CN113637167A - Branched polyaromatic ether and preparation method thereof - Google Patents
Branched polyaromatic ether and preparation method thereof Download PDFInfo
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- CN113637167A CN113637167A CN202110790923.1A CN202110790923A CN113637167A CN 113637167 A CN113637167 A CN 113637167A CN 202110790923 A CN202110790923 A CN 202110790923A CN 113637167 A CN113637167 A CN 113637167A
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- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 22
- 125000003118 aryl group Chemical group 0.000 claims abstract description 15
- 238000004519 manufacturing process Methods 0.000 claims abstract description 11
- 229920000642 polymer Polymers 0.000 claims abstract description 9
- 239000000178 monomer Substances 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 238000006116 polymerization reaction Methods 0.000 claims description 14
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 11
- 230000007062 hydrolysis Effects 0.000 claims description 10
- 238000006460 hydrolysis reaction Methods 0.000 claims description 10
- 229930185605 Bisphenol Natural products 0.000 claims description 9
- 239000006085 branching agent Substances 0.000 claims description 9
- 239000003960 organic solvent Substances 0.000 claims description 9
- 239000002585 base Substances 0.000 claims description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 claims description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- ZQBFAOFFOQMSGJ-UHFFFAOYSA-N hexafluorobenzene Chemical compound FC1=C(F)C(F)=C(F)C(F)=C1F ZQBFAOFFOQMSGJ-UHFFFAOYSA-N 0.000 claims description 4
- 235000013824 polyphenols Nutrition 0.000 claims description 4
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- 239000011593 sulfur Substances 0.000 claims description 3
- ONUFSRWQCKNVSL-UHFFFAOYSA-N 1,2,3,4,5-pentafluoro-6-(2,3,4,5,6-pentafluorophenyl)benzene Chemical group FC1=C(F)C(F)=C(F)C(F)=C1C1=C(F)C(F)=C(F)C(F)=C1F ONUFSRWQCKNVSL-UHFFFAOYSA-N 0.000 claims description 2
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 claims description 2
- ZFPGARUNNKGOBB-UHFFFAOYSA-N 1-Ethyl-2-pyrrolidinone Chemical compound CCN1CCCC1=O ZFPGARUNNKGOBB-UHFFFAOYSA-N 0.000 claims description 2
- VSJZSGXKNZYQPR-UHFFFAOYSA-N 1-bis(4-fluorophenyl)phosphoryl-4-fluorobenzene Chemical compound C1=CC(F)=CC=C1P(=O)(C=1C=CC(F)=CC=1)C1=CC=C(F)C=C1 VSJZSGXKNZYQPR-UHFFFAOYSA-N 0.000 claims description 2
- BNXZHVUCNYMNOS-UHFFFAOYSA-N 1-butylpyrrolidin-2-one Chemical compound CCCCN1CCCC1=O BNXZHVUCNYMNOS-UHFFFAOYSA-N 0.000 claims description 2
- NUHWHLSPHBVPKM-UHFFFAOYSA-N 2,4,6-tris(4-fluorophenyl)-1,3,5-triazine Chemical compound C1=CC(F)=CC=C1C1=NC(C=2C=CC(F)=CC=2)=NC(C=2C=CC(F)=CC=2)=N1 NUHWHLSPHBVPKM-UHFFFAOYSA-N 0.000 claims description 2
- BRPSWMCDEYMRPE-UHFFFAOYSA-N 4-[1,1-bis(4-hydroxyphenyl)ethyl]phenol Chemical compound C=1C=C(O)C=CC=1C(C=1C=CC(O)=CC=1)(C)C1=CC=C(O)C=C1 BRPSWMCDEYMRPE-UHFFFAOYSA-N 0.000 claims description 2
- LIDWAYDGZUAJEG-UHFFFAOYSA-N 4-[bis(4-hydroxyphenyl)-phenylmethyl]phenol Chemical compound C1=CC(O)=CC=C1C(C=1C=CC(O)=CC=1)(C=1C=CC(O)=CC=1)C1=CC=CC=C1 LIDWAYDGZUAJEG-UHFFFAOYSA-N 0.000 claims description 2
- BOCLKUCIZOXUEY-UHFFFAOYSA-N 4-[tris(4-hydroxyphenyl)methyl]phenol Chemical compound C1=CC(O)=CC=C1C(C=1C=CC(O)=CC=1)(C=1C=CC(O)=CC=1)C1=CC=C(O)C=C1 BOCLKUCIZOXUEY-UHFFFAOYSA-N 0.000 claims description 2
- LMBQOLBVWODAFG-UHFFFAOYSA-N 4-bis(4-hydroxyphenyl)phosphorylphenol Chemical compound C1=CC(O)=CC=C1P(=O)(C=1C=CC(O)=CC=1)C1=CC=C(O)C=C1 LMBQOLBVWODAFG-UHFFFAOYSA-N 0.000 claims description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 2
- 229920000877 Melamine resin Polymers 0.000 claims description 2
- DNLRPRKUMOVZJR-UHFFFAOYSA-N [3,5-bis(4-fluorobenzoyl)phenyl]-(4-fluorophenyl)methanone Chemical compound C1=CC(F)=CC=C1C(=O)C1=CC(C(=O)C=2C=CC(F)=CC=2)=CC(C(=O)C=2C=CC(F)=CC=2)=C1 DNLRPRKUMOVZJR-UHFFFAOYSA-N 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000003277 amino group Chemical group 0.000 claims description 2
- ZSTLPJLUQNQBDQ-UHFFFAOYSA-N azanylidyne(dihydroxy)-$l^{5}-phosphane Chemical compound OP(O)#N ZSTLPJLUQNQBDQ-UHFFFAOYSA-N 0.000 claims description 2
- WWQLXRAKBJVNCC-UHFFFAOYSA-N bis(2,3,4,5,6-pentafluorophenyl)methanone Chemical compound FC1=C(F)C(F)=C(F)C(F)=C1C(=O)C1=C(F)C(F)=C(F)C(F)=C1F WWQLXRAKBJVNCC-UHFFFAOYSA-N 0.000 claims description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims description 2
- MGNCLNQXLYJVJD-UHFFFAOYSA-N cyanuric chloride Chemical compound ClC1=NC(Cl)=NC(Cl)=N1 MGNCLNQXLYJVJD-UHFFFAOYSA-N 0.000 claims description 2
- 239000003822 epoxy resin Substances 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 239000011737 fluorine Substances 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims description 2
- 150000002367 halogens Chemical group 0.000 claims description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 239000003607 modifier Substances 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 229960001553 phloroglucinol Drugs 0.000 claims description 2
- 229920000647 polyepoxide Polymers 0.000 claims description 2
- 230000000379 polymerizing effect Effects 0.000 claims description 2
- 150000008442 polyphenolic compounds Chemical class 0.000 claims description 2
- 229910000160 potassium phosphate Inorganic materials 0.000 claims description 2
- 235000011009 potassium phosphates Nutrition 0.000 claims description 2
- 125000003396 thiol group Chemical group [H]S* 0.000 claims description 2
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 claims 1
- 238000009835 boiling Methods 0.000 description 8
- 239000004695 Polyether sulfone Substances 0.000 description 7
- 229920006393 polyether sulfone Polymers 0.000 description 7
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 description 4
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 4
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000004609 Impact Modifier Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 150000004820 halides Chemical group 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 2
- 229920000090 poly(aryl ether) Polymers 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- 229920000491 Polyphenylsulfone Polymers 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 229910000404 tripotassium phosphate Inorganic materials 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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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
- C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
- C08G75/20—Polysulfones
- C08G75/23—Polyethersulfones
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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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)
- Polyethers (AREA)
Abstract
The invention relates to a branched polyaromatic ether and a preparation method thereof. The polymer molecular chain of the polyaromatic ether provided by the invention has three or more terminal hydroxyl groups and aromatic groups with trivalent valence or higher valence. The polyaromatic ether provided by the invention ensures larger molecular weight on the basis of improving the content of terminal hydroxyl, and the preparation method simplifies the production link and reduces the production cost.
Description
Technical Field
The invention relates to the field of polyaromatic ether synthesis, in particular to branched polyaromatic ether and a preparation method thereof.
Technical Field
The polyaromatic ether is an important high-performance polymer material, has high thermal stability, chemical stability and mechanical strength, has various structures and wide sources, and plays an irreplaceable role in the fields of national defense and military industry, aerospace, high-end manufacturing and the like. The varieties of polysulfone, polyethersulfone and polyphenylsulfone which adopt bisphenol A, bisphenol S and biphenol as monomers in polyaromatic ether have been realized batch production, wherein the polyethersulfone containing terminal hydroxyl is widely applied in the fields of coating, adhesive and epoxy impact modifier.
The polyether sulfone is prepared by aromatic nucleophilic substitution polycondensation reaction of 4, 4-dichlorodiphenyl sulfone and bisphenol S, and two process links of water diversion and temperature rise polymerization are needed. Due to the relatively low reactivity of bisphenol S, high temperature polymerization in high boiling solvents (sulfolane, diphenylsulfone, etc.) is often required to obtain polymers of higher molecular weight. These solvents are expensive, complex in post-treatment (boiling point of sulfolane is 285 ℃, energy consumption of rectification is high, diphenyl sulfone is insoluble in water, and needs to be extracted and recovered by organic solvents such as acetone, ethanol and the like), and the capacity of dissolving polymers is limited, so that the production efficiency is low and the cost is high.
The commercialized hydroxyl-terminated polyether sulfone is straight-chain type, namely each polymer molecular chain has at most two hydroxyl-terminated groups, and when the epoxy impact modifier is applied, the polyether sulfone is required to have larger molecular weight, so that the content of the hydroxyl-terminated groups is lower, and the dosage can only be increased to achieve the modification effect.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides the polyaromatic ether with high terminal hydroxyl group content and the preparation method thereof.
The first aspect of the present invention provides a branched polyaromatic ether having a polymer molecular chain having three or more terminal hydroxyl groups and aromatic groups of a trivalent or higher valence state.
In the invention, the polymer molecular chain contains a plurality of terminal hydroxyl groups, so that on the basis of improving the content of the terminal hydroxyl groups, a larger molecular weight is ensured, and the schematic structure is shown as the following formula:
according to some embodiments of the invention, the polyaromatic ether is polyethersulfone.
According to some embodiments of the invention, a trivalent or higher aromatic group connects the hydroxyl group and the structure:
wherein each of A and B independently represents a divalent aromatic group, each of D independently represents oxygen or sulfur, and n is an integer greater than 1. According to some embodiments of the invention, preferably n is an integer greater than 5.
According to some embodiments of the invention, the trivalent or higher aromatic group is attached to at least one structure as shown below:
wherein each of A and B independently represents a divalent aromatic group, each of D independently represents oxygen or sulfur, and n is an integer greater than 1. According to some embodiments of the invention, preferably n is an integer greater than 5.
According to some embodiments of the invention, each D independently represents oxygen.
According to some embodiments of the invention, the trivalent or higher aromatic group is selected from one or more of the following structures:
according to some embodiments of the invention, the group B is selected from one or more of the following structures:
according to some embodiments of the invention, the group a is selected from one or more of the following structures:
according to some embodiments of the invention, the viscosity of the polyaromatic ether is greater than 0.3dL/g measured in a solution of 0.05M lithium bromide in NMP (N-methylpyrrolidone) at 25 ℃ using an Ubbelohde viscometer. In some embodiments, the polyaromatic ether has a viscosity of 0.5 to 2.0 dL/g. In some embodiments, the polyaromatic ether has a viscosity of 0.5 to 1.8 dL/g.
In a second aspect, the present invention provides a method for preparing a high hydroxyl-terminated polyaromatic ether, which comprises the steps of: (1) polymerizing a dihalogen monomer and a bisphenol monomer and a branching agent in the presence of a base and an organic solvent, wherein the branching agent is selected from a polyphenol monomer having three or more hydroxyl groups or mercapto groups, a polyhalogen monomer having three or more halogen groups, or a polyamino monomer having three or more amino groups; (2) adding water into the system after the polymerization reaction for hydrolysis to form the polyaromatic ether with high end hydroxyl group content.
According to some embodiments of the invention, the polymerization reaction is carried out under anhydrous conditions.
According to some embodiments of the present invention, the polymerization reaction is carried out at 120-200 ℃.
According to some embodiments of the invention, no additional base is added to the hydrolysis.
According to some embodiments of the invention, the temperature of the hydrolysis is 60 to 100 ℃ and the time of the hydrolysis is 0.5 to 5 hours.
According to some embodiments of the invention, the molar ratio of the bisphenol monomer to the branching agent is 1 (0.005-0.15).
According to some embodiments of the invention, the molar ratio of said bisphenol monomer to said dihalogen monomer is from 1.2:0.8 to 0.8:1.2, preferably from 0.95:1.05 to 1.05: 0.95.
According to some embodiments of the invention, the dihalogen monomer is selected from one or more of the following:
According to some embodiments of the invention, the bisphenol monomer is selected from one or more of the following:
according to some embodiments of the invention, the branching agent is selected from one or more of 1,3, 5-phloroglucinol, tris (4-hydroxyphenyl) phosphine oxide, tris (4-fluorophenyl) phosphine oxide, tris (4-hydroxyphenyl) methyl methane, tris (4-hydroxyphenyl) phenyl methane, tetrakis (4-hydroxyphenyl) methane, decafluorobiphenyl, hexafluorobenzene, decafluorobenzophenone, decafluorodiphenylsulfone, 2,4, 6-trichloro-1, 3, 5-triazine, 2,4, 6-tris (4-fluorophenyl) -1,3, 5-triazine, 1,3, 5-tris (4-fluorobenzoyl) benzene, phosphonitrile trichloride, and melamine.
According to some embodiments of the invention, the base comprises potassium phosphate.
According to some embodiments of the invention, the solvent comprises at least one of N, N-dimethylformamide, N '-dimethylacetamide, N-methylpyrrolidone, N-ethylpyrrolidone, N-butylpyrrolidone, 1, 3-dimethyl-2-imidazolidinone, cyclobutylsulfone, and dimethylsulfoxide, preferably N, N' -dimethylacetamide.
The preparation method of the invention adopts a polymerization process without water and an organic solvent with low boiling point and water-miscible property, eliminates the water separation process link, avoids the use of expensive organic solvent with high boiling point, and reduces the production cost.
The third aspect of the present invention provides the use of the polyaryl ether of the first aspect or the polyaryl ether obtained by the production method of the second aspect in an epoxy resin modifier.
The invention designs and synthesizes the branched chain type hydroxyl-terminated polyaromatic ether for the first time, and ensures larger molecular weight on the basis of improving the content of the terminal hydroxyl. The preparation method of the invention adopts a polymerization process without water generation and an organic solvent with low boiling point and water miscibility, eliminates the water separation process link, avoids the use of expensive organic solvent with high boiling point, and reduces the production cost. After polymerization, water is directly added, alkali is not required to be additionally added, and the terminal halide is hydrolyzed at a proper temperature and converted into phenolic hydroxyl, so that the content of the terminal hydroxyl is further ensured.
Drawings
FIG. 1 is a schematic diagram of the synthetic route for polyaromatic ethers.
Detailed Description
The present invention will be further illustrated by the following specific examples, but the scope of the present invention is not limited thereto.
The synthetic route of the polyaromatic ether is shown in figure 1.
Examples of the dihalogen monomer, the bisphenol monomer, the base, the solvent and the branching agent which are suitable for the production process of the present invention are shown in tables 1 to 5, respectively.
TABLE 1
TABLE 2
TABLE 3
| (Code) | Structure of the product |
| KP | K3PO4 |
TABLE 4
TABLE 5
Examples 1 to 16
Under the protection of nitrogen, BPS, DCDPS, KP, THPMM and DMAc are added into a 500mL four-mouth reaction bottle. Heating to 167 ℃ under electric stirring, keeping for a certain time, and cooling to a certain hydrolysis temperature. Adding a certain amount of water, stirring for a certain time for hydrolysis, pouring the mixed solution into 1M hydrochloric acid aqueous solution, heating to 80 ℃, soaking for 4h, and washing for 4 times by using deionized water at 80 ℃. Then drying in a normal pressure oven at 120 ℃ for 4h and a vacuum oven at 120 ℃ overnight under the vacuum degree (less than-0.01 mPa) to finally obtain the fibrous polymer.
The prepared fibrous polymers were subjected to viscosity measurement, respectively. The viscosity measurement method comprises the following steps: the viscosity was 0.5-1.2dL/g as measured in NMP solution containing 0.05M lithium bromide at 25 ℃ using an Ubbelohde viscometer.
The specific reaction conditions and results of examples 1-16 are shown in Table 6 below.
TABLE 6
The preparation method of the polyaromatic ether with high terminal hydroxyl content is illustrated by taking branched chain type terminal hydroxyl polyether sulfone as an example, and can be popularized to the synthesis of other terminal hydroxyl polyaromatic ethers taking aromatic nucleophilic substitution polycondensation as a preparation process. The invention adopts a polymerization process without water generation and an organic solvent with low boiling point and water miscibility, eliminates a water diversion process link, avoids the use of a high boiling point and expensive organic solvent, and reduces the production cost. And water is directly added after polymerization, alkali is not required to be additionally added, and the end-group halide is hydrolyzed at a proper temperature and converted into phenolic hydroxyl, so that the content of the terminal hydroxyl is further ensured.
It should be noted that the above-mentioned embodiments are only for explaining the present invention, and do not constitute any limitation to the present invention. The present invention has been described with reference to exemplary embodiments, but the words which have been used herein are words of description and illustration, rather than words of limitation. Although the invention has been described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, but rather extends to all other methods and applications having the same functionality.
Claims (10)
1. A branched polyaromatic ether has three or more terminal hydroxyl groups and aromatic groups of trivalent or higher valence in the polymer molecular chain.
2. The polyaromatic ether of claim 1 wherein the trivalent or higher aromatic group is linked to at least one of the structures shown below:
wherein each A and B independently represents a divalent aromatic group, each D independently represents oxygen or sulfur, n is an integer greater than 1, preferably, n is an integer greater than 5,
preferably, each D independently represents oxygen.
3. A polyaromatic ether according to claim 1 or 2 characterised in that the trivalent or higher aromatic group is selected from one or more of the following structures:
4. a polyaromatic ether according to any one of claims 2 to 3 characterised in that group B is selected from one or more of the following structures:
5. a polyaromatic ether according to any of claims 2 to 4, characterised in that group A is selected from one or more of the following structures:
6. a preparation method of polyaromatic ether with high terminal hydroxyl content comprises the following steps:
(1) polymerizing a dihalogen monomer and a bisphenol monomer and a branching agent in the presence of a base and an organic solvent, wherein the branching agent is selected from a polyphenol monomer having three or more hydroxyl groups or mercapto groups, a polyhalogen monomer having three or more halogen groups, or a polyamino monomer having three or more amino groups;
(2) adding water into the system after the polymerization reaction for hydrolysis to form the polyaromatic ether with high terminal hydroxyl content.
7. The production method according to claim 6,
the polymerization reaction is carried out under anhydrous conditions;
the polymerization reaction is carried out at 120-200 ℃;
no additional alkali is added in the hydrolysis;
the hydrolysis temperature is 60-100 ℃, and the hydrolysis time is 0.5-5 h.
8. The method according to claim 6 or 7, wherein the molar ratio of the bisphenol monomer to the branching agent is 1 (0.005-0.15); and/or
The molar ratio of the bisphenol monomer to the dihalogen monomer is 1.2:0.8-0.8:1.2, preferably 0.95:1.05-1.05: 0.95;
the dihalo monomer is selected from one or more of the following substances:
the bisphenol monomer is selected from one or more of the following substances:
the branching agent is selected from one or more of 1,3, 5-phloroglucinol, tris (4-hydroxyphenyl) phosphine oxide, tris (4-fluorophenyl) phosphine oxide, tris (4-hydroxyphenyl) methyl methane, tris (4-hydroxyphenyl) phenyl methane, tetrakis (4-hydroxyphenyl) methane, decafluorobiphenyl, hexafluorobenzene, decafluorobenzophenone, decafluorodiphenylsulfone, 2,4, 6-trichloro-1, 3, 5-triazine, 2,4, 6-tris (4-fluorophenyl) -1,3, 5-triazine, 1,3, 5-tris (4-fluorobenzoyl) benzene, phosphonitrile trichloride and melamine.
9. The production method according to any one of claims 6 to 8, wherein the polymerization reaction is carried out in the presence of a base and a solvent, the base comprising potassium phosphate,
the solvent comprises at least one of N, N-dimethylformamide, N '-dimethylacetamide, N-methylpyrrolidone, N-ethylpyrrolidone, N-butylpyrrolidone, 1, 3-dimethyl-2-imidazolidinone, sulfolane and dimethyl sulfoxide, and is preferably N, N' -dimethylacetamide.
10. Use of the polyaromatic ether according to any one of claims 1 to 5 or obtained by the process according to any one of claims 6 to 9 in a modifier for epoxy resins.
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| US20100197859A1 (en) * | 2007-09-06 | 2010-08-05 | Basf Se | Blends from branched polyaryl ethers and hydrophilic polymers |
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| CN102264798A (en) * | 2008-10-23 | 2011-11-30 | 巴斯夫欧洲公司 | Branched polyarylene ethers and thermoplastic molding compounds containing said ethers |
| CN101544759A (en) * | 2009-04-29 | 2009-09-30 | 天津师范大学 | Method for preparing irregular sulfonated poly aromatic (sulfur) ether with high efficiency |
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