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US4194038A Expired / Lapsed US ⏱️ 0.0 years remaining

Poly(ester-carbonates) from dicarboxylic acid chlorides

Assignee: Honeywell International Inc
•
Filing: 1979-01-25
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Granted: 1980-03-18
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Expires: 1999-01-25
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Abstract

Abstract A process for poly(ester-carbonates) from dihydric phenols, especially bisphenol A; aromatic or cycloaliphatic dicarboxylic acids, especially terephthalic acid; and phosgene as carbonate precursor wherein a reaction of the acid and phosgene is carried out in a first stage forming dicarboxylic acid chloride; and then phosgene and bisphenol A are added in separate streams, simultaneously during most of the second or condensation stage. Thereby only one kettle is required for carrying out the complete polymer production.

Inventors

  • 👤 Josefina T. Baker
  • 👤 Robert S. Cooke
  • 👤 Stylianos Sifniades

Bibliographic Details

Application Number —
Jurisdiction US
Data Source google_patents
Last Synchronized 2026-10-29 17:05
CPC Classifications
C; C08; C08G; C08G63/00; C08G63/64

Claims Analysis

Total Claims: 6
Claim 1
Independent Claim 290 words
In a process for production of poly(ester-carbonate) of dihydric phenol and of aromatic or cycloaliphatic dicarboxylic acid from a reaction mixture containing dichloride of at least one such acid, dissolved in a chlorinated hydrocarbon solvent inert under the reaction conditions having from 1 to 6 carbon atoms and from 1 to 4 chlorine atoms, said process employing a tertiary nitrogen base, having pK b in aqueous solution at 25° C. in the range 7-11, to catalyze condensation of such dihydric phenol with said dichloride and with phosgene employed as carbonate precursor, and to serve as HCl acceptor for the HCl generated in said condensation reactions; the improvement which comprises: (1) Feeding at least one such dihydric phenol into said dichloride solution at temperature in the range 0°-100° C., said dichloride solution containing at the start of said condensation reaction, phosgene in the range between 10% and 50% of the stoichiometric proportion of phosgene: total dihydric phenol required for formation of the poly(ester-carbonate) final product with the desired mol ratio in the range 1.00:0.05 up to 1.00:0.70 of dihydric phenol:dichloride residues; (2) Concurrently with the feeding of dihydric phenol, agitating the reaction mixture and feeding phosgene in a separate stream thereto, until all dihydric phenol for the reaction has been added and at least 80% but not over 97% of the stoichiometrically required phosgene for reaction with all hydroxyl groups has been added; (3) Maintaining during the feeding of dihydric phenol, at least a 10% molar excess of tertiary nitrogen base over that required by stoichiometry; (4) Then allowing time for the condensation reaction forming poly(ester-carbonate) to come essentially to completion while the phosgene added is being brought at least to the stoichiometrically required quantity for reaction with all hydroxyl groups.
Claim 2
Dependent Claim 290 words
In a process for production of poly(ester-carbonate) of dihydric phenol and of aromatic or cycloaliphatic dicarboxylic acid from a reaction mixture containing dichloride of at least one such acid, dissolved in a chlorinated hydrocarbon solvent inert under the reaction conditions having from 1 to 6 carbon atoms and from 1 to 4 chlorine atoms, said process employing a tertiary nitrogen base, having pK b in aqueous solution at 25° C. in the range 7-11, to catalyze condensation of such dihydric phenol with said dichloride and with phosgene employed as carbonate precursor, and to serve as HCl acceptor for the HCl generated in said condensation reactions; the improvement which comprises: (1) Feeding at least one such dihydric phenol into said dichloride solution at temperature in the range 0°-100° C., said dichloride solution containing at the start of said condensation reaction, phosgene in the range between 10% and 50% of the stoichiometric proportion of phosgene: total dihydric phenol required for formation of the poly(ester-carbonate) final product with the desired mol ratio in the range 1.00:0.05 up to 1.00:0.70 of dihydric phenol:dichloride residues; (2) Concurrently with the feeding of dihydric phenol, agitating the reaction mixture and feeding phosgene in a separate stream thereto, until all dihydric phenol for the reaction has been added and at least 80% but not over 97% of the stoichiometrically required phosgene for reaction with all hydroxyl groups has been added; (3) Maintaining during the feeding of dihydric phenol, at least a 10% molar excess of tertiary nitrogen base over that required by stoichiometry; (4) Then allowing time for the condensation reaction forming poly(ester-carbonate) to come essentially to completion while the phosgene added is being brought at least to the stoichiometrically required quantity for reaction with all hydroxyl groups.
Claim 3
Dependent Claim 45 words
In the process of claim 1: employing, as the principal dihydric phenol, bisphenol A, and as the principal dicarboxylic acid, terephthalic acid; and employing as tertiary nitrogen base, one having pK b in aqueous solution at 25° C. in the range between 7 and 9.
Claim 4
Dependent Claim 139 words
In the process of claim 2: employing dichloromethane as the inert solvent and pyridine as the tertiary nitrogen base; providing in the terephthaloyl chloride solution at the start of the condensation reaction between phenolic hydroxyl groups and phosgene, a quantity of phosgene in the range between 20% and 40% of the stoichiometric proportion of phosgene:total bisphenol A required for formation of the poly(ester-carbonate) final product having mol ratio of bisphenol A:terephthalate:carbonate residues of 1.0:0.5:0.5; feeding bisphenol A to the terephthaloyl chloride solution in total molar proportion of about 1:0.5 of bisphenol A:terephthaloyl chloride and feeding phosgene thereto in at least the stoichiometric quantity to produce said final product; maintaining temperatures between 15° and 50° C. and maintaining an excess of base in the reaction mixture of at least 30% over that required to react with hydrogen chloride being formed.
Claim 5
Dependent Claim 22 words
In the process of claim 1: employing as the principal dihydric phenol, bisphenol A and as the principal dicarboxylic acid, isophthalic acid.
Claim 6
Dependent Claim 22 words
In the process of claim 1: employing as the principal dihydric phenol, bisphenol A and as the principal dicarboxylic acid, cyclohexane-1,4-dicarboxylic acid.

References Cited (Backward Citations)

US3169121A Cited
US3313862A Cited
US4127561A Cited

USPTO Annuity & Maintenance Windows

Annuity Stage Window Opens Payment Deadline Surcharge Period Until Estimated Fee Status
3.5 Years (Year 4) 1983-03-18 1983-09-17 1984-03-18 $2000.00 Window Closed / Lapsed
7.5 Years (Year 8) 1987-03-18 1987-09-17 1988-03-18 $3760.00 Window Closed / Lapsed
11.5 Years (Year 12) 1991-03-18 1991-09-17 1992-03-18 $7700.00 Window Closed / Lapsed

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