CN108384007A - One birdss of the same feather flock together hydroxyl to phenylene first Benzo-dioxazole polymer, monomer and its preparation and application - Google Patents
One birdss of the same feather flock together hydroxyl to phenylene first Benzo-dioxazole polymer, monomer and its preparation and application Download PDFInfo
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- CN108384007A CN108384007A CN201810245057.6A CN201810245057A CN108384007A CN 108384007 A CN108384007 A CN 108384007A CN 201810245057 A CN201810245057 A CN 201810245057A CN 108384007 A CN108384007 A CN 108384007A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/22—Polybenzoxazoles
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C215/00—Compounds containing amino and hydroxy groups bound to the same carbon skeleton
- C07C215/74—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton
- C07C215/76—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton of the same non-condensed six-membered aromatic ring
- C07C215/80—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton of the same non-condensed six-membered aromatic ring containing at least two amino groups bound to the carbon skeleton
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- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/76—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring
- C07C69/84—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring of monocyclic hydroxy carboxylic acids, the hydroxy groups and the carboxyl groups of which are bound to carbon atoms of a six-membered aromatic ring
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- D—TEXTILES; PAPER
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- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
- D01F6/74—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polycondensates of cyclic compounds, e.g. polyimides, polybenzimidazoles
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Abstract
The invention discloses one to birds of the same feather flock together hydroxyl to phenylene first Benzo-dioxazole polymer, monomer and its preparation and application.The principal polymeric and its principal monomer being related to are respectively the poly- hydroxyl 1 ' of the hydroxyl random distribution as shown in formula (I), 4 ' phenylene, 8 methyl 2,6 Benzo-dioxazoles (ran HMPBO), with the preparation and its application of 2 methyl 4,6 diamino resorcin complex salt (HTMD) monomer of the hydroxyterephthalic acid as shown in formula (II).Hydroxyl is introduced on the phenylene of PBO strands by the present invention, and the light fastness of pbo fiber can be improved；Methyl is introduced on the phenyl ring of Benzo-dioxazole base of PBO strands, can the heat cross-linking of fiber reaction in, by two strands with it is several be better than hydrogen bond-CH2- covalent bond forms HMPBO C-structure shown in formula (V), and the resistance to compression effect of fiber axial direction is presented.It can be efficiently applied to advanced composite material and advanced configuration material.
Description
Technical field
The present invention relates to Benzo-dioxazole Type of Collective objects, and in particular to a hydroxyl of birdsing of the same feather flock together is poly- to phenylene first Benzo-dioxazole
Close object, monomer and its preparation and application, including the compound salt monomer of polymer and key monomers and intermediate and its preparation.
Background technology
Pbo fiber, with high-strength and high-modulus, heat-proof combustion-resistant, light soft shock resistance be it is famous, belong to organic fiber most.
However, lacking the problems such as polar group and molecule interchain are without any effect key due to existing in PBO molecular structures, cause its compound
The deficiency with axial compression resistance performance is bonded, composite material is not directly applicable.Especially pbo fiber surface is smooth, surface is lived
Property it is low and be in extremely strong chemical inertness, it is very poor with the bonding interface of resin matrix, seriously constrained it in high-performance fiber
Enhance the application in composite material.Obtain the application of field of compound material, then it must be before use, fiber be first carried out chemistry
Or the surface modification treatment of physics；But most of modification technology causes fibre damage to be hindered, original mechanical properties decrease, finally
Keep price more expensive and impracticable, there is an urgent need to can avoid first being made modified again after fiber the PBO of performance decline is caused to change thus
Property technology, research and support especially in terms of molecular structure modification.
Although using 2,5-Dihydroxyterephthalic acid (2,5-DHTA) to replace BB type monomer TPA in recent years, PBO is carried out
The substantial modification of molecule prepares 2,5-DHPBO and fiber (CN 1594398,2005-03-16) is shown in formula (1)；Or simultaneously with 2,3,
5,6- 4-aminopyridines hydrochloride (TAP3HCl) replaces AA type monomer 4,6- diamino resorcin hydrochlorates (DARH) and 2,
5-DHTA copolycondensations or be first made TAP-DHTA complex salts again from polycondensation come synthesize the good polymer M5 of compoiste adhering and add
Work at fiber research (Polymer.1998,39 (24):5981-5986；US7683122B2- Duponts, 2010-03-23)
See formula (2)；And carry out more monomer copolymerizables by adding the 3rd 4th kind of monomer：Such as exist
Hydroxyl sulfoacid group is introduced on PBO rigid macromolecule chains, it is fine to be modified PBO with preparations such as the polarity that increases pbo fiber
Tie up various reports such as (CN101358385A, 2009-02-04).But the former is 25DH-PBO, although solving surface polarity and compound
Adhesion problem and uvioresistant enhancing, but since its shortage forms the theoretical foundation of molecule interchain hydrogen bond, not to axial compression resistance contribution
Greatly, and hot property (heat decomposition temperature is only 522~543 DEG C in nitrogen) is really also worse than M5 fibers much worse than PBO；Although M5 is because strong
The effect of molecule interchain hydrogen bond can get the compression strength of tetra- times of nearly PBO or more and excellent composite performance, and show preferably
Uv-resistance energy, but since its price is high (for 1.8 times of PBO), and anti-tensile mechanical property, 50 limit oxygen index and
530~550 DEG C of heat decomposition temperature etc. is defeated by PBO, and synthesis cost performance is also far below PBO.The present inventor has used 1,2,
4,5- tetraminos benzene hydrochloride (TAB4HCl) replaces 2,3,5,6- 4-aminopyridines hydrochloride (TAP3HCl) and 2,5-
DHTA copolycondensations are prepared with the same hydrogen bond network of M5 fibers theoretically composite compression-resisting PDBI fibers identical with light fastness
(CN102532546B, 2014.07.09) is shown in formula (3)
Although making M5 prices be greatly lowered, being even also lower by 30% or more than PBO price, since its hot property declines soon
As low as 480 DEG C, the tensile strength of fiber is not also high.Therefore, to the research and development of very-high performance material, for realization axial compression resistance and again
The promotion for closing bonding and light fastness, it is real using being carried out on the PBO molecular basis with excellent stretching and heat resistance
No matter the molecular modification of matter is in industry and economically preferential selection.
Invention content
The primary purpose of the present invention is that the shortcomings that overcoming existing PBO, M5 molecular structure, technology of preparing and its economy
Deficiency provides one and birdss of the same feather flock together hydroxyl to the molecular structure and polymer of phenylene first Benzo-dioxazole, including polymer complex salt
Monomer, key monomers.
Another object of the present invention is to provide above-mentioned poly- hydroxyls to the preparation side of phenylene first Benzo-dioxazole polymer
Method, including polymer compound salt monomer, key monomers.
Application it is still another object of the present invention to provide above-mentioned poly- hydroxyl to phenylene first Benzo-dioxazole polymer.
The purpose of the invention is achieved by the following technical solution：
One birdss of the same feather flock together hydroxyl to phenylene first Benzo-dioxazole polymer, and structural formula is that the hydroxyl as shown in formula (I) randomly divides
The poly- hydroxyl -1 ' of cloth, 4 '-phenylene -8- methyl -2,6- Benzo-dioxazoles (ran-HMPBO)：
Wherein, n indicates the degree of polymerization, n preferably 80~160.
A kind of poly- hydroxyl -1 ', the compound salt monomer of 4 '-phenylene -8- methyl -2,6- Benzo-dioxazoles, structure
Formula is the 2- methyl -4,6- diamino resorcins complex salts (HTMD) of the hydroxyterephthalic acid as shown in formula (II)：
Further, the present invention provides the preparation method of compound salt monomer HTMD shown in the formula (II)：Shown in formula (III)
AA type key monomers 2- methyl -4,6- diamino resorcin hydrochlorates (MDARH) and BB type monomer 2- hydroxyl terephthaldehydes
Sour (HTA) recombination reaction occurs in alkaline aqueous solution, generates compound salt monomer shown in formula (II)：
Further, key monomers recommendation shown in formula (III) is prepared as follows：It can be by 2- methyl -4,6- dinitros
Double reduction methods of base resorcinol (MDNR), Hydrogenation is standby in alcoholic solvent；It also can be by the MDNR first selective reductions in alcoholic solvent
After key intermediate 2- methyl -4- amino-6-nitro resorcin hydrochlorides (MANRH) shown in formula (IV), then water-soluble
It is prepared by the method for fractional steps of agent hydrogenating reduction.
Poly- hydroxyl -1,4- phenylene -2,6- Benzo-dioxazoles (ran-HMPBO) polymer can shown in the formula (I)
Pass through：1) the 2- methyl -4,6- diamino resorcins complex salts (HTMD) of hydroxyterephthalic acid shown in formula (II) from
2) polycondensation the preparation method uses AA types monomer shown in formula (III) to mix polycondensation the preparation method with BB type monomer 2- hydroxyterephthalic acids
It prepares.
In this way, the poly- hydroxyl presses following wound to the random polymer of phenylene first Benzo-dioxazole (ran-HMPBO)
It is prepared by new technology route and method：
Innovation synthetic route of the poly- hydroxyl to the monomer of phenylene first Benzo-dioxazole, intermediate and its polymer
Further, 2- methyl -4,6- diamino isophthalic two of the formula (II) complex salt monomer hydroxyl terephthalic acid (TPA)
The preparation method of phenol specifically comprises the following steps：First BB type monomer 2- hydroxyterephthalic acids are dissolved in containing inorganic alkaline object
In the deoxidation aqueous solution of matter, then the deoxidation aqueous solution of AA types key monomers (MDARH) shown in formula (III) added under nitrogen protection
Enter, it is reacted at salt out, deoxidation water washing, vacuum drying method be made formula (II) shown in hydroxyterephthalic acid 2-
Methyl -4,6- diamino resorcin complex salts HTMD；Wherein, the inorganic base substance is NaOH, KOH, Na2CO3Or
K2CO3In one or more mixing, and be preferred with the alkali of Na metals；AA types monomer 4,6- diaminos shown in the formula (III)
The amount of the substance of base -2- methyl resorcinols hydrochloride, BB type monomer hydroxyl terephthalic acid (TPA)s and inorganic base substance is than preferred
It is 1.0:0.9~1.0:1.96~2.04.
Further, poly- hydroxyl-Isosorbide-5-Nitrae shown in formula (I)-phenylene -2,6- Benzo-dioxazole (ran-HMPBO) polymer
Preparation method in, the complex salt includes the following steps from polycondensation the preparation method：By hydroxyl terephthaldehyde shown in formula (II)
The complex salt HTMD of the 2- methyl -4,6- diamino resorcins of acid is dissolved in containing P2O5Polyphosphoric acids in, obtain mixed solution,
90~100 DEG C of stirrings are warming up under nitrogen protection, temperature programming obtains poly- hydroxyl -1 ', 4 '-sub- benzene to 180~200 DEG C from polycondensation
The polyphosphoric acids fiber spinning from crystalline state stoste of base -8- methyl -2,6- Benzo-dioxazole (ran-HMPBO), then continuous hot candied by hand, warp
It solidifies, wash, being drying to obtain poly- hydroxyl -1 ' shown in formula (I), 4 '-phenylene -8- methyl -2,6- Benzo-dioxazoles (ran-
HMPBO) monfil；Wherein, P in the polyphosphoric acids2O5Mass concentration is preferably 85~87%；Hydroxyl shown in formula (II)
Mass concentrations of the complex salt HTMD of the 2- methyl -4,6- diamino resorcins of base terephthalic acid (TPA) in mixed solution is preferred
It is 15~25%；The temperature programming is specially：120℃1h、150℃1h、180℃1h.
Further, poly- hydroxyl-Isosorbide-5-Nitrae shown in formula (I)-phenylene -2,6- Benzo-dioxazole (ran-HMPBO) polymer
Preparation method in, the AA types and two monomer of BB types mix polycondensation the preparation method and include the following steps：It will be crucial shown in formula (III)
Monomer 2- methyl -4,6- diamino resorcin hydrochlorates (MDARH) are dissolved in containing P2O5Polyphosphoric acids, mixed liquor is obtained, through true
The poly phosphoric acid solution that 2- methyl -4,6-diaminoresorcinol (MDAR) is obtained after sky removing hydrogen chloride, adds BB type monomers
2- hydroxyterephthalic acids are warming up under nitrogen protection after 90~100 DEG C of stirrings take off hydrogen chloride, temperature programming to 180~200
The polyphosphoric acids fiber spinning from crystalline state that DEG C mixed polycondensation obtains poly- hydroxyl -1,4- phenylene -2,6- Benzo-dioxazoles (ran-HMPBO) is former
Liquid, it is then continuous hot candied by hand, through solidification, washes, is drying to obtain poly- hydroxyl -1 ' shown in formula (I), 4 '-phenylene -8- first
Base -2,6- Benzo-dioxazoles (ran-HMPBO) monfil；Wherein, P in the polyphosphoric acids2O5Mass concentration is preferably 85
~87%；Key monomers 2- methyl -4,6- diamino resorcin hydrochlorates shown in formula (III) are with BB types monomer hydroxyl to benzene two
The amount of the substance of formic acid is than preferably 1~1.02:1；Key monomers 2- methyl -4,6- diamino resorcins shown in formula (III)
Hydrochloride and the hydroxyterephthalic acid total mass concentration in mixed liquor are preferably 15~25%；The vacuum takes off HCl temperature
It is 100 DEG C, 3h；The temperature programming is specially：120℃1h、150℃1h、180℃2h.
Further, key monomers 2- methyl -4,6-diaminoresorcinol hydrochloric acid shown in heretofore described formula (III)
Salt (MDARH) is preferably prepared by method as follows：(a) it is with 2- methyl -4,6- dinitroresorcinols (MDNR)
Raw material, the Fe in alcoholic solvent2+Under/C catalysis reflux, hydrazine hydrate selective reduction, heat filters out waste active carbon, after hydrochloric acid acidification is added
It is concentrated in vacuo and refined, obtains 4- amino -6- nitro -2- methyl resorcinols hydrochlorides (MANRH) shown in formula (IV)；(b)
4- amino -6- nitro -2- methyl resorcinol hydrochlorides shown in formula (IV) are dissolved in water, after being used in combination NaOH to neutralize, with Pd/C
For catalyst, low pressure (1MPa or less) catalytic hydrogenation, filters out hydrochloric precipitation MDARH crude products and crystal's preparation method is made
Key monomers 2- methyl shown in formula (III) -4,6-diaminoresorcinol hydrochloride (MDARH) product is used for compound salt monomer
The preparation of (HTMD salt).MDARH products are refined through second again, obtain the polymer grade monomer 2- first that purity is up to 99.8% or more
Base -4,6-diaminoresorcinol hydrochloride is directly used in mixed polycondensation as AA type monomers and prepares ran-HMPBO or complex salt list
The preparation of body (HTMD salt).Wherein, the dinitroresorcinols of 2- methyl -4,6- described in step (a) (MDNR) and hydrazine hydrate
The amount of substance is than preferably 1.0：2.2~2.4；The alcoholic solvent is preferably ethyl alcohol；The Fe2+/ C catalyst is
FeSO4·7H2O and activated carbon, 2- methyl -4,6- dinitroresorcinol (MDNR) and FeSO4·7H2O, activated carbon
Mass ratio is preferably 1.0：0.05~0.15：0.2~0.4；2- methyl -4- amino -6- shown in formula described in step (b) (IV)
The amount of the substance of nitro resorcin hydrochloride and NaOH is than preferably 1.0:1.0~1.2；The Pd/C catalyst preferably loads
The Pd/C of amount 5%, 2- methyl -4- amino-6-nitro resorcin hydrochlorides shown in the formula (IV) and 5%Pd/C (giving money as a gift)
Mass ratio be preferably 1.0:0.010~0.016；Crystal's preparation method is specially：First plus water stirring and dissolving, activated carbon are de-
Color, filtrate add hydrochloric acid acid out, filtering, washing；The amount ratio preferably 1 of the MDARH crude products and the substance of HCl in hydrochloric acid:2.0
~3.0, the mass ratio of the MDARH crude products and water and activated carbon is preferably 1:5.0~8.0:0.02~0.06.
The present invention also provides the poly- hydroxyls to prepare hydroxyl first to phenylene first Benzo-dioxazole polymer (HMPBO)
Base is modified the application in pbo fiber.It is specifically carried out in polymerizeing device for spinning, selects multi-holed jet respectively, into line (I) nothing
Advise the preparation of the modification PBO multifilament fibers of polymer.The polymerization device for spinning is mainly reacted by stirring polymeric kettle, twin-screw
Extruder, filament spinning component, coagulating tank, rinsing bowl, drying machine, receive silk machine composition.
Further, the present invention also provides described one hydroxyls of birdsing of the same feather flock together to exist to phenylene Benzo-dioxazole polymer (HMPBO)
Application in the preparation of high-performance multifilament fiber.The application process includes the following steps：Using polymerization device for spinning, with P2O5Content
85% or more polyphosphoric acids is medium, prepares the reaction solution an of fixed pattern (II) compound salt monomer (HTMD) mass concentration, program
Heating polymerize to obtain polymer liquid crystal spinning solution, and directly carries out dry-jet wet-spinning, and the poly- hydroxyl -1 ' of atactic polymer is made, and 4 '-is sub-
Phenyl -8- methyl -2,6- Benzo-dioxazoles (ran-HMPBO) fiber；P in the medium polyphosphoric acids2O5Content be 85%~
87.0%, the monomer mass concentration is 15~25%；Described program heating is polymerized to first 120 DEG C of 2h, 150 in polymeric kettle
DEG C 2h, 180 DEG C of 2h prepolymerizations obtain the liquid crystal stoste of polymer, by by the twin-screw reactive extrursion of polymer material indentation 25/48
Machine, 175 DEG C of temperature, 190 DEG C, 200 DEG C, 180 DEG C, residence time 30min polymerize again after atactic polymer fiber spinning from crystalline state it is former
Liquid；The dry-jet wet-spinning be spray in 170 DEG C of high pressures, stretched in 60 DEG C of air baths, phosphate aqueous solution wet spinning solidification, washing,
Drying process operates, and the poly- hydroxyl -1 ' of atactic polymer is made, and 4 '-phenylene -8- methyl -2,6- Benzo-dioxazoles high-performance are fine
Dimension；Wherein, phosphoric acid initial content is 20~30% in phosphate aqueous solution, and draw ratio is 15~25.
The high-performance multifilament fiber prepared to phenylene first Benzo-dioxazole polymer using the poly- hydroxyl of the present invention, anti-tensile are strong
Degree reaches 3.0GPa or more.
The present invention is in the respective advantage and disadvantage of comprehensive PBO, M5 fiber, with the compoiste adhering performance of reinforcing fiber, axial compression resistance
Performance and photodegradation performance are target, and the application expanded in advanced composite Yu structural material field is direction, by molecule
The theory of condition and photic resonance tautomeric structure that intrachain hydrogen bond is formed, the molecular structure of PBO (HPBO) is modified using monohydroxy
Design is obtaining HPBO invention patent mandates (CN104119534B, 2017.07.14), the obtained HPBO of pilot scale
Multifilament fiber, heat resistance temperature improve back 600 DEG C or more, have been enter on the basis of the quasi- industrialization stage, emphatically needle
To HPBO molecules interchain still without chemistry key connection, the axial compression resistance still problem without improvement, then activity is introduced on the main chain of HPBO
Group, to form connection by acting on molecule interchain.To introduce methyl-CH on Benzo-dioxazole ring3To be preferred, methyl
With the hydrogen atom in upper chain phenyl ring elimination reaction can be occurred for the hydrogen atom on methyl in the reaction of the heat cross-linking of fiber to realize
Crosslinking generate cross-linking type structure (HMPBO-C) polymer fiber, two molecule interchains with it is several be better than hydrogen bond-CH2- altogether
Valence link is formed, and strand axially strong compressive effect is presented.
The present invention is relative to the molecular structure of existing fiber and having the beneficial effect that for technology：
The poly- hydroxyl of the present invention (includes the ordered polymer and nothing of hydroxyl distribution to phenylene first Benzo-dioxazole polymer
Advise polymer), it is introduced on PBO strands using the substituted hydroxy on terephthalic acid (TPA) ring, improves the surface pole of fiber first
Property；Wherein hydroxyl OH forms the hexatomic ring that molecule intrachain hydrogen bond is constituted, and is the theoretical foundation that photic tautomeric structure is presented, can be improved
The ultraviolet-resistant performance of fiber, it is good with thermosetting resin base bonding property to have, and may replace the numerous surface of pbo fiber and is modified skill
Art, it is intended to which the modification purpose for reaching compoiste adhering and photodegradation while avoiding fibrous mechanical property from declining can further be sent out
Exhibition is reinforcing material for making various polymer-based fibers composite materials.
(1) the ran-HMPBO molecular structures of a hydroxyl and DHPBO the and M5 fiber phases for introducing two hydroxyls are only introduced
Than having the feature of low density, stretching and heat resistance close to pbo fiber.It is carried out from polycondensation system using compound salt monomer HTMD
Atactic polymer (ran-HMPBO) and its monfil that monohydroxy methyl is modified PBO are obtained, it is far high that heat decomposition temperature has been presented
In 60 DEG C of DHPBO and PIPD (M5) or more；The introducing of hydroxyl makes polymer and the equal polarized group of fiber, can avoid that fiber is made
It carries out the defects of surface modification causes performance to decline again afterwards, has the characteristics that be directly used in advanced composite material first；Hydroxyl
Introducing can form with the double bond N on rigid Zhi Lian oxazole heterocycles in strand after the hexatomic ring of O-H ... N hydrogen bonds again, and there are light
It causes resonance enantiotropy at the structure of O ... H-N hydrogen bonds in strand, is the foundation of photodegradation.It is that advanced composite material enhancing is fine
The important selection of dimension.
(2) the compound salt monomers of HTMD is used to carry out atactic polymer ran-HMPBO and its monfil made from the polycondensation,
Its intrinsic viscosity has been higher than 20dl/g, and the tensile strength of fiber is expected to more than PIPD, in addition polymerization process is without removing HCl, nothing
Antioxidant need to be added, polymerization time is short, monomer concentration may be up to 18% or more, and equipment is conventional, production capacity is high, and spinning solution rheological characteristic
Can be excellent, the spinnability of presentation has been better than PBO, and with the feature that can facilitate implementation industrialization.By acting on molecule interchain
Connection is formed, wherein the methyl-CH introduced3, the hydrogen atom on methyl can be made in the heat cross-linking reaction of 500 DEG C of fiber or more
Removing H occurs with the hydrogen atom in upper chain phenyl ring2After reaction realize crosslinking, by two strands with it is several be better than hydrogen bond-
CH2- covalent bond forms the HMPBO-C structures of cross-linking type, and strong resistance to compression effect is presented.
The structure of HMPBO-C and arrangement
(3) the compound salt monomers of HTMD for atactic polymer and fiber are proposed, using key monomers 2- methyl -4,6- bis-
Complex forming salt prepares HTMD to aminoresorcinol hydrochloride (MDARH) in and after removal HCl with hydroxyterephthalic acid (HTA)
Method, certain antioxygenic property is presented in the HTMD itself of preparation.Wherein key monomers MDARH can be by 2- methyl -4,6- two
In organic solvent prepared by directly double reduction methods for nitro-resorcinol (MDNR), can also be prepared by step-by-step reduction method：That is MDNR is first
Selective reduction is key intermediate 2- methyl -4- amino-6-nitro resorcin hydrochlorides (MANRH), then is passed through in aqueous solvent
Route is innovated in the reduction of the characteristic of the obtained 2- methyl -4,6- diamino resorcin hydrochlorates (MDARH) of Ji safety.With raw material
MDNR is easy to get, preparation process is conventional, and total metal ion can conveniently be made less than 100ppm and without adding SnCl2Equal antioxidant
Polymer grade monomer.
(4) atactic polymer that monohydroxy is modified PBO, characteristic is made in mixed polycondensation provided by the invention and self-condensation reaction
Viscosity number is more than 15dl/g, and good spinnability is presented in PPA solvents, premised on it can be processed into fiber, liquid crystal polymer
Concentration may be up to 18%, is far above the 13% of PBO, can be used as polymer liquid crystal stoste, be directly entered dry-jet wet-spinning and post-processing
The preparation and application for carrying out ran-HMPBO fibers, characteristic high, easy to operate with production capacity, that implementation industrialized production can be facilitated.
Method and application through the invention was, it can be achieved that can not only be greatly lowered production cost but also improve fiber ultraviolet resistance
And the modification purpose of compoiste adhering performance, two molecule interchains have by the heat cross-linked type HMPBO-C fibers being covalently keyed
Strong axial compression resistance ability, may replace PBO and M5 fiber types preferentially to become the second generation fiber of PBO (is mark with the HMPBO that abridges
Will), it is directly used in advanced composite and structural material field without being surface-treated, on the basis further optimized
On, implement the merchandized handling of second generation PBO high-performance fibers HMPBO, meets the high-technology fields such as space flight, aviation and national defence
The active demand of the update of composite material.
Description of the drawings
Fig. 1 is the infrared spectrogram of key intermediate MANRH prepared by the embodiment of the present invention 1.
Fig. 2 is the mass spectrogram of key intermediate MANRH prepared by the embodiment of the present invention 1.
Fig. 3 is key intermediate MANRH prepared by the embodiment of the present invention 11H-NMR。
Fig. 4 is the infrared spectrogram of key monomers MDARH prepared by the embodiment of the present invention 3.
Fig. 5 is the mass spectrum of key monomers MDARH prepared by the embodiment of the present invention 3.
Fig. 6 is the infrared spectrogram of complex salt HTMD prepared by the embodiment of the present invention 4.
Fig. 7 is complex salt HTMD prepared by the embodiment of the present invention 41H-NMR schemes
Fig. 8 is the infrared spectrogram of ran-HMPBO monfil prepared by the embodiment of the present invention 4.
Fig. 9 is thermogravimetric analysis figure (18.62dl/g, the temperature of ran-HMPBO monfil prepared by the embodiment of the present invention 4
556 DEG C of degree).
Figure 10 is thermogravimetric analysis figure (13.16dl/g, the temperature of ran-HMPBO monfil prepared by the embodiment of the present invention 5
540 DEG C of degree).
Specific implementation mode
With reference to specific embodiment, the present invention is described further, but protection scope of the present invention is not limited in
This.
The synthesis of -6 nitro resorcin hydrochloride (MANRH) of 1 key intermediate 2- methyl -4- amino of embodiment
(MDNR selective reductions the preparation method)
In 250mL four-hole boiling flasks, 10.00g MDNR (0.0467mol), 3.00g activated carbons, 1.00g are sequentially added
FeSO4·7H295% ethyl alcohol of O and 100mL, stirring are warming up to micro- reflux；6.32g is added dropwise by constant pressure funnel
The mixed liquor of (0.107mol) 85% hydrazine hydrate and 95% ethyl alcohol of 20mL, 60min are added dropwise, and continue under micro- reflux state anti-
After answering 20min, 50 DEG C of heat filterings are cooled to, 36.0% concentrated hydrochloric acids of 15.0g are added in ethanol filtrate after removing waste active carbon
(0.148mol), reduced under vacuum obtains 2- methyl -4- amino-6-nitro resorcin hydrochlorides to doing after stirring 30min
(MANRH) crude product 9.60g is in dark brown, yield 93.18% (HPLC purity 70.05%).MANRH crude products are dilute with the 7% of 5 times
Hydrochloric acid is refined with activated carbon decolorizing recrystallization, obtains the yellow crystal 6.97g of key intermediate MANRH highly finished product
(0.0315mol), purity 98.71%, it is 72.56% to refine yield.Total recovery 67.62% in terms of MDNR.FT-IR(KBr)
See that attached drawing 1, ESI-MS are shown in attached drawing 2,1H-NMR is shown in attached drawing 3.
1 absorption peak attribution analysis of attached drawing：In 3500~2500cm-1There is wide and scattered absorption peak in section, belongs to hydroxyl and ammonia
Caused by the association of base；1615cm-1Place is Ar-NH2The absorption of vibrations of intensity；1345cm-1Place is Ar-NO2Stretching vibration.It is attached
Fig. 2 is it is found that be MANR, molecular ion peak 183 [M] after MANRH one molecule hydrochloric acid of removing-With its theoretical relative molecular mass
184.1512 correspondence match.It was found from δ/ppm of attached drawing 3：Integrated value 2.98 (3H for belonging to phenyl ring methyl) at 2.04,7.93
Locate integrated value 1.00 (belonging to 5- hydrogen 1H on phenyl ring), shows to be consistent with product MANR structural formulas.
Equally, the HCl in MANRH molecules is measured by chemical titration analysis, the content for measuring Cl is
15.78%, the formula IV molecular structure of a molecule HCl, molecular formula C are combined with 1 molecule MANR7H8N2O4HCl, molecular weight are
220.6121, Cl theoretical content 16.07%, therefore the chemical content of quantitative analysis MANRH is 98.20%.
Comprehensive IR characteristic absorption peaks ownership, ESI-MS and1The qualitative analysis of H-NMR spectrum, is finally accurately determined as formula
(IV) MANRH (- 6 nitro resorcin hydrochloride of 2- methyl -4- amino).
Embodiment 2MANRH, which is restored, prepares key monomers MDARH
41.32g (0.187mol) 2- methyl -4- amino -6- nitro-resorcinol salt is added in four mouthfuls of glass reactors
Hydrochlorate (MANRH) and 300g water are added dropwise after stirred under nitrogen atmosphere dissolving by 80g water and 9.17g 96%NaOH (0.22mol)
The dilute alkaline soln being made into, neutralization reaction 10min, then fast transfer is to autoclave pressure, and 1.0g 5%Pd/C catalyst is added and (contains
Admittedly measuring 50%), after confining pressure kettle, N is used successively2Displaced air 4 times uses H2Replace N2After 2 times, 35~45 DEG C are controlled, low
It is depressed in the hydrogen of 1MPa, stirring catalytic hydrogenation 3h is that reaction terminates；In N2Filtrate is fast after filtering out catalyst under protection and stirring
Speed is added to 1.6g SnCl22H2In the acidic aqueous solution that O is made into 36% hydrochloric acid of 50g (0.494mol) and 50g water, 2- first
Base -4,6-diaminoresorcinol hydrochloride (MDARH) is constantly precipitated, thick through filtering, 60 DEG C of vacuum drying 5h, acquisition MDARH
Product 39.13g (0.172mol), crude yield 92.00% (purity 98.46%).
MDARH crude products use crystal's preparation method：Use the activity of 0.03 times of the deionized water and crude product quality of 6 times of crude product quality
Charcoal goes dissolving and adsorption bleaching removal of impurities processing respectively, filters out the hydrochloric acid acid out crystallization of filtrate 2 equivalent of crude product of useless charcoal, and filtering is true
The dry 5h of sky obtains the process for purification of MDARH, highly finished product (purity 99.52% refines yield 87.16%) is obtained, in terms of MANRH
Total recovery 80.19% is directly used in the preparation of the compound salt monomers of HTMD as AA monomers.
The synthesis of 3 key monomers 2- methyl -4,6- diamino resorcin hydrochlorates (MDARH) of embodiment
(MDNR restores the preparation method entirely)
1) synthesis of MDARH
In 2L autoclaves, 32.1g MDNR (0.15mol) are added, 10%Pd/C 1.0g (containing solid 35%), 600ml is just
Propyl alcohol closes autoclave；It is passed through N2Air 3 times in kettle are replaced, H is passed through2Replace N22 times, and it is 0.9- to maintain hydrogen pressure in kettle
1.0MPa；It heats and stirs, when system temperature rises to 45 DEG C or so, kettle interior suction H2Speed is accelerated, and with exothermic phenomenon；When
When temperature rises to 70 DEG C, control system hydrogen presses 1.0-1.1MPa, hydrogenation reaction 80min at 70 DEG C；Again in 75 DEG C of pressure, 1.2Mpa
Lower continuation hydrogenation reaction 5.5h；Stop hydrogenation reaction, when being cooled to 25-30 DEG C under stirring, opens autoclave, reaction solution is poured into
In the 105ml concentrated hydrochloric acids of the stannous chloride containing 2.10g, a large amount of solids are precipitated in system；10 DEG C are cooled to by ice water, is stood
30min, filtering, drying obtain gray solid 30.05g, crude yield 88.27%.
2) MDARH is refined
Above-mentioned 30.05g crude products, 130ml concentrated hydrochloric acids, 2.60g stannous chlorides and 130ml are added in 500ml four-hole boiling flasks
Deionized water is warming up to reflux 5min；Dead catalyst is filtered out while hot, 1.30g activated carbons are added in filtrate, is warming up to reflux 5min
After decoloration, heat filter again；0.45g stannous chlorides and 45ml concentrated hydrochloric acids are added in filtrate, stirring is cooled to 0 DEG C, stands
A large amount of white crystals are precipitated in system in 30min；It is dried in vacuo 5h at 70 DEG C after filtering, the white highly finished product of MDARH are made
22.50g, purity 98.68%, it is 74.88% to refine yield, the total recovery 66.09% in terms of MDNR.FT-IR (KBr) is shown in attached
Fig. 4, EI-MS are shown in attached drawing 5.
Attached drawing 4, in 2940.1cm-1There are very wide very strong-OH absorption peaks at place, since hydroxyl and amino generate association, makes-OH
Stretching vibration absworption peak to lower wave number direction move, compared with the IR of MDNR, attached drawing 4 is in 1345cm-1The fragrant nitre at place
Base vibration absorption peak disappears, in 1623.1cm-1Generate amino in-plane bending vibration absorption peak.Illustrate nitro by Restore All；
From attached drawing 5 it is found that after two molecule HCl of MDARH removings, molecular ion peak 154.2, with its theoretical relative molecular mass phase
Together.It is confirmed as the structure of MDAR.Meanwhile the HCl in MDARH molecules is measured by chemical titration analysis, measure Cl's
Content is 30.82%, and formula (III) molecular structure of two molecule HCl, molecular formula C are combined with 1 molecule MDAR7H10N2O22HCl, point
The theoretical content 31.22% that son amount is 227.09, Cl, therefore the chemical content of quantitative analysis MDARH is 98.72%.
Qualitative and HCl the quantitative analysis of comprehensive IR characteristic absorption peaks ownership, EI-MS, is ultimately determined to formula (III)
MDARH (2- methyl -4,6- diamino resorcins dihydrochloride).It can be directly used for preparing complex salt as key monomers
Monomer (HTMD)；And be directly used in mixed polycondensation as AA type monomers and prepare ran-HMPBO, then it needs to MDARH primary purifications product again
It carries out second to refine, its quality is made to reach the rank (99.8% or more purity) of polymer grade monomer, secondary refining yield 90%
More than.Total receipts of polymer grade monomer 2- methyl -4,6- diamino resorcin hydrochlorate secondary fine products in terms of MANRHCl
Rate is up to 60% or more.
4 poly- hydroxyl -1 ' of embodiment, 4 '-phenylene -8- methyl -2,6- Benzo-dioxazoles (Formulas I, ran-HMPBO) and fiber
It prepares
(the compound poly- methods of salt monomer self shrinking of HTMD)
(1) preparation of compound salt monomer (Formula II) HTMD
80g deoxygenated waters, 2.50g 96%NaOH (0.060mol) and 5.46g are sequentially added in glass reactor
(0.03mol) 2- hydroxyterephthalic acids, stirring be warming up to 50 DEG C it is to be dissolved for light brown clear solution when, in nitrogen protection
Under, it is slowly added dropwise and is dissolved in 70g by 7.04g (0.031mol) 2- methyl -4,6-diaminoresorcinol hydrochloride (MDARH)
The aqueous solution of deoxygenated water finishes stirring and is warming up to 70 DEG C of progress heat filterings, and wet cake HTMD is beaten with 300mL deoxygenated waters and is washed,
Room temperature filtering, 70 DEG C be dried in vacuo hydroxyterephthalic acid (HTA) 2- methyl -4,6- diamino resorcin complex salt lists
Body (HTMD) 8.61g (0.0256mol), the yield 85.40% in terms of HTA.FT-IR (KBr) is shown in attached drawing 6,1H-NMR is shown in attached drawing
7。
In 7 hydrogen of attached drawing spectrum：Chemical shift 7.8 (b), 7.25 (a) be 3 hydrogen of phenyl ring in HTA, ratio 1:2；Chemical potential
Move 6.42 (c) be 1 hydrogen of phenyl ring in MDAR, at 2.06 integrated value 2.70 for methyl 3 hydrogen.In this way, according to hydrogen on phenyl ring
Compose the ratio between 7.25a 2 hydrogen integrated values 2.04 and the one hydrogen integrated value 1.00 in the positions 6.42c in MDAR (HTA in HTA:MDAR=
1.02:1) can qualitative be complex salt HTMD.
In conclusion according to combine IR characteristic absorption peaks ownership and1H-NMR qualitative analyses, are accurately determined as HTMD.This
Sample uses1The content results that H-NMR carries out compound salt monomer HTMD quantitative analysis should be 98.04%.If complex salt with etc. work as
Than for standard, then in the HTMD of preparation：MDAR is less than 1.96% or HTA extra 2.00%.In HTMD from polycondensation process
It should be subject to micro-adjustment.
(2) atactic polymer ran-HMPBO and monfil
P is sequentially added in self-control glass polymerization reactor2O5The polyphosphoric acids (PPA) that mass concentration is 85.15%
22.0g and P2O53.0g and HTMD salt monomers 6.25g (0.0194mol) is made into HTMD salt monomers a concentration of 20% and P2O5It rises
The PPA polymerization reaction systems of prothyl amount a concentration of 86.93%, being warming up to 100 DEG C of stirring and dissolving 2h under nitrogen protection, (volume is swollen
It is swollen), then 125 DEG C of fluorescence are warming up to 1h and occurred, then carry out temperature programming 5h to 200 DEG C with the rate of 15 DEG C/h of heating
Terminate for polymerisation, is cooled to liquid crystal stoste (the ran-HMPBO mass concentrations of 120 DEG C or so acquisition atactic polymers
Contain 82.51%P in 15.71%, final PPA2O5)；Carry out continuous hot candied by hand and continuous, the monofilament of extraction solidifies into the water,
And the multiple washing through 70 DEG C of hot water obtains brown as-spun fibre to neutrality after 110 DEG C of dryings.Measuring intrinsic viscosity is
18.62dL/g(30℃/MSA).The IR of this nascent monfil is shown in that Fig. 8, TG-DTG are shown in Fig. 9.Thermal gravimetric analysis results are：It is weightless
Temperature is 556 DEG C when 5%.
5 poly- hydroxyl -1 ' of embodiment, 4 '-phenylene -8- methyl -2,6- Benzo-dioxazoles (Formula II, ran-HMPBO) and fibre
Dimension is prepared (MDARH and HTA mixes condensation methods)
P is sequentially added in self-control glass polymerization reactor2O5The polyphosphoric acids (PPA) that mass concentration is 85.15%
22.0g and 2- methyl -4,6-diaminoresorcinol hydrochloride (MDARH) 4.260g (0.0188mol), is warming up to 100 DEG C and stirs
The PPA solution that degassing 3h forms MDAR to clear is mixed and depressurized, P is then sequentially added2O53.0g and hydroxyl are to benzene
Dioctyl phthalate (HTA) 3.424g (0.0188mol), the gross mass percentage concentration for being made into two monomer of MDAR and HTA are 20.18% He
Starting contains 86.93%P2O5PPA polymerization reaction systems, stirred under nitrogen atmosphere be warming up to 120 DEG C reaction 2h, be warming up to 140 DEG C
Reaction 2h (140 DEG C fluorescence occur), then 160 DEG C of reaction 2h (being transferred to liquid crystal filiform state) are warming up to, finally it is warming up to 180 DEG C instead
It is to terminate to answer 2h, is cooled to 120 DEG C of liquid crystal stoste (ran-HMPBO mass concentrations for obtaining atactic polymer (ran-HMPBO)
Contain 82.46%P in 15.86%, final PPA2O5)；Carry out continuous hot candied by hand and continuous, the monofilament of extraction solidifies into the water,
And the multiple washing through 70 DEG C of hot water obtains brown as-spun fibre to neutrality after 110 DEG C of dryings.Measuring intrinsic viscosity is
13.16dL/g(30℃/MSA).The TG-DTG of this nascent monfil is shown in attached drawing 10.540 DEG C of heat decomposition temperature.
The preparation of the nascent multifilament fibers of Application Example 1ran-HMPBO
P is sequentially added in 3 liters of stainless steel polymer reactors2O5The polyphosphoric acids 1.32kg that mass concentration is 85.15%
(PPA) and P2O5180g and HTMD salt monomer 375g are made into HTMD salt monomers a concentration of 20% and P2O5Mass concentration is
The polymerization reaction system of 86.93% PPA, under nitrogen protection stirring are warming up to 100 DEG C (volume expansions when 1h), then use 1h
It is warming up to 125 DEG C of fluorescence to occur, then temperature programming 3h to 170 DEG C is carried out as prepolymerization with the rate of 15 DEG C/h of heating
(intrinsic viscosity of ran-HMPBO is 12~15dl/g at this time) is completed, by the twin-screw reactive extrursion of polymer material indentation 25/48
Machine, control screw speed are 15 revs/min, 175 DEG C of temperature, 190 DEG C, 200 DEG C, 180 DEG C, 175 DEG C of filter temperature, while by
Screw rod by ran-HMPBO mass concentrations be 15.71%, finally contain 82.51%P2O5PPA fiber spinning from crystalline state stostes be pressed into spinning meter
Amount pump, and inlet amount is accurately controlled in 5~8MPa, 175 DEG C of shredded dried bean curds sprayed through spinneret (aperture 0.22mm hole counts 50) high pressure
Rope is after the air bath of 200mm is stretched (draw ratio 18) into the coagulating bath solidification of 20% phosphate aqueous solution and rinsing bowl
Washing most afterwards through 110 DEG C of dryings of drying machine, is wound in filament cylinder with the speed of 30m/min by receive silk machine, obtains ran-
HMPBO multifilament as-spun fibre (brown) measures tensile strength 2.8GPa, the modulus 127GPa of fiber.Intrinsic viscosity 21,71dl/
g。
Listed above is only several specific examples of the present 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. hydroxyl of birdsing of the same feather flock together is to phenylene first Benzo-dioxazole polymer, structural formula is the hydroxyl random distribution as shown in formula (I)
Poly- hydroxyl -1 ', 4 '-phenylene -8- methyl -2,6- Benzo-dioxazoles：
In formula (I), n indicates that the degree of polymerization, n are 80~160.
2. poly- hydroxyl as described in claim 1 is to the compound salt monomer of phenylene first Benzo-dioxazole polymer, structural formula
2- methyl -4,6- diamino resorcin the complex salts of the hydroxyterephthalic acid as shown in formula (II)：
3. a kind of poly- hydroxyl as described in claim 1 is to the preparation method of phenylene first Benzo-dioxazole polymer, feature
It is that the method is the 2- methyl -4,6- diamino resorcin complex salts using hydroxyterephthalic acid shown in formula (II)
From polycondensation the preparation method.
4. preparation method as claimed in claim 3, it is characterised in that：The 2- of hydroxyterephthalic acid shown in the formula (II)
Methyl -4,6- diamino resorcin complex salts include the following steps from polycondensation the preparation method：By hydroxyl pair shown in formula (II)
The complex salt HTMD of the 2- methyl -4,6- diamino resorcins of phthalic acid is dissolved in containing P2O5Polyphosphoric acids in, mixed
Solution is warming up to 90~100 DEG C of stirrings under nitrogen protection, and temperature programming obtains poly- hydroxyl -1 ' to 180~200 DEG C from polycondensation,
The polyphosphoric acids fiber spinning from crystalline state stoste of 4 '-phenylene -8- methyl -2,6- Benzo-dioxazoles, it is then continuous hot candied by hand, through solidifying
Gu, wash, be drying to obtain poly- hydroxyl -1 ' shown in formula (I), 4 '-phenylene -8- methyl -2,6- Benzo-dioxazole monfil；
Wherein, P in the polyphosphoric acids2O5Mass concentration is 85~87%；The 2- first of hydroxyterephthalic acid shown in formula (II)
Mass concentrations of the complex salt HTMD of base -4,6- diamino resorcins in mixed solution is 15~25%；The program
Heating is：120℃1h、150℃1h、180℃1h.
5. preparation method as claimed in claim 3, it is characterised in that the 2- of hydroxyterephthalic acid shown in the formula (II)
Methyl -4,6- diamino resorcin complex salts are prepared as follows：AA types key monomers 2- methyl-shown in formula (III)
4,6-diaminoresorcinol hydrochloride and BB type monomer 2- hydroxyterephthalic acids occur compound anti-in alkaline aqueous solution
It answers, generates compound salt monomer shown in formula (II)；
6. preparation method as claimed in claim 5, it is characterised in that the 2- of hydroxyterephthalic acid shown in the formula (II)
Methyl -4,6- diamino resorcin complex salts are prepared as follows：First BB type monomer 2- hydroxyterephthalic acids are dissolved
In the deoxidation aqueous solution containing inorganic base substance, then by the deoxidation aqueous solution of AA type key monomers shown in formula (III) in nitrogen
Be added under gas shielded, it is reacted at salt out, deoxidation water washing, vacuum drying method be made formula (II) shown in hydroxyl to benzene
2- methyl -4,6- diamino resorcin the complex salts of dioctyl phthalate；Wherein, the inorganic base substance be NaOH, KOH,
Na2CO3Or K2CO3；4,6- diamino -2- the methyl resorcinols of AA types monomer shown in the formula (III) hydrochloride, BB type lists
The amount ratio of the substance of body hydroxyterephthalic acid and inorganic base substance is 1.0:0.9~1.0:1.96~2.04.
7. a kind of as described in claim 1 described one birdss of the same feather flock together hydroxyl to the preparation side of phenylene first Benzo-dioxazole polymer
Method, the method are that AA types monomer shown in formula (III) mixes polycondensation the preparation method preparation with BB type monomer 2- hydroxyterephthalic acids.
8. preparation method as claimed in claim 7, it is characterised in that：AA types monomer shown in the formula (III) and BB type monomers
2- hydroxyterephthalic acids mix polycondensation the preparation method and include the following steps：By key monomers 2- methyl -4,6- diaminos shown in formula (III)
Base resorcin hydrochlorate is dissolved in containing P2O5Polyphosphoric acids, obtain mixed liquor, after vacuum removal hydrogen chloride methyl -4 2-,
The poly phosphoric acid solution of 6- diamino resorcins adds BB type monomer 2- hydroxyterephthalic acids, heats up under nitrogen protection
After taking off hydrogen chloride to 90~100 DEG C of stirrings, temperature programming to 180~200 DEG C of mixed polycondensations obtains poly- hydroxyl-Isosorbide-5-Nitrae-phenylene-
The polyphosphoric acids fiber spinning from crystalline state stoste of 2,6- Benzo-dioxazoles, it is then continuous hot candied by hand, through solidification, washes, is drying to obtain formula
(I) poly- hydroxyl -1 ' shown in, 4 '-phenylene -8- methyl -2,6- Benzo-dioxazole monfil；Wherein, the poly phosphorus
P in acid2O5Mass concentration is 85~87%；Key monomers 2- methyl -4,6- diamino resorcin hydrochlorates shown in formula (III)
Amount ratio with the substance of BB type monomer hydroxyl terephthalic acid (TPA)s is 1~1.02:1；Methyl -4 key monomers 2- shown in formula (III),
6- diamino resorcin hydrochlorates and the hydroxyterephthalic acid total mass concentration in mixed liquor are 15~25%.
9. the method as described in one of claim 5~7, it is characterised in that：Key monomers are by 2- first shown in the formula (III)
The selective reduction in alcoholic solvent of base -4,6- dinitroresorcinols is key intermediate 2- methyl -4- amino-shown in formula (IV)
After 6- nitro resorcin hydrochlorides, then it is prepared in the method for fractional steps of aqueous solvent hydrogenating reduction；Shown in the formula (III)
Key monomers method as follows prepare：(a) with 2- methyl -4,6- dinitroresorcinols for raw material, in alcoholic solvent
Middle Fe2+Under/C catalysis reflux, hydrazine hydrate selective reduction, heat filters out waste active carbon, and vacuum concentration and essence after hydrochloric acid acidification is added
System, obtains 4- amino -6- nitro -2- methyl resorcinol hydrochlorides shown in formula (IV)；(b) by 4- ammonia shown in formula (IV)
Base -6- nitro -2- methyl resorcinol hydrochlorides are dissolved in water, after being used in combination NaOH to neutralize, using Pd/C as catalyst, low pressure 1MPa with
Lower catalytic hydrogenation filters out the crude product that key monomers shown in formula (III) are precipitated in hydrochloric, is denoted as MDARH crude products and crystal
- 4,6- diamino resorcin hydrochlorate the fine work of key monomers 2- methyl shown in formula (III) is made in preparation method；Wherein, in step (a)
The amount ratio of the substance of the 2- methyl -4,6- dinitroresorcinols and hydrazine hydrate is 1.0：2.2~2.4；The alcoholic solvent
For ethyl alcohol；The Fe2+/ C catalyst is FeSO4·7H2O and activated carbon, 2- methyl -4,6- dinitroresorcinol with
FeSO4·7H2O, the mass ratio of activated carbon is 1.0：0.05~0.15：0.2~0.4；Shown in formula described in step (b) (IV)
The amount ratio of the substance of 2- methyl -4- amino-6-nitro resorcin hydrochlorides and NaOH is 1.0:1.0~1.2；The Pd/C is urged
Agent is the Pd/C of load capacity 5%, 2- methyl -4- amino-6-nitro resorcin hydrochlorides shown in the formula (IV) and folding
The mass ratio of 5%Pd/C after dry is 1.0:0.010~0.016；Crystal's preparation method is：First plus water stirring and dissolving, activity
Carbon decoloring, filtrate add hydrochloric acid acid out, filtering, washing；The amount ratio of the MDARH crude products and the substance of HCl in hydrochloric acid is 1:2.0~
3.0, the MDARH crude products are 1 with the mass ratio of water and activated carbon:5.0~8.0:0.02~0.06；
10. poly- hydroxyl as described in claim 1 is preparing hydroxymethyl modification PBO to phenylene first Benzo-dioxazole polymer
Application in fiber or the preparation of high-performance multifilament fiber.
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| CN104119534A (en) * | 2014-07-10 | 2014-10-29 | 金宁人 | Polyhydroxy p-phenylene benzo bisoxazole polymer and preparation and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104119534A (en) * | 2014-07-10 | 2014-10-29 | 金宁人 | Polyhydroxy p-phenylene benzo bisoxazole polymer and preparation and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| 吴纯鑫等: "2-甲基-4-氨基-6-硝基间苯二酚盐酸盐的合成研究", 《高校化学工程学报》 * |
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