CN102030986A - 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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- CN102030986A CN102030986A CN 201010562299 CN201010562299A CN102030986A CN 102030986 A CN102030986 A CN 102030986A CN 201010562299 CN201010562299 CN 201010562299 CN 201010562299 A CN201010562299 A CN 201010562299A CN 102030986 A CN102030986 A CN 102030986A
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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, excellent dielectric properties and mechanical property, it is simple also to have synthesis technique, wide material sources, with low cost and carbon yield is high, the Tg height, dimensional stability is good, solidification process does not need catalyzer, low water absorbable and very strong numerous advantages 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 subjected to increasing attention, have broad application prospects in mold pressing and injection-molded item, novel high-performance coating, tackiness agent, electronics, aerospace, high performance structures material and other industrial circles.
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 is that inorganics combines formation with organism in nanometer range, and inorganic and organic phase two are alternate by chemical bond, hydrogen bond or only be Van der Waals force combining 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 biphase pattern, 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 its research work for preparing hybrid material seldom, people (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 compares with pure benzoxazine colophony, and curing initiation temperature reduces, and the Tg and the storage modulus of hybrid material significantly increase, and thermostability and carbon yield are improved.People (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, made Polybenzoxazine resin/SiO by in-situ blending and with di ethoxy di methyl-monosilane respectively 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 flexible, hybrid material has better tensile strength and elongation at break than pure benzoxazine colophony.Polydimethylsiloxane also serves as the effect of softening agent, makes the cross-linking density of hybrid material increase, and Tg raises, and its thermal characteristics obtains bigger raising equally.People (Materials Science Forum such as Tarek Agag, 2004,449-452:1157-1160) mix with benzoxazine monomer, after the stage is warming up to 240 ℃ of processing, made the Polybenzoxazine resin/SiO of a series of different TEOS content with tetraethoxy (TEOS)
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 the 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 to be matrix with bisphenol fluorene aniline type benzoxazine polymkeric substance, uniform nanometer SiO in described matrix
2
The monomer of described benzoxazine polymkeric substance is a 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, be warming up to 50-80 ℃ stirred 2-8 hour 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, acetate 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 present invention with the bisphenol fluorene for the bisphenol fluorene aniline type benzoxazine colophony of phenol source preparation because of containing more phenyl ring, thereby can better improve the heat decomposition temperature and the quality residual rate of material, can be used as heat-resisting and the ablation resistant material use.
2, its raw material source of the present invention is extensive, and is 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 for use 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, operation according to the following steps:
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 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 that the back that stirs drips 1mol/L 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, get performed polymer in 60 ℃ of dry 72h then;
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, operation according to the following steps:
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 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 that the back that stirs drips 1mol/L 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, get performed polymer in 70 ℃ of dry 50h then;
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, operation according to the following steps:
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 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 that the back that stirs drips 1mol/L 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, get performed polymer in 80 ℃ of dry 20h then;
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, operation according to the following steps:
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 there-necked flask, 0.2mol toluene after fully stirring, adds the deionized water of 0.2mol, and the salpeter solution that the back that stirs drips 1mol/L 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, get performed polymer in 100 ℃ of dry 10h then;
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, add 40mL bisphenol fluorene and dehydrated alcohol mixed solution b behind the stirring 30min down at 10 ℃, bisphenol fluorene is 0.005mol among the described mixed solution b, be warming up to 65 ℃ and be incubated backflow 6h, go out alcohol solvent in 50 ℃ of underpressure distillation then, viscous liquid; Described viscous liquid is dissolved in the 15mL methylene dichloride,, leaves standstill the back layering with the NaOH solution washing of 3mol/L, 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 (6)
1. Polybenzoxazine resin/SiO
2Hybrid material is characterized in that: described hybrid material is to be matrix with bisphenol fluorene aniline type benzoxazine polymkeric substance, uniform nanometer SiO in described matrix
2
The monomer of described benzoxazine polymkeric substance is a bisphenol fluorene aniline type benzoxazine;
Described nanometer SiO
2Addition be the 4-30% of described bisphenol fluorene aniline type benzoxazine quality.
2. Polybenzoxazine resin/SiO according to claim 1
2Hybrid material is characterized in that: described nanometer SiO
2Particle diameter be 1-20nm.
3. described Polybenzoxazine resin/SiO of claim 1
2The preparation method of hybrid material is characterized in that operating 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, be warming up to 50-80 ℃ stirred 2-8 hour 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.
4. Polybenzoxazine resin/SiO according to claim 3
2The preparation method of hybrid material is characterized in that: described organic solvent is ethanol, dioxane, chloroform or toluene.
5. Polybenzoxazine resin/SiO according to claim 3
2The preparation method of hybrid material is characterized in that: described organosilicon is tetraethoxy, methyl silicate or butyl silicate.
6. Polybenzoxazine resin/SiO according to claim 3
2The preparation method of hybrid material is characterized in that: described acid is hydrochloric acid, formic acid, acetate or nitric acid.
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2010
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Non-Patent Citations (2)
Title |
---|
《 European Polymer Journal》 20100201 Jun Wang et al 《Synthesis, curing behavior and thermal properties of fluorene containing benzoxazines》 第46卷, 第5期 2 * |
《Materials Science Forum》 20040331 Tarek Agag et al 《Synthesis and Properties of Silica-Modified Polybenzoxazine》 第449-452卷, 2 * |
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CN107513347A (en) * | 2016-06-17 | 2017-12-26 | 华东理工大学 | A kind of coating composition of the micro-/ nano of functionalization containing benzoxazine ball and application thereof |
CN110183817A (en) * | 2019-05-27 | 2019-08-30 | 四川东材科技集团股份有限公司 | Low dielectric fluorenyl benzoxazine resin combination of a kind of high heat resistance high tenacity and its preparation method and application |
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 |
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