CN102030986B - Polybenzoxazine resin/SiO2 hybrid material and preparation method thereof - Google Patents
Polybenzoxazine resin/SiO2 hybrid material and preparation method thereof Download PDFInfo
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- CN102030986B CN102030986B CN 201010562299 CN201010562299A CN102030986B CN 102030986 B CN102030986 B CN 102030986B CN 201010562299 CN201010562299 CN 201010562299 CN 201010562299 A CN201010562299 A CN 201010562299A CN 102030986 B CN102030986 B CN 102030986B
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Abstract
The invention discloses a polybenzoxazine resin/SiO2 hybrid material and a preparation method thereof. In the hybrid material, benzoxazine polymer is taken as a matrix, and nano SiO2 is uniformly distributed in the matrix. The preparation method comprises the following steps of: dissolving bisphenol fluorene aniline type polybenzoxazine resin in an organic solvent; then mixing the solution and organic silicon hydrolysate completely and uniformly, performing a sol-gel reaction, and drying to obtain prepolymer; and curing the prepolymer to obtain the polybenzoxazine resin/SiO2 hybrid material. The polybenzoxazine resin/SiO2 hybrid material has higher decomposition temperature and higher carbon residue rate, and is suitable for preparing ceramic precursors, high-performance composite material matrixes, ablation resistant materials and the like.
Description
One, technical field
The present invention relates to a kind of novel hybride materials, specifically a kind of Polybenzoxazine resin/SiO
2Hybrid material and preparation method thereof.
Two, background technology
Benzoxazine colophony is a class novel hot setting resin that grows up on the basis of traditional resol.Benzoxazine monomer is by phenols, the 6-membered heterocyclic compound that formaldehyde or Paraformaldehyde 96 and primary amine obtain by the Mannich condensation reaction, the heating or have catalyzer in the presence of can carry out ring-opening polymerization, form the Polybenzoxazine resin of similar resol crosslinking structure, it not only has the high temperature resistant of traditional resol, fire-retardant, good dielectric properties and mechanical property, it is simple also to have synthesis technique, wide material sources, with low cost and carbon yield is high, Tg is high, good stability of the dimension, solidification process does not need catalyzer, low water absorbable and the very strong many merits such as molecular designing.Benzoxazine can be used as the matrix of matrix material, and can utilize active group and other radical reaction on its molecule, carry out various reactions, these advantages of Polybenzoxazine resin, make it be subject to increasing attention in mold pressing and injection-molded item, novel high-performance coating, tackiness agent, electronics, aerospace, high performance structures material and other industrial circles, have broad application prospects.
Hybrid material is a kind of type material that begins to rise the 1980s, be after single component material, matrix material and gradient material the 4th generation material.Organic/inorganic hybridization material be inorganics and organism in nanometer range in conjunction with forming, inorganic phase and organic phase two are alternate by chemical bond, hydrogen bond or only be the combination of Van der Waals force on nanometer level.The character of organic/inorganic hybridization material not only depends on the character of single component, and is also relevant with two alternate reactive forces with the pattern of two-phase, and be not only institute form constitutive property simply add with.Organic/inorganic hybridization material not only has the characteristics of inorganics hardness height, good corrosion resistance and organism good toughness, also usually shows many better performances.
In recent years, benzoxazine colophony has caused the concern of a large amount of Chinese scholars as class thermosetting resin novel, that have advantageous property.But utilize the research work of its preparation hybrid material seldom, people (the Polymer such as Tarek Agag, 2004,45:7903-7910) adopt titanium tetraisopropylate complex compound and bisphenol A-type benzoxazine (3,4-dihydro-3-phenyl-1, the 3-benzoxazine) utilize sol-gel (sol-gel) process to prepare Polybenzoxazine resin/TiO
2Nano composite material, it is uniformly dispersed, and with purified petroleum benzin Bing oxazine resin-phase ratio, curing initiation temperature reduces, and Tg and the storage modulus of hybrid material significantly increase, and thermostability and carbon yield are improved.People (the Polymer such as Hosta Ardhyananta, 2008,49:4585-4591) with bisphenol A-type benzoxazine (3,4-dihydro-3-phenyl-1, the 3-benzoxazine) is matrix, respectively made Polybenzoxazine resin/SiO by in-situ blending and with di ethoxy di methyl-monosilane by sol-gel (sol-gel) process with polydimethylsiloxane
2Hybrid material.Two kinds of methods that prepare hybrid material by contrast, the hybrid material that makes with sol-gel (sol-gel) method has better homogeneity.Because the effect of polydimethylsiloxane toughness, hybrid material has better tensile strength and elongation at break than pure benzoxazine colophony.Polydimethylsiloxane also serves as the effect of softening agent, so that the cross-linking density of hybrid material increases, Tg raises, and its thermal characteristics obtains larger raising equally.People (the Materials Science Forum such as Tarek Agag, 2004,449-452:1157-1160) mix with benzoxazine monomer with tetraethoxy (TEOS), after the stage is warming up to 240 ℃ of processing, made the Polybenzoxazine resin/SiO of a series of different TEOS content
2Hybrid material shows that through infrared and DSC detection benzoxazine monomer has carried out ring-opening polymerization fully and formed silicon-dioxide after 240 ℃ of curing, and the introducing of silicon has significantly improved thermal characteristics and the mechanical property of Polybenzoxazine resin.It is not very high shortcoming that the hybrid material that more than makes exists heat decomposition temperature and quality residual rate, and as anti-ablation and heat-stable material, the heat decomposition temperature and the quality residual rate that how further to improve the Polybenzoxazine hybrid material become key issue.
Three, summary of the invention
The present invention is for fear of above-mentioned the deficiencies in the prior art part, provides a kind of preparation technology simple, with low cost, has the Polybenzoxazine resin/SiO of good thermal
2Hybrid material and preparation method thereof.
Polybenzoxazine resin/SiO of the present invention
2The characteristics of hybrid material are: described hybrid material is take bisphenol fluorene aniline type benzoxazine polymkeric substance as matrix, uniform nanometer SiO in described matrix
2
The monomer of described benzoxazine polymkeric substance is bisphenol fluorene aniline type benzoxazine;
Described nanometer SiO
2Addition be the 4-30% of described bisphenol fluorene aniline type benzoxazine quality.
Polybenzoxazine resin/SiO of the present invention
2The characteristics of hybrid material also are: described nanometer SiO
2Particle diameter be 1-20nm.
Polybenzoxazine resin/SiO of the present invention
2The preparation method's of hybrid material characteristics are to operate according to the following steps:
A, bisphenol fluorene aniline type benzoxazine is dissolved in the organic solvent, is mixed with the solution a of massfraction 5-25%;
B, with organosilicon, organic solvent and hydromassage you than 1: 2-6: 2-6 mixes also and drips sour adjust pH to 2-5, is warming up to 50-80 ℃ and stirs 2-8 hour to get solution b;
C, described solution a and described solution b mixed and stir, left standstill under the room temperature 7 days behind the film seal, again film is pricked behind the hole and left standstill 2 days under the room temperature, then in 60-100 ℃ of dry 10-72 hour performed polymer;
D, with described performed polymer 100 ℃ of insulations 2 hours, 140 ℃ of insulations 2 hours, 180 ℃ of insulations 2 hours, 200 ℃ of insulations 2 hours, 240 ℃ of insulations after 4 hours Polybenzoxazine resin/SiO
2Hybrid material.
Polybenzoxazine resin/SiO of the present invention
2The preparation method's of hybrid material characteristics also are: described organic solvent is ethanol, dioxane, chloroform or toluene.
Polybenzoxazine resin/SiO of the present invention
2The preparation method's of hybrid material characteristics also are: described organosilicon is tetraethoxy, methyl silicate or butyl silicate.
Polybenzoxazine resin/SiO of the present invention
2The preparation method's of hybrid material characteristics also are: described acid is hydrochloric acid, formic acid, acetic acid or nitric acid.
The structural formula of described bisphenol fluorene aniline type benzoxazine is:
Compared with the prior art, beneficial effect of the present invention is embodied in:
1, the bisphenol fluorene aniline type benzoxazine colophony for preparing take bisphenol fluorene as the phenol source of the present invention is because containing more phenyl ring, thereby can better improve heat decomposition temperature and the quality residual rate of material, can be used as heat-resisting and ablation resistant material uses.
2, the used raw material sources of the present invention are extensive, with low cost.
3, preparation technology of the present invention is simple, and is easy and simple to handle, reaction conditions is gentle, is easy to realize suitability for industrialized production.
4, the synthetic and organosilicon hydrolyzation liquid of benzoxazine of the present invention all can select avirulent ethanol to make solvent, and preparation process is pollution-free.
Four, description of drawings
Fig. 1 is different SiO
2Polybenzoxazine resin/the SiO of addition
2The thermal weight loss of hybrid material (TGA) graphic representation.
Five, embodiment
Embodiment 1:
A kind of Polybenzoxazine resin/SiO in the present embodiment
2The preparation method of hybrid material, according to the following steps operation:
A, 10g bisphenol fluorene aniline type benzoxazine is dissolved in the ethanol, is mixed with the solution a of massfraction 10%;
B, add the 0.05mol tetraethoxy in the there-necked flask, the 0.2mol dehydrated alcohol after fully stirring, adds the deionized water of 0.3mol, and it is to be warming up to 70 ℃ of stirring reaction 3h after 2 to get solution b that the HCl solution of the rear dropping 1mol/L that stirs is regulated the pH value;
C, with solution a and 4.25g (containing silicon-dioxide 0.42g) solution b mixing and stirring, left standstill under the room temperature 7 days behind the film seal, again film is pricked behind the hole and was left standstill 2 days under the room temperature, then get performed polymer in 60 ℃ of dry 72h;
D, with described performed polymer 100 ℃ of insulations 2 hours, 140 ℃ of insulations 2 hours, 180 ℃ of insulations 2 hours, 200 ℃ of insulations 2 hours, 240 ℃ of insulations after 4 hours Polybenzoxazine resin/SiO
2Hybrid material.
Polybenzoxazine resin/SiO that present embodiment makes
2Contained SiO in the hybrid material
2Mass percent be 4%, the temperature during this hybrid material thermal weight loss 5% is 327 ℃ as shown in Figure 1, the quality residual rate in the time of 1000 ℃ is 46.37%.
Embodiment 2:
A kind of Polybenzoxazine resin/SiO in the present embodiment
2The preparation method of hybrid material, according to the following steps operation:
A, 10g bisphenol fluorene aniline type benzoxazine is dissolved in the dioxane, is mixed with the solution a of massfraction 5%;
B, add the 0.05mol methyl silicate in the there-necked flask, the 0.1mol dioxane after fully stirring, adds the deionized water of 0.1mol, and it is to be warming up to 50 ℃ of stirring reactions after 4 to get solution b in 5 hours that the formic acid solution of the rear dropping 1mol/L that stirs is regulated pH value;
C, with solution a and 10.6g (containing silica 1 .06g) solution b mixing and stirring, left standstill under the room temperature 7 days behind the film seal, again film is pricked behind the hole and was left standstill 2 days under the room temperature, then get performed polymer in 70 ℃ of dry 50h;
D, with described performed polymer 100 ℃ of insulations 2 hours, 140 ℃ of insulations 2 hours, 180 ℃ of insulations 2 hours, 200 ℃ of insulations 2 hours, 240 ℃ of insulations after 4 hours Polybenzoxazine resin/SiO
2Hybrid material.
Polybenzoxazine resin/SiO that present embodiment makes
2Contained SiO in the hybrid material
2Mass percent be 10%, the temperature of this hybrid material thermal weight loss 5% is 320 ℃ as shown in Figure 1, the quality residual rate in the time of 1000 ℃ is 48.96%.
Embodiment 3:
A kind of Polybenzoxazine resin/SiO in the present embodiment
2The preparation method of hybrid material, according to the following steps operation:
A, 10g bisphenol fluorene aniline type benzoxazine is dissolved in the chloroform, is mixed with the solution a of massfraction 20%;
B, add the 0.05mol butyl silicate in the there-necked flask, the 0.3mol chloroform after fully stirring, adds the deionized water of 0.3mol, and it is to be warming up to 80 ℃ of stirring reactions after 5 to get solution b in 2 hours that the acetic acid solution of the rear dropping 1mol/L that stirs is regulated pH value;
C, with solution a and 21.2g (containing silicon-dioxide 2.50g) solution b mixing and stirring, left standstill under the room temperature 7 days behind the film seal, again film is pricked behind the hole and was left standstill 2 days under the room temperature, then get performed polymer in 80 ℃ of dry 20h;
D, with described performed polymer 100 ℃ of insulations 2 hours, 140 ℃ of insulations 2 hours, 180 ℃ of insulations 2 hours, 200 ℃ of insulations 2 hours, 240 ℃ of insulations after 4 hours Polybenzoxazine resin/SiO
2Hybrid material.
Polybenzoxazine resin/SiO that present embodiment makes
2Contained SiO in the hybrid material
2Mass percent be 20%, the temperature of this hybrid material thermal weight loss 5% is 330 ℃ as shown in Figure 1, the quality residual rate in the time of 1000 ℃ is 56.68%.
Embodiment 4:
A kind of Polybenzoxazine resin/SiO in the present embodiment
2The preparation method of hybrid material, according to the following steps operation:
A, 10g bisphenol fluorene aniline type benzoxazine is dissolved in the toluene, is mixed with the solution a of massfraction 25%;
B, add the 0.05mol tetraethoxy in the there-necked flask, 0.2mol toluene after fully stirring, adds the deionized water of 0.2mol, and the salpeter solution of the rear dropping 1mol/L that stirs is regulated and is warming up to 60 ℃ of stirring reactions after the pH value 3 and got solution b in 4 hours;
C, with solution a and 31.8g (containing silicon-dioxide 4.28g) solution b mixing and stirring, left standstill under the room temperature 7 days behind the film seal, again film is pricked behind the hole and was left standstill 2 days under the room temperature, then get performed polymer in 100 ℃ of dry 10h;
D, with described performed polymer 100 ℃ of insulations 2 hours, 140 ℃ of insulations 2 hours, 180 ℃ of insulations 2 hours, 200 ℃ of insulations 2 hours, 240 ℃ of insulations after 4 hours Polybenzoxazine resin/SiO
2Hybrid material.
Polybenzoxazine resin/SiO that present embodiment makes
2Contained SiO in the hybrid material
2Mass percent be 30%, the temperature of this hybrid material thermal weight loss 5% is 340 ℃ as shown in Figure 1, the quality residual rate in the time of 1000 ℃ is 60.38%.
The bisphenol fluorene aniline type benzoxazine that uses among the embodiment 1-4 be prepare as follows (Ning X., Ishida H.J Polym Sci Part A:Polym Chem.[J], 1994,32:1121-1129):
0.02mol formaldehyde solution and 10mL dehydrated alcohol mixed under condition of ice bath and stir 30min, drip 10mL aniline and dehydrated alcohol mixed solution a, aniline is 0.01mol among the described mixed solution a, behind 10 ℃ of lower 30min of stirring, add 40mL bisphenol fluorene and dehydrated alcohol mixed solution b, bisphenol fluorene is 0.005mol among the described mixed solution b, be warming up to 65 ℃ and be incubated backflow 6h, then go out alcohol solvent in 50 ℃ of underpressure distillation, get viscous liquid; Described viscous liquid is dissolved in the 15mL methylene dichloride, and the NaOH solution washing with 3mol/L leaves standstill rear layering, separate and leave and take lower floor's liquid, be washed with distilled water to neutrality behind the repeated washing 3 times, behind the standing demix lower floor's liquid be transferred in the beaker, get finished product in 50 ℃ of vacuum-drying 10h.
Claims (4)
1. Polybenzoxazine resin/SiO
2The preparation method of hybrid material is characterized in that:
Take bisphenol fluorene aniline type benzoxazine polymkeric substance as matrix, uniform nanometer SiO in described matrix
2
The monomer of described benzoxazine polymkeric substance is bisphenol fluorene aniline type benzoxazine;
Described nanometer SiO
2Addition be the 4-30% of described bisphenol fluorene aniline type benzoxazine quality;
Described nanometer SiO
2Particle diameter be 1-20nm;
Specifically according to the following steps operation:
A, bisphenol fluorene aniline type benzoxazine is dissolved in the organic solvent, is mixed with the solution a of massfraction 5-25%;
B, you mix than 1:2-6:2-6 and drip sour adjust pH to 2-5 with organosilicon, organic solvent and hydromassage, are warming up to 50-80 ℃ and stir 2-8 hour to get solution b;
C, described solution a and described solution b mixed and stir, left standstill under the room temperature 7 days behind the film seal, again film is pricked behind the hole and left standstill 2 days under the room temperature, then in 60-100 ℃ of dry 10-72 hour performed polymer;
D, with described performed polymer 100 ℃ of insulations 2 hours, 140 ℃ of insulations 2 hours, 180 ℃ of insulations 2 hours, 200 ℃ of insulations 2 hours, 240 ℃ of insulations after 4 hours Polybenzoxazine resin/SiO
2Hybrid material.
2. Polybenzoxazine resin/SiO according to claim 1
2The preparation method of hybrid material is characterized in that: organic solvent is ethanol, dioxane, chloroform or toluene described in step a and the step b.
3. Polybenzoxazine resin/SiO according to claim 1
2The preparation method of hybrid material is characterized in that: described organosilicon is tetraethoxy, methyl silicate or butyl silicate.
4. Polybenzoxazine resin/SiO according to claim 1
2The preparation method of hybrid material is characterized in that: described acid is hydrochloric acid, formic acid, acetic acid or nitric acid.
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| CN102225996B (en) * | 2011-05-06 | 2013-07-31 | 大连理工大学 | Preparation method for benzoxazine resin nano-polymer sphere and benzoxazine resin nano-polymer carbon sphere |
| CN102675894B (en) * | 2012-06-04 | 2016-01-20 | 上海卡贝尼精密陶瓷有限公司 | A kind of resin and preparation method thereof being applied to high temperature insulation cover |
| CN102702225B (en) * | 2012-06-15 | 2014-08-06 | 哈尔滨工程大学 | Four-phenolic fluorene based benzoxazine and preparation method of four-phenolic fluorine based benzoxazine |
| CN103497671B (en) * | 2013-07-21 | 2015-12-23 | 西北工业大学 | A kind of containing benzoxazine colophony high temperature resistant self-lubricating compound coating and preparation method thereof |
| CN105038355A (en) * | 2015-04-28 | 2015-11-11 | 桐城市新丰彩印包装有限公司 | High-strength high-adhesion anti-corrosion coating |
| CN107513347B (en) * | 2016-06-17 | 2019-08-23 | 华东理工大学 | A kind of coating composition and application thereof of the functionalization micro-/ nano ball containing benzoxazine |
| CN110183817B (en) * | 2019-05-27 | 2022-04-05 | 四川东材科技集团股份有限公司 | High-heat-resistance high-toughness low-dielectric fluorenyl benzoxazine resin composition and preparation method and application thereof |
| CN111117160A (en) * | 2019-12-27 | 2020-05-08 | 大连理工大学 | Epoxy/benzoxazine resin based nanoparticle reinforced composite material and preparation method thereof |
| CN112933979B (en) * | 2021-01-29 | 2022-05-10 | 三明学院 | MYNs filled polyethylene glycol composite membrane and preparation method thereof |
| CN115180949B (en) * | 2022-06-20 | 2023-03-28 | 沈阳化工大学 | Preparation method of benzoxazine/silicone rubber ceramic microspheres with double-layer structure |
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Non-Patent Citations (3)
| Title |
|---|
| Jun Wang et al.《Synthesis, curing behavior and thermal properties of fluorene containing benzoxazines》.《 European Polymer Journal》.2010,第46卷(第5期), * |
| JunWangetal.《Synthesis curing behavior and thermal properties of fluorene containing benzoxazines》.《 European Polymer Journal》.2010 |
| Tarek Agag et al.《Synthesis and Properties of Silica-Modified Polybenzoxazine》.《Materials Science Forum》.2004,第449-452卷 * |
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