CN117624586A - Polyphenyl ether resin and preparation method thereof - Google Patents
Polyphenyl ether resin and preparation method thereof Download PDFInfo
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- CN117624586A CN117624586A CN202311488436.5A CN202311488436A CN117624586A CN 117624586 A CN117624586 A CN 117624586A CN 202311488436 A CN202311488436 A CN 202311488436A CN 117624586 A CN117624586 A CN 117624586A
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- polyphenyl ether
- ether resin
- liquid
- acrylic acid
- chelating agent
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- 229920013636 polyphenyl ether polymer Polymers 0.000 title claims abstract description 35
- 239000011347 resin Substances 0.000 title claims abstract description 30
- 229920005989 resin Polymers 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title abstract description 19
- 239000002738 chelating agent Substances 0.000 claims abstract description 21
- 229910052751 metal Inorganic materials 0.000 claims abstract description 21
- 239000002184 metal Substances 0.000 claims abstract description 21
- 239000007788 liquid Substances 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 18
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000001301 oxygen Substances 0.000 claims abstract description 16
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 16
- 238000000926 separation method Methods 0.000 claims abstract description 16
- JSYPRLVDJYQMAI-ODZAUARKSA-N (z)-but-2-enedioic acid;prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)\C=C/C(O)=O JSYPRLVDJYQMAI-ODZAUARKSA-N 0.000 claims abstract description 15
- 229920002126 Acrylic acid copolymer Polymers 0.000 claims abstract description 15
- 239000002904 solvent Substances 0.000 claims abstract description 11
- 239000007789 gas Substances 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 9
- 239000011259 mixed solution Substances 0.000 claims abstract description 9
- 239000000178 monomer Substances 0.000 claims abstract description 9
- 239000003054 catalyst Substances 0.000 claims abstract description 8
- 230000009920 chelation Effects 0.000 claims abstract description 7
- 238000005691 oxidative coupling reaction Methods 0.000 claims abstract description 7
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229920002125 Sokalan® Polymers 0.000 claims abstract description 3
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 claims abstract description 3
- 239000004584 polyacrylic acid Substances 0.000 claims abstract description 3
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 claims abstract description 3
- 159000000000 sodium salts Chemical class 0.000 claims abstract description 3
- 229920001955 polyphenylene ether Polymers 0.000 claims description 38
- 239000010949 copper Substances 0.000 claims description 33
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 30
- 229910052802 copper Inorganic materials 0.000 claims description 30
- -1 amine compound Chemical class 0.000 claims description 20
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 10
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 10
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 10
- 239000011976 maleic acid Substances 0.000 claims description 10
- 150000003839 salts Chemical class 0.000 claims description 10
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- 230000000536 complexating effect Effects 0.000 claims description 2
- 239000008139 complexing agent Substances 0.000 claims description 2
- 239000000047 product Substances 0.000 description 16
- 239000007864 aqueous solution Substances 0.000 description 11
- 238000001479 atomic absorption spectroscopy Methods 0.000 description 10
- 239000012071 phase Substances 0.000 description 10
- 230000008707 rearrangement Effects 0.000 description 10
- 239000000243 solution Substances 0.000 description 9
- 125000000217 alkyl group Chemical group 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 7
- NXXYKOUNUYWIHA-UHFFFAOYSA-N 2,6-Dimethylphenol Chemical compound CC1=CC=CC(C)=C1O NXXYKOUNUYWIHA-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 229910021645 metal ion Inorganic materials 0.000 description 6
- 239000012535 impurity Substances 0.000 description 5
- 230000003068 static effect Effects 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 3
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 238000004891 communication Methods 0.000 description 3
- 229910001431 copper ion Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- QQOMQLYQAXGHSU-UHFFFAOYSA-N 2,3,6-Trimethylphenol Chemical compound CC1=CC=C(C)C(O)=C1C QQOMQLYQAXGHSU-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- MIHINWMALJZIBX-UHFFFAOYSA-N cyclohexa-2,4-dien-1-ol Chemical compound OC1CC=CC=C1 MIHINWMALJZIBX-UHFFFAOYSA-N 0.000 description 2
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- KGHYGBGIWLNFAV-UHFFFAOYSA-N n,n'-ditert-butylethane-1,2-diamine Chemical compound CC(C)(C)NCCNC(C)(C)C KGHYGBGIWLNFAV-UHFFFAOYSA-N 0.000 description 2
- DPBLXKKOBLCELK-UHFFFAOYSA-N pentan-1-amine Chemical compound CCCCCN DPBLXKKOBLCELK-UHFFFAOYSA-N 0.000 description 2
- 229920006380 polyphenylene oxide Polymers 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 description 1
- BMVXCPBXGZKUPN-UHFFFAOYSA-N 1-hexanamine Chemical compound CCCCCCN BMVXCPBXGZKUPN-UHFFFAOYSA-N 0.000 description 1
- ARSRBNBHOADGJU-UHFFFAOYSA-N 7,12-dimethyltetraphene Chemical compound C1=CC2=CC=CC=C2C2=C1C(C)=C(C=CC=C1)C1=C2C ARSRBNBHOADGJU-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- VFZRZRDOXPRTSC-UHFFFAOYSA-N DMBA Natural products COC1=CC(OC)=CC(C=O)=C1 VFZRZRDOXPRTSC-UHFFFAOYSA-N 0.000 description 1
- QZKRHPLGUJDVAR-UHFFFAOYSA-K EDTA trisodium salt Chemical compound [Na+].[Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O QZKRHPLGUJDVAR-UHFFFAOYSA-K 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 1
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 1
- 229940112669 cuprous oxide Drugs 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 125000001188 haloalkyl group Chemical group 0.000 description 1
- 125000001475 halogen functional group Chemical group 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 229910000042 hydrogen bromide Inorganic materials 0.000 description 1
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- IDFANOPDMXWIOP-UHFFFAOYSA-N n,n-dimethylpentan-1-amine Chemical compound CCCCCN(C)C IDFANOPDMXWIOP-UHFFFAOYSA-N 0.000 description 1
- AMJIVVJFADZSNZ-UHFFFAOYSA-N n-butylpentan-1-amine Chemical compound CCCCCNCCCC AMJIVVJFADZSNZ-UHFFFAOYSA-N 0.000 description 1
- PXSXRABJBXYMFT-UHFFFAOYSA-N n-hexylhexan-1-amine Chemical compound CCCCCCNCCCCCC PXSXRABJBXYMFT-UHFFFAOYSA-N 0.000 description 1
- CATWEXRJGNBIJD-UHFFFAOYSA-N n-tert-butyl-2-methylpropan-2-amine Chemical compound CC(C)(C)NC(C)(C)C CATWEXRJGNBIJD-UHFFFAOYSA-N 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- BHRZNVHARXXAHW-UHFFFAOYSA-N sec-butylamine Chemical compound CCC(C)N BHRZNVHARXXAHW-UHFFFAOYSA-N 0.000 description 1
- 230000008054 signal transmission Effects 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- YBRBMKDOPFTVDT-UHFFFAOYSA-N tert-butylamine Chemical compound CC(C)(C)N YBRBMKDOPFTVDT-UHFFFAOYSA-N 0.000 description 1
- 125000005207 tetraalkylammonium group Chemical group 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene 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
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
- C08G65/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols
- C08G65/44—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols by oxidation of phenols
-
- 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
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
- C08G65/48—Polymers modified by chemical after-treatment
- C08G65/485—Polyphenylene oxides
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Polyethers (AREA)
Abstract
The invention provides a polyphenyl ether resin and a preparation method thereof. The method comprises the following steps: in the presence of a solvent and a coordination metal catalyst, enabling oxygen-containing gas and phenolic monomers to undergo oxidative coupling reaction to form a polyphenyl ether mixed solution; adding a chelating agent into the polyphenyl ether mixed solution to carry out chelation reaction to obtain a mixed product; separating the water phase in the mixed product through liquid-liquid separation to obtain polyphenyl ether resin; wherein the chelating agent comprises one or more of polyacrylic acid, sodium polyacrylate, maleic acid-acrylic acid copolymer, and sodium salt of maleic acid-acrylic acid copolymer. The polyphenyl ether resin prepared by the method has low metal residual quantity and good electrical property.
Description
Technical Field
The invention belongs to the technical field of polyphenyl ether resin, and particularly relates to polyphenyl ether resin and a preparation method thereof.
Background
Polyphenylene ether, also known as polyphenylene oxide or polyphenylene ether, is a versatile engineering plastic. Polyphenylene ethers are resinous polymers polymerized from disubstituted phenols by oxidative coupling reactions in the presence of metal salts/amines under the action of oxygen. The polyphenyl ether has excellent water resistance and steam resistance, and the product has higher tensile strength, impact strength and creep resistance. In addition, the polyphenyl ether molecular chain has high symmetry, small polarity, excellent dimensional stability, low dielectric constant, stability and small dielectric loss. Therefore, polyphenylene ether is widely used in the fields of electric, automobile, cable, photovoltaic power generation and the like. Particularly, with the development of 5G communication technology in recent years, polyphenylene oxide has low dielectric constant and low dielectric loss, is favorable for the functional characteristics of small loss, high fidelity and the like in the electromagnetic signal transmission process, and is widely developed and applied to the communication fields of 5G radomes, signal transmitting base stations, electronic circuit boards and the like.
In the process of manufacturing the polyphenyl ether, as the catalyst is metal salt/amine, catalyst impurities such as bromine, copper and the like can remain in the resin, and the impurities destroy the electrical property of the polyphenyl ether, are resistant to solvents and weather, reduce the content of the catalyst impurities remained in the polyphenyl ether, and are beneficial to improving the performance of polyphenyl ether products.
CN104136490B discloses a method for purifying polyphenylene ether, which uses a polyphenylene ether solution as a first phase liquid and uses an alcohol-water mixed solvent as a second phase liquid, wherein the volume ratio of the first phase liquid to the second phase liquid is 1.5: 1-10:1, wherein the polyphenyl ether solvent in the mixed system is 60-95 wt%; alcohol content of 4-32 wt%; mixing water 1-36 wt%, adding metal ion chelating agent, stirring and oscillating, and final standing to separate to eliminate residual amine, residual metal ion and other impurity from the polyphenyl ether solution. The layering separation mode is low in efficiency, needs to be washed and separated for a plurality of times, and certain water remains in the solution after separation, so that the metal ion content in the final product is high.
With the development of the high-frequency, high-speed 5G communication field, the development of high-purity polyphenylene ether, particularly polyphenylene ether products in which the metal ion content is controlled to be 1ppm or less, has been a problem faced by those skilled in the art.
Disclosure of Invention
In order to solve the technical problems, the invention aims to provide a polyphenyl ether resin and a preparation method thereof. The polyphenyl ether resin prepared by the method has low copper content and good electrical property.
In order to achieve the above object, the present invention provides a method for producing a polyphenylene ether resin, comprising:
in the presence of a solvent and a coordination metal catalyst, enabling oxygen-containing gas and phenolic monomers to undergo oxidative coupling reaction to form a polyphenyl ether mixed solution;
adding a chelating agent into the polyphenyl ether mixed solution to carry out chelation reaction to obtain a mixed product;
separating the water phase in the mixed product through liquid-liquid separation to obtain the polyphenyl ether resin;
wherein the chelating agent comprises one or more than two of polyacrylic acid, sodium polyacrylate, maleic acid-acrylic acid copolymer and maleic acid-acrylic acid copolymer sodium salt.
The chelating agent selected by the invention has low cost, wide sources and convenient addition. The chelating agent is suitable for a polyphenyl ether solution system, the chelating agent with high molecular weight is adopted to remove metal ions, the metal ions are stronger and more stable, special conditions are not needed for the use of the chelating agent, the chelating agent can be conveniently used in an industrial device, copper ions can be reduced to below 0.1ppm, and the requirement of high-purity polyphenyl ether is met.
After liquid-liquid separation, the aqueous phase obtained contains a solution of a metal chelate compound, and the oil phase obtained contains polyphenylene ether. After separation of the aqueous and oil phases, the process of the invention further comprises a step of purification of the product.
In some embodiments of the invention, the purification process comprises adding the oil phase to a poor solvent for the polyphenylene ether, precipitating, then filtering, and drying to obtain the polyphenylene ether product. The product obtained by the preparation method of the invention is easy to purify and separate, and the specific process of purification can be easily implemented by a person skilled in the art.
In a specific preparation process, reference may be made to CN219463392U for parameters such as setting of the reaction apparatus, conditions of the oxidative coupling reaction, conditions of the chelation reaction, or other methods which are easy to implement for the skilled person. The preparation method does not need to adjust devices in the prior art, and is beneficial to industrialization.
In a specific embodiment of the invention, the oxidative coupling reaction is carried out by externally provided polymerizers with static mixer circulation lines.
In some embodiments of the invention, the phenolic monomer comprises a monohydric phenol and/or a dihydric phenol. Wherein the monophenol (i.e., monophenol monomer) has the following structural formula:
wherein P is 1 、P 2 Each independently selected from H, alkyl, halo, haloalkyl or alkoxy;
preferably, P 1 Selected from H and methyl;
preferably, P 2 Selected from alkyl, phenyl, and especially C1-C4 alkyl.
In some preferred embodiments of the present invention, the monohydric phenol comprises a mixture of 2, 6-Dimethylphenol (DMP) and 2,3, 6-Trimethylphenol (TMP).
In some preferred embodiments of the present invention, any ratio of DMP to TMP by mass from 99:1 to 1:99 is used. Within this range, a DMP to TMP weight ratio of at least about 1:1, more preferably at least about 3:1, and even more preferably at least about 4:1 can be preferably used. Also within this range, it may be preferable to use up to about 20:1, more preferably up to about 10:1, and even more preferably up to about 6:1.
in some preferred embodiments of the present invention, the solvent used for the oxidative coupling reaction comprises one or a combination of two or more of aliphatic alcohols, ketones, aliphatic hydrocarbons, aromatic hydrocarbons, chlorinated hydrocarbons, nitrohydrocarbons, ethers, esters, amides, mixed ether-esters, sulfones. The choice of solvents is not limited thereto, provided that they do not interfere with or enter into the oxidation reaction. In a preferred embodiment, the solvent comprises a C6-C18 aromatic hydrocarbon including toluene, xylene, and mixtures thereof. Most preferably, the solvent is toluene.
In some preferred embodiments of the present invention, the coordination metal catalyst is a complexing agent formed by complexing a metal salt and an amine compound, wherein the metal in the metal salt is selected from one or more of group VIB, group VIIB, and group IB. Wherein the metal preferably comprises one or a combination of more than two of chromium, manganese, cobalt and copper. Most preferably, the metal salt contains copper ions (Cu + And Cu 2+ )。
In some preferred embodiments of the present invention, the amine compound includes one or a combination of two or more of a primary amine compound, a secondary amine compound, a tertiary amine compound, and a diamine compound.
In some preferred embodiments of the present invention, the primary amine compound comprises n-propylamine, isopropylamine, n-butylamine, sec-butylamine, tert-butylamine, n-pentylamine, n-hexylamine, cyclohexylamine.
In some preferred embodiments of the present invention, the secondary amine compound comprises di-n-propylamine, di-n-butylamine, di-t-butylamine, n-butyl-n-pentylamine, di-n-hexylamine.
In some preferred embodiments of the present invention, the tertiary amine compound comprises triethylamine, tri-n-propylamine, tri-n-butylamine, dimethyl-n-pentylamine.
The structural formula of the diamine compound is as follows:
wherein R is 1 、R 2 、R 4 、R 5 Each independently selected from a hydrogen atom or an alkyl group, wherein the alkyl group is selected from a linear alkyl group or a branched alkyl group; r is R 3 Saturated alkyl groups having 2 or more carbon atoms.
Preferably, the amine compound includes N, N '-tetramethyl-1, 3-diaminopropane and N, N' -di-tert-butylethylenediamine.
In some preferred embodiments of the invention, the mass ratio of the chelating agent to the metal salt is (0.1-10): 1. The ratio of the two is optimized according to the conditions, so that the effect of purifying and removing metal copper ions can be remarkably improved.
Further, the mass ratio of the chelating agent to the metal salt is (1-3): 1.
In some preferred embodiments of the invention, the chelating agent has a molecular weight of 1000-10000g/mol. Preferably, the chelating agent has a molecular weight of 1000-8000g/mol. Further preferably, the molecular weight is 2000-6000g/mol.
In some preferred embodiments of the invention, the chelating agent is present in the solvent in a mass fraction of 15 to 30wt%.
In some preferred embodiments of the present invention, the ratio of maleic acid structural units to acrylic acid structural units in the maleic acid-acrylic acid copolymer is 1:1 to 10. More preferably, the ratio of maleic acid building blocks to acrylic acid building blocks is from 1:1 to 5.
In some preferred embodiments of the invention, the chelation reaction is carried out at a temperature of 50 to 80℃for a period of 1 to 2 hours.
In some preferred embodiments of the invention, the liquid-liquid separation comprises:
adding the mixed product into a centrifuge at a speed of 1-4L/min for the liquid-liquid separation;
preferably, the liquid-liquid separation process does not require a heating or cooling treatment.
In some preferred embodiments of the invention, the rotational speed of the centrifuge is 10000-20000r/min.
In some preferred embodiments of the invention, the oxygen-containing gas has an oxygen content of not less than 20vol%. In some embodiments, the oxygen-containing gas may be oxygen, air, or the like. Preferably, oxygen is used.
According to another aspect of the present invention, there is also provided a polyphenylene ether resin prepared according to the above method, having a copper content of less than 0.1ppm, which has a low copper content and thus has good electrical properties.
Compared with the prior art, the invention has the following advantages:
1. the chelating agent has wide market sources and convenient addition, and the chelating agent with high molecular weight has good and stable and firm chelating effect, and the cost for preparing the high-purity polyphenyl ether resin is reduced by only adopting single chelating treatment;
2. the chelating treatment condition is mild and simple, the condition of the existing device is not required to be changed, equipment and cold and heat sources are not required to be added, and the centrifugal separation is also not required to be carried out with additional heat sources;
3. the polyphenyl ether resin product prepared by the invention has low copper content and good electrical property.
Detailed Description
The technical solution of the present invention will be described in detail below for a clearer understanding of technical features, objects and advantageous effects of the present invention, but should not be construed as limiting the scope of the present invention.
Example 1
The preparation method of the polyphenyl ether resin with ultralow copper content in the embodiment specifically comprises the following steps:
in this example, a circulation line was provided outside a 30L cylindrical polymerizer, and a static mixer was provided in the middle of the external circulation line to dissolve cuprous oxide (Cu) dissolved in hydrogen bromide (42 g in 48wt% aqueous solution) 2 O, 2.7 g) was mixed with N, N' -di-tert-butylethylenediamine (12.0 g, DBEDA), di-N-butylamine (160 g, DBA), N-dimethylbutylamine (255 g, DMBA), tetraalkylammonium chloride surfactant (2.5 g), 2, 6-dimethylphenol (540 g) and toluene solvent (14 kg).
During the polymerization, additional 2, 6-dimethylphenol (3.75 kg) was added. In the polymerization process, setting the flow rate of nitrogen to 6.1L/min for nitrogen sealing in a gas phase above the liquid level of the polymerization liquid in a polymerization kettle; in the gas introduction part of the static mixer, the oxygen flow rate was set to 1.07NL/min kg-monomer; here, the oxygen flow rate is a gas flow rate with respect to the monomer based on oxygen, and for example, when the oxygen flow rate is 4.6NL/min with respect to 4.29kg of the monomer, the flow rate of the oxygen-containing gas is 1.07NL/min kg-monomer.
The temperature was set to slowly rise from 25.0 ℃ to 40.0 ℃. The linear velocity of the solution passing through the static mixer was set to 3m/s, and the internal pressure downstream of the static mixer was 0.13MPa. After the polymerization reaction for 120 minutes was completed, the on-line sampling and the detection were carried out until the reduced viscosity of the polymerization product reached 0.75dl/g, and the polymerization was stopped, at which time the reaction system was a polyphenylene ether mixed solution. Transferring the polyphenyl ether mixed solution into a rearrangement kettle, adding 48g of a maleic acid-acrylic acid copolymer aqueous solution with the concentration of 20wt% (the molecular weight is 4000g/mol, the ratio of the maleic acid structural unit to the acrylic acid structural unit is 1:3), uniformly stirring, and heating to 70 ℃ for 120min.
Then, continuously adding the reaction mixed solution into a high-speed tubular liquid-liquid centrifuge at a speed of 2L/min, wherein the rotating speed is 16000r/min, and no additional heating or cooling is needed in the separation process; adding the obtained oil phase into methanol, separating out to obtain solid-liquid slurry, and then filtering and drying to obtain the polyphenyl ether product.
The content of metallic copper impurities in the polyphenylene ether product was measured by atomic absorption spectrometry, and the copper content in the polyphenylene ether product was 0.02ppm.
Example 2
The preparation method of the ultralow copper content polyphenylene ether resin of this example was substantially the same as that of example 1, except that 32g of an aqueous solution of a maleic acid-acrylic acid copolymer (molecular weight 4000g/mol, ratio of maleic acid structural unit to acrylic acid structural unit 1:5) having a concentration of 20wt% was added to the rearrangement vessel.
The copper content of the polyphenylene ether was 0.05ppm by atomic absorption spectrometry.
Example 3
The preparation method of the ultralow copper content polyphenylene ether resin of this example was substantially the same as that of example 1, except that 36g of an aqueous solution of a maleic acid-acrylic acid copolymer (molecular weight 4000g/mol, ratio of maleic acid structural unit to acrylic acid structural unit 1:1) having a concentration of 20wt% was added to the rearrangement vessel.
The copper content of the polyphenylene ether was 0.02ppm by atomic absorption spectrometry.
Example 4
The preparation method of the ultralow copper content polyphenylene ether resin of this example was substantially the same as that of example 1, except that 36g of an aqueous solution of a maleic acid-acrylic acid copolymer (molecular weight 4000g/mol, ratio of maleic acid structural unit to acrylic acid structural unit 1:3) having a concentration of 30% by weight was added to the rearrangement vessel.
The copper content of the polyphenylene ether was 0.03ppm by atomic absorption spectrometry.
Example 5
The preparation method of the ultralow copper content polyphenylene ether resin of this example was substantially the same as that of example 1, except that 72g of an aqueous solution of a maleic acid-acrylic acid copolymer (molecular weight 4000g/mol, ratio of maleic acid structural unit to acrylic acid structural unit 1:2) having a concentration of 15wt% was added to the rearrangement vessel.
The copper content of the polyphenylene ether was 0.02ppm by atomic absorption spectrometry.
Example 6
The preparation method of the ultralow copper content polyphenylene ether resin of this example was substantially the same as that of example 1, except that 24g of an aqueous solution of a maleic acid-acrylic acid copolymer (molecular weight: 2000g/mol, ratio of maleic acid structural unit to acrylic acid structural unit: 1:3) having a concentration of 20wt% was added to the rearrangement vessel.
The copper content of the polyphenylene ether was measured by atomic absorption spectrometry to be 0.07ppm.
Example 7
The preparation method of the ultralow copper content polyphenylene ether resin of this example was substantially the same as that of example 1, except that 24g of an aqueous solution of a maleic acid-acrylic acid copolymer (molecular weight: 6000g/mol, ratio of maleic acid structural unit to acrylic acid structural unit: 1:3) having a concentration of 20wt% was added to the rearrangement vessel.
The copper content of the polyphenylene ether was 0.06ppm by atomic absorption spectrometry.
Comparative example 1
The preparation method of the ultralow copper content polyphenylene ether resin of this comparative example was substantially the same as in example 1, except that 48g of an aqueous solution of EDTA-2Na having a concentration of 20% by weight was added to the rearrangement vessel.
The copper content of the polyphenylene ether was 3.43ppm by atomic absorption spectrometry.
Comparative example 2
The preparation method of the ultralow copper content polyphenylene ether resin of this comparative example was substantially the same as in example 1, except that 32g of an aqueous EDTA-3Na solution having a concentration of 20% by weight was added to the rearrangement vessel.
The copper content of the polyphenylene ether was 4.02ppm by atomic absorption spectrometry.
Comparative example 3
The preparation method of the ultralow copper content polyphenylene ether resin of this comparative example was substantially the same as that of example 1, except that 32g of EDTA-2Na aqueous solution having a concentration of 20wt% was added to the rearrangement vessel for the first chelation, and after centrifugal separation, 32g of EDTA-2Na aqueous solution having a concentration of 20wt% was further added to the vessel for the second chelation.
The copper content of the polyphenylene ether was 1.22ppm by atomic absorption spectrometry.
The polyphenylene ether obtained in the examples and comparative examples each had a number average molecular weight of about 20500g/mol and an intrinsic viscosity of about 0.45dl/g in a chloroform solution at 25 ℃. According to the preparation method of the polyphenyl ether resin, disclosed by the invention, the treatment method is simple, the molecular weight and the intrinsic viscosity of the polyphenyl ether are not influenced by the additive, the copper content in the product can be reduced to 0.1ppm, and the minimum copper content reaches 0.01ppm, so that the good electrical property of the polyphenyl ether product is ensured.
Claims (10)
1. A method for producing a polyphenylene ether resin, comprising:
in the presence of a solvent and a coordination metal catalyst, enabling oxygen-containing gas and phenolic monomers to undergo oxidative coupling reaction to form a polyphenyl ether mixed solution;
adding a chelating agent into the polyphenyl ether mixed solution to carry out chelation reaction to obtain a mixed product;
separating the water phase in the mixed product through liquid-liquid separation to obtain the polyphenyl ether resin;
wherein the chelating agent comprises one or more than two of polyacrylic acid, sodium polyacrylate, maleic acid-acrylic acid copolymer and maleic acid-acrylic acid copolymer sodium salt.
2. The method according to claim 1, wherein the complex metal catalyst is a complexing agent formed by complexing a metal salt and an amine compound, and the metal in the metal salt is selected from one or a combination of two or more of group VIB, group VIIB, and group IB.
3. The production method according to claim 2, wherein the amine compound comprises one or a combination of two or more of a primary amine compound, a secondary amine compound, a tertiary amine compound, and a diamine compound.
4. The method according to claim 1 or 2, characterized in that the mass ratio of the chelating agent to the metal salt is (0.1-10): 1, preferably (1-3): 1.
5. The method of claim 1, wherein the chelating agent has a molecular weight of 1000-10000g/mol, preferably 1000-8000g/mol, more preferably 2000-6000g/mol.
6. The method of claim 1, wherein the ratio of maleic acid structural units to acrylic acid structural units in the maleic acid-acrylic acid copolymer is 1:1-10.
7. The method according to claim 1, wherein the chelating reaction is carried out at a temperature of 50 to 80 ℃ for a time of 1 to 2 hours.
8. The method of claim 1, wherein the liquid-liquid separation comprises:
adding the mixed product into a centrifuge at a speed of 1-4L/min for the liquid-liquid separation;
preferably, the liquid-liquid separation process does not require a heating or cooling treatment.
9. The production method according to claim 1, wherein the oxygen-containing gas has an oxygen content of not less than 20vol%.
10. A polyphenylene ether resin obtainable by the process according to any one of claims 1 to 9, wherein the polyphenylene ether resin has a copper content of less than 0.1ppm.
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