CN101016381A - Method of preparing polybenzoxazole-imide and its fiber - Google Patents
Method of preparing polybenzoxazole-imide and its fiber Download PDFInfo
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- CN101016381A CN101016381A CN 200710071751 CN200710071751A CN101016381A CN 101016381 A CN101016381 A CN 101016381A CN 200710071751 CN200710071751 CN 200710071751 CN 200710071751 A CN200710071751 A CN 200710071751A CN 101016381 A CN101016381 A CN 101016381A
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Abstract
The invention disclose a preparing method of polybenzoxazole-imide and its fiber involving polymer and fiber preparing method, which comprises the following steps: preparing in polyphosphoric acids without segregation; making as reacting monomer; getting together with aromatic dibasic acid anhydride; making polymeric solution as spin dope; adopting dry spray wet method; getting polybenzoxazole-imide fiber with good property. This invention possesses high molecular weight and low fiber factor of porosity, which hot strength can reach 2.2-2.7GPa.
Description
Technical field
The present invention relates to polymkeric substance and fiber preparation method thereof.
Background technology
Polybenzoxazole-imide is with its excellent mechanical property, thermal characteristics, resistance to low temperature, excellent dielectric properties, radiation-resistant property, solvent resistance, is applied in aerospace composite and civilian some high-performance fields.Present polybenzoxazole-imido synthetic employing two-step approach, a kind of method is at aprotic polar solvent such as NMP (N-Methyl pyrrolidone), obtain the polybenzoxazole amido acid by diamines that contains the benzoxazole ring structure and the polymerization of aromatic series tetracarboxylic dianhydride among DMF (dimethyl formamide) or the DMAc (N,N-DIMETHYLACETAMIDE), be spun into fiber then or make film, behind cyclodehydration, obtain polybenzoxazole-imide again.Another kind method is in aprotic polar solvent, and preparation earlier contains the polymeric amide of vicinal hydroxyl groups and ortho position carboxyl, and the back cyclodehydration is shaped.The polymericular weight that adopts these two kinds of methods to make is low, is difficult to make fiber, also can produce hole even obtain polybenzoxazole-imide fiber in fiber in the cyclodehydration stage, reduces the mechanical property of material.
Summary of the invention
The objective of the invention is in order to solve two-step approach synthetic polybenzoxazole-imide molecular weight low, be difficult to make fiber and polybenzoxazole-imide fiber and in fiber, produce hole in the cyclodehydration stage, the defective of the poor mechanical property of filamentary material, and the polybenzoxazole that provides-imido preparation method and prepare the method for polybenzoxazole-imide fiber.
Polybenzoxazole-imide I prepares according to the following steps: (one) uses phosphoric acid and P under normal pressure, stirring, protection of inert gas atmosphere
2O
5Be mixed with P
2O
5Mass concentration is 76%～86% poly phosphoric acid solution, adds the SnCl of poly phosphoric acid solution quality 0.7%～2.3% afterwards
2(2) control poly phosphoric acid solution temperature to 110～130 ℃ adds 4,6-diamino resorcin hydrochlorate and para-amino benzoic acid, wherein P
2O
5With the mol ratio of para-amino benzoic acid be 6.84～12.13: 1,4, the mol ratio of 6-diamino resorcin hydrochlorate and para-amino benzoic acid is 1: 2～2.1; (3) be heated to 160～220 ℃ of reaction 4～24h, obtain 2, and 6-two (right-amino-benzene) benzo [1,2-d; 5,4-d '] Er oxazole; (4) directly add the aromatics dibasic acid anhydride, aromatics dibasic acid anhydride and 4, the mol ratio of 6-diamino resorcin hydrochlorate are 1～1.02: 1, react 6～12h under 180～230 ℃ of conditions, promptly obtain polybenzoxazole-imide I, the structural formula of polybenzoxazole-imide I is:
Polybenzoxazole-imide II prepares according to the following steps: (one) uses phosphoric acid and P under normal pressure, stirring, protection of inert gas atmosphere
2O
5Be mixed with P
2O
5Mass concentration is 76%～86% poly phosphoric acid solution, adds the SnCl of poly phosphoric acid solution quality 0.7%～2.3% afterwards
2(2) control poly phosphoric acid solution temperature to 1 is 10～130 ℃, adds 2,4-diaminophenol hydrochloride and terephthalic acid, wherein P
2O
5With the mol ratio of terephthalic acid be 20.8～24.39: 1,2, the mol ratio of 4-diaminophenol hydrochloride and terephthalic acid is 2～2.1: 1; (3) be heated to 160～220 ℃ of reaction 4～24h, obtain right-penylene-2,2 '-two (the amino benzoxazole of 5-); (4) directly add the aromatics dibasic acid anhydride, the mol ratio of aromatics dibasic acid anhydride and terephthalic acid is 1～1.02: 1, react 6～12h under 180～230 ℃ of conditions, promptly obtain polybenzoxazole-imide II, the structural formula of polybenzoxazole-imide II is:
Polybenzoxazole-the imide that utilizes method for preparing to go out prepares the method for polybenzoxazole-imide fiber to carry out according to the following steps: the polymeric solution with polybenzoxazole-imide I or II is a spinning solution, adopts dry-jet wet spinning; Wherein the gas cloud height is 10～100cm, and the precipitation bath solvent is that water, concentration are that 2%～40% phosphoric acid solution or concentration are 2%～20% NaOH solution, and stretch ratio is 1～30 times, and the spinning drying temperature is 80～140 ℃; And then, promptly obtain polybenzoxazole-imide fiber through precipitating, washing, drying.
The invention goes out the preparation method of two kinds of isomeric polybenzoxazole-imides (polybenzoxazole-imide I and polybenzoxazole-imide II).The preparation method of polybenzoxazole-imide of the present invention (two kinds of isomerss) is " one kettle way ", promptly need not separate the benzoxazole diamines, directly as reaction monomers and the polymerization of aromatics dibasic acid anhydride.Polybenzoxazole-imide that the present invention prepares (two kinds of isomerss) molecular weight height can be used for preparing the good polybenzoxazole-imide fiber of mechanical property.Polybenzoxazole of the present invention-imido preparation method is simple, convenient, need not separate purification benzoxazole diamines, and the cheap cost of raw material is low.
The method that the present invention prepares polybenzoxazole-imide fiber is to make polybenzoxazole-imido polymeric solution directly as spinning solution processing polybenzoxazole-imide fiber, the preparation method is simple, energy consumption is low, compare with two-step approach, because the employing inorganic solvent, environmental pollution is little; The polybenzoxazole of preparing-imide fiber aftertreatment is easy, fiber molecule amount height, and the fiber porosity is low, and mechanical property is good, improves 30～50% than the polybenzoxazole that adopts two-step approach to make-imide fiber tensile strength.
Description of drawings
Fig. 1 is the infrared spectrum of polybenzoxazole-imide I of preparing of embodiment 13, and Fig. 2 is the fracture electron microscope scanning figure of polybenzoxazole-imide fiber I of preparing of embodiment 47.
Embodiment
Embodiment one: present embodiment polybenzoxazole-imide I prepares according to the following steps: (one) uses phosphoric acid and P under normal pressure, stirring, protection of inert gas atmosphere
2O
5Be mixed with P
2O
5Mass concentration is 76%～86% poly phosphoric acid solution, adds the SnCl of poly phosphoric acid solution quality 0.7%～2.3% afterwards
2(2) control poly phosphoric acid solution temperature to 110～130 ℃ adds 4,6-diamino resorcin hydrochlorate and para-amino benzoic acid, wherein P
2O
5With the mol ratio of para-amino benzoic acid be 6.84～12.13: 1,4, the mol ratio of 6-diamino resorcin hydrochlorate and para-amino benzoic acid is 1: 2～2.1; (3) be heated to 160～220 ℃ of reaction 8～24h, obtain 2, and 6-two (right-amino-benzene) benzo [1,2-d; 5,4-d '] Er oxazole; (4) directly add the aromatics dibasic acid anhydride, aromatics dibasic acid anhydride and 4, the mol ratio of 6-diamino resorcin hydrochlorate is 1～1.02: 1, reacts 6～12h under 180～230 ℃ of conditions, promptly obtains polybenzoxazole-imide I.
It is in 95%～98% the sulfuric acid, to be mixed with the solution that polymer concentration is 0.5g/dL that the polybenzoxazole that present embodiment is prepared-imide I adds concentration, is 4.8～5.2dL/g in 25 ℃ of logarithmic specific concentration viscosities with determination of ubbelohde viscometer.
Embodiment two: the difference of present embodiment and embodiment one is: use phosphoric acid and P in the step ()
2O
5Be mixed with P
2O
5Mass concentration is 78%～83% poly phosphoric acid solution, adds the SnCl of poly phosphoric acid solution quality 0.9%～2.2% afterwards
2Other step is identical with embodiment one.
The logarithmic specific concentration viscosity of the polybenzoxazole that present embodiment is prepared-imide I is 5.0～5.2dL/g.
Embodiment three: the difference of present embodiment and embodiment one is: use phosphoric acid and P in the step ()
2O
5Be mixed with P
2O
5Mass concentration is 82% poly phosphoric acid solution, adds the SnCl of poly phosphoric acid solution quality 1.1%～2.0% afterwards
2Other step is identical with embodiment one.
The logarithmic specific concentration viscosity of the polybenzoxazole-imide I that present embodiment is prepared is 5.1dL/g.
Embodiment four: the difference of present embodiment and embodiment one is: use phosphoric acid and P in the step ()
2O
5Be mixed with P
2O
5Mass concentration is 85% poly phosphoric acid solution, adds the SnCl of poly phosphoric acid solution quality 1.5% afterwards
2Other step is identical with embodiment one.
The logarithmic specific concentration viscosity of the polybenzoxazole that present embodiment is prepared-imide I is 5.2dL/g.
Embodiment five: the difference of present embodiment and embodiment one is: P in the step (two)
2O
5With the mol ratio of para-amino benzoic acid be 7～12: 1,4, the mol ratio of 6-diamino resorcin hydrochlorate and para-amino benzoic acid is 1: 2.01～2.08.Other step is identical with embodiment one.
Embodiment six: the difference of present embodiment and embodiment one is: P in the step (two)
2O
5With the mol ratio of para-amino benzoic acid be 9～10: 1,4, the mol ratio of 6-diamino resorcin hydrochlorate and para-amino benzoic acid is 1: 2.05.Other step is identical with embodiment one.
Embodiment seven: the difference of present embodiment and embodiment one is: step (three) is heated to 160～220 ℃ of reaction 8～24h.Other step is identical with embodiment one.
Embodiment eight: the difference of present embodiment and embodiment one is: step (three) is heated to 170～210 ℃ of reaction 6～12h.Other step is identical with embodiment one.
Embodiment nine: the difference of present embodiment and embodiment one is: step (three) is heated to 160 ℃ of insulation reaction 4h, is warming up to 200 ℃ of insulation reaction 4h again, is cooled to 180 ℃ afterwards.Other step is identical with embodiment one.
Embodiment ten: the difference of present embodiment and embodiment one is: aromatics dibasic acid anhydride and 4 in the step (four), the mol ratio of 6-diamino resorcin hydrochlorate is 1.01: 1, reacts 7～10h under 190～220 ℃ of conditions.Other step is identical with embodiment one.
Embodiment 11: the difference of present embodiment and embodiment one is: aromatics dibasic acid anhydride and 4 in the step (four), the mol ratio of 6-diamino resorcin hydrochlorate is 1: 1, reacts 8h under 200 ℃ of conditions.Other step is identical with embodiment one.
Embodiment 12: the difference of present embodiment and embodiment one is: in the step (four) the aromatics dibasic acid anhydride be 3,3 ', 4,4 '-phenyl ether tetracarboxylic dianhydride, 3,3 ', 4,4 '-BPDA or 3,3 ', 4,4 '-triphen bis ether tetracarboxylic dianhydride.Other step is identical with embodiment one.
Embodiment 13: the difference of present embodiment and embodiment one is: in the step (four) the aromatics dibasic acid anhydride be 3,3 ', 4,4 '-the phenyl ether tetracarboxylic dianhydride.Other step is identical with embodiment one.
The structural formula of present embodiment polybenzoxazole-imide I is
, wherein Ar1 is
The infrared spectrum of present embodiment polybenzoxazole-imide I as shown in Figure 1.
Embodiment 14: the difference of present embodiment and embodiment one is: in the step (four) the aromatics dibasic acid anhydride be 3,3 ', 4,4 '-BPDA.Other step is identical with embodiment one.
The structural formula of present embodiment polybenzoxazole-imide I is
, wherein Ar1 is
Embodiment 15: the difference of present embodiment and embodiment one is: in the step (four) the aromatics dibasic acid anhydride be 3,3 ', 4,4 '-triphen bis ether tetracarboxylic dianhydride.Other step is identical with embodiment one.
The structural formula of present embodiment polybenzoxazole-imide I is
, wherein Ar1 is
Embodiment 16: present embodiment polybenzoxazole-imide II prepares according to the following steps: (one) uses phosphoric acid and P under normal pressure, stirring, protection of inert gas atmosphere
2O
5Be mixed with P
2O
5Mass concentration is 76%～86% poly phosphoric acid solution, adds the SnCl of poly phosphoric acid solution quality 0.7%～2.3% afterwards
2(2) rising poly phosphoric acid solution temperature to 140～150 ℃ add 2,4-diaminophenol hydrochloride and terephthalic acid, wherein P
2O
5With the mol ratio of terephthalic acid be 20.8～24.39: 1,2, the mol ratio of 4-diaminophenol hydrochloride and terephthalic acid is 2～2.1: 1; (3) be heated to 160～220 ℃ of reaction 8～24h, obtain right-penylene-2,2 '-two (the amino benzoxazole of 5-); (4) directly add the aromatics dibasic acid anhydride, the mol ratio of aromatics dibasic acid anhydride and terephthalic acid is 1～1.02: 1, reacts 6～12h under 180～230 ℃ of conditions, promptly obtains polybenzoxazole-imide II.
The polybenzoxazole that present embodiment is prepared-imide II adding concentration is 95%～98% sulphuric acid soln, is mixed with the solution that polymer concentration is 0.5g/dL, is 4.6～5.3dL/g in 25 ℃ of logarithmic specific concentration viscosities with determination of ubbelohde viscometer.
Embodiment 17: the difference of present embodiment and embodiment 16 is: use phosphoric acid and P in the step ()
2O
5Be mixed with P
2O
5Mass concentration is 78%～83% poly phosphoric acid solution, adds the SnCl of poly phosphoric acid solution quality 0.9%～2.2% afterwards
2Other step is identical with embodiment 16.
The logarithmic specific concentration viscosity of the polybenzoxazole that present embodiment is prepared-imide II is 4.9～5.3dL/g.
Embodiment 18: the difference of present embodiment and embodiment 16 is: use phosphoric acid and P in the step ()
2O
5Be mixed with P
2O
5Mass concentration is 83% poly phosphoric acid solution, adds the SnCl of poly phosphoric acid solution quality 1.1%～2.0% afterwards
2Other step is identical with embodiment 16.
The logarithmic specific concentration viscosity of the polybenzoxazole that present embodiment is prepared-imide II is 5.1～5.3dL/g.
Embodiment 19: the difference of present embodiment and embodiment 16 is: use phosphoric acid and P in the step ()
2O
5Be mixed with P
2O
5Mass concentration is 85% poly phosphoric acid solution, adds the SnCl of poly phosphoric acid solution quality 1.5% afterwards
2Other step is identical with embodiment 16.
The logarithmic specific concentration viscosity of the polybenzoxazole that present embodiment is prepared-imide II is 5.3dL/g.
Embodiment 20: the difference of present embodiment and embodiment 16 is: P in the step (two)
2O
5With the mol ratio of terephthalic acid be 21～24: 1,2, the mol ratio of 4-diaminophenol hydrochloride and terephthalic acid is 2.01～2.08: 1.Other step is identical with embodiment 16.
Embodiment 21: the difference of present embodiment and embodiment 16 is: P in the step (two)
2O
5With the mol ratio of terephthalic acid be 22～23: 1,2, the mol ratio of 4-diaminophenol hydrochloride and terephthalic acid is 2.05: 1.Other step is identical with embodiment 16.
Embodiment 22: the difference of present embodiment and embodiment 16 is: step (three) is heated to 160～220 ℃ of reaction 8～24h.Other step is identical with embodiment 16.
Embodiment 23: the difference of present embodiment and embodiment 16 is: step (three) is heated to 170～210 ℃ of reaction 8.5～12h.Other step is identical with embodiment 16.
Embodiment 24: the difference of present embodiment and embodiment 16 is: step (three) is heated to 160 ℃ of insulation reaction 4h, is warming up to 200 ℃ of insulation reaction 4h again, is cooled to 180 ℃ afterwards.Other step is identical with embodiment 16.
Embodiment 25: the difference of present embodiment and embodiment 16 is: the mol ratio of aromatics dibasic acid anhydride and terephthalic acid is 1.01: 1 in the step (four), reacts 7～10h under 190～220 ℃ of conditions.Other step is identical with embodiment 16.
Embodiment 26: the difference of present embodiment and embodiment 16 is: the mol ratio of aromatics dibasic acid anhydride and terephthalic acid is 1: 1 in the step (four), reacts 8h under 200 ℃ of conditions.Other step is identical with embodiment 16.
Embodiment 27: the difference of present embodiment and embodiment 16 is: in the step (four) the aromatics dibasic acid anhydride be 3,3 ', 4,4 '-phenyl ether tetracarboxylic dianhydride, 3,3 ', 4,4 '-BPDA or 3,3 ', 4,4 '-triphen bis ether tetracarboxylic dianhydride.Other step is identical with embodiment 16.
Embodiment 28: the difference of present embodiment and embodiment 16 is: in the step (four) the aromatics dibasic acid anhydride be 3,3 ', 4,4 '-the phenyl ether tetracarboxylic dianhydride.Other step is identical with embodiment 16.
The structural formula of present embodiment polybenzoxazole-imide II is
, wherein Ar1 is
Embodiment 29: the difference of present embodiment and embodiment 16 is: in the step (four) the aromatics dibasic acid anhydride be 3,3 ', 4,4 '-BPDA.Other step is identical with embodiment 16.
The structural formula of present embodiment polybenzoxazole-imide II is
, wherein Ar1 is
Embodiment 30: the difference of present embodiment and embodiment 16 is: in the step (four) the aromatics dibasic acid anhydride be 3,3 ', 4,4 '-triphen bis ether tetracarboxylic dianhydride.Other step is identical with embodiment 16.
The structural formula of present embodiment polybenzoxazole-imide II is
, wherein Ar1 is
The embodiment hentriaconta-: polybenzoxazole-imide that present embodiment is prepared with embodiment one or embodiment 16 prepares polybenzoxazole-imide fiber: the polymeric solution with polybenzoxazole-imide I or II is a spinning solution, adopts dry-jet wet spinning; Wherein the gas cloud height is 10～100cm, and the precipitation bath solvent is that water, concentration are that 2%～40% phosphoric acid solution or concentration are 2%～20% NaOH solution, and stretch ratio is 1～30 times, and the spinning drying temperature is 80～140 ℃; And then, promptly obtain polybenzoxazole-imide fiber through precipitating, washing, drying.
The polybenzoxazole that present embodiment is prepared-imido tensile strength of fiber is 2.2～2.7GPa.
Embodiment 32: the difference of present embodiment and embodiment hentriaconta-is: the gas cloud height is 20～90cm, the precipitation bath solvent is that water, concentration are that 4%～35% phosphoric acid solution or concentration are 4%～18% NaOH solution, stretch ratio is 2～27 times, and the spinning drying temperature is 85～135 ℃.Other step is identical with the embodiment hentriaconta-.
Embodiment 33: the difference of present embodiment and embodiment hentriaconta-is: the gas cloud height is 30～80cm.Other step is identical with the embodiment hentriaconta-.
Embodiment 34: the difference of present embodiment and embodiment hentriaconta-is: the gas cloud height is 50cm.Other step is identical with the embodiment hentriaconta-.
Embodiment 35: the difference of present embodiment and embodiment hentriaconta-is: the precipitation bath solvent is a water.Other step is identical with the embodiment hentriaconta-.
Embodiment 36: the difference of present embodiment and embodiment hentriaconta-is: the precipitation bath solvent is that concentration is 5%～10% phosphoric acid solution.Other step is identical with the embodiment hentriaconta-.
Embodiment 37: the difference of present embodiment and embodiment hentriaconta-is: the precipitation bath solvent is that concentration is that concentration is 2%～5% NaOH solution.Other step is identical with the embodiment hentriaconta-.
Embodiment 38: the difference of present embodiment and embodiment hentriaconta-is: the precipitation bath solvent is that concentration is that concentration is 3% NaOH solution.Other step is identical with the embodiment hentriaconta-.
Embodiment 39: the difference of present embodiment and embodiment hentriaconta-is: stretch ratio is 3 times.Other step is identical with the embodiment hentriaconta-.
Embodiment 40: the difference of present embodiment and embodiment hentriaconta-is: the spinning drying temperature is 100 ℃.Other step is identical with the embodiment hentriaconta-.
Embodiment 41: the difference of present embodiment and embodiment hentriaconta-is: the polybenzoxazole that present embodiment is prepared with embodiment one-imide I prepares polybenzoxazole-imide fiber I.Other step is identical with the embodiment hentriaconta-.
The tensile strength of the polybenzoxazole that present embodiment is prepared-imide fiber I is 2.2～2.6GPa.
Embodiment 42: the difference of present embodiment and embodiment hentriaconta-is: the polybenzoxazole that present embodiment is prepared with embodiment 16-imide II prepares polybenzoxazole-imide fiber II.Other step is identical with the embodiment hentriaconta-.
The tensile strength of the polybenzoxazole that present embodiment is prepared-imide fiber II is 2.2～2.7GPa.
Embodiment 43: the difference of present embodiment and embodiment one is: rare gas element is a nitrogen in the step ().Other step is identical with embodiment one.
Embodiment 44: the difference of present embodiment and embodiment 16 is: rare gas element is a nitrogen in the step ().Other step is identical with embodiment 16.
Embodiment 45: the polybenzoxazole-imide I that present embodiment is prepared with embodiment four prepares polybenzoxazole-imide fiber I: with polybenzoxazole-imide I polymeric solution is spinning solution, adopts dry-jet wet spinning; Wherein the gas cloud height is 50cm, and the precipitation bath solvent is a water, and stretch ratio is 3 times, and the spinning drying temperature is 105 ℃; And then, promptly obtain polybenzoxazole-imide fiber I through precipitating, washing, drying.
The tensile strength of the polybenzoxazole that present embodiment is prepared-imide fiber I is 2.6GPa.
Embodiment 46: the polybenzoxazole that present embodiment is prepared with embodiment 18-imide II prepares polybenzoxazole-imide fiber II: with polybenzoxazole-imide II polymeric solution is spinning solution, adopts dry-jet wet spinning; Wherein the gas cloud height is 60cm, and the precipitation bath solvent is a water, and stretch ratio is 4 times, and the spinning drying temperature is 115 ℃; And then, promptly obtain polybenzoxazole-imide fiber II through precipitating, washing, drying.
The tensile strength of the polybenzoxazole that present embodiment is prepared-imide fiber II is 2.7GPa.
Embodiment 47: the polybenzoxazole-imide I that present embodiment is prepared with embodiment 13 prepares polybenzoxazole-imide fiber I: with polybenzoxazole-imide I polymeric solution is spinning solution, adopts dry-jet wet spinning; Wherein the gas cloud height is 70cm, and the precipitation bath solvent is a water, and stretch ratio is 5 times, and the spinning drying temperature is 110 ℃; And then, promptly obtain polybenzoxazole-imide fiber I through precipitating, washing, drying.
The tensile strength of the polybenzoxazole that present embodiment is prepared-imide fiber I is 2.6GPa, its fracture apperance as shown in Figure 2, the Fibre diameter that this shows the polybenzoxazole-imide fiber I of present embodiment preparation is 30 μ m, and the fiber hole is few, and is dense.
Claims (10)
1, the preparation method of polybenzoxazole-imide I is characterized in that polybenzoxazole-imide I prepares according to the following steps: (one) uses phosphoric acid and P under normal pressure, stirring, protection of inert gas atmosphere
2O
5Be mixed with P
2O
5Mass concentration is 76%～86% poly phosphoric acid solution, adds the SnCl of poly phosphoric acid solution quality 0.7%～2.3% afterwards
2(2) control poly phosphoric acid solution temperature to 110～130 ℃ adds 4,6-diamino resorcin hydrochlorate and para-amino benzoic acid, wherein P
2O
5With the mol ratio of para-amino benzoic acid be 6.84～12.13: 1,4, the mol ratio of 6-diamino resorcin hydrochlorate and para-amino benzoic acid is 1: 2～2.1; (3) be heated to 160～220 ℃ of reaction 8～24h, obtain 2, and 6-two (right-amino-benzene) benzo [1,2-d; 5,4-d '] Er oxazole; (4) directly add the aromatics dibasic acid anhydride, aromatics dibasic acid anhydride and 4, the mol ratio of 6-diamino resorcin hydrochlorate are 1～1.02: 1, react 6～12h under 180～230 ℃ of conditions, promptly obtain polybenzoxazole-imide I, the structural formula of polybenzoxazole-imide I is:
2, the preparation method of polybenzoxazole-imide I according to claim 1 is characterized in that in the step () with phosphoric acid and P
2O
5Be mixed with P
2O
5Mass concentration is 78%～83% poly phosphoric acid solution, adds the SnCl of poly phosphoric acid solution quality 0.9%～2.2% afterwards
2
3, the preparation method of polybenzoxazole-imide I according to claim 1 is characterized in that P in the step (two)
2O
5With the mol ratio of para-amino benzoic acid be 7～12: 1,4, the mol ratio of 6-diamino resorcin hydrochlorate and para-amino benzoic acid is 1: 2.05.
4, the preparation method of polybenzoxazole-imide I according to claim 1, it is characterized in that in the step (four) the aromatics dibasic acid anhydride be 3,3 ', 4,4 '-phenyl ether tetracarboxylic dianhydride, 3,3 ', 4,4 '-BPDA or 3,3 ', 4,4 '-triphen bis ether tetracarboxylic dianhydride.
5, the preparation method of polybenzoxazole-imide II is characterized in that polybenzoxazole-imide II prepares according to the following steps: (one) uses phosphoric acid and P under normal pressure, stirring, protection of inert gas atmosphere
2O
5Be mixed with P
2O
5Mass concentration is 76%～86% poly phosphoric acid solution, adds the SnCl of poly phosphoric acid solution quality 0.7%～2.3% afterwards
2(2) control poly phosphoric acid solution temperature to 110～130 ℃ adds 2,4-diaminophenol hydrochloride and terephthalic acid, wherein P
2O
5With the mol ratio of terephthalic acid be 20.8～24.39: 1,2, the mol ratio of 4-diaminophenol hydrochloride and terephthalic acid is 2～2.1: 1; (3) be heated to 160～220 ℃ of reaction 8～24h, obtain right-penylene-2,2 '-two (the amino benzoxazole of 5-); (4) directly add the aromatics dibasic acid anhydride, the mol ratio of aromatics dibasic acid anhydride and terephthalic acid is 1～1.02: 1, react 6～12h under 180～230 ℃ of conditions, promptly obtain polybenzoxazole-imide II, the structural formula of polybenzoxazole-imide II is:
6, the preparation method of polybenzoxazole-imide II according to claim 5 is characterized in that rare gas element is a nitrogen in the step ().
7, the preparation method of polybenzoxazole-imide II according to claim 5 is characterized in that P in the step (two)
2O
5With the mol ratio of terephthalic acid be 21～24: 1,2, the mol ratio of 4-diaminophenol hydrochloride and terephthalic acid is 2.05: 1.
8, the preparation method of polybenzoxazole-imide II according to claim 5, it is characterized in that in the step (four) the aromatics dibasic acid anhydride be 3,3 ', 4,4 '-phenyl ether tetracarboxylic dianhydride, 3,3 ', 4,4 '-BPDA or 3,3 ', 4,4 '-triphen bis ether tetracarboxylic dianhydride.
9, the polybenzoxazole-imide of preparing with claim 1 or 5 prepares the method for polybenzoxazole-imide fiber, it is characterized in that the polybenzoxazole-imide fiber carries out according to the following steps: the polymeric solution with polybenzoxazole-imide I or II is a spinning solution, adopts dry-jet wet spinning; Wherein the gas cloud height is 10～100cm, and the precipitation bath solvent is that water, concentration are that 2%～40% phosphoric acid solution or concentration are 2%～20% NaOH solution, and stretch ratio is 1～30 times, and the spinning drying temperature is 80～140 ℃; And then, promptly obtain the polybenzoxazole-imide fiber through precipitating, washing, drying.
10, the method for preparing the polybenzoxazole-imide fiber according to claim 9, it is characterized in that the gas cloud height is 20～90cm, the precipitation bath solvent is that water, concentration are that 4%～35% phosphoric acid solution or concentration are 4%～18% NaOH solution, stretch ratio is 2～27 times, the spinning drying temperature is 85～135 ℃, promptly obtains the polybenzoxazole-imide fiber.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007100717512A CN100519627C (en) | 2007-02-07 | 2007-02-07 | Method of preparing polybenzoxazole-imide and its fiber |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007100717512A CN100519627C (en) | 2007-02-07 | 2007-02-07 | Method of preparing polybenzoxazole-imide and its fiber |
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| Publication Number | Publication Date |
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| CN101016381A true CN101016381A (en) | 2007-08-15 |
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