CN114790290A - Synthetic method of hydroxyl modified biphenyl structure PBO composite monomer - Google Patents
Synthetic method of hydroxyl modified biphenyl structure PBO composite monomer Download PDFInfo
- Publication number
- CN114790290A CN114790290A CN202210513685.4A CN202210513685A CN114790290A CN 114790290 A CN114790290 A CN 114790290A CN 202210513685 A CN202210513685 A CN 202210513685A CN 114790290 A CN114790290 A CN 114790290A
- Authority
- CN
- China
- Prior art keywords
- hydroxyl
- composite monomer
- formula
- biphenyl structure
- modified biphenyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000178 monomer Substances 0.000 title claims abstract description 64
- 239000002131 composite material Substances 0.000 title claims abstract description 56
- 238000010189 synthetic method Methods 0.000 title abstract description 3
- 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 26
- 238000010438 heat treatment Methods 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 22
- 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
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 4
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims description 37
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 33
- 238000003756 stirring Methods 0.000 claims description 30
- 239000000203 mixture Substances 0.000 claims description 24
- 229920000137 polyphosphoric acid Polymers 0.000 claims description 17
- 229910052757 nitrogen Inorganic materials 0.000 claims description 16
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 15
- 239000000835 fiber Substances 0.000 claims description 15
- 239000012065 filter cake Substances 0.000 claims description 15
- 238000005406 washing Methods 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 12
- 238000001914 filtration Methods 0.000 claims description 12
- 230000002194 synthesizing effect Effects 0.000 claims description 10
- 239000003638 chemical reducing agent Substances 0.000 claims description 9
- 239000012295 chemical reaction liquid Substances 0.000 claims description 4
- 239000004973 liquid crystal related substance Substances 0.000 claims description 4
- 239000011550 stock solution 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
- 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
- 239000000243 solution Substances 0.000 claims description 2
- HAWRZRZSKGSQDX-UHFFFAOYSA-N 2,5-dihydroxyterephthalic acid;sodium Chemical compound [Na].OC(=O)C1=CC(O)=C(C(O)=O)C=C1O HAWRZRZSKGSQDX-UHFFFAOYSA-N 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 72
- 239000012265 solid product Substances 0.000 abstract description 16
- VIQSRHWJEKERKR-UHFFFAOYSA-L disodium;terephthalate Chemical compound [Na+].[Na+].[O-]C(=O)C1=CC=C(C([O-])=O)C=C1 VIQSRHWJEKERKR-UHFFFAOYSA-L 0.000 abstract description 3
- 239000006227 byproduct Substances 0.000 abstract 1
- 231100000331 toxic Toxicity 0.000 abstract 1
- 230000002588 toxic effect Effects 0.000 abstract 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 19
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 description 15
- 238000006116 polymerization reaction Methods 0.000 description 8
- 239000007853 buffer solution Substances 0.000 description 6
- 238000001514 detection method Methods 0.000 description 6
- GBMDVOWEEQVZKZ-UHFFFAOYSA-N methanol;hydrate Chemical compound O.OC GBMDVOWEEQVZKZ-UHFFFAOYSA-N 0.000 description 5
- 238000006068 polycondensation reaction Methods 0.000 description 5
- 230000000630 rising effect Effects 0.000 description 5
- 239000011521 glass Substances 0.000 description 4
- 230000035484 reaction time Effects 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
- 230000000694 effects Effects 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000007872 degassing Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000047 product Substances 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
- 125000003277 amino group Chemical group 0.000 description 1
- POJOORKDYOPQLS-UHFFFAOYSA-L barium(2+) 5-chloro-2-[(2-hydroxynaphthalen-1-yl)diazenyl]-4-methylbenzenesulfonate Chemical compound [Ba+2].C1=C(Cl)C(C)=CC(N=NC=2C3=CC=CC=C3C=CC=2O)=C1S([O-])(=O)=O.C1=C(Cl)C(C)=CC(N=NC=2C3=CC=CC=C3C=CC=2O)=C1S([O-])(=O)=O POJOORKDYOPQLS-UHFFFAOYSA-L 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000012822 chemical development Methods 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
- 238000010586 diagram Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000003779 heat-resistant material Substances 0.000 description 1
- 229920006253 high performance fiber Polymers 0.000 description 1
- 239000000463 material Substances 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
- 229920000927 poly(p-phenylene benzobisoxazole) Polymers 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 230000001603 reducing effect Effects 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 238000005491 wire drawing Methods 0.000 description 1
Images
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
Landscapes
- 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-dihydroxy terephthalic acid as a raw material, adding sodium hydroxide and deoxygenated water in a nitrogen atmosphere, heating to 30-50 ℃ to perform a neutralization reaction for 0.2-0.5 hour to obtain an intermediate 2, 5-dihydroxy sodium terephthalate; and then, taking the intermediate 2, 5-dihydroxy sodium terephthalate and 3,3 '-diamino-4, 4' -dihydroxybiphenyl hydrochloride as raw materials, adding stannous chloride in a nitrogen atmosphere, and reacting at the temperature of 60-80 ℃ for 0.3-0.6 hour to obtain a white solid product, namely the hydroxyl modified biphenyl structure PBO composite monomer. The method has the advantages of easily controlled reaction process parameters, no generation of toxic byproducts, high atom utilization rate, high yield, high purity and simple post-treatment.
Description
(I) technical field
The invention relates to a synthesis method of a hydroxyl modified biphenyl PBO composite monomer.
(II) background of the invention
A composite monomer represented by formula (1) is a compound monomer of a hydroxyl-modified biphenyl structure PBO, is a raw material for preparing a hydroxyl-modified poly-p-phenylene benzobisoxazole by polymerization, and is applicable to the fields of high-performance fibers, photoelectric materials, heat-resistant materials, and the like (long, royal brilliant red, venous, poly-p-phenylene benzobisoxazole fiber modification technology, synthetic fiber industry, 2018,41(1): 47-52.).
At present, 3 '-diamino-4, 4' -dihydroxybiphenyl hydrochloride and 2, 5-dihydroxyterephthalic acid are subjected to mixed polycondensation reaction at high temperature in polyphosphoric acid by using a hydroxyl modified poly-p-phenylene benzobisoxazole polymerization method, and the defects that the polymerization effect is influenced because two monomers are difficult to be subjected to uniform polycondensation in equal equivalent ratio, the fiber strength is influenced in the HCl removal process and the like exist. Therefore, starting from a polymerization method of PBO fibers, a hydroxyl modified biphenyl PBO composite monomer is synthesized, and the composite monomer is used for carrying out self-polycondensation reaction in polyphosphoric acid at a high temperature, so that the method realizes the uniform polycondensation of two monomers with an equivalent ratio, avoids a degassing process, shortens the reaction time and improves the reaction efficiency. (Wu Chun Xin, Lou Lu Tu Di Tu, Chen Di Tu et al. synthesis of hydroxyl modified poly-p-phenylene benzo dioxazole monomer 3,3 '-diamino-4, 4' -dihydroxy biphenyl hydrochloride, chemical development 2020,39(2):696 + 701.).
In view of the situation of the hydroxyl modified poly (p-phenylene benzobisoxazole), a new method for industrially and easily synthesizing the PBO composite monomer with the hydroxyl modified biphenyl structure more reasonably is searched and provided.
(three) summary of 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 purpose of the invention, 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 hydroxyl-modified biphenyl-structure PBO composite monomer represented by formula (1), the method comprising:
taking 2, 5-dihydroxy terephthalic acid as a raw material, adding sodium hydroxide and deoxygenated water in a nitrogen atmosphere, heating to 30-50 ℃ (preferably 40-50 ℃) to perform neutralization reaction for 0.2-0.5 hour (preferably 0.3-0.4 hour), and obtaining a solution containing an intermediate 2, 5-dihydroxy sodium terephthalate; adding 3,3 '-diamino-4, 4' -dihydroxybiphenyl hydrochloride and a reducing agent, reacting for 0.3-0.6 h (preferably 0.5-0.6 h) at 60-80 ℃ (preferably 70-80 ℃), and carrying out aftertreatment 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-dihydroxy terephthalic 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 deoxygenated water is 20 to 40mL/g (preferably 25.5mL/g) based on the mass of the 2, 5-dihydroxyterephthalic acid.
Further, the post-treatment is: washing and filtering the obtained reaction liquid by using deoxygenated water, and drying the obtained filter cake in vacuum to obtain the hydroxyl modified biphenyl PBO composite monomer shown in the formula (1).
The invention uses deoxidized water for washing and filtering after the reaction is finished, in order to remove the water-soluble product sodium chloride and the added reducing agent, and obtain the water-insoluble hydroxyl modified biphenyl PBO composite monomer. In addition, the reducing properties of reducing agents such as stannous chloride can prevent the amino group of 3,3 '-diamino-4, 4' -dihydroxybiphenyl hydrochloride from being oxidized.
The invention also provides application of the hydroxyl modified biphenyl PBO composite monomer shown in the formula (1) in preparation of modified PBO fibers.
Specifically, the application is as follows: under the protection of nitrogen, stirring a polyphosphoric acid mixture containing phosphorus pentoxide, a hydroxyl modified biphenyl structure PBO composite monomer shown in a formula (1), and phosphorus pentoxide to react for 1 hour at 100 ℃, continuously heating to 120 ℃ to react for 1 hour, reacting at 140 ℃ for 1 hour, reacting at 160 ℃ for 1 hour, reacting at 180 ℃ for 1 hour, heating to 190 ℃ again to react for 1 hour, and then manually drawing, washing and drying the obtained liquid crystal stock solution to obtain the hydroxyl modified biphenyl structure PBO fiber;
the total mass of the phosphorus pentoxide and the phosphorus pentoxide contained in the phosphorus pentoxide-containing polyphosphoric acid mixture is 85-90% (preferably 87%) of the total mass of the phosphorus pentoxide-containing polyphosphoric acid mixture and the 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 the phosphorus pentoxide.
Further, the polyphosphoric acid mixture containing phosphorus pentoxide (polyphosphoric acid in the examples) is obtained from Shanghai Michelin Biochemical technology, Inc., Lot #: C12710785, and the phosphorus pentoxide content is not less than 85%.
Compared with the prior art, the invention has the beneficial effects that: the invention provides a method for preparing the high-purity hydroxyl modified biphenyl PBO composite monomer with the structure, 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 of synthesizing the modified PBO fiber, improves the thermal stability and reflects larger molecular weight of the polymer.
(IV) description of the drawings
FIG. 1:for the HPLC profile of example 1, analytical conditions: the column temperature is 35 ℃, and the mobile phase is 60 percent methanol-water buffer solution, ODS C 18 The chromatographic column (6.0X 150mm) had a detection wavelength of 254nm and a flow rate of 1.0 mL/min.
FIG. 2 is a schematic diagram: analytical conditions for the HPLC profile of example 2: the column temperature is 35 ℃, and the mobile phase is 60 percent methanol-water buffer solution, ODS C 18 The chromatographic column (6.0X 150mm) had a detection wavelength of 254nm and a flow rate of 1.0 mL/min.
FIG. 3: for the HPLC profile of example 3, analytical conditions: the column temperature is 35 ℃, the mobile phase is 60 percent methanol-water buffer solution, ODS C 18 The chromatographic column (6.0X 150mm) had a detection wavelength of 254nm and a flow rate of 1.0 mL/min.
FIG. 4: the HPLC profile for example 4, analytical conditions: the column temperature is 35 ℃, the mobile phase is 60 percent methanol-water buffer solution, ODS C 18 The chromatographic column (6.0X 150mm) had a detection wavelength of 254nm and a flow rate of 1.0 mL/min.
FIG. 5: analytical conditions for the HPLC profile of example 5: the column temperature is 35 ℃, and the mobile phase is 60 percent methanol-water buffer solution, ODS C 18 The chromatographic column (6.0X 150mm) had a detection wavelength of 254nm and a flow rate of 1.0 mL/min.
(V) detailed description of the preferred embodiments
The present invention is illustrated in more detail by 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 deoxygenated water and 1g of sodium hydroxide are added into a four-neck flask provided with a stirring and condensing tube and a thermometer, nitrogen is introduced, stirring is started, heating is carried out, the reaction temperature is controlled at 50 ℃, a neutralization reaction is carried out, and the reaction lasts for 0.3 h. 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 raised to 70 ℃ for reaction for 0.6 h. After the reaction is finished, the mixture is washed and filtered by deoxidized water, a filter cake is dried in vacuum, and a white solid product, namely the hydroxyl modified biphenyl PBO composite monomer 3.63g is obtained, the HPLC analysis mass fraction 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 are as follows: ODS C 18 Column, 6.0 × 150mm, mobile phase: methanol/water buffer solution (60/40 (V/V)), detection wavelength 254nm, flow rate 1.0 mL/min.
Examples 2 to 10
In examples 2 to 10, the same operation steps as in example 1 were adopted, and different parameters were taken according to the parameter ranges described in the present invention, and it can be seen that the purity of the obtained hydroxyl-modified biphenyl structure PBO composite monomer was all over 91%, and the net yield of the hydroxyl-modified biphenyl structure PBO composite monomer product was all over 67%, and all the above-mentioned process conditions can be applied to the industrial synthesis of hydroxyl-modified biphenyl structure PBO composite monomer.
Example 2
2.35g of 2, 5-dihydroxyterephthalic acid, 60mL of deoxygenated water and 1g of sodium hydroxide are added into a four-neck flask provided with a stirring and condensing tube and a thermometer, nitrogen is introduced, stirring is started, heating is carried out, the reaction temperature is controlled at 40 ℃, a neutralization reaction is carried out, and the reaction lasts for 0.3 h. 3.2g of 3,3 '-diamino-4, 4' -dihydroxybiphenyl hydrochloride and 0.03g of stannous chloride are added into a four-neck flask, the temperature is continuously raised to 70 ℃, and the reaction is carried out for 0.6 h. And after the reaction is finished, washing and filtering the mixture by using deoxygenated water, and drying a filter cake in vacuum to obtain 3.64g of a white solid product, namely the hydroxyl-modified biphenyl structure PBO composite monomer, wherein the mass fraction is 96.73% by HPLC analysis, and the yield is 78.99%.
Example 3
2.35g of 2, 5-dihydroxyterephthalic acid, 60mL of deoxygenated water and 1g of sodium hydroxide are added into a four-neck flask provided with a stirring and condensing tube and a thermometer, nitrogen is introduced, stirring is started, heating is carried out, the reaction temperature is controlled at 50 ℃, a neutralization reaction is carried out, and the reaction lasts for 0.5 h. 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 raised to 70 ℃ for reaction for 0.6 h. After the reaction is finished, the mixture is washed and filtered by deoxidized water, a filter cake is dried in vacuum, and a white solid product, namely the hydroxyl modified biphenyl PBO composite monomer with 3.55g is obtained, wherein the mass fraction is 94.10% by HPLC analysis, and the yield is 74.95%.
Example 4
2.35g of 2, 5-dihydroxyterephthalic acid, 60mL of deoxygenated water and 1g of sodium hydroxide are added into a four-neck flask provided with a stirring and condensing tube and a thermometer, nitrogen is introduced, stirring is started, heating is carried out, the reaction temperature is controlled at 50 ℃, a neutralization reaction is carried out, and the reaction lasts for 0.3 h. 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 raised to 60 ℃ for reaction for 0.6 h. After the reaction is finished, the mixture is washed and filtered by deoxidized water, a filter cake is dried in vacuum, and a white solid product, namely the hydroxyl modified biphenyl PBO composite monomer with 3.43g is obtained, wherein the mass fraction is 93.99% by HPLC analysis, and the yield is 72.33%.
Example 5
2.35g of 2, 5-dihydroxyterephthalic acid, 60mL of deoxygenated water and 1g of sodium hydroxide are added into a four-neck flask provided with a stirring and condensing tube and a thermometer, nitrogen is introduced, stirring is started, heating is carried out, the reaction temperature is controlled at 50 ℃, a neutralization reaction is carried out, and the reaction lasts for 0.3 h. 3.2g of 3,3 '-diamino-4, 4' -dihydroxybiphenyl hydrochloride and 0.03g of stannous chloride are added into a four-neck flask, the temperature is continuously raised to 80 ℃, and the reaction lasts for 0.6 h. And after the reaction is finished, washing and filtering the mixture by using deoxygenated water, and drying a filter cake in vacuum to obtain 3.44g of a white solid product, namely the hydroxyl-modified biphenyl structure PBO composite monomer, wherein the HPLC analysis mass fraction is 91.08%, and the yield is 70.29%.
Example 6
In a four-neck flask with a stirring, condensing tube and thermometer, 2.35g of 2, 5-dihydroxyterephthalic acid, 60mL of deoxygenated water and 1g of sodium hydroxide are added, nitrogen is introduced, stirring is started, heating and temperature rising are carried out, the reaction temperature is controlled at 50 ℃, neutralization reaction is carried out, and the reaction lasts for 0.3 h. 3.2g of 3,3 '-diamino-4, 4' -dihydroxybiphenyl hydrochloride and 0.03g of stannous chloride are added into a four-neck flask, the temperature is continuously raised to 70 ℃, and the reaction is carried out for 0.3 h. And (3) after the reaction is finished, washing and filtering the mixture by using deoxygenated water, and drying a filter cake in vacuum to obtain 3.23g of a white solid product, namely the hydroxyl modified biphenyl structure PBO composite monomer, wherein the HPLC analysis mass fraction is 93.21%, and the yield is 67.55%.
Example 7
In a four-neck flask equipped with a stirring, condensing tube and thermometer, 2.35g of 2, 5-dihydroxyterephthalic acid, 60mL of deoxygenated water and 0.94g of sodium hydroxide are added, nitrogen is introduced, stirring is started, heating and temperature rising are carried out, the reaction temperature is controlled at 50 ℃, neutralization reaction is carried out, and the reaction lasts for 0.3 h. 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 raised to 70 ℃ for reaction for 0.6 h. After the reaction is finished, deoxygenated water is used for washing and filtering, a filter cake is dried in vacuum, and 3.38g of white solid product PBO composite monomer with the hydroxyl modified biphenyl structure is obtained, the HPLC analysis mass fraction is 95.56%, and the yield is 72.47%.
Example 8
2.35g of 2, 5-dihydroxyterephthalic acid, 47mL of deoxygenated water and 1g of sodium hydroxide were added into a four-necked flask equipped with a stirring and condensing tube and a thermometer, nitrogen gas was introduced, stirring was started, the temperature was raised by heating, the reaction temperature was controlled at 50 ℃ to carry out a neutralization reaction, and the reaction was carried out for 0.3 hour. 3.2g of 3,3 '-diamino-4, 4' -dihydroxybiphenyl hydrochloride and 0.03g of stannous chloride are added into a four-neck flask, the temperature is continuously raised to 70 ℃, and the reaction is carried out for 0.6 h. And after the reaction is finished, washing and filtering the mixture by using deoxygenated water, and drying a filter cake in vacuum to obtain 3.47g of a white solid product, namely the hydroxyl-modified biphenyl structure PBO composite monomer, wherein the mass fraction is 94.78% by HPLC analysis, and the yield is 73.79%.
Example 9
2.35g of 2, 5-dihydroxyterephthalic acid, 60mL of deoxygenated water and 1g of sodium hydroxide are added into a four-neck flask provided with a stirring and condensing tube and a thermometer, nitrogen is introduced, stirring is started, heating is carried out, the reaction temperature is controlled at 50 ℃, a neutralization reaction is carried out, and the reaction lasts for 0.3 h. 2.61g 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 raised to 70 ℃ for reaction for 0.6 h. And after the reaction is finished, washing and filtering the mixture by using deoxygenated water, and drying a filter cake in vacuum to obtain 3.28g of a white solid product, namely the hydroxyl-modified biphenyl structure PBO composite monomer, wherein the HPLC analysis mass fraction is 93.72%, and the yield is 68.97%.
Example 10
In a four-neck flask with a stirring, condensing tube and thermometer, 2.35g of 2, 5-dihydroxyterephthalic acid, 60mL of deoxygenated water and 1g of sodium hydroxide are added, nitrogen is introduced, stirring is started, heating and temperature rising are carried out, the reaction temperature is controlled at 50 ℃, neutralization reaction is carried out, and the reaction lasts for 0.3 h. 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 further raised to 70 ℃ to react for 0.6 h. After the reaction is finished, deoxygenated water is used for washing and filtering, a filter cake is dried in vacuum, and 3.68g of white solid product PBO composite monomer with the hydroxyl modified biphenyl structure is obtained, wherein the mass fraction is 92.34% through HPLC analysis, and the yield is 76.24%.
Examples 11 to 13
The preparation process of example 1 was used, and the results of the tests were poor, taking conditions other than the parameters described in the present invention.
Example 11
2.35g of 2, 5-dihydroxyterephthalic acid, 30mL of deoxygenated water and 1g of sodium hydroxide are added into a four-neck flask provided with a stirring and condensing tube and a thermometer, nitrogen is introduced, stirring is started, heating is carried out, the reaction temperature is controlled at 50 ℃, a neutralization reaction is carried out, and the reaction lasts for 0.3 h. 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 further raised to 70 ℃ to react for 0.6 h. After the reaction is finished, the mixture is washed and filtered by deoxidized water, and a filter cake is dried in vacuum to obtain 3.27g of a white solid product PBO composite monomer with the hydroxyl modified biphenyl structure, wherein the mass fraction of the white solid product PBO composite monomer is 82.34 percent by HPLC analysis, and the yield of the white solid product PBO composite monomer is 60.41 percent.
Example 12
In a four-neck flask with a stirring, condensing tube and thermometer, 2.35g of 2, 5-dihydroxyterephthalic acid, 60mL of deoxygenated water and 2g of sodium hydroxide are added, nitrogen is introduced, stirring is started, heating and temperature rising are carried out, the reaction temperature is controlled at 50 ℃, neutralization reaction is carried out, and the reaction lasts for 0.3 h. 3.2g of 3,3 '-diamino-4, 4' -dihydroxybiphenyl hydrochloride and 0.05g of stannous chloride are added into a four-neck flask, and the temperature is continuously raised to 70 ℃ for reaction for 0.6 h. And after the reaction is finished, washing and filtering the mixture by using deoxygenated water, and drying a filter cake in vacuum to obtain 3.67g of a white solid product, namely the hydroxyl modified biphenyl structure PBO composite monomer, wherein the HPLC analysis mass fraction is 80.56%, and the yield is 66.33%.
Example 13
In a four-neck flask with a stirring, condensing tube and thermometer, 2.35g of 2, 5-dihydroxyterephthalic acid, 60mL of deoxygenated water and 1g of sodium hydroxide are added, nitrogen is introduced, stirring is started, heating and temperature rising are carried out, the reaction temperature is controlled at 50 ℃, neutralization reaction is carried out, and the reaction lasts for 0.3 h. 3.2g of 3,3 '-diamino-4, 4' -dihydroxybiphenyl hydrochloride and 0.05g of stannous chloride are added into a four-neck flask, and the temperature is continuously raised to 90 ℃ for reaction for 0.6 h. And after the reaction is finished, washing and filtering the mixture by using deoxygenated water, and drying a filter cake in vacuum to obtain 3.52g of a white solid product, namely the hydroxyl modified biphenyl structure PBO composite monomer, wherein the HPLC analysis mass fraction is 78.67%, and the yield is 62.13%.
Example 14
3.55g of synthesized hydroxyl modified biphenyl structure PBO composite monomer, 2.70g of phosphorus pentoxide (the content is more than or equal to 98 percent) and 15.70g of polyphosphoric acid (Hn +2PnO3n +1, Shanghai Michelin Biochemical technology Co., Ltd., Lot #: C12710785, the content of phosphorus pentoxide is more than or equal to 85 percent) are weighed and sequentially added into a glass reactor, nitrogen is introduced into the reactor, stirring is started, the temperature is increased to 100 ℃ for reaction for 1 hour, the reaction system mixture is blackened, the temperature is continuously increased to 120 ℃ for reaction for 1 hour, the temperature is increased to 140 ℃ for reaction for 1 hour, the temperature is increased to 160 ℃ for reaction for 1 hour, the temperature is increased to 190 ℃ for reaction for 1 hour, the mixture is reacted for 1 hour to generate yellow fluorescence, and the reaction end point is reached. After the polymerization reaction is finished, manually drawing the liquid crystal stock solution by using a clean glass rod to obtain monofilament fibers, and putting the monofilament fibers into hot water to wash off excessive polyphosphoric acid. And (3) drying the monofilament fiber at 100 ℃ in vacuum to obtain the reddish brown modified PBO fiber.
Comparative example 1
Weighing 2g of 3,3 '-diamino-4, 4' -dihydroxybiphenyl hydrochloride and 15g of polyphosphoric acid (Hn +2PnO3n +1, Shanghai Michelin Biochemical technology Co., Ltd., Lot #: C12710785, phosphorus pentoxide content is more than or equal to 85%) and adding into a glass reactor, introducing nitrogen into the reactor, stirring, heating to 80 ℃ for removing HCl, detecting to be neutral by using pH test paper after 7h, adding 1.5g of 2, 5-dihydroxyterephthalic acid and 2.5g of phosphorus pentoxide (content is more than or equal to 98%), heating to 100 ℃ for reaction for 1h, changing the reaction system mixture to be black, continuously heating to 120 ℃ for reaction for 1h, 140 ℃ for reaction for 1h, 160 ℃ for reaction for 1h, 180 ℃ for reaction for 1h, and heating to 190 ℃ for reaction for 1h to obtain a small amount of yellow fluorescence, and reaching the reaction end point. After the polymerization reaction is finished, manually drawing the liquid crystal stock solution by using a clean glass rod, and putting monofilament fiber into hot water to wash off excessive polyphosphoric acid to obtain a small-section solid. And (3) putting the small-section solid at 100 ℃ for vacuum drying to obtain the purple modified PBO fiber.
TABLE 1
Compared with a mixed polycondensation method of two monomers, the method has the following positive effects: (1) the reaction technological parameters of the composite monomer method provided by the invention are easy to control, the equal equivalent ratio polymerization of 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 wire drawing effect, improves the thermal stability and reflects that the molecular weight of the polymer is larger.
Claims (10)
2. the method for synthesizing the hydroxyl-modified biphenyl structure PBO composite monomer shown in the formula (1) according to claim 1, wherein the method comprises the following steps:
taking 2, 5-dihydroxy terephthalic acid as a raw material, adding sodium hydroxide and deoxygenated water in a nitrogen atmosphere, heating to 30-50 ℃ to perform a neutralization reaction for 0.2-0.5 hour to obtain a solution containing an intermediate 2, 5-dihydroxy terephthalic acid sodium; adding 3,3 '-diamino-4, 4' -dihydroxybiphenyl hydrochloride and a reducing agent, reacting for 0.3-0.6 h at the temperature of 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.
3. The method for synthesizing the hydroxyl-modified biphenyl structure PBO composite monomer represented by the formula (1) according to claim 2, wherein: the volume of the deoxygenated water is 20-40 mL/g based on the mass of the 2, 5-dihydroxyterephthalic acid.
4. The method for synthesizing the hydroxyl-modified biphenyl structure PBO composite monomer shown in the formula (1) according to claim 2, wherein: the reducing agent is stannous chloride.
5. The method for synthesizing the hydroxyl-modified biphenyl structure PBO composite monomer represented by the formula (1) according to claim 2, wherein: the mass ratio of the 2, 5-dihydroxyterephthalic acid to the sodium hydroxide is 1: 0.4 to 0.45.
6. The method for synthesizing the hydroxyl-modified biphenyl structure PBO composite monomer shown in the formula (1) according to claim 2, wherein: 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.
7. The method for synthesizing the hydroxyl-modified biphenyl structure PBO composite monomer shown in the formula (1) according to claim 2, wherein the post-treatment is: washing and filtering the obtained reaction liquid by using deoxygenated water, and drying the obtained filter cake in vacuum to obtain the hydroxyl modified biphenyl PBO composite monomer shown in the formula (1).
8. An application of the hydroxyl modified biphenyl PBO composite monomer shown in the formula (1) in preparing modified PBO fiber.
9. The use according to claim 8, characterized in that the use is: under the protection of nitrogen, stirring a polyphosphoric acid mixture containing phosphorus pentoxide, a hydroxyl modified biphenyl structure PBO composite monomer shown in a formula (1), and phosphorus pentoxide to react for 1 hour at 100 ℃, continuously heating to 120 ℃ to react for 1 hour, reacting at 140 ℃ for 1 hour, reacting at 160 ℃ for 1 hour, reacting at 180 ℃ for 1 hour, heating to 190 ℃ again to react for 1 hour, and then manually drawing, washing and drying the obtained liquid crystal stock solution to obtain the hydroxyl modified biphenyl structure PBO fiber;
the total mass of the phosphorus pentoxide and the phosphorus pentoxide contained in the polyphosphoric acid mixture containing the phosphorus pentoxide accounts for 85-90% of the total mass of the polyphosphoric acid mixture containing the phosphorus pentoxide and the phosphorus pentoxide; the mass of the hydroxyl modified biphenyl structure PBO composite monomer shown in the formula (1) is 10-20% 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 the phosphorus pentoxide.
10. The use of claim 8, wherein: the polyphosphoric acid mixture containing phosphorus pentoxide is obtained from Shanghai Maxin Biochemical technology Co., Ltd, Lot #: C12710785, and the content of phosphorus pentoxide is more than or equal to 85%.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202210513685.4A CN114790290B (en) | 2022-05-11 | 2022-05-11 | Synthesis method of hydroxyl modified biphenyl structure PBO composite monomer |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202210513685.4A CN114790290B (en) | 2022-05-11 | 2022-05-11 | Synthesis method of hydroxyl modified biphenyl structure PBO composite monomer |
Publications (2)
Publication Number | Publication Date |
---|---|
CN114790290A true CN114790290A (en) | 2022-07-26 |
CN114790290B CN114790290B (en) | 2024-02-13 |
Family
ID=82462797
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202210513685.4A Active CN114790290B (en) | 2022-05-11 | 2022-05-11 | Synthesis method of hydroxyl modified biphenyl structure PBO composite monomer |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN114790290B (en) |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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 |
-
2022
- 2022-05-11 CN CN202210513685.4A patent/CN114790290B/en active Active
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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 (3)
Title |
---|
JIANTING ZHANG等: "Theoretical study and experimental verification of a novel conjugated and coplanar HPBO polymers with hydrogen bond structure", POLYMER, vol. 160, pages 11 - 18, XP085570744, DOI: 10.1016/j.polymer.2018.11.040 * |
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, vol. 39, no. 2, pages 696 - 701 * |
赵德明等: "2,6-二羟基改性PBO 的AB 型新单体的合成", 化工进展, vol. 34, no. 2, pages 519 - 523 * |
Also Published As
Publication number | Publication date |
---|---|
CN114790290B (en) | 2024-02-13 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN106243352B (en) | A kind of polyphenylene triazole formic acid esters and preparation method and application | |
CN107325284B (en) | Hyperbranched polyphenyl triazole formate as well as preparation method and application thereof | |
CN106750289A (en) | A kind of benzoxazine oligomer of maleimide base group end-sealed type and preparation method thereof | |
CN111187410A (en) | Poly (p-phenylene terephthalamide) liquid crystal polymer and preparation method thereof | |
CN103224625A (en) | Preparation method for poly(2,5-dihydroxyl-1,4-phenylene pyridobisimidazole) | |
CN113480442A (en) | Cross-linkable diamine monomer, preparation method and application thereof in preparation of polyimide | |
CN113292719A (en) | Polyamide resin containing imide structure and preparation method thereof | |
CN109293921B (en) | Rosin-cellulose-based polyester imide polymer and preparation method and application thereof | |
CN114573998A (en) | Pigment yellow 139 synthesis process | |
CN114790290A (en) | Synthetic method of hydroxyl modified biphenyl structure PBO composite monomer | |
CN114133391A (en) | Mother nucleus substituted naphthalene diimide electrochemical polymerization monomer and preparation method thereof | |
CN114805099B (en) | Monohydroxy modified trans-PBO composite monomer and synthesis method thereof | |
CN113896675A (en) | Organic luminescent material based on carbazole-triphenylamine derivative and preparation method thereof | |
CN112210078A (en) | Phosphorus-containing flame-retardant polyoxadiazole and preparation method thereof | |
CN102584610B (en) | Bisphenol 2 (m-amino p-hydroxy phenyl) ether hydrochloride and preparation method and application thereof | |
CN116574017A (en) | Dihydroxyl modified trans-PBO composite monomer and synthesis method thereof | |
CN115448898B (en) | Preparation method and application of aromatic diamine monomer containing phenolphthalein Cardo and alkyl structure and polyimide thereof | |
CN114516860B (en) | Multi-substituted aromatic diamine monomer containing amide and preparation method thereof | |
CN114853615B (en) | Diamine monomer, polyimide film, and preparation methods and applications thereof | |
CN1164563C (en) | 1,3,5-tri (4-amino phenoxy) benzene and preparation method thereof | |
CN114133341B (en) | Continuous synthesis method and device of phthalonitrile-terminated polyarylether nitrile oligomer | |
CN117050198B (en) | High-stability cellulose acetate and preparation method thereof | |
CN115850703B (en) | Preparation method of bio-based intrinsic photosensitive shape memory polyimide and three-dimensional intelligent polyimide | |
CN117363049A (en) | Reactive anthraquinone dye compound with flame retardant function and preparation method thereof | |
CN113512074B (en) | (E) -4-methyl-7-hydroxy-8- (3- (ferrocenyl) acryloyl) coumarin, and preparation method and application thereof |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |