CN101955586B - Epoxy terminated polyarylether resins with phthalonitrile side group and curing materials and preparation methods thereof - Google Patents
Epoxy terminated polyarylether resins with phthalonitrile side group and curing materials and preparation methods thereof Download PDFInfo
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Abstract
The invention belongs to the field of synthesis of high polymer materials and in particular relates to epoxy terminated polyarylether resins with phthalonitrile side group and curing materials and preparation methods thereof. The preparation method of the epoxy terminated polyarylether resins with phthalonitrile side group is characterized by taking 4-(3,5-dihydroxy phenoxy)-phthalonitrile or derivatives thereof and commercial aromatic di-halogen compounds as polycondensation monomers and simultaneously adding other aromatic bisphenol monomers to carry out nucleophilic substitution reaction and then taking 3-chloro-1,2-epoxypropane as a terminator, thus preparing a series of epoxy terminated polyarylether resins with phthalonitrile side group. The method is simple in steps and convenient and feasible. The polyarylether resins show better dissolubility in the common polar solvents, can be processed in various forms and have good adhesive properties and higher curing reaction activities. The resins are precured at 0-200 DEG C in the presence of aromatic diamines and the like and then are heated to 250-350 DEG C to undergo heat treatment, thus obtaining the resin curing materials with stable dimensions, excellent heat resistance and high strength. The epoxy terminated polyarylether resins with phthalonitrile side group are used in such fields as high-temperature resistant coatings, paints, adhesives, thin films, composites and the like and have extensive application prospect.
Description
Technical field
The invention belongs to the synthetic field of high performance polymer material.Be specifically related to epoxy-capped-phthalonitrile pendant group polyarylether resin, cured article and preparation method thereof.
Background technology
Epoxy resin has characteristics such as excellent processability, good electrical properties, high adhesive strength and activity of curing reaction, but fragility is big behind the common epoxy resin cure, and impact resistance is poor.And adopt toughner such as active liquid rubber to carry out the reduction that modification causes thermotolerance and medium-resistance often.In recent years, receive much concern with high-performance thermoplastics such as the epoxy resin toughened research of polyarylether, the polyarylether material that successively is applied to modified epoxy has polyether sulphone, polyaryletherketone and polyarylether imide etc.The introducing of polyarylether has significantly increased the mechanical property of matrix resin, but because modified resins cured article two phase consistencies are not good enough, and a little less than making interface interaction power, cause modified effect not good.
Use the polyarylether material of end-functionalization; Or between epoxy-functional, introduce rigidity aryl oxide structure or aryl oxide oligomer molecules chain and the synthesizing new heat resistant epoxide resin; Be the epoxy resin two phase consistencies of improving after solidifying, and then improve the effective method of resin mechanical property.For example, [Hedrick, J.H. such as Hedrick; Yilgor, I.; Wilkens, G.L.; Mcgrath, J.E.Polym.Bull., 13,201 (1985)] with phenolic hydroxyl group terminated polyether sulfone modified bisphenol A type epoxy resin, obviously be superior to commercial polysulfones modification, its fracture toughness property is doubled.Hedrick [Hedrick, J.H.; Lewis, D.A.; Ward, T.C.; McGrath, J.E Polym.Prep.Am.Soc., Div.Polym.Chem., 29,363 (1988)] and Fu, Z [Fu, Z.; Sun, Y.Polym.Prep.Am.Soc., Div.Polym.Chem., 26,293 (1985)] etc. be used for modified epoxy with amino and hydroxy-end capped polyether sulphone respectively, also obtained good effect.Comparatively speaking, between epoxide group, introduce the molecular skeleton of high-performance polyarylether, make epoxy-terminated thermoplastic poly aryl oxide and be a kind of more convenient and high-efficiency method.This resinoid both can replace conventional epoxies and as the structured material matrix resin, also can be used as toughner comes the modification conventional epoxies, and effectively solved the not good enough problem of cured article two phase consistencies.For example, [Liao Weilin, Ceng Xiaojun such as Liao Weilin; Cui Guodi; king's Shen. SCI, 19,661 (1998)] synthesized and contained epoxy-terminated phenolphthalein poly (arylene ether nitrile) resin; It can directly solidify with diamines or acid anhydride type curing agent with commercial epoxy resin is the same, solidifies the toughness of effectively having improved pour mass with epoxy blend.Not smoothgoing tin high [Xuan Yingnan, not smoothgoing tin is high, Tian Shizhe. polymer journal, 4,407 (2000); Xuan Yingnan, not smoothgoing tin is high, Xu Zhiyong; Zhou Qingbing. polymer science and engineering, 17,57 (2001)] come end-blocking naphthyridine ketone structure polyaryletherketone and polyether sulphone with epoxide group respectively; Make neo-epoxy resin, its cured article thermotolerance and shock resistance obviously improve.Epoxy-capped polythioethers, cured article and preparation method thereof have been studied in [CN.P.No 200480019930] such as Sa Wante .S.Cross-linking polyphenyl ether resin, its compsn and the method for manufacture thereof of epoxy group(ing) announced in [CN.P.No 01118108.7] such as careful alliance pines.Ppe after the epoxy-terminated modification, and consistency increases substantially between the epoxy resin.But sum up, after epoxy-capped polyarylether material solidified, though its physical strength and second-order transition temperature can be significantly improved, heat decomposition temperature tended to than the end-blocking polyarylether is also not low, therefore caused this resinoid use temperature lower.Like epoxy-terminated phenolphthalein type polyarylether nitrile, at amine type accelerator as 4, gained cured article under the effect of 4 '-diaminodiphenylsulfone(DDS), its second-order transition temperature is at 234-258 ℃, and its 5% thermal weight loss temperature is below 350 ℃.
Along with the fast development of new and high technology, have higher requirement to the temperature classification and the use temperature of polymkeric substance in the sophisticated technology field.Like epoxy encapsulant, coating and tackiness agent commonly used in the application of aerospace field; The epoxy resin gluing agent of high frequency microelectronic component encapsulation usefulness all hopes to have the characteristics of high temperature classification and use temperature, to satisfy the request for utilization under extreme severe condition.Heat-staple aromatic ring of crosslinked generation or heterocycle structure are one of valid approach that improves polymkeric substance thermotolerance and use temperature.This is because cross-linked high polymer because the generation of the new chemical bond of interchain has hindered the motion of molecular chain, has not only increased the thermotolerance of polymkeric substance, and helped improving its physical and mechanical property.Poly-o-phthalonitrile is one type of novel relatively thermosetting resin, mainly is one type of performance resins forming of the hot addition-crosslinked curing reaction through cyanic acid at high temperature by phthalonitrile structural units derived thing or end-blocking oligopolymer.The phthalonitrile cured product mainly forms fragrant heterocycle structure, like the s-triazine ring structure.People such as Keller [Chem.Mater.6,302 (1994); Polym.Compos.25,554 (2004); Polymer 46,4614 (2005); J.Polym.Sci.:Part A:Polym.Chem.43,4136 (2005); Polymer 48,91 (2007); US.P.No 4408035to Keller; U.S.P.No 4410676 tokeller] reported the applied research of curing action and these cured articles of biphenyl type, bisphenol A-type, metaphenylene and Bisphenol F type phthalonitrile monomer and a series of novel aromatic diamines respectively at advanced composite material.That not smoothgoing tin high [Chinese patent publication number CN 101619131A] discloses is phthalonitrile-terminated-contain diazanaphthalene terphenyl polyarylether resin, cured article.Liu Xiaobo etc. [Chinese patent publication number CN 1876615A] have studied the phthalonitrile monomer, the cured article that contain rigid structure primitive such as phenyl ether, sulfobenzide and benzophenone.Their research mainly concentrate on the phthalonitrile derivatives monomer synthetic, the crosslinked behavior of fusion, its cured product thermal property with and the research of aspect such as mechanical property and mechanical property during as spun glass or carbon fibre reinforced composite.Yang Gang etc. [Chinese patent publication number CN 101143928A] have reported O-phthalic carbonitrile derivatives or the polyether nitrile of being with amino or hydroxyl on the molecule structure, can play toughening effect to poly-o-phthalonitrile resin.Lei Yi etc. [Chinese patent publication number CN 1944486A] disclose phthalonitrile structural motif modified phenolic resins and preparation method thereof.The introducing of phthalonitrile structure and curing reaction thereof make resol be improved in high temperature carbon residue rate.Liu Xiaobo etc. [Chinese patent publication number CN 1944400A] have studied double end group ortho-benzene dimethyl nitrile-benzo oxazine resin, cured article, and the resin thermostability has obvious improvement after the modification.
Though the o-phthalonitrile resin cured article of having reported at present has excellent heat resisting, also there are a series of problems in its processing and the application process.As the phthalonitrile-terminated polymer dissolution property before solidifying is relatively poor, and because its rigid structure, fusing point height and glutinousness are poor; In addition, the O-phthalic carbonitrile derivatives carries out under its molten state when solidifying usually, thereby often exists the machine-shaping energy consumption excessive, and tooling cost also improves thereupon, and application is restricted; And in the solidification process, possibly follow shortcomings such as degraded generation and process window are narrow in ubiquity starting temperature too high (usually more than 250 ℃), the crosslinking curing.
Therefore, the synthetic research that has epoxy resin and the novel polyarylether resin of o-phthalonitrile resin good characteristic concurrently of design helps addressing the above problem or defective, academicly or all significant in the industry.If promptly epoxy-capped phthalonitrile pendant group polyarylether can have the good glutinousness of epoxy resin and solvability and high low-temperature curing activity simultaneously; And the excellent heat resistance of o-phthalonitrile resin and the characteristics of high mechanical strength; Then being expected to obtain one type can be cured and moulding in several ways; And have one type of novel fire resistant polyarylether material of excellent over-all properties, and then widen its Application Areas.In sum; For obtaining to have excellent heat resistance and good mechanical strength, be prone to the solidified fire resistant resin; Pass through molecule design method; But optionally introduce the single or a plurality of phthalonitrile structural motifs of solidified under moderate temperature or the high temperature at the polyarylether side chain, it is crosslinked that polymkeric substance is cured, and obtains to have concurrently the cured article of superior heat-stability and high mechanical strength; On polyarylether molecular chain end group, introduce epoxide group; To improve this base polymer glutinousness and the solvability in organic solvent; And then improve the polymer processing processability; And the introducing of epoxide group can give polymkeric substance higher low-temperature curing reactive behavior, thereby the Application Areas that further expands polymkeric substance.It should be noted that; Polymkeric substance about containing epoxy and phthalonitrile crosslinkable groups simultaneously is particularly epoxy-capped-and phthalonitrile pendant group polyarylether resin, cured article and preparation method thereof be not shown in relevant patented technology report, never at home and abroad occur in the public publication yet.
Summary of the invention
One of the object of the invention is to overcome the problem that prior art exists; In the curable phthalonitrile structure of introducing on the polyarylether macromolecule side chain; The epoxide group of high crosslinking activity is introduced in the above-mentioned main polymer chain structure with the form of end group, thereby a kind of epoxy-capped-phthalonitrile pendant group polyarylether resin that has good solubility and glutinousness, excellent processability and under moderate temperature or high temperature, all have high activity of curing reaction is provided.
Two of the object of the invention provide a kind of easy, be easy to control, fast prepare above-mentioned epoxy-capped-method of phthalonitrile pendant group polyarylether resin.
Three of the object of the invention provides a kind of epoxy-capped-phthalonitrile pendant group polyarylether resin cured article with excellent properties.This resin cured matter by above-mentioned epoxy-capped-the phthalonitrile pendant group polyarylether resin solidifies and to obtain.
Four of the object of the invention provides a kind of easy, method of being easy to control, fast prepare epoxy-capped-phthalonitrile pendant group polyarylether resin cured article.
Technical scheme of the present invention is following:
As fragrant biphenol monomer, adding has Ar with the 4-shown in the formula II (3,5-dihydroxyl phenoxy)-phthalonitrile or derivatives thereof
2The two halogen monomers of the fragrance of agent structure are as the polycondensation raw material, and adding has Ar again
1The fragrant biphenol monomer of agent structure carries out the solution polycondensation reaction in polar solvent, add epichlorohydrin again and carry out end-blocking, thereby make epoxy-capped-phthalonitrile pendant group polyarylether resin.
Formula II
With this resin is raw material, can obtain epoxy-capped-phthalonitrile pendant group polyarylether resin cured article through solidifying.
Provided by the invention epoxy-capped-the phthalonitrile pendant group polyarylether resin, its general structure is suc as formula shown in the V:
Formula V
Wherein, n is 1,2,3 ... 20 integer; M is 1,2, the integer between 3...100; Ar in the formula
1Being the agent structure of fragrant biphenol monomer, can be in the structure any one or a few:
Ar in the formula
2Being the monomeric agent structure of two halogen, can be in the structure any one or a few:
Provided by the invention epoxy-capped-preparation method of phthalonitrile pendant group polyarylether resin, comprise following steps:
A, add 4-(3,5-dihydroxyl the phenoxy)-phthalonitrile or derivatives thereof of n mole and (n+m) part two halogen moles of mole fragrance as polycondensation monomer; Add fragrant biphenol monomer B (m+1) mole more simultaneously; Even with catalyst mix, and add high boiling solvent and azeotropy dehydrant, under 150～200 ℃, carry out the solution polycondensation reaction; After the polymerization 1～8 hour; With precipitating in reaction soln impouring water, alcohol or the alcohol-water mixture, to wash through filtration, washing and alcohol successively, vacuum-drying then (preferred 75～85 ℃) makes the hydroxy-end capped polymkeric substance that has shown in general formula VI:
Formula VI
Wherein, n is 1,2,3 ... 20 integer; M=1,2, the integer of 3...100; Fragrance biphenol monomer B is 4-(3,5-dihydroxyl phenoxy)-phthalonitrile or derivatives thereof, Resorcinol, Resorcinol, 1,4-naphthalenediol, 1,5-naphthalenediol, 2; 6-naphthalenediol, 3,3 '-'-biphenyl diphenol, 4,4 '-'-biphenyl diphenol, 3,3 '-dihydroxy diphenyl ether, 4; 4 '-dihydroxy diphenyl ether, 3,3 '-dihydroxyl diphenyl sulfide, 4,4 '-dihydroxyl diphenyl sulfide, 3,3 '-dihydroxy benzophenone, 4; 4 '-dihydroxy benzophenone, 3,3 '-dioxydiphenyl methane, 4,4 '-dioxydiphenyl methane, 2; Two (3-hydroxy phenyl) propane, 2 of 2-, two (4-hydroxy phenyl) propane, 3 of 2-, 3 '-dihydroxy diphenylsulphone, 4; 4 '-dihydroxy diphenylsulphone, 2, two (3-hydroxy phenyl) HFC-236fas and 2 of 2-, any one or a few in two (4-hydroxy phenyl) HFC-236fas of 2-is as fragrant biphenol monomer;
The two halogen monomer A of fragrance wherein are 4,4 '-dihalo-benzophenone, 3,3 '-dihalo-benzophenone, 4; 4 '-dihalo-sulfobenzide, 3,3 '-dihalo-sulfobenzide, 1,4-two (4-halobenzene formyl radical) benzene, 1; 4-two (3-halobenzene formyl radical) benzene, 2; 4-two halobenzene nitriles, 2,6-two halobenzene nitriles or 3, any one or a few in the 5-two halobenzene nitriles;
Catalyzer wherein is anhydrous alkali metal or alkaline earth metal carbonate or both mixtures; High boiling solvent wherein can be N, one or more of non-proton type polar organic solvents such as dinethylformamide (DMF), DMAC N,N (DMAc), DMSO 99.8MIN. (DMSO), N-Methyl pyrrolidone (NMP) or tetramethylene sulfone; Azeotropy dehydrant wherein is halogeno-benzene or korenyl etc. and the immiscible organic solvent of water.
B, mix, add highly basic then and make catalyzer, heat up, react, after 1～12 hour, obtain the solution of epoxy group(ing) terminated polymer at above-mentioned hydroxy-end capped polymkeric substance and epichlorohydrin shown in general formula VI.Its reaction formula is suc as formula shown in the VII:
Formula VII
Wherein, n is 1,2,3 ... 20 integer; M is 1,2, the integer between 3...100; Catalyzer wherein is a highly basic, like sodium hydroxide or Pottasium Hydroxide etc.
C, treat excessive 3-chloro-1; After the distillation of 2-propylene oxide is removed; With precipitating in the end capped polymers soln impouring of above-mentioned epoxy group(ing) water, alcohol or the alcohol-water mixture; Wash through filtration, washing and alcohol successively, vacuum-drying then (preferred 55～65 ℃) obtains epoxy-capped-phthalonitrile pendant group polyarylether resin.
With of the present invention epoxy-capped-the phthalonitrile pendant group polyarylether resin is a raw material, can obtain epoxy-capped-phthalonitrile pendant group polyarylether resin cured article through solidifying.
The present invention is carrying out epoxy group(ing) end-blocking process, and what the present invention preferably adopted is to add epichlorohydrin to carry out end-blocking.
Provided by the invention epoxy-capped-preparation method of phthalonitrile pendant group polyarylether resin cured article, be that from the above mentioned epoxy-capped-phthalonitrile pendant group polyarylether resin solidifies and obtains.The possible structure of cured article is shown in general formula VIII, general formula I X and general formula X:
Formula VIII
Or
Formula IX
Or
Formula X
Wherein, Ar
3Being the agent structure of aromatic diamine, can be in the structure any one or a few:
is following structural unit:
Wherein, n is 1,2,3 ... 20 integer; M is 1,2, the integer between 3...100; The agent structure Ar of fragrant biphenol monomer wherein
1, can be in the structure any one or a few:
The two monomeric agent structure Ar of halogen of fragrance wherein
2, can be in the structure any one or a few:
Provided by the invention epoxy-capped-preparation method of phthalonitrile pendant group polyarylether resin cured article, comprise following steps:
A, according to account for exsiccant epoxy-capped-phthalonitrile pendant group polyarylether resin cured article quality adds aromatic diamine than the ratio of 1-10%.
Aromatic diamine wherein comprises Ursol D, mphenylenediamine, 4,4 '-benzidine, 4,4 '-diaminodiphenyl oxide, 3; 3 '-diaminodiphenyl oxide, 4,4 '-diaminodiphenyl sulfide, 3,3 '-diaminodiphenyl sulfide, 4; 4 '-diaminodiphenylsulfone(DDS), 3,3 '-diaminodiphenylsulfone(DDS), 4,4 '-diaminobenzophenone, 3; 3 '-diaminobenzophenone, 4,4 '-MDA, 3,3 '-MDA, 2; Two (4-aminophenyl) propane and 2 of 2-, any one or a few in two (3-aminophenyl) propane of 2-etc.
B, carried out Procuring 3-12 hour, after 250～400 ℃ of thermal treatment 3-12 hours, can obtain the polyarylether resin cured article again at 0～200 ℃.
Effect of the present invention and benefit have been to provide the new type resin that contains crosslinkable phthalonitrile side group and epoxy-terminated structure in a kind of molecular chain simultaneously, have not only had high glutinousness but also solubilized, and machine-shaping property is good.And the high characteristics of epoxide group curing reaction capable of using; Be heating and curing in low thermophase condition; But solidified characteristics under phthalonitrile primitive moderate temperature capable of using again or the high temperature are heating and curing and obtain having the polyarylether resin cured article of higher temperature classification and use temperature and good mechanical properties.Epoxy-capped-phthalonitrile pendant group polyarylether resin and the cured article thereof that the present invention relates to can be used for preparing coating, insullac, tackiness agent, film and high performance composite etc., have wide application prospect.
Description of drawings
Fig. 1 is with 4-(3,5-dihydroxyl phenoxy)-phthalonitrile, 4,4 '-dichloro diphenyl sulfone and end-capping reagent epichlorohydrin be the starting raw material synthetic epoxy-capped-ir spectra of phthalonitrile pendant group p-phenyl polyaryl ether sulphone resin.
Embodiment
Through embodiment the present invention is specifically described below; Be necessary to be pointed out that at this embodiment only is used for the present invention is further specified; Can not be interpreted as the restriction to protection domain of the present invention, the technician in this field can make some nonessential improvement and adjustment according to the present invention.
In following embodiment, except that specifying, said umber is molfraction, and said feed composition is effective feed composition.Contain double-terminal phthalonitrile and phthalazine biphenyl structure polymkeric substance and cured article structure thereof in the specific embodiment of the invention and confirm, with the sample preparation of KBr pressed disc method by on Nicolet-20DXB type IR, carrying out FT-IR.The thermal performance test of polymkeric substance and cured article thereof: differential scanning calorimetry (DSC) carries out on Mettler DSC822, under the nitrogen atmosphere, and 10 ℃/min of temperature rise rate, second-order transition temperature (T
g) value is the mid point that hot melt changes on the scanning curve, 50～450 ℃ of test specifications.The decomposition temperature test of thermogravimetic analysis (TGA) (TGA) polymkeric substance is carried out on Mettler TGA/SDTA851, under the nitrogen atmosphere, and 20 ℃/min of temperature rise rate, 100～800 ℃ of test specifications are got 5% thermal weight loss temperature as the polymer unwinds temperature.The solubility property test of polymkeric substance and cured article thereof: the polymkeric substance of about 20mg is fully immersed in the solvent to be measured of 0.5mL, at room temperature tests its solvability.Separator column model 5mm Phenogel columns (linear 300 * 4.6mm 5micro), 36 ℃ of column temperatures are carried out in the polymericular weight test on HP 1090HPLC type gel permeation chromatograph.Adopting chloroform or THF is moving phase, flow velocity 0.4mL/min.PS is a standard substance, and the UV detector detects wavelength 254nm.The cured article shock strength is carried out on Charpy XCJ-4 type freely-supported beam type pendulum impact test instrument.
The preparation and the performance of embodiment 1 epoxy-capped-phthalonitrile pendant group polyarylether (sulfone nitrile ketone) resin and cured article
In the dry 100mL there-necked flask that has mechanical stirring, reflux condensing tube, water trap and gas tube, add 2.0 parts of 0.5 part of 4-(3,5-dihydroxyl phenoxy) phthalonitrile and Resorcinol; 2.6 parts of Anhydrous potassium carbonates; 4,4 '-dichloro diphenyl sulfone, 2,6-dichlorobenzonitrile, 4; Totally 2.0 parts in 4 '-two chloro benzophenones or their mixture, toluene 20mL and DMSO 99.8MIN. (DMSO) 10mL.Under the nitrogen atmosphere after methylbenzene azeotropic refluxes band water, be warming up to the 140-180 ℃ of about 3-8h of reaction after, cool.Add 20 parts of epichlorohydrins then, be warmed up to 70-90 ℃ of reaction 5-10h again.To be distilled remove epichlorohydrin after, polymers soln is under agitation; With boiling water as precipitation agent, with polymkeric substance through sedimentation, deionized water repetitive scrubbing with drain vacuum-drying; Obtain epoxy-capped-phthalonitrile pendant group p-phenyl polyarylether (sulfone nitrile ketone) resin, yield 94%.This resin is a buff powder, has preferable consistency with commercially available epoxy resin and other epoxy compoundss.
With epoxy-capped-phthalonitrile pendant group p-phenyl polyaryl ether sulphone resin is example, and polymer architecture is confirmed through ir spectra, and its solubility property characterizes through solubility experiment.
The polymkeric substance infrared spectrum is seen Fig. 1, therefrom can observe the following characteristics absorption band:
3071cm
-1C-H stretching vibration absorption band on the aromatic ring;
2240cm
-1Cyanic acid C ≡ N characteristic stretching vibration absorption band
1597cm
-1Aromatic ring C=C stretching vibration absorption band;
1485cm
-1Aromatic ring C=C stretching vibration absorption band;
1310cm
-1Aromatic ring SO
2Stretching vibration symmetry absorption band;
1230cm
-1Aryl oxide C-O stretching vibration absorption band;
1180cm
-1Aromatic ring SO
2Stretching vibration unsymmetrically absorption band
920cm
-1Epoxide group stretching vibration absorption band
The solubility property test result of polymkeric substance shows, is dissolvable in water polar solvents commonly used such as NMP (N-Methyl pyrrolidone), DMAc (DMAC N,N), DMF (N, dinethylformamide), DMSO, acetone, THF under this resin room temperature.In addition, resin even in chloroform and methylene dichloride isopolarity solvent, also have certain dissolubility.GPC table with test results ming tree fat number-average molecular weight (M
n) be 2.18 * 10
3G/mol, the MWD width is 2.1, explains to obtain the lower molecular weight terminated polymer.
This resin can add 4 of 1-5wt%, under the effect of 4 '-diaminodiphenylsulfone(DDS), is cured in 100～230 ℃, further solidifies the resin cured matters that obtain high thermal stability at 250～350 ℃ again.Impact Test shows: cured article notch specimen shock strength is at 2.0KJ/m
2More than.Resin cured matter and metal, plastics etc. have good adhesive property, and the tensile shear strength to metal under its room temperature is higher than 13MPa.0-450 ℃ DSC scanning result shows that cured article does not detect tangible second-order transition temperature.The TGA scanning result shows that cured article decomposition temperature (5%) is 368 ℃, and the following 800 ℃ of carbon yields of nitrogen atmosphere are 70%.The solvability test result shows that cured article is insoluble to aforementioned polar solvent.And according to ASTM D2765 testing method, the cured article gel fraction is more than 70%.
The preparation and the performance of embodiment 2 epoxy-capped-phthalonitrile pendant group poly arylidene thio-esters (sulfone nitrile ketone) resin and cured article
In the dry 100mL there-necked flask that has mechanical stirring, reflux condensing tube, water trap and gas tube, add 0.5 part of 4-(3,5-dihydroxyl phenoxy) phthalonitrile and 4; 2.0 parts of 4-dihydroxyl diphenyl sulfides, 2.6 parts of Anhydrous potassium carbonates, 4; 4 '-dichloro diphenyl sulfone, 2; 6-dichlorobenzonitrile, 4, totally 2.0 parts in 4 '-two chloro benzophenones or their mixture, toluene 20mL and DMSO 99.8MIN. (DMSO) 10mL.Under the nitrogen atmosphere after methylbenzene azeotropic refluxes band water, be warming up to the 140-180 ℃ of about 3-8h of reaction after, cool.Add 20 parts of epichlorohydrins then, be warmed up to 70-90 ℃ of reaction 5-10h again.To be distilled remove epichlorohydrin after, polymers soln is under high-speed stirring; With boiling water as precipitation agent, with polymkeric substance through sedimentation, deionized water repetitive scrubbing with drain vacuum-drying; Obtain epoxy-capped-phthalonitrile pendant group polyarylether (sulfone nitrile ketone) resin, yield 93%.This resin is a pale powder, has preferable consistency with commercially available epoxy resin and other epoxy compoundss.
Gained resinous polymer structure confirms that through ir spectra and nuclear magnetic spectrum its solubility property characterizes through solubility experiment.The solubility property result of polymkeric substance shows that this resin is dissolvable in water polar solvents commonly used such as NMP, DMAc, DMF, chloroform, sym.-tetrachloroethane, tetramethylene sulfone and THF.GPC table with test results ming tree fat number-average molecular weight (M
n) be 3.25 * 10
3G/mol, the MWD width is 1.9, explains to obtain the lower molecular weight terminated polymer.
This resin can be at 4 of 1-5wt%, under the effect of 4 '-diaminodiphenylsulfone(DDS), carries out Procuring in 150～250 ℃, further solidifies the resin cured matters that obtain high thermal stability at 350～400 ℃ again.Impact Test shows that cured article notch specimen shock strength is at 2.3KJ/m
2More than.0-450 ℃ DSC scanning result shows that cured article does not detect tangible second-order transition temperature.The TGA scanning result shows that cured article decomposition temperature (5%) is 391 ℃, and the following 800 ℃ of carbon yields of nitrogen atmosphere are 73%.The solvability test result shows that cured article is insoluble to aforementioned polar solvent.And according to ASTM D2765 testing method, the cured article gel fraction is more than 72%.
The preparation and the performance of embodiment 3 epoxy-capped-phthalonitrile pendant group bisphenol A-type polyarylether (sulfone nitrile ketone) resins and cured article
In the dry 100mL there-necked flask that has mechanical stirring, reflux condensing tube, water trap and gas tube, add 0.5 part of 4-(3,5-dihydroxyl phenoxy) phthalonitrile and 2; 2.0 parts in two (4-hydroxy phenyl) propane of 2-, 2.6 parts of Anhydrous potassium carbonates, 4; 4 '-dichloro diphenyl sulfone, 2; 6-dichlorobenzonitrile, 4, totally 2.0 parts in 4 '-two chloro benzophenones or their mixture, toluene 20mL and DMSO 99.8MIN. (DMSO) 10mL.Under the nitrogen atmosphere after methylbenzene azeotropic refluxes band water, be warming up to the 140-180 ℃ of about 3-8h of reaction after, cool.Add 20 parts of epichlorohydrins then, be warmed up to 70-90 ℃ of reaction 5-10h again.To be distilled remove epichlorohydrin after, polymers soln is under high-speed stirring; With boiling water as precipitation agent, with polymkeric substance through sedimentation, deionized water repetitive scrubbing with drain vacuum-drying; Obtain epoxy-capped-phthalonitrile pendant group polyarylether (sulfone nitrile ketone) resin, yield 90%.This resin is the yellow-white powder, has preferable consistency with commercially available epoxy resin and other epoxy compoundss.
The resulting polymers structure confirms that through ir spectra and nuclear magnetic spectrum its solubility property characterizes through solubility experiment.The solubility property result of polymkeric substance shows that this resin is dissolvable in water polar solvents commonly used such as NMP, DMAc, DMF, chloroform, methylene dichloride, tetramethylene sulfone and THF.GPC table with test results ming tree fat number-average molecular weight (M
n) be 3.98 * 10
3G/mol, the MWD width is 2.2, explains to obtain the lower molecular weight terminated polymer.
This resin can be at 4 of 1-5wt%, under the effect of 4 '-diaminodiphenylsulfone(DDS), carries out Procuring in 150～250 ℃, further solidifies the resin cured matters that obtain high thermal stability at 350～400 ℃ again.Impact Test shows that cured article notch specimen shock strength is at 2.1KJ/m
2More than.0-450 ℃ DSC scanning result shows that cured article does not detect tangible second-order transition temperature.The TGA scanning result shows that cured article decomposition temperature (5%) is 365 ℃, and the following 800 ℃ of carbon yields of nitrogen atmosphere are 69%.The solvability test result shows that cured article is insoluble to aforementioned polar solvent.And according to ASTM D2765 testing method, the cured article gel fraction is more than 70%.
Claims (5)
1. epoxy-capped-phthalonitrile pendant group polyarylether resin is characterized in that, contains suc as formula general structure shown in the I:
Wherein, n is 1,2,3 ... 20 integer; M is 1,2, the integer between 3...100; Ar
1Being the agent structure of fragrant biphenol monomer, is in the structure any one or a few:
Ar
2Being the two monomeric agent structures of halogen of fragrance, is in the structure any one or a few:
2. the preparation method of epoxy-capped-phthalonitrile pendant group polyarylether resin is characterized in that, as a kind of fragrant biphenol monomer, adding has Ar with the 4-shown in structural formula II (3,5-dihydroxyl phenoxy)-phthalonitrile
2The two halogen monomers of the fragrance of agent structure are raw material, add to have Ar again
1The fragrant biphenol monomer of agent structure through polycondensation, after the epoxy group(ing) end-blocking, thereby makes epoxy-capped-phthalonitrile pendant group polyarylether resin in polar solvent;
Wherein, the agent structure Ar of described fragrant biphenol monomer
1Be in the structure any one or a few:
The two monomeric agent structure Ar of halogen of described fragrance
2Be in the structure any one or a few:
3. the preparation method of epoxy-capped-phthalonitrile pendant group polyarylether resin is characterized in that, comprises the steps:
The two halogen monomer A of a, adding 4-(3,5-dihydroxyl phenoxy)-phthalonitrile and fragrance are as polycondensation monomer; Add fragrant biphenol monomer B again, even with catalyst mix, and add high boiling solvent and azeotropy dehydrant; Under 150～200 ℃, carry out the solution polycondensation reaction, polymerization is after 1～8 hour, with precipitating in reaction soln impouring water, alcohol or the alcohol-water mixture; Wash through filtration, washing and alcohol successively, vacuum-drying makes hydroxy-end capped polymkeric substance then; Wherein fragrant biphenol monomer B is 4-(3,5-dihydroxyl phenoxy)-phthalonitrile, Resorcinol, Resorcinol, 1,4-naphthalenediol, 1,5-naphthalenediol, 2; 6-naphthalenediol, 3,3 '-'-biphenyl diphenol, 4,4 '-'-biphenyl diphenol, 3,3 '-dihydroxy diphenyl ether, 4; 4 '-dihydroxy diphenyl ether, 3,3 '-dihydroxyl diphenyl sulfide, 4,4 '-dihydroxyl diphenyl sulfide, 3,3 '-dihydroxy benzophenone, 4; 4 '-dihydroxy benzophenone, 3,3 '-dioxydiphenyl methane, 4,4 '-dioxydiphenyl methane, 2; Two (3-hydroxy phenyl) propane, 2 of 2-, two (4-hydroxy phenyl) propane, 3 of 2-, 3 '-dihydroxy diphenylsulphone, 4; 4 '-dihydroxy diphenylsulphone, 2, two (3-hydroxy phenyl) HFC-236fas and 2 of 2-, any one or a few in two (4-hydroxy phenyl) HFC-236fas of 2-is as the copolycondensation monomer;
The two halogen monomer A of fragrance wherein are 4,4 '-dihalo-benzophenone, 3,3 '-dihalo-benzophenone, 4; 4 '-dihalo-sulfobenzide, 3,3 '-dihalo-sulfobenzide, 1,4-two (4-halobenzene formyl radical) benzene, 1; 4-two (3-halobenzene formyl radical) benzene, 2; 4-two halobenzene nitriles, 2,6-two halobenzene nitriles or 3, any one or a few in the 5-two halobenzene nitriles;
Catalyzer wherein is anhydrous alkali metal or alkaline earth metal carbonate or above both mixture; High boiling solvent wherein is N, one or more of non-proton type polar organic solvents such as dinethylformamide (DMF), DMAC N,N (DMAc), DMSO 99.8MIN. (DMSO), N-Methyl pyrrolidone (NMP) or tetramethylene sulfone; Azeotropy dehydrant wherein is halogeno-benzene or korenyl and the immiscible organic solvent of water;
B, mix, add highly basic then and make catalyzer, heat up, react, after 1～12 hour, obtain the solution of epoxy group(ing) terminated polymer at above-mentioned hydroxy-end capped polymkeric substance and epichlorohydrin;
C, treat excessive 3-chloro-1; After the distillation of 2-propylene oxide is removed; With precipitating in the end capped polymers soln impouring of above-mentioned epoxy group(ing) water, alcohol or the alcohol-water mixture, wash through filtration, washing and alcohol successively, vacuum-drying obtains epoxy-capped-phthalonitrile pendant group polyarylether resin then.
4. epoxy-capped-phthalonitrile pendant group polyarylether resin cured article, it is characterized in that: cured article is that the epoxy-capped-phthalonitrile pendant group polyarylether resin by claim 1 or 2 or 3 solidifies and to form.
Claim 4 said epoxy-capped-preparation method of phthalonitrile pendant group polyarylether resin cured article, it is characterized in that may further comprise the steps:
A, in account for described epoxy-capped-ratio of phthalonitrile pendant group polyarylether resin mass ratio 1-10% adds aromatic diamine, aromatic diamine wherein comprises Ursol D, mphenylenediamine, 4,4 '-benzidine, 4; 4 '-diaminodiphenyl oxide, 3,3 '-diaminodiphenyl oxide, 4,4 '-diaminodiphenyl sulfide, 3; 3 '-diaminodiphenyl sulfide, 4,4 '-diaminodiphenylsulfone(DDS), 3,3 '-diaminodiphenylsulfone(DDS), 4; 4 '-diaminobenzophenone, 3; 3 '-diaminobenzophenone, 4,4 '-MDA, 3,3 '-MDA, 2; Two (4-aminophenyl) propane and 2 of 2-, any one or a few in two (3-aminophenyl) propane of 2-;
B, 0～200 ℃ carry out Procuring 3-12 hour after, again after 250～400 ℃ of thermal treatment 3-12 hours, obtain the polyarylether resin cured article.
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| CN102964594B (en) * | 2012-12-03 | 2014-06-25 | 河北工业大学 | Method for preparing naphthyl polystyrene nitrile resin |
| CN105358605A (en) * | 2013-05-02 | 2016-02-24 | 巴斯夫欧洲公司 | Polyaryl ether sulphone copolymers |
| CN104845349B (en) * | 2015-05-25 | 2017-03-08 | 吉林大学 | Toughness reinforcing bi-phthalonitrile resin material of polyether sulfone and preparation method thereof |
| JP6928314B2 (en) * | 2015-06-02 | 2021-09-01 | 日産化学株式会社 | Solvent-free photocurable adhesive composition |
| CN105801880B (en) * | 2016-05-11 | 2018-05-08 | 上海瀚海检测技术股份有限公司 | The separation method of poly(aryl ether ketone) system epoxy resin |
| CN106928659A (en) * | 2017-03-15 | 2017-07-07 | 中南大学 | A kind of high wear resistant photo-cured aryl oxide based epoxy acrylate/nanometer silicon dioxide composite material and preparation method thereof |
| CN113683585B (en) * | 2021-09-26 | 2023-07-11 | 齐鲁工业大学 | Preparation method of epoxy group-containing phthalonitrile monomer |
| CN117551378A (en) * | 2023-12-07 | 2024-02-13 | 山东晨之阳机械有限公司 | Toughened and modified epoxy resin anticorrosive material and preparation process thereof |
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