CA1133945A - Bis(4-hydroxyphenyl thiphenyl)biphenyl disulfones - Google Patents
Bis(4-hydroxyphenyl thiphenyl)biphenyl disulfonesInfo
- Publication number
- CA1133945A CA1133945A CA331,698A CA331698A CA1133945A CA 1133945 A CA1133945 A CA 1133945A CA 331698 A CA331698 A CA 331698A CA 1133945 A CA1133945 A CA 1133945A
- Authority
- CA
- Canada
- Prior art keywords
- polymer
- biphenyl
- monomer
- bis
- hydroxyphenyl
- 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
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 title claims description 11
- 239000004305 biphenyl Substances 0.000 title description 5
- 235000010290 biphenyl Nutrition 0.000 title description 5
- 125000004203 4-hydroxyphenyl group Chemical group [H]OC1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 title 1
- 239000000178 monomer Substances 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 12
- 229920000515 polycarbonate Polymers 0.000 claims abstract description 8
- 239000004417 polycarbonate Substances 0.000 claims abstract description 8
- 229920000728 polyester Polymers 0.000 claims abstract description 7
- 229920000570 polyether Polymers 0.000 claims abstract description 7
- 239000004814 polyurethane Substances 0.000 claims abstract description 7
- 229920002635 polyurethane Polymers 0.000 claims abstract description 6
- 229920002492 poly(sulfone) Polymers 0.000 claims abstract description 5
- 238000004519 manufacturing process Methods 0.000 claims abstract 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 27
- 229920000642 polymer Polymers 0.000 claims description 12
- 230000015572 biosynthetic process Effects 0.000 claims description 8
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 8
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 8
- OZUNPRDEUXITBO-UHFFFAOYSA-N 1-(4-chlorophenyl)sulfonyl-4-[4-(4-chlorophenyl)sulfonylphenyl]benzene Chemical group C1=CC(Cl)=CC=C1S(=O)(=O)C1=CC=C(C=2C=CC(=CC=2)S(=O)(=O)C=2C=CC(Cl)=CC=2)C=C1 OZUNPRDEUXITBO-UHFFFAOYSA-N 0.000 claims description 6
- 238000003786 synthesis reaction Methods 0.000 claims description 6
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 5
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 5
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 4
- BXAVKNRWVKUTLY-UHFFFAOYSA-N 4-sulfanylphenol Chemical compound OC1=CC=C(S)C=C1 BXAVKNRWVKUTLY-UHFFFAOYSA-N 0.000 claims description 3
- -1 diaryl carbonates Chemical class 0.000 claims description 3
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims 1
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 claims 1
- 239000004721 Polyphenylene oxide Substances 0.000 claims 1
- 125000003118 aryl group Chemical group 0.000 claims 1
- MOIPGXQKZSZOQX-UHFFFAOYSA-N carbonyl bromide Chemical compound BrC(Br)=O MOIPGXQKZSZOQX-UHFFFAOYSA-N 0.000 claims 1
- 150000002148 esters Chemical class 0.000 claims 1
- 235000015320 potassium carbonate Nutrition 0.000 claims 1
- 235000011181 potassium carbonates Nutrition 0.000 claims 1
- SECSQPFVZRBLLR-UHFFFAOYSA-N 4-[2-[4-[4-[3-(4-hydroxyphenyl)thiophen-2-yl]phenyl]phenyl]thiophen-3-yl]phenol Chemical group OC1=CC=C(C=C1)C1=C(SC=C1)C1=CC=C(C=C1)C1=CC=C(C=C1)C=1SC=CC=1C1=CC=C(C=C1)O SECSQPFVZRBLLR-UHFFFAOYSA-N 0.000 abstract description 9
- 239000000460 chlorine Substances 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 229910052801 chlorine Inorganic materials 0.000 description 5
- 239000011541 reaction mixture Substances 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 4
- 239000012043 crude product Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 3
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 3
- OTFAWEIFBPUXOH-UHFFFAOYSA-N 4-(4-chlorosulfonylphenyl)benzenesulfonyl chloride Chemical compound C1=CC(S(=O)(=O)Cl)=CC=C1C1=CC=C(S(Cl)(=O)=O)C=C1 OTFAWEIFBPUXOH-UHFFFAOYSA-N 0.000 description 2
- ZLYBFBAHAQEEQQ-UHFFFAOYSA-N 4-chlorobenzenesulfonyl chloride Chemical compound ClC1=CC=C(S(Cl)(=O)=O)C=C1 ZLYBFBAHAQEEQQ-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 102100034757 Thiol S-methyltransferase METTL7B Human genes 0.000 description 2
- 101710082490 Thiol S-methyltransferase METTL7B Proteins 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000012429 reaction media Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229960000583 acetic acid Drugs 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- RMVRSNDYEFQCLF-UHFFFAOYSA-M benzenethiolate Chemical compound [S-]C1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-M 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 230000000269 nucleophilic effect Effects 0.000 description 1
- 125000003854 p-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Cl 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000012258 stirred mixture Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Polyurethanes Or Polyureas (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Polyethers (AREA)
- Polyesters Or Polycarbonates (AREA)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
The present invention relates to novel monomers generically identified as bis(4-hydroxyphenyl thiophenyl) biphenyl disulfones, to a process for their production and to their use in the preparation of polycarbonates, polyurethanes, polyesters, polysulfones and polyethers.
The present invention relates to novel monomers generically identified as bis(4-hydroxyphenyl thiophenyl) biphenyl disulfones, to a process for their production and to their use in the preparation of polycarbonates, polyurethanes, polyesters, polysulfones and polyethers.
Description
`~ Mo-1901 ~39~'~S PC-018 BIS(4-HYDROXYPHENYL THIOPHENYL) BIPHENYL DISULFONES
SUMMARY OF THE INVENTION
The present invention comprises novel monomers generi-cally identified as bis(4-hydroxyphenyl thiophenyl)biphenyl disulfones of the structural formula:
( 1) ~R2~ (~3) (R4) (R5) (R6) nl n2 I n3 ~ n4 \ n5 ~ n6 HO ~ ~ S ~ ~ ~ S ~ S ~ OH
wherein Rl, R2, R3, R4, R5 and R6,which may be the same or different,are Cl-C4-alkyl, Cl or Br, and nl, n2, n3, n4, n5 and n6, which may be the same or different, are 0, 1 or 2, to a process for their synthesis and to polycarbonates, poly-urethanes, polyesters, polysul:fones and polyethers prepared from these novel monomers.
DETAILED DESCRIPTION OF THE INVENTION
The bis(4-hydroxyphenyl thiophenyl)biphenyl disul-fones of the present invention have the general structural formula:
~ 2)n l3 n ~4 n4 \5 n5 ~ n6 HO ~ S ~ S ~ S ~ S ~ OH
O O
wherein Rl, R2, R3, R4, R5 and R6, which may be the same or different,are Cl-C4 alkyl, Cl or Br and PC-018/Mo-1901 39 ~5 nl, n2, n3, n4, n5 and n6, which may be the same or different, are 0, 1 or 2.
A route suitable for the synthesis of the generic bis(4-hydroxyphenyl thiophenyl)biphenyl disulfones is illus-trated by the following general reaction scheme for thesynthesis of bis(4-hydroxyphenyl thiophenyl)biphenyl disulfone (nl-n6 = 0), the preferred monomer of the present invention:
Cl-S ~ S-CL + ~ Cl or ~ ~ C1 ~ S-Cl Cl ~ S ~ ~ - S ~ Cl (I) HO ~ SH ~ ~2C03/Dimethyl formamide HO ~ S ~ S ~ ~ ~ S ~ S ~ H (II) As indicated in the above suitable reaction scheme, the 4,4'-bis(4-chlorophenyl sulfonyl)biphenyl precursor (I) of the novel monomers of the invention can be made by two lS routes, i.e., (1) by the ferric chloride catalyzed condensation of 4,4'-biphenyl disulfonyl dichloride and chlorobenzene wherein the chlorobenzene is used as both a reactant and a solvent or (2) by the ferric chloride catalyzed condensation of PC-018/Mo-1901 biphenyl and 4-chlorobenzene sulfonyl chloride. The resulting 4,4'-bis(4-chlorophenyl sulfonyl)biphenyl precursor (I) iS next reacted with 4-mercaptophenol in the presence of potassium carbonate and dimethylformamide to produce the preferred bis(4-hydroxyphenyl thiophenyl)biphenyl disul~one (II) o~ the present invention.
The generic bis(4-hydroxyphenyl thiophenyl)biphenyl disulfones of the invention are useful as monomers or one of the comonomers in the synthesis of polycarbonates, polyurethanes, polyesters, polysulfones, polyethers and other polymers.
Such polycarbonates may be produced using the novel monomers of the invention by well-known methods, such as dis-closed in U.S. Patent Nos. 2,964,794; 2,970,131; 2,991,237;
SUMMARY OF THE INVENTION
The present invention comprises novel monomers generi-cally identified as bis(4-hydroxyphenyl thiophenyl)biphenyl disulfones of the structural formula:
( 1) ~R2~ (~3) (R4) (R5) (R6) nl n2 I n3 ~ n4 \ n5 ~ n6 HO ~ ~ S ~ ~ ~ S ~ S ~ OH
wherein Rl, R2, R3, R4, R5 and R6,which may be the same or different,are Cl-C4-alkyl, Cl or Br, and nl, n2, n3, n4, n5 and n6, which may be the same or different, are 0, 1 or 2, to a process for their synthesis and to polycarbonates, poly-urethanes, polyesters, polysul:fones and polyethers prepared from these novel monomers.
DETAILED DESCRIPTION OF THE INVENTION
The bis(4-hydroxyphenyl thiophenyl)biphenyl disul-fones of the present invention have the general structural formula:
~ 2)n l3 n ~4 n4 \5 n5 ~ n6 HO ~ S ~ S ~ S ~ S ~ OH
O O
wherein Rl, R2, R3, R4, R5 and R6, which may be the same or different,are Cl-C4 alkyl, Cl or Br and PC-018/Mo-1901 39 ~5 nl, n2, n3, n4, n5 and n6, which may be the same or different, are 0, 1 or 2.
A route suitable for the synthesis of the generic bis(4-hydroxyphenyl thiophenyl)biphenyl disulfones is illus-trated by the following general reaction scheme for thesynthesis of bis(4-hydroxyphenyl thiophenyl)biphenyl disulfone (nl-n6 = 0), the preferred monomer of the present invention:
Cl-S ~ S-CL + ~ Cl or ~ ~ C1 ~ S-Cl Cl ~ S ~ ~ - S ~ Cl (I) HO ~ SH ~ ~2C03/Dimethyl formamide HO ~ S ~ S ~ ~ ~ S ~ S ~ H (II) As indicated in the above suitable reaction scheme, the 4,4'-bis(4-chlorophenyl sulfonyl)biphenyl precursor (I) of the novel monomers of the invention can be made by two lS routes, i.e., (1) by the ferric chloride catalyzed condensation of 4,4'-biphenyl disulfonyl dichloride and chlorobenzene wherein the chlorobenzene is used as both a reactant and a solvent or (2) by the ferric chloride catalyzed condensation of PC-018/Mo-1901 biphenyl and 4-chlorobenzene sulfonyl chloride. The resulting 4,4'-bis(4-chlorophenyl sulfonyl)biphenyl precursor (I) iS next reacted with 4-mercaptophenol in the presence of potassium carbonate and dimethylformamide to produce the preferred bis(4-hydroxyphenyl thiophenyl)biphenyl disul~one (II) o~ the present invention.
The generic bis(4-hydroxyphenyl thiophenyl)biphenyl disulfones of the invention are useful as monomers or one of the comonomers in the synthesis of polycarbonates, polyurethanes, polyesters, polysulfones, polyethers and other polymers.
Such polycarbonates may be produced using the novel monomers of the invention by well-known methods, such as dis-closed in U.S. Patent Nos. 2,964,794; 2,970,131; 2,991,237;
2,999,835; 2,999,846; 3,028,365; 3,153,008; 3,187,065;
15 3,215,668; and 3,248,414, and in the monograph H. Schnell, Chemistry and Physics of Polycarbonates, Interscience Publishers, New York, New York, 1964.
Such polyurethanes may be produced using the novel monomers of the invention by well-known methods, such as dis-20 closed in U.S. Patent Nos. 2,266,777; 2,284,637; 2,284,896;
2,511,544, and in the text Polyurethanes: Chemistry and Technolo~y, Vol. 1, J. H. Saunders and K. C. Frisch, Inter-science Publishers, New York, New York, 1964.
Such polyesters may be produced using the novel monomers of the invention by well-known methods, such as dis-closed in U.S. Patent Nos. 2,980,650; 3,185,668; 3,185,670; and
15 3,215,668; and 3,248,414, and in the monograph H. Schnell, Chemistry and Physics of Polycarbonates, Interscience Publishers, New York, New York, 1964.
Such polyurethanes may be produced using the novel monomers of the invention by well-known methods, such as dis-20 closed in U.S. Patent Nos. 2,266,777; 2,284,637; 2,284,896;
2,511,544, and in the text Polyurethanes: Chemistry and Technolo~y, Vol. 1, J. H. Saunders and K. C. Frisch, Inter-science Publishers, New York, New York, 1964.
Such polyesters may be produced using the novel monomers of the invention by well-known methods, such as dis-closed in U.S. Patent Nos. 2,980,650; 3,185,668; 3,185,670; and
3,268,482, and in the text Polyesters (two parts), edited by Norman G. Gaylord, PC-018/Mo-1901 1~3~ S
Interscience Publishers, New York, 1962.
Such polysulfones may be produced using the novel monomers of the invention by well-known methods, such as dis-closed in U.S. Patent Nos. 3,236,808; 3,Z36,809; 3,409,599;
and 3,742,087.
Such polyethers may be produced using the novel monomers of the invention by well-known methods, such as dis-closed in U.S. Patent Nos. 1,922,459; 2,253,723; 2,991,313;
and 3,651,151, and in the text Polyethers (three parts), edited by Norman G. Gaylord, Interscience Publishers, New York, 1962.
The invention will be further illustrated, but is not intended to be limited, by the following examples.
PC-018/Mo-].901 , . ' :, .
,.. :.
, .
~3L339~S
EXAMPLES
Synthesis of 4,4'-bis(4-chlorophenyl sulfonyl)biphenyl precurcor (I) Route 1:
To a three-necked 12 liter flask fitted with a stirrer, a condenser, a thermometer, nitrogen gas inlet and out-let ~the outlet being connected to the bubbler to absorb the evolved hydrogen chloride gas during the reaction) was added 7.8 liters of distilled monochlorobenzene (MCB) and 5 lbs. of
Interscience Publishers, New York, 1962.
Such polysulfones may be produced using the novel monomers of the invention by well-known methods, such as dis-closed in U.S. Patent Nos. 3,236,808; 3,Z36,809; 3,409,599;
and 3,742,087.
Such polyethers may be produced using the novel monomers of the invention by well-known methods, such as dis-closed in U.S. Patent Nos. 1,922,459; 2,253,723; 2,991,313;
and 3,651,151, and in the text Polyethers (three parts), edited by Norman G. Gaylord, Interscience Publishers, New York, 1962.
The invention will be further illustrated, but is not intended to be limited, by the following examples.
PC-018/Mo-].901 , . ' :, .
,.. :.
, .
~3L339~S
EXAMPLES
Synthesis of 4,4'-bis(4-chlorophenyl sulfonyl)biphenyl precurcor (I) Route 1:
To a three-necked 12 liter flask fitted with a stirrer, a condenser, a thermometer, nitrogen gas inlet and out-let ~the outlet being connected to the bubbler to absorb the evolved hydrogen chloride gas during the reaction) was added 7.8 liters of distilled monochlorobenzene (MCB) and 5 lbs. of
4,4'-biphenyl disulfonyl dichloride (referred to as ALDI, commercially available from Uniroyal, Inc.). This mixture was heated to 70C in a nitrogen atmosphere, and the ALDI was completely dissolved in MCB. 65 gms of anhydrous ferric chloride was added and the reaction mixture heated to 130C and held at this temperature until the evolution of hydrogen chloride gas subsided (about 20 hrs.). The tan colored product which separated out from the reaction medium was filtered and air dried to give 5 lbs. (about 84% yield) of crude product.
The crude product was crystallized from dimethyl formamide to give white crystals (m.p. 269-272C) and was identified by infrared (IR) and nuclear magnetic resonance (NMR) spectra as 4,4'-bis(4-chlorophenyl sulfonyI)biphenyl.
Analysis - Calcd. for C~4H16S2O4C12 (m. wt. 503.4) Theory: % Cj 57.26; % H, 3.20; % S,12.71; % Cl, 14.11 Found: ~ C, 57.17; % H, 3~18î % S~ 12.55; % Cl, 13~90 Route 2:
To a stirred mixture of biphenyl (30~8 g) and 4-chlorobenzene sulfonyl chloride (95.95 g) (1:2.25 molar ratio) pc-ol8/Mo-l9ol ~3~5 at 70C was added anhydrous ferric chloride (6 g). The temperature was increased to 140C in 1 hr. causing a steady evolution of hydrogen chloride gas. After approximately one hour, the reaction mixture solidified. Heating was continued for another two hours in the solid state. The solid mass was dissolved in dimethyl formamide (DMF) and upon cooling 4,4'-bis~4-chlorophenyl sulfonyl)biphenyl crystallized out. A
second purification from DME led to pale yellow crystalline product (m.p. 269-272C). A ~5% conversion was obtained after purification.
Products obtained by Route l and Route 2 had identical infrared spectrum, even though formation of isomeric products was possible by Route l. As the reaction product separated quite readily from the reaction medium, it can be filtered and purified easily. From this point of view as well as higher conversion, Route l is the preferred method.
Synthesis of bis(4-hydroxyphenyl thiophenyl)biphenyl disulfone ~II) .
To a three-necked 3 liter flask fitted with a stirrer, nitrogen inlet and outlet, a thermometer, a condenser and addition funnel was added 63 g (0.5 mol) of 4-mercaptophenol (available from Crown Zellerback), 76 g (0.55 mol) of anhydrous potassium carbonate (granular) and 750 ml of distilled dimethyl formamide. The mixture was heated to 90C under nitrogen atmosphere. A bright yellow color, due to formation of the thiophenoxy anion was observed around 60-90C. The reaction mixture was stirred at 90C for 2 hrs. and then 126 g (0.25 mol) of bis(4-chlorophenyl sulfonyl)biphenyl dissolved in 300 ml of warm dimethyl formamide was added in 30 min. The intensity of bright yellow color faded slowly as the nucleophilic displace-PC-018/Mo-l901 ~33~ 5 ment of chlorine by the thiophenoxide anion progressed. The reaction mixture was held at 90-100C for 3 hrs. The reaction mixture while hot was filtered to remove potassium salts. The filtrate was diluted with 2 liters of water and then acidified to pH6. The white precipitate was filtered and dried to yield 165 g (97% yield) of crude product. The crude product, on crystallization from glacial acetic acid, gave a white powdery material (m.p. 235-237C) and was identified by infrared and NMR spectra as bis(4-hydroxyphenyl thiophenyl)biphenyl disulfone, Analysis - Calcd. for C36H28S~06 (M.Wt. 682.57) Theory: % C, 63.34; % H, 3.84; % S, 18.75 Found: % C, 63.23, % H, 3.80; % S, 19002 The diacetate of this monomer with m.p. 195C was synthesized as an aid to further characterization with the following analysis:
Analysis - Calcd. for C40H30S408 (M. Wt. 766.64) Theory: ~ C, 62.66; % H, 3.94; g S, 16.74 Found: % C, 62.66; % H, 3.54; ~ S 16.74 Although the invention has been described in detail in the foregoing for the purpose of illustration, it is to be understood that such detail is solely for that purpose and that variations can be made therein by those skilled in the art without departing from the spirit and scope of the invention except as it may be limited by the claims.
PC-018/Mo-1901
The crude product was crystallized from dimethyl formamide to give white crystals (m.p. 269-272C) and was identified by infrared (IR) and nuclear magnetic resonance (NMR) spectra as 4,4'-bis(4-chlorophenyl sulfonyI)biphenyl.
Analysis - Calcd. for C~4H16S2O4C12 (m. wt. 503.4) Theory: % Cj 57.26; % H, 3.20; % S,12.71; % Cl, 14.11 Found: ~ C, 57.17; % H, 3~18î % S~ 12.55; % Cl, 13~90 Route 2:
To a stirred mixture of biphenyl (30~8 g) and 4-chlorobenzene sulfonyl chloride (95.95 g) (1:2.25 molar ratio) pc-ol8/Mo-l9ol ~3~5 at 70C was added anhydrous ferric chloride (6 g). The temperature was increased to 140C in 1 hr. causing a steady evolution of hydrogen chloride gas. After approximately one hour, the reaction mixture solidified. Heating was continued for another two hours in the solid state. The solid mass was dissolved in dimethyl formamide (DMF) and upon cooling 4,4'-bis~4-chlorophenyl sulfonyl)biphenyl crystallized out. A
second purification from DME led to pale yellow crystalline product (m.p. 269-272C). A ~5% conversion was obtained after purification.
Products obtained by Route l and Route 2 had identical infrared spectrum, even though formation of isomeric products was possible by Route l. As the reaction product separated quite readily from the reaction medium, it can be filtered and purified easily. From this point of view as well as higher conversion, Route l is the preferred method.
Synthesis of bis(4-hydroxyphenyl thiophenyl)biphenyl disulfone ~II) .
To a three-necked 3 liter flask fitted with a stirrer, nitrogen inlet and outlet, a thermometer, a condenser and addition funnel was added 63 g (0.5 mol) of 4-mercaptophenol (available from Crown Zellerback), 76 g (0.55 mol) of anhydrous potassium carbonate (granular) and 750 ml of distilled dimethyl formamide. The mixture was heated to 90C under nitrogen atmosphere. A bright yellow color, due to formation of the thiophenoxy anion was observed around 60-90C. The reaction mixture was stirred at 90C for 2 hrs. and then 126 g (0.25 mol) of bis(4-chlorophenyl sulfonyl)biphenyl dissolved in 300 ml of warm dimethyl formamide was added in 30 min. The intensity of bright yellow color faded slowly as the nucleophilic displace-PC-018/Mo-l901 ~33~ 5 ment of chlorine by the thiophenoxide anion progressed. The reaction mixture was held at 90-100C for 3 hrs. The reaction mixture while hot was filtered to remove potassium salts. The filtrate was diluted with 2 liters of water and then acidified to pH6. The white precipitate was filtered and dried to yield 165 g (97% yield) of crude product. The crude product, on crystallization from glacial acetic acid, gave a white powdery material (m.p. 235-237C) and was identified by infrared and NMR spectra as bis(4-hydroxyphenyl thiophenyl)biphenyl disulfone, Analysis - Calcd. for C36H28S~06 (M.Wt. 682.57) Theory: % C, 63.34; % H, 3.84; % S, 18.75 Found: % C, 63.23, % H, 3.80; % S, 19002 The diacetate of this monomer with m.p. 195C was synthesized as an aid to further characterization with the following analysis:
Analysis - Calcd. for C40H30S408 (M. Wt. 766.64) Theory: ~ C, 62.66; % H, 3.94; g S, 16.74 Found: % C, 62.66; % H, 3.54; ~ S 16.74 Although the invention has been described in detail in the foregoing for the purpose of illustration, it is to be understood that such detail is solely for that purpose and that variations can be made therein by those skilled in the art without departing from the spirit and scope of the invention except as it may be limited by the claims.
PC-018/Mo-1901
Claims (11)
1. A monomer of the structural formula wherein R1, R2, R3, R4, R5 and R6, which may be the same or different, are C1-C4-alkyl, C1 or Br, and n1, n2, n3, n4, n5 and n6, which may be the same or different, are 0, 1 or 2.
2. The monomer of Claim 1 of the structural formula ,
3. A process for the production of the monomer of Claim 2 comprising the synthesis (I) K2CO3/Dimethyl formamide PC-018/Mo-1901 (II).
4. A process for the production of the monomer of Claim 2 comprising (a) reacting monochlorobenzene and 4,4'-biphenyl disulfonyl in the presence of ferric chloride to produce 4,4'-bis(4-chlorophenyl sulfonyl) biphenyl, and (b) reacting the 4,4'-bis(4-chlorophenyl sulfonyl) biphenyl in the presence of 4-mercaptophenol, potassium carbonate and dimethyl formamide to produce said monomer.
5. A polymer selected from the group consisting of polycarbonates, polyurethanes, polyesters, polysulfones and polyethers containing structural units derived from the monomer of Claim 1.
6. The polymer of Claim 5 wherein the polymer is a polycarbonate.
7. The polymer of Claim 5 wherein the polymer is a polyurethane.
8. The polymer of Claim 5 wherein the polymer is a polyester.
9. The polymer of Claim 5 wherein the polymer is a polysulfone.
10. The polymer of Claim 5 wherein the polymer is a polyether.
11. A process for preparing an aromatic polycarbonate comprising reacting the monomer as produced by the process of Claim 4 with a member selected from the group consisting of carbonyl bromide, phosgene, the bis-chloroformic ester of the monomer produced by the process of Claim 4 and diaryl carbonates.
PC-018/Mo-1901
PC-018/Mo-1901
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US94340178A | 1978-09-18 | 1978-09-18 | |
| US943,401 | 1978-09-18 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1133945A true CA1133945A (en) | 1982-10-19 |
Family
ID=25479587
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA331,698A Expired CA1133945A (en) | 1978-09-18 | 1979-07-12 | Bis(4-hydroxyphenyl thiphenyl)biphenyl disulfones |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JPS5540693A (en) |
| CA (1) | CA1133945A (en) |
-
1979
- 1979-07-12 CA CA331,698A patent/CA1133945A/en not_active Expired
- 1979-09-17 JP JP11801579A patent/JPS5540693A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5540693A (en) | 1980-03-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA1133943A (en) | Bis(4-hydroxyphenyl sulfonylphenyl)biphenyl disulfones | |
| JPH0219107B2 (en) | ||
| CA1133945A (en) | Bis(4-hydroxyphenyl thiphenyl)biphenyl disulfones | |
| CA1133942A (en) | Bis(4-hydroxyphenyl sulfonyl)benzenes | |
| JPS61122245A (en) | Production of bisphenol compound | |
| Kobayashi | Organic Sulfur Compounds. III. The Reactions of Toluenesulfinic Acid with Acyl Chlorides | |
| CA1246609A (en) | Process for producing 1-hydroxy ketones | |
| EP0853077B1 (en) | Process for producing alkyl 3-amino-4-substituted benzoates | |
| JPH01265051A (en) | Production of diaryloxyalkane | |
| EP0010595A1 (en) | Bis(4-hydroxyphenylthiophenyl)biphenyldisulphones and bis(4-hydroxyphenyl-sulphonylphenyl)-biphenyldisulphones, their preparation and their use | |
| CN102812001A (en) | Novel diaryl sulfone compound, and manufacturing method for same | |
| US4612385A (en) | Process for the preparation of phenyl N-(2-biphenylylsulfonyl) carbamate | |
| US4558162A (en) | 4,4'-Bis(4-hydroxyphenyl thio)biphenyls | |
| JPS61286346A (en) | Production of 2,2-bis(4'-acryloyloxy-3',5'-dibromophenyl) propane | |
| JPH0368019B2 (en) | ||
| US4929753A (en) | Preparation of trifluoromethylbenzoic acid from hexafluoroxylene | |
| US4943655A (en) | Salt of 5-acetyl-2-alkylbenzenesulfonic acid | |
| JPH0570583A (en) | Production of modified polycarbonate | |
| KR100553246B1 (en) | Solid phase synthesis of aromatic ether derivatives | |
| SU1004401A1 (en) | Process for producing coordination compounds of metal with aromatic diazole | |
| CA1110385A (en) | Polymeric activated esters of 3,4-di-hydroxy-2,5- diphenyl-thiophene-1,1-di-oxide | |
| JPS5813528A (en) | New phenolic compounds and their production method | |
| DE3318356A1 (en) | 4,4'-BIS (4-HYDROXYPHENYLTHIO) BIPHENYLE | |
| SU690007A1 (en) | Method of preparing 4-bromo-1-aminoanthraquinone | |
| JPS61122246A (en) | Production of bisphenol compound |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry |