GB1119914A - Improvements in "equilibration of poly-(1,4-phenylene ethers)" - Google Patents
Improvements in "equilibration of poly-(1,4-phenylene ethers)"Info
- Publication number
- GB1119914A GB1119914A GB15708/67A GB1570867A GB1119914A GB 1119914 A GB1119914 A GB 1119914A GB 15708/67 A GB15708/67 A GB 15708/67A GB 1570867 A GB1570867 A GB 1570867A GB 1119914 A GB1119914 A GB 1119914A
- Authority
- GB
- United Kingdom
- Prior art keywords
- phenol
- poly
- formula
- acetamide
- trimethylsilyl
- 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.)
- Expired
Links
- 238000011067 equilibration Methods 0.000 title 1
- -1 alkyl radical Chemical group 0.000 abstract 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 abstract 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 abstract 6
- SIOVKLKJSOKLIF-UHFFFAOYSA-N bis(trimethylsilyl)acetamide Chemical compound C[Si](C)(C)OC(C)=N[Si](C)(C)C SIOVKLKJSOKLIF-UHFFFAOYSA-N 0.000 abstract 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract 5
- 125000004432 carbon atom Chemical group C* 0.000 abstract 4
- 229910052739 hydrogen Inorganic materials 0.000 abstract 4
- 239000001257 hydrogen Substances 0.000 abstract 4
- 238000010992 reflux Methods 0.000 abstract 4
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 abstract 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 abstract 3
- 238000006243 chemical reaction Methods 0.000 abstract 3
- 229910052736 halogen Inorganic materials 0.000 abstract 3
- 150000002367 halogens Chemical class 0.000 abstract 3
- 238000010438 heat treatment Methods 0.000 abstract 3
- KHUXNRRPPZOJPT-UHFFFAOYSA-N phenoxy radical Chemical compound O=C1C=C[CH]C=C1 KHUXNRRPPZOJPT-UHFFFAOYSA-N 0.000 abstract 3
- NXXYKOUNUYWIHA-UHFFFAOYSA-N 2,6-Dimethylphenol Chemical compound CC1=CC=CC(C)=C1O NXXYKOUNUYWIHA-UHFFFAOYSA-N 0.000 abstract 2
- GVLZQVREHWQBJN-UHFFFAOYSA-N 3,5-dimethyl-7-oxabicyclo[2.2.1]hepta-1,3,5-triene Chemical compound CC1=C(O2)C(C)=CC2=C1 GVLZQVREHWQBJN-UHFFFAOYSA-N 0.000 abstract 2
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 abstract 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 abstract 2
- 125000001931 aliphatic group Chemical group 0.000 abstract 2
- 229910052799 carbon Inorganic materials 0.000 abstract 2
- 150000001875 compounds Chemical class 0.000 abstract 2
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 abstract 2
- 238000004508 fractional distillation Methods 0.000 abstract 2
- UQEAIHBTYFGYIE-UHFFFAOYSA-N hexamethyldisiloxane Chemical class C[Si](C)(C)O[Si](C)(C)C UQEAIHBTYFGYIE-UHFFFAOYSA-N 0.000 abstract 2
- 150000002431 hydrogen Chemical group 0.000 abstract 2
- 230000007062 hydrolysis Effects 0.000 abstract 2
- 238000006460 hydrolysis reaction Methods 0.000 abstract 2
- 239000000203 mixture Substances 0.000 abstract 2
- 229920000642 polymer Polymers 0.000 abstract 2
- 239000000047 product Substances 0.000 abstract 2
- NAXRQXCJBOHQRG-UHFFFAOYSA-N 4-[4-(4-bromophenoxy)-2,6-dimethylphenoxy]-2,6-dimethylphenol Chemical compound BrC1=CC=C(OC2=CC(=C(OC3=CC(=C(C(=C3)C)O)C)C(=C2)C)C)C=C1 NAXRQXCJBOHQRG-UHFFFAOYSA-N 0.000 abstract 1
- 239000004342 Benzoyl peroxide Substances 0.000 abstract 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 abstract 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 abstract 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract 1
- SUVSWSZDUPTNMK-UHFFFAOYSA-N OC1=CC=CC=C1.OC1=CC=C(Br)C=C1 Chemical compound OC1=CC=CC=C1.OC1=CC=C(Br)C=C1 SUVSWSZDUPTNMK-UHFFFAOYSA-N 0.000 abstract 1
- 150000001266 acyl halides Chemical class 0.000 abstract 1
- 235000019400 benzoyl peroxide Nutrition 0.000 abstract 1
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 abstract 1
- 239000000539 dimer Substances 0.000 abstract 1
- 238000004821 distillation Methods 0.000 abstract 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 abstract 1
- 239000000706 filtrate Substances 0.000 abstract 1
- 239000011874 heated mixture Substances 0.000 abstract 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 abstract 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 abstract 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 abstract 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract 1
- 239000003999 initiator Substances 0.000 abstract 1
- 238000000034 method Methods 0.000 abstract 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 abstract 1
- 125000001624 naphthyl group Chemical group 0.000 abstract 1
- 150000002989 phenols Chemical class 0.000 abstract 1
- 229920001955 polyphenylene ether Polymers 0.000 abstract 1
- 239000011541 reaction mixture Substances 0.000 abstract 1
- 239000007858 starting material Substances 0.000 abstract 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/66—Polyesters containing oxygen in the form of ether groups
- C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/672—Dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/14—Preparation of ethers by exchange of organic parts on the ether-oxygen for other organic parts, e.g. by trans-etherification
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
-
- 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)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- General Chemical & Material Sciences (AREA)
- Polyethers (AREA)
Abstract
The invention relates to a process of equilibrating poly-(1,4-phenylene ethers) which comprises reacting (1) a poly-(1,4-phenylene ether) having the formula <FORM:1119914/C2/1> where n is an integer and is at least 10, R is an alkyl radical containing 1 to 8 carbon atoms, free of an aliphatic, tertiary a -carbon atom, or phenyl and R1 is the same as R and in addition, biphenylyl, terphenylyl or naphthyl and (2) a phenol having the formulae (A), (B) or (C): <FORM:1119914/C2/2> where m is O or 1, R2 is hydrogen, an alkyl radical having 1 to 8 carbons free of an aliphatic tertiary a -carbon atom, phenyl or halogen; R3 is the same as R2 and, in addition, hydroxyl; R4 is an alkyl radical having 1 to 8 carbon atoms, an alkoxy radical having 1 to 8 carbon atoms, an acyl radical having 1 to 8 carbon atoms, hydrogen or phenyl, and in addition, R4 is halogen when each R2 on the same benzene ring as R4 is hydrogen or halogen, and R5 is hydrogen, methyl, ethyl or phenyl, said reaction being initiated by a free phenoxy radical derived from the polyphenylene ether of (1), and/or a free phenoxy radical derived from the phenol of (2), the reaction being carried out at a temperature in the range from room temperature up to the reflux temperature of the reaction mixture. After the reaction any residual polymer is separated and the remaining oligomeric products are reacted with a mono-functional silylating agent, an acyl halide or an acyl anhydride, and the derivatives of the oligomers separated. The invention also relates to compounds of the general formula <FORM:1119914/C2/3> where Z is: <FORM:1119914/C2/4> In an example poly-(2,6-dimethyl-1,4-phenylene ether) is equilibrated with 2,6-dimethyl-phenol using 3,31,5,51 - tetramethyl - 4,41 - diphenoquinone to produce the phenoxy radical initiator. Unreacted starting material and reduction product are removed and any polymer precipitated. The filtrate was concentrated and treated with bis(trimethylsilyl) acetamide to convert the oligomers to their trimethylsilyl ethers. Silyl ethers may also be prepared by the use of trimethylsilylchloride in place of the bis(trimethylsilyl) acetamide, and a hydrogen chloride acceptor. On fractional distillation three fractions have the formula: <FORM:1119914/C2/5> and the corresponding tri- and tetra-compounds were obtained. The corresponding phenols were obtained by treating with methanol. In another example instead of the acetamide of the previous example, acetic anhydride is used and on distillation three fractions having the formula <FORM:1119914/C2/6> and the corresponding tri- and tetra-compounds were obtained. In another example poly-(2,6-dimethyl - 1,4 - phenylene ether), p - bromo-phenol phenol and benzoyl peroxide were heated to reflux and bis(trimethylsilyl) acetamide added and heating continued at reflux and on fractional distillation two fractions having the formul, <FORM:1119914/C2/7> <FORM:1119914/C2/8> are obtained. Hydrolysis of these silyl ethers produced 4 - (4 - bromophenoxy) - 2,6, - dimethylphenol and 4 - [4 - (4 - bromophenoxy) - 2,6 -dimethylphenoxy] - 2,6 - dimethyl - phenol. In another example to a heated mixture of 3,31,5,51-tetramethyl-4,41-biphenol, 3,31,5,51-tetramethyl -4,41-diphenoquinone and benzene was added poly - (2,6 - dimethyl - 1,4 - phenylene ether). After heating for 16 hours at reflux, bis(trimethylsilyl)-acetamide, was added and after 2 hours the mixture was fractionally distilled to obtain the ether of the dimer of the formula <FORM:1119914/C2/9> Hydrolysis of this fraction produced the compound of the formula <FORM:1119914/C2/10> In another example 4,41-isopropylidenediphenol, poly - (2,6 - dimethyl - 1,4 - phenylene ether), 3,31,5,51 - tetramethyl - 4,41 - diphenoquinone in benzene was heated for two hours at 80 DEG C. and bis(trimethyl-silyl)acetamide was then added and after further heating the mixture was fractionally distilled and bis(trimethylsilyl) ether of 4,41-isopropylidenephenol of the general formula <FORM:1119914/C2/11> was obtained. On treating with methanol the corresponding phenol of the formula <FORM:1119914/C2/12> was obtained.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US54718066A | 1966-05-03 | 1966-05-03 | |
| US547182A US3367978A (en) | 1966-05-03 | 1966-05-03 | 4-(phenoxy)phenols |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| GB1119914A true GB1119914A (en) | 1968-07-17 |
Family
ID=27068475
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB15708/67A Expired GB1119914A (en) | 1966-05-03 | 1967-04-05 | Improvements in "equilibration of poly-(1,4-phenylene ethers)" |
Country Status (1)
| Country | Link |
|---|---|
| GB (1) | GB1119914A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1996001865A1 (en) * | 1994-07-11 | 1996-01-25 | Dsm N.V. | Multihydroxy-functional oligophenylene oxide |
| US5880221A (en) * | 1997-02-14 | 1999-03-09 | General Electric Company | Redistribution of polyphenylene ethers and polyphenylene ethers with novel structure |
| EP1471090A1 (en) * | 2003-04-24 | 2004-10-27 | Mitsubishi Gas Chemical Company, Inc. | Polyester, its film and laminate |
| CN112469684A (en) * | 2018-09-14 | 2021-03-09 | 株式会社Lg化学 | Diol compound, polycarbonate and preparation method thereof |
| CN115477748A (en) * | 2022-09-20 | 2022-12-16 | 广东省科学院化工研究所 | Low-molecular-weight dihydroxy polyphenyl ether and preparation method and application thereof |
-
1967
- 1967-04-05 GB GB15708/67A patent/GB1119914A/en not_active Expired
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1996001865A1 (en) * | 1994-07-11 | 1996-01-25 | Dsm N.V. | Multihydroxy-functional oligophenylene oxide |
| US5880221A (en) * | 1997-02-14 | 1999-03-09 | General Electric Company | Redistribution of polyphenylene ethers and polyphenylene ethers with novel structure |
| EP1471090A1 (en) * | 2003-04-24 | 2004-10-27 | Mitsubishi Gas Chemical Company, Inc. | Polyester, its film and laminate |
| CN112469684A (en) * | 2018-09-14 | 2021-03-09 | 株式会社Lg化学 | Diol compound, polycarbonate and preparation method thereof |
| EP3808726A4 (en) * | 2018-09-14 | 2021-08-04 | Lg Chem, Ltd. | Diol compound, polycarbonate, and method for producing same |
| CN112469684B (en) * | 2018-09-14 | 2023-06-30 | 株式会社Lg化学 | Diol compound, polycarbonate and process for producing the same |
| US11884777B2 (en) | 2018-09-14 | 2024-01-30 | Lg Chem, Ltd. | Diol compound, polycarbonate, and preparation method of the same |
| CN115477748A (en) * | 2022-09-20 | 2022-12-16 | 广东省科学院化工研究所 | Low-molecular-weight dihydroxy polyphenyl ether and preparation method and application thereof |
| CN115477748B (en) * | 2022-09-20 | 2023-10-13 | 广东省科学院化工研究所 | Low-molecular-weight dihydroxy polyphenyl ether and preparation method and application thereof |
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