CN113956284A - Porphyrin structure derivative, preparation method thereof and dyeing-flame-retardant-anti-dripping integrated polyester - Google Patents
Porphyrin structure derivative, preparation method thereof and dyeing-flame-retardant-anti-dripping integrated polyester Download PDFInfo
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- 150000004032 porphyrins Chemical class 0.000 title claims abstract description 134
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- 229920000728 polyester Polymers 0.000 title claims description 28
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 35
- 238000004043 dyeing Methods 0.000 claims abstract description 33
- 239000000835 fiber Substances 0.000 claims abstract description 30
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 15
- 230000008569 process Effects 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims description 55
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 claims description 42
- 239000000243 solution Substances 0.000 claims description 41
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 32
- 239000011574 phosphorus Substances 0.000 claims description 32
- IBGBGRVKPALMCQ-UHFFFAOYSA-N 3,4-dihydroxybenzaldehyde Chemical compound OC1=CC=C(C=O)C=C1O IBGBGRVKPALMCQ-UHFFFAOYSA-N 0.000 claims description 28
- 238000001035 drying Methods 0.000 claims description 27
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 22
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 21
- 239000007788 liquid Substances 0.000 claims description 17
- 150000003233 pyrroles Chemical class 0.000 claims description 17
- 238000005886 esterification reaction Methods 0.000 claims description 15
- 239000002904 solvent Substances 0.000 claims description 15
- 229960003371 protocatechualdehyde Drugs 0.000 claims description 14
- 238000006482 condensation reaction Methods 0.000 claims description 13
- 230000035484 reaction time Effects 0.000 claims description 12
- 238000002791 soaking Methods 0.000 claims description 12
- 235000019260 propionic acid Nutrition 0.000 claims description 11
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 11
- 239000002184 metal Substances 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 150000007524 organic acids Chemical class 0.000 claims description 10
- -1 phosphonyl chloride Chemical compound 0.000 claims description 10
- 150000003839 salts Chemical class 0.000 claims description 10
- 239000003153 chemical reaction reagent Substances 0.000 claims description 7
- 230000014759 maintenance of location Effects 0.000 claims description 7
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 5
- 125000001664 diethylamino group Chemical group [H]C([H])([H])C([H])([H])N(*)C([H])([H])C([H])([H])[H] 0.000 claims description 4
- WTPLJWRVJPWPEW-UHFFFAOYSA-N C(C)Cl(P(=O)(Cl)Cl)CC Chemical compound C(C)Cl(P(=O)(Cl)Cl)CC WTPLJWRVJPWPEW-UHFFFAOYSA-N 0.000 claims description 3
- FJDQFPXHSGXQBY-UHFFFAOYSA-L Cs2CO3 Substances [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims description 3
- DAZAXJFKBGPJCX-UHFFFAOYSA-N [P].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 Chemical group [P].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 DAZAXJFKBGPJCX-UHFFFAOYSA-N 0.000 claims description 3
- AVMNFQHJOOYCAP-UHFFFAOYSA-N acetic acid;propanoic acid Chemical compound CC(O)=O.CCC(O)=O AVMNFQHJOOYCAP-UHFFFAOYSA-N 0.000 claims description 3
- 229910000024 caesium carbonate Inorganic materials 0.000 claims description 3
- IBDMRHDXAQZJAP-UHFFFAOYSA-N dichlorophosphorylbenzene Chemical compound ClP(Cl)(=O)C1=CC=CC=C1 IBDMRHDXAQZJAP-UHFFFAOYSA-N 0.000 claims description 3
- CNTIXUGILVWVHR-UHFFFAOYSA-N diphosphoryl chloride Chemical compound ClP(Cl)(=O)OP(Cl)(Cl)=O CNTIXUGILVWVHR-UHFFFAOYSA-N 0.000 claims description 3
- 238000001125 extrusion Methods 0.000 claims description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- KGENPKAWPRUNIG-UHFFFAOYSA-N 1-[chloro(ethyl)phosphoryl]ethane Chemical compound CCP(Cl)(=O)CC KGENPKAWPRUNIG-UHFFFAOYSA-N 0.000 claims description 2
- XGRJZXREYAXTGV-UHFFFAOYSA-N chlorodiphenylphosphine Chemical compound C=1C=CC=CC=1P(Cl)C1=CC=CC=C1 XGRJZXREYAXTGV-UHFFFAOYSA-N 0.000 claims description 2
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 claims description 2
- 230000032050 esterification Effects 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000012192 staining solution Substances 0.000 claims 1
- 239000005020 polyethylene terephthalate Substances 0.000 abstract description 23
- 229920004933 Terylene® Polymers 0.000 abstract description 22
- 230000004048 modification Effects 0.000 abstract description 19
- 238000012986 modification Methods 0.000 abstract description 19
- 239000003063 flame retardant Substances 0.000 abstract description 14
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 abstract description 13
- 239000004753 textile Substances 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 5
- 239000003086 colorant Substances 0.000 abstract description 3
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 230000000979 retarding effect Effects 0.000 abstract 1
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 54
- 238000005406 washing Methods 0.000 description 22
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical group O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 18
- 238000001914 filtration Methods 0.000 description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 14
- 239000012065 filter cake Substances 0.000 description 13
- 238000003756 stirring Methods 0.000 description 13
- 238000010438 heat treatment Methods 0.000 description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- 239000008367 deionised water Substances 0.000 description 10
- 229910021641 deionized water Inorganic materials 0.000 description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 9
- 238000001704 evaporation Methods 0.000 description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- KAESVJOAVNADME-UHFFFAOYSA-N 1H-pyrrole Natural products C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 5
- 230000009920 chelation Effects 0.000 description 5
- 238000002329 infrared spectrum Methods 0.000 description 5
- 230000007935 neutral effect Effects 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- 238000004566 IR spectroscopy Methods 0.000 description 4
- QPQGTZMAQRXCJW-UHFFFAOYSA-N [chloro(phenyl)phosphoryl]benzene Chemical compound C=1C=CC=CC=1P(=O)(Cl)C1=CC=CC=C1 QPQGTZMAQRXCJW-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 238000007865 diluting Methods 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- RLLBWIDEGAIFPI-UHFFFAOYSA-N 3-ethyl-1h-pyrrole Chemical compound CCC=1C=CNC=1 RLLBWIDEGAIFPI-UHFFFAOYSA-N 0.000 description 3
- FEKWWZCCJDUWLY-UHFFFAOYSA-N 3-methyl-1h-pyrrole Chemical compound CC=1C=CNC=1 FEKWWZCCJDUWLY-UHFFFAOYSA-N 0.000 description 3
- UYGMPZSLJYVODL-UHFFFAOYSA-N 3-prop-1-enyl-1h-pyrrole Chemical compound CC=CC=1C=CNC=1 UYGMPZSLJYVODL-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 239000003599 detergent Substances 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- 238000002074 melt spinning Methods 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- LGTLXDJOAJDFLR-UHFFFAOYSA-N diethyl chlorophosphate Chemical compound CCOP(Cl)(=O)OCC LGTLXDJOAJDFLR-UHFFFAOYSA-N 0.000 description 2
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000011085 pressure filtration Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000012209 synthetic fiber Substances 0.000 description 2
- 229920002994 synthetic fiber Polymers 0.000 description 2
- VEORPZCZECFIRK-UHFFFAOYSA-N 3,3',5,5'-tetrabromobisphenol A Chemical compound C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(O)C(Br)=C1 VEORPZCZECFIRK-UHFFFAOYSA-N 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- 229910021592 Copper(II) chloride Inorganic materials 0.000 description 1
- 229910021577 Iron(II) chloride Inorganic materials 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 1
- BTVWZWFKMIUSGS-UHFFFAOYSA-N dimethylethyleneglycol Natural products CC(C)(O)CO BTVWZWFKMIUSGS-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical group 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L magnesium chloride Substances [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 150000004033 porphyrin derivatives Chemical class 0.000 description 1
- 125000000168 pyrrolyl group Chemical group 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/08—Esters of oxyacids of phosphorus
- C07F9/09—Esters of phosphoric acids
- C07F9/094—Esters of phosphoric acids with arylalkanols
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/30—Phosphinic acids [R2P(=O)(OH)]; Thiophosphinic acids ; [R2P(=X1)(X2H) (X1, X2 are each independently O, S or Se)]
- C07F9/304—Aromatic acids (P-C aromatic linkage)
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/30—Phosphinic acids [R2P(=O)(OH)]; Thiophosphinic acids ; [R2P(=X1)(X2H) (X1, X2 are each independently O, S or Se)]
- C07F9/36—Amides thereof
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
- D06P1/667—Organo-phosphorus compounds
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
- D06P3/34—Material containing ester groups
- D06P3/52—Polyesters
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
Abstract
The invention relates to the technical field of organic synthesis and textiles, and provides a porphyrin structure derivative, a preparation method thereof and dyeing-flame-retardant-anti-dripping integrated terylene. The porphyrin structure derivative provided by the invention contains a large amount of P, N flame retardant elements, can perform a flame retardant effect in cooperation with metal ions chelated in the porphyrin structure derivative, the porphyrin ring is also a highly conjugated system, the anti-dripping performance of terylene can be effectively improved, and porphyrin and different metal ions can be chelated to present different colors, so that the synthesized porphyrin structure derivative has the functions of dyeing, flame retarding and anti-dripping modification. The porphyrin structure derivative is used for dyeing and finishing the terylene, so that the dyeing, flame retardance and anti-dripping triple modification of the terylene can be realized in one step, the operation process is simple, the cost is low, the modification process does not influence the performances of the mechanical strength and the like of the fiber, and the modification effect is excellent.
Description
Technical Field
The invention relates to the technical field of organic synthesis and textiles, in particular to a porphyrin structure derivative, a preparation method thereof and dyeing-flame-retardant-anti-dripping integrated terylene.
Background
The polyester fiber (PET) is prepared by melt spinning polyethylene terephthalate, is a synthetic fiber with the largest world output, occupies 70-80% of the total amount of the synthetic fiber per year, and has a plurality of excellent performances such as good wear resistance, strong heat resistance, chemical corrosion resistance, high mechanical strength and the like. However, PET is a linear thermoplastic polymer, has a limiting oxygen index of only about 21%, burns and shrinks due to melting after being heated, and generates a serious dripping phenomenon. High-temperature drops easily cause secondary fire, accelerate flame propagation and enlarge the fire scale. Therefore, flame retardant anti-drip modification of polyester fibers is imminent.
Aiming at the problem of flammability of PET, technical means such as copolymerization, blending and the like are commonly adopted at home and abroad for flame retardant modification. The modification method mainly comprises the following steps: (1) copolymerization flame-retardant modification, such as using tetrabromobisphenol A hydroxyethyl ether or phosphorus-containing compound as comonomer, preparing a copolymer with dimethyl terephthalate and ethylene glycol through ester exchange and polycondensation, and then carrying out melt spinning and stretching to obtain the flame-retardant modified tetrabromobisphenol A/ethylene glycol copolymer; (2) blending flame-retardant modification, adding a phosphorus-containing compound or a halogen-antimony composite flame retardant into a spinning melt, and then carrying out melt spinning and stretching to obtain the flame-retardant modified fiber. However, the halogen-containing flame retardant can generate toxic gas in the combustion process and has great harm to the environment and human health, and the phosphorus-containing flame retardant can promote the accelerated decomposition of PET, so that the melt viscosity and strength are reduced sharply, and the melt dripping phenomenon is more serious.
Disclosure of Invention
In view of the above, the invention provides a porphyrin structure derivative, a preparation method thereof and dyeing-flame retardant-anti-dripping integrated terylene. The porphyrin structure derivative provided by the invention has the functions of dyeing, flame retardance and anti-dripping modification, and the finishing of terylene by utilizing the porphyrin structure derivative can realize triple modification of dyeing, flame retardance and anti-dripping in one step, and meanwhile, the modification process does not influence the performances of the fiber such as mechanical strength and the like, and the modification effect is excellent.
In order to achieve the above object, the present invention provides the following technical solutions:
a porphyrin structure derivative has a structure shown in formula I:
in formula I: m is a metal ion;
R1is H,
R2Is composed of
Preferably, M is Pd2+、Cu2+、Fe2+、Ni2+、Zn2+、Co2+、Mn2+、Fe3+、Al3+、Mg2+Or Ca2+。
The invention also provides a preparation method of the porphyrin structure derivative, which comprises the following steps:
mixing protocatechualdehyde and pyrrole derivatives for condensation reaction to obtain a porphyrin structure intermediate; the structure of the pyrrole derivative is shown as a formula II, and the structural formula of the porphyrin structure intermediate is shown as a formula III:
formula II through formula III: r1The species of (a) is the same as in formula I;
mixing the porphyrin structure intermediate with phosphorus oxychloride for esterification reaction to obtain a phosphorus-containing porphyrin structure intermediate; the structural formula of the phosphorus-containing porphyrin structural intermediate is shown as a formula IV; the phosphoryl chloride is phosphorus oxychloride, phenylphosphonic dichloride, diphenylphosphine chloride, diphenoxy phosphoryl chloride, diethyl phosphorous oxychloride, diethyl phosphoryl chloride, bis (diethylamino) phosphonyl chloride, bis (dimethylamino) phosphonyl chloride or pyrophosphoryl chloride;
in the formula IV, R1And R2The species of (a) is the same as in formula I;
the intermediate containing the phosphorus porphyrin structure and soluble metal salt are mixed for a chelating reaction to obtain the porphyrin structure derivative with the structure shown in the formula I.
Preferably, the condensation reaction is carried out under organic acid conditions, and the organic acid comprises propionic acid or a propionic acid-acetic acid mixed solution.
Preferably, the condensation reaction temperature is 130-150 ℃, and the reaction time is 1-3 h; the molar ratio of the protocatechualdehyde to the pyrrole derivative is 1: 1.1-1.5.
Preferably, the temperature of the esterification reaction is 50-70 ℃, and the reaction time is 6-8 h; the molar ratio of the porphyrin structure intermediate to the phosphoryl chloride is 1: 8-10.
Preferably, the esterification reaction is carried out under the action of a basic reagent, and the basic reagent comprises triethylamine and K2CO3、Cs2CO3And NaH.
Preferably, the temperature of the chelation reaction is 60-80 ℃, and the reaction time is 1-3 h; the molar ratio of the phosphorus-containing porphyrin structure intermediate to metal ions in the soluble metal salt is 1: 1.1-1.5.
The invention also provides dyeing-flame-retardant-anti-dripping integrated polyester prepared by the method comprising the following steps of:
dissolving the porphyrin structure derivative in the scheme into a solvent to obtain a dyeing solution;
and soaking the polyester fiber in the dyeing solution, and then sequentially extruding and drying to obtain the dyeing-flame-retardant-anti-dripping integrated polyester.
Preferably, the bath ratio of the soaking is 1g: 10-60 mL; the soaking temperature is 60-80 ℃, and the soaking time is 60-100 min;
the liquid retention rate of the extrusion is 30-110%;
the drying temperature is 50-90 ℃, and the drying time is 0.5-2.5 h.
The invention provides a porphyrin structure derivative which has a structure shown in a formula I. The derivative provided by the invention contains a large amount of P, N flame retardant elements, can perform a flame retardant effect with a metal ion chelated in a porphyrin structure derivative, has 26 pi electrons in a porphyrin ring, is a highly conjugated system, has good potential char forming capability due to the structure, can improve the melt viscosity and strength of the terylene in a high temperature and combustion process, and effectively improves the anti-dripping performance of the terylene; in addition, the porphyrin ring has strong metal ion chelating capacity, and can present different colors when being chelated with different metal ions. Therefore, the porphyrin structure derivative provided by the invention has the functions of dyeing, flame retardance and anti-droplet modification.
The invention also provides a preparation method of the porphyrin structure derivative. The method comprises the steps of synthesizing a porphyrin structure intermediate by using biomass protocatechualdehyde as a raw material, reacting the porphyrin structure intermediate with phosphoryl chloride to synthesize a phosphorus-containing porphyrin structure intermediate, and chelating the phosphorus-containing porphyrin structure intermediate with metal ions to obtain the porphyrin structure derivative with the structure shown in the formula I. The preparation method provided by the invention has the advantages of wide raw material source, environmental protection, simple steps and easy operation.
The invention also provides dyeing-flame-retardant-anti-dripping integrated polyester which is obtained by dyeing and finishing the porphyrin structure derivative. The invention utilizes the porphyrin structure derivative to dye and finish the terylene, can realize triple modification of dyeing, flame retardance and molten drop resistance of the terylene in one step, has simple operation process and low cost, does not influence the performances of the fiber such as mechanical strength and the like in the modification process, and has excellent modification effect. The results of the examples show that the washing fastness of the terylene dyed by the porphyrin derivative can reach 4 grades, and the LOI value of the fiber can reach 32 percent.
Drawings
FIG. 1 is an infrared spectrum of the porphyrin structure intermediate prepared in example 1.
Detailed Description
The invention provides a porphyrin structure derivative, which has a structure shown in a formula I:
in formula I: m is a metal ion;
R1is H,
R2Is composed of
In the present invention, M is preferably Pd2+、Cu2+、Fe2+、Ni2+、Zn2+、Co2+、Mn2+、Fe3+、Al3+、Mg2+Or Ca2 +。
The invention also provides a preparation method of the porphyrin structure derivative, which comprises the following steps:
mixing protocatechualdehyde and pyrrole derivatives for condensation reaction to obtain a porphyrin structure intermediate; the structure of the pyrrole derivative is shown as a formula II; the structural formula of the porphyrin structure intermediate is shown as a formula III:
formula II through formula III: r1The species of (a) is the same as in formula I;
mixing the porphyrin structure intermediate with phosphorus oxychloride for esterification reaction to obtain a phosphorus-containing porphyrin structure intermediate; the structural formula of the phosphorus-containing porphyrin structural intermediate is shown as a formula IV:
in the formula IV, R1And R2The species of (a) is the same as in formula I;
the intermediate containing the phosphorus porphyrin structure and soluble metal salt are mixed for a chelating reaction to obtain the porphyrin structure derivative with the structure shown in the formula I.
Mixing protocatechualdehyde and pyrrole derivatives for condensation reaction to obtain a porphyrin structure intermediate; the structure of the pyrrole derivative is shown as a formula II; the structural formula of the porphyrin structure intermediate is shown as a formula III. In the present invention, when R is1When is H, the pyrrole derivative is pyrrole; in a particular embodiment of the invention, the pyrrole derivative is preferably 3-propenyl pyrrole, 3-methyl pyrrole or 3-ethyl pyrrole. In the present invention, the condensation reaction is preferably carried out under organic acid conditions, and the organic acid preferably includes propionic acid or a propionic acid-acetic acid mixed solution; the dosage ratio of the protocatechualdehyde to the organic acid is preferably 1g: 5-25 mL, and more preferably 1g: 10-20 mL; the organic acid acts as a solvent and as an acid initiator.
In the invention, the molar ratio of the protocatechualdehyde to the pyrrole derivative is preferably 1: 1.1-1.5, more preferably 1: 1.2-1.4; the temperature of the condensation reaction is preferably 130-150 ℃, more preferably 135-145 ℃, and the time of the condensation reaction is preferably 1-3 hours, more preferably 1.5-2.5 hours.
In the specific embodiment of the present invention, preferably, protocatechuic aldehyde and organic acid are added into a reactor, the pyrrole derivative is dissolved in the organic acid to obtain a pyrrole derivative solution, the pyrrole derivative solution is added into the reactor dropwise, and after the dropwise addition is completed, the reaction is continued under the condition of keeping warm; in the present invention, the time of the condensation reaction is measured from the completion of the dropwise addition of the pyrrole derivative solution.
After the condensation reaction is finished, the obtained product liquid is preferably subjected to post-treatment to obtain a porphyrin structure intermediate with a structure shown in a formula III; the post-treatment preferably comprises the steps of: mixing the product liquid with methanol, cooling and crystallizing the obtained mixed liquid, then filtering, and sequentially washing and drying the obtained filter cake to obtain a porphyrin structure intermediate with a structure shown in formula III; the washing detergent is preferably methanol.
After a porphyrin structure intermediate is obtained, the porphyrin structure intermediate and phosphorus oxychloride are mixed for esterification reaction to obtain a phosphorus-containing porphyrin structure intermediate; the structural formula of the phosphorus-containing porphyrin structural intermediate is shown as a formula IV. In the present invention, the phosphorus oxychloride is phosphorus oxychloride, phenylphosphonic dichloride, diphenylphosphinic chloride, diphenylphosphonic chloride, diphenoxy phosphorus oxychloride, diethylphosphorous oxychloride, bis (diethylamino) phosphonic chloride, bis (dimethylamino) phosphonic chloride or pyrophosphoryl chloride; the molar ratio of the porphyrin structure intermediate to the phosphorus oxychloride is preferably 1: 8-10, and more preferably 1: 8.5-9.5.
In the present invention, the esterification reaction is preferably carried out under the action of a basic reagent, and the basic reagent preferably comprises triethylamine and K2CO3、Cs2CO3And NaH; the dosage of the alkaline reagent is preferably more than 1.5 times of the molar weight of the phenolic hydroxyl in the porphyrin structure intermediate. In the present invention, the alkaline agent functions as an acid-binding agent and a catalyst.
In the invention, the esterification reaction is preferably carried out in an organic solvent, and the organic solvent is preferably one or more of chloroform, dichloromethane, N-dimethylformamide, tetrahydrofuran and acetonitrile; the invention has no special requirements on the dosage of the organic solvent, and can ensure that the esterification reaction is smoothly carried out.
In the invention, the temperature of the esterification reaction is preferably 50-70 ℃, more preferably 55-65 ℃, and the time of the esterification reaction is preferably 6-8 h, more preferably 6.5-7.5 h.
In the specific embodiment of the present invention, it is preferable that the porphyrin structure intermediate and the alkaline reagent are dissolved in an organic solvent to obtain a mixed solution, the phosphoryl chloride is dissolved in the organic solvent, the obtained phosphoryl chloride solution is dropwise added to the mixed solution, and then the temperature is raised to the esterification reaction temperature for reaction.
After the esterification reaction is finished, preferably using a hydrochloric acid solution to adjust the pH value of the obtained product liquid to be neutral, and then sequentially filtering, washing and drying to obtain a phosphorus-containing porphyrin structure intermediate; the filtration is preferably a reduced pressure filtration and the washing detergent is preferably deionized water.
After the intermediate with the phosphorus-containing porphyrin structure is obtained, the intermediate with the phosphorus-containing porphyrin structure and soluble metal salt are mixed for a chelating reaction to obtain the porphyrin structure derivative with the structure shown in the formula I. In the present invention, the metal ion in the soluble metal salt is preferably Pd2+、Pt2+、Cu2+、Fe2+、Ni2+、Zn2+、Co2+、Mn2+、Fe3+、Al3+、Mg2+And Ca2+One or more of the above; the anion of the soluble metal salt is preferably Cl-Or NO3 2-The molar ratio of the phosphorus-containing porphyrin structure intermediate to the metal ions in the soluble metal salt is preferably 1: 1.1-1.5, and more preferably 1: 1.2-1.3. The porphyrin ring can show different colors by chelating with different metal ions, when the metal ions are more than two, a mixture of porphyrin structure derivatives with different metal ions can be obtained, and the color can be adjusted by selecting and matching the metal ions.
In the invention, the chelating reaction is preferably carried out in a solvent, and the solvent is preferably one or more of water, chloroform, ethanol, ethyl acetate, N-dimethylformamide, tetrahydrofuran, acetonitrile and acetone; the invention has no special requirement on the dosage of the solvent, and can ensure the successful implementation of the chelation reaction.
In the invention, the temperature of the chelation reaction is preferably 60-80 ℃, more preferably 65-75 ℃, and the time of the chelation reaction is preferably 1-3 hours, more preferably 1.5-2.5 hours.
In the embodiment of the present invention, it is preferable to add the intermediate having a phosphorus-containing porphyrin structure and the solvent into the reactor, then add the solid metal salt, and heat the mixture to the chelating reaction temperature under stirring for reaction.
After the chelation reaction is finished, the solvent in the obtained product liquid is preferably distilled out, and then the product liquid is filtered, washed and dried to obtain the porphyrin structure derivative; the filtration is preferably a reduced pressure filtration and the washing detergent is preferably deionized water.
The invention also provides dyeing-flame-retardant-anti-dripping integrated polyester prepared by the method comprising the following steps of:
dissolving the porphyrin structure derivative in the scheme into a solvent to obtain a dyeing solution;
and soaking the polyester fiber in the dyeing solution, and then sequentially extruding and drying to obtain the dyeing-flame-retardant-anti-dripping integrated polyester.
In the invention, the solvent is preferably one or more of water, ethanol, ethyl acetate, N-dimethylformamide, chloroform, tetrahydrofuran, acetonitrile and acetone; the solubility of the porphyrin structure derivatives with different structures is different, and can be divided into water solubility and fat solubility, and in the specific embodiment of the present invention, the solvent is preferably selected according to the solubility of the porphyrin structure derivatives.
In the invention, the concentration of the dyeing solution is preferably 1-100 g/L, and more preferably 10-50 g/L.
In the invention, the bath ratio of the soaking is preferably 1g: 10-60 mL, more preferably 1g: 20-40 mL; the soaking temperature is preferably 60-80 ℃, more preferably 65-75 ℃, and the soaking time is preferably 60-100 min, more preferably 70-90 min; the liquid retention rate of the extrusion is preferably 30-110%, and more preferably 50-100%; the drying temperature is preferably 50-90 ℃, more preferably 60-80 ℃, and the drying time is preferably 0.5-2.5 hours, more preferably 1-2 hours.
According to the invention, the porphyrin structure derivative is adopted to dye and finish the terylene, in the dyeing process, the flame retardant element P, N and metal ions are introduced into the terylene, and the dyeing-flame retardant-anti-dripping integrated terylene with good durability can be obtained by one-step modification by combining the high conjugated structure of the porphyrin ring and the color development capability of chelated metal ions.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention.
Example 1
Preparation of porphyrin structure derivatives of formula I, wherein: m is Cu2+，R1Is H, R2Is composed of
The preparation method comprises the following specific steps:
(1) preparation of porphyrin structure intermediate: adding 50g of protocatechualdehyde and 500mL of propionic acid into a reactor, starting stirring and heating, controlling the reaction temperature to be 130 ℃, then diluting 27g of pyrrole into 50mL of propionic acid, dropwise adding a pyrrole solution into the reaction system through a constant-pressure dropping funnel, maintaining the reaction temperature after the addition is finished, and continuing to react for 1 h; after the reaction is finished, adding 500mL of methanol into a reaction system, refrigerating and standing for 12h in a refrigerator, filtering under reduced pressure, washing a filter cake with ethanol, and drying to obtain a porphyrin structure intermediate; the infrared spectrum of the porphyrin structure intermediate is shown in figure 1; in fig. 1: at 3323cm-1，973cm-1The absorption peaks are respectively the stretching vibration peak and the bending vibration peak of N-H in the upper surface of the porphyrin ring, 1317cm-1、1475cm-1The absorption peak is C ═ N telescopic vibration absorption peak, 1597cm-1The absorption peak is the framework vibration peak of the porphyrin ring, which proves that the porphyrin structure intermediate is successfully synthesized;
(2) preparation of phosphorus-containing porphyrin structure intermediate: adding 15g of porphyrin structure intermediate prepared in the step (1), 32g of triethylamine and 150mL of chloroform into a reactor, dissolving 25g of phosphorus oxychloride into 20mL of chloroform, adding the obtained chloroform solution of phosphorus oxychloride into the reactor, stirring and heating, controlling the reaction temperature at 50 ℃ and the reaction time at 6 h; after the reaction is finished, evaporating chloroform, adding a hydrochloric acid solution to adjust the reaction system to be neutral, filtering under reduced pressure, washing a filter cake by deionized water, and drying to obtain a phosphorus-containing porphyrin structure intermediate;
(3) preparation of porphyrin structure derivatives: adding 10g of phosphorus-containing porphyrin structure intermediate prepared in the step (2) and 100mL of chloroform into a reactor, and then adding 1.2g of CuCl2Stirring and heating the solid, controlling the reaction temperature to be 60 ℃ and the reaction time to be 1 h; after the reaction is finished, evaporating chloroform, filtering under reduced pressure, washing a filter cake by deionized water, and drying to obtain the porphyrin structure derivative; the structure identification is carried out through infrared spectroscopy, and the result shows that the porphyrin structure derivative has the structure in the formula I;
(4) preparing a terylene dyeing liquid: weighing the mass of the polyester, calculating according to a bath ratio of 1:10 to obtain the volume of a dye solution, preparing a dyeing solution with the concentration of 1g/L from the porphyrin structure derivative prepared in the step (3) by using water as a solvent, placing the polyester fiber in the dyeing solution, and fully dyeing for 60min at the temperature of 60 ℃ in a water bath;
(5) and (4) squeezing the fibers dyed in the step (4) to remove redundant solution, enabling the liquid retention rate to be 30%, and then drying for 0.5h at the temperature of 50 ℃ to obtain the dyeing-flame-retardant-anti-dripping integrated polyester.
The color fastness to washing and the limiting oxygen index of the dyeing-flame-retardant-anti-dripping integrated polyester are tested according to a method in GB/T3921-2008 textile color fastness experiments, and the result shows that the color fastness of the fiber reaches 4 grade and the Limiting Oxygen Index (LOI) value is 28.5%.
Example 2
Preparation of porphyrin structure derivatives of formula I, wherein: m is Fe2+，R1Is composed of
R2Is composed of
The preparation method comprises the following specific steps:
(1) preparation of porphyrin structure intermediate: adding 50g of protocatechualdehyde and 600mL of propionic acid into a reactor, starting stirring and heating, controlling the reaction temperature to be 135 ℃, then diluting 40g of 3-propenyl pyrrole in 50mL of propionic acid, dropwise adding a 3-propenyl pyrrole solution into the reaction system through a constant-pressure dropping funnel, maintaining the reaction temperature after the addition is finished, and continuing to react for 1.5 hours; after the reaction is finished, adding 600mL of methanol into a reaction system, refrigerating and standing for 12h in a refrigerator, filtering under reduced pressure, washing a filter cake with ethanol, and drying to obtain a porphyrin structure intermediate; the infrared spectrum identification shows that the porphyrin structure intermediate with the target structure is successfully synthesized in the step;
(2) preparation of phosphorus-containing porphyrin structure intermediate: adding 15g of porphyrin structure intermediate prepared in the step (1), 32g of triethylamine and 150mL of chloroform into a reactor, dissolving 39g of diphenylphosphinic chloride into 20mL of chloroform, adding the obtained chloroform solution of diphenylphosphinic chloride into the reactor, stirring and heating, controlling the reaction temperature to be 55 ℃ and the reaction time to be 7 hours; after the reaction is finished, evaporating chloroform, adding a hydrochloric acid solution to adjust the reaction system to be neutral, filtering under reduced pressure, washing a filter cake by deionized water, and drying to obtain a phosphorus-containing porphyrin structure intermediate;
(3) preparation of porphyrin structure derivatives: adding 10g of the phosphorus-containing porphyrin structure intermediate prepared in the step (2) and 100mL of chloroform into a reactor, and adding 1.0g of FeCl2Stirring and heating the solid, controlling the reaction temperature to be 65 ℃ and the reaction time to be 1.5 h; after the reaction is finished, evaporating chloroform, filtering under reduced pressure, washing a filter cake by deionized water, and drying to obtain the porphyrin structure derivative; the structure identification is carried out through infrared spectroscopy, and the result shows that the porphyrin structure derivative has the structure in the formula I;
(4) preparing a terylene dyeing liquid: firstly weighing the mass of the terylene, and then calculating according to the bath ratio of 1:20 to obtain the volume of the dye solution. Preparing the porphyrin structure derivative prepared in the step (3) into a dyeing solution with the concentration of 10g/L by using ethanol as a solvent, placing the polyester fiber in the dyeing solution, and fully dyeing for 70min under the condition of water bath at 70 ℃;
(5) and (4) squeezing the fibers dyed in the step (4) to remove redundant solution, wherein the liquid retention rate is 50%, and then drying for 1h at the temperature of 60 ℃ to obtain the dyeing-flame-retardant-anti-dripping integrated polyester.
The color fastness to washing and the limiting oxygen index of the dyeing-flame-retardant-anti-dripping integrated polyester are tested according to a method in GB/T3921-2008 textile color fastness experiments, and the result shows that the color fastness of the fiber reaches 4 grades, and the LOI value of the fiber is 31%.
Example 3
Preparation of porphyrin structure derivatives of formula I, wherein: m is Mg2+，R1Is composed of
R2Is composed of
The preparation method comprises the following specific steps:
(1) preparation of porphyrin structure intermediate: adding 10g of protocatechualdehyde and 140mL of propionic acid into a reactor, starting stirring and heating, controlling the reaction temperature to be 140 ℃, then diluting 7.6g of 3-methylpyrrole in 10mL of propionic acid, dropwise adding a 3-methylpyrrole solution into the reaction system through a constant-pressure dropping funnel, maintaining the reaction temperature after the addition is finished, and continuing to react for 2 hours; adding 140mL of methanol into a reaction system after the reaction is finished, refrigerating and standing for 12h in a refrigerator, filtering under reduced pressure, washing a filter cake with ethanol, and drying to obtain a porphyrin structure intermediate; the infrared spectrum identification shows that the porphyrin structure intermediate with the target structure is successfully synthesized in the step;
(2) preparation of phosphorus-containing porphyrin structure intermediate: adding 15g of porphyrin structure intermediate prepared in the step (1), 32g of triethylamine and 150mL of chloroform into a reactor, dissolving 30g of diethoxy phosphoryl chloride into 20mL of chloroform, adding the obtained chloroform solution of diethoxy phosphoryl chloride into the reactor, stirring and heating, controlling the reaction temperature at 60 ℃ and the reaction time at 8 h; after the reaction is finished, evaporating chloroform, adding a hydrochloric acid solution to adjust the reaction system to be neutral, filtering under reduced pressure, washing a filter cake by deionized water, and drying to obtain a phosphorus-containing porphyrin structure intermediate;
(3) preparation of porphyrin structure derivatives: adding 10g of phosphorus-containing porphyrin structure intermediate prepared in the step (2) and 100mL of chloroform into a reactor, and then adding 0.85g of MgCl2Stirring and heating the solid, controlling the reaction temperature to be 70 ℃ and the reaction time to be 2 h; after the reaction is finished, evaporating chloroform, filtering under reduced pressure, washing a filter cake by deionized water, and drying to obtain the porphyrin structure derivative; the structure identification is carried out through infrared spectroscopy, and the result shows that the porphyrin structure derivative has the structure in the formula I;
(4) preparing a terylene dyeing liquid: firstly weighing the mass of the terylene, and then calculating according to the bath ratio of 1:30 to obtain the volume of the dye solution. Preparing the porphyrin structure derivative prepared in the step (3) into a dyeing solution with the concentration of 1g/L by using N, N-dimethylformamide as a solvent, placing the polyester fiber in the dyeing solution, and fully dyeing for 80min under the condition of water bath at 80 ℃;
(5) squeezing the fibers dyed in the step (4) to remove redundant solution, wherein the liquid retention rate is 70%, and then drying the fibers at 70 ℃ for 1.5h to obtain the dyeing-flame-retardant-anti-dripping integrated polyester.
The color fastness to washing and the limiting oxygen index of the dyeing-flame-retardant-anti-dripping integrated polyester are tested according to a method in GB/T3921-2008 textile color fastness experiments, and the result shows that the color fastness of the fiber is level 4, and the LOI value of the fiber is 33%.
Example 4
Preparation of porphyrin structure derivatives of formula I, wherein: m is Ni2+，R1Is composed of
R2Is composed of
The preparation method comprises the following specific steps:
(1) preparation of porphyrin structure intermediate: adding 10g of protocatechualdehyde and 160mL of propionic acid into a reactor, starting stirring and heating, controlling the reaction temperature to 145 ℃, then diluting 9.6g of 3-ethylpyrrole in 10mL of propionic acid, dropwise adding a 3-ethylpyrrole solution into the reaction system through a constant-pressure dropping funnel, maintaining the reaction temperature after the addition is finished, and continuing to react for 2.5 hours; adding 160mL of methanol into a reaction system after the reaction is finished, refrigerating and standing for 12h in a refrigerator, filtering under reduced pressure, washing a filter cake with ethanol, and drying to obtain a porphyrin structure intermediate; the infrared spectrum identification shows that the porphyrin structure intermediate with the target structure is successfully synthesized in the step;
(2) preparation of phosphorus-containing porphyrin structure intermediate: adding 15g of porphyrin structure intermediate prepared in the step (1), 32g of triethylamine and 150mL of chloroform into a reactor, dissolving 38g of bis (diethylamino) phosphonyl chloride into 20mL of chloroform, adding the chloroform solution of the obtained bis (diethylamino) phosphonyl chloride into the reactor, stirring and heating, controlling the reaction temperature to be 65 ℃ and the reaction time to be 9 hours; after the reaction is finished, evaporating chloroform, adding a hydrochloric acid solution to adjust the reaction system to be neutral, filtering under reduced pressure, washing a filter cake by deionized water, and drying to obtain a phosphorus-containing porphyrin structure intermediate;
(3) preparation of porphyrin structure derivatives: adding 10g of phosphorus-containing porphyrin structure intermediate prepared in the step (2) and 100mL of chloroform into a reactor, and then adding 1.2g of NiCl2Stirring and heating the solid, controlling the reaction temperature to be 75 ℃ and the reaction time to be 2.5 h; after the reaction is finished, evaporating chloroform, filtering under reduced pressure, washing a filter cake by deionized water, and drying to obtain the porphyrin structure derivative; the structure identification is carried out through infrared spectroscopy, and the result shows that the porphyrin structure derivative has the structure in the formula I;
(4) preparing a terylene dyeing liquid: firstly weighing the mass of the terylene, and then calculating according to the bath ratio of 1:90 to obtain the volume of the dye solution. Preparing the porphyrin structure derivative prepared in the step (3) into a dyeing solution with the concentration of 1g/L by using ethyl acetate and N, N-dimethylformamide as solvents, placing the polyester fiber in the dyeing solution, and fully dyeing for 90min under the condition of water bath at 90 ℃;
(5) squeezing the fibers dyed in the step (4) to remove redundant solution, wherein the liquid retention rate is 30%, and then drying the fibers at the temperature of 80 ℃ for 2h to obtain the dyeing-flame-retardant-anti-dripping integrated polyester.
The color fastness to washing and the limiting oxygen index of the dyeing-flame-retardant-anti-dripping integrated polyester are tested according to a method in GB/T3921-2008 textile color fastness experiments, and the result shows that the color fastness of the fiber is level 4, and the LOI value of the fiber is 32%.
In addition, the tensile strength of the fibers before and after dyeing in examples 1 to 4 was measured, and the results showed that the tensile strength of the fibers before and after dyeing did not change significantly.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A porphyrin structure derivative has a structure shown in formula I:
in formula I: m is a metal ion;
R1is H,
R2Is composed of
2. The porphyrin structure derivative of claim 1, wherein M is Pd2+、Cu2+、Fe2+、Ni2+、Zn2+、Co2+、Mn2+、Fe3+、Al3+、Mg2+Or Ca2+。
3. A process for the preparation of derivatives of porphyrin structure according to claim 1 or 2, characterized in that it comprises the following steps:
mixing protocatechualdehyde and pyrrole derivatives for condensation reaction to obtain a porphyrin structure intermediate; the structure of the pyrrole derivative is shown as a formula II, and the structural formula of the porphyrin structure intermediate is shown as a formula III:
formula II through formula III: r1The species of (a) is the same as in formula I;
mixing the porphyrin structure intermediate with phosphorus oxychloride for esterification reaction to obtain a phosphorus-containing porphyrin structure intermediate; the structural formula of the phosphorus-containing porphyrin structural intermediate is shown as a formula IV; the phosphoryl chloride is phosphorus oxychloride, phenylphosphonic dichloride, diphenylphosphine chloride, diphenoxy phosphoryl chloride, diethyl phosphorous oxychloride, diethyl phosphoryl chloride, bis (diethylamino) phosphonyl chloride, bis (dimethylamino) phosphonyl chloride or pyrophosphoryl chloride;
in the formula IV, R1And R2The species of (a) is the same as in formula I;
the intermediate containing the phosphorus porphyrin structure and soluble metal salt are mixed for a chelating reaction to obtain the porphyrin structure derivative with the structure shown in the formula I.
4. The production method according to claim 3, wherein the condensation reaction is carried out under an organic acid condition, and the organic acid comprises propionic acid or a propionic acid-acetic acid mixed solution.
5. The preparation method according to claim 3 or 4, wherein the condensation reaction is carried out at a temperature of 130-150 ℃ for 1-3 h; the molar ratio of the protocatechualdehyde to the pyrrole derivative is 1: 1.1-1.5.
6. The preparation method according to claim 3, wherein the temperature of the esterification reaction is 50-70 ℃ and the reaction time is 6-8 h; the molar ratio of the porphyrin structure intermediate to the phosphoryl chloride is 1: 8-10.
7. The method according to claim 3 or 6, wherein the esterification is carried out with the aid of a basic reagent comprising triethylamine, K2CO3、Cs2CO3And NaH.
8. The preparation method according to claim 3, wherein the chelating reaction is carried out at 60-80 ℃ for 1-3 h; the molar ratio of the phosphorus-containing porphyrin structure intermediate to metal ions in the soluble metal salt is 1: 1.1-1.5.
9. The dyeing-flame-retardant-anti-dripping integrated polyester is characterized by being prepared by the following steps:
dissolving the porphyrin structure derivative of claim 1 or 2 in a solvent to obtain a staining solution;
and soaking the polyester fiber in the dyeing solution, and then sequentially extruding and drying to obtain the dyeing-flame-retardant-anti-dripping integrated polyester.
10. The dyeing-flame-retardant-anti-dripping integrated polyester fiber as claimed in claim 9, wherein the bath ratio of soaking is 1g: 10-60 mL; the soaking temperature is 60-80 ℃, and the soaking time is 60-100 min;
the liquid retention rate of the extrusion is 30-110%;
the drying temperature is 50-90 ℃, and the drying time is 0.5-2.5 h.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPH0782285A (en) * | 1993-09-10 | 1995-03-28 | Eiken Chem Co Ltd | Porphyrin-phosphoric ester derivative |
| CN105949207A (en) * | 2016-05-16 | 2016-09-21 | 广东工业大学 | Preparation method of Meso-tetra(3,4-dihydroxy phenyl) zinc porphyrin |
| CN113583047A (en) * | 2021-08-16 | 2021-11-02 | 合肥学院 | Porphyrin phosphate compound, preparation method and application of porphyrin phosphate compound as flame retardant |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0782285A (en) * | 1993-09-10 | 1995-03-28 | Eiken Chem Co Ltd | Porphyrin-phosphoric ester derivative |
| CN105949207A (en) * | 2016-05-16 | 2016-09-21 | 广东工业大学 | Preparation method of Meso-tetra(3,4-dihydroxy phenyl) zinc porphyrin |
| CN113583047A (en) * | 2021-08-16 | 2021-11-02 | 合肥学院 | Porphyrin phosphate compound, preparation method and application of porphyrin phosphate compound as flame retardant |
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