CN112321783B - Elastic aerogel material based on water-based benzoxazine emulsion and preparation method and application thereof - Google Patents
Elastic aerogel material based on water-based benzoxazine emulsion and preparation method and application thereof Download PDFInfo
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Abstract
The application discloses an elastic aerogel material based on a water-based benzoxazine emulsion, and a preparation method and application thereof. The method utilizes a hydrophilic group-containing water-based benzoxazine monomer to react with an initiator and a template under illumination, and obtains the aerogel material after freeze drying. The prepared aerogel material has the advantages of low density, good rebound resilience, low thermal conductivity and adjustable surface wettability, and can be applied to the fields of heat insulation materials, adsorption materials, electronic skins and the like; the preparation method has the advantages of easily available raw materials, mild reaction conditions and the like, can be used for industrial large-scale production, and has good practicability.
Description
Technical Field
The invention belongs to the technical field of intelligent materials and polymers. In particular to an elastic aerogel material based on water-based benzoxazine emulsion and a preparation method and application thereof.
Background
Electronic skin is a wearable device which simulates human skin and has multifunctional performance, and is widely applied to the fields of robot arms, artificial limbs, human health monitoring and the like. Materials used in electronic skins are often required to be comfortable, lightweight, excellent in mechanical properties and sensing ability. Aerogel is a special porous material, and has the advantages of high porosity, low density, low thermal conductivity, and the like, and the types of aerogel include graphene aerogel, inorganic aerogel, organic aerogel, carbon aerogel, and the like. The method is widely applied to the fields of aerospace, intelligent wearable equipment, energy storage and the like.
There are several methods to achieve the preparation of elastic aerogels, such as the application of bacterial nanocellulose and nanofibers. However, the use of nano-fiber and bacterial cellulose greatly increases the preparation cost, which is not suitable for industrial mass production. The hydrophobicity of the aerogel surface is of great significance. The aerogel with the hydrophobic surface can be effectively stored and used for a long time, and the problems of structural collapse, unstable performance and the like caused by the existence of the hydrophilic surface are avoided. Most of the existing methods utilize surface modification of silane coupling agents and fluorocarbon resins, so that the preparation process is more complicated, the process is more complex, and certain influence is caused on the continuous pore structure of the aerogel. Therefore, the problems of complex process conditions, high cost and the like still exist in the preparation of the aerogel at present. Organic aerogel has more regulatable and controllable molecular design for inorganic aerogel, can adjust the mechanical properties of aerogel, and the aerogel that has special molecular structure simultaneously can prepare out the aerogel surface that can regulate and control. However, the current organic aerogel with molecular design generally has brittleness problem, and the compression performance needs to be further improved. Wang et al (Wang, Z.; Dai, Z.; Wu, J.; ZHao, N.; Xu, J., Vacuum-dried robust branched silane advanced materials 2013,25(32),4494-7.) synthesized a silane coupling agent with thioether using a click chemistry reaction, and prepared a novel silicon aerogel, which was improved in mechanical properties and free from significant cracking at 60% compression set. Recently Yu et al (Yu, z.l.; Yang, n.; apostolocoulou-kalkalkamura, v.; Qin, b.; Ma, z.y.; Xing, w.y.; Qiao, c.; Bergstrom, l.; Antonietti, m.; Yu, s.h., Fire-Retardant and thermal Insulating Phenolic-silica aerogels, angelwalwandte Chemie 2018,57(17), 4538-.
Disclosure of Invention
Aiming at the problems in the prior art, the technical problem to be solved by the invention is to provide a preparation method of an elastic aerogel material based on a water-based benzoxazine emulsion, which has the advantages of easily available raw materials, mild reaction conditions, simple process and the like. The invention aims to solve another technical problem of providing an elastic aerogel material based on the water-based benzoxazine emulsion, wherein the aerogel material has the advantages of good compression performance, low density, low thermal conductivity, adjustable surface wettability and the like. The invention aims to solve another technical problem of providing an application of the elastic aerogel material based on the water-based benzoxazine emulsion, and the elastic aerogel material has a very good application prospect in the fields of heat insulation materials, oil-water separation, electronic skin and the like.
The technical scheme is as follows: in order to solve the problems, the technical scheme adopted by the invention is as follows:
a preparation method of an elastic aerogel material based on aqueous benzoxazine emulsion comprises the following steps:
1) the preparation method comprises the following steps of (1) reacting amino-terminated polydimethylsiloxane with a side chain containing a hydrophilic group with paraformaldehyde and phenol at 30-100 ℃ to obtain a water-based benzoxazine monomer; the structural general formula of the waterborne benzoxazine monomer is shown as follows;
in the formula, R1Is selected from-S (CH)2)nCOO—，-S(CH2)nSO3—，-S(CH2)nSO4N ═ 2 or 3;
R2is selected from
2) Fully stirring and mixing the water-based benzoxazine monomer, the initiator and the template agent at 25-40 ℃ to obtain emulsion; performing a freezing illumination reaction at a temperature below-100-0 ℃ to obtain a primary frozen product; wherein the mass ratio of the water-based benzoxazine monomer to the template to the initiator is 10:1: 0.1-10: 5: 0.5;
3) and 3) placing the primary frozen product obtained in the step 2) into a freeze dryer for freeze-drying to obtain the elastic aerogel material.
The molecular weight of the vinyl-containing polydimethylsiloxane with the amino end-capped and hydrophilic group-containing side chain is 1000-10000.
The hydrophilic group is one or more of carboxylate, sulfonate, sulfate and polyether.
In the waterborne benzoxazine monomer, the mass fraction of hydrophilic groups is 5-80%, and the mass fraction of vinyl groups is 1-50%.
The phenol is one or a mixture of phenol, p-diphenol and naphthol;
the template agent is one or a mixture of more of graphene, chitosan, montmorillonite and sodium alginate.
The initiator is one or a mixture of more of benzoin dimethyl ether, diphenylethanone, benzophenone and diisobutylamine hydrochloride.
In the step 2), the obtained emulsion is placed in a copper pipe, and is frozen at the temperature of-100-0 ℃ and is subjected to illumination reaction for 1-8 hours to obtain a primary frozen product;
and 3) freeze-drying the primary frozen product in a freeze dryer for 1-96 hours to obtain the multifunctional aerogel material.
The elastic multifunctional aerogel material is prepared by the preparation method of the elastic aerogel material based on the water-based benzoxazine emulsion.
The multifunctional aerogel material is applied to the preparation of heat insulation materials, oil-water separation materials and electronic skins.
Fully mixing 1-30% of waterborne benzoxazine monomer, photoinitiator and template agent by mass percent at 25-40 ℃, and stirring for 1-60min to obtain emulsion; freezing at-100-0 deg.C, and simultaneously performing illumination reaction for 0-10 hr to obtain primary frozen product;
the waterborne benzoxazine monomer in the step 3) is one or more of benzoxazine monomers simultaneously containing a photocrosslinkable group and hydrophilic groups such as carboxylate, sulfonate, sulfate, polyether and the like.
Has the advantages that: compared with the prior art, the invention has the advantages that:
(1) the preparation method of the aerogel material provided by the invention has the advantages of easily available raw materials, mild reaction conditions and simple preparation process, and can be used for industrial large-scale production;
(2) the aerogel material prepared by the invention has the advantages of good compression performance, low density, low thermal conductivity, adjustable surface wettability and the like, can be widely applied to the fields of electronic devices such as pressure sensors, electronic skins and the like, and also has potential application in the fields of oil-water separation materials, heat insulation and warm keeping materials and the like.
Drawings
FIG. 1 is an infrared spectrum of an aerogel.
Detailed Description
The invention is further described with reference to specific examples.
Example 1
1g of amino-terminated vinyl-containing polydimethylsiloxane with the molecular weight of 1000, 0.07g of ammonium persulfate serving as a thermal initiator and 0.3g of mercaptopropionic acid are reacted at 50 ℃, and then the product is reacted with 0.24g of paraformaldehyde and 0.37g of phenol at 60 ℃ for 10 hours to obtain the benzoxazine monomer containing carboxylate. Mixing 1g of benzoxazine monomer containing carboxylate, 0.1g of benzoin dimethyl ether and 0.01g of graphene in 9mL of water, and stirring at room temperature for 10min to obtain emulsion; placing the obtained emulsion in a copper pipe, and performing illumination reaction for 4 hours at the temperature of-80 ℃ to obtain a primary frozen product; and (3) placing the primary frozen product in a freeze dryer, and freeze-drying for 24h at-50 ℃ to obtain the aerogel.
Example 2
1g of amino-terminated vinyl-containing polydimethylsiloxane with the molecular weight of 10000 is reacted with 0.8g of mercaptoacetic acid at the temperature of 60 ℃ by taking 0.01g of azobisisobutyronitrile as a thermal initiator, and then the product is reacted with 0.024 paraformaldehyde and 0.056g of naphthol at the temperature of 80 ℃ for 16 hours to obtain the benzoxazine monomer containing carboxylate. Mixing 2g of benzoxazine monomer containing carboxylate, 0.2g of benzoin dimethyl ether and 0.02g of graphene in 9mL of water, and stirring at room temperature for 10min to obtain emulsion; placing the obtained emulsion in a copper pipe, and then placing the copper pipe at-80 ℃ for 4 hours under illumination to obtain a primary frozen product; and (3) placing the primary frozen product in a freeze dryer, and freeze-drying at-50 ℃ for 24h to obtain the aerogel.
Example 3
1g of amino-terminated vinyl-containing polydimethylsiloxane with the molecular weight of 8000 and 0.02g of dimethylphenylphosphine as a thermal initiator reacts with 0.6g of mercaptopropionic acid at the temperature of 80 ℃, and then the product reacts with 0.015g of paraformaldehyde and 0.041g of eugenol at the temperature of 90 ℃ for 24 hours to obtain the benzoxazine monomer containing carboxylate. Mixing 3g of benzoxazine monomer containing carboxylate, 0.3g of benzoin dimethyl ether and 0.03g of graphene in 9mL of water, and stirring at room temperature for 10min to obtain emulsion; placing the obtained emulsion in a copper pipe, and then placing the copper pipe at-80 ℃ for 4 hours under illumination to obtain a primary frozen product; and (3) placing the primary frozen product in a freeze dryer, and freeze-drying at-50 ℃ for 24h to obtain the aerogel.
Example 4
1g of amino-terminated vinyl-containing polydimethylsiloxane with the molecular weight of 5000, 0.005g of tert-butyl peroxide as a thermal initiator and 0.7g of 2-mercaptoethanesulfonic acid are reacted at 60 ℃, and then the product is reacted with 0.024g of paraformaldehyde and 0.074g of phenol at 60 ℃ for 18h to obtain the benzoxazine monomer containing sulfonate. Mixing 1g of benzoxazine monomer containing sulfonate, 0.1g of diphenylethanone and 0.01g of chitosan into 9mL of water, and stirring for 30min at room temperature to obtain emulsion; placing the obtained emulsion in a copper pipe, and then placing the copper pipe at-80 ℃ for 6 hours under illumination to obtain a primary frozen product; and (3) placing the primary frozen product in a freeze dryer, and freeze-drying at-50 ℃ for 48h to obtain the aerogel.
Example 5
1g of amino-terminated, vinyl-containing polydimethylsiloxane having a molecular weight of 6000, with 0.01g of dimethyl azodiisobutyrate as a thermal initiator, was reacted with 0.7g of 2-mercaptoethanesulfonic acid at 60 ℃ and the product was then reacted with 0.02g of paraformaldehyde and 0.062g of eugenol at 60 ℃ for 18h to give a sulfonate-containing benzoxazine monomer. Mixing 1g of benzoxazine monomer containing sulfonate, 0.1g of diphenylethanone and 0.01g of chitosan into 9mL of water, and stirring for 30min at room temperature to obtain emulsion; placing the obtained emulsion in a copper pipe, and then placing the copper pipe at-80 ℃ for 6 hours under illumination to obtain a primary frozen product; and (3) placing the primary frozen product in a freeze dryer, and freeze-drying at-50 ℃ for 48h to obtain the aerogel.
Example 6
1g of amino-terminated vinyl-containing polydimethylsiloxane with the molecular weight of 7000 and 0.005g of tert-butyl peroxide as a thermal initiator are reacted with 0.5g of 2-mercaptoethanesulfonic acid at 70 ℃, and then the product is reacted with 0.025g of paraformaldehyde and 0.054g of naphthol at 40 ℃ for 20 hours to obtain the benzoxazine monomer containing sulfonate. Mixing 1g of benzoxazine monomer containing sulfonate, 0.1g of diphenylethanone and 0.01g of chitosan into 9mL of water, and stirring for 30min at room temperature to obtain emulsion; placing the obtained emulsion in a copper pipe, and then placing the copper pipe at-80 ℃ for 8 hours under illumination to obtain a primary frozen product; and (3) placing the primary frozen product in a freeze dryer, and freeze-drying at-50 ℃ for 48h to obtain the aerogel.
Example 7
1g of amino-terminated vinyl-containing polydimethylsiloxane with molecular weight of 8000 and 0.01g of azobisisobutyronitrile as a thermal initiator is reacted with 0.4g of polyvinyl sulfate at 65 ℃, and then the product is reacted with 0.018g of paraformaldehyde and 0.072g of eugenol at 80 ℃ for 10 hours to obtain the sulfate-containing benzoxazine monomer. Mixing 1g of a benzoxazine monomer containing sulfate, 0.5g of diisobutyl amidine hydrochloride and 0.05g of sodium alginate in 9mL of water, and stirring at room temperature for 60min to obtain an emulsion; placing the obtained emulsion in a copper pipe, and then placing the copper pipe at-80 ℃ for 8 hours under illumination to obtain a primary frozen product; and (3) placing the primary frozen product in a freeze dryer, and freeze-drying for 96h at-40 ℃ to obtain the aerogel.
Example 8
1g of amino-terminated vinyl-containing polydimethylsiloxane with the molecular weight of 10000 and 0.14g of ammonium persulfate serving as a thermal initiator react with 0.7g of polyvinyl sulfate at 85 ℃, and then the product reacts with 0.014g of paraformaldehyde and 0.033g of phenol at 90 ℃ for 8 hours to obtain a sulfate-containing benzoxazine monomer. Mixing 1g of a benzoxazine monomer containing sulfate, 0.3g of diisobutyl amidine hydrochloride and 0.03g of sodium alginate in 9mL of water, and stirring at room temperature for 60min to obtain an emulsion; placing the obtained emulsion in a copper pipe, and then placing the copper pipe at-80 ℃ for 8 hours under illumination to obtain a primary frozen product; and (3) placing the primary frozen product in a freeze dryer, and freeze-drying for 96h at-40 ℃ to obtain the aerogel.
Example 9
1g of amino-terminated vinyl-containing polydimethylsiloxane with the molecular weight of 10000, 0.008g of dimethyl azodiisobutyrate serving as a thermal initiator, and 1g of vinyl glycidyl ether are reacted at 85 ℃, and then the product is reacted with 0.014 paraformaldehyde and 0.064g of naphthol at 90 ℃ for 8 hours to obtain a benzoxazine monomer containing polyether salt. Mixing 2g of benzoxazine monomer containing polyether salt, 0.5g of diisobutyl amidine hydrochloride and 0.05g of sodium alginate in 9mL of water, and stirring at room temperature for 60min to obtain emulsion; placing the obtained emulsion in a copper pipe, and then placing the copper pipe at-80 ℃ for 8 hours under illumination to obtain a primary frozen product; and (3) placing the primary frozen product in a freeze dryer, and freeze-drying for 96h at-40 ℃ to obtain the aerogel.
Example 10
1g of amino-terminated, vinyl-containing polydimethylsiloxane having a molecular weight of 2000, with 0.005g of dimethyl azodiisobutyrate as a thermal initiator, was reacted with 0.4g of a polyether-containing hydrophilic monomer at 60 ℃ and the product was then reacted with 0.024g of paraformaldehyde and 0.056g of naphthol at 80 ℃ for 16 hours to give a benzoxazine monomer containing a polyether salt. Mixing 1g of benzoxazine monomer containing polyether salt, 0.1g of benzophenone and 0.01g of sodium alginate in 9mL of water, and stirring at room temperature for 30min to obtain emulsion; placing the obtained emulsion in a copper pipe, and then placing the copper pipe at-50 ℃ for 4 hours under illumination to obtain a primary frozen product; and (3) placing the primary frozen product in a freeze dryer, and freeze-drying at-50 ℃ for 48h to obtain the aerogel.
Example 11
Taking the multifunctional aerogel material prepared in any one of the embodiments 1 to 10, carrying out compression performance test on a cylinder sample, measuring the height and two side areas of the sample, wherein the compression rate is 10 mm/min: the aerogel material can recover after compression, no obvious crack is generated after the aerogel material is compressed to 50-90% of the original thickness of the material, and the result is shown in table 1, which indicates that the obtained aerogel material has good compression performance.
Table 1 compression performance test results
| Product(s) | Compression displacement (%) | Compressive stress (kPa) |
| Example 1 | 50 | 25 |
| Example 2 | 50 | 28 |
| Example 3 | 70 | 65 |
| Example 4 | 70 | 68 |
| Example 5 | 50 | 23 |
| Example 6 | 70 | 70 |
| Example 7 | 70 | 66 |
| Example 8 | 90 | 120 |
| Example 9 | 90 | 110 |
| Example 10 | 90 | 126 |
Performing DLS test on the water-based benzoxazine emulsion prepared in any one of examples 1-10, preparing a solution with the mass fraction of 5%, performing ultrasonic treatment for 10min, and performing the test, wherein the water-based benzoxazines with different hydrophilic group contents show good water solubility and narrow particle size distribution; fig. 1 is an infrared spectrum prepared from an aerogel prepared using the benzoxazine emulsion.
Claims (8)
1. A preparation method of an elastic aerogel material based on a water-based benzoxazine emulsion is characterized by comprising the following steps:
1) the preparation method comprises the following steps of reacting amino-terminated polydimethylsiloxane with a side chain containing a hydrophilic group with paraformaldehyde and phenol at 30-100 ℃ to obtain a water-based benzoxazine monomer, wherein the structural general formula of the water-based benzoxazine monomer is shown as follows;
in the formula, R1Is selected from-COO—，-SO3 —；
R2Is selected from
，
，
；
2) Fully stirring and mixing the water-based benzoxazine monomer, the initiator and the template agent at 25-40 ℃ to obtain emulsion; performing a freezing illumination reaction at a temperature below-100-0 ℃ to obtain a primary frozen product; wherein the mass ratio of the water-based benzoxazine monomer to the template to the initiator is 10:1: 0.1-10: 5: 0.5;
3) and 3) placing the primary frozen product obtained in the step 2) into a freeze dryer for freeze-drying to obtain the elastic aerogel material.
2. The preparation method of the elastic aerogel material based on the aqueous benzoxazine emulsion according to claim 1, wherein the molecular weight of the amino-terminated vinyl-containing polydimethylsiloxane with a side chain containing hydrophilic groups is 1000-10000.
3. The preparation method of the elastic aerogel material based on the aqueous benzoxazine emulsion according to claim 1, wherein the template agent is one or a mixture of several of graphene, chitosan, montmorillonite and sodium alginate.
4. The method for preparing the elastic aerogel material based on the aqueous benzoxazine emulsion according to claim 1, wherein the initiator is one or a mixture of benzoin dimethyl ether, diphenylethanone, benzophenone and diisobutyramidine hydrochloride.
5. The method for preparing the elastic aerogel material based on the aqueous benzoxazine emulsion according to claim 1, wherein in the step 2), the obtained emulsion is placed in a copper tube, and is frozen at-100 to 0 ℃ and simultaneously subjected to light reaction for 1 to 8 hours to obtain a primary frozen product.
6. The preparation method of the elastic aerogel material based on the aqueous benzoxazine emulsion according to claim 1, wherein the primary frozen product is freeze-dried in a freeze-drying machine for 1-96 hours to obtain the multifunctional aerogel material.
7. An elastic multifunctional aerogel material obtained by the preparation method of the elastic aerogel material based on aqueous benzoxazine emulsion according to claims 1-6.
8. Use of the multifunctional aerogel material of claim 7 in the preparation of thermal insulation materials, oil-water separation materials, and e-skin.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104363884A (en) * | 2012-06-21 | 2015-02-18 | 莱雅公司 | Matt-effect composition comprising hydrophobic aerogel particles and silicone elastomer particles |
| CN106082170A (en) * | 2016-06-15 | 2016-11-09 | 泰山医学院 | A kind of benzoxazine resins base carbon aerogels and preparation method thereof |
| CN108690191A (en) * | 2018-06-05 | 2018-10-23 | 中国人民解放军国防科技大学 | Polybenzoxazine aerogel heat insulation material and preparation method thereof |
| CN108884225A (en) * | 2016-04-13 | 2018-11-23 | 汉高股份有限及两合公司 | Copolymer aeroge based on benzoxazine |
| CN109867792A (en) * | 2019-01-16 | 2019-06-11 | 江苏大学 | Poly- (benzoxazine-siloxanes) copolymer of one kind and preparation method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104363884A (en) * | 2012-06-21 | 2015-02-18 | 莱雅公司 | Matt-effect composition comprising hydrophobic aerogel particles and silicone elastomer particles |
| CN108884225A (en) * | 2016-04-13 | 2018-11-23 | 汉高股份有限及两合公司 | Copolymer aeroge based on benzoxazine |
| CN106082170A (en) * | 2016-06-15 | 2016-11-09 | 泰山医学院 | A kind of benzoxazine resins base carbon aerogels and preparation method thereof |
| CN108690191A (en) * | 2018-06-05 | 2018-10-23 | 中国人民解放军国防科技大学 | Polybenzoxazine aerogel heat insulation material and preparation method thereof |
| CN109867792A (en) * | 2019-01-16 | 2019-06-11 | 江苏大学 | Poly- (benzoxazine-siloxanes) copolymer of one kind and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| "Dynamic mechanical and shape memory properties of polybenzoxazines based on aminopropyl-terminated siloxanes";Xuehui Su et al.;《J. APPL. POLYM. SCI.》;20161231;第133卷;44121（共9页） * |
| "Elastic Aerogel with Tunable Wettability for Self-Cleaning Electronic Skin";Wencan Ma et al.;《ACS Materials Lett.》;20201028;第2卷;第1575-1582页 * |
| "Thermally insulating polybenzoxazine aerogels based on 4,4’-diamino-diphenylmethane benzoxazine";Yunyun Xiao et al.;《Polymers & biopolymers》;20190627;第54卷;第12951–12961页 * |
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