CN1657548A

CN1657548A - Polyetherketone containing biphenyl hetero naphthalene ring structure and its preparation method

Info

Publication number: CN1657548A
Application number: CN 200510051529
Authority: CN
Inventors: 范世均; 韩自力
Original assignee: Individual
Current assignee: Individual
Priority date: 2005-03-04
Filing date: 2005-03-04
Publication date: 2005-08-24

Abstract

A refractory polyaryletherone resin is prepared from biphenol and phthalic acid anhydride through synthesizing 4-[4-(4-hydroxyphenyl)phenyl]-2,3-diazanaphthalene-1-one, and catalytic polymerizing reaction on bihalogen monomer, X-Ar-X in non-protonic polar solvent, where X is chosen from F and Cl. It has high strength, toughness and high-temp resistance.

Description

A kind of novel polyetherketone and preparation method thereof that contains biphenyl hetero naphthalene ring structure

It is synthetic to the present invention relates to the high temperature resistant amorphous polyaryletherketone resin of a kind of novel soluble, belongs to the synthetic field of special engineering plastics.

Polyaryletherketone is meant to have general formula-Ar-O-, and has at least a part to contain the superpolymer of carbonyl-CO-structure among its aryl Ar.

The polyetherketone (PEK) that English Patent BP 1414421 is reported contains following repeated structural unit:

This is a kind of crystal polymer thing, and its fusing point is 367 ℃, and second-order transition temperature is 154 ℃.This polymkeric substance be with 4,4 ' dihydroxy benzophenone is a biphenol monomer, is prepared into corresponding bisphenolate salt through alkaline purification, again with by the two halogen monomers 4 of carbonyl activatory, 4 '-dihalo-benzophenone (wherein halogen can be F, CL, BR, I, particularly F, CL) polycondensation and making.Because this biphenol monomer is all very expensive with two halogen monomers, is difficult to apply in practice.

U.S. Pat P 4320224 and Johnson et.al., Journal of Polym.Sci., Part A-1,5,2394 (1967) have reported another crystal type polyaryletherketone kind (PEEK), it contains following repeating unit:

This melting point substance is 335, and second-order transition temperature is 144 ℃, can be at 250 ℃ of following life-time service.This polymkeric substance is with ' the dihalo-benzophenone is polymerized in the presence of alkaline carbonate by the two halogen monomers 4,4 of carbonyl activatory with relatively inexpensive Resorcinol.In order to obtain the high-molecular weight toughness polymer, it is solvent that this patent has adopted high boiling sulfobenzide, 350 ℃ of polymerization temperatures.Compare with PEK, because PEEK does not dissolve, the aftertreatment of polymkeric substance is difficulty relatively.

U.S. Pat 4638044 and US 4774314 successively reported and prepared improving one's methods of above-mentioned polyaryletherketone, principal character be to improve catalyst system such as the composite catalyst that adopts different an alkali metal salts with fast reaction speed, shorten the reaction times etc.But the structure itself to polymkeric substance there is no change.Chinese patent CN 85108751 has reported a kind of amorphous polyaryletherketone (PEK-C), and it contains following repeated structural unit:

Its second-order transition temperature is 228 ℃.PEK-C is to be biphenol monomer with phenolphthalein, and ' polycondensation of dihalo-benzophenone forms, and it has solvability preferably, thereby its synthesis condition and aftertreatment purification etc. all are greatly improved with two halogen monomers 4,4.But, its heat-resisting and chemical resistance is greatly reduced owing to contain the cyclic ester group on its molecule segment.

Another Chinese patent CN 93109179.9 has reported the amorphous polyetherketone (PPEK) of another kind of novelty, contains following structural unit:

This polymkeric substance is to be monomer with 4-(4-hydroxy phenyl)-2-1-ketone, with the dihalo-benzophenone following reaction takes place:

Owing to have the naphthyridine ring structure that contains Pyrogentisinic Acid's group in the above-mentioned molecular structure, this polymer glass temperature has a distinct increment than conventional P EK and reaches 260 ℃, can be at 220-230 ℃ of following life-time service, and because the twist structure of naphthyridine group uniqueness, make this polymkeric substance that certain solvability be arranged in the minority aprotic solvent, thereby make its synthetic preparation become simple relatively, but its heat resisting temperature and processing characteristics are still not ideal enough, have limited it and have applied.

The most synthesis condition harshness of existing crystal type polyetherketone, product does not dissolve, the aftertreatment difficulty, production cost is high.Though existing amorphous polyetherketone PEK-C and PPEK solubilized but heat-resisting and chemical resistance is still relatively low.Thereby synthetic thermotolerance is higher, and excellent combination property and soluble novel polyether ketone resin have urgent realistic meaning.

The present invention is from Molecular Structure Design, has synthesized a kind of novel polyaryletherketone resin that contains biphenyl group-naphthyridine ring structure, and its second-order transition temperature reaches 287 ℃, can satisfy the requirement at 250-260 ℃ of following life-time service.

Content of the present invention is novel class biphenol monomer 4-[4-(4-hydroxy phenyl) phenyl that contains biphenyl group-naphthyridine structure with our up-to-date development]-2,3-naphthyridine-1-ketone (DHPZ-P) and 4,4 '-dihalo-benzophenone monomer is a raw material, in aprotic polar solvent, with the alkalies and alkaline earth salt is catalyzer, azeotropic dehydration reaction at high temperature 5-50 hour is precipitated out subject polymer with alcohols again from reaction system, filtering separation and getting.Product has following feature structure:

Novel class biphenol monomer 4-[4-(4-hydroxy phenyl) phenyl that the present invention is used]-2-1-ketone feature structure is as follows:

The used two halogen monomers of the present invention are that 4,4 ' the dihalo-benzophenone, wherein halogen can be fluorine, chlorine.

Polymerization temperature of the present invention is controlled in the 120-300 ℃ of scope, and polymerization reaction time is 5-50 hour.

Reaction is omnidistance as follows:

If adopt simultaneously to contain-the dihalo-benzophenone of CO-structure and-the dihalo-sulfobenzide of SO2-structure, then the polymkeric substance of Sheng Chenging is a sulfone ketone interpolymer, this reaction is expressed as follows:

Reaction process of the present invention can be divided into three phases.

Fs is the monomer synthesis phase, mainly is xenol and phthalic anhydride reaction generation are contained special class biphenol monomer: 4-[4-(4-hydroxy phenyl) phenyl]-2-1-ketone.

Subordinate phase is the dehydration pre-polymerization stage, and with class biphenol monomer 4-[4-(4-hydroxy phenyl) phenyl]-2-1-ketone and dihalo-benzophenone, be solvent with the tetramethylene sulfone, basic metal or alkaline-earth metal are catalyzer, and system adopts toluene or dimethylbenzene or chlorobenzene azeotropic dehydration.This stage mainly generates oligopolymer, and system viscosity changes less, and moisture removes in a large number.To be with the water entrainer to steam, heating up to continue to react promptly enters the phase III.

Phase III mainly is the reaction that aggregates into superpolymer between the oligopolymer mutually.This elementary reaction system viscosity progressively increases, and polymericular weight is more and more higher, treats that system viscosity enlarges markedly, reach requirement after, stop the heating and the termination reaction that cools gradually.Reacting the end back is that precipitation agent stirs down polymer precipitation is come out with the alcohols, and filtration drying gets white purified polyaryletherketone resin.

The structure of polymkeric substance can be confirmed through infrared spectra and nuclear magnetic resonance spectroscopy.

The synthesizing new polyaryletherketone resin according to the present invention, the monomer starting material are cheap and easy to get, and polymer process is simple, and product postprocessing is purified easy to implement.The product second-order transition temperature has remarkable resistance toheat up to 287 ℃.And test charts such as the electrical property that carries out behind the forming polymer, mechanical property, corrosion resistance nature to understand that the every performance index of this polymkeric substance all show good, be the good novel thermoplastic polyaryletherketone resin of over-all properties.

The novel polyaryletherketone resin of synthetic according to the present invention, have good thermostability, second-order transition temperature Tg=287 ℃, and have characteristics such as good electrical property, mechanical property, radiation resistance, burning self-extinguishing, and flow properties of polymer melts is better, is easy to extrude with injection moulding process.

[most preferred embodiment 1]

Agitator is being housed, azeotropic reflux water-dividing device, temperature is taken into account in the reactor of nitrogen inlet, 4-[4-(4-hydroxy phenyl) phenyl that adds 78.52G (0.25mol) under the logical nitrogen successively]-2,3-naphthyridine-1-one monomers, 55.05G difluoro benzophenone (0.25mol), the 270ml tetramethylene sulfone, the 500ml chlorobenzene, 43.3G (0.35mol) Anhydrous potassium carbonate, reflux, begin branch water in 140 ℃, treat to heat after branch water finishes to 200 ℃ and continue reaction 5-15 hour down, the system for the treatment of reaches stopped reaction after the required viscosity, cooling is with reaction solution sedimentation in 4 times of amount ethanolic solns, and the product filtration drying promptly gets white powdery subject polymer.Product is that to record limiting viscosity be 0.58 to solvent (Ubbelohde viscometer, 25 ℃, four-point method) with the chloroform.

[most preferred embodiment 2]

In that being housed, agitator, azeotropic reflux water-dividing device, temperature take into account in the reactor of nitrogen inlet; following 4-[4-(4-hydroxy phenyl) phenyl of logical nitrogen protection with 376.8 grams (1.2mol)]-2; 4 of 3-naphthyridine-1-ketone biphenol monomer and 261.8 grams (1.2mol); 4-difluoro benzophenone, 248.8 gram (1.8mol) anhydrous K 2CO3,1600ml N,N-DIMETHYLACETAMIDE and 400ml dimethylbenzene join in the reactor temperature reaction under the violent stirring.Begin branch water about 140 ℃, azeotropic refluxed 5 hours, treated to steam a large amount of toluene after moisture takes off to the greatest extent, was warming up to 170 ℃, kept certain reaction down 10-25 hour that refluxes.The reaction system color from light to dark, system viscosity significantly strengthens.Question response finishes the back and adds N,N-DIMETHYLACETAMIDE diluted reaction mixture and filtration.The adding ethanol sedimentation also filters and drains polymkeric substance, again with the chloroform dissolving, and uses ethanol sedimentation once more, so repeats twice.At last with polymkeric substance 100 ℃ of following vacuum-dryings 24 hours, purified novel polyaryletherketone resin.Product is that to record limiting viscosity be 0.57 to solvent (Ubbelohde viscometer, 25 ℃, four-point method) with the chloroform.

Claims

1, a kind of novel polyether ketone resin that contains biphenyl hetero naphthalene ring structure, its feature repeated structural unit is as follows:

2, a kind of is reaction solvent with non-proton type polar solvent and mixed solvent thereof, is catalyzer with the salt of basic metal or alkaline-earth metal, the method for the novel polyether ketone described in the preparation claim 1.It is characterized in that from xenol and Tetra hydro Phthalic anhydride, at first synthesize and have novel class biphenol monomer 4-[4-(4-hydroxy phenyl) phenyl shown in the feature structure (II)]-2,3-naphthyridine-1-ketone, again with this monomer and 4,4 '-dihalo-benzophenone monomer is a raw material, at high temperature carry out polyreaction, carry out azeotropic dehydration in the reaction, it is precipitation agent that reaction finishes back adding ethanol, stirs down polymer precipitation is come out, filtering separation obtains the polymkeric substance of tool feature structure (III).

Feature structure (II): feature structure (III):

Reaction is omnidistance as follows:

3, according to the preparation method of the novel polyether ketone that contains feature structure (III) described in the claim 2, it is characterized in that with tetramethylene sulfone be solvent, best polymeric reaction temperature is 190-220 ℃, the reaction times is 5-15 hour.

4, according to the preparation method of the novel polyether ketone that contains feature structure (III) described in the claim 2, it is characterized in that with N,N-DIMETHYLACETAMIDE be solvent, best polymeric reaction temperature is 160-190 ℃, the reaction times is 10-25 hour.

5,, it is characterized in that toluene, dimethylbenzene or chlorobenzene are azeotropy dehydrant according to the preparation method of the novel polyether ketone that contains feature structure (III) described in the claim 3,4.