CN114790290B - Synthesis method of hydroxyl modified biphenyl structure PBO composite monomer - Google Patents
Synthesis method of hydroxyl modified biphenyl structure PBO composite monomer Download PDFInfo
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- CN114790290B CN114790290B CN202210513685.4A CN202210513685A CN114790290B CN 114790290 B CN114790290 B CN 114790290B CN 202210513685 A CN202210513685 A CN 202210513685A CN 114790290 B CN114790290 B CN 114790290B
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- 239000000178 monomer Substances 0.000 title claims abstract description 55
- 239000002131 composite material Substances 0.000 title claims abstract description 46
- 238000001308 synthesis method Methods 0.000 title claims description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 57
- OYFRNYNHAZOYNF-UHFFFAOYSA-N 2,5-dihydroxyterephthalic acid Chemical compound OC(=O)C1=CC(O)=C(C(O)=O)C=C1O OYFRNYNHAZOYNF-UHFFFAOYSA-N 0.000 claims abstract description 52
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 37
- -1 3,3 '-diamino-4, 4' -dihydroxybiphenyl hydrochloride Chemical compound 0.000 claims abstract description 25
- 238000010438 heat treatment Methods 0.000 claims abstract description 20
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims abstract description 19
- 239000001119 stannous chloride Substances 0.000 claims abstract description 19
- 235000011150 stannous chloride Nutrition 0.000 claims abstract description 19
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 16
- 239000002994 raw material Substances 0.000 claims abstract description 5
- QAGQFDYITIKYIW-UHFFFAOYSA-L disodium;2,5-dicarboxybenzene-1,4-diolate Chemical compound [Na+].[Na+].OC1=CC(C([O-])=O)=C(O)C=C1C([O-])=O QAGQFDYITIKYIW-UHFFFAOYSA-L 0.000 claims abstract description 4
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 19
- 239000012065 filter cake Substances 0.000 claims description 15
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 10
- 239000003638 chemical reducing agent Substances 0.000 claims description 9
- 230000002194 synthesizing effect Effects 0.000 claims description 9
- 239000012295 chemical reaction liquid Substances 0.000 claims description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 2
- 239000011790 ferrous sulphate Substances 0.000 claims description 2
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 2
- 235000011152 sodium sulphate Nutrition 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 47
- 239000000203 mixture Substances 0.000 abstract description 22
- 239000012265 solid product Substances 0.000 abstract description 14
- 239000006227 byproduct Substances 0.000 abstract 1
- 238000010189 synthetic method Methods 0.000 abstract 1
- 231100000331 toxic Toxicity 0.000 abstract 1
- 230000002588 toxic effect Effects 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 32
- 238000003756 stirring Methods 0.000 description 29
- 238000004128 high performance liquid chromatography Methods 0.000 description 19
- 229910052757 nitrogen Inorganic materials 0.000 description 16
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 description 15
- DLYUQMMRRRQYAE-UHFFFAOYSA-N phosphorus pentoxide Inorganic materials O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 15
- 239000000835 fiber Substances 0.000 description 12
- 229920000137 polyphosphoric acid Polymers 0.000 description 12
- 238000006116 polymerization reaction Methods 0.000 description 8
- 238000001514 detection method Methods 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 5
- 239000007853 buffer solution Substances 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- GBMDVOWEEQVZKZ-UHFFFAOYSA-N methanol;hydrate Chemical compound O.OC GBMDVOWEEQVZKZ-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 239000004973 liquid crystal related substance Substances 0.000 description 4
- 239000011550 stock solution Substances 0.000 description 4
- ICXAPFWGVRTEKV-UHFFFAOYSA-N 2-[4-(1,3-benzoxazol-2-yl)phenyl]-1,3-benzoxazole Chemical class C1=CC=C2OC(C3=CC=C(C=C3)C=3OC4=CC=CC=C4N=3)=NC2=C1 ICXAPFWGVRTEKV-UHFFFAOYSA-N 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000006068 polycondensation reaction Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229920000927 poly(p-phenylene benzobisoxazole) Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 241000218378 Magnolia Species 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003779 heat-resistant material Substances 0.000 description 1
- 229920006253 high performance fiber Polymers 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000001603 reducing effect Effects 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 238000005491 wire drawing Methods 0.000 description 1
Classifications
-
- 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
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
- D01F6/94—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of other polycondensation products
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Textile Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A synthetic method of a hydroxyl modified biphenyl structure PBO composite monomer comprises the following steps: taking 2, 5-dihydroxyterephthalic acid as a raw material, adding sodium hydroxide and deoxidized water in a nitrogen atmosphere, and then heating to 30-50 ℃ for neutralization reaction for 0.2-0.5 hour to obtain an intermediate sodium 2, 5-dihydroxyterephthalate; then, intermediate sodium 2, 5-dihydroxyterephthalate and 3,3 '-diamino-4, 4' -dihydroxybiphenyl hydrochloride are used as raw materials, stannous chloride is added in a nitrogen atmosphere, and the mixture reacts for 0.3 to 0.6 hour at the temperature of 60 to 80 ℃ to obtain a white solid product of the hydroxyl modified biphenyl structure PBO composite monomer. The reaction process parameters of the scheme of the invention are easy to control, no toxic byproducts are generated, the atomic utilization rate is high, the yield is high, the purity is high, and the post-treatment is simple.
Description
Field of the art
The invention relates to a synthesis method of a hydroxyl modified biphenyl structure PBO composite monomer.
(II) background art
The compound monomer shown in the formula (1) is a raw material for preparing the hydroxy-modified poly-p-phenylene benzobisoxazole by polymerization, and can be applied to the fields of high-performance fibers, photoelectric materials, heat-resistant materials and the like (Lu Shanshan, wang Yangong, hu Zhen. Research progress of poly-p-phenylene benzobisoxazole fiber modification technology, synthetic fiber industry, 2018,41 (1): 47-52.).
At present, the polymerization method of the hydroxyl modified poly (p-phenylene benzobisoxazole) carries out mixed polycondensation reaction in polyphosphoric acid at high temperature by using 3,3 '-diamino-4, 4' -dihydroxybiphenyl hydrochloride and 2, 5-dihydroxyterephthalic acid, and has the defects that the equal equivalent ratio of two monomers is difficult to uniformly polycondense to influence the polymerization effect, the HCl removal process influences the fiber strength and the like. Therefore, starting from the polymerization method of PBO fiber, a hydroxyl modified biphenyl structure PBO composite monomer is synthesized, and the composite monomer is utilized to carry out self-polycondensation reaction under the condition of high temperature in polyphosphoric acid. (Wu Chunxin, chang Yuxi, chen Di, supra.) Synthesis of hydroxy-modified poly (p-phenylene benzobisoxazole) monomer 3,3 '-diamino-4, 4' -dihydroxybiphenyl hydrochloride, chemical progress, 2020,39 (2): 696-701.
In view of the above-described situation of hydroxy-modified poly-p-phenylene benzobisoxazole, we have sought to provide a new method for synthesizing hydroxy-modified biphenyl structural PBO complex monomers that is industrially easy to achieve more rationally.
Content of the invention
The invention aims to provide a method for preparing a high-purity hydroxyl modified biphenyl structure PBO composite monomer, which ensures the equivalent ratio of two monomers, has high reaction selectivity, short reaction time, high atom utilization rate, simple post-treatment and high yield and is industrially feasible.
In order to achieve the aim, the invention adopts the following technical scheme:
in a first aspect, the invention provides a hydroxyl modified biphenyl structure PBO composite monomer shown in formula (1),
in a second aspect, the present invention provides a method for synthesizing a hydroxy-modified biphenyl structure PBO monomer represented by the above formula (1), where the method is as follows:
taking 2, 5-dihydroxyterephthalic acid as a raw material, adding sodium hydroxide and deoxidized water in a nitrogen atmosphere, and then heating to 30-50 ℃ (preferably 40-50 ℃) to perform neutralization reaction for 0.2-0.5 hour (preferably 0.3-0.4 h) to obtain a solution containing an intermediate sodium 2, 5-dihydroxyterephthalate; adding 3,3 '-diamino-4, 4' -dihydroxybiphenyl hydrochloride and a reducing agent, reacting for 0.3-0.6 hours (preferably 0.5-0.6 hours) at 60-80 ℃ (preferably 70-80 ℃), and performing post-treatment on the obtained reaction liquid to obtain the hydroxyl modified biphenyl structure PBO composite monomer shown in the formula (1); the mass ratio of the 2, 5-dihydroxyterephthalic acid to the sodium hydroxide is 1:0.3 to 0.5 (preferably 1:0.4 to 0.45); the mass ratio of the 3,3 '-diamino-4, 4' -dihydroxybiphenyl hydrochloride to the 2, 5-dihydroxyterephthalic acid is 1:0.6 to 0.9 (preferably 1:0.7 to 0.74); the mass ratio of the reducing agent to the 3,3 '-diamino-4, 4' -dihydroxybiphenyl hydrochloride is 1: 90-110 (preferably 1:100-110); the reducing agent is stannous chloride, ferrous sulfate or sodium sulfate (preferably stannous chloride).
Further, the volume of the deoxidized water is 20 to 40mL/g (preferably 25.5 mL/g) based on the mass of the 2, 5-dihydroxyterephthalic acid.
Further, the post-treatment is as follows: filtering the obtained reaction liquid with deoxidized water, and vacuum drying the obtained filter cake to obtain the hydroxyl modified biphenyl structure PBO composite monomer shown in the formula (1).
The invention is to wash and filter with deoxidized water after the reaction is finished to remove sodium chloride which is a water-soluble product and a reducing agent which is added, and obtain the water-insoluble hydroxyl modified biphenyl structure PBO composite monomer. In addition, the reducing agent such as stannous chloride has a reducing property of preventing the amino group of 3,3 '-diamino-4, 4' -dihydroxybiphenyl hydrochloride from being oxidized.
The invention also provides an application of the hydroxyl modified biphenyl structure PBO composite monomer shown in the formula (1) in preparing modified PBO fibers.
Specifically, the application is: under the protection of nitrogen, stirring and reacting a polyphosphoric acid mixture containing phosphorus pentoxide, a hydroxyl modified biphenyl structure PBO composite monomer shown in a formula (1) and phosphorus pentoxide for 1 hour at 100 ℃, continuously heating to 120 ℃ and reacting for 1 hour, 140 ℃ and reacting for 1 hour, 160 ℃ and reacting for 1 hour, 180 ℃ and reacting for 1 hour, and then manually drawing, washing and drying the liquid crystal stock solution obtained after the liquid crystal stock solution is heated to 190 ℃ and reacting for 1 hour to obtain the hydroxyl modified biphenyl structure PBO fiber;
the total mass of phosphorus pentoxide and phosphorus pentoxide contained in the phosphorus pentoxide-containing polyphosphoric acid mixture is 85-90% (preferably 87%) of the total mass of phosphorus pentoxide-containing polyphosphoric acid mixture and phosphorus pentoxide; the mass of the hydroxyl modified biphenyl structure PBO composite monomer shown in the formula (1) is 10-20% (preferably 16%) of the total mass of the polyphosphoric acid mixture containing phosphorus pentoxide, the hydroxyl modified biphenyl structure PBO composite monomer shown in the formula (1) and phosphorus pentoxide.
Further, the polyphosphoric acid mixture containing phosphorus pentoxide (polyphosphoric acid in the examples) was purchased from Shanghai Michelia Biochemical technology Co., ltd., lot#: C12710785, and the phosphorus pentoxide content was not less than 85%.
Compared with the prior art, the invention has the beneficial effects that: the invention provides a method for preparing a high-purity hydroxyl modified biphenyl structure PBO composite monomer, which ensures the equivalent ratio of two monomers, has high reaction selectivity, short reaction time, high atom utilization rate, simple post-treatment, high yield and industrial feasibility, and the obtained PBO composite monomer has better polymerization effect for synthesizing modified PBO fibers, improves thermal stability and reflects the larger molecular weight of polymers.
(IV) description of the drawings
Fig. 1: for the HPLC diagram of example 1, the analysis conditions were: column temperature 35 ℃, mobile phase 60% methanol-water buffer solution, ODS C 18 The detection wavelength of the chromatographic column (6.0X106 mm) was 254nm, and the flow rate was 1.0mL/min.
Fig. 2: for the HPLC diagram of example 2, the analysis conditions were: column temperature 35 ℃, mobile phase 60% methanol-water buffer solution, ODS C 18 The detection wavelength of the chromatographic column (6.0X106 mm) was 254nm, and the flow rate was 1.0mL/min.
Fig. 3: for the HPLC diagram of example 3, the analysis conditions were: column temperature 35 ℃, mobile phase 60% methanol-water buffer solution, ODS C 18 The detection wavelength of the chromatographic column (6.0X106 mm) was 254nm, and the flow rate was 1.0mL/min.
Fig. 4: for the HPLC diagram of example 4, the analysis conditions were: column temperature 35 ℃, mobile phase 60% methanol-water buffer solution, ODS C 18 The detection wavelength of the chromatographic column (6.0X106 mm) was 254nm, and the flow rate was 1.0mL/min.
Fig. 5: for the HPLC diagram of example 5, the analysis conditions were: column temperature 35 ℃, mobile phase 60% methanol-water buffer solution, ODS C 18 The detection wavelength of the chromatographic column (6.0X106 mm) was 254nm, and the flow rate was 1.0mL/min.
(fifth) detailed description of the invention
The present invention will be described in more detail by way of examples, but the scope of the present invention is not limited by the examples.
Example 1
2.35g of 2, 5-dihydroxyterephthalic acid, 60mL of deoxidized water and 1g of sodium hydroxide are added into a four-neck flask with a stirring pipe, a condensing pipe and a thermometer, nitrogen is introduced, stirring is started, heating is carried out, the reaction temperature is controlled to be 50 ℃, and neutralization reaction is carried out for 0.3h. 3.2g of 3,3 '-diamino-4, 4' -dihydroxybiphenyl hydrochloride and 0.03g of stannous chloride were added into a four-necked flask, and the temperature was continuously raised to 70 ℃ to react for 0.6h. After the reaction is finished, the mixture is filtered by deoxidized water, a filter cake is dried in vacuum, and 3.63g of white solid product hydroxyl modified biphenyl structure PBO composite monomer is obtained, the mass fraction of HPLC analysis is 98.36%, and the yield is 80.10%.
FT-IR(KBr，cm -1 )：3610.8(s)，3368.9(s)，1658.8(s)，1417.8(s)，1355.1(s)，1108.3(s)。
1 H-NMR(DMSO，δ，ppm)：7.23(2H，s，CH)，6.91(2H，s，CH),6.75(4H，s，CH)。
HPLC analysis conditions of the hydroxyl modified biphenyl structure PBO composite monomer: ODS C 18 Column, 6.0X105 mm, mobile phase: methanol/water buffer=60/40 (V/V), detection wavelength 254nm, flow rate 1.0mL/min.
Examples 2 to 10
Examples 2 to 10, which are obtained by using the same operation steps as in example 1 and taking different parameters according to the parameter ranges described in the present invention, show that the purity of the obtained hydroxy-modified biphenyl structure PBO composite monomer is above 91% under these process conditions, and the net yield of the hydroxy-modified biphenyl structure PBO composite monomer product is above 67%, and can be applied to the industrial synthesis of the hydroxy-modified biphenyl structure PBO composite monomer.
Example 2
2.35g of 2, 5-dihydroxyterephthalic acid, 60mL of deoxidized water and 1g of sodium hydroxide are added into a four-neck flask with a stirring pipe, a condensing pipe and a thermometer, nitrogen is introduced, stirring is started, heating is carried out, the reaction temperature is controlled to be 40 ℃, and neutralization reaction is carried out for 0.3h. 3.2g of 3,3 '-diamino-4, 4' -dihydroxybiphenyl hydrochloride and 0.03g of stannous chloride were added into a four-necked flask, and the temperature was continuously raised to 70 ℃ to react for 0.6h. After the reaction is finished, the mixture is filtered by deoxidized water, a filter cake is dried in vacuum, and 3.64g of white solid product of hydroxyl modified biphenyl structure PBO composite monomer is obtained, and the HPLC analysis mass fraction is 96.73%, and the yield is 78.99%.
Example 3
2.35g of 2, 5-dihydroxyterephthalic acid, 60mL of deoxidized water and 1g of sodium hydroxide are added into a four-neck flask with a stirring pipe, a condensing pipe and a thermometer, nitrogen is introduced, stirring is started, heating is carried out, the reaction temperature is controlled to be 50 ℃, and neutralization reaction is carried out for 0.5h. 3.2g of 3,3 '-diamino-4, 4' -dihydroxybiphenyl hydrochloride and 0.03g of stannous chloride were added into a four-necked flask, and the temperature was continuously raised to 70 ℃ to react for 0.6h. After the reaction is finished, the mixture is filtered by deoxidized water, and a filter cake is dried in vacuum to obtain a white solid product, namely 3.55g of the hydroxyl modified biphenyl structure PBO composite monomer, wherein the mass fraction of the HPLC analysis is 94.10%, and the yield is 74.95%.
Example 4
2.35g of 2, 5-dihydroxyterephthalic acid, 60mL of deoxidized water and 1g of sodium hydroxide are added into a four-neck flask with a stirring pipe, a condensing pipe and a thermometer, nitrogen is introduced, stirring is started, heating is carried out, the reaction temperature is controlled to be 50 ℃, and neutralization reaction is carried out for 0.3h. 3.2g of 3,3 '-diamino-4, 4' -dihydroxybiphenyl hydrochloride and 0.03g of stannous chloride were added into a four-necked flask, and the temperature was continuously raised to 60 ℃ to react for 0.6h. After the reaction is finished, the mixture is filtered by deoxidized water, and a filter cake is dried in vacuum to obtain 3.43g of white solid product, namely the hydroxyl modified biphenyl structure PBO composite monomer, with the mass fraction of 93.99 percent by HPLC analysis, and the yield is 72.33 percent.
Example 5
2.35g of 2, 5-dihydroxyterephthalic acid, 60mL of deoxidized water and 1g of sodium hydroxide are added into a four-neck flask with a stirring pipe, a condensing pipe and a thermometer, nitrogen is introduced, stirring is started, heating is carried out, the reaction temperature is controlled to be 50 ℃, and neutralization reaction is carried out for 0.3h. 3.2g of 3,3 '-diamino-4, 4' -dihydroxybiphenyl hydrochloride and 0.03g of stannous chloride are added into a four-neck flask, and the temperature is continuously increased to 80 ℃ to react for 0.6h. After the reaction is finished, the mixture is filtered by deoxidized water, and a filter cake is dried in vacuum to obtain 3.44g of white solid product, namely the hydroxyl modified biphenyl structure PBO composite monomer, with the mass fraction of 91.08 percent by HPLC analysis, and the yield is 70.29 percent.
Example 6
2.35g of 2, 5-dihydroxyterephthalic acid, 60mL of deoxidized water and 1g of sodium hydroxide are added into a four-neck flask with a stirring pipe, a condensing pipe and a thermometer, nitrogen is introduced, stirring is started, heating is carried out, the reaction temperature is controlled to be 50 ℃, and neutralization reaction is carried out for 0.3h. 3.2g of 3,3 '-diamino-4, 4' -dihydroxybiphenyl hydrochloride and 0.03g of stannous chloride are added into a four-neck flask, and the temperature is continuously increased to 70 ℃ to react for 0.3h. After the reaction is finished, the mixture is filtered by deoxidized water, a filter cake is dried in vacuum, and 3.23g of white solid product hydroxyl modified biphenyl structure PBO composite monomer is obtained, the mass fraction of HPLC analysis is 93.21%, and the yield is 67.55%.
Example 7
Into a four-neck flask equipped with a stirring, condensing tube and thermometer, 2.35g of 2, 5-dihydroxyterephthalic acid, 60mL of deoxidized water and 0.94g of sodium hydroxide are added, nitrogen is introduced, stirring is started, heating is carried out, the reaction temperature is controlled to be 50 ℃, and neutralization reaction is carried out for 0.3h. 3.2g of 3,3 '-diamino-4, 4' -dihydroxybiphenyl hydrochloride and 0.03g of stannous chloride were added into a four-necked flask, and the temperature was continuously raised to 70 ℃ to react for 0.6h. After the reaction is finished, the mixture is filtered by deoxidized water, a filter cake is dried in vacuum, and 3.38g of white solid product of hydroxyl modified biphenyl structure PBO composite monomer is obtained, the mass fraction of HPLC analysis is 95.56%, and the yield is 72.47%.
Example 8
2.35g of 2, 5-dihydroxyterephthalic acid, 47mL of deoxidized water and 1g of sodium hydroxide are added into a four-neck flask with a stirring pipe, a condensing pipe and a thermometer, nitrogen is introduced, stirring is started, heating is carried out, the reaction temperature is controlled to be 50 ℃, and neutralization reaction is carried out for 0.3h. 3.2g of 3,3 '-diamino-4, 4' -dihydroxybiphenyl hydrochloride and 0.03g of stannous chloride were added into a four-necked flask, and the temperature was continuously raised to 70 ℃ to react for 0.6h. After the reaction is finished, the mixture is filtered by deoxidized water, and a filter cake is dried in vacuum to obtain 3.47g of white solid product, namely the hydroxyl modified biphenyl structure PBO composite monomer, with the mass fraction of 94.78 percent by HPLC analysis, and the yield is 73.79 percent.
Example 9
2.35g of 2, 5-dihydroxyterephthalic acid, 60mL of deoxidized water and 1g of sodium hydroxide are added into a four-neck flask with a stirring pipe, a condensing pipe and a thermometer, nitrogen is introduced, stirring is started, heating is carried out, the reaction temperature is controlled to be 50 ℃, and neutralization reaction is carried out for 0.3h. 2.61g of 3,3 '-diamino-4, 4' -dihydroxybiphenyl hydrochloride and 0.03g of stannous chloride are added into a four-necked flask, and the temperature is continuously increased to 70 ℃ to react for 0.6h. After the reaction is finished, the mixture is filtered by deoxidized water, a filter cake is dried in vacuum, and 3.28g of white solid product of hydroxyl modified biphenyl structure PBO composite monomer is obtained, the mass fraction of HPLC analysis is 93.72%, and the yield is 68.97%.
Example 10
2.35g of 2, 5-dihydroxyterephthalic acid, 60mL of deoxidized water and 1g of sodium hydroxide are added into a four-neck flask with a stirring pipe, a condensing pipe and a thermometer, nitrogen is introduced, stirring is started, heating is carried out, the reaction temperature is controlled to be 50 ℃, and neutralization reaction is carried out for 0.3h. 3.2g of 3,3 '-diamino-4, 4' -dihydroxybiphenyl hydrochloride and 0.05g of stannous chloride were added into a four-necked flask, and the temperature was continuously raised to 70 ℃ to react for 0.6h. After the reaction is finished, the mixture is filtered by deoxidized water, and a filter cake is dried in vacuum to obtain 3.68g of white solid product, namely the hydroxyl modified biphenyl structure PBO composite monomer, with the mass fraction of 92.34 percent by HPLC analysis, and the yield is 76.24 percent.
Examples 11 to 13
The preparation process of example 1 was adopted, and conditions outside the parameters described in the present invention were adopted for the test, so that the obtained product was poor in effect.
Example 11
2.35g of 2, 5-dihydroxyterephthalic acid, 30mL of deoxidized water and 1g of sodium hydroxide are added into a four-neck flask with a stirring pipe, a condensing pipe and a thermometer, nitrogen is introduced, stirring is started, heating is carried out, the reaction temperature is controlled to be 50 ℃, and neutralization reaction is carried out for 0.3h. 3.2g of 3,3 '-diamino-4, 4' -dihydroxybiphenyl hydrochloride and 0.05g of stannous chloride were added into a four-necked flask, and the temperature was continuously raised to 70 ℃ to react for 0.6h. After the reaction is finished, the mixture is filtered by deoxidized water, and a filter cake is dried in vacuum to obtain 3.27g of white solid product, namely the hydroxyl modified biphenyl structure PBO composite monomer, with the mass fraction of 82.34 percent by HPLC analysis, and the yield is 60.41 percent.
Example 12
2.35g of 2, 5-dihydroxyterephthalic acid, 60mL of deoxidized water and 2g of sodium hydroxide are added into a four-neck flask with a stirring pipe, a condensing pipe and a thermometer, nitrogen is introduced, stirring is started, heating is carried out, the reaction temperature is controlled to be 50 ℃, and neutralization reaction is carried out for 0.3h. 3.2g of 3,3 '-diamino-4, 4' -dihydroxybiphenyl hydrochloride and 0.05g of stannous chloride were added into a four-necked flask, and the temperature was continuously raised to 70 ℃ to react for 0.6h. After the reaction is finished, the mixture is filtered by deoxidized water, a filter cake is dried in vacuum, and a white solid product of the hydroxyl modified biphenyl structure PBO composite monomer 3.67g is obtained, and the HPLC analysis mass fraction is 80.56 percent, and the yield is 66.33 percent.
Example 13
2.35g of 2, 5-dihydroxyterephthalic acid, 60mL of deoxidized water and 1g of sodium hydroxide are added into a four-neck flask with a stirring pipe, a condensing pipe and a thermometer, nitrogen is introduced, stirring is started, heating is carried out, the reaction temperature is controlled to be 50 ℃, and neutralization reaction is carried out for 0.3h. 3.2g of 3,3 '-diamino-4, 4' -dihydroxybiphenyl hydrochloride and 0.05g of stannous chloride were added into a four-necked flask, and the temperature was continuously raised to 90 ℃ to react for 0.6h. After the reaction is finished, the mixture is filtered by deoxidized water, a filter cake is dried in vacuum, and 3.52g of white solid product of hydroxyl modified biphenyl structure PBO composite monomer is obtained, the mass fraction of HPLC analysis is 78.67%, and the yield is 62.13%.
Example 14
Weighing 3.55g of synthesized PBO composite monomer with a hydroxyl modified biphenyl structure, 2.70g of phosphorus pentoxide (the content is more than or equal to 98 percent), 15.70g of polyphosphoric acid (Hn+2PnO3n+1, shanghai microphone Biochemical technology Co., ltd., lot#: C12710785, the phosphorus pentoxide content is more than or equal to 85 percent), sequentially adding the mixture into a glass reactor, introducing nitrogen into the reactor, starting stirring, heating to 100 ℃ for reaction for 1h, blackening the reaction system mixture, continuously heating to 120 ℃ for reaction for 1h, 140 ℃ for reaction for 1h, 160 ℃ for reaction for 1h, and 180 ℃ for reaction for 1h, and heating to 190 ℃ for reaction for 1h to obtain yellow fluorescence, thereby reaching the reaction end point. After the polymerization reaction is finished, the liquid crystal stock solution is manually drawn by a clean glass rod, and the obtained monofilament fiber is put into hot water to wash out excessive polyphosphoric acid. The monofilament fiber was dried in vacuo at 100℃to give a reddish brown modified PBO fiber.
Comparative example 1
2g of 3,3 '-diamino-4, 4' -dihydroxybiphenyl hydrochloride and 15g of polyphosphoric acid (Hn+2PnO3n+1, shanghai microphone Biochemical technology Co., ltd., lot#: C12710785, phosphorus pentoxide content more than or equal to 85%) are weighed and added into a glass reactor, nitrogen is introduced into the reactor, stirring is started, the temperature is raised to 80 ℃ for carrying out a HCl removal process, after 7h, pH test paper is used for detecting to be neutral, 1.5g of 2, 5-dihydroxyterephthalic acid is added, 2.5g of phosphorus pentoxide (content more than or equal to 98%) is added, the temperature is raised to 100 ℃ for reaction for 1h, the reaction system mixture turns black, the temperature is raised to 120 ℃ for reaction for 1h, the temperature is raised to 140 ℃ for reaction for 1h, the temperature is raised to 160 ℃ for reaction for 1h, the temperature is raised to 190 ℃ for reaction for 1h, and a small amount of yellow fluorescence is generated until the reaction end point is reached. After the polymerization reaction is finished, the liquid crystal stock solution is manually drawn by a clean glass rod, and the monofilament fiber is put into hot water to wash out excessive polyphosphoric acid, so that small-section solid is obtained. The small solid segments were dried in vacuo at 100deg.C to give purple modified PBO fibers.
TABLE 1
Compared with the two monomer mixing polycondensation methods, the method has the following positive effects: (1) The reaction process parameters of the composite monomer method provided by the invention are easy to control, the equivalent ratio polymerization of the two monomers is ensured, the degassing process is avoided, the reaction time can be greatly shortened, the reaction efficiency is improved, the energy consumption is less, and the industrial feasibility is higher. (2) The composite monomer method adopted by the invention for synthesizing the modified PBO fiber has better wiredrawing effect, improves the thermal stability and reflects the larger molecular weight of the polymer.
Claims (6)
1. A synthesis method of a hydroxyl modified biphenyl structure PBO composite monomer shown in a formula (1) is characterized by comprising the following steps:
taking 2, 5-dihydroxyterephthalic acid as a raw material, adding sodium hydroxide and deoxidized water in a nitrogen atmosphere, and then heating to 30-50 ℃ for neutralization reaction for 0.2-0.5 hour to obtain a solution containing an intermediate sodium 2, 5-dihydroxyterephthalate; adding 3,3 '-diamino-4, 4' -dihydroxybiphenyl hydrochloride and a reducing agent, reacting for 0.3-0.6 hour at 60-80 ℃, and performing post-treatment on the obtained reaction liquid to obtain the hydroxyl modified biphenyl structure PBO composite monomer shown in the formula (1); the mass ratio of the 2, 5-dihydroxyterephthalic acid to the sodium hydroxide is 1:0.3 to 0.5; the mass ratio of the 3,3 '-diamino-4, 4' -dihydroxybiphenyl hydrochloride to the 2, 5-dihydroxyterephthalic acid is 1:0.6 to 0.9; the mass ratio of the reducing agent to the 3,3 '-diamino-4, 4' -dihydroxybiphenyl hydrochloride is 1: 90-110; the reducing agent is stannous chloride, ferrous sulfate or sodium sulfate.
2. The method for synthesizing the hydroxy-modified biphenyl structure PBO composite monomer shown in formula (1) in claim 1, which is characterized in that: the volume of the deoxidized water is 20-40 mL/g based on the mass of the 2, 5-dihydroxyterephthalic acid.
3. The method for synthesizing the hydroxy-modified biphenyl structure PBO composite monomer shown in formula (1) in claim 1, which is characterized in that: the reducing agent is stannous chloride.
4. The method for synthesizing the hydroxy-modified biphenyl structure PBO composite monomer shown in formula (1) in claim 1, which is characterized in that: the mass ratio of the 2, 5-dihydroxyterephthalic acid to the sodium hydroxide is 1:0.4 to 0.45.
5. The method for synthesizing the hydroxy-modified biphenyl structure PBO composite monomer shown in formula (1) in claim 1, which is characterized in that: the mass ratio of the 3,3 '-diamino-4, 4' -dihydroxybiphenyl hydrochloride to the 2, 5-dihydroxyterephthalic acid is 1:0.7 to 0.74.
6. The method for synthesizing a hydroxyl-modified biphenyl structure PBO composite monomer represented by formula (1) according to claim 1, wherein the post-treatment is: filtering the obtained reaction liquid with deoxidized water, and vacuum drying the obtained filter cake to obtain the hydroxyl modified biphenyl structure PBO composite monomer shown in the formula (1).
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| CN102532546A (en) * | 2011-11-11 | 2012-07-04 | 浙江工业大学 | Preparation and application of hydroxyl modified poly-p-phenylene benzo imidazolinyl resin |
| CN112390721A (en) * | 2020-10-27 | 2021-02-23 | 浙江工业大学 | Synthetic method of 3,3 '-diamino-4, 4' dihydroxybiphenyl hydrochloride |
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| CN102532546A (en) * | 2011-11-11 | 2012-07-04 | 浙江工业大学 | Preparation and application of hydroxyl modified poly-p-phenylene benzo imidazolinyl resin |
| CN112390721A (en) * | 2020-10-27 | 2021-02-23 | 浙江工业大学 | Synthetic method of 3,3 '-diamino-4, 4' dihydroxybiphenyl hydrochloride |
Non-Patent Citations (4)
| Title |
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| 2,6-二羟基改性PBO 的AB 型新单体的合成;赵德明等;化工进展;第34卷(第2期);519-523 * |
| Theoretical study and experimental verification of a novel conjugated and coplanar HPBO polymers with hydrogen bond structure;Jianting Zhang等;Polymer;第160卷;第11-18页 * |
| 吴纯鑫等.羟基改性聚对亚苯基苯并二唑单体3,3′-二氨基-4,4′-二羟基联苯盐酸盐的合成.化工进展.2019,第39卷(第2期),第696-701页. * |
| 羟基改性聚对亚苯基苯并二唑单体3,3′-二氨基-4,4′-二羟基联苯盐酸盐的合成;吴纯鑫等;化工进展;第39卷(第2期);第696-701页 * |
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