CN113637167B - Branched polyaromatic ether and preparation method thereof - Google Patents
Branched polyaromatic ether and preparation method thereof Download PDFInfo
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- CN113637167B CN113637167B CN202110790923.1A CN202110790923A CN113637167B CN 113637167 B CN113637167 B CN 113637167B CN 202110790923 A CN202110790923 A CN 202110790923A CN 113637167 B CN113637167 B CN 113637167B
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- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 13
- 239000000178 monomer Substances 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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 13
- 238000006116 polymerization reaction Methods 0.000 claims description 12
- 229930185605 Bisphenol Natural products 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 9
- 239000003960 organic solvent Substances 0.000 claims description 9
- 239000006085 branching agent Substances 0.000 claims description 8
- 230000007062 hydrolysis Effects 0.000 claims description 8
- 238000006460 hydrolysis reaction Methods 0.000 claims description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- 239000002585 base Substances 0.000 claims description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 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
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims description 4
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 3
- 239000000126 substance 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 group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical group [Cl] ZAMOUSCENKQFHK-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
- 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 Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052794 bromium Chemical group 0.000 claims description 2
- 239000000460 chlorine Chemical group 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 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
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 239000011737 fluorine Substances 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
- 239000003607 modifier Substances 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
- 229910000160 potassium phosphate Inorganic materials 0.000 claims description 2
- 235000011009 potassium phosphates Nutrition 0.000 claims description 2
- 150000003457 sulfones Chemical class 0.000 claims description 2
- 125000001153 fluoro group Chemical group F* 0.000 claims 1
- 125000003118 aryl group Chemical group 0.000 abstract description 10
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- 229920000642 polymer Polymers 0.000 abstract description 8
- 238000009835 boiling Methods 0.000 description 8
- 239000004695 Polyether sulfone Substances 0.000 description 7
- 229920006393 polyether sulfone Polymers 0.000 description 7
- 239000002904 solvent Substances 0.000 description 5
- 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
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 235000013824 polyphenols Nutrition 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
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 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
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 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
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 150000002367 halogens Chemical group 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 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
- 239000003973 paint Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- -1 poly (arylene ether Chemical compound 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 150000008442 polyphenolic compounds Chemical class 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- 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
Landscapes
- 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 trivalent or higher-valence aromatic groups. The polyaromatic ether provided by the invention ensures larger molecular weight on the basis of improving the content of hydroxyl end groups, and the preparation method simplifies the production link and reduces the production cost.
Description
Technical Field
The invention relates to the field of synthesis of polyaromatic ether, 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 polyaromatic ether adopts bisphenol A, bisphenol S and bisphenol as monomers to realize batch production of polysulfone, polyethersulfone and polyphenylsulfone, wherein the polyethersulfone containing terminal hydroxyl groups is widely applied in the fields of paint, coating, adhesive and epoxy impact modifier.
The polyether sulfone is prepared by aromatic nucleophilic substitution polycondensation reaction of 4, 4-dichloro diphenyl sulfone and bisphenol S, and two process links of water diversion and temperature rising polymerization are needed. Due to the low reactivity of bisphenol S, high temperature polymerization in high boiling solvents (sulfolane, diphenyl sulfone, etc.) is often required to obtain polymers with higher molecular weights. The solvents are expensive, the post-treatment is complex (sulfolane boiling point 285 ℃, high energy consumption for rectification, insoluble diphenyl sulfone in water, and the like, and the solvents such as acetone, ethanol and the like are required to be extracted and recovered), and the capability of dissolving the polymer is limited, so that the production efficiency is lower and the cost is higher.
The commercial hydroxyl-terminated polyethersulfone is linear, namely, each polymer molecular chain has two hydroxyl-terminated groups at most, and when the epoxy impact modifier is applied, the polyethersulfone needs 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 hydroxyl end content and the preparation method thereof.
In a first aspect, the present invention provides a branched polyaromatic ether having a polymer molecular chain with three or more terminal hydroxyl groups and an aromatic group in a trivalent or higher valence state.
In the invention, the molecular chain of the polymer contains a plurality of hydroxyl-terminated groups, and on the basis of improving the content of the hydroxyl-terminated groups, the molecular weight is ensured to be larger, 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, an aromatic group of trivalent or higher valence links a terminal 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 valent aromatic group is attached to at least one of the structures 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 valent aromatic group is selected from one or more of the following structures:
wherein R is an alkyl or aryl group, such as methyl, ethyl or phenyl,
according to some embodiments of the invention, group B is selected from one or more of the following structures:
according to some embodiments of the invention, group a is selected from one or more of the following structures:
according to some embodiments of the invention, the polyaromatic ether has a viscosity of greater than 0.3dL/g measured in an NMP (N-methylpyrrolidone) solution containing 0.05M lithium bromide at 25℃using an Ubbelohde viscometer. In some embodiments, the viscosity of the polyaromatic ether is from 0.5 to 2.0dL/g. In some embodiments, the polyaromatic ether has a viscosity of 0.5 to 1.8dL/g.
In a second aspect, the present invention provides a process for preparing a high hydroxyl end poly (arylene ether), comprising 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) And adding water into the system after the polymerization reaction to hydrolyze to form the polyaromatic ether with high hydroxyl end content.
According to some embodiments of the invention, the polymerization is carried out under anhydrous conditions.
According to some embodiments of the invention, the polymerization 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 60-100 ℃ and the time of the hydrolysis is 0.5-5h.
According to some embodiments of the invention, the molar ratio of bisphenol monomer to branching agent is 1 (0.005-0.15).
According to some embodiments of the invention, the molar ratio of bisphenol monomer to dihalogen monomer is 1.2:0.8-0.8:1.2, preferably 0.95:1.05-1.05:0.95.
According to some embodiments of the invention, the dihalogen monomer is selected from one or more of the following:
wherein X is halogen or hydroxy, preferably fluorine, chlorine or bromine.
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, decafluorodiphenyl sulfone, 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, sulfolane, dimethylsulfoxide, preferably N, N' -dimethylacetamide.
The preparation method adopts a polymerization process without water generation and a low-boiling point water-miscible organic solvent, eliminates the water diversion process link, avoids the use of a high-boiling point expensive organic solvent, and reduces the production cost.
In a third aspect, the present invention provides the use of a polyaromatic ether according to the first aspect or a polyaromatic ether obtained by a process according to the second aspect in an epoxy resin modifier.
The invention synthesizes the branched hydroxyl-terminated polyaromatic ether for the first time, and ensures larger molecular weight on the basis of improving the content of hydroxyl-terminated groups. The preparation method adopts a polymerization process without water generation and a low-boiling point water-miscible organic solvent, eliminates a water diversion process link, avoids the use of a high-boiling point expensive organic solvent, and reduces the production cost. After polymerization, water is directly added, no extra alkali is needed, and the end halide is hydrolyzed at a proper temperature to be converted into phenolic hydroxyl, so that the content of the end hydroxyl is further ensured.
Drawings
FIG. 1 is a schematic diagram of the synthetic route to a polyaromatic ether.
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 dihalogen monomers, bisphenol monomers, bases, solvents and branching agents suitable for use in the preparation process of the present invention are shown in tables 1-5, respectively.
TABLE 1
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TABLE 2
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TABLE 3 Table 3
| (Code) | Structure of the |
| KP | K 3 PO 4 |
TABLE 4 Table 4
TABLE 5
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Examples 1 to 16
Under nitrogen, BPS, DCDPS, KP, THPMM and DMAc were added to a 500mL four-port reaction flask. Heating to 167 ℃ under electric stirring, maintaining for a certain time, and then cooling to a certain hydrolysis temperature. Adding a certain amount of water, stirring for hydrolysis for a certain time, pouring the mixed solution into a 1M hydrochloric acid aqueous solution, heating to 80 ℃ for soaking for 4 hours, and washing with deionized water at 80 ℃ for 4 times. Then placing the mixture into an atmospheric pressure oven for drying at 120 ℃ for 4 hours, and drying the mixture overnight in a vacuum oven at 120 ℃ to obtain the fibrous polymer at the vacuum degree (less than-0.01 mPa).
The viscosity of the prepared fibrous polymer was measured separately. The viscosity measurement method comprises the following steps: the viscosity was measured in NMP solution containing 0.05M lithium bromide using an Ubbelohde viscometer at 25℃and was 0.5-1.2dL/g.
The specific reaction conditions and results for examples 1-16 are shown in Table 6 below.
TABLE 6
The invention relates to a preparation method of a polyaromatic ether with high hydroxyl-terminated content, which is illustrated by taking branched hydroxyl-terminated polyethersulfone as an example, and can be popularized to the synthesis of other hydroxyl-terminated polyaromatic ethers with aromatic nucleophilic substitution polycondensation reaction as a preparation process. The invention adopts a polymerization process without water generation and a low-boiling point water-miscible organic solvent, eliminates the water diversion process link, avoids the use of a high-boiling point expensive organic solvent and reduces the production cost. And water is directly added after polymerization, no extra alkali is needed, and the end halide is hydrolyzed at a proper temperature to be converted into phenolic hydroxyl, so that the content of the end hydroxyl is further ensured.
It should be noted that the above-described embodiments are only for explaining the present invention and do not constitute any limitation of the present invention. The invention has been described with reference to exemplary embodiments, but it is understood that the words which have been used are words of description and illustration, rather than words of limitation. Although the invention is described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, as the invention extends to all other means and applications which perform the same function.
Claims (5)
1. A method for preparing branched polyaromatic ether, comprising the following steps:
(1) Polymerizing a dihalogen monomer and a bisphenol monomer with a branching agent in the presence of a base and an organic solvent, and the polymerization is carried out under anhydrous conditions at 120-200 ℃;
(2) Adding water into the system after the polymerization reaction to hydrolyze to form the polyaromatic ether with high-end hydroxyl content, wherein the hydrolysis temperature is 60-100 ℃, the hydrolysis time is 0.5-5h, and no alkali is added in the hydrolysis;
wherein the dihalogen monomer is selected from one or more of the following substances:
wherein X is fluorine, chlorine or bromine;
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, decafluorodiphenyl sulfone, 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.
2. The method according to claim 1, wherein the molar ratio of bisphenol monomer to 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.
3. The method of claim 2, wherein the molar ratio of bisphenol monomer to dihalogen monomer is from 0.95:1.05 to 1.05:0.95.
4. The method of claim 1, wherein the base comprises potassium phosphate,
the organic 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.
5. The use of the polyaromatic ether prepared by the preparation method according to any one of claims 1-4 in an epoxy resin modifier.
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