CN117186386A - Polyphenyl ether and preparation method thereof - Google Patents
Polyphenyl ether and preparation method thereof Download PDFInfo
- Publication number
- CN117186386A CN117186386A CN202311230747.1A CN202311230747A CN117186386A CN 117186386 A CN117186386 A CN 117186386A CN 202311230747 A CN202311230747 A CN 202311230747A CN 117186386 A CN117186386 A CN 117186386A
- Authority
- CN
- China
- Prior art keywords
- polyphenyl ether
- polyphenylene ether
- polyphenyl
- hydrogen
- amine
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229920013636 polyphenyl ether polymer Polymers 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 15
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N 1,4-Benzenediol Natural products OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000001723 curing Methods 0.000 claims abstract description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 14
- 239000003054 catalyst Substances 0.000 claims abstract description 12
- 150000002989 phenols Chemical class 0.000 claims abstract description 12
- 150000001879 copper Chemical class 0.000 claims abstract description 10
- 238000009826 distribution Methods 0.000 claims abstract description 10
- 150000003751 zinc Chemical class 0.000 claims abstract description 10
- 150000003512 tertiary amines Chemical class 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 8
- 239000000843 powder Substances 0.000 claims abstract description 6
- 239000003960 organic solvent Substances 0.000 claims abstract description 5
- 238000001556 precipitation Methods 0.000 claims abstract description 5
- 239000013522 chelant Substances 0.000 claims abstract description 4
- 125000000687 hydroquinonyl group Chemical class C1(O)=C(C=C(O)C=C1)* 0.000 claims abstract 4
- 229920001955 polyphenylene ether Polymers 0.000 claims description 41
- 229910052739 hydrogen Inorganic materials 0.000 claims description 32
- 239000001257 hydrogen Substances 0.000 claims description 20
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 16
- -1 aminocarboxylic acid compound Chemical class 0.000 claims description 12
- 238000001914 filtration Methods 0.000 claims description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 10
- 239000001301 oxygen Substances 0.000 claims description 10
- 229910052760 oxygen Inorganic materials 0.000 claims description 10
- 150000001412 amines Chemical class 0.000 claims description 8
- 239000000203 mixture Chemical group 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 7
- 230000003647 oxidation Effects 0.000 claims description 7
- 238000007254 oxidation reaction Methods 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 125000001188 haloalkyl group Chemical group 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 5
- 239000010949 copper Substances 0.000 claims description 4
- 238000005859 coupling reaction Methods 0.000 claims description 4
- 238000005227 gel permeation chromatography Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 239000000178 monomer Substances 0.000 claims description 4
- 239000011701 zinc Substances 0.000 claims description 4
- 230000008878 coupling Effects 0.000 claims description 3
- 238000010168 coupling process Methods 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 3
- 150000002431 hydrogen Chemical class 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- 239000008247 solid mixture Substances 0.000 claims description 3
- 239000004952 Polyamide Substances 0.000 abstract description 8
- 229920002647 polyamide Polymers 0.000 abstract description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 7
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 abstract description 7
- 229920000642 polymer Polymers 0.000 abstract description 5
- 150000003839 salts Chemical class 0.000 abstract description 4
- 239000004793 Polystyrene Substances 0.000 abstract description 3
- 238000002156 mixing Methods 0.000 abstract description 3
- 229920002223 polystyrene Polymers 0.000 abstract description 3
- 230000004048 modification Effects 0.000 abstract description 2
- 238000012986 modification Methods 0.000 abstract description 2
- 238000005691 oxidative coupling reaction Methods 0.000 abstract description 2
- 238000007306 functionalization reaction Methods 0.000 abstract 1
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 13
- CNHDIAIOKMXOLK-UHFFFAOYSA-N toluquinol Chemical compound CC1=CC(O)=CC=C1O CNHDIAIOKMXOLK-UHFFFAOYSA-N 0.000 description 11
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- NXXYKOUNUYWIHA-UHFFFAOYSA-N 2,6-Dimethylphenol Chemical compound CC1=CC=CC(C)=C1O NXXYKOUNUYWIHA-UHFFFAOYSA-N 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 235000005074 zinc chloride Nutrition 0.000 description 7
- 239000011592 zinc chloride Substances 0.000 description 7
- 150000005208 1,4-dihydroxybenzenes Chemical class 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 6
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000004721 Polyphenylene oxide Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 229920006380 polyphenylene oxide Polymers 0.000 description 4
- DDTHMESPCBONDT-UHFFFAOYSA-N 4-(4-oxocyclohexa-2,5-dien-1-ylidene)cyclohexa-2,5-dien-1-one Chemical compound C1=CC(=O)C=CC1=C1C=CC(=O)C=C1 DDTHMESPCBONDT-UHFFFAOYSA-N 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 235000010290 biphenyl Nutrition 0.000 description 3
- 239000004305 biphenyl Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 3
- 125000001033 ether group Chemical group 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- QQOMQLYQAXGHSU-UHFFFAOYSA-N 2,3,6-Trimethylphenol Chemical compound CC1=CC=C(C)C(O)=C1C QQOMQLYQAXGHSU-UHFFFAOYSA-N 0.000 description 2
- NKTOLZVEWDHZMU-UHFFFAOYSA-N 2,5-xylenol Chemical compound CC1=CC=C(C)C(O)=C1 NKTOLZVEWDHZMU-UHFFFAOYSA-N 0.000 description 2
- SGWZVZZVXOJRAQ-UHFFFAOYSA-N 2,6-Dimethyl-1,4-benzenediol Chemical compound CC1=CC(O)=CC(C)=C1O SGWZVZZVXOJRAQ-UHFFFAOYSA-N 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229920006351 engineering plastic Polymers 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 238000006462 rearrangement reaction Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229920001935 styrene-ethylene-butadiene-styrene Polymers 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- VNDYJBBGRKZCSX-UHFFFAOYSA-L zinc bromide Chemical compound Br[Zn]Br VNDYJBBGRKZCSX-UHFFFAOYSA-L 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- METWAQRCMRWDAW-UHFFFAOYSA-N 2,6-diethylphenol Chemical compound CCC1=CC=CC(CC)=C1O METWAQRCMRWDAW-UHFFFAOYSA-N 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical class NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- 229910021589 Copper(I) bromide Inorganic materials 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- 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 1
- 229920002633 Kraton (polymer) Polymers 0.000 description 1
- DJEQZVQFEPKLOY-UHFFFAOYSA-N N,N-dimethylbutylamine Chemical compound CCCCN(C)C DJEQZVQFEPKLOY-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- ODWXUNBKCRECNW-UHFFFAOYSA-M bromocopper(1+) Chemical compound Br[Cu+] ODWXUNBKCRECNW-UHFFFAOYSA-M 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- AJPXTSMULZANCB-UHFFFAOYSA-N chlorohydroquinone Chemical compound OC1=CC=C(O)C(Cl)=C1 AJPXTSMULZANCB-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 1
- NKNDPYCGAZPOFS-UHFFFAOYSA-M copper(i) bromide Chemical compound Br[Cu] NKNDPYCGAZPOFS-UHFFFAOYSA-M 0.000 description 1
- 229960003280 cupric chloride Drugs 0.000 description 1
- 229940045803 cuprous chloride Drugs 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- PWSKHLMYTZNYKO-UHFFFAOYSA-N heptane-1,7-diamine Chemical compound NCCCCCCCN PWSKHLMYTZNYKO-UHFFFAOYSA-N 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N hydroquinone methyl ether Natural products COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- 229940030980 inova Drugs 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- DWFKOMDBEKIATP-UHFFFAOYSA-N n'-[2-[2-(dimethylamino)ethyl-methylamino]ethyl]-n,n,n'-trimethylethane-1,2-diamine Chemical compound CN(C)CCN(C)CCN(C)CCN(C)C DWFKOMDBEKIATP-UHFFFAOYSA-N 0.000 description 1
- CLZGJKHEVKJLLS-UHFFFAOYSA-N n,n-diheptylheptan-1-amine Chemical compound CCCCCCCN(CCCCCCC)CCCCCCC CLZGJKHEVKJLLS-UHFFFAOYSA-N 0.000 description 1
- MTHFROHDIWGWFD-UHFFFAOYSA-N n-butyl-n-methylbutan-1-amine Chemical compound CCCCN(C)CCCC MTHFROHDIWGWFD-UHFFFAOYSA-N 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 238000009864 tensile test Methods 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
- 150000003739 xylenols Chemical class 0.000 description 1
- 229940102001 zinc bromide Drugs 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
Landscapes
- Polyethers (AREA)
Abstract
The application relates to a polyphenyl ether and a preparation method thereof, wherein the polyphenyl ether consists of polyphenyl ethers with three structures of I, II and III, wherein the proportion of phenolic hydroxyl groups blocked by an X group is more than 45%, the proportion of blocked by a Y structure is less than 5%, and the content of a Z structure is less than 0.3% calculated by total mass; the nitrogen content of the polyphenyl ether is lower than 60ppm, and the molecular weight distribution is 1.2-1.6; the method for preparing the polyphenyl ether comprises the steps of mixing substituted hydroquinone with substituted phenol, adding an organic solvent, carrying out oxidative coupling reaction by taking a copper salt and zinc salt mixed salt and tertiary amine or mixed tertiary amine chelate as catalysts, and obtaining polyphenyl ether powder through the working procedures of curing, precipitation, drying and the like after polymerization. A polyphenyl ether has relatively high phenolic hydroxyl content, very narrow molecular weight distribution, improved compatibility with polymers such as polystyrene and polyamide, excellent temperature resistance and contribution to functionalization modification by using phenolic hydroxyl.
Description
Technical Field
The application relates to a polyphenyl ether with high phenolic hydroxyl content and a preparation method thereof.
Background
Polyphenylene oxide is a general engineering plastic. The composite material has excellent comprehensive performance, excellent size stability and excellent electric insulation under long-term load and wide use temperature range. Has self-extinguishing property. The product has excellent water resistance and steam resistance, high tensile strength and impact strength, and good creep resistance. In addition, the wear resistance and the electrical property are better. It is usually blended with other polymers to make MPPO (modified polyphenylene oxide) such as polystyrene, polyamide, polyester, polyolefin, etc.
Polyphenylene oxide is generally obtained by oxidation coupling reaction of xylenol as a raw material with oxygen in an organic solvent using a metal salt and an amine as a catalyst, such as CN108017791B.
The phenol compound can form a byproduct of diphenoquinone in the oxidation process, the diphenoquinone reacts with the polyphenyl ether in the oxidation polymerization or balance period, and the biphenyl structure is coupled into the polyphenyl ether molecular structure, so that the polyphenyl ether molecular chain is broken, a low molecular weight polymer is formed, the molecular weight distribution is widened, and the problems of easiness in oxidation, physical property reduction and the like of the polyphenyl ether are caused. US4140675 utilizes the rearrangement reaction of diphenoquinone and polyphenylene ether to obtain polyphenylene ether containing biphenyl structure, wherein the proportion of phenolic hydroxyl groups in the specific structure is uncertain, and the nitrogen content in the structure is high, which is not beneficial to extrusion molding processing. The structure and molecular weight of the product obtained by the rearrangement reaction are not controllable.
The molecular structure with higher phenolic hydroxyl content in the polyphenyl ether structure can improve the compatibility of the polyphenyl ether and other polymers, and is beneficial to the chemical modification of the polyphenyl ether end group by utilizing the reaction activity of the phenolic hydroxyl.
Disclosure of Invention
Problems to be solved by the application
As described above, the polyphenylene ether phenolic hydroxyl groups obtained by the heretofore disclosed techniques concentrate on the small molecular weight polyphenylene ether moiety, resulting in a decrease in heat resistance, and cannot exert advantages in terms of improving compatibility of the phenolic hydroxyl groups, and the like. Polyphenylene ethers having higher molecular weights and also higher phenolic hydroxyl groups are not found in the presently disclosed materials.
Accordingly, an object of the present application is to provide a polyphenylene ether having a high phenolic hydroxyl group content and an extremely narrow molecular weight distribution and having good compatibility with other polymers.
Means for solving the problems
As a result of intensive studies on the above problems, the inventors have found that, in the polymerization of polyphenylene ether, substituted hydroquinone and substituted phenol are used as reaction monomers, a copper salt and a zinc salt are mixed in a certain ratio and then chelated with one or more tertiary amine mixtures to form a catalyst, and the catalyst is subjected to oxidative coupling polymerization to obtain polyphenylene ether.
The application is as follows:
[1] polyphenylene ether characterized by comprising polyphenylene ether of the structure shown in I and II and III, and having a ratio of capping with X groups of more than 45%, a ratio of capping with Y structures of less than 5%, and a Z structure content of less than 0.3% by total mass:
（I）
（II）
（III）
wherein R is 1 ,R 2 ，R 3 Is H, C 1-8 Alkyl, haloalkyl, but R 1 And R is 3 Are not hydrogen at the same time; x is
；
Y is
；
Z is
；
Wherein R is 1 ,R 2 ，R 3 ，R 4 ，R 5 ，R 6 ，R 7 Is H, C 1-8 Alkyl, haloalkyl, but R 1 And R is 3 Not simultaneously being hydrogen, R 4-7 Are not hydrogen at the same time;
m and n are natural numbers, m=10-500, n=10-500; p and q are natural numbers, p=0-499, q=0-499, and p+q=10-500.
[2] The polyphenylene ether is characterized in that the total nitrogen content is less than 60ppm as measured by a nitrogen analyzer.
[3] The polyphenyl ether is characterized in that the molecular weight distribution is 1.2-1.6 measured by a sol-gel chromatograph.
[4] The polyphenyl ether is characterized in that the preparation method comprises the following steps:
polymerization process: the monomer containing substituted hydroquinone and substituted phenol is dissolved in good solvent of polyphenyl ether, chelate solution containing copper salt, zinc salt and amine is mixed, oxygen-containing gas is introduced into a reactor for oxidation coupling polymerization reaction, and oxygen is stopped after the target polymerization degree is reached;
curing process: adding an aminocarboxylic acid compound into the mixed material, and heating and curing under the protection of nitrogen, wherein the curing temperature is 45-79 ℃;
and (3) a precipitation step: after curing, liquid-liquid separation is carried out, a water layer is removed, and the oil phase dissolved with the polyphenyl ether is separated out and precipitated by using a poor solvent of the polyphenyl ether;
and (3) a filtering procedure: filtering the liquid-solid mixture;
and (3) a drying procedure: and drying the wet polyphenyl ether containing the organic solvent obtained by filtering to obtain polyphenyl ether powder.
[5] The polyphenyl ether is characterized in that the polyphenyl ether manufacturing method comprises the following steps of replacing hydroquinone in a polymerization process to obtain a structure shown In (IV):
（IV）
wherein R is 4-7 Is H, C 1-8 Is not hydrogen at the same time.
[6] The polyphenyl ether is characterized in that the structure of the substituted phenol in the polymerization process is shown as (V):
（V）
wherein R is 1-3 Is H, C 1-8 Is not hydrogen at the same time.
[7] The polyphenylene ether is characterized in that the molar ratio of the substituted hydroquinone to the substituted phenol in the polymerization process is 1:1000 to 1:8.
[8] The polyphenyl ether is characterized in that the molar ratio of the copper salt to the zinc salt of the catalyst is M (Cu)/M (Zn) =4.2-6.6 in the polyphenyl ether manufacturing method.
[9] The polyphenyl ether is characterized in that the catalyst amine is tertiary mono-amine, tertiary di-amine, tertiary poly-amine or a mixture of tertiary amines in the polyphenyl ether manufacturing method.
ADVANTAGEOUS EFFECTS OF INVENTION
1. The application can provide the polyphenyl ether with high phenolic hydroxyl content, wherein the end capping ratio of an X structure is more than 45%, the end capping ratio of a Y structure is less than 5%, the mass content of a Z structure is less than 0.3%, the molecular weight distribution is 1.2-1.6, the nitrogen content is extremely low and is less than 100ppm, and the polyphenyl ether has good temperature resistance.
2. The polyphenyl ether provided by the application has good compatibility with polyamide, and the blend has good heat resistance and good mechanical property.
Description of the embodiments
The mode for carrying out the application (hereinafter referred to as "the present embodiment") will be described in detail. The present embodiment described below is an example for explaining the present application, and the present application is not limited to the present embodiment, and can be implemented by appropriately modifying the present application within the scope of the gist thereof.
[ polyphenylene ether ]
The polyphenylene ether of the present embodiment is characterized by comprising a polyphenylene ether having the structure shown in I and II and III, wherein the ratio of the end capping with the X group is more than 45%, the ratio of the end capping with the Y structure is less than 5%, and the Z structure content is less than 0.3% by total mass:
（I）
（II）
（III）
wherein R is 1 ,R 2 ，R 3 Is H, C 1-8 Alkyl, haloalkyl, but R 1 And R is 3 Are not hydrogen at the same time; x is
；
Y is
；
Z is
；
Wherein R is 1 ,R 2 ，R 3 ，R 4 ，R 5 ，R 6 ，R 7 Is H, C 1-8 Alkyl, haloalkyl, but R 1 And R is 3 Not simultaneously being hydrogen, R 4-7 Are not hydrogen at the same time;
m and n are natural numbers, m=10-500, n=10-500; p and q are natural numbers, p=0-499, q=0-499, and p+q=10-500.
The polyphenylene ether of the present embodiment has a molecular weight distribution in the range of 1.2 to 1.6 as measured by sol-gel chromatography (GPC).
The polyphenylene ether of this embodiment has a total nitrogen content of less than 60ppm as measured by a azotometer.
[ method of production ]
The method for producing polyphenylene ether according to the present embodiment comprises the steps of: a polymerization step, a curing step, a precipitation step, a filtration step and a drying step.
Polymerization process: the monomer containing substituted hydroquinone and substituted phenol is dissolved in good solvent of polyphenyl ether, chelate solution containing copper salt, zinc salt and tertiary amine is mixed, oxygen-containing gas is introduced into a reactor for oxidation coupling polymerization reaction, and oxygen is stopped after the target polymerization degree is reached;
curing process: adding an aminocarboxylic acid compound into the mixed material, and heating and curing under the protection of nitrogen, wherein the curing temperature is 81-85 ℃;
and (3) a precipitation step: after curing, liquid-liquid separation is carried out, a water layer is removed, and the oil phase dissolved with the polyphenyl ether is separated out and precipitated by using a poor solvent of the polyphenyl ether;
and (3) a filtering procedure: filtering the liquid-solid mixture;
and (3) a drying procedure: and drying the wet polyphenyl ether containing the organic solvent obtained by filtering to obtain polyphenyl ether powder.
The substituted hydroquinone in this embodiment has a structure such as (IV) as a methyl hydroquinone, a chlorohydroquinone, a 2, 6-dimethyl hydroquinone, etc., but is not limited to the above-mentioned compounds.
（IV）
Wherein R is 4-7 Is H, C 1-8 Is not hydrogen at the same time.
The substituted phenol in this embodiment has a structure such as (V), and the substituted phenol is exemplified by 2, 6-dimethylphenol, 2, 5-dimethylphenol, 2,3, 6-trimethylphenol, 2, 6-diethylphenol, o-cresol and the like, but is not limited to the above-mentioned compounds.
（V）
Wherein R is 1-3 Is H, C 1-8 Is not hydrogen at the same time.
In this embodiment, the molar ratio of substituted hydroquinone to substituted phenol is from 1:1000 to 1:8, preferably from 1:200 to 1:20.
The metal salt in the present embodiment refers to a mixture of a copper salt and a zinc salt, wherein the copper salt refers to a mixture of one or more of copper chloride, copper bromide, cuprous chloride, cuprous bromide, cupric nitrate, cupric sulfate, and the like; zinc salts refer to zinc chloride, zinc bromide, zinc nitrate, zinc sulfate.
In this embodiment, the molar ratio of copper salt to zinc salt is M (Cu)/M (Zn) =4.2 to 6.6, preferably M (Cu)/M (Zn) =0.75 to 0.83.
Tertiary amines, which refer to tertiary mono-amines such as trimethylamine, triethylamine, tripropylamine, tributylamine, triheptylamine, dimethylbutylamine, monomethyl dibutylamine, and the like, but are not limited to the above-mentioned compounds; tertiary dibasic amines such as tetramethyl ethylenediamine, tetramethyl propylenediamine, tetramethyl butylenediamine, tetramethyl pentylene diamine, tetramethyl heptylenediamine, etc., but are not limited to the above-mentioned compounds; a tertiary polyamine such as 1,1,4,7,10,10-hexamethyltriethylenetetramine, but not limited to the above. A catalyst is formed from a tertiary amine or a mixture of tertiary amines and a metal salt.
The oxygen in this example is greater than 95% pure oxygen, preferably greater than 98% pure oxygen.
Aminocarboxylic acid compounds for termination of the reaction, such as EDTA, sodium salt of EDTA, and the like.
The method for producing polyphenylene ether of the present application is not limited to the method for producing polyphenylene ether powder of the present embodiment, and the order, the number of times, and the like of specific operations in the polymerization process and the post-treatment process may be appropriately adjusted.
Examples
The present embodiment will be specifically described below with reference to specific examples and comparative examples, but the present embodiment is not limited to the following examples.
The measurement methods of physical properties, characteristics, and the like applied to examples and comparative examples are as follows.
(1) Determination of intrinsic viscosity
The temperature was measured at 30℃using an Ubbelohde viscometer with toluene as a solvent.
(2) Determination of molecular weight and molecular weight distribution
The standard polystyrene sample was measured by using a Shimadzu LC-20ADXR sol-Gel Permeation Chromatograph (GPC), mobile phase chloroform, 25 ℃.
(3) Determination of the terminal Structure
The measurement was performed by using a Vrian Unity Inova MHz nuclear magnetic resonance spectrometer of Varian company of America, 1 H-NMR，d 6 -chloroform.
(4) Determination of nitrogen content
A Jinan Alwa KN680 type full-automatic Kaplan azotometer is adopted.
(5) Determination of mechanical Properties
Blending granulation was carried out using an LTE26/40 twin screw extruder from LABECH, switzerland.
The method is characterized by adopting Ningbo plastic machinery SZ-800NB-A type injection molding machine to prepare the spline.
The mechanical property test is carried out by using a Z010 type universal electronic tensile testing machine of the Germany Zwick company.
Example 1
In a 4L double-layer glass reactor, 1900g of toluene, 12g of triethylamine, 2g of tetramethyl ethylenediamine, 0.33g of cupric chloride and 0.06g of zinc chloride are added, after stirring and dissolving, 190g of 2, 6-dimethylphenol and 0.85g of o-methyl hydroquinone are added, the temperature of the materials is regulated to 30 ℃, oxygen with the purity of 98.5% and the speed of 300mL/min is introduced from the bottom of the reactor under the stirring condition, and polymerization is initiated. Controlling the temperature of the materials to be between 40 and 43 ℃ through a jacket of the reactor, stopping oxygen after polymerization for 60min, adding 2.6g of EDTA-2Na into the reactor after polymerization, heating to 82 ℃ under the protection of nitrogen, and preserving heat for 20min to obtain the organic mixed solution containing the polyphenyl ether.
100mL of distilled water is added into the mixed solution, the mixed solution is vigorously stirred for 2min, then the mixed solution is kept stand for 15min, a colored water layer is removed, a light yellow oil phase is slowly added into 3000mL of methanol, and meanwhile, the mixed solution is vigorously stirred, so that white precipitate of the polyphenyl ether is separated out. And then filtering to obtain a wet cake of polyphenylene ether. The filter cake was heated at 120℃under nitrogen for 3 hours to obtain white polyphenylene ether powder.
The obtained polyphenyl ether is subjected to 1 H-NMR measurement, specific structure was calibrated.
The chemical shift of benzene ring hydrogen in the O-methyl phenol hydroxyl structure (X) end capping of polyphenyl ether is (1H) 6.28ppm;
the chemical shift of benzene ring hydrogen in the benzene ring structure (Y) end capping of 2, 6-dimethylbenzyloxy in polyphenyl ether is (3H) 7.10ppm;
the chemical shift of benzene ring hydrogen in the biphenyl structure (Z) in the polyphenyl ether is 7.34ppm (4H);
the chemical shift of benzene ring hydrogen in 2, 6-dimethylphenol hydroxyl end capping in polyphenyl ether is (2H) 6.35ppm;
the chemical shift of methyl hydrogen in the 2, 6-dimethylbenzyloxy structure of polyphenyl ether is (6H) 2.15ppm;
the method for calculating the end capping ratio of the X structure is as follows:
(1)
Wherein A (X) is an integral area at 6.28ppm, A (Y) is an integral area at 7.10ppm, and A (P) is an integral area at 6.35ppm;
the method for calculating the end capping duty ratio of the Y structure is as follows:
(2)
The mass content calculation method of the Z structure accounting for the 2, 6-dimethylbenzyloxy structure is as follows:
(A-3)
Wherein A (Q) is the integrated area at 2.15 ppm.
Example 2
Zinc chloride was 0.08g. Other conditions were the same as in example 1.
Example 3
The content of the o-methyl hydroquinone is 1.2g. Other conditions were the same as in example 1.
Example 4
The content of the o-methyl hydroquinone is 0.6g. Other conditions were the same as in example 1.
Example 5
The content of the o-methyl hydroquinone is 0.2g. Other conditions were the same as in example 1.
Example 6
The amount of the o-methyl hydroquinone was 3.6g. Other conditions were the same as in example 1.
Example 7
The content of the o-methyl hydroquinone is 12.8g. Other conditions were the same as in example 1.
Comparative example 1
The catalyst was 0.39g of copper chloride, and no zinc chloride was added. Other conditions were the same as in example 1.
Comparative example 2
0.2g of o-methyl hydroquinone, 0.39g of copper chloride as a catalyst, and no zinc chloride. Other conditions were the same as in example 1.
Comparative example 3
190g of 2, 6-dimethylphenol, 0.39g of copper chloride as a catalyst without adding o-methyl hydroquinone and zinc chloride. Other conditions were the same as in example 1.
Comparative example 4
Zinc chloride 0.2g. Other conditions were the same as in example 1.
Comparative example 5
0.6g of hydroquinone was added, and no o-methyl hydroquinone was added. Other conditions were the same as in example 1.
Comparative example 6
6g of triethylamine, 1g of tetramethyl ethylenediamine and 8g of morpholine. Other conditions were the same as in example 1.
Preparation of modified polyphenylene oxide by blending polyamide
The material ratio is as follows:
33 parts by mass of polyphenylene ether (polyphenylene ether obtained in examples, comparative examples and commercial products)
60 parts by mass of polyamide (PA 66, EPR27, god engineering plastics Co., ltd.)
SEBS (G1651, kraton Co., U.S.A.) 5 parts by mass
2 parts by mass of an antioxidant (Irganox 1010, steam refining)
The polyphenyl ether, polyamide and SEBS are dried for 3 hours at 60 ℃ before being used, mixed according to the metering, granulated by an extruder, and then prepared into test bars by an injection molding machine.
Table-1 describes the characteristics of polyphenylene ether obtained under different conditions for examples 1 to 7 and comparative examples 1 to 5. The polyphenylene ethers obtained in examples 1 to 6 all had a very high phenolic hydroxyl group content, a very low Z structure content and a very narrow molecular weight distribution. The polyphenylene ether obtained in the comparative example did not have the above-described characteristics.
Table-2 describes the performance comparisons of the polyphenylene ether obtained in example 5, comparative examples 2 and 6, and commercial polyphenylene ether with polyamide, wherein the polyphenylene ether obtained in example 5 has better strength and toughness; the polyphenylene ether and polyamide blends obtained in comparative examples 2 and 6 have lower strength and poorer toughness; commercial ZM050 performs poorly in terms of strength and toughness, and is odorous.
It should be understood that the examples are illustrative of the present application and are not intended to limit the scope of the present application. Further, it is understood that various changes and modifications may be made by those skilled in the art after reading the disclosure herein, and such equivalents are intended to be within the scope of the application as defined in the appended claims.
Claims (9)
1. Polyphenylene ether characterized by comprising polyphenylene ether of the structure shown in I and II and III wherein the ratio of capping with X groups is greater than 45%, the ratio of capping with Y structures is less than 5%, the Z structure content is less than 0.3% by total mass:
（I）
（II）
（III）
wherein R is 1 ,R 2 ，R 3 Is H, C 1-8 Alkyl, haloalkyl, but R 1 And R is 3 Are not hydrogen at the same time; x is
；
Y is
；
Z is
；
Wherein R is 1 ,R 2 ，R 3 ，R 4 ，R 5 ，R 6 ，R 7 Is H, C 1-8 Alkyl, haloalkyl, but R 1 And R is 3 Not simultaneously being hydrogen, R 4-7 Are not hydrogen at the same time;
m and n are natural numbers, m=10-500, n=10-500; p and q are natural numbers, p=0-499, q=0-499, and p+q=10-500.
2. The polyphenylene ether according to claim 1, wherein the total nitrogen content is less than 60ppm as measured by a nitrogen analyzer.
3. The polyphenylene ether according to claim 1, characterized in that the molecular weight distribution is 1.2-1.6 as measured by sol gel chromatography.
4. The polyphenylene ether according to claim 1, characterized in that the preparation method comprises:
polymerization process: the monomer containing substituted hydroquinone and substituted phenol is dissolved in good solvent of polyphenyl ether, chelate solution containing copper salt, zinc salt and amine is mixed, oxygen-containing gas is introduced into a reactor for oxidation coupling polymerization reaction, and oxygen is stopped after the target polymerization degree is reached;
curing process: adding an aminocarboxylic acid compound into the mixed material, and heating and curing under the protection of nitrogen, wherein the curing temperature is 45-79 ℃;
and (3) a precipitation step: after curing, liquid-liquid separation is carried out, a water layer is removed, and the oil phase dissolved with the polyphenyl ether is separated out and precipitated by using a poor solvent of the polyphenyl ether;
and (3) a filtering procedure: filtering the liquid-solid mixture;
and (3) a drying procedure: and drying the wet polyphenyl ether containing the organic solvent obtained by filtering to obtain polyphenyl ether powder.
5. The polyphenylene ether according to claim 1 to 4, wherein the substituted hydroquinone in the polymerization step has the structure shown In (IV):
（IV）
wherein R is 4-7 Is H, C 1-8 Is not hydrogen at the same time.
6. The polyphenylene ether according to claim 1 to 4, wherein the substituted phenol in the polymerization step has a structure represented by (V):
（V）
wherein R is 1-3 Is H, C 1-8 Is not hydrogen at the same time.
7. The polyphenylene ether according to claim 1 to 4, wherein the molar ratio of substituted hydroquinone to substituted phenol in the polymerization step is 1:1000 to 1:8.
8. The polyphenylene ether according to claim 1 to 4, characterized in that the molar ratio of copper salt to zinc salt of the catalyst is M (Cu)/M (Zn) =4.2 to 6.6.
9. The polyphenylene ether according to claim 1 to 4, wherein the catalyst amine is a tertiary mono-amine, a tertiary di-amine, a tertiary poly-amine or a mixture of the above-mentioned tertiary amines.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311230747.1A CN117186386A (en) | 2023-09-22 | 2023-09-22 | Polyphenyl ether and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311230747.1A CN117186386A (en) | 2023-09-22 | 2023-09-22 | Polyphenyl ether and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117186386A true CN117186386A (en) | 2023-12-08 |
Family
ID=88996050
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311230747.1A Pending CN117186386A (en) | 2023-09-22 | 2023-09-22 | Polyphenyl ether and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117186386A (en) |
-
2023
- 2023-09-22 CN CN202311230747.1A patent/CN117186386A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP2311898B1 (en) | High molecular weight poly(2,6-dimethyl-1,4-phenylene ether) and process therefor | |
| CN101842411B (en) | Poly(arylene ether) preparation method | |
| US3318959A (en) | Symmetrically terminated polyphenylene ether | |
| EP1307500B1 (en) | Preparation of high intrinsic viscosity poly(arylene ether) resins | |
| CN109517164B (en) | Synthesis method of double-end hydroxyl polyphenylene oxide oligomer | |
| EP3307806B1 (en) | Method for poly(phenylene ether) manufacture and associated poly(phenylene ether) | |
| KR101558446B1 (en) | Poly(phenylene ether) copolymer and method of making | |
| CN114409900B (en) | Preparation method of polysulfone with low cyclic dimer content | |
| US11472920B2 (en) | Method for preparing a poly(phenylene ether) and poly(phenylene ether) prepared thereby | |
| CN117186386A (en) | Polyphenyl ether and preparation method thereof | |
| EP0193741B1 (en) | Block copolymers containing unsubstituted or substituted poly (1,4 oxyphenylene) segments and liquid crystalline segments | |
| JPS60163925A (en) | Production of polyphenylene oxide and polyphenylene oxide of excellent heat resistance obtained thereby | |
| CN108368255B (en) | Methods of forming high molecular weight poly (phenylene ether), poly (phenylene ether) formed therefrom, and fibers and articles comprising poly (phenylene ether) | |
| EP4006079B1 (en) | Polyarylene ether ketone resin, manufacturing method therefor, and molded body | |
| CN108641077B (en) | Synthetic method of polyphenyl ether | |
| CN112552510A (en) | Phthalonitrile-terminated polyphenyl ether and preparation method and application thereof | |
| US3392147A (en) | Process for the formation of 2, 6-diaryl polyphenylene ethers | |
| CN111057232A (en) | High molecular weight polyphenylene ether and process for producing the same | |
| US5629405A (en) | Method for making polyarylene ethers with pyridine catalysts | |
| JP5588297B2 (en) | Polyphenylene ether | |
| US12024589B2 (en) | Method of preparing a poly (phenylene ether), poly(phenylene ether) made thereby, and article comprising the poly(phenylene ether) | |
| JPH0639526B2 (en) | Block polyphenylene ether-polycarbonate manufacturing method | |
| CN104245792A (en) | Process for preparing poly(N-acylamides) and poly(N-acylamides) as obtained |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |