CN114621449B - Fluorine-containing phenyl aluminum phosphonate polymer and preparation method thereof - Google Patents
Fluorine-containing phenyl aluminum phosphonate polymer and preparation method thereof Download PDFInfo
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- CN114621449B CN114621449B CN202210410793.9A CN202210410793A CN114621449B CN 114621449 B CN114621449 B CN 114621449B CN 202210410793 A CN202210410793 A CN 202210410793A CN 114621449 B CN114621449 B CN 114621449B
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- pentafluorophenyl
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- chloride
- octafluorobiphenyl
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- -1 phenyl aluminum phosphonate Chemical compound 0.000 title claims abstract description 92
- 229920000642 polymer Polymers 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title claims abstract description 43
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 39
- 239000011737 fluorine Substances 0.000 title claims abstract description 39
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 49
- 125000000538 pentafluorophenyl group Chemical group FC1=C(F)C(F)=C(*)C(F)=C1F 0.000 claims abstract description 45
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims abstract description 22
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 21
- YDRXOJBEHHQUJW-UHFFFAOYSA-N [Cl-].FC1=C(C(=C(C(=C1[PH3+])F)F)F)F Chemical compound [Cl-].FC1=C(C(=C(C(=C1[PH3+])F)F)F)F YDRXOJBEHHQUJW-UHFFFAOYSA-N 0.000 claims abstract description 21
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 20
- 125000005499 phosphonyl group Chemical group 0.000 claims abstract description 20
- QLZHNIAADXEJJP-UHFFFAOYSA-N Phenylphosphonic acid Chemical compound OP(O)(=O)C1=CC=CC=C1 QLZHNIAADXEJJP-UHFFFAOYSA-N 0.000 claims abstract description 18
- CRDJTBOGTABIOK-UHFFFAOYSA-N bis(2,3,4,5,6-pentafluorophenyl)phosphane;hydrochloride Chemical compound Cl.FC1=C(F)C(F)=C(F)C(F)=C1PC1=C(F)C(F)=C(F)C(F)=C1F CRDJTBOGTABIOK-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 14
- XEKTVXADUPBFOA-UHFFFAOYSA-N 1-bromo-2,3,4,5,6-pentafluorobenzene Chemical compound FC1=C(F)C(F)=C(Br)C(F)=C1F XEKTVXADUPBFOA-UHFFFAOYSA-N 0.000 claims abstract description 12
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims abstract description 11
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims abstract description 11
- YXLMNFVUNLCJJY-UHFFFAOYSA-N 1-bromo-4-(4-bromo-2,3,5,6-tetrafluorophenyl)-2,3,5,6-tetrafluorobenzene Chemical group FC1=C(Br)C(F)=C(F)C(C=2C(=C(F)C(Br)=C(F)C=2F)F)=C1F YXLMNFVUNLCJJY-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 10
- 238000003747 Grignard reaction Methods 0.000 claims abstract description 9
- 230000003647 oxidation Effects 0.000 claims abstract description 8
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims description 23
- 239000002904 solvent Substances 0.000 claims description 19
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 238000001914 filtration Methods 0.000 claims description 12
- NTHREYPJFCBZLI-UHFFFAOYSA-N 1-bromo-2,3,4,5,6-pentafluorobenzene;magnesium Chemical compound [Mg].FC1=C(F)C(F)=C(Br)C(F)=C1F NTHREYPJFCBZLI-UHFFFAOYSA-N 0.000 claims description 11
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 10
- DRNJFFYTADAYNB-UHFFFAOYSA-H dialuminum;dioxido-oxo-phenyl-$l^{5}-phosphane Chemical compound [Al+3].[Al+3].[O-]P([O-])(=O)C1=CC=CC=C1.[O-]P([O-])(=O)C1=CC=CC=C1.[O-]P([O-])(=O)C1=CC=CC=C1 DRNJFFYTADAYNB-UHFFFAOYSA-H 0.000 claims description 10
- OTCKOJUMXQWKQG-UHFFFAOYSA-L magnesium bromide Chemical compound [Mg+2].[Br-].[Br-] OTCKOJUMXQWKQG-UHFFFAOYSA-L 0.000 claims description 10
- 229910001623 magnesium bromide Inorganic materials 0.000 claims description 10
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 claims description 9
- AMQDBUIQKQUCKY-UHFFFAOYSA-M magnesium;1,2,3,4,5-pentafluorobenzene-6-ide;bromide Chemical compound [Mg+2].[Br-].FC1=[C-]C(F)=C(F)C(F)=C1F AMQDBUIQKQUCKY-UHFFFAOYSA-M 0.000 claims description 8
- 230000035484 reaction time Effects 0.000 claims description 8
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 claims description 5
- 229910052698 phosphorus Inorganic materials 0.000 claims description 4
- 239000011574 phosphorus Substances 0.000 claims description 4
- DBKFYOISCCPYTQ-UHFFFAOYSA-K C1(=CC=CC=C1)P([O-])=O.[Al+3].C1(=CC=CC=C1)P([O-])=O.C1(=CC=CC=C1)P([O-])=O Chemical class C1(=CC=CC=C1)P([O-])=O.[Al+3].C1(=CC=CC=C1)P([O-])=O.C1(=CC=CC=C1)P([O-])=O DBKFYOISCCPYTQ-UHFFFAOYSA-K 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 5
- 229910052782 aluminium Inorganic materials 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 19
- 239000003063 flame retardant Substances 0.000 abstract description 15
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$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 10
- 230000000694 effects Effects 0.000 abstract description 4
- 239000007818 Grignard reagent Substances 0.000 abstract 1
- 150000004795 grignard reagents Chemical class 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 36
- 238000012360 testing method Methods 0.000 description 31
- 229910052757 nitrogen Inorganic materials 0.000 description 18
- 238000003756 stirring Methods 0.000 description 18
- 238000010992 reflux Methods 0.000 description 15
- 229910052760 oxygen Inorganic materials 0.000 description 10
- 239000001301 oxygen Substances 0.000 description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 9
- 239000012535 impurity Substances 0.000 description 9
- 150000003839 salts Chemical class 0.000 description 9
- 238000001816 cooling Methods 0.000 description 6
- 238000000967 suction filtration Methods 0.000 description 6
- 238000002834 transmittance Methods 0.000 description 5
- 239000011521 glass Substances 0.000 description 4
- 238000001704 evaporation Methods 0.000 description 3
- 150000003384 small molecules Chemical class 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- WCRZYCXJFFOULB-UHFFFAOYSA-N (2,3,4,5,6-pentafluorophenyl)phosphonic acid Chemical compound OP(O)(=O)C1=C(F)C(F)=C(F)C(F)=C1F WCRZYCXJFFOULB-UHFFFAOYSA-N 0.000 description 2
- KQSRUTOPUQZWIE-UHFFFAOYSA-N O=P(OC(C(F)=C(C(F)=C1F)F)=C1F)OC(C(F)=C(C(F)=C1F)F)=C1F Chemical compound O=P(OC(C(F)=C(C(F)=C1F)F)=C1F)OC(C(F)=C(C(F)=C1F)F)=C1F KQSRUTOPUQZWIE-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 241000764238 Isis Species 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000000214 effect on organisms Effects 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000010137 moulding (plastic) Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 description 1
- 150000003008 phosphonic acid esters Chemical class 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G79/00—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule
- C08G79/10—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule a linkage containing aluminium
-
- 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
- C08G79/00—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule
- C08G79/02—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule a linkage containing phosphorus
- C08G79/04—Phosphorus linked to oxygen or to oxygen and carbon
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
Abstract
The invention relates to a fluorine-containing phenyl aluminum phosphonate polymer and a preparation method thereof, wherein the preparation method comprises the following steps: reacting bromopentafluorobenzene and 4,4 '-dibromo-octafluoro-biphenyl with magnesium powder in tetrahydrofuran to prepare a Grignard reagent, and sequentially carrying out Grignard reaction to generate bis (pentafluorophenyl) phosphonium chloride and 4,4' -octafluoro-biphenyl bis (pentafluorophenyl phosphonium chloride); then carrying out high-temperature oxidation in phenylphosphonic acid to generate bis (pentafluorophenyl) phosphonyl chloride and 4,4' -octafluorobiphenyl bis (pentafluorophenyl phosphonyl chloride); and (3) carrying out dehydration reaction on aluminum hydroxide, bis (pentafluorophenyl) phosphonyl chloride and 4,4' -octafluorobiphenyl bis (pentafluorophenyl phosphonyl chloride) in a toluene solvent to obtain the fluorine-containing phenyl aluminum phosphonate polymer. The method synthesizes a novel high molecular polymer, and the fluorine-containing phenyl aluminum phosphonate polymer not only has excellent flame retardant effect, but also has excellent heat resistance, impact resistance, wear resistance, water repellency, fog resistance and other performances.
Description
Technical Field
The invention belongs to the technical field of high molecular materials, and particularly relates to a fluorine-containing phenyl aluminum phosphonate polymer and a preparation method thereof.
Background
Because the phosphorus flame retardant has low toxicity and good flame retardant effect, the using amount is continuously increased. Therefore, new varieties of phosphoric acid or phosphonic acid ester flame retardants emerge endlessly. The aluminum phenylphosphinate has the molecular weight of 450.235, the initial decomposition temperature of 350 ℃, is white, nontoxic, good in thermal stability and hydrolytic stability, non-volatile, good in oil resistance, free of polymer decomposition in the processing of the product, free of influence on a plastic molding composition, and strong in cold resistance and weather resistance. The synergistic flame retardant can complement the advantages of other flame retardants when used in a synergistic manner, has a catalytic carbonization effect on organism substances, enhances the flame retardant performance, and is a high-efficiency synergistic flame retardant.
At present, flame retardants are prepared into small-molecule additives, the addition amount of the flame retardants is usually 10-40%, phenylphosphinic acid aluminum belongs to small-molecule organic phosphonate, and the addition of the small-molecule flame retardants inevitably affects the performance of organic materials, such as impact resistance, wear resistance, water repellency, heat resistance and the like.
The present invention has been made in view of the above circumstances.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a fluorine-containing phenyl aluminum phosphonate polymer and a preparation method thereof.
The invention provides a preparation method of a fluorine-containing phenyl aluminum phosphonate polymer, which comprises the following steps:
(1) Preparation of pentafluorophenyl phosphine dichloride: reacting bromopentafluorobenzene with magnesium powder in a solvent to obtain magnesium pentafluorophenyl bromide, and carrying out Grignard reaction on the magnesium pentafluorophenyl bromide and excessive phosphorus trichloride to obtain phosphorus pentafluorophenyl dichloride;
(2) Preparation of bis (pentafluorophenyl) phosphonium chloride and 4,4' -octafluorobiphenyl bis (pentafluorophenyl phosphonium chloride): reacting 4,4 '-dibromo octafluorobiphenyl with magnesium powder in a solvent to prepare 4,4' -octafluorobiphenyl bis (magnesium bromide), and carrying out Grignard reaction on pentafluorophenyl magnesium bromide or the 4,4 '-octafluorobiphenyl bis (magnesium bromide) and excessive pentafluorophenyl phosphine dichloride to obtain bis (pentafluorophenyl) phosphine chloride or 4,4' -octafluorobiphenyl bis (pentafluorophenyl phosphine chloride);
(3) Preparation of bis (pentafluorophenyl) phosphonyl chloride and 4,4' -octafluorobiphenyl bis (pentafluorophenyl phosphonyl chloride): performing high-temperature oxidation on the bis (pentafluorophenyl) phosphonyl chloride or the 4,4 '-octafluorobiphenyl bis (pentafluorophenyl phosphonium chloride) in phenylphosphonic acid to generate bis (pentafluorophenyl) phosphonyl chloride or 4,4' -octafluorobiphenyl bis (pentafluorophenyl phosphonyl chloride);
(4) Preparation of the fluorine-containing phenyl aluminum phosphonate polymer: reacting the bis (pentafluorophenyl) phosphonyl chloride, the 4,4' -octafluorobiphenyl bis (pentafluorophenyl phosphonyl chloride) and aluminum hydroxide in toluene at the temperature of 0-20 ℃, filtering out aluminum trichloride, heating to 121-141 ℃ for dehydration reaction for 6-10 hours, and distilling out toluene to obtain the fluorine-containing phenyl aluminum phosphonate polymer.
Further, the solvent in the steps (1) and (2) is one or two of tetrahydrofuran or 2-methyltetrahydrofuran.
Further, in the step (1), the reaction temperature of the bromopentafluorobenzene and the magnesium powder is 50-65 ℃, the reaction time is 5-7 hours, the temperature of the Grignard reaction is 71-86 ℃, and the reaction time is 6-8 hours.
Further, in the step (1), the molar ratio of bromopentafluorobenzene to magnesium powder is 1.0-1.1, the mass ratio of the total mass of bromopentafluorobenzene and magnesium powder to the solvent is 350-500, and the molar ratio of magnesium pentafluorophenyl bromide to phosphorus trichloride is 1.
Further, in the step (2), the reaction temperature of the 4,4' -dibromo octafluorobiphenyl and the magnesium powder is 50-65 ℃, the reaction time is 5-7 hours, the temperature of the Grignard reaction is 71-86 ℃, and the reaction time is 6-8 hours.
Further, in the step (2), the molar ratio of the 4,4' -dibromo-octafluoro-biphenyl to the magnesium powder is 1.
Further, in the step (3), the mass ratio of the bis (pentafluorophenyl) phosphonyl chloride or the 4,4' -octafluorobiphenyl bis (pentafluorophenyl phosphonium chloride) to the phenylphosphonic acid is 100-250.
Further, the temperature of the high-temperature oxidation in the step (3) is 240-260 ℃, and the oxidation time is 6-7 hours.
The phenylphosphonic acid in the invention plays a role as a solvent and a catalyst, and oxygen with the purity of 99.99 percent is introduced during high-temperature oxidation.
Further, in the step (4), the molar ratio of 4,4' -octafluorobiphenyl bis (pentafluorophenyl phosphonyl chloride) to bis (pentafluorophenyl) phosphonyl chloride is 1.
In the invention, bis (pentafluorophenyl) phosphonyl chloride, 4' -octafluorobiphenyl bis (pentafluorophenyl phosphonyl chloride) and part of aluminum hydroxide react to generate bis (pentafluorophenyl) phosphonic acid, 4' -octafluorobiphenyl bis (pentafluorophenyl phosphonic acid) and aluminum trichloride, the generated aluminum trichloride is firstly removed by filtration, and the bis (pentafluorophenyl) phosphonic acid, the 4,4' -octafluorobiphenyl bis (pentafluorophenyl phosphonic acid) and the rest aluminum hydroxide undergo dehydration reaction (toluene carries water) at the temperature of 121-141 ℃ to prepare the fluorine-containing phenyl aluminum phosphonate polymer.
The invention also provides a fluorine-containing phenyl aluminum phosphonate polymer prepared by the method, wherein the weight average molecular weight of the fluorine-containing phenyl aluminum phosphonate polymer is not less than 5.58 multiplied by 10 6 。
The fluorine-containing phenyl aluminum phosphonate polymer prepared by the invention is off-white powder, and the specific chemical structural formula of the fluorine-containing phenyl aluminum phosphonate polymer is as follows:
wherein the content of the first and second substances,
r is
R' is
Is a connecting key.
Compared with the prior art, the invention has the beneficial effects that:
the fluorine-containing phenyl aluminum phosphonate polymer has excellent flame retardant effect, excellent heat resistance, impact resistance, wear resistance, water repellency, fog resistance and other performances, and can be used for preparing high-temperature flame retardant instruments or appliances, high-precision instrument and meter waterproof and explosion-proof covers, airplane and automobile glass.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be described in detail below. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the examples given herein without any inventive step, are within the scope of the present invention.
Example 1
The preparation method of the fluorine-containing phenyl aluminum phosphonate polymer comprises the following steps:
(1) Preparation of pentafluorophenyl phosphine dichloride:
adding 4.9g of magnesium powder and 250g of tetrahydrofuran into a 500mL reactor, introducing nitrogen, starting stirring, heating to 55 ℃, slowly dropwise adding 49.4g of bromopentafluorobenzene, reacting for 6.0 hours to generate magnesium pentafluorophenyl bromide, slowly dropwise adding a magnesium pentafluorophenyl bromide solution into 100g of phosphorus trichloride, gradually heating to 72 ℃, performing reflux reaction for 6 hours, performing suction filtration to remove salts, and distilling to remove tetrahydrofuran, redundant phosphorus trichloride and other impurities to obtain phosphorus pentafluorophenyl dichloride;
(2) Preparation of bis (pentafluorophenyl) phosphonium chloride:
preparing pentafluorophenyl magnesium bromide according to the method in the step (1), slowly dripping the prepared pentafluorophenyl magnesium bromide solution into 300g of pentafluorophenyl phosphine dichloride, then gradually heating to 74 ℃, carrying out reflux reaction for 5 hours, carrying out suction filtration to remove salt, and then distilling to remove tetrahydrofuran, redundant pentafluorophenyl phosphine dichloride and other impurities to obtain bis (pentafluorophenyl) phosphine chloride;
preparation of 4,4' -octafluorobiphenyl bis (pentafluorophenyl phosphonium chloride):
adding 4.9g of magnesium powder and 250g of tetrahydrofuran into a 500mL reactor, introducing nitrogen, starting stirring, heating to 60 ℃, slowly dropwise adding 45.6g of 4,4 '-dibromo octafluorobiphenyl for 5.0 hours to react to generate 4,4' -octafluorobiphenyl bis (magnesium bromide), then slowly dropwise adding a 4,4 '-octafluorobiphenyl bis (magnesium bromide) solution into 100g of pentafluorophenyl phosphine dichloride, gradually heating to 71 ℃, carrying out reflux reaction for 6 hours, carrying out suction filtration to remove salts, distilling to remove tetrahydrofuran, redundant pentafluorophenyl phosphine dichloride and other impurities to obtain 4,4' -octafluorobiphenyl bis (pentafluorophenyl phosphine chloride);
(3) Preparation of bis (pentafluorophenyl) phosphonyl chloride:
adding 51.2g of bis (pentafluorophenyl) phosphine chloride and 80g of anhydrous phenylphosphonic acid into a 500mL reactor, introducing nitrogen, stirring, heating to 240 ℃, slowly introducing oxygen with the purity of 99.99%, observing the reflux condition, reacting for 7 hours, and then ending, evaporating the phenylphosphonic acid under reduced pressure to obtain bis (pentafluorophenyl) phosphonyl chloride;
preparation of 4,4' -octafluorobiphenyl bis (pentafluorophenyl phosphonyl chloride):
adding 91.2g of 4,4 '-octafluorobiphenyl bi (pentafluorophenyl phosphonium chloride) and 140g of anhydrous phenylphosphonic acid into a 500mL reactor, introducing nitrogen, stirring, heating to 250 ℃, slowly introducing oxygen with the purity of 99.99%, observing the reflux condition, reacting for 6 hours, and then distilling the phenylphosphonic acid under reduced pressure to obtain 4,4' -octafluorobiphenyl bi (pentafluorophenyl phosphonium chloride);
(4) Preparation of fluorine-containing phenyl aluminum phosphonate polymer:
adding 250g of toluene into a 500mL reactor, adjusting the temperature to 15 ℃, adding 15.6g of aluminum hydroxide, introducing nitrogen, stirring, slowly adding 52.9g of bis (pentafluorophenyl) phosphonyl chloride and 103g of 4,4' -octafluorobiphenyl bis (pentafluorophenyl phosphonyl chloride) into the reactor, cooling and filtering to remove aluminum trichloride after the reaction is stable, slowly raising the temperature to 121 ℃, performing dehydration reaction for 7 hours, evaporating the solvent toluene according to the fact that water distilled from a water separator meets the metering requirement, thus obtaining the off-white fluorine-containing phenyl aluminum phosphonate polymer with the weight-average molecular weight of 5.58 multiplied by 10 6 。
Example 2
The preparation method of the aluminum fluorophenylphosphonate-containing polymer of the embodiment comprises the following steps:
(1) Preparation of pentafluorophenyl phosphine dichloride:
adding 4.8g of magnesium powder and 190g of tetrahydrofuran into a 500mL reactor, introducing nitrogen, starting stirring, heating to 50 ℃, slowly and dropwise adding 49.4g of bromopentafluorobenzene, reacting for 7.0 hours to generate magnesium pentafluorophenyl bromide, slowly and dropwise adding a magnesium pentafluorophenyl bromide solution into 100g of phosphorus trichloride, gradually heating to 71 ℃, and carrying out reflux reaction for 8 hours. Filtering to remove salt, and distilling to remove tetrahydrofuran, redundant phosphorus trichloride and other impurities to obtain pentafluorophenyl phosphine dichloride;
(2) Preparation of bis (pentafluorophenyl) phosphonium chloride:
preparing pentafluorophenyl magnesium bromide according to the method in the step (1), slowly dripping the prepared pentafluorophenyl magnesium bromide solution into 150g of pentafluorophenyl phosphine dichloride, then gradually heating to 84 ℃, carrying out reflux reaction for 5 hours, carrying out suction filtration to remove salt, and then distilling to remove the solvent, redundant pentafluorophenyl phosphine dichloride and other impurities to obtain bis (pentafluorophenyl) phosphine chloride;
preparation of 4,4' -octafluorobiphenyl bis (pentafluorophenyl phosphonium chloride):
adding 4.8g of magnesium powder and 250g of tetrahydrofuran into a 500mL reactor, introducing nitrogen, starting stirring, heating to 65 ℃, slowly dropwise adding 45.6g of 4,4 '-dibromo octafluorobiphenyl for 5.0 hours to react to generate 4,4' -octafluorobiphenyl bis (magnesium bromide), then slowly dropwise adding the 4,4 '-octafluorobiphenyl bis (magnesium bromide) solution into 82g of pentafluorophenyl phosphine dichloride, gradually heating to 78 ℃, refluxing for 7 hours, performing suction filtration to remove salts, distilling to remove the solvent, redundant fluorophenyl phosphine dichloride and other impurities to obtain 4,4' -octafluorobiphenyl bis (pentafluorophenyl phosphine chloride);
(3) Preparation of bis (pentafluorophenyl) phosphonyl chloride:
adding 51.2g of bis (pentafluorophenyl) phosphine chloride and 100g of anhydrous phenylphosphonic acid into a 500mL reactor, introducing nitrogen, stirring, heating to 240 ℃, slowly introducing oxygen with the purity of 99.99%, observing the reflux condition, reacting for 6.5 hours, and then ending, evaporating the phenylphosphonic acid under reduced pressure to obtain bis (pentafluorophenyl) phosphonyl chloride;
preparation of 4,4' -octafluorobiphenyl bis (pentafluorophenyl phosphonyl chloride):
adding 91.2g of 4,4 '-octafluorobiphenyl bis (pentafluorophenyl phosphonium chloride) and 180g of anhydrous phenylphosphonic acid into a 500mL reactor, stirring by introducing nitrogen, heating to 260 ℃, slowly introducing oxygen with the purity of 99.99%, observing the reflux condition, reacting for 6.5 hours, and then ending, distilling out the phenylphosphonic acid under reduced pressure to obtain 4,4' -octafluorobiphenyl bis (pentafluorophenyl phosphonium chloride);
(4) Preparation of fluorine-containing phenyl aluminum phosphonate polymer:
adding 250g of toluene into a 500mL reactor, adjusting the temperature to 0 ℃, adding 15.6g of aluminum hydroxide, introducing nitrogen, stirring, slowly adding 52.9g of bis (pentafluorophenyl) phosphonyl chloride and 103g of 4,4' -octafluorobiphenyl bis (pentafluorophenyl phosphonyl chloride) into the reactor, cooling and filtering to remove aluminum trichloride after the reaction is stable, slowly raising the temperature to 131 ℃, performing dehydration reaction for 6 hours, and distilling water out of a water separator according to the metering requirement. The solvent toluene was distilled off to obtain an off-white aluminum fluorophenylphosphonate polymer having a weight-average molecular weight of 6.42X 10 6 。
Example 3
The preparation method of the aluminum fluorophenylphosphonate-containing polymer of the embodiment comprises the following steps:
(1) Preparation of pentafluorophenyl phosphine dichloride:
adding 5.28g of magnesium powder and 270g of 2-methyltetrahydrofuran into a 500mL reactor, introducing nitrogen, starting stirring, heating to 65 ℃, slowly and dropwise adding 49.4g of bromopentafluorobenzene, reacting for 5.0 hours to generate magnesium pentafluorophenyl bromide, then slowly and dropwise adding a magnesium pentafluorophenyl bromide solution into 100g of phosphorus trichloride, gradually heating to 86 ℃, and carrying out reflux reaction for 6 hours. Filtering to remove salt, and distilling to remove 2-methyltetrahydrofuran, redundant phosphorus trichloride and other impurities to obtain pentafluorophenyl phosphine dichloride;
(2) Preparation of bis (pentafluorophenyl) phosphonium chloride:
preparing pentafluorophenyl magnesium bromide according to the method in the step (1), slowly dripping the prepared pentafluorophenyl magnesium bromide solution into 150g of pentafluorophenyl phosphine dichloride, then gradually heating to 74 ℃, carrying out reflux reaction for 5 hours, carrying out suction filtration to remove salt, and then distilling to remove the solvent, redundant pentafluorophenyl phosphine dichloride and other impurities to obtain bis (pentafluorophenyl) phosphine chloride;
preparation of 4,4' -octafluorobiphenyl bis (pentafluorophenyl phosphonium chloride):
adding 5.28g of magnesium powder and 210g of 2-methyltetrahydrofuran into a 500mL reactor, introducing nitrogen, starting stirring, heating to 65 ℃, slowly dropwise adding 45.6g of 4,4 '-dibromo octafluoro biphenyl for 5.0 hours to react to generate 4,4' -octafluoro biphenyl bis (magnesium bromide), then slowly dropwise adding the 4,4 '-octafluoro biphenyl bis (magnesium bromide) solution into 130g of pentafluorophenyl phosphine dichloride, gradually heating to 86 ℃, refluxing for 6 hours, filtering to remove salts, distilling to remove the solvent, redundant fluorophenyl phosphine dichloride and other impurities, and obtaining 4,4' -octafluoro biphenyl bis (pentafluorophenyl phosphine chloride);
(3) Preparation of bis (pentafluorophenyl) phosphonyl chloride:
adding 51.2g of bis (pentafluorophenyl) phosphine chloride and 130g of anhydrous phenylphosphonic acid into a 500mL reactor, introducing nitrogen, stirring, heating to 260 ℃, slowly introducing oxygen with the purity of 99.99%, observing the reflux condition, reacting for 7 hours, and then ending, decompressing and distilling out the phenylphosphonic acid to obtain bis (pentafluorophenyl) phosphonyl chloride;
preparation of 4,4' -octafluorobiphenyl bis (pentafluorophenyl phosphonyl chloride):
adding 91.2g of 4,4 '-octafluorobiphenyl bis (pentafluorophenyl phosphonium chloride) and 228g of anhydrous phenylphosphonic acid into a 500mL reactor, stirring by introducing nitrogen, heating to 240 ℃, slowly introducing oxygen with the purity of 99.99%, observing the reflux condition, reacting for 7 hours, and then distilling out the phenylphosphonic acid under reduced pressure to obtain 4,4' -octafluorobiphenyl bis (pentafluorophenyl phosphonium chloride);
(4) Preparation of fluorine-containing phenyl aluminum phosphonate polymer:
adding 250g of toluene into a 500mL reactor, adjusting the temperature to 25 ℃, adding 15.6g of aluminum hydroxide, introducing nitrogen, stirring, slowly adding 52.9g of bis (pentafluorophenyl) phosphonyl chloride and 103g of 4,4' -octafluorobiphenyl bis (pentafluorophenyl phosphonyl chloride) into the reactor, cooling and filtering to remove aluminum trichloride after the reaction is stable, slowly raising the temperature to 141 ℃, performing dehydration reaction for 10 hours, and distilling water out of a water separator according to the metering requirement. The solvent toluene was distilled off to obtain an off-white aluminum fluorophenylphosphonate polymer having a weight-average molecular weight of 6.62X 10 6 。
Example 4
The preparation method of the fluorine-containing phenyl aluminum phosphonate polymer comprises the following steps:
(1) - (3) Steps (1) to (3) in the same manner as in example 1;
(4) Preparation of fluorine-containing phenyl aluminum phosphonate polymer:
adding 250g of toluene into a 500mL reactor, adjusting the temperature to 15 ℃, adding 15.6g of aluminum hydroxide, introducing nitrogen, stirring, slowly adding 52.9g of bis (pentafluorophenyl) phosphonyl chloride and 103.1g of 4,4' -octafluorobiphenyl bis (pentafluorophenyl phosphonyl chloride) into the reactor, cooling and filtering to remove aluminum trichloride after the reaction is stable, slowly raising the temperature to 132 ℃, performing dehydration reaction for 6 hours, and distilling water from a water separator to meet the metering requirement. Steaming to remove the solvent ABenzene to give an off-white polymer of aluminum fluorophenylphosphonate having a weight average molecular weight of 6.76X 10 6 。
Example 5
The preparation method of the fluorine-containing phenyl aluminum phosphonate polymer comprises the following steps:
(1) - (3) Steps (1) to (3) in the same manner as in example 1;
(4) Preparation of fluorine-containing phenyl aluminum phosphonate polymer:
adding 250g of toluene into a 500mL reactor, adjusting the temperature to 15 ℃, adding 15.6g of aluminum hydroxide, introducing nitrogen, stirring, slowly adding 39.6g of bis (pentafluorophenyl) phosphonyl chloride and 128.8g of 4,4' -octafluorobiphenyl bis (pentafluorophenyl phosphonyl chloride) into the reactor, cooling and filtering to remove aluminum trichloride after the reaction is stable, slowly raising the temperature to 128 ℃, performing dehydration reaction for 8h, and according to the fact that water distilled out of a water separator meets the metering requirement. The solvent toluene was distilled off to obtain an off-white aluminum phenylphosphonate-containing polymer having a weight-average molecular weight of 7.87X 10 6 。
Example 6
The preparation method of the fluorine-containing phenyl aluminum phosphonate polymer comprises the following steps:
(1) - (3) Steps (1) to (3) of example 1;
(4) Preparation of fluorine-containing phenyl aluminum phosphonate polymer:
adding 250g of toluene into a 500mL reactor, adjusting the temperature to 15 ℃, adding 15.6g of aluminum hydroxide, introducing nitrogen, stirring, slowly adding 26.5g of bis (pentafluorophenyl) phosphonyl chloride and 154.5g of 4,4' -octafluorobiphenyl bis (pentafluorophenyl phosphonyl chloride) into the reactor, cooling and filtering to remove aluminum trichloride after the reaction is stable, slowly raising the temperature to 135 ℃, performing dehydration reaction for 7 hours, and distilling water from a water separator according to the metering requirement. The solvent toluene was distilled off to obtain an off-white fluorine-containing aluminum phenylphosphonate polymer having a weight-average molecular weight of 8.46X 10 6 。
Test example 1
(1) Flame retardancy test
The fluorine-containing phenyl aluminum phosphonate polymers prepared in examples 1 to 6 were sampled and designated as test samples 1 to 6.
The limit oxygen index of the sample is measured by referring to GB/T2406-2008 'test method for plastic combustion performance-oxygen index method', and the result is shown in Table 1.
TABLE 1
| Sample (I) | Test sample 1 | Test sample 2 | Test sample No. 3 | Test sample 4 | Test sample No. 5 | Test sample 6 |
| LOI | 35.3 | 36.5 | 37.5 | 35.6 | 36.9 | 37.8 |
LOI 28 is a flame-retardant limiting oxygen index, and the table 1 shows that the fluorine-containing phenyl aluminum phosphonate polymer prepared by the invention has excellent flame-retardant effect.
(2) Heat resistance test
The fluorine-containing phenyl aluminum phosphonate polymers prepared in examples 1 to 6 were sampled and designated as test samples 1 to 6.
The Vicat softening points of the test samples 1-6 were measured according to GB/T1633-2000 "determination of Vicat Softening Temperature (VST) of thermoplastics" and the results are shown in Table 2.
TABLE 2
It can be seen from Table 2 that the aluminum fluorophenylphosphonate containing polymer prepared by the invention has high temperature resistance.
(3) Light transmittance test
The fluorinated aluminum phenylphosphonate-containing polymers prepared in examples 1 to 6 were pressed at 335 to 350 ℃ to form glass slides having a thickness of 5mm, and the glass slides were recorded as test samples 1 to 6, and the light transmittance (%) was measured with reference to GB/T40415-2021 "method for measuring light transmittance of photovoltaic glass module for construction", and is shown in Table 3.
TABLE 3
| Sample(s) | Test sample 1 | Test sample 2 | Test sample No. 3 | Test sample 4 | Test sample No. 5 | Test sample No. 6 |
| Light transmittance(％) | 92.4 | 91.8 | 90.7 | 91.6 | 90.5 | 89.3 |
As can be seen from the data in Table 3, the fluorine-containing aluminum phenylphosphonate polymer prepared by the method of the present invention has good light transmittance.
(4) Impact resistance test
The fluorinated phenylphosphonic acid aluminum polymers prepared in examples 1 to 6 were prepared into dumbbell-shaped sample bars, which were recorded as test samples 1 to 6, and the impact strength (KJ/m) at the notch of the simple beam was measured with reference to GB/T1043-92 method for testing impact strength of simple beam for rigid plastics 2 ) The results are shown in Table 4.
TABLE 4
As can be seen from the data in Table 4, the fluorinated aluminum phenylphosphonate-containing polymer prepared by the method of the present invention has excellent impact strength.
(5) Water repellency test
The fluorinated aluminum phenylphosphonate polymers prepared in examples 1 to 6 were respectively formed into films and designated as test samples 1 to 6, and the contact angles of the samples were measured in accordance with GB/T30693 to 2014, which is a measurement of contact angles between plastic films and water, and the results are shown in Table 5.
TABLE 5
| Sample (I) | Test sample 1 | Test sample 2 | Test sample 3 | Test sample 4 | Test sample No. 5 | Test sample No. 6 |
| Contact angle (degree) | 131 | 138 | 145 | 133 | 142 | 147 |
As can be seen from the contact angles in Table 5, the fluorinated aluminum phenylphosphonate-containing polymer prepared by the present invention has excellent antifogging and water repellency.
The above description is only for the specific embodiments of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can easily conceive of the changes or substitutions within the technical scope of the present invention, and all the changes or substitutions should be covered within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the appended claims.
Claims (10)
1. A preparation method of a fluorine-containing phenyl aluminum phosphonate polymer is characterized by comprising the following steps:
(1) Preparation of pentafluorophenyl phosphine dichloride: reacting bromopentafluorobenzene with magnesium powder in a solvent to obtain magnesium pentafluorophenyl bromide, and carrying out Grignard reaction on the magnesium pentafluorophenyl bromide and excessive phosphorus trichloride to obtain phosphorus pentafluorophenyl dichloride;
(2) Preparation of bis (pentafluorophenyl) phosphonium chloride and 4,4' -octafluorobiphenyl bis (pentafluorophenyl phosphonium chloride): reacting 4,4 '-dibromo octafluorobiphenyl with magnesium powder in a solvent to prepare 4,4' -octafluorobiphenyl bis (magnesium bromide), and carrying out Grignard reaction on pentafluorophenyl magnesium bromide or the 4,4 '-octafluorobiphenyl bis (magnesium bromide) and excessive pentafluorophenyl phosphine dichloride to obtain bis (pentafluorophenyl) phosphine chloride or 4,4' -octafluorobiphenyl bis (pentafluorophenyl phosphine chloride);
(3) Preparation of bis (pentafluorophenyl) phosphonyl chloride and 4,4' -octafluorobiphenyl bis (pentafluorophenyl phosphonyl chloride): carrying out high-temperature oxidation on the bis (pentafluorophenyl) phosphonium chloride or the 4,4 '-octafluorobiphenyl bis (pentafluorophenyl phosphonium chloride) in phenylphosphonic acid to generate bis (pentafluorophenyl) phosphonyl chloride or 4,4' -octafluorobiphenyl bis (pentafluorophenyl phosphonyl chloride);
(4) Preparation of the fluorine-containing phenyl aluminum phosphonate polymer: reacting the bis (pentafluorophenyl) phosphonyl chloride, the 4,4' -octafluorobiphenyl bis (pentafluorophenyl phosphonyl chloride) and aluminum hydroxide in toluene at the temperature of 0-20 ℃, filtering out aluminum trichloride, heating to 121-141 ℃ for dehydration reaction for 6-10 hours, and distilling out toluene to obtain the fluorine-containing phenyl aluminum phosphonate polymer.
2. The method for preparing a fluorinated aluminum phenylphosphinate polymer according to claim 1, wherein the solvent used in steps (1) and (2) is one or both of tetrahydrofuran and 2-methyltetrahydrofuran.
3. The method for preparing a fluorine-containing aluminum phenylphosphonate polymer as claimed in claim 1 or 2, wherein in the step (1), the reaction temperature of bromopentafluorobenzene with magnesium powder is 50-65 ℃ and the reaction time is 5-7 hours, the temperature of the Grignard reaction is 71-86 ℃ and the reaction time is 6-8 hours.
4. The method for preparing a fluorine-containing phenyl aluminum phosphonate polymer according to claim 1, wherein in the step (1), the molar ratio of bromopentafluorobenzene to magnesium powder is 1.0-1.1, the mass ratio of the total mass of the bromopentafluorobenzene and magnesium powder to the solvent is 100.
5. The method for producing a fluorinated aluminum phenylphosphonate polymer as claimed in claim 1 or 2, wherein in the step (2), the reaction temperature of 4,4' -dibromooctafluorobiphenyl with magnesium powder is 50 to 65 ℃ and the reaction time is 5 to 7 hours, and the temperature of the grignard reaction is 71 to 86 ℃ and the reaction time is 6 to 8 hours.
6. The method for producing a fluorinated aluminum phenylphosphonate polymer according to claim 1, wherein in the step (2), the molar ratio of 4,4' -dibromooctafluorobiphenyl to magnesium powder is 1.
7. The method for producing a fluorophenylphoshine-aluminum polymer according to claim 1, wherein the mass ratio of bis (pentafluorophenyl) phosphonium chloride or 4,4' -octafluorobiphenylbis (pentafluorophenyl phosphonium chloride) to phenylphosphonic acid in step (3) is 100.
8. The method for producing a fluorinated phenylphosphonic acid aluminum polymer according to claim 1 or 7, wherein the temperature of the high-temperature oxidation in the step (3) is 240 to 260 ℃ and the oxidation time is 6 to 7 hours.
9. The method for producing a fluorinated phenyl aluminum phosphonate polymer according to claim 1, wherein the molar ratio of 4,4' -octafluorobiphenyl bis (pentafluorophenyl phosphonyl chloride) to bis (pentafluorophenyl) phosphonyl chloride in step (4) is 1.
10. The fluorine-containing phenyl aluminum phosphonate polymer prepared by any method of claims 1-9, characterized in that the weight average molecular weight of the fluorine-containing phenyl aluminum phosphonate polymer is not less than 5.58 x 10 6 。
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