CN104130406A - Novel co-blending and synergistic curing method for carbon-carbon unsaturated group-containing terminated imide compound and aromatic nitrile-containing compound - Google Patents
Novel co-blending and synergistic curing method for carbon-carbon unsaturated group-containing terminated imide compound and aromatic nitrile-containing compound Download PDFInfo
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- 239000011203 carbon fibre reinforced carbon Substances 0.000 title claims abstract description 82
- 150000001875 compounds Chemical class 0.000 title claims abstract description 72
- -1 imide compound Chemical class 0.000 title claims abstract description 72
- 238000002156 mixing Methods 0.000 title claims abstract description 30
- 238000001723 curing Methods 0.000 title abstract description 26
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 title abstract description 3
- 230000002195 synergetic effect Effects 0.000 title abstract 2
- 239000000203 mixture Substances 0.000 claims description 110
- 229910052799 carbon Inorganic materials 0.000 claims description 75
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 56
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 44
- 238000000034 method Methods 0.000 claims description 36
- 238000010438 heat treatment Methods 0.000 claims description 26
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 24
- 239000002904 solvent Substances 0.000 claims description 22
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 18
- 238000004821 distillation Methods 0.000 claims description 17
- 150000003949 imides Chemical class 0.000 claims description 16
- 238000005086 pumping Methods 0.000 claims description 16
- OMFXVFTZEKFJBZ-HJTSIMOOSA-N corticosterone Chemical compound O=C1CC[C@]2(C)[C@H]3[C@@H](O)C[C@](C)([C@H](CC4)C(=O)CO)[C@@H]4[C@@H]3CCC2=C1 OMFXVFTZEKFJBZ-HJTSIMOOSA-N 0.000 claims description 13
- SFHYNDMGZXWXBU-LIMNOBDPSA-N 6-amino-2-[[(e)-(3-formylphenyl)methylideneamino]carbamoylamino]-1,3-dioxobenzo[de]isoquinoline-5,8-disulfonic acid Chemical compound O=C1C(C2=3)=CC(S(O)(=O)=O)=CC=3C(N)=C(S(O)(=O)=O)C=C2C(=O)N1NC(=O)N\N=C\C1=CC=CC(C=O)=C1 SFHYNDMGZXWXBU-LIMNOBDPSA-N 0.000 claims description 9
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- 238000003756 stirring Methods 0.000 claims description 8
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- UOXJNGFFPMOZDM-UHFFFAOYSA-N 2-[di(propan-2-yl)amino]ethylsulfanyl-methylphosphinic acid Chemical compound CC(C)N(C(C)C)CCSP(C)(O)=O UOXJNGFFPMOZDM-UHFFFAOYSA-N 0.000 claims description 3
- 125000004802 cyanophenyl group Chemical group 0.000 claims description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 2
- 238000012545 processing Methods 0.000 abstract description 10
- 238000007669 thermal treatment Methods 0.000 abstract description 4
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- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 26
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- 230000008023 solidification Effects 0.000 description 13
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- 229920001187 thermosetting polymer Polymers 0.000 description 4
- UEXCJVNBTNXOEH-UHFFFAOYSA-N Ethynylbenzene Chemical group C#CC1=CC=CC=C1 UEXCJVNBTNXOEH-UHFFFAOYSA-N 0.000 description 3
- LWLSVNFEVKJDBZ-UHFFFAOYSA-N N-[4-(trifluoromethoxy)phenyl]-4-[[3-[5-(trifluoromethyl)pyridin-2-yl]oxyphenyl]methyl]piperidine-1-carboxamide Chemical compound FC(OC1=CC=C(C=C1)NC(=O)N1CCC(CC1)CC1=CC(=CC=C1)OC1=NC=C(C=C1)C(F)(F)F)(F)F LWLSVNFEVKJDBZ-UHFFFAOYSA-N 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
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- 150000002825 nitriles Chemical class 0.000 description 3
- 229920006391 phthalonitrile polymer Polymers 0.000 description 3
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- 238000006116 polymerization reaction Methods 0.000 description 3
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- 150000003384 small molecules Chemical class 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
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- 229920003192 poly(bis maleimide) Polymers 0.000 description 2
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- 229920006305 unsaturated polyester Polymers 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
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- 238000006957 Michael reaction Methods 0.000 description 1
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- 239000004642 Polyimide Substances 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
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- 230000006978 adaptation Effects 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
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- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- IXSZQYVWNJNRAL-UHFFFAOYSA-N etoxazole Chemical compound CCOC1=CC(C(C)(C)C)=CC=C1C1N=C(C=2C(=CC=CC=2F)F)OC1 IXSZQYVWNJNRAL-UHFFFAOYSA-N 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
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- 125000000623 heterocyclic group Chemical group 0.000 description 1
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- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
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- 238000000197 pyrolysis Methods 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Indole Compounds (AREA)
Abstract
The invention discloses a novel co-blending and synergistic curing method for a carbon-carbon unsaturated group (carbon-carbon double bond or carbon-carbon triple bond)-containing terminated imide compound and an aromatic nitrile-containing compound. The carbon-carbon double bond or carbon-carbon triple bond-containing terminated imide compound and the aromatic nitrile-containing compound are co-blended and heated in different molar ratios. Rapid curing of the aromatic nitrile-containing compound can be initiated by the carbon-carbon double bond or carbon-carbon triple bond-containing terminated imide compound, and the two types of compounds are synergistically cured through thermal treatment. Meanwhile, the processing characteristics of a co-blended target product are improved, and a novel thought is provided for curing of the aromatic nitrile-containing compound.
Description
Technical field
The present invention relates to a kind of curing novel method of high-performance poly o-phthalonitrile resin, be particularly related to the imide compound of a class carbon containing carbon unsaturated group (carbon-carbon double bond or carbon carbon triple bond) end-blocking and work in coordination with and solidify novel method containing the blend of fragrant itrile group compound, belong to processing of high molecular material Application Areas.
Background technology
Poly-o-phthalonitrile resin (PN resin) is the high-performance thermosetting material that a class has outstanding processibility and over-all properties, network structure taking fragrant heterocycle as cross-linking set is given the high temperature resistant of its uniqueness, heat and thermo-oxidative stability, in the course of processing, volatilize without small-molecule substance, the product tight generating, there is high glass-transition temperature, low water absorbable, resistance to chemical attack, flame retardant resistance, excellent dimensional stability and mechanical behavior under high temperature, after the further pyrolysis of polymkeric substance, also there is electroconductibility, these performances make them at high performance composite matrix resin, High-temp.-resistant hot-melt adhesive, sun power tabula rasa, electrical conductor material, the high-tech sectors such as aerospace have very large potential using value.
But the factor such as rigidity, low reaction activity of molecular structure makes the polymerization of pure o-phthalonitrile resin very slow, need within nearly hundred hours, just can observe obvious gel 280 DEG C of thermal treatments, this has limited the range of application of this resin system greatly.Research discovery, can be by adding the solidifying agent such as phenol, primary aromatic amine, organic acid, acid anhydrides, organic acid/ammonium salt and metal-salt or additive to shorten set time, accelerates solidifying of o-phthalonitrile resin.
Research discovery, the O-phthalic nitrile compound that a class self contains amino or hydroxyl has autoacceleration effect.But this resinoid after solidifying is because high-crosslinking-degree, high rigidity are enbrittled.Meanwhile, its processibility is also because high-melting-point or the softening temperature of O-phthalic nitrile compound and be restricted compared with narrow processing temperature window.
Recently, mainly concentrate on and on main polymer chain, introduce flexible aryl oxide chain and fetch and improve processibility about the research of phthalonitrile.Meanwhile, owing to there is a large amount of flexible ether links in phthalonitrile-terminated structure, its degree of crosslinking of resin after solidifying is reduced, thereby also avoided fragility.But the thermostability of cured product has reduced.Therefore, large quantity research concentrates on by introducing flexible link and reduces its fusing point or softening temperature, widen processing temperature window improving o-phthalonitrile resin processibility when, introduce thermotolerance structure as imide ring or after solidifying, can obtain having the reactive functional groups of high-crosslinking-degree and high heat resistance product, system improves processibility and other performances of o-phthalonitrile resin on the whole.From 20 century 70s, US Naval Research Laboratory, for phthalonitrile system, has carried out comparatively systematic research from monomer molecule structure design to aspects such as solidification process rheology and curing performances.From reducing the second-order transition temperature of o-phthalonitrile resin or fusing point to widen the angle of process window, the related fields such as the Keller of US Naval Research Laboratory and his colleagues introduce the amine curing agents such as m-APB, m-BAPS, p-BAPS in phthalonitrile system, the performance of curing action, processibility and the curing rear resin of two end-blocking O-phthalic nitrile compounds that research contains acid amides, imide or aryl ether ketone link structure.Result shows, o-phthalonitrile resin processibility by gain of parameters such as regulation and control curing additive concentration or solidification values improves, but whole system is inevitably due to the easily volatilization or decompose when the high-temperature heat treatment of the small-molecule substances such as amine curing agent, cause solidification rate to decline, the performance of the resin after solidifying also decreases to a certain extent.
On the other hand, contain potential thermal response group and also obtained broad research as the thermoset performance resins of acetylene, phenylacetylene base end-blocking.As bismaleimides, phenylacetylene-capped imide.Phenylacetylene group is as the reflecting point of the crosslinked precursor of thermosetting material, not only show thermostability and wider process window relatively preferably, and can provide relatively excellent toughness, well solvent resistance, excellent thermostability for the material after crosslinking curing, this makes it become the main study hotspot of Thermocurable polyimide material.But its curing reaction thermal discharge is large, and curing speed is too fast, reaction is difficult to control, and these problems have limited the particularly application in heavy wall composite product field that is widely used of this resin to a great extent.
The carbon-carbon double bond of N-substituted maleimide amine has very high electron deficiency, activity is very high, easily carry out nucleophilic addition, as Diels-Alder addition reaction (Diene-addition) and Michael reaction, also easily carry out anionic polymerisation, photosensitive induced polymerization reaction and free radical reaction and copolyreaction.Meanwhile, poly-N-substituted maleimide amine has excellent thermostability.Bismaleimides (BMI) resin has good mechanical property and resistance toheat etc., but BMI solidification value is high, curing cross-linked density is large, make resin have the shortcomings such as fusing point is high, poorly soluble, mold temperature is high, cured article fragility is large, thereby make its application be subject to very big restriction.At present, the modification of BMI resin mainly contains following research direction: improve toughness; Improve workability, to meet the requirement of machine-shaping and adaptation novel processing technology; Reduce costs etc.
Summary of the invention
The object of this invention is to provide the imide compound of the carbon containing carbon unsaturated group end-blocking that a kind of solidification value is lower, curing speed fast, blend target product processibility is more excellent and work in coordination with and solidify novel method containing the blend of fragrant itrile group compound.
The present invention relates to the imide compound of a class carbon containing carbon unsaturated group (carbon-carbon double bond or carbon carbon triple bond) end-blocking and work in coordination with and solidify novel method containing the blend of fragrant itrile group compound, by the fragrant itrile group compound that contains of the imide compound of carbon-carbon double bonds or carbon carbon triple bond end-blocking and different mol ratio example is carried out to physical blending, and by thermal treatment, the imide compound of carbon-carbon double bonds or carbon carbon triple bond end-blocking can cause containing fragrant itrile group compound fast setting, between two compounds, there is collaborative solidifying by thermal treatment, for the curing new approaches that provide containing fragrant itrile group compound.
The present invention opens up one and solves the approach that traditional fragrant nitrile resin solidification speed is slow, set time is oversize, and the novel hot setting resin system for exploitation with different curing characteristicss and excellent machining property provides thinking.Carry out physical blending by the imide compound of carbon containing carbon unsaturated group (carbon-carbon double bond or carbon carbon triple bond) end-blocking and containing fragrant itrile group compound, obtain the class new type resin system that curing reaction speed is obviously accelerated, obviously shorten set time, solidified after-product has excellent properties.
In order to realize foregoing invention object, the invention provides following technical scheme: the imide compound of a class carbon containing carbon unsaturated group (carbon-carbon double bond or carbon carbon triple bond) end-blocking is worked in coordination with curing novel method with containing the blend of fragrant itrile group compound, comprises following content and process:
1, the imide compound of carbon containing carbon unsaturated group end-blocking, is mainly the imide compound of carbon-carbon double bonds or carbon carbon triple bond end-blocking, and its general formula of molecular structure is as follows:
Wherein, R
1, R
2, R
3be expressed as follows R
2and R
3can be simultaneously identical, also can be simultaneously different.
Wherein, R
4, R
5, R
6be expressed as follows R
5and R
6can be simultaneously identical, also can be simultaneously different.
2, containing fragrant itrile group compound, be mainly the benzene-like compounds that contains mononitrile base or two itrile group end-blockings, its general formula of molecular structure is as follows:
Wherein, the structural formula of R is as follows:
Note: R
4identical with the R4 in the imide compound general structure of carbon containing carbon unsaturated group end-blocking.
3, master operation step
(1) by the imide compound of above-mentioned carbon containing carbon unsaturated group (carbon-carbon double bond or carbon carbon triple bond) end-blocking and the blend mixing that obtains different mol ratio example containing fragrant itrile group compound by solution blending or melt blending.While considering melt blending, in melting process, may relate to unsaturated group faint reaction occurs, generally adopt the mode of solution blending to obtain blend.
Wherein, the imide compound of carbon containing carbon unsaturated group (carbon-carbon double bond or carbon carbon triple bond) end-blocking can be arbitrary proportion with mole blend ratio containing fragrant itrile group compound, and the molar ratio that is preferably the imide compound of carbon containing carbon unsaturated group (carbon-carbon double bond or carbon carbon triple bond) end-blocking is more than or equal to the molar ratio containing fragrant itrile group compound.
For solution blending, need to first investigate the solvability of the respective compound for the treatment of blend, then select low boiling point solvent to consider and carry out solution blending, until abundant stirring and dissolving or after being uniformly dispersed, underpressure distillation pumps low boiling point solvent, more fully ground sample obtains the uniform blend of blend.Low boiling point solvent can be selected methylene dichloride, acetone, chloroform, methyl alcohol, tetrahydrofuran (THF), normal hexane, tetracol phenixin, ethyl acetate, ethanol, butanone, acetonitrile, Isosorbide-5-Nitrae-dioxane, toluene equal solvent.
For melt blending, need first to investigate fusing point or the softening temperature of the respective compound for the treatment of blend, and curing exotherm temperature, consider and carry out melt blending.In the compound of molten state, add another kind of compound, after stirring, be cooled to rapidly room temperature, obtain a kind of mixture of vitreous state, more fully ground sample obtains the uniform blend of blend.The melt temperature that blend is selected must be lower than the initial curing exotherm temperature of corresponding single compound.
(2) blend of the different mol ratio example of above-mentioned gained waits heat treatment mode by heating, the imide compound that can obviously observe carbon containing carbon unsaturated group (carbon-carbon double bond or carbon carbon triple bond) end-blocking can promote solidifying containing fragrant itrile group compound greatly, the method has shortened the set time of fragrant itrile group compound, improve curing efficiency, meanwhile, the collaborative solidification occurring between this two compounds has also been improved the processibility of blend target product.
Wherein, the original position infrared test condition that heats up is: air atmosphere, and scanning temperature range is generally room temperature to before sample weightless temperature 20～50 DEG C, and top temperature is limited to sample weightless temperature.Sweep limit is 4000～400cm
-1, scanning times 16 times, resolving power 4cm
-1.For the absorption intensity of corresponding functional group in obvious ground observing response process changes, change according to infrared absorption peak position and absorption intensity simultaneously, we select relevant functional group's characteristic peak, taking the C=O on imide ring as interior mark group, integral area is normalized, and calculate transformation efficiency, calculation formula is:
Wherein, 2210cm
-1, 3255cm
-1, 690cm
-1, 2234cm
-1represent respectively the infrared absorption peak position of C ≡ C, ≡ C-H ,=C-H, C ≡ N, 1720cm
-1(or 1713cm
-1, 1712cm
-1near) and 1780cm
-1(or 1776cm
-1, 1775cm
-1near) be the infrared absorption peak position of C=O in respective compound.α
cC, α
cH, α
cNbe respectively C ≡ C, ≡ C-H or=transformation efficiency of the functional groups such as C-H, C ≡ N, I is near the absorption integral area of corresponding functional group respective absorption peak.T=0 and t are illustrated respectively in initial time and the real-time time in reaction process.
By original position intensification infrared test, can observe in blend, the infrared absorption peak intensity of the carbon-carbon double bond of the imide compound of unsaturated group end-blocking or carbon carbon triple bond obviously declines even almost nil; Meanwhile, also obviously decline even almost nil containing the infrared absorption peak intensity of the itrile group functional group in fragrant itrile group compound.Therefore, in essence, between this two compounds, there is collaborative solidifying.
Wherein, the concrete grammar that blend carries out original position intensification infrared test is: the Potassium Bromide (KBr that takes the mixed uniformly blend of 1mg and 150mg left and right on analytical balance, spectroscopically pure), grinding is pressed into Φ 1cm disc-shaped, put into homemade Intelligent heating device, connect infrared test instrument and carry out after light path correction, setting corresponding test top temperature, starting test from room temperature.In temperature-rise period, synchronously carry out the in-situ ft-ir test of sample disk, to observe the Strength Changes of corresponding functional group (C ≡ C, ≡ C-H or=C-H and C ≡ N) infrared absorption peak and to confirm to have occurred between above-mentioned blend collaborative curing reaction.
Compared with prior art, beneficial effect of the present invention:
For the problems referred to above, the inventor carries out physical blending by the compound that contains different carbon carbon unsaturated groups (carbon-carbon double bond or carbon carbon triple bond) end-blocking and containing fragrant itrile group compound, to solidifying fragrant nitrile resin with unsaturated polyester, reach the object that improves fragrant nitrile resin solidification speed, on the other hand, also improve the relevant processing characteristics of unsaturated polyester, make two resinoids give play to by collaborative solidifying the better performance having than after original single resin solidification, obtain a class and have the novel hot setting polymkeric substance of different curing characteristicss and excellent machining property.
Tradition o-phthalonitrile resin is very long set time, and solidification value is high; In this invention, the imide compound of carbon containing carbon unsaturated group (carbon-carbon double bond or carbon carbon triple bond) end-blocking is at relatively low temperature, just can effectively promote solidifying containing fragrant itrile group compound, greatly shorten the set time containing fragrant itrile group compound, improve curing efficiency, meanwhile, the collaborative solidification occurring between this two compounds has also been improved the processibility of blend target product.
The imide compound of carbon containing carbon unsaturated group (carbon-carbon double bond or carbon carbon triple bond) end-blocking has good thermostability, in solidification process, volatilizees without obvious by product; Containing the melting viscosity very low (<0.3Pa.s) of fragrant itrile group compound; The polyaddition reaction of itrile group generates the small molecule by-product of non-volatility in its solidification process; The polymerization velocity of resin and viscosity can be controlled by the addition of the imide compound containing unsaturated group end-blocking and processing hot temperature degree.Therefore, the processing of poly-o-phthalonitrile resin based composites can by traditional autoclave laying, injection moulding machine injection moulding or by device for automatically molding as thermosetting resin reaction injection molding machine is extruded, transmission and wire drawing Wrapping formed, also can pass through resin transfer moulding (RTM) moulding cheaply, and easily make baroque thick walled part.
Embodiment
According to following embodiment, can make better those skilled in the art understand the present invention.But, the described concrete material proportion of each embodiment, processing condition in the present invention, it is only the specific case that object of the present invention, technical scheme and beneficial effect are further elaborated, the present invention is not defined in this.All any amendments of making, be equal to replacement, improvement etc., within being all included in protection scope of the present invention within scope of disclosure of the present invention.
Each process in following embodiment all carries out under normal pressure, and the amount of all substances is all based on molecular fraction, and all temperature condition are degree Celsius, and all raw material is by nuclear-magnetism, infrared and ultimate analysis checking resulting structures, except as otherwise noted.
In following examples, the structural formula of the compound relating generally to is as follows:
Carbon containing carbon unsaturated group end-blocking imide compound structural formula and numbering thereof:
Described containing cyanophenyl based compound structural formula and numbering thereof:
Embodiment mono-carbon-carbon double bond end-blocking imide compound A1 solidifies with two itrile group compound B-11 mol ratio 5:5 blend are collaborative
Molar ratio is that the carbon-carbon double bond end-blocking imide compound A1 of 5:5 adopts acetone solvent to carry out solution blending with two itrile group compound B-11s, and underpressure distillation is fully ground the blend that obtains equimolar ratio after pumping acetone.Blend adopts KBr pressed disc method, and uses homemade Intelligent heating device and the coupling of infrared test instrument, carries out original position intensification infrared test.Probe temperature is room temperature to 330 DEG C, and the test duration is about 19min altogether.In-situ Infrared test result shows, before 150 DEG C, and 690cm
-1place=C-H infrared absorption peak and 2232cm
-1the C ≡ N of place infrared absorption peak intensity, without considerable change, sharply raises at the transformation efficiency of 195 DEG CHou Liang class functional groups, and in blend, the speed of response of carbon-carbon double bond is very fast, simultaneously C ≡ N be swift in response and its transformation efficiency higher.195 DEG C time, 690cm
-1place=C-H transformation efficiency is 34%, 2232cm
-1place's C ≡ N transformation efficiency is 31%; 330 DEG C time ,=C-H transformation efficiency is that 97%, C ≡ N transformation efficiency has reached 61%.
Embodiment bis-carbon-carbon double bond end-blocking imide compound A1 solidify with two itrile group compd B 3 mol ratio 5:5 blend are collaborative
Molar ratio is that the carbon-carbon double bond end-blocking imide compound A1 of 5:5 adopts acetone solvent to carry out solution blending with two itrile group compd Bs 3, and underpressure distillation is fully ground the blend that obtains equimolar ratio after pumping acetone.Blend adopts KBr pressed disc method, and uses homemade Intelligent heating device and the coupling of infrared test instrument, carries out original position intensification infrared test.Probe temperature is room temperature to 340 DEG C, and the test duration is about 20min altogether.In-situ Infrared test result shows, before 145 DEG C, and 690cm
-1place=C-H infrared absorption peak and 2235cm
-1the C ≡ N of place infrared absorption peak intensity, without considerable change, starts slow rising at the transformation efficiency of 182 DEG CHou Liang class functional groups, and in blend, the speed of response of carbon-carbon double bond is very fast and cause C ≡ N rapid reaction.205 DEG C time, 690cm
-1place=C-H transformation efficiency is 36%, 2235cm
-1place's C ≡ N transformation efficiency is 17%; 340 DEG C time ,=C-H transformation efficiency is that 90%, C ≡ N transformation efficiency has reached 38%.
Embodiment tri-carbon-carbon double bond end-blocking imide compound A2 solidify with two itrile group compound B-11 mol ratio 5:5 blend are collaborative
Molar ratio is that the carbon-carbon double bond end-blocking imide compound A2 of 5:5 adopts acetone solvent to carry out solution blending with two itrile group compound B-11s, and underpressure distillation is fully ground the blend that obtains equimolar ratio after pumping acetone.Blend adopts KBr pressed disc method, and uses homemade Intelligent heating device and the coupling of infrared test instrument, carries out original position intensification infrared test.Probe temperature is room temperature to 310 DEG C, and the test duration is about 18min altogether.In-situ Infrared test result shows, before 170 DEG C, and 699cm
-1place=C-H infrared absorption peak and 2232cm
-1the C ≡ N of place infrared absorption peak intensity, without considerable change, sharply raises at the transformation efficiency of 240 DEG CHou Liang class functional groups, and in blend, the speed of response of carbon-carbon double bond is very fast, simultaneously C ≡ N be swift in response and its transformation efficiency higher.240 DEG C time, 699cm
-1place=C-H transformation efficiency is 58%, 2232cm
-1place's C ≡ N transformation efficiency is 41%; 310 DEG C time ,=C-H transformation efficiency is that 83%, C ≡ N transformation efficiency has reached 81%.
Embodiment tetra-carbon-carbon double bond end-blocking imide compound A2 solidify with two itrile group compd B 2 mol ratio 6:4 blend are collaborative
Molar ratio is that the carbon-carbon double bond end-blocking imide compound A2 of 6:4 adopts scorification to carry out blend with two itrile group compd Bs 2, be heated to 200 DEG C, in the compd A 2 of molten state, add compd B 2, after stirring, be cooled to rapidly room temperature, obtain a kind of mixture of vitreous state, more fully ground sample obtains uniform blend.Blend adopts KBr pressed disc method, and uses homemade Intelligent heating device and the coupling of infrared test instrument, carries out original position intensification infrared test.Probe temperature is room temperature to 340 DEG C, and the test duration is about 20min altogether.In-situ Infrared test result shows, before 210 DEG C, and 699cm
-1place=C-H infrared absorption peak and 2231cm
-1the C ≡ N of place infrared absorption peak intensity, without considerable change, sharply raises at the transformation efficiency of 270 DEG CHou Liang class functional groups, and in blend, the speed of response of carbon-carbon double bond is very fast, simultaneously C ≡ N be swift in response and its transformation efficiency higher.270 DEG C time, 699cm
-1place=C-H transformation efficiency is 31%, 2231cm
-1place's C ≡ N transformation efficiency is 29%; 340 DEG C time ,=C-H transformation efficiency is that 91%, C ≡ N transformation efficiency has reached 87%, and primitive reaction is complete.
Embodiment five carbon-carbon double bond end-blocking imide compound A2 solidify with two itrile group compd B 3 mol ratio 5:5 blend are collaborative
Molar ratio is that the carbon-carbon double bond end-blocking imide compound A2 of 5:5 adopts acetone solvent to carry out solution blending with two itrile group compd Bs 3, and underpressure distillation is fully ground the blend that obtains equimolar ratio after pumping acetone.Blend adopts KBr pressed disc method, and uses homemade Intelligent heating device and the coupling of infrared test instrument, carries out original position intensification infrared test.Probe temperature is room temperature to 325 DEG C, and the test duration is about 19min altogether.In-situ Infrared test result shows, before 190 DEG C, and 699cm
-1place=C-H infrared absorption peak and 2235cm
-1the C ≡ N of place infrared absorption peak intensity, without considerable change, sharply raises at the transformation efficiency of 210 DEG CHou Liang class functional groups, and in blend, the speed of response of carbon-carbon double bond is very fast, simultaneously C ≡ N be swift in response and its transformation efficiency higher.210 DEG C time, 699cm
-1place=C-H transformation efficiency is 21%, 2235cm
-1place's C ≡ N transformation efficiency is 25%; 325 DEG C time ,=C-H transformation efficiency is that 68%, C ≡ N transformation efficiency has reached 79%.
Embodiment six carbon-carbon double bond end-blocking imide compound A3 solidify with two itrile group compd B 2 mol ratio 9:1 blend are collaborative
Molar ratio is that the carbon-carbon double bond end-blocking imide compound A3 of 9:1 adopts scorification to carry out blend with two itrile group compd Bs 2, be heated to 220 DEG C, in the compound A-13 of molten state, add compd B 2, after stirring, be cooled to rapidly room temperature, obtain a kind of mixture of vitreous state, more fully ground sample obtains uniform blend.Blend adopts KBr pressed disc method, and uses homemade Intelligent heating device and the coupling of infrared test instrument, carries out original position intensification infrared test.Probe temperature is room temperature to 310 DEG C, and the test duration is about 18min altogether.In-situ Infrared test result shows, before 236 DEG C, and 700cm
-1place=C-H infrared absorption peak and 2231cm
-1the C ≡ N of place infrared absorption peak intensity, without considerable change, starts slow rising at the transformation efficiency of 295 DEG CHou Liang class functional groups, and in blend, the speed of response of carbon-carbon double bond is very fast and cause C ≡ N rapid reaction.295 DEG C time, 700cm
-1place=C-H transformation efficiency is 23%, 2231cm
-1place's C ≡ N transformation efficiency is 17%; 310 DEG C time ,=C-H transformation efficiency is that 82%, C ≡ N transformation efficiency has reached 55%.
Embodiment seven carbon-carbon double bond end-blocking imide compound A4 and mononitrile based compound B4 mol ratio 7:3 blend are collaborative solidifies
Molar ratio is that carbon-carbon double bond end-blocking imide compound A4 and the mononitrile based compound B4 of 7:3 adopts acetone solvent to carry out solution blending, and underpressure distillation is fully ground and obtained uniform blend after pumping acetone.Blend adopts KBr pressed disc method, and uses homemade Intelligent heating device and the coupling of infrared test instrument, carries out original position intensification infrared test.Probe temperature is room temperature to 340 DEG C, and the test duration is about 20min altogether.In-situ Infrared test result shows, before 135 DEG C, and 691cm
-1place=C-H infrared absorption peak and 2227cm
-1the C ≡ N of place infrared absorption peak intensity, without considerable change, sharply raises at the transformation efficiency of 260 DEG CHou Liang class functional groups, and in blend, the speed of response of carbon-carbon double bond is very fast, simultaneously C ≡ N be swift in response and its transformation efficiency higher.260 DEG C time, 691cm
-1place=C-H transformation efficiency is 25%, 2227cm
-1place's C ≡ N transformation efficiency is 17%; 340 DEG C time ,=C-H transformation efficiency is about 93%, and primitive reaction is complete, and C ≡ N transformation efficiency has also reached 80%.
Embodiment eight carbon carbon triple bond end-blocking imide compound A5 solidify with two itrile group compound B-11 mol ratio 5:5 blend are collaborative
Molar ratio is that the carbon carbon triple bond end-blocking imide compound A5 of 5:5 adopts dichloromethane solvent to carry out solution blending with two itrile group compound B-11s, and underpressure distillation is fully ground the blend that obtains equimolar ratio after pumping methylene dichloride.Blend adopts KBr pressed disc method, and uses homemade Intelligent heating device and the coupling of infrared test instrument, carries out original position intensification infrared test.Probe temperature is room temperature to 330 DEG C, and the test duration is about 19min altogether.In-situ Infrared test result shows, before 182 DEG C, and 3255cm
-1place's ≡ C-H infrared absorption peak and 2232cm
-1the C ≡ N of place infrared absorption peak intensity, without considerable change, sharply raises at the transformation efficiency of 210 DEG CHou Liang class functional groups, and in blend, the speed of response of carbon carbon triple bond is very fast, simultaneously C ≡ N be swift in response and its transformation efficiency higher.210 DEG C time, 3255cm
-1place's ≡ C-H transformation efficiency is 10%, 2232cm
-1place's C ≡ N transformation efficiency is 25%; 330 DEG C time, ≡ C-H transformation efficiency is about 100%, and primitive reaction is complete, and C ≡ N transformation efficiency has also reached 61%.
Embodiment nine carbon carbon triple bond end-blocking imide compound A5 solidify with two itrile group compd B 2 mol ratio 8:2 blend are collaborative
Molar ratio is that the carbon carbon triple bond end-blocking imide compound A5 of 8:2 adopts scorification to carry out blend with two itrile group compd Bs 2, be heated to 240 DEG C, in the compd B 2 of molten state, add compound A-45, after stirring, be cooled to rapidly room temperature, obtain a kind of mixture of vitreous state, more fully ground sample obtains uniform blend.Blend adopts KBr pressed disc method, and uses homemade Intelligent heating device and the coupling of infrared test instrument, carries out original position intensification infrared test.Probe temperature is room temperature to 350 DEG C, and the test duration is about 21min altogether.In-situ Infrared test result shows, before 250 DEG C, and 3255cm
-1place's ≡ C-H infrared absorption peak and 2231cm
-1the C ≡ N of place infrared absorption peak intensity, without considerable change, sharply raises at the transformation efficiency of 260 DEG CHou Liang class functional groups, and in blend, the speed of response of carbon carbon triple bond is very fast, simultaneously C ≡ N be swift in response and its transformation efficiency higher.260 DEG C time, 3255cm
-1place's ≡ C-H transformation efficiency is 23%, 2231cm
-1place's C ≡ N transformation efficiency is 37%; 350 DEG C time, ≡ C-H transformation efficiency is about 95%, and primitive reaction is complete, and C ≡ N transformation efficiency has also reached 83%.
Embodiment ten carbon carbon triple bond end-blocking imide compound A5 solidify with two itrile group compd B 3 mol ratio 5:5 blend are collaborative
Molar ratio is that the carbon carbon triple bond end-blocking imide compound A5 of 5:5 adopts dichloromethane solvent to carry out solution blending with two itrile group compd Bs 3, and underpressure distillation is fully ground the blend that obtains equimolar ratio after pumping methylene dichloride.Blend adopts KBr pressed disc method, and uses homemade Intelligent heating device and the coupling of infrared test instrument, carries out original position intensification infrared test.Probe temperature is room temperature to 390 DEG C, and the test duration is about 24min altogether.In-situ Infrared test result shows, before 206 DEG C, and 3255cm
-1place's ≡ C-H infrared absorption peak and 2235cm
-1the C ≡ N of place infrared absorption peak intensity, without considerable change, sharply raises at the transformation efficiency of 245 DEG CHou Liang class functional groups, and in blend, the speed of response of carbon carbon triple bond is very fast, simultaneously C ≡ N be swift in response and its transformation efficiency higher.245 DEG C time, 3255cm
-1place's ≡ C-H transformation efficiency is 8%, 2235cm
-1place's C ≡ N transformation efficiency is 21%; 390 DEG C time, ≡ C-H transformation efficiency is about 92%, and primitive reaction is complete, and C ≡ N transformation efficiency has also reached 57%.
Embodiment 11 carbon carbon triple bond end-blocking imide compound A6 solidify with two itrile group compd B 3 mol ratio 5:5 blend are collaborative
Molar ratio is that the carbon carbon triple bond end-blocking imide compound A6 of 5:5 adopts ethyl acetate solvent to carry out solution blending with two itrile group compd Bs 3, and underpressure distillation is fully ground the blend that obtains equimolar ratio after pumping ethyl acetate.Blend adopts KBr pressed disc method, and uses homemade Intelligent heating device and the coupling of infrared test instrument, carries out original position intensification infrared test.Probe temperature is room temperature to 420 DEG C, and the test duration is about 28min altogether.In-situ Infrared test result shows, before 225 DEG C, and 2210cm
-1place's C ≡ C infrared absorption peak and 2234cm
-1the C ≡ N of place infrared absorption peak intensity, without considerable change, starts slow rising at the transformation efficiency of 316 DEG CHou Liang class functional groups, and in blend, the speed of response of carbon carbon triple bond is very fast and cause C ≡ N and start reaction.390 DEG C time, 2210cm
-1place's C ≡ C transformation efficiency is 22%, 2234cm
-1place's C ≡ N transformation efficiency is 17%; 420 DEG C time, C ≡ C transformation efficiency is about 63%,, C ≡ N transformation efficiency has reached 40%.
Claims (10)
1. the imide compound of a class carbon containing carbon unsaturated group end-blocking is worked in coordination with curing novel method with containing the blend of fragrant itrile group compound, it is characterized in that, a compounds is the imide compound of carbon-carbon double bonds or carbon carbon triple bond end-blocking, and its general formula of molecular structure is as follows:
Wherein, R1, R2, R3 are expressed as follows, and R2 and R3 can be simultaneously identical, also can be simultaneously different,
Wherein, R4, R5, R6 are expressed as follows, and R5 and R6 can be simultaneously identical, also can be simultaneously different,
Another kind of compound is that its general formula of molecular structure is as follows containing fragrant itrile group compound:
Wherein, the structural formula of R is as follows:
Carry out according to the following steps: the blend mixing that above-mentioned two compounds is obtained to different mol ratio example by solution blending or melt blending, again by heat treated mode, the imide compound of carbon-carbon double bonds or carbon carbon triple bond end-blocking can promote solidifying containing fragrant itrile group compound fast, between two compounds, there is collaborative solidifying by heat treated, thereby shorten set time, improve curing efficiency.
The imide compound of a class carbon containing carbon unsaturated group end-blocking according to claim 1 with containing the collaborative novel method of solidifying of fragrant itrile group compound blend, it is characterized in that, the solvent of the solution of described above-mentioned two compounds is selected from methylene dichloride, acetone, chloroform, methyl alcohol, tetrahydrofuran (THF), normal hexane, tetracol phenixin, ethyl acetate, ethanol, butanone, acetonitrile, Isosorbide-5-Nitrae-dioxane or toluene;
Described carbon containing carbon unsaturated group end-blocking imide compound is preferably from one of following:
Described containing cyanophenyl based compound preferably from one of following:
The molar ratio of described carbon-carbon double bonds end-blocking imide compound is more than or equal to the molar ratio containing cyanophenyl based compound.
The imide compound of a class carbon containing carbon unsaturated group end-blocking according to claim 2 with containing the collaborative novel method of solidifying of fragrant itrile group compound blend, it is characterized in that, described molar ratio is the carbon-carbon double bonds end-blocking imide compound A1 of 5:5 and adopts acetone solvents to carry out solution blending containing two itrile group compound B-11s, underpressure distillation is fully ground the blend that obtains equimolar ratio after pumping acetone, and described blend Heating temperature is 330 DEG C.
The imide compound of a class carbon containing carbon unsaturated group end-blocking according to claim 2 with containing the collaborative novel method of solidifying of fragrant itrile group compound blend, it is characterized in that, described molar ratio is the carbon-carbon double bonds end-blocking imide compound A1 of 5:5 and adopts acetone solvent to carry out solution blending containing two itrile group compd Bs 3, underpressure distillation is fully ground the blend that obtains equimolar ratio after pumping acetone, and described Heating temperature is 340 DEG C.
The imide compound of a class carbon containing carbon unsaturated group end-blocking according to claim 2 with containing the collaborative novel method of solidifying of fragrant itrile group compound blend, it is characterized in that, described molar ratio is the carbon-carbon double bonds end-blocking imide compound A2 of 5:5 and adopts acetone solvents to carry out solution blending containing two itrile group compound B-11s, underpressure distillation is fully ground the blend that obtains equimolar ratio after pumping acetone, and described blend Heating temperature is 310 DEG C.
The imide compound of a class carbon containing carbon unsaturated group end-blocking according to claim 2 with containing the collaborative novel method of solidifying of fragrant itrile group compound blend, it is characterized in that, described molar ratio is the carbon-carbon double bonds end-blocking imide compound A2 of 6:4 and adopts scorification to carry out blend containing two itrile group compd Bs 2, be heated to 200 DEG C, in the compd A 2 of molten state, add compd B 2, after stirring, be cooled to rapidly room temperature, obtain a kind of mixture of vitreous state, fully ground sample obtains uniform blend again, and described Heating temperature is 340 DEG C.
The imide compound of a class carbon containing carbon unsaturated group end-blocking according to claim 2 with containing the collaborative novel method of solidifying of fragrant itrile group compound blend, it is characterized in that, described molar ratio is the carbon-carbon double bonds end-blocking imide compound A2 of 5:5 and adopts acetone solvent to carry out solution blending containing two itrile group compd Bs 3, underpressure distillation is fully ground the blend that obtains equimolar ratio after pumping acetone, and described Heating temperature is 325 DEG C.
The imide compound of a class carbon containing carbon unsaturated group end-blocking according to claim 2 with containing the collaborative novel method of solidifying of fragrant itrile group compound blend, it is characterized in that, described molar ratio is the carbon-carbon double bonds end-blocking imide compound A3 of 9:1 and adopts scorification to carry out blend containing two itrile group compd Bs 2, be heated to 220 DEG C, in the compound A-13 of molten state, add compd B 2, after stirring, be cooled to rapidly room temperature, obtain a kind of mixture of vitreous state, fully ground sample obtains uniform blend again, and described blend Heating temperature is 295 DEG C.
The imide compound of a class carbon containing carbon unsaturated group end-blocking according to claim 2 with containing the collaborative novel method of solidifying of fragrant itrile group compound blend, it is characterized in that, described molar ratio is the carbon-carbon double bonds end-blocking imide compound A4 of 7:3 and adopts acetone solvent to carry out solution blending containing mononitrile based compound B4, underpressure distillation is fully ground and is obtained uniform blend after pumping acetone, and described blend Heating temperature is 340 DEG C.
The imide compound of a class carbon containing carbon unsaturated group end-blocking according to claim 2 with containing the collaborative novel method of solidifying of fragrant itrile group compound blend, it is characterized in that, described molar ratio is the carbon containing carbon triple bond end-blocking imide compound A5 of 5:5 and adopts dichloromethane solvents to carry out solution blending containing two itrile group compound B-11s, underpressure distillation is fully ground the blend that obtains equimolar ratio after pumping methylene dichloride, and described blend Heating temperature is 330 DEG C; Or,
Molar ratio is the carbon containing carbon triple bond end-blocking imide compound A5 of 8:2 and adopts scorification to carry out blend containing two itrile group compd Bs 2, be heated to 240 DEG C, in the compd B 2 of molten state, add compound A-45, after stirring, be cooled to rapidly room temperature, obtain a kind of mixture of vitreous state, more fully ground sample obtains uniform blend, the Heating temperature of described blend is 350 DEG C; Or,
Molar ratio is the carbon containing carbon triple bond end-blocking imide compound A5 of 5:5 and adopts dichloromethane solvent to carry out solution blending containing two itrile group compd Bs 3, underpressure distillation is fully ground the blend that obtains equimolar ratio after pumping methylene dichloride, and the Heating temperature of described blend is 390 DEG C; Or,
Molar ratio is the carbon containing carbon triple bond end-blocking imide compound A6 of 5:5 and adopts ethyl acetate solvent to carry out solution blending containing two itrile group compd Bs 3, underpressure distillation is fully ground the blend that obtains equimolar ratio after pumping ethyl acetate, and the Heating temperature of described blend is 420 DEG C.
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| CN110938029A (en) * | 2019-12-17 | 2020-03-31 | 中国工程物理研究院总体工程研究所 | Six-membered alicyclic imide derivative monomer, preparation and application thereof, and method for curing phthalonitrile resin |
| CN110964329A (en) * | 2019-12-17 | 2020-04-07 | 中国工程物理研究院总体工程研究所 | Hollow glass bead composite phthalonitrile resin rigid foam and preparation method thereof |
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