US4319017A
Expired / Lapsed
US
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Semi or fully continuous process for polyester of bisphenol and dicarboxylic acid by transesterification polymerization and product thereof
Assignee: Celanese Corp
•
Filing: 1980-03-10
•
Granted: 1982-03-09
•
Expires: 2000-03-10
Abstract
Abstract Linear aromatic polyesters of bisphenols and dicarboxylic compounds are prepared by transesterification polymerization in either a fully continuous process or in a semi-continuous process wherein a first stage is conducted batchwise and a second stage is conducted in a continuous manner wherein the second stage employs a wiped film reactor. The processes are preferably conducted in the presence of a catalyst in liquid form, and further under conditions wherein the catalyst is introduced to the polymerization concurrent with the introduction of liquid phase reactants to avoid substantial heating of the reactants in contact with the catalyst prior to onset of the transesterification reaction. The products of the processes have an unexpectedly low polydispersity.
Inventors
- 👤 George M. Kosanovich
- 👤 Gideon Salee
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-08 03:34
CPC Classifications
C; C08; C08G; C08G63/00; C08G63/02; C08G63/12; C08G63/16; C08G63/18; C08G63/19; C08G63/78
Claims Analysis
Total Claims: 86
Claim 1
Independent Claim
135 words
In the process of preparing a linear aromatic polyester by transesterification melt polymerization of monomer reactants consisting essentially of a bisphenol and a diaryl ester of a dicarboxylic acid in a polymerization reaction zone which comprises reacting said bisphenol and said diaryl ester in a first reaction stage of said zone to prepare a polyester oligomer, and thereafter continuing the reaction in a second reaction stage of said zone to produce the polyester product, the improvement wherein the polymerization is carried out in the first reaction stage either batchwise or substantially continuously, and the polymerization is continued in the second reaction stage substantially continuously, with the provision that when the polymerization in the first reaction stage is carried out batchwise, the polymerization in the second stage is carried out in a wiped film reaction zone.
Claim 2
Dependent Claim
135 words
In the process of preparing a linear aromatic polyester by transesterification melt polymerization of monomer reactants consisting essentially of a bisphenol and a diaryl ester of a dicarboxylic acid in a polymerization reaction zone which comprises reacting said bisphenol and said diaryl ester in a first reaction stage of said zone to prepare a polyester oligomer, and thereafter continuing the reaction in a second reaction stage of said zone to produce the polyester product, the improvement wherein the polymerization is carried out in the first reaction stage either batchwise or substantially continuously, and the polymerization is continued in the second reaction stage substantially continuously, with the provision that when the polymerization in the first reaction stage is carried out batchwise, the polymerization in the second stage is carried out in a wiped film reaction zone.
Claim 3
Dependent Claim
34 words
The process of claim 1 wherein the polymerization is conducted in the presence of a catalyst that is normally solid at 30° C. but which is introduced to the polymerization process in liquid form.
Claim 4
Dependent Claim
28 words
The process of claims 1 or 2 wherein the wiped film reaction zone provides for countercurrent flow of the reaction mixture and the vapor by-product of the reaction.
Claim 5
Dependent Claim
13 words
The process of claims 1 or 2 wherein the bisphenol is bisphenol A.
Claim 6
Dependent Claim
20 words
The process of claims 1 or 2 wherein the diaryl ester is diphenyl isophthalate, diphenyl terephthalate or a mixture thereof.
Claim 7
Dependent Claim
32 words
The process of claims 1 or 2 wherein the liquid catalyst is a normally solid material in molten form or a normally solid material in solution in a solvent for the catalyst.
Claim 8
Dependent Claim
18 words
The process of claim 6 wherein the liquid catalyst is a solution of a metal phenoxide in phenol.
Claim 9
Dependent Claim
12 words
The process of claim 7 wherein the metal phenoxide is potassium phenoxide.
Claim 10
Dependent Claim
12 words
The process of claim 7 wherein the metal phenoxide is rubidium phenoxide.
Claim 11
Dependent Claim
12 words
The process of claim 7 wherein the metal phenoxide is lithium phenoxide.
Claim 12
Dependent Claim
12 words
The process of claim 7 wherein the metal phenoxide is sodium phenoxide.
Claim 13
Dependent Claim
18 words
The process of claim 6 wherein the liquid catalyst is the reaction product of potassium borohydride and phenol.
Claim 14
Dependent Claim
59 words
In the process of preparing a linear aromatic polyester by transesterification melt polymerization of monomer reactants consisting essentially of a bisphenol and a diaryl ester of a dicarboxylic acid in a polymerization reaction zone, the improvement which comprises introducing said reactants substantially continuously to said polymerization reaction zone, and withdrawing said polyester product substantially continuously from the polymerization zone.
Claim 15
Dependent Claim
59 words
In the process of preparing a linear aromatic polyester by transesterification melt polymerization of monomer reactants consisting essentially of a bisphenol and a diaryl ester of a dicarboxylic acid in a polymerization reaction zone, the improvement which comprises introducing said reactants substantially continuously to said polymerization reaction zone, and withdrawing said polyester product substantially continuously from the polymerization zone.
Claim 16
Dependent Claim
11 words
The process of claim 13 wherein the bisphenol is bisphenol A.
Claim 17
Dependent Claim
18 words
The process of claim 13 wherein the diaryl ester is diphenyl isophthalate, diphenyl terephthalate or a mixture thereof.
Claim 18
Dependent Claim
84 words
In the process of preparing a linear aromatic polyester by transesterification melt polymerization of monomer reactants consisting essentially of a bisphenol and a diaryl ester of a dicarboxylic acid in the presence of a basic catalyst for the polymerization in a polymerization reaction zone, the improvement which comprises introducing said monomer reactants and a basic catalyst that is normally solid at 30° C., in liquid form substantially continuously to said polymerization reaction zone, and withdrawing the polyester product substantially continuously from the polymerization zone.
Claim 19
Dependent Claim
84 words
In the process of preparing a linear aromatic polyester by transesterification melt polymerization of monomer reactants consisting essentially of a bisphenol and a diaryl ester of a dicarboxylic acid in the presence of a basic catalyst for the polymerization in a polymerization reaction zone, the improvement which comprises introducing said monomer reactants and a basic catalyst that is normally solid at 30° C., in liquid form substantially continuously to said polymerization reaction zone, and withdrawing the polyester product substantially continuously from the polymerization zone.
Claim 20
Dependent Claim
11 words
The process of claim 16 wherein the bisphenol is bisphenol A.
Claim 21
Dependent Claim
18 words
The process of claim 16 wherein the diaryl ester is diphenyl isophthalate, diphenyl terephthalate or a mixture thereof.
Claim 22
Dependent Claim
30 words
The process of claim 16 wherein the liquid catalyst is a normally solid material in molten form or a normally solid material in solution in a solvent for the catalyst.
Claim 23
Dependent Claim
18 words
The process of claim 19 wherein the liquid catalyst is a solution of a metal phenoxide in phenol.
Claim 24
Dependent Claim
12 words
The process of claim 20 wherein the metal phenoxide is potassium phenoxide.
Claim 25
Dependent Claim
12 words
The process of claim 20 wherein the metal phenoxide is rubidium phenoxide.
Claim 26
Dependent Claim
12 words
The process of claim 20 wherein the metal phenoxide is lithium phenoxide.
Claim 27
Dependent Claim
12 words
The process of claim 20 wherein the metal phenoxide is sodium phenoxide.
Claim 28
Dependent Claim
18 words
The process of claim 19 wherein the liquid catalyst is the reaction product of potassium borohydride and phenol.
Claim 29
Dependent Claim
70 words
In the process of preparing a linear aromatic polyester by transesterification melt polymerization of monomer reactants consisting essentially of a bisphenol and a diaryl ester of a dicarboxylic acid in a polymerization zone, said zone comprising a series of at least two reaction stages, the improvement which comprises carrying out the polymerization reaction continuously in a film reactor in the final polymerization reaction stage, in a wiped film reaction zone.
Claim 30
Dependent Claim
70 words
In the process of preparing a linear aromatic polyester by transesterification melt polymerization of monomer reactants consisting essentially of a bisphenol and a diaryl ester of a dicarboxylic acid in a polymerization zone, said zone comprising a series of at least two reaction stages, the improvement which comprises carrying out the polymerization reaction continuously in a film reactor in the final polymerization reaction stage, in a wiped film reaction zone.
Claim 31
Dependent Claim
26 words
The process of claim 26 wherein the wiped film reaction zone provides for countercurrent flow of the reaction mixture and the vapor by-product of the reaction.
Claim 32
Dependent Claim
11 words
The process of claim 26 wherein the bisphenol is bisphenol A.
Claim 33
Dependent Claim
18 words
The process of claim 26 wherein the diaryl ester is diphenyl isophthalate, diphenyl terephthalate or a mixture thereof.
Claim 34
Dependent Claim
104 words
In the process of preparing a linear aromatic polyester by transesterification melt polymerization of monomer reactants consisting essentially of a bisphenol and a diaryl ester of a dicarboxylic acid in the presence of a basic catalyst for the polymerization reaction, the improvement which comprises introducing a basic catalyst that is normally solid at 30° C., to the polymerization reaction in liquid form, said polymerization reaction being carried out in a polymerization zone which comprises a series of at least two reaction stages wherein the polymerization reaction in the final reaction stage of said series is carried out continuously in a wiped film reaction zone.
Claim 35
Dependent Claim
104 words
In the process of preparing a linear aromatic polyester by transesterification melt polymerization of monomer reactants consisting essentially of a bisphenol and a diaryl ester of a dicarboxylic acid in the presence of a basic catalyst for the polymerization reaction, the improvement which comprises introducing a basic catalyst that is normally solid at 30° C., to the polymerization reaction in liquid form, said polymerization reaction being carried out in a polymerization zone which comprises a series of at least two reaction stages wherein the polymerization reaction in the final reaction stage of said series is carried out continuously in a wiped film reaction zone.
Claim 36
Dependent Claim
25 words
The process of claim 30 wherein the wiped film reaction zone provides for countercurrent flow of the reaction mixture and thevapor by-product of the reaction.
Claim 37
Dependent Claim
11 words
The process of claim 30 wherein the bisphenol is bisphenol A.
Claim 38
Dependent Claim
18 words
The process of claim 30 wherein the diaryl ester is diphenyl isophthalate, diphenyl terephthalate or a mixture thereof.
Claim 39
Dependent Claim
30 words
The process of claim 30 wherein the liquid catalyst is a normally solid material in molten form or a normally solid material in solution in a solvent for the catalyst.
Claim 40
Dependent Claim
18 words
The process of claim 30 wherein the liquid catalyst is a solution of a metal phenoxide in phenol.
Claim 41
Dependent Claim
12 words
The process of claim 35 wherein the metal phenoxide is potassium phenoxide.
Claim 42
Dependent Claim
12 words
The process of claim 35 wherein the metal phenoxide is rubidium phenoxide.
Claim 43
Dependent Claim
12 words
The process of claim 35 wherein the metal phenoxide is lithium phenoxide.
Claim 44
Dependent Claim
12 words
The process of claim 35 wherein the metal phenoxide is sodium phenoxide.
Claim 45
Dependent Claim
18 words
The process of claim 34 wherein the liquid catalyst is the reaction product of potassium borohydride and phenol.
Claim 46
Dependent Claim
109 words
In the process of preparing a linear aromatic polyester by transesterification melt polymerization of monomer reactants consisting essentially of a bisphenol and a diaryl ester of a dicarboxylic acid in the presence of a basic catalyst for said polymerization wherein said reactants are introduced to the polymerization reaction in the liquid state, the improvement which comprises introducing a basic catalyst that is normally solid at 30° C., in liquid form to the polymerization reaction substantially concurrently with introduction of the liquid state reactants to the polymerization, and introducing the catalyst and reactants to the polymerization reaction substantially continuously and withdrawing the polyester product from the polymerization reaction substantially continuously.
Claim 47
Dependent Claim
109 words
In the process of preparing a linear aromatic polyester by transesterification melt polymerization of monomer reactants consisting essentially of a bisphenol and a diaryl ester of a dicarboxylic acid in the presence of a basic catalyst for said polymerization wherein said reactants are introduced to the polymerization reaction in the liquid state, the improvement which comprises introducing a basic catalyst that is normally solid at 30° C., in liquid form to the polymerization reaction substantially concurrently with introduction of the liquid state reactants to the polymerization, and introducing the catalyst and reactants to the polymerization reaction substantially continuously and withdrawing the polyester product from the polymerization reaction substantially continuously.
Claim 48
Dependent Claim
18 words
The process of claim 41 wherein at least one reactant is melted prior to mixing with the catalyst.
Claim 49
Dependent Claim
128 words
In the process of preparing a linear aromatic polyester by transesterification melt polymerization of monomer reactants consisting essentially of a bisphenol and a diaryl ester of a dicarboxylic acid in the presence of a basic catalyst for said polymerization wherein said reactants are introduced to the polymerization reaction in the liquid state, the improvement which comprises introducing a basic catalyst that is normally solid at 30° C., in liquid form to the polymerization reaction substantially concurrently with introduction of the liquid state reactants to the polymerization, wherein the polymerization reaction is carried out in a polymerization zone which comprises a series of at least two reaction stages wherein the polymerization reaction in the final stage of the series is carried out continuously in a wiped film reaction zone.
Claim 50
Dependent Claim
128 words
In the process of preparing a linear aromatic polyester by transesterification melt polymerization of monomer reactants consisting essentially of a bisphenol and a diaryl ester of a dicarboxylic acid in the presence of a basic catalyst for said polymerization wherein said reactants are introduced to the polymerization reaction in the liquid state, the improvement which comprises introducing a basic catalyst that is normally solid at 30° C., in liquid form to the polymerization reaction substantially concurrently with introduction of the liquid state reactants to the polymerization, wherein the polymerization reaction is carried out in a polymerization zone which comprises a series of at least two reaction stages wherein the polymerization reaction in the final stage of the series is carried out continuously in a wiped film reaction zone.
Claim 51
Dependent Claim
16 words
The process of claim 43 wherein the first stage of the reaction is carried out batchwise.
Claim 52
Dependent Claim
47 words
The process of claim 41 wherein the polymerization reaction is carried out in a polymerization zone which comprises a series of at least two reaction stages wherein the polymerization reaction in the final stage of the series is carried out continuously in a wiped film reaction zone.
Claim 53
Dependent Claim
35 words
The process of claims 41, 42, 43, 44 or 45 wherein the liquid catalyst is a normally solid material in molten form or a normally solid material in solution in a solvent for the catalyst.
Claim 54
Dependent Claim
18 words
The process of claim 46 wherein the liquid catalyst is a solution of a metal phenoxide in phenol.
Claim 55
Dependent Claim
18 words
The process of claim 47 wherein the liquid catalyst is the reaction product of potassium borohydride and phenol.
Claim 56
Dependent Claim
14 words
The process of claims 45, 47 or 48 wherein the bisphenol is bisphenol A.
Claim 57
Dependent Claim
17 words
The process of claim 49 wherein the diaryl ester is diphenyl isophthalate, diphenyl terephthalate or mixtures thereof.
Claim 58
Dependent Claim
82 words
In the process of preparing a linear aromatic polyester by transesterification melt polymerization of monomer reactants consisting essentially of a bisphenol and a diaryl ester of a dicarboxylic acid in the presence of a basic catalyst for said polymerization wherein said reactants are introduced to the polymerization reaction in the liquid state, the improvement which comprises introducing the catalyst and liquid state reactants substantially concurrently and continuously to a polymerization zone and withdrawing said polyester product substantially continuously from said polymerization zone.
Claim 59
Dependent Claim
82 words
In the process of preparing a linear aromatic polyester by transesterification melt polymerization of monomer reactants consisting essentially of a bisphenol and a diaryl ester of a dicarboxylic acid in the presence of a basic catalyst for said polymerization wherein said reactants are introduced to the polymerization reaction in the liquid state, the improvement which comprises introducing the catalyst and liquid state reactants substantially concurrently and continuously to a polymerization zone and withdrawing said polyester product substantially continuously from said polymerization zone.
Claim 60
Dependent Claim
47 words
The process of claim 51 wherein the polymerization reaction is carried out in a polymerization zone which comprises a series of at least two reaction stages wherein the polymerization reaction in the final stage of the series is carried out continuously in a wiped film reaction zone.
Claim 61
Dependent Claim
16 words
The process of claim 52 wherein the first stage of the reaction is carried out batchwise.
Claim 62
Dependent Claim
33 words
The process of claims 51, 52 or 53 wherein the liquid catalyst is a normally solid material in molten form or a normally solid material in solution in a solvent for the catalyst.
Claim 63
Dependent Claim
18 words
The process of claim 54 wherein the liquid catalyst is a solution of a metal phenoxide in phenol.
Claim 64
Dependent Claim
18 words
The process of claim 55 wherein the liquid catalyst is the reaction product of potassium borohydride and phenol.
Claim 65
Dependent Claim
14 words
The process of claim 51, 55 or 56 wherein the bisphenol is bisphenol A.
Claim 66
Dependent Claim
17 words
The process of claim 57 wherein the diaryl ester is diphenyl isophthalate, diphenyl terephthalate or mixtures thereof.
Claim 67
Dependent Claim
113 words
In the process of preparing a linear aromatic polyester by transesterification melt polymerization of monomer reactants consisting essentially of a bisphenol and a diaryl ester of a dicarboxylic acid in the presence of a basic catalyst for said polymerization wherein said reactants are introduced to the polymerization reaction in the liquid state, the improvement which comprises introducing the catalyst to the polymerization substantially concurrently with introduction of the reactants to the polymerization, said polymerization reaction being carried out in a polymerization zone which comprises a series of at least two reaction stages wherein the polymerization reaction in the final stage of said series is carried out continuously in a wiped film reaction zone.
Claim 68
Dependent Claim
113 words
In the process of preparing a linear aromatic polyester by transesterification melt polymerization of monomer reactants consisting essentially of a bisphenol and a diaryl ester of a dicarboxylic acid in the presence of a basic catalyst for said polymerization wherein said reactants are introduced to the polymerization reaction in the liquid state, the improvement which comprises introducing the catalyst to the polymerization substantially concurrently with introduction of the reactants to the polymerization, said polymerization reaction being carried out in a polymerization zone which comprises a series of at least two reaction stages wherein the polymerization reaction in the final stage of said series is carried out continuously in a wiped film reaction zone.
Claim 69
Dependent Claim
16 words
The process of claim 59 wherein the first stage of the reaction is carried out batchwise.
Claim 70
Dependent Claim
32 words
The process of claims 59 or 60 wherein the liquid catalyst is a normally solid material in molten form or a normally solid material in solution in a solvent for the catalyst.
Claim 71
Dependent Claim
18 words
The process of claim 61 wherein the liquid catalyst is a solution of a metal phenoxide in phenol.
Claim 72
Dependent Claim
18 words
The process of claim 62 wherein the liquid catalyst is the reaction product of potassium borohydride and phenol.
Claim 73
Dependent Claim
14 words
The process of claims 59, 62 or 63 wherein the bisphenol is bisphenol A.
Claim 74
Dependent Claim
17 words
The process of claim 64 wherein the diaryl ester is diphenyl isophthalate, diphenyl terephthalate or mixtures thereof
Claim 75
Dependent Claim
32 words
The process of claims 27, 30, 43, 45, 52, or 59 wherein said wiped film reaction zone provides for countercurrent flow of the reaction mixture and the vapor by-product of the reaction.
Claim 76
Dependent Claim
8 words
The product of the process of claim 1.
Claim 77
Dependent Claim
8 words
The product of the process of claim 2.
Claim 78
Dependent Claim
8 words
The product of the process of claim 13.
Claim 79
Dependent Claim
8 words
The product of the process of claim 16.
Claim 80
Dependent Claim
8 words
The product of the process of claim 26.
Claim 81
Dependent Claim
8 words
The product of the process of claim 30.
Claim 82
Dependent Claim
8 words
The product of the process of claim 41.
Claim 83
Dependent Claim
8 words
The product of the process of claim 43.
Claim 84
Dependent Claim
8 words
The product of the process of claim 45.
Claim 85
Dependent Claim
8 words
The product of the process of claim 51.
Claim 86
Dependent Claim
8 words
The product of the process of claim 59.
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USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1985-03-08 | 1985-09-07 | 1986-03-09 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1989-03-08 | 1989-09-07 | 1990-03-09 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1993-03-08 | 1993-09-07 | 1994-03-09 | $7700.00 | Window Closed / Lapsed |