CN101914204A - 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 PDF

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CN101914204A
CN101914204A CN 201010202010 CN201010202010A CN101914204A CN 101914204 A CN101914204 A CN 101914204A CN 201010202010 CN201010202010 CN 201010202010 CN 201010202010 A CN201010202010 A CN 201010202010A CN 101914204 A CN101914204 A CN 101914204A
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polybenzoxazole
contain
acid
dihydroxy diamine
reaction
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CN101914204B (en
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蹇锡高
刘程
王锦艳
张守海
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Dalian University of Technology
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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

Based on polybenzoxazole that contains the phthalazine biphenyl structure dihydroxy diamine and preparation method thereof
Technical field
The invention belongs to the polymer science technical field, relate to high performance polymer material and preparation method thereof, specially refer to a class based on polybenzoxazole that contains the phthalazine biphenyl structure dihydroxy diamine and preparation method thereof.
Background technology
Polybenzoxazole is the special engineering plastics of a class 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 the matrix material reinforcing fiber materials that the eighties in 20th century, the U.S. developed for development space flight and aviation cause.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 height of molecular structure 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 harshness of PBO.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 processing units and processing condition harshness, a tooling cost high-technology difficult problem thus, simultaneously poorly solublely also cause the application of PBO to be restricted.
At 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, by 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, the polymerization single polymerization monomer that poly-benzene that relates to master thesis that people such as the Zhu Xiu tinkling of pieces of jade before publishes and two oxazoles adopt is 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 homemade 4-[4-(4-amino-3-hydroxy oxygen base) phenyl]-the dihydroxy diamine monomer of 2-(4-amino-3-hydroxy base) naphthyridine-1-ketone or derivatives thereof and di-carboxylic acid and derivative thereof are 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 as follows:
Figure GDA0000022423630000021
Wherein, R 1, R 2, R 4, R 4Be hydrogen, halogenic substituent, phenyl, phenoxy group, 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 selected 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:
Figure GDA0000022423630000022
Between the position, ortho position or contraposition;
Figure GDA0000022423630000023
1,4,1,5,1,6,2,6 or 2,7;
Figure GDA0000022423630000024
Figure GDA0000022423630000025
2,2 ', 3,3 ' or 4,4 ', wherein, X=-, O, S, CO, SO 2, CH 2, C (CH 3) 2Or C (CF 3) 2
Figure GDA0000022423630000026
1,4,1,5,2,6 or 2,7;
Figure GDA0000022423630000027
2,2 ', 3,3 ' or 4,4 ', wherein, Y=-, O, S, CO, SO 2, CH 2, C (CH 3) 2Or C (CF 3) 2
Figure GDA0000022423630000031
Ar 3Structure is that corresponding dihydroxyl aromatic diamines or the reaction of its hydrochloride produces, by the structures shape of selected dihydroxyl aromatic diamines or its hydrochloride, Ar 3Structural formula be following one or more:
Figure GDA0000022423630000032
Wherein, R 1, R 2, R 3, R 4Be hydrogen, halogenic substituent, phenyl, phenoxy group, 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:
Figure GDA0000022423630000041
Figure GDA0000022423630000042
Wherein X=-, O, S, CO, SO 2, CH 2, C (CH 3) 2Or C (CF 3) 2
Wherein, Y=-, O, S, CO, SO 2, CH 2, C (CH 3) 2Or C (CF 3) 2
Figure GDA0000022423630000044
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 concrete preparation process is as follows:
(1) the reinforced stage, at first use rare gas element (as 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, 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, the dihydroxy diamine or the AB type monomer (containing carboxyl and ortho-aminophenol reactive group simultaneously) that also can add 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 remaining solvent and be washed to neutrality in available bases or the weakly alkaline inorganic salt and in the polymerisate 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 derivative has following molecular structure:
Figure GDA0000022423630000051
Wherein, R 1, R 2, R 3And R 4Be hydrogen, halogenic substituent, phenyl, phenoxy group 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, tetrahydrofuran (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.By 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 embodiments of the 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 airway, 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 is slowly poured in the deionized water of 1L, agitating deionized water constantly in the process of pouring into, obtain strip solid russet at last, wash with water to 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 infrared spectra and spectral analysis of the nuclear magnetic resonance, and the result shows that this polymer architecture is consistent with project organization.
Embodiment 2:
In the dry 100mL there-necked flask that has stirring, reflux condensing tube, water trap and airway, 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, the 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 down at 100 ℃, reacted 10 hours down at 150 ℃, 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, obtain strip solid russet at last, wash with water to 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 naphthyridine ketone structure polybenzoxazole copolymer 1 .5349g, and yield is 98.3%.
Institute's synthetic polymkeric substance is carried out infrared spectra and spectral analysis of the nuclear magnetic resonance, and the result shows that this polymer architecture is consistent with project organization.

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 group, 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 selected 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:
Figure FDA0000022423620000012
Between the position, ortho position or contraposition;
Figure FDA0000022423620000013
1,4,1,5,1,6,2,6 or 2,7;
Figure FDA0000022423620000015
2,2 ', 3,3 ' or 4,4 ', wherein, X=-, O, S, CO, SO 2, CH 2, C (CH 3) 2Or C (CF 3) 2
1,4,1,5,2,6 or 2,7;
Figure FDA0000022423620000017
2,2 ', 3,3 ' or 4,4 ', wherein, Y=-, O, S, CO, SO 2, CH 2, C (CH 3) 2Or C (CF 3) 2
Figure FDA0000022423620000021
Ar 3Structure is that corresponding dihydroxyl aromatic diamines or the reaction of its hydrochloride produces, by the structures shape of selected dihydroxyl aromatic diamines or its hydrochloride, Ar 3Structural formula be following one or more:
Figure FDA0000022423620000022
Wherein, R 1, R 2, R 3, R 4Be hydrogen, halogenic substituent, phenyl, phenoxy group, 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:
Figure FDA0000022423620000031
Figure FDA0000022423620000032
Wherein X=-, O, S, CO, SO 2, CH 2, C (CH 3) 2Or C (CF 3) 2
Figure FDA0000022423620000033
Wherein, Y=-, O, S, CO, SO 2, CH 2, C (CH 3) 2Or C (CF 3) 2
Figure FDA0000022423620000034
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 concrete preparation process is as follows:
(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, or 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, remaining solvent or with solvent remaining in alkali or the weakly alkaline inorganic salt and in the polymerisate and be washed to neutrality in the repetitive scrubbing polymerisate obtains after the final drying based on the polybenzoxazole that contains the phthalazine biphenyl structure dihydroxy diamine then.
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 in the polycondensation monomer that it is characterized in that being adopted]-2-(4-amino-3-hydroxy base) naphthyridine-1-ketone or derivatives thereof, it has following molecular structure:
Figure FDA0000022423620000035
Wherein, R 1, R 2, R 3And R 4Be hydrogen, halogenic substituent, phenyl, phenoxy group 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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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102219903A (en) * 2011-05-05 2011-10-19 大连理工大学 Polybenzoxazole copolymer with phthalazinone terphenyl structure and preparation method thereof
CN102585225A (en) * 2011-05-20 2012-07-18 大连理工大学 Preparation method of diaza-naphthalenone-biphenyl-polybenzoxazole, monomer and polymer
CN106633033A (en) * 2016-11-30 2017-05-10 大连理工大学 Intrinsic microporous copolymer containing phthalazinone biphenyl structure and preparation method thereof

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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
WO2007052834A1 (en) * 2005-11-04 2007-05-10 Teijin Limited Polyazole fiber and method for producing same

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102219903A (en) * 2011-05-05 2011-10-19 大连理工大学 Polybenzoxazole copolymer with phthalazinone terphenyl structure and preparation method thereof
CN102219903B (en) * 2011-05-05 2013-06-19 大连理工大学 Polybenzoxazole copolymer with phthalazinone terphenyl structure and preparation method thereof
CN102585225A (en) * 2011-05-20 2012-07-18 大连理工大学 Preparation method of diaza-naphthalenone-biphenyl-polybenzoxazole, monomer and polymer
CN102585225B (en) * 2011-05-20 2014-10-22 大连理工大学 Preparation method of diaza-naphthalenone-biphenyl-polybenzoxazole, monomer and polymer
CN106633033A (en) * 2016-11-30 2017-05-10 大连理工大学 Intrinsic microporous copolymer containing phthalazinone biphenyl structure and preparation method thereof
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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