CN109761816A - One birdss of the same feather flock together (hydroxyl) to penylene benzo diimidazole-benzoxazoles PBIO liquid crystal copolymer and monomer, preparation and application - Google Patents
One birdss of the same feather flock together (hydroxyl) to penylene benzo diimidazole-benzoxazoles PBIO liquid crystal copolymer and monomer, preparation and application Download PDFInfo
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Abstract
The invention discloses one to birds of the same feather flock together (hydroxyl) to penylene benzo diimidazole-benzoxazoles PBIO liquid crystal copolymer and monomer, preparation and application.The present invention provides a kind of compound salt monomers (II), wherein k=0,1 or 2；Certain antioxygenic property is presented in the compound salt monomer itself.The compound salt monomer is made by BB type monomer hydrochloride (IV) and AA type monomer (V) through recombination reaction, economical and conveniently.(hydroxyl) is birdsed of the same feather flock together to penylene benzo diimidazole-benzoxazoles PBIO liquid crystal copolymer (I) the present invention provides one, wherein m/n=2.It is that raw material is made through copolycondensation that the PBIO liquid crystal copolymer, which is with AB type monomer (III) and compound salt monomer (II), does not generate corrosive gas in the process, polymerization speed is fast, and production capacity is high, easy to implement.The PBIO liquid crystal copolymer has good spinnability and heat resistance, and can be used for preparing has good fast light, heat-resisting and composite compression-resisting performance PBIO alloy fiber.
Description
Technical field
The present invention relates to one to birds of the same feather flock together (hydroxyl) to penylene benzo diimidazole-benzoxazoles PBIO liquid crystal copolymer and its list
Body, preparation and application.
Background technique
Polycondensation and spinning monopolization production (trade name uniquely are mixed by formula (1) by Toyobo, Japan from pbo fiber 1998
Zylon) and technology blockage is carried out to China and product prohibits pin.American-European and Japan is sold primarily as military supplies, price is high
Up to 3000 yuan/kg.
Since the source monomer 4,6- diamino resorcin hydrochlorate (DARH) is difficult, formula (1) process takes off HCl time > 30h
And semi-continuous polymerization is complicated for operation, industrialization process is extremely difficult.Although Toyobo company also uses and complex salt is first made
TDH prepares pbo fiber from polycondensation again, is not required to de- HCl and waits when the patented technology for obtaining higher molecular weight than polymerization, sees formula
(2):
But due to
The oxidation ratio DARH of complex salt TDH faster makes industrialization operation more difficult, causes in industrialization transformation from polycondensation route quilt
Toyobo voluntarily gives up.
The present inventor innovatively has found 4- (5- amino -6- hydroxy benzo oxazole -2- base) ammonium benzoate (ABAA) conduct
The superiority of AB type PBO monomer, is efficiently applied to the manufacture of pbo fiber by formula (3), has showed particular advantages.
And it is applied to the O of preparation structure protection by formula (4) and (HABA) copolycondensation of 3- hydroxy-4-aminobenzoic acid3-
PBO tencel when 0.44:1 (641.6 DEG C of heat resisting temperature when 1.7:1,669.8 DEG C of heat resisting temperature).
Obtained the patents of invention such as the U.S., Japan, China authorization (US 6046827 B2 of 9725424 B2, JP,
CN102977045B, CN102942533B), and key intermediate patented product is synthesized by resorcinol for starting material
The authorization of the Chinese invention patents such as ANRHCl and ABA forms from basic organic chemical industry raw material, produces intermediate, new monomer
And the intellectual property system that series of products monopolization produces in manufacture PBO fiber industrial chain,
But there are still following two large problems to need to break through:
1) process of manufacturing ABAA is complicated, production capacity is low, expands using limitation problem due to valence height
Cause AB type monomer price higher because of the numerous length of preparation process, complex process, the width that the pbo fiber of preparation can make a price reduction
Degree is little, it is difficult to reach 1800 yuan/kg and following: can only use for defence and military special occasions, in particular for that need to guarantee PBO
The copolycondensation composite fibre of chain link integrality prepare it is more particularly suitable, be not able to satisfy industry with civil field high performance-price ratio expand apply
Urgent need.
2) compound, fast light caused by PBO molecular structure itself and compression performance shortcoming and Upgrade Problem
Due to lacking polar group and molecule interchain in PBO molecular structure without any effect key and the non-ordinary light of fiber surface
The problems such as sliding, lead to that its is compound, be compressed axially, ultraviolet-resistant performance is poor, significantly limits pbo fiber directly advanced
The application of field of compound material, there is an urgent need to without surface modification treatment, research especially in terms of molecular structure modification and
Support.
Therefore, for problem 2) improve interfacial bond property between fibrous material and resin matrix, enhance PBO macromolecular chain
Between interaction, improve fiber axial compression strength and ultraviolet resistance stability, have become pbo fiber as enhancing
Material may be directly applied to the key in advanced composite material field.Although having in recent years using 2,3,5,6- 4-aminopyridine hydrochloric acid
Salt (TAPH) replaces AA type monomer DARH and 2,5- dihydric para-phthalic acid (DHTA) that BB type monomer TPA is replaced to carry out mixed contracting
Complex salt DT is first made with DHTA and synthesizes the fast light good polymer P IPD of composite compression-resisting from polycondensation again and processes by poly- or TAPH
At the research (Polymer.1998,39 (24): 5981-5986 of fiber M5；US7683122B2,2010), see formula (6)；And it is logical
It crosses the 3rd 4th kind of monomer of addition and is modified the various reports such as research (CN101358385B) formula (7) of PBO copolymer and fiber.
However, the M5 of formula (6) preparation, although because the effect of strong molecule interchain hydrogen bond can get the anti-of tetra- times of nearly PBO or more
Compressive Strength and excellent composite performance also show that preferable uv-resistance energy, but since its price is high (for 1.8 times of PBO),
In addition anti-tensile mechanical property, 50 limit oxygen index and 530~550 DEG C of heat resisting temperature etc. be defeated by PBO.Substantial M5 should claim
The PBI (polyparaphenylene's benzo diimidazole) that dihydroxy and pyridine are modified.
The present inventor has used 1,2,4,5- tetramino benzene hydrochloride (TAB4HCl) to replace 2,3,5,6- 4-aminopyridine
Hydrochloride (TAPH) and DHTA copolycondensation are prepared with M5 fiber same hydrogen bond network, theoretically composite compression-resisting and light fastness
Same PDBI fiber (CN 102532546 B, 2014.07.09) is shown in formula (8),
Although PDBI price is significantly down to the 80% of pbo fiber, its initial decomposition temperature is 470 DEG C, weightless
Temperature when 10% is also only 508.3 DEG C；And the spinnability of liquid crystal stoste is bad, and it is larger to be processed into fiber difficulty, and liquid crystal
Stoste caking property extra-heavy (including with stainless steel equipment), cleaning kettle operation are very difficult.Further, since formula (8) uses TAB hydrochloric acid
Salt and DHTA mix the preparation method of polycondensation, have a large amount of HCl gases to release in the process, and the requirement of industrial device material is very harsh,
There is an urgent need to be replaced with the monomer of no HCl to facilitate industrialized implementation again.Meanwhile PBI because the phenylene of contraposition it is rigidly very big,
Be unable to spinning, resin can only be made into, the weightless temperature of the PBI resin thermogravimetric analysis 5% is 528 DEG C, 10% it is weightless when temperature
It is 560 DEG C.
Therefore, the substantial modification of molecule is carried out, to PBI, PDBI etc. to improve its spinnability, obtain with good resistance to
The Fresh fats of the modification PBI of hot, light resistance, crushing resistance and composite performance and offer are suitable for the preparation method of industrialized implementation
Have become new research direction.
Summary of the invention
The primary purpose of the present invention is that providing a kind of inexpensive, polymer grade compound salt monomer, its own presents certain
Antioxygenic property, can be used for preparing PBI quasi polymer.
A second object of the present invention is to provide a kind of methods of economic, convenient compound salt monomer for preparing polymer grade.
Third object of the present invention is to provide a kind of poly- (hydroxyls) to penylene benzo diimidazole-benzoxazoles PBIO liquid crystal
Copolymer, to improve spinnability.
Fourth object of the present invention is to provide a kind of poly- (hydroxyl) to penylene benzo diimidazole-benzoxazoles PBIO liquid crystal
The preparation method of copolymer does not generate any corrosive gas in preparation process, and polymerization speed is fast, and production capacity is high, easy to implement.
Fifth object of the present invention is to provide poly- (hydroxyls) to penylene benzo diimidazole-benzoxazoles PBIO Liquid crystal copolyesters
Object has the application in good fast light and heat resistance PBIO alloy fiber in preparation.
The purpose of the invention is achieved by the following technical solution:
In a first aspect, the present invention provides a kind of compound salt monomer, shown in structure such as formula (II):
In formula (II), k=0,1 or 2.
Specifically, the compound salt monomer is 1,2,4,5- tetramino benzene complex salts (TATAB) of terephthalic acid (TPA), 2-
The 1 of hydroxyterephthalic acid, 2,4,5- tetramino benzene complex salts (HTAB), the 1 of 2,5-Dihydroxyterephthalic acid, 2,4,5- tetra-
Aminobenzene complex salt (DHTAB), the structure of three are as follows:
Second aspect, the present invention provides a kind of preparation method of compound salt monomer shown in formula (II), the systems
Preparation Method are as follows: shown in BB type monomer hydrochloride shown in formula (IV) (TABH 1,2,4,5- tetramino benzene hydrochloride) and formula (V)
AA type monomer (i.e. terephthalic acid (TPA) (HA), 2- dihydric para-phthalic acid (HTA) or 2,5-Dihydroxyterephthalic acid
(DHTA)) recombination reaction occurs in the alkaline aqueous solution of deoxidation, generates compound salt monomer shown in formula (II)；
In formula (V), k=0,1 or 2.
Preferably, the preparation method is specifically implemented in accordance with the following steps: first that AA type monomer shown in formula (V) is molten
Solution is in the deoxidation aqueous solution containing inorganic base substance, then by the deoxygenated water of BB type monomer hydrochloride (TABH) shown in formula (IV)
Solution is added under nitrogen protection, it is reacted at salt out, deoxidation water washing, vacuum drying are made multiple shown in formula (II) respectively
Close salt monomer.
As a further preference, the inorganic base substance is NaOH, KOH, Na2CO3Or K2CO3One of or
A variety of mixing, and be preferred with the alkaline matter containing Na.
As a further preference, the substance of the BB type monomer hydrochloride and AA type monomer, inorganic base substance
Amount is than being 1.0:0.9~1.0:1.96~2.04.
As a further preference, reaction described in step (1) carries out at 50-80 DEG C.
The third aspect, the present invention provides one birds of the same feather flock together (hydroxyl) it is total to penylene benzo diimidazole-benzoxazoles PBIO liquid crystal
Polymers, shown in structure such as formula (I), intrinsic viscosity 6.5-15dl/g；
In formula (I), k=0,1 or 2；M, n respectively represents the number of corresponding chain element, and m/n=2.
Preferably, poly- (hydroxyl) is with formula to penylene benzo diimidazole-benzoxazoles PBIO liquid crystal copolymer
(III) compound salt monomer shown in AB type monomer shown in and formula (II) is raw material, is prepared in PPA medium through copolycondensation
It obtains；
Preferably, poly- (hydroxyl) is to penylene benzo diimidazole-benzoxazoles PBIO liquid crystal copolymer structure
It is as follows:
As a further preference, the polyparaphenylene's benzo diimidazole-benzoxazoles is PBIO4、H-PBIO4、DH-
PBIO4Or DH-PBIO3；It is still more preferably PBIO4、H-PBIO4Or DH-PBIO4, advantage, which is embodied in, preferably may be used
The property spun, heat resisting temperature and cost advantage.
Fourth aspect, it is total to penylene benzo diimidazole-benzoxazoles PBIO liquid crystal that the present invention provides a kind of poly- (hydroxyls)
The preparation method of polymers, comprising:
(1) BB type monomer hydrochloride shown in formula (IV) (TABH, i.e., 1,2,4,5- tetramino benzene hydrochlorides) and formula (V) institute
AA type monomer (i.e. terephthalic acid (TPA) (HA), 2- dihydric para-phthalic acid (HTA) or the 2,5-Dihydroxyterephthalic acid shown
(DHTA)) recombination reaction occurs in the alkaline aqueous solution of deoxidation, generates compound salt monomer shown in formula (II)；
In formula (V), k=0,1 or 2；
(2) using compound salt monomer shown in AB type monomer shown in formula (III) and formula (II) as raw material, in PPA medium
Poly- (hydroxyl) is prepared to penylene benzo diimidazole-benzoxazoles PBIO liquid crystal copolymer through temperature programming copolycondensation
Liquid crystal stoste；
About step (1), second aspect has done specific discussion, and details are not described herein.
The AB type monomer, including isomer 3,4-AHBA (AHBA) and 3- hydroxyl -4- amino
Benzoic acid (HABA),
Preferably, the step (2) is according to being implemented as follows:
1) quantitative P is sequentially added in glass polymerization reaction column2O5To in polyphosphoric acids (PPA), make P2O5Basic dissolution
(those skilled in the art can promote to dissolve using modes such as stirring, heating according to actual needs), is made into PPA polymerisation medium；Institute
It states in PPA polymerisation medium, P2O5Mass concentration be 85~88%；
2) lead to N2Compound salt monomer shown in AB type monomer shown in formula (III) and formula (II) is slowly sequentially added under protection
(or being directly added into after mixing) forms the polymerization reaction system that total mass concentration containing copolymer is 15~17% (calculated values),
It finishes and is to slowly warm up to 150-180 DEG C from room temperature with 0.1~2h under the mixing speed of 350-400r/min, occur entire body at this time
Fluorescence, then in 160-190 DEG C of insulation reaction to there is filiform, and continue stirring to revolving speed and drop to 320r/min or less Shi Weiju
Closing reaction terminates, and stops stirring up to poly- (hydroxyl) to penylene benzo diimidazole-benzoxazoles PBIO liquid crystal copolymer PPA liquid crystal
Stoste.
5th aspect, the present invention provides poly- (hydroxyls) to penylene benzo diimidazole-benzoxazoles PBIO liquid crystal copolymer
Preparing the application in PBIO alloy fiber.
Specifically, the present invention provides poly- (hydroxyls) exists to penylene benzo diimidazole-benzoxazoles PBIO liquid crystal copolymer
Prepare the application in PBIO monofilament composite fibre, the application are as follows: control polybenzoxazoles-is to penylene benzo diimidazole PBIO
The material temperature of the PPA liquid crystal stoste of liquid crystal copolymer is 130~150 DEG C, continuously pulls out (pumping) from liquid crystal stoste and goes out monofilament, extraction
Shredded dried bean curd solidifies into the water, again after hot water repeatedly washs, and it is mono- that vacuum drying (preferably 110 DEG C vacuum drying 3-5h) obtains PBIO
Silk composite fibre.
Poly- (hydroxyl) of the present invention can also be used for doing to penylene benzo diimidazole-benzoxazoles PBIO liquid crystal copolymer
Squirt the standby PBIO multifilament composite fibre of spinning.
The present invention is relative to the molecular structure of existing fiber and having the beneficial effect that for technology
(1) compound salt monomer DHTAB, HTAB and TATAB proposed by the present invention are polymer grade monomers, at low cost, and itself
Certain antioxygenic property is presented, wherein DHTAB, HTAB are since the presence of hydroxyl is with good antioxygenic property, i.e.,
Make the TATAB for being free from hydroxyl, can also save two weeks, quality is basically unchanged.It can be used as monomer and is used to prepare PBI Type of Collective
Object.
(2) preparation method of compound salt monomer provided by the invention, can the obtained polymer grade monomer of economic and convenience.
(3) poly- (hydroxyl) prepared by the present invention to penylene benzo diimidazole-benzoxazoles PBIO liquid crystal copolymer especially
PBIO4, the spinnability of PBI is efficiently solved on the basis of keeping good sunproof and polymer enters asking for liquid crystal state
Topic, improves heat resistance.
(4) H-PBIO and DH-PBIO prepared by the present invention be on the basis of being presented good compound, fast light, compressive property,
There is better spinnability than HPBI and PDBI, and significantly improve heat resistance (heat resisting temperature increase rate is at 40-50 DEG C),
And solves PDBI bonding stainless steel equipment ability by force without easy-operating industrialization obstacle.Especially H-PBIO4Or DH-
PBIO4, there is better spinnability, heat resistance and cost advantage.
(5) poly- (hydroxyl) provided by the invention is to the preparation of penylene benzo diimidazole-benzoxazoles PBIO liquid crystal copolymer
Method, polymerization process without remove HCl, without plus antioxidant, polymerization time is short, fluorescence and liquid crystal occur early, and monomer concentration can
Up to 18-20%, equipment is conventional, production capacity is high, and spinning solution rheological property is excellent, and the spinnability of presentation has been better than PBO, convenient
Implement industrialization.
(6) poly- (hydroxyl) provided by the invention to penylene benzo diimidazole-benzoxazoles PBIO liquid crystal copolymer, in PPA
Good spinnability is presented in solvent, the concentration of liquid crystal polymer may be up to 16%, and higher than the 13% of PBO, they can be without taking
It directly uses out, the preparation applied to corresponding high-performance fiber.Liquid crystal stoste can continuous hot candied effect be by hand in embodiment
Embody the feasibility that fiber is made in further dry-jet wet-spinning.
Detailed description of the invention
Fig. 1-a, 1-b, 1-c are the infrared light for the compound salt monomer DHTAB that in the embodiment of the present invention 1 prepared by (1) respectively
The infrared spectroscopy of compound salt monomer TATAB prepared by spectrogram, the infrared spectrogram of the compound salt monomer HTAB of (2) preparation, (3)
Figure.
Fig. 2-a, 2-b are DH-PBIO prepared by the embodiment of the present invention 2 respectively4The infrared spectroscopy and thermogravimetric of monfil
Analysis chart (545 DEG C).
Fig. 3 is the infrared spectroscopy of PBO-PDBI (1:1) monfil prepared by comparing embodiment 1 of the invention.
Fig. 4 is O prepared by comparing embodiment 2 of the invention4The infrared spectrogram of-PDBI (1:1) monfil.
Fig. 5-a, 5-b are DH-PBIO prepared by the embodiment of the present invention 33The infrared spectroscopy of monfil and thermogravimetric analysis
Scheme (517 DEG C).
Fig. 6-a, 6-b are H-PBIO prepared by the embodiment of the present invention 44The infrared spectroscopy and thermogravimetric analysis figure of monfil
(533℃)。
Fig. 7-a, 7-b are PBIO prepared by the embodiment of the present invention 54The infrared spectroscopy and thermogravimetric analysis figure of monfil
(548℃)。
Specific embodiment
Further detailed description is done to the present invention below with reference to embodiment, embodiments of the present invention are not limited thereto.
The preparation of the compound salt monomer of 1 Formula II of embodiment
(1) preparation of compound salt monomer DHTAB (the 1,2,4,5- tetramino benzene of 2,5- dihydric para-phthalic acid)
200g deoxygenated water, 10.697g Na are sequentially added in glass reactor2CO3(0.1009mol) and 9.98g
(0.0504mol) 2,5-Dihydroxyterephthalic acid (DHTA), stirring be warming up to 70 DEG C it is to be dissolved for light brown clear solution when,
Under nitrogen protection, it is added by 1,2,4,5- tetramino benzene hydrochloride (TABH) of 14.34g (0.0505mol), finishes 70-80 DEG C
It is slowly cooled to room temperature, filters after stirring 15min, wet cake is stood with 30mL deoxygenated water and washed, and is crossed after being filtered dry, and 70 DEG C of vacuum are dry
Dry 1,2,4,5- tetramino benzene complex salt (DHTAB) 15.43g (0.0459mol) for obtaining 2,5-Dihydroxyterephthalic acid, with
The yield 91.09% of DHTA meter.FT-IR (KBr) is shown in attached drawing 1-a.
(2) preparation of compound salt monomer HTAB (the 1,2,4,5- tetramino benzene of 2- hydroxyterephthalic acid)
200g deoxygenated water, 10.697g Na are sequentially added in glass reactor2CO3(0.1009mol) and 9.18g
(0.0504mol) 2- hydroxyterephthalic acid (HTA), stirring be warming up to 70 DEG C it is to be dissolved for light brown clear solution when, in nitrogen
Under gas shielded, it is added by 1,2,4,5- tetramino benzene hydrochloride (TABH) of 14.34g (0.0505mol), finishes 70-80 DEG C of stirring
It is slowly cooled to room temperature, filters after 15min, wet cake is stood with 30mL deoxygenated water and washed, and is crossed after being filtered dry, 70 DEG C are dried in vacuo
The 1 of 2- hydroxyterephthalic acid, 2,4,5- tetramino benzene complex salt (HTAB) 11.54g (0.0360mol), the yield in terms of HTA
71.42%.FT-IR (KBr) is shown in attached drawing 1-b.
(3) preparation of compound salt monomer TATAB (the 1,2,4,5- tetramino benzene of terephthalic acid (TPA))
200g deoxygenated water, 10.697g Na are sequentially added in glass reactor2CO3(0.1009mol) and 8.384g
(0.0504mol) terephthalic acid (TPA) (TA), stirring be warming up to 70 DEG C it is to be dissolved for light brown clear solution when, in nitrogen protection
Under, it is added by 1,2,4,5- tetramino benzene hydrochloride (TABH) of 14.34g (0.0505mol), after finishing 70-80 DEG C of stirring 15min
It is slowly cooled to room temperature, filters, wet cake is stood with 30mL deoxygenated water and washed, and is crossed after being filtered dry, 70 DEG C are dried in vacuo to benzene two
The 1 of formic acid, 2,4,5- tetramino benzene complex salt (TATAB) 12.80g (0.0421mol), the yield 83.35% in terms of TA.FT-
IR (KBr) is shown in attached drawing 1-c.
2 DH-PBIO of embodiment4(poly- 2,5- dihydroxy is to penylene benzo diimidazole -2,5- benzoxazoles) and its monofilament are fine
Dimension
P is sequentially added in glass polymerization reaction column2O5Mass concentration be 85.3% polyphosphoric acids (PPA) 18.0g and
P2O53.40g, opens auger and the revolving speed stirring 30min for the 100 DEG C of control 350r/min that heat up waits for P2O5After reaction dissolution,
Logical N2Lower 3min is protected slowly to sequentially add DHTAB 2.69g and AHBA2.45g (mol ratio 1:2, mass ratio 0.523:0.477),
It finishes to be stirred down with 20min and is slowly increased to yellow-green fluorescence occur at 152 DEG C, in 152-155 DEG C of insulation reaction 10min to golden yellow
Dichroic liquid crystal is Filamentous, then in 156-165 DEG C of stirring polyase 13 0min, until bronze-colored filiform be decreased obviously to revolving speed to 200r/min and
Terminate when following for polymerization reaction, stops stirring.Up to DH-PBIO4Binary liquid crystal copolymer (O4PBO-co-PDBI liquid crystal) is poly-
Close spinning solution.120-130 DEG C of material temperature of control, the long filament of (pumping) silk to 2.5m or more is pulled out using tweezers from liquid crystal stoste, is taken out
Shredded dried bean curd out solidifies into the water, then after hot water washs, and the modified PBIO of dihydroxy is obtained after 110 DEG C of vacuum drying 3h4List
Silk composite fibre (sepia).Measuring intrinsic viscosity is 15.18dl/g, and the IR of nascent monfil is shown in Fig. 2-a, heat resisting temperature
(temperature when fiber weightlessness 5%, similarly hereinafter) is 545 DEG C (see Fig. 2-b).The good spinning property of liquid crystal stoste.
In view of the ion bond structure of complex salt DHTAB monomer, can be expressed by TAB and DHTA, polymerization reaction should substantially be expressed
Are as follows:
It can be seen that DH-PBIO4Middle m=2n, each chain link is by following four kinds of segment random combines (1DHTAB+2AHBA)
It wherein a) combines and b) each chain link of combination only forms a molecule interchain hydrogen bond, and c) combining each chain link can shape
At two molecule interchain hydrogen bonds, performance exhibit more than PDBI contribution should have level.
1 PBO-PDBI of comparing embodiment (polyparaphenylene's benzo dioxazole -2,5- dihydroxy is to penylene benzo diimidazole) and
Its monfil
P is sequentially added in glass polymerization reaction column2O5Mass concentration be 85.3% polyphosphoric acids (PPA) 18.0g and
P2O53.40g, opens auger and the revolving speed stirring 30min for the 100 DEG C of control 350r/min that heat up waits for P2O5After reaction dissolution,
Logical N2Protect lower 3min slowly sequentially add DHTAB 2.69g and ABAA 2.30g (mol ratio 1:1, mass ratio 0.539:
0.461) it, finishes to be stirred down with 20min and is slowly increased to yellow-green fluorescence occur at 152 DEG C, in 152-155 DEG C of insulation reaction
10min is Filamentous to golden yellow dichroic liquid crystal, then in 156-165 DEG C of stirring polyase 13 0min, until bronze-colored filiform to revolving speed be decreased obviously to
200r/min and it is following when terminate for polymerization reaction, stop stirring.Up to PBO-PDBI binary liquid crystal copolymer (PBO-co-PDBI,
Modified chain link n/ (n+m)=50%) polymerizable mesogenic spinning solution.120-130 DEG C of material temperature of control, using tweezers from liquid crystal stoste
In pull out the long filament of (pumping) silk to 2.5m or more, the shredded dried bean curd of extraction solidifies into the water, then after hot water washs, and 110 DEG C of vacuum are dry
The monofilament composite fibre (sepia) of 50%PBO modified PDBI (PBO-PDBI) is obtained after dry 3h.Measuring intrinsic viscosity is
14.62dl/g, the IR of nascent monfil are shown in that Fig. 3, heat resisting temperature are 518 DEG C.The good spinning property of liquid crystal stoste.
The each chain link of m=n is by following three segment random combine (1DHTAB+1ABAA) in comparison PBO-PDBI
In all combinations, the feature of each chain link of m=n also only one molecule interchain hydrogen bond, less than using embodiment
2DH-PBIO4Molecule interchain is greater than 1 hydrogen bond number, therefore compares O at least in compressive property4DH- made from the modified PDBI of PBO-
PBIO4Want poor, heat resisting temperature is than embodiment 2DH-PBIO4Low 27 DEG C.Use DH-PBIO4It is PDBI more modified than with PBO, at least anti-
More there is adjection advantage in pressure and heat resistance.
In addition economically, due to replacing 2 cheap molecule AHBA, raw material monomer cost using 1 expensive molecule ABAA
Rise 1.5 times or more, therefore PBO-PDBI economy is much worse than DH-PBIO4。
2 50% monosubstituted oxazolyl of comparing embodiment is modified PDBI
P is sequentially added in glass polymerization reaction column2O5Mass concentration be 85.3% polyphosphoric acids (PPA) 18.0g and
P2O53.40g, opens auger and the revolving speed stirring 30min for the 100 DEG C of control 350r/min that heat up waits for P2O5After reaction dissolution,
Logical N2It protects lower 3min slowly to sequentially add DHTAB 3.598g and AHBA 1.639g (mol ratio 1:1), finishes and stirred with 20min
Under be slowly increased to yellow-green fluorescence occur at 152 DEG C, it is Filamentous to golden yellow dichroic liquid crystal in 152-155 DEG C of insulation reaction 10min, then
156-165 DEG C of stirring polyase 13 0min, until it is bronze-colored it is Filamentous when revolving speed be decreased obviously to 200r/min and it is following when for polymerization reaction
Terminate, stops stirring.Up to O4- PDBI binary liquid crystal copolymer (O4It is PBO-co-PDBI, modified chain link m/ (n+m)=50%) liquid
Crystalline substance polymerization spinning solution.120-130 DEG C of material temperature of control, the length of (pumping) silk to 2.5m or more is pulled out using tweezers from liquid crystal stoste
Silk, the shredded dried bean curd of extraction solidify into the water, then after hot water washs, and it is single imidazole modified that 50% is obtained after 110 DEG C of vacuum drying 3h
PDBI(O4- PDBI) monofilament composite fibre (sepia).Measuring intrinsic viscosity is 12.71dl/g, monfil of coming into being
IR is shown in that Fig. 4, heat resisting temperature are 520 DEG C (than embodiment 2DH-PBIO4Low 25 DEG C).The good spinning property of liquid crystal stoste.
3 DH-PBIO of embodiment3(poly- 2,5- dihydroxy is to penylene benzo diimidazole -2,6- benzoxazoles) and its monofilament are fine
Dimension
P is sequentially added in glass polymerization reaction column2O5Mass concentration be 85.3% polyphosphoric acids (PPA) 18.0g and
P2O53.40g, opens auger and the revolving speed stirring 30min for the 100 DEG C of control 350r/min that heat up waits for P2O5After reaction dissolution,
Logical N2Lower 3min is protected slowly to sequentially add DHTAB 2.69g and HABA2.45g (mol ratio 1:2, mass ratio 0.523:0.477),
It finishes to be stirred down with 20min and is slowly increased to yellow-green fluorescence occur at 152 DEG C, in 152-155 DEG C of insulation reaction 10min to golden yellow
Dichroic liquid crystal is Filamentous, then in 156-165 DEG C of stirring polyase 13 0min, until bronze-colored filiform be decreased obviously to revolving speed to 200r/min and
Terminate when following for polymerization reaction, stops stirring.Up to DH-PBIO3Binary liquid crystal copolymer (O3PBO-co-PDBI liquid crystal) is poly-
Close spinning solution.120-130 DEG C of material temperature of control, the long filament of (pumping) silk to 2.5m or more is pulled out using tweezers from liquid crystal stoste, is taken out
Shredded dried bean curd out solidifies into the water, then after hot water washs, and the modified PBIO of dihydroxy is obtained after 110 DEG C of vacuum drying 3h3List
Silk composite fibre (sepia).Measuring intrinsic viscosity is 6.86dl/g, and the IR of nascent monfil is shown in Fig. 5-a, heat resisting temperature
For 517 DEG C (see Fig. 5-b).The spinnability of liquid crystal stoste is fine.
4 H-PBIO of embodiment4(poly- hydroxyl is to penylene benzo diimidazole -2,5- benzoxazoles) and its monfil
P is sequentially added in glass polymerization reaction column2O5Mass concentration be 85.3% polyphosphoric acids (PPA) 18.0g and
P2O53.40g, opens auger and the revolving speed stirring 30min for the 100 DEG C of control 350r/min that heat up waits for P2O5After reaction dissolution,
Logical N2Lower 3min is protected slowly to sequentially add HTAB 2.58g and AHBA2.45g (mol ratio 1:2, mass ratio 0.513:0.487),
It finishes to be stirred down with 40min and is slowly increased to yellow-green fluorescence occur at 165 DEG C, in 165-172 DEG C of insulation reaction 20min to golden yellow
Dichroic liquid crystal is Filamentous, then in 172-175 DEG C of stirring polyase 13 0min, until bronze-colored filiform be decreased obviously to revolving speed to 320r/min and
Terminate when following for polymerization reaction, stops stirring.Up to H-PBIO4Binary liquid crystal copolymer (O4PBO-co-PHBI polymerizable mesogenic)
Spinning solution (polymer concentration 14.63%).120-130 DEG C of material temperature of control, pulls out (pumping) silk extremely using tweezers from liquid crystal stoste
The shredded dried bean curd of the long filament of 2.5m or more, extraction solidifies into the water, then after hot water washs, and obtains after 110 DEG C of vacuum drying 3h single
Hydroxyl modification PBIO4Monofilament composite fibre (sepia).Measuring intrinsic viscosity is 8.70dl/g, the IR for monfil of coming into being
See that Fig. 6-a, heat resisting temperature are 533 DEG C (see Fig. 6-b).The good spinning property of liquid crystal stoste.
5 PBIO of embodiment4(polyparaphenylene benzo diimidazole -2,5- benzoxazoles) and its monfil
P is sequentially added in glass polymerization reaction column2O5Mass concentration be 85.3% polyphosphoric acids (PPA) 18.0g and
P2O53.40g, opens auger and the revolving speed stirring 30min for the 100 DEG C of control 350r/min that heat up waits for P2O5After reaction dissolution,
Logical N2Lower 3min is protected slowly to sequentially add TATAB 2.449g and AHBA2.45g (mol ratio 1:2, mass ratio 0.50:0.50),
It finishes to be stirred down with 60min and is slowly increased to occur lilac fluorescence at 172 DEG C, in 172-178 DEG C of insulation reaction 20min to bronze
Dichroic liquid crystal is Filamentous, when revolving speed be decreased obviously to 320r/min and it is following when terminate for polymerization reaction, stop stirring.Up to PBIO4Two
First liquid crystal copolymer (O4PBO-co-PBI liquid crystal polymer spinning solution (polymer concentration 14.21%)).Control material temperature
120-130 DEG C, the long filament of (pumping) silk to 2.5m or more is pulled out from liquid crystal stoste using tweezers, the shredded dried bean curd of extraction coagulates into the water
Gu obtaining PBIO after 110 DEG C of vacuum drying 3h then after hot water washs4Monofilament composite fibre (sepia).It is viscous to measure characteristic
Number is 12.06dl/g, and the IR of nascent monfil is shown in that Fig. 7-a, heat resisting temperature are 548 DEG C (see Fig. 7-b).Liquid crystal stoste can
The property spun is good.
Listed above is only several specific examples of the invention.It, can be with it is clear that the invention is not restricted to above example
There are many deformations.All changes that those skilled in the art directly can export or associate from present disclosure
Shape is considered as protection scope of the present invention.
Claims (10)
1. a kind of compound salt monomer, shown in structure such as formula (II):
In formula (II), k=0,1 or 2.
2. a kind of preparation method of compound salt monomer shown in formula as described in claim 1 (II), the preparation method is that: formula
(IV) BB type monomer hydrochloride shown in occurs in the alkaline aqueous solution of deoxidation compound anti-with AA type monomer shown in formula (V)
It answers, generates compound salt monomer shown in formula (II)；
In formula (V), k=0,1 or 2.
3. preparation method as claimed in claim 2, it is characterised in that: the preparation method is specifically real in accordance with the following steps
It applies: first AA type monomer shown in formula (V) being dissolved in the deoxidation aqueous solution containing inorganic base substance, then will be shown in formula (IV)
The deoxidation aqueous solution of BB type monomer hydrochloride is added under nitrogen protection, it is reacted at salt out, deoxidation water washing, vacuum drying
Compound salt monomer shown in formula (II) is made respectively.
4. preparation method as claimed in claim 2 or claim 3, it is characterised in that: the inorganic base substance be NaOH, KOH,
Na2CO3Or K2CO3One of or a variety of mixing, and be preferred with the alkaline matter containing Na；The BB type monomer hydrochloric acid
The mass ratio of the material of salt and AA type monomer, inorganic base substance is 1.0:0.9~1.0:1.96~2.04；Described in step (1)
Reaction carries out at 50-80 DEG C.
5. birdsing of the same feather flock together (hydroxyl) to penylene benzo diimidazole-benzoxazoles PBIO liquid crystal copolymer, structure such as formula (I) is shown,
Its intrinsic viscosity is 6.5-15dl/g；
In formula (I), k=0,1 or 2；M, n respectively represents the number of corresponding chain element, and m/n=2.
6. poly- (hydroxyl) as claimed in claim 5 is to penylene benzo diimidazole-benzoxazoles PBIO liquid crystal copolymer, feature
Be: poly- (hydroxyl) is with AB shown in formula (III) to penylene benzo diimidazole-benzoxazoles PBIO liquid crystal copolymer
Compound salt monomer shown in type monomer and formula (II) is raw material, is prepared in PPA medium through copolycondensation；
7. if poly- (hydroxyl) described in claim 5 or 6 is to penylene benzo diimidazole-benzoxazoles PBIO liquid crystal copolymer,
Be characterized in that: poly- (hydroxyl) is as follows to penylene benzo diimidazole-benzoxazoles PBIO liquid crystal copolymer structure:
8. a kind of poly- (hydroxyl) as claimed in claim 5 is to penylene benzo diimidazole-benzoxazoles PBIO liquid crystal copolymer
Preparation method, comprising:
(1) BB type monomer hydrochloride shown in formula (IV) is sent out in the alkaline aqueous solution of deoxidation with AA type monomer shown in formula (V)
Raw recombination reaction, generates compound salt monomer shown in formula (II)；
In formula (V), k=0,1 or 2；
(2) using compound salt monomer shown in AB type monomer shown in formula (III) and formula (II) as raw material, through journey in PPA medium
Poly- (hydroxyl) is prepared to penylene benzo diimidazole-benzoxazoles PBIO liquid crystal copolymer liquid crystal in sequence heating copolycondensation
Stoste；
9. preparation method as claimed in claim 8, it is characterised in that: the step (2) is according to being implemented as follows:
1) quantitative P is sequentially added in glass polymerization reaction column2O5Into polyphosphoric acids, make P2O5Basic dissolution, it is poly- to be made into PPA
Close medium；In the PPA polymerisation medium, P2O5Mass concentration be 85~88%；
2) lead to N2Compound salt monomer shown in AB type monomer shown in formula (III) and formula (II) is slowly sequentially added under protection or is incited somebody to action
The two is directly added into after mixing, is formed the polymerization reaction system that total mass concentration containing copolymer is 15~17%, is finished
It is to slowly warm up to 150-180 DEG C from room temperature with 0.1~2h under the mixing speed of 350-400r/min, occurs entire body fluorescence at this time,
Again in 160-190 DEG C of insulation reaction to there is filiform, and continue anti-for polymerization when stirring drops to 320r/min or less to revolving speed
It should terminate, stop stirring up to poly- (hydroxyl) to penylene benzo diimidazole-benzoxazoles PBIO liquid crystal copolymer PPA mesogen
Liquid.
10. poly- (hydroxyl) as claimed in claim 7 is preparing penylene benzo diimidazole-benzoxazoles PBIO liquid crystal copolymer
Application in PBIO alloy fiber.
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| WO2021098136A1 (en) * | 2019-11-19 | 2021-05-27 | 金宁人 | Class of multi-mixed composite salt monomers having anti-oxidation stability and polybenzodiazole liquid crystal polymers, and preparations and applications thereof |
| CN114805099A (en) * | 2022-05-11 | 2022-07-29 | 浙江工业大学 | Monohydroxy modified trans-PBO composite monomer and synthesis method thereof |
| CN115626990A (en) * | 2022-09-20 | 2023-01-20 | 浙江理工大学 | Synthesis and polymerization method of AB type polybenzoxazole monomer containing benzimidazole structure |
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