water absorption rate is less than 0.1% at room temperature.
Embodiment 5.
(1) mass fraction is pressed, by 110 part 3,3 ', 4,4 '-xenyl tetracarboxylic dianhydrides are dissolved in 70 parts of polarity in reaction kettle
In solvent n,N-Dimethylformamide, 15 parts of ethylene glycol are then added, is heated to 110 DEG C and reacts 1.5 hours, be then cooled to room
Temperature, then successively it is proportionally added into the containing hydrogen silicone oil of 100 parts of hydrogen contents 0.18%, 8 parts of triethylenediamine catalyst, 15 parts of SiOC
Type polyether modified silicon oil, stirs evenly, and obtains foam precursors.
(2) foam precursors obtained and the more methyl polyisocyanates of phenyl more than 250 parts are stirred by paddle mixer
It is uniformly mixed, pours into foaming in mold and obtain foam intermediate.
(3) foam intermediate is placed in micro-wave oven, with microwave heating 1 hour, solidifies it further.Then by foam
It is placed in infrared baking oven and is heated to 250 DEG C, obtain finished product after 2 hours.
Obtained foam density is 8kg/m3, there is super-hydrophobicity, water absorption rate is less than 0.1% at room temperature.
Comparative example.
A kind of hydrophobic type polyimide foam, the component comprising following mass fraction: 70 parts of aromatic dianhydride, polar solvent
Part 140 parts, 20 parts of low mass molecule alcohol, 15 parts of polyether modified silicon oil, 0.5 part of catalyst, 90 parts of polyisocyanates.
Wherein: 3,3 ', 4,4 '-benzophenone of aromatic dianhydride tetracid dianhydride, polar solvent are dimethylformamide, low molecule
Alcohol is ethylene glycol, polyether modified silicon oil is SiOC type polyether modified silicon oil, catalyst is stannous octoate, polyisocyanates is sub-
Methylxylene diisocyanate.
By said components and proportion, obtained foam density is 9kg/m3, water absorption rate is 2.1% at room temperature.
It can be seen that polyimide foam can be effectively reduced in component of the present invention and proportion from the index of comparative example
Water absorption rate improves its hydrophobic performance.
A kind of super-hydrophobic polyimide foam and preparation method thereof is provided for the embodiments of the invention above to have carried out in detail
Thin to introduce, used herein a specific example illustrates the principle and implementation of the invention, and above embodiments are said
It is bright to be merely used to help understand method and its core concept of the invention；At the same time, for those skilled in the art, foundation
Thought of the invention, there will be changes in the specific implementation manner and application range, in conclusion the content of the present specification is not
It is interpreted as limitation of the present invention.
Claims (8)
1. a kind of super-hydrophobic polyimide foam, which is characterized in that the component including following mass fraction: aromatic dianhydride 80-120
Part, 20-90 parts of polar solvent, 5-100 parts of containing hydrogen silicone oil, 5-20 parts of low mass molecule alcohol, 5-20 parts of polyether modified silicon oil, catalyst 5-
10 parts, 150-300 parts of polyisocyanates；The active hydrogen of Si-H in containing hydrogen silicone oil strand, under the effect of the catalyst with it is more
In isocyanates-NCO group reacted, the side of longer polydimethylsiloxane is introduced in polyimide foam strand
Chain forms super-hydrophobic group.
2. a kind of super-hydrophobic polyimide foam as described in claim 1, it is characterised in that: the aromatic dianhydride is equal benzene four
Acid dianhydride, 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydrides, 3,3 ', 4,4 '-xenyl tetracarboxylic dianhydrides, 3,3 ', 4,4 '-hexichol first
One of ketone tetracarboxylic dianhydride, 3,3 ', 4,4 '-diphenyl sulphone (DPS) tetracarboxylic dianhydrides, 3,3 ', 4,4 '-diphenyl ether tetracid dianhydrides are several
Kind.
3. a kind of super-hydrophobic polyimide foam as described in claim 1, it is characterised in that: the polar solvent is N, N '-
Dimethylformamide, N, N '-dimethyl acetamide, n-methyl-2-pyrrolidone, dimethyl sulfoxide, it is a kind of in tetrahydrofuran or
It is several.
4. a kind of super-hydrophobic polyimide foam as described in claim 1, it is characterised in that: the containing hydrogen silicone oil, hydrogen content
For 0.01-1.6%.
5. a kind of super-hydrophobic polyimide foam as described in claim 1, it is characterised in that: the polyether modified silicon oil is
One or both of SiOC type silicone oil or SiC type silicone oil.
6. a kind of super-hydrophobic polyimide foam as described in claim 1, it is characterised in that: the catalyst is three ethyl alcohol
One or more of amine, triethylenediamine, stannous octoate, two fourth tin of dilaurate.
7. a kind of super-hydrophobic polyimide foam as described in claim 1, it is characterised in that: the polyisocyanates is more benzene
The one or more of Quito methylene polyisocyanates, xylene diisocyanate or toluene di-isocyanate(TDI).
8. a kind of preparation method of super-hydrophobic polyimide foam, it is characterised in that preparation step is as follows: (1) aromatic dianhydride existing
It is dissolved in polar solvent in reaction kettle, is then proportionally added into low mass molecule alcohol, be heated to 80-120 DEG C of reaction 1-2 hours, then
It is cooled to room temperature, then is successively proportionally added into containing hydrogen silicone oil, catalyst, polyether modified silicon oil, is stirred evenly, before obtaining foam
Body；(2) foam precursors are uniform by stirring or high-pressure atomization collisional mixing with polyisocyanates, pour into foaming in mold
Obtain foam intermediate；(3) foam intermediate is placed in micro-wave oven, with microwave heating 0.5-2 hours, keeps it further solid
Change, then foam is placed in infrared baking oven and is heated to 150-300 DEG C, obtains finished product after 0.5-2 hours.
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| CN108715636B (en) * | 2018-06-12 | 2021-07-27 | 常州天晟新材料股份有限公司 | Halogen-free flame-retardant polyimide foam material and preparation method thereof |
| CN110229340B (en) * | 2019-06-17 | 2022-03-08 | 中国科学院宁波材料技术与工程研究所 | Polyimide aerogel based on silane hydrophobic modification and preparation method thereof |
| CN112480353A (en) * | 2020-11-30 | 2021-03-12 | 山东一诺威聚氨酯股份有限公司 | Super-oil-resistant heat-resistant TPU material and preparation method thereof |
| CN112592454B (en) * | 2020-12-14 | 2021-12-17 | 南京大学 | Amino silicone oil modified polyimide foam material and preparation method thereof |
| CN114316193A (en) * | 2021-11-25 | 2022-04-12 | 江苏德恩医疗器械有限公司 | Slow-resilience sponge, manufacturing process and application |
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| CN103342818A (en) * | 2013-07-16 | 2013-10-09 | 扬州晨化科技集团有限公司 | Preparation method of polyether modified polysiloxane foam stabilizer |
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