US4297455A
Expired / Lapsed
US
⏱️ 0.0 years remaining
Process for the preparation of carbonic acid aryl esters of polyester-diols lengthened via carbonate groups and their use for the preparation of polyester-diol bis-diphenol carbonates and polyester/polycarbonates
Assignee: Bayer AG
•
Filing: 1978-05-30
•
Granted: 1981-10-27
•
Expires: 1998-05-30
Abstract
Abstract The present invention relates to a process for the preparation of bis-carbonic acid aryl esters of polyester-diols, lengthened via --OCOO-- groups, characterized in that polyester-diols with molecular weights Mn (number-average) of over 250, preferably over 600, are heated with carbonic acid bis-aryl esters at temperatures between about 100° C. and 200° C., preferably between about 110° C. and 180° C., in vacuo below about 35 mm Hg, preferably between about 25 and 1 mm Hg, in the presence of catalysts, less than one mol of carbonic acid bis-aryl ester being employed per OH group of the polyester-diol and the hydroxyaryl compounds formed being distilled off. The invention further relates to the bis-carbonic acid aryl esters of polyester-diols lengthened via --OCOO-- groups obtained according to the instant invention and their use for the preparation of polyester diol bis-diphenol carbonates, lengthened via carbonate groups, characterized in that polyester-diol bis-aryl carbonates are reacted with a diphenol at a temperature of from about 100° to about 200° C. in vacuo below about 35 mm Hg in the presence of a catalyst, wherein more than 1 mol of diphenol is employed per mol of carbonic acid aryl ester groups of the polyester-diol bis-aryl carbonate, lengthened via carbonate groups, and the resulting hydroxyaryl compound is distilled off. The invention finally relates to the polyester-diol bis-diphenol carbonates, lengthened via carbonate groups obtained according to the instant invention and their use for the preparation of polyester/polycarbonates and the polycarbonate/polyesters so prepared.
Inventors
- 👤 Christian Lindner
- 👤 Carlhans Suling
- 👤 Herbert Bartl
- 👤 Manfred Schreckenberg
- 👤 Dieter Freitag
- 👤 Klaus Konig
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-29 12:21
CPC Classifications
C; C08; C08G; C08G63/00; C08G63/64
Claims Analysis
Total Claims: 54
Claim 1
Independent Claim
159 words
A process for the preparation of a polyesterdiol bis-diphenol carbonate, lengthened via carbonate groups, comprising: (i) heating a polyester-diol having a molecular weight Mn (number-averrage) of over 250 with a carbonic acid bis-aryl ester (a) at a temperature between about 100° C. and about 200° C., (b) in vacuo below about 35 mm Hg, and (c) in the presence of a catalyst, characterized in that less than 1 mol of carbonic acid bis-aryl ester is employed per mol of OH-groups of the polyester diol, and (ii) heating the resulting polyester-diol bis-carbonic acid aryl ester, lengthened via carbonate groups, with a diphenol (a) at a temperature between about 100° C. and about 200° C., (b) in vacuo below about 35 mm Hg, and (c) in the presence of a catalyst, characterized in that more then 1 mol of diphenol is employed per mol of carbonic acid aryl ester groups of the polyester-diol bis-carbonic acid aryl ester, lengthened via carbonate groups.
Claim 2
Dependent Claim
159 words
A process for the preparation of a polyesterdiol bis-diphenol carbonate, lengthened via carbonate groups, comprising: (i) heating a polyester-diol having a molecular weight Mn (number-averrage) of over 250 with a carbonic acid bis-aryl ester (a) at a temperature between about 100° C. and about 200° C., (b) in vacuo below about 35 mm Hg, and (c) in the presence of a catalyst, characterized in that less than 1 mol of carbonic acid bis-aryl ester is employed per mol of OH-groups of the polyester diol, and (ii) heating the resulting polyester-diol bis-carbonic acid aryl ester, lengthened via carbonate groups, with a diphenol (a) at a temperature between about 100° C. and about 200° C., (b) in vacuo below about 35 mm Hg, and (c) in the presence of a catalyst, characterized in that more then 1 mol of diphenol is employed per mol of carbonic acid aryl ester groups of the polyester-diol bis-carbonic acid aryl ester, lengthened via carbonate groups.
Claim 3
Dependent Claim
31 words
The process according to claim 1 wherein the resulting polyester diol bis-carbonic acid aryl ester, lengthened via carbonate groups, together with excess carbonic acid bis-aryl ester, are reacted with a diphenol.
Claim 4
Dependent Claim
128 words
A process for the preparation of a polyester-diol bis-diphenol carbonate, lengthened via carbonate groups, comprising (i) heating a compound of the general formula ##STR14## wherein Ar is a substituted or unsubstituted aryl radical having 6 to 18 carbon atoms, "-(polyester)-" is a bivalent radical of a polyester-diol having a molecular weight Mn greater than 250, and n is an integer from 2 to 20, with a diphenol at a temperature between about 100° C. and about 200° C. in vacuo below about 35 mm Hg in the presence of a catalyst, characterized in that more than 1 mol of diphenol is employed per mol of carbonic acid aryl ester groups of the polyester-diol bis-carbonic acid aryl ester, lengthened via carbonate groups, and (ii) distilling-off the resulting hydroxyaryl compound.
Claim 5
Dependent Claim
128 words
A process for the preparation of a polyester-diol bis-diphenol carbonate, lengthened via carbonate groups, comprising (i) heating a compound of the general formula ##STR14## wherein Ar is a substituted or unsubstituted aryl radical having 6 to 18 carbon atoms, "-(polyester)-" is a bivalent radical of a polyester-diol having a molecular weight Mn greater than 250, and n is an integer from 2 to 20, with a diphenol at a temperature between about 100° C. and about 200° C. in vacuo below about 35 mm Hg in the presence of a catalyst, characterized in that more than 1 mol of diphenol is employed per mol of carbonic acid aryl ester groups of the polyester-diol bis-carbonic acid aryl ester, lengthened via carbonate groups, and (ii) distilling-off the resulting hydroxyaryl compound.
Claim 6
Dependent Claim
18 words
The process according to either claim 1 or 3 when carried out in the absence of a solvent.
Claim 7
Dependent Claim
19 words
The process according to either claim 1 or 3 when carried out in the presence of an inert solvent.
Claim 8
Dependent Claim
70 words
The process according to either claim 1 or 3 wherein a polyester-diol bis-carbonic acid aryl ester, lengthened via carbonate groups, is reacted with bisphenol-A (a) in a molar ratio of biscarbonic acid monoaryl ester to bisphenol-A of about 1:3, (b) in the presence of the disodium phenolate of bisphenol-A as the catalyst, (c) at a temperature of about 150°, (d) in vacuo between about 25 mm and 0.1 mm Hg.
Claim 9
Dependent Claim
18 words
A polyester-diol-bis-diphenol carbonate, lengthened via carbonate groups, prepared by the process according to either claim 1 or 3.
Claim 10
Dependent Claim
27 words
The process of claim 1, wherein the polyester-diol is the reaction product of adipic acid and a mixture of n-hexane-1,6-diol and neopentylglycol and the diphenol is 2,2-bis-(4-hydroxyphenol)-propane.
Claim 11
Dependent Claim
127 words
A process for the preparation of a polyester/polycarbonate, comprising reacting a polyester-diol bis-diphenol carbonate prepared by the process according to Claim 1 with a diphenol, chain stoppers and phosgene in a liquid mixture comprising an inert organic solvent and an alkaline aqueous solution, at a temperature of between about 0° C. and 80° C. at a pH value between about 9 and 14, wherein after the addition of phosgene, polycondensation is carried out by adding from about 0.2 mol % to about 10 mol %, relative to the molar amount of diphenol, of a tertiary amine, the weight ratio of polyester-diol bis-diphenol carbonate, lengthened via carbonate groups, to the diphenol being determined by the desired proportion of polycarbonate and the proportion of polyester in the resulting polyester/polycarbonate.
Claim 12
Dependent Claim
41 words
The process according to claim 9, wherein the diphenol has the general formula ##STR15## wherein x denotes--Ch 2 --, ##STR16## X O, S or SO 2 and Y 1 to Y 4 are identical or different and denote hydrogen or halogen.
Claim 13
Dependent Claim
22 words
The process according to claim 9, wherein the tertiary amine has from about 3 to about 15 C atoms per amine molecule.
Claim 14
Dependent Claim
26 words
The process according to claim 9, wherein between about 0.05 and about 2 mol % of trifunctional or more than trifunctional phenolic hydroxy compounds are employed.
Claim 15
Dependent Claim
10 words
A polyester/polycarbonate prepared by the process according to claim 9.
Claim 16
Dependent Claim
14 words
The process according to claim 9 wherein said chain stoppers are polyester-monool mono-diphenol carbonates.
Claim 17
Dependent Claim
28 words
The process according to claim 9, wherein the polyester/polycarbonates are subjected to gelling, shearing or heat treatment in the course of isolation whereby the recovered polymer is multi-phase.
Claim 18
Dependent Claim
95 words
A polyester/polycarbonate the molecular chain of which is terminated by residues of chain stoppers comprising from about 30 to about 95% by weight of aromatic polycarbonate structural units of the formula ##STR17## wherein X denotes ##STR18## O, S or SO 2 and Y 1 to Y 4 are identical or different and denote hydrogen or halogen and from about 70 to about 5% by weight of polyester-diolate block units, lengthened via carbonate groups, of the simplified formula ##STR19## wherein -(polyester)-represents the bivalent radical of a polyester-diol, and n denotes an integer from 2 to 20.
Claim 19
Dependent Claim
95 words
A polyester/polycarbonate the molecular chain of which is terminated by residues of chain stoppers comprising from about 30 to about 95% by weight of aromatic polycarbonate structural units of the formula ##STR17## wherein X denotes ##STR18## O, S or SO 2 and Y 1 to Y 4 are identical or different and denote hydrogen or halogen and from about 70 to about 5% by weight of polyester-diolate block units, lengthened via carbonate groups, of the simplified formula ##STR19## wherein -(polyester)-represents the bivalent radical of a polyester-diol, and n denotes an integer from 2 to 20.
Claim 20
Dependent Claim
45 words
The process according to either claim 1 or 3 wherein the diphenol has the general formula ##STR20## wherein X denotes --CH 2 --, ##STR21## O, S or SO 2 , and Y 1 to Y 4 are identical or different and denote hydrogen or halogen.
Claim 21
Dependent Claim
17 words
The process according to claim 3, wherein the molecular weight of the polyester diol is over 600.
Claim 22
Dependent Claim
18 words
The process according to claim 3, wherein the reaction temperature is between about 110° C. and 180° C.
Claim 23
Dependent Claim
18 words
The process according to claim 3, wherein the pressure is between about 25 mm and 1 mm Hg.
Claim 24
Dependent Claim
32 words
The process according to claim 3, wherein the amount of diphenol is between about 1.1 and about 2 mols per carbonic acid aryl ester group of the polyester-diol biscarbonic acid aryl ester.
Claim 25
Dependent Claim
52 words
A polyester-diol bis-diphenol carbonate of the formula ##STR22## wherein -(polyester)- represents the bivalent radical of a polyester-diol, n denotes an integer from 2 to 20, X denotes --CH 2 --, ##STR23## O, S or SO 2 , and Y 1 to Y 4 are identical or different and denote hydrogen or halogen.
Claim 26
Dependent Claim
52 words
A polyester-diol bis-diphenol carbonate of the formula ##STR22## wherein -(polyester)- represents the bivalent radical of a polyester-diol, n denotes an integer from 2 to 20, X denotes --CH 2 --, ##STR23## O, S or SO 2 , and Y 1 to Y 4 are identical or different and denote hydrogen or halogen.
Claim 27
Dependent Claim
26 words
A polyester-diol bis-diphenol carbonate of the formula ##STR24## wherein -(polyester)- represents the bivalent radical of a polyester-diol, and n denotes an integer from 2 to 20.
Claim 28
Dependent Claim
26 words
A polyester-diol bis-diphenol carbonate of the formula ##STR24## wherein -(polyester)- represents the bivalent radical of a polyester-diol, and n denotes an integer from 2 to 20.
Claim 29
Dependent Claim
26 words
A polyester-diol bis-diphenol carbonate of the formula ##STR25## wherein -(polyester)- represents the bivalent radical of a polyester-diol, and n denotes an integer from 2 to 20.
Claim 30
Dependent Claim
26 words
A polyester-diol bis-diphenol carbonate of the formula ##STR25## wherein -(polyester)- represents the bivalent radical of a polyester-diol, and n denotes an integer from 2 to 20.
Claim 31
Dependent Claim
26 words
A polyester-diol bis-diphenol carbonate of the formula ##STR26## wherein -(polyester)- represents the bivalents radical of a polyester-diol, and n denotes an integer from 2 to 20.
Claim 32
Dependent Claim
26 words
A polyester-diol bis-diphenol carbonate of the formula ##STR26## wherein -(polyester)- represents the bivalents radical of a polyester-diol, and n denotes an integer from 2 to 20.
Claim 33
Dependent Claim
26 words
A polyester-diol bis-diphenol carbonate of the formula ##STR27## wherein -(polyester)- represents the bivalent radical of a polyester-diol, and n denotes an integer from 2 to 20.
Claim 34
Dependent Claim
26 words
A polyester-diol bis-diphenol carbonate of the formula ##STR27## wherein -(polyester)- represents the bivalent radical of a polyester-diol, and n denotes an integer from 2 to 20.
Claim 35
Dependent Claim
27 words
A polyester-diol bis-diphenol carbonate of the formula ##STR28## wherein -(polyester)- represents the bivalent radical of a polyester-diol and n denotes an integer from about 2 to 20.
Claim 36
Dependent Claim
27 words
A polyester-diol bis-diphenol carbonate of the formula ##STR28## wherein -(polyester)- represents the bivalent radical of a polyester-diol and n denotes an integer from about 2 to 20.
Claim 37
Dependent Claim
26 words
A polyester-diol bis-diphenol carbonate of the formula ##STR29## wherein -(polyester)- represents the bivalent radical of a polyester-diol, and n denotes an integer from 2 to 20.
Claim 38
Dependent Claim
26 words
A polyester-diol bis-diphenol carbonate of the formula ##STR29## wherein -(polyester)- represents the bivalent radical of a polyester-diol, and n denotes an integer from 2 to 20.
Claim 39
Dependent Claim
26 words
A polyester-diol bis-diphenol carbonate of the formula ##STR30## wherein -(polyester)- represents the bivalent radical of a polyester-diol, and n denotes an integer from 2 to 20.
Claim 40
Dependent Claim
26 words
A polyester-diol bis-diphenol carbonate of the formula ##STR30## wherein -(polyester)- represents the bivalent radical of a polyester-diol, and n denotes an integer from 2 to 20.
Claim 41
Dependent Claim
27 words
The polyester-diol bis-diphenol carbonate of claim 29, wherein "-(polyester)-" represents the bivalent radical of a polyester-diol obtained from adipic acid and a mixture of n-hexane-1,6-diol and neopentylglycol.
Claim 42
Dependent Claim
26 words
A polyester-diol bis-diphenol carbonate of the formula ##STR31## wherein -(polyester)- represents the bivalent radical of a polyester-diol, and n denotes an integer from 2 to 20.
Claim 43
Dependent Claim
26 words
A polyester-diol bis-diphenol carbonate of the formula ##STR31## wherein -(polyester)- represents the bivalent radical of a polyester-diol, and n denotes an integer from 2 to 20.
Claim 44
Dependent Claim
45 words
A polyester/polycarbonate according to claim 16 comprising from about 35 to about 80% by weight of structural units of the formula IIIa and from about 65 to about 20% by weight of the polyester-diolate block units, lengthened via carbonate groups, of the simplified formula VI.
Claim 45
Dependent Claim
28 words
The polyester/polycarbonate according to either claim 16 or 32, wherein the average molecular weight M w (weight-average) of the resultant polyester/polycarbonate is between about 25,000 and about 250,000.
Claim 46
Dependent Claim
26 words
The polyester/polycarbonate according to claim 16 wherein the aromatic polycarbonate structural units have the formula ##STR32## wherein Y is H, Cl, Br or CH 3 .
Claim 47
Dependent Claim
50 words
A process for the thermoplastic processing of a polyester/polycarbonate according to either claim 13, 16 or 32, wherein the thermoplastic processing is carried out below or in the region of the crystallite melting point of the crystalline portion of polycarbonate at a temperature between about 130° and about 250° C.
Claim 48
Dependent Claim
9 words
Articles made by the process according to claim 35.
Claim 49
Dependent Claim
37 words
The process of claim 9, wherein a polyester-diol bis-diphenol carbonate of the formula IV(g) ##STR33## wherein "-(polyester)-" represents the bivalent radical of a polyester-diol obtained from adipic acid and a mixture of n-hexane-1,6-diol and neopentylglycol is employed.
Claim 50
Dependent Claim
35 words
The process of claim 3, wherein the "-(polyester)-" of the formula II is the bivalent radical of a polyester-diol obtained from adipic acid and a mixture of n-hexane-1,6-diol and neopentylglycol and the diphenol is 2,2-bis-(4-hydroxyphenol)-propane.
Claim 51
Dependent Claim
44 words
The polyester/polycarbonate according to claim 16, wherein "-(polyester)-" of the formula VI represents the bivalent radical of a polyester-diol obtained from adipic acid and a mixture of n-hexane-1,6-diol and neopentylglycol and in the formula III(a) ##STR34## and Y 1 to Y 4 are hydrogen.
Claim 52
Dependent Claim
12 words
The polyester/polycarbonate of claim 16 wherein said chain stoppers are monofunctional phenols.
Claim 53
Dependent Claim
13 words
The polyester/polycarbonate of claim 16 wherein said chain stoppers are polyester-monool mono-diphenol carbonates.
Claim 54
Dependent Claim
13 words
The process according to claim 9 wherein said chain stoppers are monofunctional phenols.
References Cited (Backward Citations)
US3161615A
Cited
US3169121A
Cited
US3030331A
Cited
US3220976A
Cited
GB898775A
Cited
US3030335A
Cited
GB965085A
Cited
US3553167A
Cited
GB954500A
Cited
US3207814A
Cited
US3290409A
Cited
US3287442A
Cited
GB1139413A
Cited
US3449467A
Cited
US3441141A
Cited
US3461187A
Cited
US3549682A
Cited
GB1190303A
Cited
US3843708A
Cited
US3641200A
Cited
US3549570A
Cited
GB1270077A
Cited
DE1964998C3
Cited
US3714125A
Cited
US3843752A
Cited
GB1422676A
Cited
FR2235965B1
Cited
US3998908A
Cited
US4137221A
Cited
US4191705A
Cited
US4216298A
Cited
US4217297A
Cited
US4105633A
Cited
US4255555A
Cited
USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1984-10-26 | 1985-04-27 | 1985-10-27 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1988-10-26 | 1989-04-27 | 1989-10-27 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1992-10-26 | 1993-04-27 | 1993-10-27 | $7700.00 | Window Closed / Lapsed |