CN106750275A - A kind of preparation method of naphthyl type phthalonitrile and epoxy resin composite material - Google Patents
A kind of preparation method of naphthyl type phthalonitrile and epoxy resin composite material Download PDFInfo
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- CN106750275A CN106750275A CN201710116614.XA CN201710116614A CN106750275A CN 106750275 A CN106750275 A CN 106750275A CN 201710116614 A CN201710116614 A CN 201710116614A CN 106750275 A CN106750275 A CN 106750275A
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- epoxy resin
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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
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
-
- 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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
- C08G59/5033—Amines aromatic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/04—Polymer mixtures characterised by other features containing interpenetrating networks
Abstract
The present invention is a kind of naphthyl type phthalonitrile and the preparation method of epoxy resin composite material.The method is by the naphthyl type phthalonitrile monomer for adding a kind of processing characteristics excellent in epoxy resin and its copolymerization, with epoxy resin, aromatic amine curing agent temperature-programmed reaction, finally giving the phthalonitrile modified epoxy resin composite present invention has very excellent resistance to elevated temperatures, mechanical property, anti-flammability.Epoxy resin need to only be added on a small quantity（30 wt%）Naphthyl type phthalonitrile when, its under nitrogen atmosphere 1000 DEG C when carbon yield can from 8% lifting to 31%, corresponding limited oxygen index is promoted to 29.9 from 20.7, so that epoxy resin becomes fire proofing.
Description
Technical field
The invention belongs to high temperature polymeric materialses preparation field, it is related to one kind by naphthyl type phthalonitrile and asphalt mixtures modified by epoxy resin
Resin composite material and preparation method.
Background technology
It by phthalonitrile monomer is raw material that polyphenyl nitrile resin is, poly- by body addition with aromatic amine, phenol as catalyst
Close the high-performance thermosetting resin of reaction generation.The resin have excellent heat endurance, thermo oxidative stability, agent of low hygroscopicity,
Anti-flammability, chemical stability, mechanical performance, have a wide range of applications in fields such as machinery, Aero-Space, electronics, ships.
Since the eighties in 20th century, the research that US Naval Research Laboratory takes the lead in polyphenyl nitrile resin development system.Keller
Connected group is chained Deng by changing monomer, the different polyphenyl nitrile resin of combination property is obtained, including：Biphenyl type
(Keller TM.Phthalonitrile-based high temperature resin.Journal of Polymer
Science:Part A 1988,26:3199-3212；Sastri SB,Keller TM.Phthalonitrile cure
reaction with aromatic diamines.Journal of Polymer Science:Part A:Polymer
Chemistry 1998,36:1885-1890.), metaphenylene (Keller TM, Dominguez DD.High temperature
resorcinol-based phthalonitrile polymer.Polymer,2005,46:4614-4618.), bisphenol A-type
(Laskoski M,Dominguez DD,Keller TM.Synthesis and properties of a biphenyl A
based phthalonitrile resin.Journal of Polymer Science:Part A:Polymer
Chemistry,2005,43:4136-4143.) and the cyanophenyl monomer [U.S.P4,409,382 containing phenoxy group, sulfone chain link
(1983)]。
With naphthyl type polyphenyl nitrile resin (Zhao FH, Liu that 1,6- naphthalenediols, 4- nitrophthalonitriles are prepared as raw material
RJ,Kang C,et al.A novel high-temperature naphthyl-based phthalonitrile
polymer:synthesis and properties.RSC Advances,2014,4:8383-8390) there is processing very wide
Window and very excellent heat endurance, it is especially prominent in the polyphenyl nitrile resin being currently known, show good application prospect.
Epoxy resin is to refer to the organic compound containing two or more epoxide groups in molecule, due to molecule knot
Contain active epoxide group in structure, make that they can crosslink reaction with polytype curing agent and being formed insoluble has
The high polymer of three-dimensional network structure.Epoxy resin after solidification has good physics, chemical property, and such as adhesive strength is high,
Dielectric properties are good, and cure shrinkage is small, and product size good stability, hardness is high, and pliability is preferable, to alkali and most of solvent
Stabilization, thus is widely used in national defence, each department of national economy, pours into a mould, impregnates, the purposes such as lamination material, bonding agent, coating.
Glass transition temperature and heat decomposition temperature are relatively low in itself for epoxy resin, are difficult to meet demand under the high temperature conditions,
At present, most of researchers' selection addition inorganic nano-filler comes the more excellent composite of processability, this composite
Performance be heavily dependent on the surface modification of Nano filling and the dispersion in epoxy resin-base, and Nano filling
Moditied processing process it is typically more complicated, and final material glass transition temperature lifting amplitude it is smaller, be usually no more than 50 DEG C.
Additionally, also there is researcher to select to add other compounds to prepare composite with the common reaction of epoxy resin, but, on the one hand,
Such material major part starting point is toughening modifying, thus contributes limited in terms of lifting epoxy resin heat, mechanical property, separately
On the one hand, the compound of general structure also is difficult to accomplish the heat endurance for being obviously improved epoxy resin and mechanical property.Polyphenyl nitrile
Resin, as unique extraordinary high score for meeting MILSTD (MIL-STD-2031) fire resistant requirements under the conditions of unmodified
Son, advantageous heat endurance and fire resistance for reinforced epoxy, meanwhile, polyphenyl nitrile have higher than the overwhelming majority
The super-high glass transition temperature (typically larger than 400 DEG C) of macromolecular material, it is also possible to make epoxy resin obtain at a higher temperature
With the mechanical property for keeping its excellent, its lifting effect will also be substantially better than general epoxy resin composite material.However, big portion
The monomer fusing point of segregation cyanophenyl resin is very high, and processing characteristics is very poor, it is difficult to compound with epoxy resin under relatively mild environment, because
This, there is presently no composite prepared by both document reports.
The content of the invention
Present invention is primarily aimed in order to improve the combination property of epoxy resin, it is set to be suitable for microelectronics, aviation
The fields such as space flight to the high requirement of material, to the naphthyl type phthalonitrile for adding a kind of processing characteristics excellent in epoxy resin
Monomer and its copolymerization, there is provided the preparation method of this phthalonitrile and epoxy resin composite material.This composite is in epoxy
On the basis of resin, by the addition of naphthyl type phthalonitrile monomer, the epoxy resin composite material of excellent performance has been obtained.
Synthesis cycle of the present invention is short, and yield is high, composite processing process is simple.
The technical scheme is that：
A kind of naphthyl type phthalonitrile and the preparation method of epoxy resin composite material, comprise the following steps：
(1) naphthyl type phthalonitrile monomer is prepared：1,6- naphthalenediol, 4- nitrophthalonitriles and potassium carbonate are added to
In basic solvent, 80-90 DEG C is reacted 4-8 hours, is then poured the mixture into watery hydrochloric acid, and distilled water is used after placing 8-12 hours
Neutrality is washed till, after vacuum drying, compound A is obtained；
Wherein, feed molar proportioning 1,6- naphthalenediols：4- nitrophthalonitriles：Potassium carbonate=1：2：(2-3)；Described
Watery hydrochloric acid concentration is 0.3-0.5mol/L, and 8-10L watery hydrochloric acid is needed per mole compound A；Add 750-1000mL per mole compound A
Basic solvent；
(2) the compound A for obtaining step (1) melts mixed with epoxy resin, aromatic amine curing agent at 130-180 DEG C
Close uniform, then pour into mould while hot, then successively at 180-185 DEG C, 210-215 DEG C, 230-235 DEG C, 250-255 DEG C and
270-275 DEG C of five temperature sections carry out temperature-programmed reaction, and each temperature section respectively reacts 2-4 hours, so as to obtain O-phthalic
Nitrile modified epoxy resin composite；
The mass ratio of compound A and epoxy resin described in step (2) is 1:10-1:1, the two mixture and curing agent
Mass ratio be 1:0.25-1:0.4.
Epoxy resin described in step (2) is bisphenol A type epoxy resin, bisphenol-s epoxy resin or bisphenol F type epoxy
Resin；
Aromatic amine curing agent described in step (2) is 4,4 '-diaminodiphenyl ether, 3,4 '-diaminodiphenyl ether or
4,4 '-DADPS.
Basic solvent described in step (1) is dimethyl sulfoxide (DMSO), N,N-dimethylformamide, DMAC N,N' dimethyl acetamide
Or one or more in 1-METHYLPYRROLIDONE.
Described chemical reagent is commercially available acquisition.
Beneficial effects of the present invention are：
What a kind of naphthyl type phthalonitrile and epoxy resin were composited is that a kind of novel hot setting macromolecule is combined
Material, by using a kind of curing agent, the two collaboration solidify to form interpenetrating polymer networks and introduces substantial amounts of heteroaromatic, thus
With very excellent resistance to elevated temperatures, mechanical property, anti-flammability.Epoxy resin need to only add the naphthyl type of a small amount of (30wt%)
During phthalonitrile, its under nitrogen atmosphere 1000 DEG C when carbon yield can be from 8% lifting to 31% (see Fig. 2), accordingly
Limited oxygen index is promoted to 29.9 (being calculated according to Krevelen formula) from 20.7, so that epoxy resin becomes fire proofing；
Meanwhile, the glass transition temperature of composite is lifted to 208 DEG C from 120 DEG C of epoxy resin, and its mechanical property can be in height
It is maintained under temperature, significantly increases the Applicable temperature upper limit of material.In addition, naphthyl type phthalonitrile involved in the present invention
Monomer synthesis cycle is short, and yield is high, and fusing point is less than most cyanophenyl monomers, and the preparation method is simple of composite both expanded
The range of application of polyphenyl nitrile resin, improves Properties of Epoxy Resin, thus have good in fields such as microelectronics, Aero-Space again
Good application prospect.
Brief description of the drawings
Fig. 1 is the nucleus magnetic hydrogen spectrum of the compound of 1 Chinese style of embodiment 1.
Fig. 2 is that the mass ratio of the compound of 1,2,3,4 Chinese style of embodiment 1 and bisphenol A type epoxy resin is respectively 1：10、2：
10、3：When 10 and pure epoxy resin solidified after-product TGA collection of illustrative plates.
Fig. 3 is that the mass ratio of the compound of 1,2,3,4 Chinese style of embodiment 1 and bisphenol A type epoxy resin is respectively 1：10、2：
10、3：When 10 and pure epoxy resin solidified after-product DMA collection of illustrative plates.
Specific embodiment
Embodiment 1
Monomer synthesizes：To addition 16.02g (0.1mol) 1,6- naphthalenediols, 34.63g (0.2mol) 4- nitros in reactor
Phthalonitrile and 34.55g (0.25mol) Anhydrous potassium carbonate, add anhydrous dimethyl sulphoxide 75mL, and be heated to 80-90
DEG C, stir 8 hours.Room temperature is cooled to after stopping heating, product is stirred down the watery hydrochloric acid of the 0.5mol/L for pouring into 800mL
In, 8 hours are stood, after filtrate is washed till into neutrality repeatedly with distilled water, it is vacuum dried 24 hours at 80 DEG C, the compound of formula 1 is obtained,
Faint yellow solid powder 38.44g, yield 93%.
Wherein, the nucleus magnetic hydrogen spectrum figure of the compound of formula 1 is as shown in Figure 1.
Solidification：The compound of formula 1 for obtaining will above be synthesized with bisphenol A type epoxy resin with mass ratio 1：10 are added to beaker
In, add the 30% of the compound of formula 1 and bisphenol A type epoxy resin gross mass curing agent 4,4 '-diaminodiphenyl ether, mixing
After thing melting mixing at 150 DEG C is uniform, pour into rectangular die, and be placed in Muffle furnace with 180 DEG C/3 hours, 210 DEG C/
2 hours, 230 DEG C/2 hours, 250 DEG C/2 hours, the temperature-programmed mode solidification of 270 DEG C/2 hours, then take out and are cooled to room
Temperature, is prepared into naphthyl type phthalonitrile and epoxy resin composite material.
Embodiment 2
Other steps are with embodiment 1, difference：The compound of formula 1 is 2 with the mass ratio of bisphenol A type epoxy resin:
10。
Embodiment 3
Other steps are with embodiment 1, difference：The compound of formula 1 is 3 with the mass ratio of bisphenol A type epoxy resin:
10。
Embodiment 4
Other steps are with embodiment 1, difference：Bisphenol A type epoxy resin is only selected, the compound of formula 1 is added without.
Fig. 1 is the compound nucleus magnetic hydrogen spectrum figure of 1 Chinese style of embodiment 1.It can be seen that the baseline of spectrogram is smooth, and peak
Shape is clear, without miscellaneous peak, illustrate synthesized by monomer purity it is high.By calculating, each hydrogen is all in nucleus magnetic hydrogen spectrum spectrogram in monomer structure
In be proven, illustrate to successfully synthesize the compound of formula 1.
Fig. 2 is that the mass ratio of the compound of 1,2,3,4 Chinese style of embodiment 1 and bisphenol A type epoxy resin is respectively 1：10、2：
10、3：The TGA collection of illustrative plates of solidified after-product and pure epoxy resin cured article when 10.As can be seen that in nitrogen atmosphere in TGA figures
Under, the content of the compound of formula 1 is more, and temperature of initial decomposition is bigger, and carbon yield is also higher, and this compound of formula 1 can increase
The heat endurance of epoxy resin.
Fig. 3 is that the mass ratio of the compound of 1,2,3,4 Chinese style of embodiment 1 and bisphenol A type epoxy resin is respectively 1：10、2：
10、3：The DMA collection of illustrative plates of solidified after-product and pure epoxy resin cured article when 10.As can be seen that compared to pure from DMA figures
Epoxy resin, the addition of the compound of formula 1 has been obviously improved the glass transition temperature of material, and 200 DEG C of left sides have been brought up to from 120 DEG C
The right side, and the content of the compound of formula 1 is more, and glass transition temperature is higher, and copolymer net is made after illustrating phthalonitrile monomer solidification
The rigidity of network is significantly increased, therefore composite is possessed more excellent mechanical property, and can be kept at higher temperatures.
Embodiment 5
The compound of formula 1 for obtaining will be synthesized in embodiment 1 with bisphenol f type epoxy resin with mass ratio 1：10 are added to beaker
In, the 30% of the compound of formula 1 and bisphenol f type epoxy resin gross mass curing agent DDS is added, mix
After thing melting mixing at 150 DEG C is uniform, pour into rectangular die, and be placed in Muffle furnace with 190 DEG C/3 hours, 210 DEG C/
2 hours, 240 DEG C/4 hours, the temperature-programmed mode solidification of 270 DEG C/2 hours, then take out and are cooled to room temperature, are prepared into naphthyl
Type phthalonitrile and epoxy resin composite material.
Embodiment 6
Other steps are with embodiment 5, difference：The compound of formula 1 is 2 with the mass ratio of bisphenol f type epoxy resin:
10。
Embodiment 7
Other steps are with embodiment 5, difference：The compound of formula 1 is 3 with the mass ratio of bisphenol A type epoxy resin:
10。
Embodiment 8
Other steps are with embodiment 5, difference：Bisphenol f type epoxy resin is only selected, the compound of formula 1 is added without.
The correlated performance of the composite that embodiment 5,6,7,8 is obtained is similar to embodiment 1,2,3,4.
Embodiment 9
The compound of formula 1 for obtaining will be synthesized in embodiment 1 with bisphenol-s epoxy resin with mass ratio 1：10 are added to beaker
In, add the 30% of the compound of formula 1 and bisphenol-s epoxy resin gross mass curing agent 3,4 '-diaminodiphenyl ether, mixing
After thing melting mixing at 150 DEG C is uniform, pour into rectangular die, and be placed in Muffle furnace with 180 DEG C/3 hours, 200 DEG C/
2 hours, 220 DEG C/2 hours, 240 DEG C/2 hours, the temperature-programmed mode solidification of 260 DEG C/2 hours, then take out and are cooled to room
Temperature, is prepared into naphthyl type phthalonitrile and epoxy resin composite material.
Embodiment 10
Other steps are with embodiment 9, difference：The compound of formula 1 is 2 with the mass ratio of bisphenol-s epoxy resin:
10。
Embodiment 11
Other steps are with embodiment 9, difference：The compound of formula 1 is 3 with the mass ratio of bisphenol-s epoxy resin:
10。
Embodiment 12
Other steps are with embodiment 9, difference：Bisphenol-s epoxy resin is only selected, the compound of formula 1 is added without.
The correlated performance of the composite that embodiment 9,10,11,12 is obtained is similar to embodiment 1,2,3,4.
Described chemical reagent is commercially available acquisition.
Unaccomplished matter of the present invention is known technology.
Claims (4)
1. the preparation method of a kind of naphthyl type phthalonitrile and epoxy resin composite material, it is characterized by the method include it is following
Step：
（1）Prepare naphthyl type phthalonitrile monomer：1,6- naphthalenediol, 4- nitrophthalonitriles and potassium carbonate are added to alkalescence
In solvent, 80-90oC reacts 4-8 hours, then pours the mixture into watery hydrochloric acid, is washed with distillation after placing 8-12 hours
To neutral, after vacuum drying, compound A is obtained；
Wherein, feed molar proportioning 1,6- naphthalenediols：4- nitrophthalonitriles：Potassium carbonate=1：2：(2-3) ；Described dilute salt
Acid concentration is 0.3-0.5 mol/L, and 8-10 L watery hydrochloric acid is needed per mole compound A；Add 750-1000 mL per mole compound A
Basic solvent；
(2) the compound A for obtaining step (1) and epoxy resin, aromatic amine curing agent are in 130-180oMelting mixing under C
Uniformly, then pour into mould while hot, then successively in 180-185oC、210-215oC、230-235 oC、250-255oC and
270-275 oFive temperature sections of C carry out temperature-programmed reaction, and each temperature section respectively reacts 2-4 hours, so as to obtain O-phthalic
Nitrile modified epoxy resin composite；
The mass ratio of compound A and epoxy resin described in step (2) is 1:10-1:1, the matter of the two mixture and curing agent
Amount is than being 1:0.25-1:0.4.
2. the preparation method of naphthyl type phthalonitrile as claimed in claim 1 and epoxy resin composite material, it is characterized by
Epoxy resin described in step (2) is bisphenol A type epoxy resin, bisphenol-s epoxy resin or bisphenol f type epoxy resin.
3. the preparation method of naphthyl type phthalonitrile as claimed in claim 1 and epoxy resin composite material, it is characterized by
Aromatic amine curing agent described in step (2) is 4,4 '-diaminodiphenyl ether, 3,4 '-diaminodiphenyl ether or 4,4 '-diamino
Base diphenyl sulphone (DPS).
4. the preparation method of naphthyl type phthalonitrile as claimed in claim 1 and epoxy resin composite material, it is characterized by
Basic solvent described in step (1) is dimethyl sulfoxide (DMSO), N, N- dimethylformamides, N, N- dimethylacetylamides or N-
One or more in methyl pyrrolidone.
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| CN201710116614.XA CN106750275A (en) | 2017-03-01 | 2017-03-01 | A kind of preparation method of naphthyl type phthalonitrile and epoxy resin composite material |
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| CN201710116614.XA CN106750275A (en) | 2017-03-01 | 2017-03-01 | A kind of preparation method of naphthyl type phthalonitrile and epoxy resin composite material |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110183821A (en) * | 2019-06-04 | 2019-08-30 | 河北工业大学 | A kind of preparation method of vinylpyridine type phthalonitrile and epoxy resin composite material |
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| US20040181028A1 (en) * | 2002-04-26 | 2004-09-16 | Keller Teddy M. | Oligomeric hydroxy arylether phthalonitiles and synthesis thereof |
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| CN102964594A (en) * | 2012-12-03 | 2013-03-13 | 河北工业大学 | Method for preparing naphthyl polystyrene nitrile resin |
| CN105255109A (en) * | 2015-10-16 | 2016-01-20 | 中科院广州化学有限公司南雄材料生产基地 | Phthalonitrile modified benzoxazine and epoxy resin composite material, preparation and application |
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2017
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| US5939508A (en) * | 1995-09-01 | 1999-08-17 | The United States Of America As Represented By The Secretary Of The Navy | High temperature epoxy-phthalonitrile blends |
| US20040181028A1 (en) * | 2002-04-26 | 2004-09-16 | Keller Teddy M. | Oligomeric hydroxy arylether phthalonitiles and synthesis thereof |
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| CN102964594A (en) * | 2012-12-03 | 2013-03-13 | 河北工业大学 | Method for preparing naphthyl polystyrene nitrile resin |
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| FENGHUA ZHAO等: "《A novel high-temperature naphthyl-based phthalonitrile polymer: synthesis and properties》", 《RSC ADVANCES》 * |
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| XIN ZHAO等: "《Preparation and properties of halogen-free flame-retarded phthalonitrile-epoxy blends》", 《JOURNAL OF APPLIED POLYMER SCIENCE BANNER》 * |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110183821A (en) * | 2019-06-04 | 2019-08-30 | 河北工业大学 | A kind of preparation method of vinylpyridine type phthalonitrile and epoxy resin composite material |
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Application publication date: 20170531 |