CN101914204B - Polybenzoxazole based on dihydroxy diamine containing phthalazinone structure and preparation method thereof - Google Patents
Polybenzoxazole based on dihydroxy diamine containing phthalazinone structure and preparation method thereof Download PDFInfo
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- CN101914204B CN101914204B CN2010102020105A CN201010202010A CN101914204B CN 101914204 B CN101914204 B CN 101914204B CN 2010102020105 A CN2010102020105 A CN 2010102020105A CN 201010202010 A CN201010202010 A CN 201010202010A CN 101914204 B CN101914204 B CN 101914204B
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- 229920002577 polybenzoxazole Polymers 0.000 title claims abstract description 29
- 150000004985 diamines Chemical class 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- IJAPPYDYQCXOEF-UHFFFAOYSA-N phthalazin-1(2H)-one Chemical group C1=CC=C2C(=O)NN=CC2=C1 IJAPPYDYQCXOEF-UHFFFAOYSA-N 0.000 title abstract 3
- 239000000178 monomer Substances 0.000 claims abstract description 23
- 229920000137 polyphosphoric acid Polymers 0.000 claims abstract description 15
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 12
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 11
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims abstract description 10
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical group NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 claims abstract description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 5
- GXSMYGYXVBRAQA-UHFFFAOYSA-N C1(=CC=CC=C1)C1=CC=CC=C1.C1=NN=CC2=CC=CC=C12 Chemical group C1(=CC=CC=C1)C1=CC=CC=C1.C1=NN=CC2=CC=CC=C12 GXSMYGYXVBRAQA-UHFFFAOYSA-N 0.000 claims description 23
- 229910052799 carbon Inorganic materials 0.000 claims description 16
- 125000004432 carbon atom Chemical group C* 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- 229910052760 oxygen Inorganic materials 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 8
- 238000006116 polymerization reaction Methods 0.000 claims description 8
- -1 4Be hydrogen Chemical class 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 125000003545 alkoxy group Chemical group 0.000 claims description 6
- 150000004984 aromatic diamines Chemical class 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 125000001424 substituent group Chemical group 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 5
- 238000001556 precipitation Methods 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 230000001112 coagulating effect Effects 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 claims description 2
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 2
- 230000007935 neutral effect Effects 0.000 claims description 2
- 238000012805 post-processing Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 230000003252 repetitive effect Effects 0.000 claims description 2
- 238000005201 scrubbing Methods 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 239000002585 base Substances 0.000 claims 6
- 125000000355 1,3-benzoxazolyl group Chemical group O1C(=NC2=C1C=CC=C2)* 0.000 claims 1
- 239000003513 alkali Substances 0.000 claims 1
- 150000003839 salts Chemical class 0.000 claims 1
- 239000011347 resin Substances 0.000 abstract description 5
- 229920005989 resin Polymers 0.000 abstract description 5
- 239000000835 fiber Substances 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 4
- 239000002131 composite material Substances 0.000 abstract description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 abstract 1
- 239000000853 adhesive Substances 0.000 abstract 1
- 230000001070 adhesive effect Effects 0.000 abstract 1
- 239000011248 coating agent Substances 0.000 abstract 1
- 238000000576 coating method Methods 0.000 abstract 1
- 238000009833 condensation Methods 0.000 abstract 1
- 230000005494 condensation Effects 0.000 abstract 1
- 239000012528 membrane Substances 0.000 abstract 1
- 229940098779 methanesulfonic acid Drugs 0.000 abstract 1
- 239000003973 paint Substances 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 0 Cc(cc1)c(C)cc1*(c1ccc(C)c(C)c1)=C Chemical compound Cc(cc1)c(C)cc1*(c1ccc(C)c(C)c1)=C 0.000 description 5
- 229910005965 SO 2 Inorganic materials 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- 229910002091 carbon monoxide Inorganic materials 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- ZCQWOFVYLHDMMC-UHFFFAOYSA-N Oxazole Chemical compound C1=COC=N1 ZCQWOFVYLHDMMC-UHFFFAOYSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229920006253 high performance fiber Polymers 0.000 description 2
- 239000010977 jade Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000008520 organization Effects 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 235000017550 sodium carbonate Nutrition 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000010183 spectrum analysis Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- 229920000265 Polyparaphenylene Polymers 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 239000004922 lacquer Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000002916 oxazoles Chemical class 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920006389 polyphenyl polymer Polymers 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
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- 239000012783 reinforcing fiber Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 1
- 229960001755 resorcinol Drugs 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
Landscapes
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
The invention relates to polybenzoxazole based on dihydroxy diamine containing the phthalazinone structure and a preparation method thereof, belonging to the technical field of macromolecular material. 4-[4-(4-amino-3-hydroxyphenoxy)phenyl]-2-(4-amino-3-hydroxyphenyl)phthalazinone-1-one or derivative thereof and dicarboxylic acid or derivative thereof are used as monomer for condensation, another dihydroxy diamine or AB type monomer containing carboxyl groups and o-hydroxy-aniline groups can also be added; a solution polycondensation reaction is performed in polyphosphoric acid or methanesulfonic acid to obtain polybenzoxazole resin containing the phthalazinone structure with excellent heat resistance. The polybenzoxazole resin can be used in the fields such as high-temperature resistant fiber, paint, coating, adhesive, membrane and composite material and have wide application prospect.
Description
Technical field
The invention belongs to the polymer science technical field, relate to high performance polymer material and preparation method thereof, specially refer to one type based on polybenzoxazole that contains the phthalazine biphenyl structure dihydroxy diamine and preparation method thereof.
Background technology
Polybenzoxazole is the special engineering plastics of one type of excellent combination property; Be polybenzoxazole fibers at first by the research and development of United States Air Force material laboratory; Being polyparaphenylene Ben Bing Er oxazole (abbreviation PBO) fiber, is that the matrix material that the eighties in 20th century, the U.S. developed for development space flight and aviation cause is used reinforcing fiber materials.The tear strength of pbo fiber and Young's modulus also surpass Mechanical Properties of Steel Wire all above other high-performance fiber, and density is far below steel wire, not fusion at high temperature.Spin (Toyobo) company by Japanese Japan and realized suitability for industrialized production in 1998 at first, and begin to be applied in aerospace, fire prevention and field such as shellproof.Yet because the molecular chain of PBO is the rigid rod structure, the symmetry of molecular structure is high, makes can not be dissolved in organic solvent by the poorly soluble of PBO, can only be dissolved in the strong acid such as the vitriol oil, thereby cause the synthetic and processing conditions of PBO harsh.Can't the melt-processed moulding because the melt temperature of PBO is too high, therefore, PBO can only be in strong acid spinning processing, produce thus that processing units and processing condition are harsh, a tooling cost high-technology difficult problem, the while is poorly soluble also to cause the application of PBO to be restricted.
To the poorly soluble technical barrier of PBO, the researchist has carried out corresponding research work both at home and abroad.People [Xuan Genhai such as this school Zhu Xiu tinkling of pieces of jade; Synthetic, the sign of novel polyphenyl Bing Er oxazole and performance study thereof; Dalian University of Technology's master thesis, 2009] the novel naphthyridine ketone structure diacid monomer that contains with the exploitation of this study group is a raw material, through introducing distortion, non-coplanar naphthyridine ketone structure; Acquisition has the Ju Ben Bing Er oxazole new type resin of good solubility and excellent heat resistance, and limiting viscosity can reach 3dL/g.
The polybenzoxazole that this patent relates to is to be polycondensation monomer to contain phthalazine biphenyl structure dihydroxy diamine monomer and di-carboxylic acid; Also can add simultaneously other dihydroxy diamine monomer; The preparation of employing solution polycondensation; Such polybenzoxazole contains phthalazine biphenyl structure, with master thesis that people such as the Zhu Xiu tinkling of pieces of jade before publishes relate to gather the polymerization single polymerization monomer that benzene and two oxazoles adopt different, and molecular structure is also different.
Summary of the invention
The invention provides a kind of based on containing polybenzoxazole novel high-performance macromolecular material of phthalazine biphenyl structure dihydroxy diamine and preparation method thereof.With the dihydroxy diamine monomer of homemade 4-[4-(4-amino-3-hydroxy oxygen base) phenyl]-2-(4-amino-3-hydroxy base) naphthyridine-1-ketone or derivatives thereof and di-carboxylic acid and verivate thereof is polycondensation monomer; Also can add simultaneously other dihydroxy diamine monomer or AB type polycondensation monomer (containing carboxyl and ortho-aminophenol reactive group simultaneously); Carry out the high temperature solution polycondensation reaction, the synthetic polybenzoxazole resin that has excellent heat resistance and good solubility concurrently.
The present invention relates to based on the polybenzoxazole that contains the phthalazine biphenyl structure dihydroxy diamine, its structure expression is following:
Wherein, R
1, R
2, R
4, R
4Be hydrogen, halogenic substituent, phenyl, phenoxy, contain at least 1 carbon atom straight chained alkyl, contain the branched alkyl of at least 1 carbon atom or contain the branched alkoxyl group of at least 1 carbon atom, R
1, R
2, R
3And R
4Structure identical or different;
Ar
1And Ar
2Structure be that corresponding di-carboxylic acid or derivatives thereof reaction produces, by the structures shape of selecting for use di-carboxylic acid or derivatives thereof, the Ar here
1And Ar
2Structure identical or different; Ar
1Or Ar
2Structural formula be following one or more:
Position between
, ortho position or contraposition;
Ar
3Structure is that corresponding dihydroxyl aromatic diamines or the reaction of its hydrochloride produces, by the structures shape of selecting for use dihydroxyl aromatic diamines or its hydrochloride, Ar
3Structural formula be following one or more:
Wherein, R
1, R
2, R
3, R
4Be hydrogen, halogenic substituent, phenyl, phenoxy, contain at least 1 carbon atom straight chained alkyl, contain the branched alkyl of at least 1 carbon atom or contain the branched alkoxyl group of at least 1 carbon atom, R
1, R
2, R
3And R
4Structure identical or different;
Ar
4Structure produce by AB type monomer reaction, described AB type monomer contains carboxyl and ortho-aminophenol reactive group simultaneously,
Ar
4Structural formula be following one or more:
The present invention's preparation is a solution polycondensation based on the method for the polybenzoxazole that contains the phthalazine biphenyl structure dihydroxy diamine, and it is following specifically to prepare process:
(1) the reinforced stage; At first use rare gas element (like nitrogen or argon gas) polyphosphoric acid or methylsulfonic acid to be carried out deoxidation at 50～200 ℃; Then with the di-carboxylic acid or derivatives thereof with contain the phthalazine biphenyl structure dihydroxy diamine; It is 4-[4-(4-amino-3-hydroxy oxygen base) phenyl]-2-(4-amino-3-hydroxy base) naphthyridine-1-ketone or derivatives thereof; Join together in polyphosphoric acid or the methylsulfonic acid, also can add the dihydroxy diamine or the AB type monomer (containing carboxyl and ortho-aminophenol reactive group simultaneously) of other structure simultaneously, reaction system is stirred; The ratio of the mole number sum of the mole number of above-mentioned dihydroxyl aromatic diamines or its hydrochloride and di-carboxylic acid monomer or derivatives thereof is between 0.98～1.02, and the monomer mass percentage composition is between 0.2%～60% in this solution polymerization system;
(2) polymerization stage adopts progressively temperature-raising method, carries out the solution polycondensation reaction at 50～250 ℃, and the reaction times is 2～500 hours, and the temperature interval value that wherein heats up is controlled at 5～60 ℃, and at each temperature spot, duration of the reaction is between 0.1～100 hour;
(3) post-processing stages; After polyreaction finishes; Reaction soln directly or after adding thinner is poured in the precipitation agent, with the polymkeric substance coagulative precipitation, remaining solvent in the repetitive scrubbing polymerisate then; Also in available bases or the weakly alkaline inorganic salt with polymerisate in remaining solvent and washing to neutral, can obtain based on the polybenzoxazole that contains the phthalazine biphenyl structure dihydroxy diamine after the final drying.
Of the present inventionly contain the naphthyridine ketone structure dihydroxy diamine or its hydrochloride verivate has following molecular structure:
Wherein, R
1, R
2, R
3And R
4Be hydrogen, halogenic substituent, phenyl, phenoxy or the straight chain that contains at least 1 carbon atom or branched alkyl or alkoxyl group, R
1, R
2, R
3And R
4Structure identical or different.
The polymerization solvent that the present invention adopts is polyphosphoric acid (concentration is 80%～120%) or the methanesulfonic acid solution that contains Vanadium Pentoxide in FLAKES.
The thinner that the present invention uses has phosphoric acid, polyphosphoric acid, methylsulfonic acid or the vitriol oil, and its quality consumption is 0.1～200 times of initial polyphosphoric acid.
The sinking agent that the present invention uses comprises water, sodium bicarbonate aqueous solution, methyl alcohol, ethanol, THF or ether.
Synthetic is based on the polybenzoxazole resin that contains the phthalazine biphenyl structure dihydroxy diamine according to the present invention; Have that heat-resistant stability excellence, mechanical property are good, advantage such as solubilized and good film-forming property; In high-performance fiber, lacquer, tackiness agent, film, prepare composite, wide application prospect is arranged.
The present invention develops on the basis of existing technology, and related above-mentioned dihydroxy diamine monomer and polybenzoxazole thereof all contain phthalazine biphenyl structure.Through in the molecular backbone chain of polybenzoxazole, introducing distortion, non-coplanar phthalazine biphenyl structure, can improve the solvability of polybenzoxazole; Simultaneously, complete fragrant heterocycle structure can be given the polybenzoxazole excellent heat resisting.
Embodiment
Be described in detail specific embodiment of the present invention below in conjunction with technical scheme.
Embodiment 1:
In the dry 100mL there-necked flask that has stirring, reflux condensing tube, water trap and gas tube, add the polyphosphoric acid (PPA) of 20mL116%, lead to nitrogen protection, and there-necked flask is entered into oil bath, be warming up to 100 ℃, stirred 1 hour.Then, in there-necked flask, add 0.4984g (3mmol) terephthalic acid and 1.3574g (3mmol) 4-[4-(4-amino-3-hydroxy oxygen base) phenyl]-2-(4-amino-3-hydroxy base) naphthyridine-1-ketone, polymerization system reacted 2 hours down at 100 ℃; Reacted 10 hours down at 150 ℃, 190 ℃ were reacted 7 hours down, then the thick liquid of gained are slowly poured in the deionized water of 1L; Agitating deionized water constantly in the process of pouring into obtains strip solid russet at last, and water is washed till weak-type; Use the aqueous solution soaking of yellow soda ash again; Be washed till neutrality with deionized water, filter, vacuum-drying is 24 hours in 100 ℃ of vacuum drying ovens; Can contain phthalazine biphenyl structure polybenzoxazole 1.6168g, yield is 98.6%.
Institute's synthetic polymkeric substance is carried out ir spectra and spectral analysis of the nuclear magnetic resonance, and the result shows that this polymer architecture and project organization are consistent.
Embodiment 2:
In the dry 100mL there-necked flask that has stirring, reflux condensing tube, water trap and gas tube, add the polyphosphoric acid (PPA) of 20mL116%, logical nitrogen protection; And there-necked flask entered into oil bath; Be warming up to 100 ℃, stirred 1 hour, with the air in the system of removing.Then, in there-necked flask, add 0.2803g (2mmol) 4,6-diamino resorcin, 0.9049g (2mmol) 4-[4-(4-amino-3-hydroxy oxygen base) phenyl]-2-(4-amino-3-hydroxy base) naphthyridine-1-ketone and 0.6646g (4mmol) terephthalic acid; Polymerization system reacted 2 hours under 100 ℃, reacted 10 hours down at 150 ℃, and 190 ℃ were reacted 7 hours down; Then the thick liquid of gained is slowly poured in the deionized water of 1L, agitating deionized water constantly in the process of pouring into obtains strip solid russet at last; Water is washed till weak-type, uses the aqueous solution soaking of yellow soda ash again, is washed till neutrality with deionized water; Filter; Vacuum-drying is 24 hours in 100 ℃ of vacuum drying ovens, can contain naphthyridine ketone structure polybenzoxazole copolymer 1 .5349g, and yield is 98.3%.
Institute's synthetic polymkeric substance is carried out ir spectra and spectral analysis of the nuclear magnetic resonance, and the result shows that this polymer architecture and project organization are consistent.
Claims (6)
1. one kind based on the polybenzoxazole that contains the phthalazine biphenyl structure dihydroxy diamine; It is characterized in that polymkeric substance contains the phthalazine biphenyl structure dihydroxy diamine; And contain phthalazine biphenyl structure and benzoxazole structure in the molecular chain, its structure expression is:
Wherein, R
1, R
2, R
3, R
4Be hydrogen, halogenic substituent, phenyl, phenoxy, contain at least 1 carbon atom straight chained alkyl, contain the branched alkyl of at least 1 carbon atom or contain the branched alkoxyl group of at least 1 carbon atom, R
1, R
2, R
3And R
4Structure identical or different;
Ar
1And Ar
2Structure be that corresponding di-carboxylic acid or derivatives thereof reaction produces, by the structures shape of selecting for use di-carboxylic acid or derivatives thereof, the Ar here
1And Ar
2Structure identical or different; Ar
1Or Ar
2Structural formula be following one or more:
Ar
3Structure is that corresponding dihydroxyl aromatic diamines or the reaction of its hydrochloride produces, by the structures shape of selecting for use dihydroxyl aromatic diamines or its hydrochloride, Ar
3Structural formula be following one or more:
Wherein, R
1, R
2, R
3, R
4Be hydrogen, halogenic substituent, phenyl, phenoxy, contain at least 1 carbon atom straight chained alkyl, contain the branched alkyl of at least 1 carbon atom or contain the branched alkoxyl group of at least 1 carbon atom, R
1, R
2, R
3And R
4Structure identical or different;
Ar
4Structure produce by AB type monomer reaction, described AB type monomer contains carboxyl and ortho-aminophenol reactive group, Ar simultaneously
4Structural formula be following one or more:
2. the preparation method based on the polybenzoxazole that contains the phthalazine biphenyl structure dihydroxy diamine according to claim 1 is characterized in that adopting the method for solution polycondensation, and it is following specifically to prepare process:
(1) the reinforced stage; At first use rare gas element polyphosphoric acid or methylsulfonic acid to be carried out deoxidation at 50 ~ 200 ℃; Then with the di-carboxylic acid or derivatives thereof with contain the phthalazine biphenyl structure dihydroxy diamine; Be 4-[4-(4-amino-3-hydroxy oxygen base) phenyl)-2-(4-amino-3-hydroxy base) naphthyridine-1-ketone or derivatives thereof; Join together in polyphosphoric acid or the methylsulfonic acid, add the dihydroxy diamine or the AB type monomer of other structure simultaneously, reaction system is stirred; The ratio of the mole number sum of the mole number of above-mentioned dihydroxyl aromatic diamines or its hydrochloride and di-carboxylic acid monomer or derivatives thereof is between 0.98 ~ 1.02, and the monomer mass percentage composition is between 0.2% ~ 60% in this solution polymerization system;
(2) polymerization stage adopts progressively temperature-raising method, carries out the solution polycondensation reaction at 50 ~ 250 ℃, and the reaction times is 2 ~ 500 hours, and the temperature interval value that wherein heats up is controlled at 5 ~ 60 ℃, and at each temperature spot, duration of the reaction is between 0.1 ~ 100 hour;
(3) post-processing stages; After polyreaction finishes; Reaction soln directly or after adding thinner is poured in the precipitation agent; With the polymkeric substance coagulative precipitation, then in the repetitive scrubbing polymerisate remaining solvent or with in alkali or the weakly alkaline inorganic salt with polymerisate in remaining solvent and washing to neutral, obtain after the final drying based on the polybenzoxazole that contains the phthalazine biphenyl structure dihydroxy diamine.
3. the preparation method based on the polybenzoxazole that contains the phthalazine biphenyl structure dihydroxy diamine according to claim 2; Must contain 4-[4-(4-amino-3-hydroxy oxygen base) phenyl]-2-(4-amino-3-hydroxy base) naphthyridine-1-ketone or derivatives thereof in the polycondensation monomer that it is characterized in that being adopted, it has following molecular structure:
Wherein, R
1, R
2, R
3And R
4Be hydrogen, halogenic substituent, phenyl, phenoxy or the straight chain that contains at least 1 carbon atom or branched alkyl or alkoxyl group, R
1, R
2, R
3And R
4Structure identical or different.
4. the preparation method based on the polybenzoxazole that contains the phthalazine biphenyl structure dihydroxy diamine according to claim 2 is characterized in that the polymerization solvent that adopts is the polyphosphoric acid of concentration 80%～120% or the methanesulfonic acid solution that contains Vanadium Pentoxide in FLAKES.
5. the preparation method based on the polybenzoxazole that contains the phthalazine biphenyl structure dihydroxy diamine according to claim 2; It is characterized in that thinner is phosphoric acid, polyphosphoric acid, methylsulfonic acid or the vitriol oil, add-on is 0.1～200 times of polyphosphoric acid in the system.
6. the preparation method based on the polybenzoxazole that contains the phthalazine biphenyl structure dihydroxy diamine according to claim 2 is characterized in that precipitation agent is the aqueous solution, methyl alcohol, ethanol or the alcohol-water mixture of water, weak base or weak base salt.
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| CN2010102020105A CN101914204B (en) | 2010-06-17 | 2010-06-17 | Polybenzoxazole based on dihydroxy diamine containing phthalazinone structure and preparation method thereof |
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|---|---|---|---|
| CN2010102020105A CN101914204B (en) | 2010-06-17 | 2010-06-17 | Polybenzoxazole based on dihydroxy diamine containing phthalazinone structure and preparation method thereof |
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| Publication Number | Publication Date |
|---|---|
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| CN101914204B true CN101914204B (en) | 2012-09-12 |
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| CN102219903B (en) * | 2011-05-05 | 2013-06-19 | 大连理工大学 | Polybenzoxazole copolymer with phthalazinone terphenyl structure and preparation method thereof |
| CN102585225B (en) * | 2011-05-20 | 2014-10-22 | 大连理工大学 | Preparation method of diaza-naphthalenone-biphenyl-polybenzoxazole, monomer and polymer |
| CN106633033B (en) * | 2016-11-30 | 2018-10-16 | 大连理工大学 | Have micro-porous copolymers and preparation method thereof certainly containing diazanaphthalene terphenyl structure |
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| CN1644578A (en) * | 2004-12-18 | 2005-07-27 | 浙江工业大学 | AB type poly(p-phenyl) benzdioxan monomer and its preparation and use |
| CN1709942A (en) * | 2005-06-16 | 2005-12-21 | 上海交通大学 | Method for preparing polybenzoxazole |
| CN1948364A (en) * | 2006-09-15 | 2007-04-18 | 华东理工大学 | Benzooxazole kind block copolymer |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1644578A (en) * | 2004-12-18 | 2005-07-27 | 浙江工业大学 | AB type poly(p-phenyl) benzdioxan monomer and its preparation and use |
| CN1709942A (en) * | 2005-06-16 | 2005-12-21 | 上海交通大学 | Method for preparing polybenzoxazole |
| CN1948364A (en) * | 2006-09-15 | 2007-04-18 | 华东理工大学 | Benzooxazole kind block copolymer |
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