GB2229187A - High molecular weight polyethylene terephthalate in solution - Google Patents
High molecular weight polyethylene terephthalate in solution Download PDFInfo
- Publication number
- GB2229187A GB2229187A GB9003726A GB9003726A GB2229187A GB 2229187 A GB2229187 A GB 2229187A GB 9003726 A GB9003726 A GB 9003726A GB 9003726 A GB9003726 A GB 9003726A GB 2229187 A GB2229187 A GB 2229187A
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- GB
- United Kingdom
- Prior art keywords
- solution
- polymer
- diisocyanate
- polyethylene terephthalate
- filament
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- 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.)
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Classifications
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
- D01F6/62—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyesters
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/0838—Manufacture of polymers in the presence of non-reactive compounds
- C08G18/0842—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents
- C08G18/0847—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents in the presence of solvents for the polymers
- C08G18/0852—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents in the presence of solvents for the polymers the solvents being organic
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4205—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups
- C08G18/4208—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups
- C08G18/4211—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic dicarboxylic acids and dialcohols
- C08G18/4213—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic dicarboxylic acids and dialcohols from terephthalic acid and dialcohols
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- General Chemical & Material Sciences (AREA)
- Textile Engineering (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
A method of producing a solution of polyethylene terephthalate having a higher intrinsic viscosity than that of the original polymer comprises reacting a diisocyanate with the polymer in a hot solution of the polymer. A process for dry jet wet spinning such a solution into a filament or a film is also described. Suitable solvents for forming the solution of the polymer are disclosed.
Description
HIGH MOLECULAR WEIGHT POLYETHYLENE TEREPHTHALATE IN SOLUTION
This invention relates to the preparation of solutions of polyethylene terephthalate of high molecular weight and the use of such solutions to produce filaments or films of polyethylene terephthalate.
It is already known from United States Patent 2,829,153 that in the polymerisation of polyethylene terephthalate, physical reasons prevent the polycondensation reaction from proceeding to completion. The polycondensation reaction in polyethylene terephthalate depends on the rate of diffusion and elimination of ethylene glycol through the melt, and this process becomes progressively more difficult as the viscosity rises. A further complication is that thermal decomposition occurs at the temperatures used in melt polycondensation, which tends to reduce the reaction rate due to an increase in carboxyl end groups and a decrease in hydroxyl end groups.Consequently it has been difficult to attain a molecular weight in excess of about IV 0.9 dl/g (measured in o-chlorophenol) and a carboxyl value of below 15 equiv/106g polyethylene terephthalate, although in practice, modern continuous polymerisation reactors can obtain somewhat higher IV's and lower carboxyl values.
To increase the molecular weight substantially further, either solid state polymerisation or chain extension in the melt is commonly employed.
Among those chain extenders which may be used in the melt, the following have been reported: diphenyl terephthalate, diaryl carbonates, diphenyl oxalate, aromatic dianhydrides or bis-phthalimides, diphenyl malonate, bis-ketenimides, bis-2-oxazolines, bis-5-oxazolones, diphenyl isophthalate, triphenyl phosphite, terephthaloyl bisphthalimide, hexaphenyl orthoterephthalate, diisocyanates, bis-epoxides, 2,2'-m-phenylene bis(l,3-oxazoline), 2,2'-bis(1,3-oxazoline), bisphenol
A-diglycidyl ether, caprolactam-blocked diphenyl methane-4,4'-diisocyanate, terephthaloyl-bis-caprolactam and terephthaloyl-bis-laurolactam.
The selection of chain extender for melt polycondensation is based on several factors; there is a requirement to produce either a volatile byproduct which can diffuse easily through the melt and thereby be removed, or to react quickly with polyethylene terephthalate chain ends without forming a byproduct; the equilibrium rate constant should not favour the back or reverse reaction; there is a requirement for thermal stability of the reaction product at the high melt polymerisation temperatures (280-2900C) to avoid adverse effects on polyethylene terephthalate molecular weight which might be caused by long polymerisation times. All these requirements limit the choice of chain extender which can be used.
Polymerisation in solution, in the absence of chain extenders, has been described in a number of publications including British Patent Nos: 720,120; 755,975; and 766,912.
We have now found that the use of a diisocyanate as a chain extender in solutions of polyethylene terephthalate increases the intrinsic viscosity thereof and this offers considerable advantages over either the use of a chain extender in a melt polymerisation process or of solution polymerisation in the absence of a chain extender.
Lower temperatures are generally employed and this causes less degradation of the reactants and products. Also a solution is of lower viscosity and therefore more easily handleable than a melt and mixing efficiency between chain extender and polymer is greater in solution than in a melt.
A further) and very important, advantage is that the polymer solution of high intrinsic viscosity so produced can be used directly in a gel spinning, wet spinning or dry spinning process. This advantage is particularly significant as it has been hitherto difficult to prepare a polymer solution for these purposes from high intrinsic viscosity polyethylene terephthalate.
According to the invention we provide a method of producing a solution of polyethylene terephthalate having a higher intrinsic viscosity than that of the original polymer which comprises reacting a diisocyanate with the polymer in a hot solution of the polymer.
According to another aspect of the invention we provide a method of producing a solution of polyethylene terephthalate having a higher intrinsic viscosity than that of the original polymer comprising (1) forming, at an elevated temperature, a solution of the polymer in a solvent therefor, (2) introducing a diisocyanate into the solution produced in (1), and (3) maintaining the combined solution at an elevated temperature until an increase in intrinsic viscosity occurs.
In preference the combined solution is maintained at as low an elevated temperature as possible conducive with the polymer remaining in solution while the reaction takes place. We have found that by doing this, there is a tendency for polymer having a higher intrinsic viscosity to be produced.
Examples of suitable diisocyanates are diphenylmethane-4, 4' -diisocyanate (MDI), tolylene-2 , 4- diisocyanate, tolylene-2 , 6-diisocyanate and hexamethylene diisocyanate (1,6-diisocyanatohexane).
We have found that there is an optimum amount of the diisocyanate for a given end group concentration in the original polymer. If the added quantity of the diisocyanate is less than that which is theoretically required, it is found that the polyethylene terephthalate, after initially increasing in molecular weight, subsequently decreases in molecular weight when held at the reaction temperature for a number of hours; however, when the quantity of the diisocyanate is equal to, or in excess of the theoretical requirement based on polymer end group concentration, the molecular weight (intrinsic viscosity) of the polyethylene terephthalate, after increasing, remains constant in the solvent over a similar period of time.
It is possible to add the diisocyanate in stages to the reaction mixture, and even to optimise the level of diisocyanate by monitoring the viscosity of the solution. When an excess of the diisocyanate has been added it is possible to raise the molecular weight of the polyethylene terephthalate still further by providing sufficient quantities of difunctional reactive compounds to couple the diisocyanate end groups e.g. diols or diamines.
Those solvents which may be used in the method of the invention are generally high temperature solvents. On the other hand for convenience we prefer to use a solvent which is liquid at, or near to, room temperature. Suitable solvents are diphenyl ether, a-methyl naphthalene, a mixture of diphenyl ether and biphenyl, diphenyl methane, compounds of the type C6H5-(CH2)n -C6H5 where n=1-4, dimethyl sulphoxide, N-formyl piperidine,
N-methyl pyrrolidone, biphenyl, nitrobenzene, 1,2,4-trichlorobenzene, 1,2-dimethoxybenzene, 1,3-dimethoxybenzene and 1,2,4 trimethoxybenzene.
The diisocyanate may conveniently be added as a pre-formed solution in the solvent at an elevated temperature, or may be added without pre-formation of a solution.
The solutions made in accordance with the invention can be readily spun into filaments or films by a dry jet wet spinning process.
Accordingly, we also provide a process for producing a filament or film of polyethylene terephthalate comprising forming a solution -of the polyethylene terephthalate in the manner of the invention, extruding the solution through a spinneret or slot die, through air and into a cooling bath to form a gel filament or film, removing residual solvent from the filament or film and drawing the filament or film to improve the modulus and tenacity thereof.
We also provide filaments or films of polyethylene terephthalate made by this process.
Whilst we have stated above that we prefer to use a solvent which is liquid at, or near to, room temperature in which case water at room temperature can provide the cooling bath, it should be understood that it would be possible to use a solvent which is'solid at room temperature and to operate the cooling bath at a temperature above the melting point of the solvent.
The invention will now be described with reference to the following Examples 1 to 18. Comparative Examples A, B and C are provided in order to establish the improvement which can be achieved with the method of the invention compared with conventional solution polymerisation methods. Comparative
Example D is provided to establish the need to work at a temperature which keeps the polymer in solution.
EXAMPLE 1
55 grams of dried polyethylene terephthalate of intrinsic viscosity (IV) of 0.54 (measured by solution viscosity in dichloroacetic acid at 250C) were added to 225 grams of dried phenyl ether/biphenyl (73.5/26.5) and heated to 255 to 2600C under dry nitrogen and with vigorous stirring until the polymer was completely dissolved (30-60 mins). The polymer solution was then allowed to cool to 1900C, whilst being stirred under nitrogen. 1.0 gram (4.0 x 10 3 moles) of diphenylmethane-4, 4'-diisocyanate (MDI) was dissolved in 50 grams of phenyl ether/biphenyl (73.5/26.5) at 50 C, taking care to avoid degradation of the diisocyanate.
The diisocyanate solution was then added dropwise to the polymer solution over a period of 5 minutes, whilst maintaining the temperature of the reaction mixture at 1900C.
Samples of the reaction mixture were withdrawn at intervals, extracted with acetone, dried, and the IV's (measured by solution viscosity in dichloroacetic acid at 250C) determined.
After 10 minutes reaction time, the IV of the polymer was found to be 0.88 dl/g and remained at this value over the next two hours.
EXAMPLE 2
The polymerisation conditions were kept substantially the same as in Example 1 except that 2.0 grams (8.0 x 10 3 moles) of MDI were used. After 10 minutes reaction time, the polymer IV (measured by solution viscosity in dichloroacetic acid at 250C) was 1.23 dl/g.
EXAMPLE 3
The polymerisation conditions were kept substantially the same as in Example 1 except that 2.25 grams (9 x 10 3 moles) of MDI were used. After 10 minutes reaction time, the polymer IV (measured by solution viscosity in dichloroacetic acid at 250C) was 1.35 dl/g rising to 1.40 dl/g after 30 minutes, and 1.47 dl/g after 3 hours.
EXAMPLE 4
The polymerisation conditions were kept substantially the same as in Example 1 except that 2.5 grams (1 x 10 2 moles) of MDI were used. After 10 minutes reaction time, the polymer IV (measured by solution viscosity in dichloroacetic acid at 250C) was 1.14 dl/g and remained substantially the same over the next two hours.
EXAMPLE 5
The polymerisation conditions were kept substantially the same as in Example 1 except that 2.75 grams (11 x 10 3 moles) of MDI were used. After 10 minutes reaction time, the polymer IV (measured by solution viscosity in dichloroacetic acid at 250C) was no 96 dl/g.
EXAMPLE 6
Polymerisation conditions were kept substantially the same as in Example 1 except that 3.0 grams (12 x 10-3 moles) of MDI were used. After 10 minutes reaction time, the IV (measured by solution viscosity in dichloroacetic acid at 250C) of the polymer was 0.97 dl/g and remained substantially the same over the next two hours.
In Examples 1-6, there is an indication that for the polymer used, the optimum level of the diisocyanate required to give the highest polymer IV was around 2.25 grams of MDI per 55 grams of polymer ie 4.1% of MDI based on polymer.
COMPARATIVE EXAMPLE A
55 grams of dried polyethylene terephthalate of IV 0.54 dl/g (measured by solution viscosity in dichloroacetic acid at 25"C) were added to 275 grams dry phenyl ether/biphenyl (73.5/26.5) and heated to 255 to 260"C under dry nitrogen and with vigorous stirring until the polyethylene terephthalate was completely dissolved (30-60 minutes). The reaction mixture was then continuously distilled under nitrogen, replenishing the distillate with equivalent amounts of fresh solvent. After two hours reaction time, the polymer IV (measured by solution viscosity in dichloroacetic acid at 250C) was 0.70 dl/g.
COMPARATIVE EXAMPLE B
The polymerisation conditions were kept substantially the same as in Comparative Example A, except that 0.038 grams (1.3 x 10 4 moles) of antimony trioxide were added. After 2 hours reaction time, the polymer IV (measured by solution viscosity in dichloroacetic acid at 250C) was 0.68 dl/g.
COMPARATIVE EXAMPLE C
The polymerisation conditions were kept substantially the same as in Comparative Example A, except that 0.14 grams (4.8 x 10 4 moles) of antimony trioxide were added. After 2 hours reaction time, the polymer IV (measured by solution viscosity in dichloroacetic acid at 250C) was 0.72 dl/g.
The accompanying Figure shows a graphic r presentation of the effect of addition of MDI on the polymerisation rate of polyethylene terephthalate.
EXAMPLE 7
55 grams of dried polyethylene terephthalate of intrinsic viscosity (IV) of 0.73 (measured by solution viscosity in a trifluoroacetic acid (TFA)/dichloromethane (DCM) mixture (1:1 wt/wt) at 250C) were added to 225 grams of dried phenylether/biphenyl (73.5/26.5) and heated to 255 to 2600C under dry nitrogen and with vigorous stirring until the polymer was completely dissolved (30-60 mins). The polymer solution was then allowed to cool to 2100C. 1.1 grams of MDI was dissolved in 50 grams of phenylether/biphenyl (73.5/26.5) at 500C, taking care to avoid degradation of the diisocyanate.
The diisocyanate solution was then added drop wise to the polymer solution over a period of 5 minutes, whilst maintaining the temperature of the reaction at 2100C. After 90 minutes at 2100C the reaction mixture was allowed to cool to room temperature, extracted with acetone, dried, and the IV of the resulting polymer determined, and found to be 1.59 dl/g (TFA/DCM).
EXAMPLE 8
Polymerisation conditions were kept substantially the 3 same as in Example 7 except that 1.65 grams of MDI (6.6 x 10- mol) were used. After 90 minutes reaction time, the polymer IV was 1.65 dl/g (measured by solution viscosity in a TFA/DCM mixture - 11 wt/wt - at 250C).
EXAMPLE 9
Polymerisation conditions were kept substantially the same as in Example 7 except that 2.2 grams of MDI were used.
After 90 minutes reaction time, the polymer IV was 1.21 dl/g (measured by solution viscosity in a TFA/DCM mixture - 1:1 wt/wt at 25"C).
EXAMPLE 10
Polymerisation conditions were kept substantially the same as in Example 7 except that 2.75 grams of MDI were used.
After 90 minutes reaction time, the polymer IV was 1.20 dl/g (measured by solution viscosity in a TFA/DCM mixture - 1:1 wt/wt at 25"C).
EXAMPLE 11
Polymerisation conditions were kept substantially the same as in Example 7 except that 3.3 grams of MDI were used.
After 90 minutes reaction time, the polymer IV was 1.09 dl/g (measured by solution viscosity in a TFA/DCM mixture - 1:1 wt/wt at 25"C).
Examples 7-11 indicate that for the polymer used in these examples the optimum level of the diisocyanate, to give the highest polymer IV, was around 1.65 grams of MDI per 55 grams of polymer ie 3.0% of MDI based on polymer. Examples 1-6 and
Examples 7-11 show that there is an optimum amount of diisocyanate for a given end group concentration in the original polymer.
EXAMPLE 12
Polymerisation conditions were kept substantially the same as in Example 8 except that the reaction temperature was 195"C. After 90 minutes reaction time, the polymer IV was 1.76 dl/g (measured by solution viscosity in a TFA/DCM mixture - 1:1 wt/wt at 250C).
EXAMPLE 13
Polymerisation conditions were kept substantially the same as in Example 8 except that the reaction temperature was 230"C. After 90 minutes reaction time, the polymer IV was 1.42 dl/g (measured by solution viscosity in a TFA/DCM mixture - 1:1 wt/wt at 250C).
COMPARATIVE EXAMPLE D
Polymerisation conditions were kept substantially the same as in Example 8 except the target reaction temperature was 1850C. On cooling down to this temperature the reaction mass gelled making reaction impossible.
Examples 8, 12, 13 and comparative example D demonstrate that as lower temperature as possible which keeps the polymer in solution is desired, in order to produce the highest
IV polymer.
EXAMPLE 14
Polymerisation conditions were kept substantially the same as in Example 8 except that 1.15 grams of 2,4-tolylene 3 diisocyanate (technical grade 80%, 6.6 x 10 ml) were used in place of the MDI; After 90 minutes reaction time, the polymer IV was 1.01 dl/g (measured by solution viscosity in a TFA/DCM mixture - 1:1 wt/wt at 250C).
EXAMPLE 15
Polymerisation conditions were kept substantially the same as in Example 8 except that 1.11 grams of 1,6-diisocyanatohexane (6.6 x 10-3 mol) were used in place of MDI. After 90 minutes reaction time, the polymer IV was 1.62 dl/g (measured by solution viscosity in a TFA/DCM mixture - 1:1 wt/wt at 250C).
Examples 8, 14 and 15 show that the process is applicable to diisocyanates in general.
EXAMPLE 16
Polymerisation conditions were kept substantially the same as in Example 8 except that 1,2,4-trichlorobenzene was used in place of phenylether/biphenyl, and the reaction temperature was 200"C. After 90 minutes reaction time, the polymer IV was 1.27 dl/g (measured by solution viscosity in a TFA/DCM mixture 1:1 wt/wt at 250C).
EXAMPLE 17
Polymerisation conditions were kept substantially the same as in Example 8 except that l-methylnaphthanlene was used in place of phenylether/biphenyl, and the reaction temperature was 21O0C. After 90 minutes reaction time, the polymer IV was 1.15 dl/g (measured by solution viscosity in a TFA/DCM mixture - 1:1 wt/wt at 250C).
EXAMPLE 18
Polymerisation conditions were kept substantially the same as Example 8 except that 1,2-dimethoxybenzene was used in place of phenylether/biphenyl, and the reaction temperature was 195"C. After 90 minutes reaction time, the polymer IV was 1.35 dl/g (measured by solution viscosity in a TFA/DCM mixture - 1:1 wt/wt at 250C).
Examples 8, 16, 17 and 18 indicate that a wide variety of substantially aromatic compounds, or mixtures of two or more of these, which are capable of dissolving the polymer and keeping the polymer dissolved at the reaction temperature, may be used.
Claims (7)
1. A method of producing a solution of polyethylene terephthalate having a higher intrinsic viscosity than that of the original polymer which comprises reacting a diisocyanate with the polymer in a hot solution of the polymer.
2. A method of producing a solution of polyethylene terephthalate having a higher intrinsic viscosity than that of the original polymer comprising (1) forming, at an elevated temperature, a solution of a polymer in a solvent therefor, (2) introducing a diisocyanate into the solution produced in (1), and (3) maintaining the combined solution at an elevated temperature until an intrinsic viscosity occurs.
3. A method as claimed in claim 2 in which the combined solution is maintained at as low an elevated temperature as possible conducive with the polymer remaining in solution.
4. A method as claimed in any one of the preceding claims in which the diisocyanate is selected from diphenylmethane-4, 4'-diisocyanate (MDI), tolylene-2,4-diisocyanate, tolylene-2, 6-diisocyanate and hexamethylene diisocyanate (1,6-diisocyanatohexane).
5. A method as claimed in any one of the preceding claims in which the solution of the polymer is formed in a solvent selected from diphenyl ether, a-methyl naphthalene, mixtures of diphenyl ether and biphenyl, diphenyl methane, compounds of the type C6H5-(CH2)n-C6H5 where n = 1-4, dimethyl sulphoxide,
N-formyl piperidine, N-methyl pyrrolidone, biphenyl, nitrobenzene, 1,2,4-trichlorobenzene, 1,2-dimethoxybenzene, 1,3-dimethoxybenzene and 1,2,4 trimethoxybenzene.
6. A process for producing a filament or film of polyethylene terephthalate comprising forming a solution of polyethylene terephthalate by a method as claimed in any one of the preceding claims, extruding the solution through a spinneret or slot die, through air and into a cooling bath to form a gel filament or film, removing residual solvent from the filament or film and drawing the filament or film to improve the modulus and tenacity thereof.
7. Filaments or films of polyethylene terephthalate made by the process of claim 6.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB898905902A GB8905902D0 (en) | 1989-03-15 | 1989-03-15 | High molecular weight polyethylene terephthalate |
| GB898907210A GB8907210D0 (en) | 1989-03-30 | 1989-03-30 | High molecular weight polyethylene terephthalate in solution |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| GB9003726D0 GB9003726D0 (en) | 1990-04-18 |
| GB2229187A true GB2229187A (en) | 1990-09-19 |
Family
ID=26295093
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB9003726A Withdrawn GB2229187A (en) | 1989-03-15 | 1990-02-19 | High molecular weight polyethylene terephthalate in solution |
Country Status (1)
| Country | Link |
|---|---|
| GB (1) | GB2229187A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0617148A1 (en) * | 1993-03-24 | 1994-09-28 | Teijin Limited | Process for producing high molecular weight polyester fibers |
| WO2024094633A1 (en) * | 2022-11-01 | 2024-05-10 | Avantium Knowledge Centre B.V. | Process for the production of a high molecular weight polyester (co)polymer |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1578472A (en) * | 1976-03-22 | 1980-11-05 | Celanese Corp | Polymers for extrusion applications |
| GB1599119A (en) * | 1977-06-18 | 1981-09-30 | Dynamit Nobel Ag | Polyesters |
| EP0056293A2 (en) * | 1981-01-13 | 1982-07-21 | E.I. Du Pont De Nemours And Company | Process for extruding a modified high molecular weight poly(ethylene terephthalate) resin |
-
1990
- 1990-02-19 GB GB9003726A patent/GB2229187A/en not_active Withdrawn
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1578472A (en) * | 1976-03-22 | 1980-11-05 | Celanese Corp | Polymers for extrusion applications |
| GB1599119A (en) * | 1977-06-18 | 1981-09-30 | Dynamit Nobel Ag | Polyesters |
| EP0056293A2 (en) * | 1981-01-13 | 1982-07-21 | E.I. Du Pont De Nemours And Company | Process for extruding a modified high molecular weight poly(ethylene terephthalate) resin |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0617148A1 (en) * | 1993-03-24 | 1994-09-28 | Teijin Limited | Process for producing high molecular weight polyester fibers |
| US5451359A (en) * | 1993-03-24 | 1995-09-19 | Teijin Limited | Process for producing high molecular weight polyester fibers |
| WO2024094633A1 (en) * | 2022-11-01 | 2024-05-10 | Avantium Knowledge Centre B.V. | Process for the production of a high molecular weight polyester (co)polymer |
| WO2024094621A1 (en) * | 2022-11-01 | 2024-05-10 | Avantium Knowledge Centre B.V. | Process for the production of a high molecular weight polyester (co)polymer |
Also Published As
| Publication number | Publication date |
|---|---|
| GB9003726D0 (en) | 1990-04-18 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| WAP | Application withdrawn, taken to be withdrawn or refused ** after publication under section 16(1) |