CN106398171A - High-strength polyaryletherketone material with stable size and preparation method thereof - Google Patents

High-strength polyaryletherketone material with stable size and preparation method thereof Download PDF

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CN106398171A
CN106398171A CN201610796206.9A CN201610796206A CN106398171A CN 106398171 A CN106398171 A CN 106398171A CN 201610796206 A CN201610796206 A CN 201610796206A CN 106398171 A CN106398171 A CN 106398171A
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phenyl
paek
double
strength
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周光远
王红华
姜国伟
苏小龙
王志鹏
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Changchun Institute of Applied Chemistry of CAS
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Changchun Institute of Applied Chemistry of CAS
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Abstract

The invention provides a high-strength polyaryletherketone material with the stable size and a preparation method thereof, and belongs to the technical field of macromolecules. The material is prepared from a polyaryletherketone copolymer, surface-modified inorganic filler and inorganic fibers, wherein the polyaryletherketone copolymer is a polyaryletherketone biopolymer or a terpolymer or a polyaryletherketone quadripolymer. The invention further provides the preparation method of the high-strength polyaryletherketone material with the stable size. Accordingly, the surface-modified inorganic filler is high-strength, high-toughness and wear-resistant spherical nanometer inorganic filler, and therefore the size stability of the overall material can be improved; the technological process is simple and easy to control, and the high processing efficiency is achieved.

Description

High-strength PAEK material of a kind of dimensionally stable and preparation method thereof
Technical field
The invention belongs to technical field of macromolecules, the high-strength PAEK material of more particularly, to a kind of dimensionally stable and its preparation Method.
Background technology
Phenolphthalein polyaryletherketone (PEK-C) is as a kind of unformed polyarylether being obtained with dihalo benzophenone polycondensation by phenolphthalein Ketone resin, its glass transition temperature is 231 DEG C, and it is high-strength to have temperature classification height, endurance, impact resistance, a dimensionally stable, resistance to height Pressure hydrolysis and resistance to irradiation, the premium properties such as acid and alkali resistance and aromatic alkanes chemical reagent, its combination property can be with polyether-ether-ketone (PEEK) compare favourably, and its dissolving processing characteristics has one's own knack, and has in high-tech sectors such as Aeronautics and Astronautics, petrochemical industries It is widely applied.
It is successfully applied to from the polyether-ether-ketone (PEEK) of ICI company of Britain exploitation as High temperature polymer composites Since military affairs, space flight, aviation, the various product of PAEK (PAEK) causes the extensive concern of people.Due to this kind of product Product have the series of advantages such as high intensity, high-moduluss, high temperature resistant, radiation hardness and good stability of the dimension.
PAEK is the aromatic heterocyclic polymer that a class main chain contains ehter bond and carbonyl, and ehter bond and carbonyl pass through phenylene with difference Sequence is connected, thus constituting various types of PAEK.Aromatic ring present in strand, heterocycle, formed " spiral shell shape ", " lamellar " and " trapezoidal " structure, thus chemical bond energy is high, segment rigidity is big, thus having very high vitrification point Tg, higher thermal decomposition Temperature and relatively low combustibility；Conjugated double bond on its molecular backbone, makes the regularity of molecule good, thus its mechanical property is excellent Different；The construction featuress such as the stronger strand intermolecular forces (as hydrogen bond) of rigidity and crystallinity so that strand is closely piled up, solvent Molecule is difficult to penetrate into, thus has good solvent resistance and chemical proofing again.Macromole contains substantial amounts of ehter bond simultaneously Give its toughness, ehter bond is more, its toughness is better again.Its toughness and fatigue durability can also be improved by increasing molecular weight, and Its melt viscosity can be adjusted to be suitable for injection mo(u)lding.Because PAEK resin has above-mentioned excellent properties, not only exist after appearance National defense and military battle line is succeeded application at first, and is promoted in high technology for civilian use field quickly.
Content of the invention
It is an object of the invention to provide high-strength PAEK material of a kind of dimensionally stable and preparation method thereof, the present invention carries For PAEK material have that high temperature resistant, dimensionally stable is high-strength, the characteristic of corrosion-resistant and high intensity.
The present invention provides a kind of dimensionally stable high-strength PAEK material, including：
Poly (aryl ether ketone) copolymer；
The inorganic filler of surface modification；
Inorfil；
Described poly (aryl ether ketone) copolymer is PAEK bipolymer, PAEK terpolymer or PAEK Quadripolymer；
Described PAEK quadripolymer includes the repetitives shown in formula 101 and formula 102：
The amount of the repetitives shown in described formula 101 and the material of repetitives shown in formula 102 is than for 0.01～100: 1；
Described M is bisphenol compound dehydroxylation residue；
Described X is that the double halogen compound containing phenyl ring removes remaining group or the double nitro compounds containing phenyl ring after two halogens Thing removes remaining group after two nitros；
Described R is bisphenol compound dephenolize hydroxyl hydrogen residue, formula 201, formula 202, formula 203, formula 204, formula 205, formula 206 Or structure shown in formula 207：
In formula 201, described R1And R2Independently selected from H, NH2、NO2, the alkyl of C1～C5, methoxyl group, phenoxy group or benzene first Acyl group；
In formula 202, described R3And R4The phenyl replacing independently selected from H, phenyl or alkyl；
Described Z is that the double halogen compound containing phenyl ring removes remaining group after two halogens；
Described X and Z is not same structure.
Preferably, the repetitives shown in described formula 101 are
Repetitives shown in described formula 102 are
Mass fraction in a kind of high-strength PAEK material of described dimensionally stable for the described PAEK quadripolymer For 60～99%.
Preferably, described bisphenol compound includes hydroquinone, 4,4'- dihydroxybiphenyl, 4,4'- dihydroxy hexichol Ketone, 4,4' dihydroxydiphenyl sulfone, 4,4'- dihydroxy diphenyl ether, 4,4'- dihydroxy diphenyl sulfide, 2,2- are double (4- hydroxy phenyl) Double (the 4- hydroxy benzeness of propane, 4,4'- (hexafluoroisopropyli,ene) bis-phenol, 4,4'- (1,4- phenylene diisopropyl) biphenol, 3,3- Base) -1 (3H)-isobenzofuranone, double (4- hydroxy phenyl) phthalimidine of 3,3'-, 9,9- bis- (4- hydroxy phenyl) fluorenes, 6, The double triptycene diphenol of 13-, 2,5- triptycene diphenol, double (the 4- hydroxyl of 5,5'- double (2-4- (hydroxy phenyl)-benzimidazole), 2,6- Phenoxy group) -4'- (2,3,4,5,6- pentapheneyl phenyl) benzophenone and one or more of structure shown in Formulas I；
In Formulas I, described R5For C1～C12 alkyl, expoxy propane base, trifluoromethyl, phenyl, 4- trifluoromethyl, 4- Ethenylphenyl, 4- ethynyl phenyl or 4- cyano-phenyl.
Preferably, the described double halogen compound containing phenyl ring include 4,4'- dichlorobenzophenone, 4,4'- difluoro benzophenone, 4, 4'- dichloro diphenyl sulfone, 4,4'- difluorodiphenyl sulfone, double (4- fluorophenyl) phenyl phosphine oxide, double (4- chlorphenyl) phenyl phosphine oxide, 2,6- dichlorobenzonitrile, 2,6- difluorobenzonilyile, 2,4- bis- (4- fluorophenyl) -6- phenyl -1,3,5- triazine, 2,4- bis- (4- chlorobenzene Base) -6- phenyl -1,3,5- triazine, 4,4'- dichloro triphen diketone, in 4,4'- difluoro triphen diketone and structure shown in Formula II one Plant or multiple；
In Formula II, described E is fluorine, chlorine or bromine；
Described R6For C1～C12 alkyl, expoxy propane base, trifluoromethyl, phenyl, 4- trifluoromethyl, 4- vinyl Phenyl, 4- ethynyl phenyl or 4- cyano-phenyl；
Described double nitro compounds containing phenyl ring are the compound of structure shown in formula III：
Described R7For C1～C12 alkyl, expoxy propane base, trifluoromethyl, phenyl, 4- trifluoromethyl, 4- vinyl Phenyl, 4- ethynyl phenyl or 4- cyano-phenyl.
Preferably, the inorganic filler of described surface modification is that as surface modifier, inorganic filler is changed with coupling agent Property, described inorganic filler includes：One of titanium dioxide, silicon dioxide, boron nitride, carborundum, Kaolin, aluminium oxide or several Kind；
Mass fraction in a kind of dimensionally stable high-strength PAEK material for the described inorganic filler is 0.01～30%.
Preferably, described coupling agent includes titanate coupling agent, silane coupler, cadmium complex coupling agent, the coupling of zirconium class One or more of agent, aluminate coupling agent and aluminium titanium composite coupler；
Mass fraction in a kind of dimensionally stable high-strength PAEK material for the described coupling agent is 0.01～10%.
Preferably, described inorfil includes：One or more of glass fibre, carbon fiber, basalt fibre；
Preferably, described PAEK terpolymer includes the repetitives shown in formula 103 and formula 104：
The amount of the repetitives shown in described formula 103 and the material of repetitives shown in formula 104 is than for 0.01～100: 1；
Described M ' is bisphenol compound dehydroxylation residue；
Described X ' is that the double halogen compound containing phenyl ring removes remaining group or the double nitrations containing phenyl ring after two halogens Compound removes remaining group after two nitros；
Described R ' is bisphenol compound dephenolize hydroxyl hydrogen residue, as formula 201, formula 202, formula 203, formula 204, formula 205, formula 206 or structure shown in formula 207：
In formula 201, described R1' and R2' independently selected from H, NH2、NO2, the alkyl of C1～C5, methoxyl group, phenoxy group or benzene Formoxyl；
In formula 202, described R3' and R4' independently selected from H, phenyl or alkyl replace phenyl；
Described Z ' is that the double halogen compound containing phenyl ring removes remaining group after two halogens；
Described X ' and Z ' is same structure or-O-M '-O- and R ' is same structure.
Preferably, described PAEK bipolymer includes the repetitives of formula 401：
Described M " is bisphenol compound dehydroxylation residue；
Described X " is that the double halogen compound containing phenyl ring removes remaining group or the double nitrations containing phenyl ring after two halogens Compound removes remaining group after two nitros.
The present invention also provides a kind of preparation method of dimensionally stable high-strength PAEK material, and the method includes：
Step one：Surface modification is carried out to inorganic filler；
Step 2：The inorganic filler of surface modification, inorfil and poly (aryl ether ketone) copolymer are mixed, obtains dimensionally stable High-strength PAEK material.
The method that described inorganic filler carries out surface modification includes：Method for pretreating and many components mixing method；
Described method for pretreating is first through coupling agent treatment by inorganic filler, is then added in resin, according to mode Difference, is divided into two kinds of dry and wet again；
Described dry method is also referred to as nebulization, is equably to be sprayed onto no coupling agent or coupling agent treatment liquid while stirring On machine filler surface, mix homogeneously post-drying；
Described wet method is also called infusion process, refers in inorganic filler manufacturing process, with coupling agent treatment immersion stain, or Coupling agent is added in the serosity of inorganic filler person；
Described coupling agent treatment liquid is coupling agent water or organic solvent suspension；
The serosity of described inorganic filler is inorganic filler water or organic solvent aaerosol solution；
Described organic solvent is：Ethanol, methanol, acetone, oxolane, white oil, petroleum ether, transformer oil, isopropanol, third Alcohol etc.；
Described many components mixing method is to be added in inorganic filler coupling agent directly or by compound.
Beneficial effects of the present invention
The present invention provides a kind of dimensionally stable high-strength PAEK material, including：Poly (aryl ether ketone) copolymer, surface modification Inorganic filler and inorfil；Described poly (aryl ether ketone) copolymer is PAEK bipolymer, PAEK ternary polymerization Thing or PAEK quadripolymer；The inorganic filler of surface modification of the present invention is high-strength, high-ductility, wear-resistant spherical receive Rice inorganic filler, is conducive to improving the overall dimensional stability of material.
The present invention provides a kind of preparation method of dimensionally stable high-strength PAEK material, the polyarylether of preparation in the present invention Ketone is amorphous (non-crystalline type high molecular polymer), does not therefore need crystallization process to be incubated as PEEk, can be direct Cooling and shaping, technical process is simple, easily controllable, has high working (machining) efficiency.
Brief description
In order to be illustrated more clearly that the embodiment of the present invention or technical scheme of the prior art, below will be to embodiment or existing Have technology description in required use accompanying drawing be briefly described it should be apparent that, drawings in the following description be only this Inventive embodiment, for those of ordinary skill in the art, on the premise of not paying creative work, can also basis The accompanying drawing providing obtains other accompanying drawings.
Fig. 1 is the infrared spectrum of the PAEK quadripolymer of the embodiment of the present invention 1 preparation；
Fig. 2 is the hydrogen nuclear magnetic resonance spectrogram of the PAEK quadripolymer of the embodiment of the present invention 1 preparation；
Fig. 3 is the DSC curve figure of the PAEK quadripolymer of the embodiment of the present invention 1 preparation；
Fig. 4 is the TGA curve chart of the PAEK quadripolymer of the embodiment of the present invention 1 preparation；
Fig. 5 is the GPC curve chart of the PAEK quadripolymer of the embodiment of the present invention 1 preparation.
Specific embodiment
The invention provides a kind of high-strength PAEK material of dimensionally stable, including：The inorganic filler of surface modification, inorganic Fiber and poly (aryl ether ketone) copolymer；Described poly (aryl ether ketone) copolymer is PAEK bipolymer, PAEK ternary is common Polymers or PAEK quadripolymer；
Described PAEK quadripolymer includes the repetitives shown in formula 101 and formula 102：
The amount of the repetitives shown in described formula 101 and the material of repetitives shown in formula 102 is than for 0.01～100: 1；
Described M is bisphenol compound dehydroxylation residue；
Described X is that the double halogen compound containing phenyl ring removes remaining group or the double nitro compounds containing phenyl ring after two halogens Thing removes remaining group after two nitros；
Described R is bisphenol compound dephenolize hydroxyl hydrogen residue, formula 201, formula 202, formula 203, formula 204, formula 205, formula 206 Or structure shown in formula 207：
In formula 201, described R1And R2Independently selected from H, NH2、NO2, the alkyl of C1～C5, methoxyl group, phenoxy group or benzene first Acyl group；
In formula 202, described R3And R4The phenyl replacing independently selected from H, phenyl or alkyl；
Described Z is that the double halogen compound containing phenyl ring removes remaining group after two halogens；
Described X and Z is not same structure.
A kind of dimensionally stable high-strength PAEK material that the present invention provides is preferable to the adhesive ability of metallic matrix.
A kind of dimensionally stable high-strength PAEK material that the present invention provides includes PAEK quadripolymer, described poly- The number-average molecular weight of aryl ether ketone quadripolymer is preferably 4 × 104～1 × 105Da, more preferably 4.5 × 104～6.8 × 104Da；The weight average molecular weight of PAEK quadripolymer is preferably 8.5 × 104～1.5 × 105Da, more preferably 8.9 × 104～1.3 × 105Da；The polydispersity coefficient PDI of PAEK quadripolymer is 1.3～2.5.
In the present invention, the end group of described PAEK quadripolymer is hydroxyl, hydrogen, secondary amine or halogen；Described halogen Element is preferably fluorine or chlorine.
In the present invention, the repetitives shown in described formula 101 are preferably：
Repetitives shown in described formula 102 are preferably：
In the present invention, in the repetitives shown in described formula 101, X end and R end in the repetitives shown in formula 102 connect Connect, or in the repetitives shown in described formula 101, Z end is connected with O end in the repetitives shown in formula 102；
In the present invention, the amount of the repetitives shown in described formula 101 and the material of repetitives shown in formula 102 is than excellent Elect 0.01～100 as:1, more preferably 0.1～90:1.
In the present invention, described M is bisphenol compound dehydroxylation residue, and described bisphenol compound dehydroxylation residue is Bisphenol compound removes remaining group after hydroxyl-removal；Described bisphenol compound preferably includes hydroquinone, 4,4'- dihydroxy Biphenyl, 4,4'- dihydroxy benzophenone, 4,4' dihydroxydiphenyl sulfone, 4,4'- dihydroxy diphenyl ether, 4,4'- dihydroxy diphenyl sulfide Ether, 2,2- double (4- hydroxy phenyl) propane, 4,4'- (hexafluoroisopropyli,ene) bis-phenol, 4,4'- (1,4- phenylene diisopropyl) hexichol Double (4- hydroxy phenyl) -1 (the 3H)-isobenzofuranone of phenol, 3,3-, 3,3'- double (4- hydroxy phenyl) phthalimidine, 9,9- bis- The double triptycene diphenol of (4- hydroxy phenyl) fluorenes, 6,13-, 2,5- triptycene diphenol, the double (2-4- (hydroxy phenyl)-benzo miaow of 5,5'- Azoles), in 2,6- double (4- hydroxyphenoxy) -4'- (2,3,4,5,6- pentapheneyl phenyl) benzophenone and structure shown in Formulas I one Plant or multiple；
Described R5For C1～C12 alkyl, expoxy propane base, trifluoromethyl, phenyl, 4- trifluoromethyl, 4- vinyl Phenyl, 4- ethynyl phenyl or 4- cyano-phenyl；
Described bisphenol compound more preferably include double (4- hydroxy phenyl) -1 (the 3H)-isobenzofuranone of 3,3- and/or 9,9- bis- (4- hydroxy phenyl) fluorenes.
In the present invention, described X is double nitro compounds that the double halogen compound containing phenyl ring removes two halogens or contains phenyl ring Thing removes remaining group after two nitros；The described double halogen compound containing phenyl ring includes 4,4'- dichlorobenzophenone, 4,4'- bis- Fluorine benzophenone, 4,4'- dichloro diphenyl sulfone, 4,4'- difluorodiphenyl sulfone, double (4- fluorophenyl) phenyl phosphine oxide, double (4- chlorphenyls) Phenyl phosphine oxide, 2,6- dichlorobenzonitrile, 2,6- difluorobenzonilyile, 2,4- bis- (4- fluorophenyl) -6- phenyl -1,3,5- triazine, 2,4- Shown in two (4- chlorphenyl) -6- phenyl -1,3,5- triazine, 4,4'- dichloro triphen diketone, 4,4'- difluoro triphen diketone and Formula II One or more of structure；
In Formula II, described E is fluorine, chlorine or bromine；
Described R6For C1～C12 alkyl, expoxy propane base, trifluoromethyl, phenyl, 4- trifluoromethyl, 4- vinyl Phenyl, 4- ethynyl phenyl or 4- cyano-phenyl；
The described double halogen compound containing phenyl ring more preferably include 4,4'- difluoro benzophenone, 2,6- dichlorobenzonitrile and N- ethyl- One or more of double (4- fluoro benzoyl) carbazole of 3,6-.
In the present invention, described double nitro compounds containing phenyl ring are preferably the compound of structure shown in formula III：
Described R7For C1～C12 alkyl, expoxy propane base, trifluoromethyl, phenyl, 4- trifluoromethyl, 4- vinyl Phenyl, 4- ethynyl phenyl or 4- cyano-phenyl.
In the present invention, described R be bisphenol compound dephenolize hydroxyl hydrogen residue, formula 201, formula 202, formula 203, formula 204, Formula 205, formula 206 or structure shown in formula 207：
In formula 201, described R1And R2Independently selected from the alkyl of H, NH2, NO2, C1～C5, methoxyl group, phenoxy group or benzene first Acyl group；
In formula 202, described R3And R4The phenyl replacing independently selected from H, phenyl or alkyl；
In the present invention, described bisphenol compound dephenolize hydroxyl hydrogen residue removes after phenolic hydroxyl group hydrogen for bisphenol compound Remaining group.In the present invention, described-O-M-O- and described-R- is not same structure.
In the present invention, described Z is double nitro compounds that the double halogen compound containing phenyl ring removes two halogens or contains phenyl ring Thing removes remaining group after two nitros；
In PAEK quadripolymer of the present invention, described X and Z is not same structure；Described-O-M-O- It is not same structure with R yet.
In the present invention, the structure after described PAEK quadripolymer removes end group is specially：
The present invention preferably prepares described PAEK quadripolymer according to following steps：
First compound, second compound, the 3rd compound and the 4th compound are carried out polycondensation reaction in a solvent, obtains To PAEK quadripolymer；
Described first compound is bisphenol compound；
Described second compound is the double halogen compound containing phenyl ring or the double nitro compounds containing phenyl ring；
Described 3rd compound is bisphenol compound, contains compound or the phenols chemical combination containing secondary amine of imidazolone structure Thing；
The described compound containing imidazolone structure includes imidazolone, benzimidazolone, 5- methyl benzimidazolone, 5- amino Benzimidazolone, 5-Nitro-2-benzimidazolinone, 5,6- dimethylbenzimidazole quinoline ketone, 5,6- diaminourea Benzimidazolinone, 5- Benzoyl benzimidazole quinoline ketone and 5- methoxybenzimidazol quinoline ketone；
The described phenolic compound containing secondary amine includes 2- hydroxycarbazole, 4- hydroxycarbazole, 6- (2- hydroxy phenyl)-rattle away Piperazine -3 (2H) -one, 6- (4- hydroxy phenyl)-pyridazine -3 (2H) -one and diazanaphthalene terphenyl phenol；
Described 4th compound is the double halogen compound containing phenyl ring or the double nitro compounds containing phenyl ring；
Described first compound and the 3rd compound are not same bisphenol compound；
Described second compound and the 4th compound are not the same double halogen compound containing phenyl ring or the double nitre containing phenyl ring Based compound.
In the present invention, described first compound is bisphenol compound, preferably includes hydroquinone, 4,4'- dihydroxy Biphenyl, 4,4'- dihydroxy benzophenone, 4,4' dihydroxydiphenyl sulfone, 4,4'- dihydroxy diphenyl ether, 4,4'- dihydroxy diphenyl sulfide Ether, 2,2- double (4- hydroxy phenyl) propane, 4,4'- (hexafluoroisopropyli,ene) bis-phenol, 4,4'- (1,4- phenylene diisopropyl) hexichol Double (4- hydroxy phenyl) -1 (the 3H)-isobenzofuranone of phenol, 3,3-, 3,3'- double (4- hydroxy phenyl) phthalimidine, 9,9- bis- The double triptycene diphenol of (4- hydroxy phenyl) fluorenes, 6,13-, 2,5- triptycene diphenol, the double (2-4- (hydroxy phenyl)-benzo miaow of 5,5'- Azoles), in 2,6- double (4- hydroxyphenoxy) -4'- (2,3,4,5,6- pentapheneyl phenyl) benzophenone and structure shown in Formulas I one Plant or multiple；
Described R5For C1～C12 alkyl, expoxy propane base, trifluoromethyl, phenyl, 4- trifluoromethyl, 4- vinyl Phenyl, 4- ethynyl phenyl or 4- cyano-phenyl；More preferably include double (4- hydroxy phenyl) -1 (the 3H)-isobenzofuranone of 3,3- And/or 9,9- bis- (4- hydroxy phenyl) fluorenes.
In the present invention, described second compound is the double halogen compound containing phenyl ring or the double nitro compounds containing phenyl ring, Preferably include 4,4'- difluoro benzophenone, 4,4'- dichloro diphenyl sulfone, 4,4'- difluorodiphenyl sulfone, the oxidation of double (4- fluorophenyl) phenyl Phosphine, double (4- chlorphenyl) phenyl phosphine oxide, 2,6- dichlorobenzonitrile, 2,6- difluorobenzonilyile, 2,4- bis- (4- fluorophenyl) -6- phenyl - 1,3,5- triazine, 2,4- bis- (4- chlorphenyl) -6- phenyl -1,3,5- triazine, 4,4'- dichloro triphen diketone, 4,4'- difluoro triphen One or more of structure shown in diketone and Formula II；
In Formula II, described E is fluorine, chlorine or bromine；
Described R6For C1～C12 alkyl, expoxy propane base, trifluoromethyl, phenyl, 4- trifluoromethyl, 4- vinyl Phenyl, 4- ethynyl phenyl or 4- cyano-phenyl；The described double halogen compound containing phenyl ring more preferably includes 4,4'- difluorodiphenyl One or more of ketone, 4,4'- dichloro diphenyl sulfone, 2,6- dichlorobenzonitrile and 4,4'- dichlorobenzophenone.
In the present invention, described double nitro compounds containing phenyl ring are the compound of structure shown in formula III：
Described R7For C1～C12 alkyl, expoxy propane base, trifluoromethyl, phenyl, 4- trifluoromethyl, 4- vinyl Phenyl, 4- ethynyl phenyl or 4- cyano-phenyl.
In the present invention, described 3rd compound is bisphenol compound, contains the compound of imidazolone structure or contain secondary amine The phenolic compound of base, the described compound containing imidazolone structure includes imidazolone, benzimidazolone, 5- tolimidazole Ketone, 5-Amino-2-benzimidazolinone, 5-Nitro-2-benzimidazolinone, 5,6- dimethylbenzimidazole quinoline ketone, 5,6- diaminourea benzo miaow Oxazoline ketone, 5- benzoyl benzimidazole quinoline ketone and 5- methoxybenzimidazol quinoline ketone；Described 3rd compound preferably includes benzene And imidazolone and/or 5,6- dimethylbenzimidazole quinoline ketone.
In the present invention, described 4th compound is the double halogen compound containing phenyl ring or the double nitro compounds containing phenyl ring； The double halogen compound containing phenyl ring included by described 4th compound or the category of double nitro compounds containing phenyl ring and the The category of the double halogen compound containing phenyl ring included by two compounds or the double nitro compounds containing phenyl ring is consistent, but described 4th compound and second compound are not the same double halogen compound containing phenyl ring or the double nitro compounds containing phenyl ring.
In the present invention, the amount of total material of described first compound and the 3rd compound and described second compound and the The amount ratio preferably 0.8～1.2 of the total material of four compounds, more preferably 0.9～1.1, most preferably 0.95～1.05.At this In invention, the amount ratio preferably 0.01～100 of the material of described first compound and the 3rd compound:1, more preferably 0.1～ 90:1；The amount ratio preferably 0.01～100 of the material of described second compound and the 4th compound:1, more preferably 0.1～90: 1.
In the present invention, described polycondensation reaction is preferably carried out in the presence of a catalyst, and described catalyst is preferably alkalescence Compound, described alkali compoundss preferably include sodium carbonate, Calcium Carbonate, potassium carbonate, potassium bicarbonate, sodium bicarbonate, cesium fluoride, hydrogen One or more of sodium oxide and potassium hydroxide, more preferably include one or more of sodium carbonate, Calcium Carbonate and potassium carbonate. In the present invention, the amount of the material of described catalyst and the amount of described second compound and the total material of the 4th compound are than preferably For 1～3：1, more preferably 1～2：1, most preferably 1～1.3：1.
The present invention carries out polycondensation reaction preferably in the presence of water entrainer, and described water entrainer preferably includes benzene, toluene and two One or more of toluene.In the present invention, described water entrainer and the volume ratio of solvent are 0.5～2:1.
In an embodiment of the present invention, the present invention preferably by the first compound, second compound, the 3rd compound, the 4th Compound, solvent, catalyst and water entrainer are added sequentially in reaction vessel carry out polycondensation reaction.Present invention preferably employs ability There-necked flask known to field technique personnel is as reaction vessel.
In the present invention, described polycondensation reaction is carried out preferably in oxygen-free environment.The present invention preferably pass through noble gases or Nitrogen realizes oxygen-free environment；Described noble gases are preferably argon.
First compound, second compound, the 3rd compound, the 4th compound and water entrainer are preferably heated to by the present invention Azeotropic, insulation, remove water entrainer, be heated to that polycondensation reaction is temperature required to carry out polycondensation reaction.Specific embodiment in the present invention In, when described water entrainer is toluene, preferably azeotropic, to 120 DEG C of removing water, is incubated 1～2h, removes toluene.
In the present invention, the temperature of described polycondensation reaction is preferably 150 DEG C～300 DEG C, more preferably 150 DEG C～250 DEG C； The time of described polycondensation reaction is preferably 0.5h～12h, more preferably 1h～8h.
After polycondensation reaction terminates, polycondensation product is preferably lowered the temperature by the present invention, adds diluent, then by the contracting of dilution Polybutadiene reaction product precipitates in mixed solvent, is precipitated thing；Precipitate is filtered, pulverized and is washed, obtained polyarylether Ketone quadripolymer.In the present invention, described mixed solvent is preferably the mixed solvent of second alcohol and water.
In the present invention, described diluent preferably includes N-Methyl pyrrolidone (NMP), N, N- diethylformamide And N, (DMAc) one or more of N- diethylformamide (DMF)；More preferably N, N- diethylformamide (DMAc).? In the present invention, described diluent is 0.5～3 with the volume ratio of solvent:1.
The method that the present invention is filtered to precipitate, pulverized and washed does not have special restriction, using art technology The technical scheme of the filtration known to personnel, pulverizing and washing.
In the present invention, described PAEK quadripolymer is in a kind of high-strength PAEK material of described dimensionally stable Mass fraction be preferably 60～99%, more preferably 70～97%, most preferably 75～95%.
A kind of dimensionally stable high-strength PAEK material that the present invention provides includes the inorganic filler of surface modification, described table The modified inorganic filler in face, can improve mechanical strength of resin, toughness and hardness, improve dimensional stability.Described surface modification Inorganic filler is that as surface modifier, inorganic filler is modified with coupling agent, and described inorganic filler includes：Titanium dioxide, two One or more of silicon oxide, boron nitride, carborundum, Kaolin, aluminium oxide；
Mass fraction in a kind of dimensionally stable high-strength PAEK material for the described inorganic filler is 0.01～30%.
Described coupling agent is adhesion promoters, can improve the interface interaction between inorganic matters and Organic substance, thus greatly The big performance improving composite, improves bonding force under hygrometric state for the product, weatherability, improves pigment-dispersing, improve size Stablize the cross-linking properties of high epistasis and resin.In the present invention, described coupling agent preferably includes titanate coupling agent, silane coupled One or more of agent, chromium complex coupling agent, zirconium class coupling agent, aluminate coupling agent and aluminium titanium composite coupler, specifically , in an embodiment of the present invention, can using isopropyl three (dioctylphyrophosphoric acid acyloxy) titanate esters (TMC-201), two (ethyl acetoacetate base) aluminic acid isopropyl ester (HY1804), the silane coupler of model SCA1103, γ-methacryloxypropyl One or more of base propyl trimethoxy silicane (KH570) and methacrylic acid chromium complex；Described coupling agent exists Mass fraction in a kind of high-strength PAEK material of dimensionally stable is preferably 0.01～20%, more preferably 3～15%, optimum Elect 5～10% as.
A kind of dimensionally stable high-strength PAEK material that the present invention provides includes inorfil, described inorfil bag Include：One or more of glass fibre, carbon fiber, basalt fibre；
Mass fraction in a kind of dimensionally stable high-strength PAEK material for the described inorfil is 0.01～20%.
PAEK terpolymer of the present invention includes the repetitives shown in formula 103 and formula 104：
The amount of the repetitives shown in described formula 103 and the material of repetitives shown in formula 104 is than for 0.01～100: 1；
Described M ' is bisphenol compound dehydroxylation residue；
Described X ' is that the double halogen compound containing phenyl ring removes remaining group or the double nitrations containing phenyl ring after two halogens Compound removes remaining group after two nitros；
Described R ' is bisphenol compound dephenolize hydroxyl hydrogen residue, as formula 201, formula 202, formula 203, formula 204, formula 205, formula 206 or structure shown in formula 207：
In formula 201, described R1' and R2' independently selected from H, NH2、NO2, the alkyl of C1～C5, methoxyl group, phenoxy group or benzene Formoxyl；
In formula 202, described R3' and R4' independently selected from H, phenyl or alkyl replace phenyl；
Described Z ' is that the double halogen compound containing phenyl ring removes remaining group after two halogens；
Described X ' and Z ' is same structure or-O-M '-O- and R ' is same structure.
Repetitives shown in described formula 103 are
Repetitives shown in described formula 104 are
The M ' in repetitives formula 103 in described PAEK terpolymer and PAEK in technique scheme The M in repetitives formula 101 in quadripolymer, species consistent, but, specific structure can identical can not also With；The species of X ' in repetitives formula 103 in described PAEK terpolymer is poly- fragrant with technique scheme The species of the X in repetitives formula 101 in ether ketone quadripolymer is consistent, but, concrete structure can be identical, also may be used With difference；The species of R ' in repetitives formula 104 in described PAEK terpolymer with technique scheme in The species of the R in repetitives formula 102 in PAEK quadripolymer is consistent, but, concrete structure can be identical, Can also be different；The species of Z ' in repetitives formula 104 in described PAEK terpolymer with above-mentioned technical side The species of the Z in repetitives formula 102 in PAEK quadripolymer in case is consistent, but, concrete structure is permissible Identical it is also possible to different；Except for the difference that, the Z ' in X ' and formula 104 in described PAEK terpolymer, in formula 103 It is same structure for the R ' in-the O-M '-O- in same structure, or formula 103 and formula 104.Specifically, described PAEK three The structure of membered copolymer and preparation method can refer to the Chinese patent of Application No. 201210071242.0.
PAEK bipolymer of the present invention includes the repetitives of formula 401：
Described M " is bisphenol compound dehydroxylation residue；
Described X " is that the double halogen compound containing phenyl ring removes remaining group or the double nitrations containing phenyl ring after two halogens Compound removes remaining group after two nitros.
Repetitives shown in described formula 401 are
The M in repetitives formula 401 in described PAEK bipolymer " and PAEK in technique scheme The M in repetitives formula 101 in quadripolymer, species consistent, but, specific structure can identical can not also With；The species of the X in repetitives formula 401 in described PAEK bipolymer " is poly- fragrant with technique scheme The species of the X in repetitives formula 101 in ether ketone quadripolymer is consistent, but, concrete structure can be identical, also may be used With difference；Specifically, the structure of described PAEK bipolymer and preparation method can refer to Publication No. CN85108751A Chinese patent.
The present invention also provides a kind of dimensionally stable high-strength PAEK material preparation method, and the method includes：
Step one：Surface modification is carried out to inorganic filler；
Step 2：The inorganic filler of surface modification, inorfil and poly (aryl ether ketone) copolymer are mixed, obtains dimensionally stable High-strength PAEK material.
The inorganic filler surface method of modifying that the present invention provides includes：Method for pretreating (the direct facture of inorganic particle) and many Component mixing method, inorganic matters first through coupling agent treatment, are then added to by described method for pretreating (the direct facture of inorganic particle) In resin, different according to mode, it is divided into two kinds of dry and wet again.Dry method is also referred to as nebulization, while stirring by coupling agent Aqueous solution is equably sprayed onto on mineral surfaces；Wet method is also called infusion process, refers to, in inorganic fillers manufacturing process, use Coupling agent treatment immersion stain, or coupling agent is added in the serosity of filler；Described many components mixing method will coupling agent straight Connect or be added in resin by compound, its advantage is that the consumption of coupling agent can arbitrarily change as needed；
Described dry method is also referred to as nebulization, while stirring by coupling agent or coupling agent water or organic solvent solution equably It is sprayed onto on mineral surfaces, mix homogeneously post-drying；Described coupling agent treatment liquid is coupling agent water or organic solvent hangs Supernatant liquid；The serosity of described inorganic filler is inorganic filler water or organic solvent solution；
Described wet method is also called infusion process, refers in inorganic fillers manufacturing process, with coupling agent treatment immersion stain, Or coupling agent is added in the serosity of inorganic filler；
Described coupling agent treatment liquid is coupling agent water or organic solvent suspension；
The serosity of described inorganic filler is inorganic filler water or organic solvent aaerosol solution；
Described organic solvent is：Ethanol, methanol, acetone, oxolane, white oil, petroleum ether, transformer oil, isopropanol, third Alcohol etc.；
Described many components mixing method will coupling agent be added in resin directly or by compound, and its advantage is coupling agent Consumption can arbitrarily change as needed；
Specifically, inorganic filler adopts coupling agent to adopt method for pretreating (the direct facture of inorganic particle) or the mixing of many components A kind of method in method, carries out surface modification, add inorfil, PAEK Binary Aggregation powder or PAEK ternary, Quarternary copolymerized powder, after mix homogeneously in homogenizer, is dried more than 3 hours, twin-screw extrusion is made at 150 DEG C Grain；
Described each section of temperature of double screw extruder, design temperature is：One area's temperature 280-360 DEG C, two area's temperature 300-380 DEG C, three area's temperature 320-400 DEG C, four area's temperature 320-400 DEG C, five area's temperature 300-380 DEG C, head temperature is 300-380 DEG C.
Described coupling agent is surface modifier, can improve the interface interaction between inorganic matters and Organic substance, thus significantly Improve the performance of composite, improve bonding force under hygrometric state for the product, weatherability, improve pigment-dispersing, improve size steady Fixed high epistasis and the cross-linking properties of resin.In the present invention, described coupling agent preferably includes titanate coupling agent, silane coupled One or more of agent, chromium complex coupling agent, zirconium class coupling agent, aluminate coupling agent and aluminium titanium composite coupler compound, Specifically, in an embodiment of the present invention, isopropyl three (dioctylphyrophosphoric acid acyloxy) titanate esters (TMC- can be adopted 201), two (ethyl acetoacetate base) aluminic acid isopropyl ester (HY1804), the silane coupler of model SCA1103, γ-methyl-prop One or more of alkene acryloxypropylethoxysilane trimethoxy silane (KH570) and methacrylic acid chromium complex；Described idol A kind of connection mass fraction in titanium dioxide for the agent is preferably 0.01～20%, more preferably 3～15%, most preferably 5～10%.
The present invention tests by ASTM-D638 standard according to tensile strength：Specimen types are I type, batten size (mm)： 180 (length) × (12.68 ± 0.2) (neck width) × (3.23 ± 0.2) (thickness), draw speed is 50mm/ minute.
The present invention tests by ASTM-D790 standard according to bending strength and bending moduluses：Specimen types are sample chi Very little (mm)：(128 ± 2) × (12.8 ± 0.2) × (3.21 ± 0.2), rate of bending is 20mm/ minute.
The present invention tests by ASTM-D256 standard according to notch impact strength：Specimen types are V mouth breach type, examination Sample ruler cun (mm)：(63±2)×(12.58±0.2)×(4.21±0.2)；Breach type is V mouth class, and breach residual thickness is 2.44mm.
The present invention tests by ASTM-D648 standard according to heat distortion temperature, loads as 1.82MPa, and span is 100mm, specimen size (mm)：(128 ± 2) × (13 ± 0.2) × (6.4 ± 0.2), maximum deformation quantity is 0.25mm.
In order to further illustrate the present invention, a kind of the dimensionally stable with reference to embodiments present invention being provided is high-strength PAEK material and metal material are described in detail, but can not be understood as limiting the scope of the present invention.
Embodiment 1
0.268g (0.002mol) benzimidazolone, 2.547g is sequentially added in 100mL three neck round bottom flask (0.008mol) phenolphthalein, 0.671g (0.003075mol) 4,4'- difluoro benzophenone, 1.234g (0.007175mol) 2,6- bis- 6-chlorophenyl nitrile, 1.589g potassium carbonate, 15g sulfolane and 20mL toluene, are heated to 120 DEG C of azeotropic water removings, are incubated 1.5h, except nor- Benzene, continues to be heated to 210 DEG C, reacts 2.5h, cooling, adds 20mL DMAc dilution, precipitates in ethanol/water, precipitate passes through After filter, pulverizing, boil in deionized water and wash 5 times, remove the impurity such as inorganic salt and reaction dissolvent, obtain that there is formula III structure PAEK quadripolymer；
Take titanium dioxide 180g and silica 1 80g, spraying under agitation adds the acetic acid hot water of KH570 silane coupler Solution (PH is 3-6, and the mass content of silane coupler is 20%, and temperature control is at 40-80 DEG C) 200g, high-speed stirred mixing is all After even, it is dried 5 hours at 150 DEG C, obtains product；
There is after taking above-mentioned prepared removing end group the PAEK quarternary copolymerized powder 600g of formula IV structure, take above-mentioned Prepared surface modification titanium dioxide and silica mixture 200g, add carbon fiber 200g, mix in homogenizer After uniformly, it is dried more than 3 hours at 150 DEG C, double-screw extruding pelletizing, then batten test is molded on injection machine；
Each section of design temperature of double screw extruder be：One 325 DEG C of area's temperature, two 355 DEG C of area's temperature, three 360 DEG C of area's temperature, Four 360 DEG C of area's temperature, five 345 DEG C of area's temperature, head temperature is 345 DEG C.
The PAEK quadripolymer that the present invention is obtained to the present embodiment 1 carry out infrared, proton nmr spectra, DSC, TGA tests, and respectively as shown in Figure 1, Figure 2, Figure 3 and Figure 4, wherein, Fig. 1 is the polyarylether of the embodiment of the present invention 1 preparation to test chart The infrared spectrum of ketone quadripolymer；Fig. 2 is the hydrogen nuclear magnetic resonance of the PAEK quadripolymer of the embodiment of the present invention 1 preparation Spectrogram；Fig. 3 is the DSC curve figure of the PAEK quadripolymer of the embodiment of the present invention 1 preparation；Fig. 4 is the embodiment of the present invention 1 The TGA curve chart of the PAEK quadripolymer of preparation.Can be drawn by Fig. 1 and Fig. 2：The embodiment of the present invention 1 preparation PAEK quadripolymer has formula IV structure after removing end group.From figure 3, it can be seen that it is manufactured in the present embodiment quarternary copolymerized The glass transition temperature Tg of thing is 244 DEG C.As can be seen from Figure 4：The initial decomposition of quadripolymer manufactured in the present embodiment Temperature is 476 DEG C, decomposes the corresponding temperature of maximum rate and is 507 DEG C.
The present invention carries out gel osmoticing chromatogram analysis to the PAEK quadripolymer of preparation, during test, dissolves quaternary The solvent of copolymer is chloroform, and standard sample is polystyrene；Test is as shown in figure 5, Fig. 5 is the embodiment of the present invention 1 preparation The GPC curve chart of PAEK quadripolymer；As shown in table 1, table 1 is the poly- of the embodiment of the present invention 1～5 preparation to test result The GPC result of aryl ether ketone quadripolymer.
Table 1
Embodiment Mn/Da Mw/Da PDI
Embodiment 1 43586 89147 2.0
Embodiment 2 61052 114458 1.9
Embodiment 3 57455 115087 2.0
Embodiment 4 60258 135481 2.2
Embodiment 5 65212 124572 1.9
The present invention tests the properties of the batten that the present embodiment obtains according to the method for testing in technique scheme, Test result is：Tensile strength：138MPa；Bending strength：157MPa；Elastic modelling quantity：3.5GPa；Impact strength：54KJ/m2； Heat distortion temperature：240℃；Linear expansion coefficient：25*10-5.
Embodiment 2
1.592g (0.005mol) phenolphthalein, 0.671g (0.005mol) benzene is sequentially added in 100mL three neck round bottom flask And imidazolone, 1.091g (0.005mol) difluoro benzophenone, 0.860g (0.005mol) 2,6- dichlorobenzonitrile, catalyst are mixed Close alkali, described mixed base includes 2.763g potassium carbonate and 1.060g sodium carbonate, 10g sulfolane, 5g diphenyl sulphone (DPS) and 25mL toluene, plus Heat, to 130 DEG C of azeotropic water removings, is incubated 2h, removes toluene, continues to be heated to 200 DEG C, reacts 5h, cooling, adds 20mL DMAc dilute Release, precipitate in ethanol/water, precipitate, after filtering, pulverizing, boils in deionized water and washes 7 times, remove inorganic salt and reaction is molten The impurity such as agent, have the PAEK quadripolymer of Formula VIII structure after the end group that is removed, glass transition temperature is 279 ℃.
Take titanium dioxide 180g and silica 1 80g, spraying under agitation adds KH570：10g and KH550：10g silane is even Acetic acid hydrothermal solution (PH is 3-6, and the mass content of silane coupler is 20%, and temperature control is at the 40-80 DEG C) 200g of connection agent, After high-speed stirred mix homogeneously, it is dried 5 hours at 150 DEG C, obtains product；
There is after taking above-mentioned prepared removing end group the PAEK quarternary copolymerized powder 600g of Formula VIII structure, take State prepared surface modification titanium dioxide and silica mixture 100g, carbon fiber 150g, glass fibre 250g, in high-speed stirred After mix homogeneously in machine, it is dried more than 3 hours at 150 DEG C, double-screw extruding pelletizing, then batten is molded on injection machine and survey Examination；
Each section of design temperature of double screw extruder be：One 325 DEG C of area's temperature, two 355 DEG C of area's temperature, three 360 DEG C of area's temperature, Four 360 DEG C of area's temperature, five 345 DEG C of area's temperature, head temperature is 345 DEG C.
The present invention tests the properties of the batten that the present embodiment obtains according to the method for testing in technique scheme, Test result is：Tensile strength：136MPa；Bending strength：158MPa；Elastic modelling quantity：3.3GPa；Impact strength：62KJ/m2； Heat distortion temperature：255℃；Linear expansion coefficient：28*10-5.
The quadripolymer that the present invention is obtained to the present embodiment 2 carries out gel osmoticing chromatogram analysis, and test result is shown in Table 1 institute Show.
Embodiment 3
100mL three neck round bottom flask sequentially adds 1.752g (0.005mol) bisphenol fluorene, 0.671g (0.005mol), 5,6- dimethylbenzimidazole ketone, 1.436g (0.005mol) dichloro diphenyl sulfone, 0.860g (0.005mol) 2,6- dichlorobenzonitrile, Catalyst is mixed base, and described mixed base includes 2.763g potassium carbonate and 1.060g sodium carbonate, 15g sulfolane and 20mL benzene, plus Heat, to 90 DEG C of azeotropic water removings, is incubated 3h, removes benzene, continues to be heated to 190 DEG C, reacts 12h, cooling, adds 20mL DMAc dilute Release, precipitate in ethanol/water, precipitate, after filtering, pulverizing, boils in deionized water and washes 6 times, remove inorganic salt and reaction is molten The impurity such as agent, have the PAEK quadripolymer of Formula V structure after the end group that is removed, glass transition temperature is 298 DEG C.
Take boron nitride 50g, carborundum 60g, titanium dioxide 100g and silicon dioxide 90g, spraying under agitation adds KH570 silicon The ethanol acetate solution (PH is 3-6, and the mass content of silane coupler is 20%, and temperature control is at 40-80 DEG C) of alkane coupling agent 200g, after high-speed stirred mix homogeneously, is dried 5 hours at 150 DEG C, obtains product；
There is after taking above-mentioned prepared removing end group the PAEK quarternary copolymerized powder 600g of Formula V structure, take above-mentioned Prepared surface modification titanium dioxide and silica mixture 200g, add glass fibre 150g, carbon fiber 100g, basalt Fiber 50, after mix homogeneously in homogenizer, is dried more than 3 hours, double-screw extruding pelletizing at 150 DEG C, then in note Batten test is molded on molding machine；
Each section of design temperature of double screw extruder be：One 325 DEG C of area's temperature, two 355 DEG C of area's temperature, three 360 DEG C of area's temperature, Four 360 DEG C of area's temperature, five 345 DEG C of area's temperature, head temperature is 345 DEG C.
The present invention tests the properties of the batten that the present embodiment obtains according to the method for testing in technique scheme, Test result is：Tensile strength：128MPa；Bending strength：159MPa；Elastic modelling quantity：3.4GPa；Impact strength：56KJ/m2； Heat distortion temperature：243℃；Linear expansion coefficient：35*10-5.
The quadripolymer that the present invention is obtained to the present embodiment 3 carries out gel osmoticing chromatogram analysis, and test result is shown in Table 1 institute Show.
Embodiment 4
100mL three neck round bottom flask sequentially adds 1.752g (0.005mol) bisphenol fluorene, 0.671g (0.005mol), 5,6- dimethylbenzimidazole ketone, 2.187g (0.005mol) N- ethyl -3,6- double (4- hydroxy benzoyl) carbazole, 0.860g (0.005mol) 2,6- dichlorobenzonitrile, 1.382g potassium carbonate, 1.560g sodium carbonate, 15g sulfolane and 20mL benzene, are heated to 90 DEG C Azeotropic water removing, be incubated 3h, remove benzene, continue to be heated to 180 DEG C, react 12h, cooling, add 20mL DMAc dilution, ethanol/ Precipitate in water, precipitate, after filtering, pulverizing, boils in deionized water and washes 7 times, removes the impurity such as inorganic salt and reaction dissolvent, It is removed and there is after end group the PAEK quadripolymer of Formula IV structure, the glass transition temperature of product is 271 DEG C.
Take carborundum 50g, Kaolin 50g, aluminium oxide 100g and silica 1 00g, add deionized water under agitation, It is made into the suspension of carborundum, Kaolin, aluminium oxide and silica mixture, add TMC-201 metatitanic acid under high velocity agitation Ester coupling agent 40g, after high-speed stirred mix homogeneously, is dried 5 hours at 150 DEG C after filtration, obtains product；
There is after taking above-mentioned prepared removing end group the PAEK quarternary copolymerized powder 600g of Formula IV structure, take above-mentioned Prepared surface modification titanium dioxide and silica mixture 200g, add carbon fiber 120g, basalt fibre 100g, glass Fiber 80g, after mix homogeneously in homogenizer, is dried more than 3 hours, double-screw extruding pelletizing at 150 DEG C, then in note Batten test is molded on molding machine；
Each section of design temperature of double screw extruder be：One 325 DEG C of area's temperature, two 355 DEG C of area's temperature, three 360 DEG C of area's temperature, Four 360 DEG C of area's temperature, five 345 DEG C of area's temperature, head temperature is 345 DEG C.
The present invention tests the properties of the batten that the present embodiment obtains according to the method for testing in technique scheme, Test result is：Tensile strength：135MPa；Bending strength：167MPa；Elastic modelling quantity：3.6GPa；Impact strength：67KJ/m2； Heat distortion temperature：243℃；Linear expansion coefficient：29*10-5.
The quadripolymer that the present invention is obtained to the present embodiment 4 carries out gel osmoticing chromatogram analysis, and test result is shown in Table 1 institute Show.
Embodiment 5
100mL three neck round bottom flask sequentially adds 1.752g (0.005mol) bisphenol fluorene, 1.592g (0.005mol), Phenolphthalein, 2.187g (0.005mol) N- ethyl -3,6- double (4- hydroxy benzoyl) carbazole, 0.860g (0.005mol) 2,6- bis- 6-chlorophenyl nitrile, 2.763g potassium carbonate, 15g sulfolane and 20mL dimethylbenzene, it is heated to 160 DEG C of azeotropic water removings, is incubated 3h, remove diformazan Benzene, continues to be heated to 200 DEG C, reacts 4.5h, cooling, adds 20mL DMAc dilution, precipitates in ethanol/water, precipitate passes through After filter, pulverizing, boil in deionized water and wash 10 times, remove the impurity such as inorganic salt and reaction dissolvent, have after the end group that is removed The PAEK quadripolymer of Formula VII structure, the glass transition temperature of product is 285 DEG C.
Take carborundum 50g, Kaolin 50g, aluminium oxide 100g and silica 1 00g, spraying under agitation adds HY1804 Ethanol solution (mass content of silane coupler the is 20%) 200g of aluminate coupling agent, after high-speed stirred mix homogeneously, It is dried 5 hours at 150 DEG C, obtain product；
There is after taking above-mentioned prepared removing end group the PAEK quarternary copolymerized powder 620g of Formula VII structure, take State prepared surface modification carborundum, Kaolin, aluminium oxide and silica mixture 180g, add basalt fibre 100g, carbon fiber 100g, after mix homogeneously in homogenizer, are dried more than 3 hours, twin-screw extrusion is made at 150 DEG C Grain, then batten test is molded on injection machine；
Each section of design temperature of double screw extruder be：One 325 DEG C of area's temperature, two 355 DEG C of area's temperature, three 360 DEG C of area's temperature, Four 360 DEG C of area's temperature, five 345 DEG C of area's temperature, head temperature is 345 DEG C.
The present invention tests the properties of the batten that the present embodiment obtains according to the method for testing in technique scheme, Test result is：Tensile strength：124MPa；Bending strength：167MPa；Elastic modelling quantity：3.5GPa；Impact strength：63KJ/m2； Heat distortion temperature：245℃；Linear expansion coefficient：25*10-5.
The quadripolymer that the present invention is obtained to the present embodiment 5 carries out gel osmoticing chromatogram analysis, and test result is shown in Table 1 institute Show.
Embodiment 6
3.184g (0.01mol) phenolphthalein, 1.720g (0.01mol) 2,6- is sequentially added in 100mL three neck round bottom flask Dichlorobenzonitrile, 2.763g potassium carbonate, 15g sulfolane and 20mL dimethylbenzene, it is heated to 160 DEG C of azeotropic water removings, is incubated 3h, remove two Toluene, continues to be heated to 200 DEG C, reacts 4.5h, cooling, adds 20mL DMAc dilution, precipitates, precipitate warp in ethanol/water After filtration, pulverizing, boil in deionized water and wash 10 times, remove the impurity such as inorganic salt and reaction dissolvent, have after the end group that is removed There is the PAEK bipolymer of formula Ⅸ structure, the glass transition temperature of product is 278 DEG C.
Take chromic oxide 50g, carborundum 60g, corundum 40g, Kaolin 50g, aluminium oxide 80g and silicon dioxide 80g, The lower spraying of stirring adds ethanol solution (mass content of silane coupler the is 20%) 200g of HY1804 aluminate coupling agent, high After speed is uniformly mixed, it is dried 5 hours at 150 DEG C, obtains product；
There is after taking above-mentioned prepared removing end group the PAEK binary copolymerization powder 600g of formula Ⅸ structure, take above-mentioned Prepared surface modification chromic oxide, carborundum, corundum, Kaolin, aluminium oxide and silica mixture 200g, add Carbon fiber 58g basalt fibre 60g, after mix homogeneously in homogenizer, is dried more than 3 hours, twin screw at 150 DEG C Extruding pelletization, then batten test is molded on injection machine；
Each section of design temperature of double screw extruder be：One 325 DEG C of area's temperature, two 355 DEG C of area's temperature, three 360 DEG C of area's temperature, Four 360 DEG C of area's temperature, five 345 DEG C of area's temperature, head temperature is 345 DEG C.
The present invention tests the properties of the batten that the present embodiment obtains according to the method for testing in technique scheme, Test result is：Tensile strength：123MPa；Bending strength：157MPa；Elastic modelling quantity：3.5GPa；Impact strength：65KJ/m2； Heat distortion temperature：265℃；Linear expansion coefficient：27*10-5.
Embodiment 7
3.184g (0.010mol) phenolphthalein 1.091g (0.005mol) difluoro is sequentially added in 100mL three neck round bottom flask Benzophenone, 0.860g (0.005mol) 2,6- dichlorobenzonitrile, catalyst are mixed base, and described mixed base includes 2.763g carbonic acid Potassium and 1.060g sodium carbonate, 10g sulfolane, 5g diphenyl sulphone (DPS) and 25mL toluene, are heated to 130 DEG C of azeotropic water removings, are incubated 2h, remove Toluene, continues to be heated to 200 DEG C, reacts 5h, cooling, adds 20mL DMAc dilution, precipitates in ethanol/water, precipitate passes through After filter, pulverizing, boil in deionized water and wash 10 times, remove the impurity such as inorganic salt and reaction dissolvent, have after the end group that is removed The PAEK terpolymer of formula Ⅹ structure, glass transition temperature is 256 DEG C.
Take chromic oxide 60g, aluminium sesquioxide 80g, titanium dioxide 60g, Kaolin 80g and silicon dioxide 80g, in stirring Lower spraying adds KH570：10g and KH550：(PH is 3-6 to the acetic acid hydrothermal solution of 10g silane coupler, the matter of silane coupler Amount content is 20%, and temperature control is at 40-80 DEG C) 200g, after high-speed stirred mix homogeneously, it is dried 5 hours at 150 DEG C, obtains To product；
There is after taking above-mentioned prepared removing end group the PAEK ternary polymerization powder 600g of formula Ⅹ structure, take above-mentioned Prepared surface modification chromic oxide, aluminium sesquioxide, titanium dioxide, Kaolin and silica mixture 200g, add Carbon fiber 88g, after mix homogeneously in homogenizer, is dried more than 3 hours, double-screw extruding pelletizing at 150 DEG C, then Batten test is molded on injection machine；
Each section of design temperature of double screw extruder be：One 325 DEG C of area's temperature, two 355 DEG C of area's temperature, three 360 DEG C of area's temperature, Four 360 DEG C of area's temperature, five 345 DEG C of area's temperature, head temperature is 345 DEG C.
The present invention tests the properties of the batten that the present embodiment obtains according to the method for testing in technique scheme, Test result is：Tensile strength：130MPa；Bending strength：168MPa；Elastic modelling quantity：3.9GPa；Impact strength：62KJ/m2； Heat distortion temperature：251℃；Linear expansion coefficient：30*10-5.

Claims (11)

1. the high-strength PAEK material of a kind of dimensionally stable, including：
Poly (aryl ether ketone) copolymer；
The inorganic filler of surface modification；
Inorfil；
Described poly (aryl ether ketone) copolymer is PAEK bipolymer, PAEK terpolymer or PAEK quaternary Copolymer；
Described PAEK quadripolymer includes the repetitives shown in formula 101 and formula 102：
The amount of the repetitives shown in described formula 101 and the material of repetitives shown in formula 102 is than for 0.01～100:1；
Described M is bisphenol compound dehydroxylation residue；
Described X is that after double halogen compound containing phenyl ring removes two halogens, remaining group or the double nitro compounds containing phenyl ring go Except remaining group after two nitros；
Described R is bisphenol compound dephenolize hydroxyl hydrogen residue, formula 201, formula 202, formula 203, formula 204, formula 205, formula 206 or formula Structure shown in 207：
In formula 201, described R1And R2Independently selected from H, NH2、NO2, the alkyl of C1～C5, methoxyl group, phenoxy group or benzoyl；
In formula 202, described R3And R4The phenyl replacing independently selected from H, phenyl or alkyl；
Described Z is that the double halogen compound containing phenyl ring removes remaining group after two halogens；
Described X and Z is not same structure.
2. a kind of high-strength PAEK material of dimensionally stable according to claim 1 it is characterised in that
Repetitives shown in described formula 101 are
Repetitives shown in described formula 102 are
Mass fraction in a kind of high-strength PAEK material of described dimensionally stable for the described PAEK quadripolymer is 10 ～25%.
3. the high-strength PAEK material of a kind of dimensionally stable according to claim 1 is it is characterised in that described bisphenols Compound includes hydroquinone, 4,4' dihydroxy diphenyl, 4,4'- dihydroxy benzophenone, 4,4' dihydroxydiphenyl sulfone, 4,4'- bis- Double (4- hydroxy phenyl) propane of dihydroxy diphenyl ether, 4,4'- dihydroxy diphenyl sulfide, 2,2-, 4,4'- (hexafluoroisopropyli,ene) bis-phenol, Double (4- hydroxy phenyl) -1 (the 3H)-isobenzofuranone of 4,4'- (1,4- phenylene diisopropyl) biphenol, 3,3-, 3,3'- are double The double triptycene diphenol of (4- hydroxy phenyl) phthalimidine, 9,9- bis- (4- hydroxy phenyl) fluorenes, 6,13-, 2,5- triptycene diphenol, Double (4- hydroxyphenoxy) -4'- (the 2,3,4,5,6- pentapheneyl benzene of 5,5'- double (2-4- (hydroxy phenyl)-benzimidazole), 2,6- Base) benzophenone and one or more of structure shown in Formulas I；
In Formulas I, described R5For C1～C12 alkyl, expoxy propane base, trifluoromethyl, phenyl, 4- trifluoromethyl, 4- vinyl Phenyl, 4- ethynyl phenyl or 4- cyano-phenyl.
4. a kind of high-strength PAEK material of dimensionally stable according to claim 1 it is characterised in that described containing phenyl ring Double halogen compound includes 4,4'- dichlorobenzophenone, 4,4'- difluoro benzophenone, 4,4'- dichloro diphenyl sulfone, 4,4'- difluorodiphenyl Sulfone, double (4- fluorophenyl) phenyl phosphine oxide, double (4- chlorphenyl) phenyl phosphine oxide, 2,6- dichlorobenzonitrile, 2,6- difluorobenzonilyile, 2, 4- bis- (4- fluorophenyl) -6- phenyl -1,3,5- triazine, 2,4- bis- (4- chlorphenyl) -6- phenyl -1,3,5- triazine, 4,4'- dichloro Triphen diketone, 4,4'- difluoro triphen diketone and one or more of structure shown in Formula II；
In Formula II, described E is fluorine, chlorine or bromine；
Described R6For C1～C12 alkyl, expoxy propane base, trifluoromethyl, phenyl, 4- trifluoromethyl, 4- ethenylphenyl, 4- ethynyl phenyl or 4- cyano-phenyl；
Described double nitro compounds containing phenyl ring are the compound of structure shown in formula III：
Described R7For C1～C12 alkyl, expoxy propane base, trifluoromethyl, phenyl, 4- trifluoromethyl, 4- ethenylphenyl, 4- ethynyl phenyl or 4- cyano-phenyl.
5. the high-strength PAEK material of a kind of dimensionally stable according to claim 1 is it is characterised in that described surface modification Inorganic filler be that coupling agent is modified as surface modifier to inorganic filler, described inorganic filler includes：Corundum, gold In emery, chromic oxide, antimony oxide, titanium dioxide, silicon dioxide, boron nitride, carborundum, Kaolin, aluminium sesquioxide One or more；
Mass fraction in a kind of dimensionally stable high-strength PAEK material for the described inorganic filler is 0.01～50%.
6. the high-strength PAEK material of a kind of dimensionally stable according to claim 5 is it is characterised in that described coupling agent bag Include titanate coupling agent, silane coupler, cadmium complex coupling agent, zirconium class coupling agent, aluminate coupling agent and aluminum titanium to be combined occasionally One or more of connection agent；
Mass fraction in a kind of dimensionally stable high-strength PAEK material for the described coupling agent is 0.01～15%.
7. the high-strength PAEK material of a kind of dimensionally stable according to claim 1 is it is characterised in that described inorfil Including：One or more of glass fibre, carbon fiber, basalt fibre；
Mass fraction in a kind of dimensionally stable high-strength PAEK material for the described inorfil is 0.01～30%.
8. the high-strength PAEK material of a kind of dimensionally stable according to claim 1 is it is characterised in that described PAEK Terpolymer includes the repetitives shown in formula 103 and formula 104：
The amount of the repetitives shown in described formula 103 and the material of repetitives shown in formula 104 is than for 0.01～100:1；
Described M ' is bisphenol compound dehydroxylation residue；
Described X ' is that the double halogen compound containing phenyl ring removes remaining group or the double nitro compounds containing phenyl ring after two halogens Remove remaining group after two nitros；
Described R ' is bisphenol compound dephenolize hydroxyl hydrogen residue, as formula 201, formula 202, formula 203, formula 204, formula 205, formula 206 Or structure shown in formula 207：
In formula 201, described R1' and R2' independently selected from H, NH2、NO2, the alkyl of C1～C5, methoxyl group, phenoxy group or benzoyl Base；
In formula 202, described R3' and R4' independently selected from H, phenyl or alkyl replace phenyl；
Described Z ' is that the double halogen compound containing phenyl ring removes remaining group after two halogens；
Described X ' and Z ' is same structure or-O-M '-O- and R ' is same structure.
9. the high-strength PAEK material of a kind of dimensionally stable according to claim 1 is it is characterised in that described PAEK Bipolymer includes formula 401 repetitives：
Described M " is bisphenol compound dehydroxylation residue；
Described X " is that the double halogen compound containing phenyl ring removes remaining group or the double nitro compounds containing phenyl ring after two halogens Remove remaining group after two nitros.
10. a kind of high-strength PAEK material of dimensionally stable according to claim 1 preparation method it is characterised in that Including：
Step one：Surface modification is carried out to inorganic filler；
Step 2：The inorganic filler of surface modification, inorfil and poly (aryl ether ketone) copolymer are mixed, obtains dimensionally stable high-strength PAEK material.
A kind of preparation method of the high-strength PAEK material of 11. dimensionally stables according to claim 10 it is characterised in that The method that described inorganic filler carries out surface modification includes：Method for pretreating and many components mixing method；
Described method for pretreating is first through coupling agent treatment by inorganic filler, is then added in resin, different according to mode, It is divided into two kinds of dry and wet again；
Described dry method is also referred to as nebulization, is while stirring coupling agent or coupling agent treatment liquid to be equably sprayed onto inorganic filling out On material surface, mix homogeneously post-drying；
Described wet method is also called infusion process, refers in inorganic filler manufacturing process, with coupling agent treatment immersion stain, or will Coupling agent is added in the serosity of inorganic filler；
Described coupling agent treatment liquid is coupling agent water or organic solvent suspension；
The serosity of described inorganic filler is inorganic filler water or organic solvent aaerosol solution；
Described organic solvent is：Ethanol, methanol, acetone, oxolane, white oil, petroleum ether, transformer oil, isopropanol, propanol Deng；
Described many components mixing method is to be added in inorganic filler coupling agent directly or by compound.
CN201610796206.9A 2016-08-31 2016-08-31 High-strength polyaryletherketone material with stable size and preparation method thereof Pending CN106398171A (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108456411A (en) * 2018-03-14 2018-08-28 吉林大学 A kind of cross-linking type polyarylether ketone group dielectric composite material and its preparation method and application
CN110218501A (en) * 2018-08-13 2019-09-10 宁波高新区诠宝绶新材料科技有限公司 A kind of preparation method of the polyether-ether-ketone enamel new material with superior heat-stability
CN111944143A (en) * 2018-02-05 2020-11-17 大连理工大学 Bio-based polyarylether resin containing furan ring structure and preparation method thereof
CN112778472A (en) * 2018-10-09 2021-05-11 刘鹏 Polyaryletherketone modified core-shell structure acrylic acid water-based resin emulsion
CN114901731A (en) * 2019-12-27 2022-08-12 三菱化学株式会社 Member for composite material, moving body, and method for producing film for composite material

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1154292A (en) * 1996-01-10 1997-07-16 中国科学院长春应用化学研究所 Preparation method of high-temperature wear-resistant sealing valve plate
CN104725987A (en) * 2015-04-17 2015-06-24 中国科学院长春应用化学研究所 Coating combination and metal material

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1154292A (en) * 1996-01-10 1997-07-16 中国科学院长春应用化学研究所 Preparation method of high-temperature wear-resistant sealing valve plate
CN104725987A (en) * 2015-04-17 2015-06-24 中国科学院长春应用化学研究所 Coating combination and metal material

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111944143A (en) * 2018-02-05 2020-11-17 大连理工大学 Bio-based polyarylether resin containing furan ring structure and preparation method thereof
CN111944143B (en) * 2018-02-05 2021-05-25 大连理工大学 Bio-based polyarylether resin containing furan ring structure and preparation method thereof
CN108456411A (en) * 2018-03-14 2018-08-28 吉林大学 A kind of cross-linking type polyarylether ketone group dielectric composite material and its preparation method and application
CN110218501A (en) * 2018-08-13 2019-09-10 宁波高新区诠宝绶新材料科技有限公司 A kind of preparation method of the polyether-ether-ketone enamel new material with superior heat-stability
CN110218501B (en) * 2018-08-13 2021-04-16 威海中塑新材料科技有限公司 Preparation method of novel polyether-ether-ketone wire-covering paint material with excellent thermal stability
CN112778472A (en) * 2018-10-09 2021-05-11 刘鹏 Polyaryletherketone modified core-shell structure acrylic acid water-based resin emulsion
CN112778472B (en) * 2018-10-09 2022-09-27 广州麦吉高分子新材料科技有限公司 Polyaryletherketone modified core-shell structure acrylic acid water-based resin emulsion
CN114901731A (en) * 2019-12-27 2022-08-12 三菱化学株式会社 Member for composite material, moving body, and method for producing film for composite material

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