AU652233B2 - High molecular weight copolyester resins having low melting points - Google Patents
High molecular weight copolyester resins having low melting points Download PDFInfo
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- AU652233B2 AU652233B2 AU14343/92A AU1434392A AU652233B2 AU 652233 B2 AU652233 B2 AU 652233B2 AU 14343/92 A AU14343/92 A AU 14343/92A AU 1434392 A AU1434392 A AU 1434392A AU 652233 B2 AU652233 B2 AU 652233B2
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- Prior art keywords
- copolyethylenterephthalate
- weight
- resin
- copet
- melt
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- 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/20—Polyesters having been prepared in the presence of compounds having one reactive group or more than two reactive groups
-
- 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/181—Acids containing aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
Description
_1 L OPI DATE 02/11/92 AOJP DATE 10/12/92 APPLN. ID 14343 92 PCT NUMBER PCT/EP92/00669 i
INTERNA
(51) International Patent Classification 5 C08G 63/181, 63/20, C08L 67/02 (11) International Publication Number: Al (43) International Publication Date: TREATY (PCT) WO 92/17519 15 October 1992 (15.10.92) (21) International Application Number: (22) International Filing Date: Priority data: MI91A000885 29 March PCT/EP92/00669 26 March 1992 (26.03.92) 1991 (29.03.91) (81) Designated State: AT (European patent), AU, BE (European patent), BR, CA, CH (European patent), DE (European patent), DK (European patent), ES (European patent), FI, FR (European patent), GB (European patent), GR (ELropean patent), HU, IT (European patent), JP, KR, LU (European patent), MC (European patent), NL (European patent), NO, RU, SE (European patent),
US.
Published With international search report.
(71) Applicant (for all designated States except US): M. G. Rl- CERCHE S.P.A. [IT/IT]; Localita Triverno, Zona Industriale, 1-86077 Pozzilli (IT).
(72) Inventor; and Inventor/Applicant (for US only) GHISOLFI, Guido [IT/ IT]; Via Pedenovi, 1, 1-15057 Tortona (IT).
(74) Agents: GERBINO, Angelo et al.; Jacobacci-Casetta Perani Via Alfieri, 17, 1-10121 Torino (IT).
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'3 (54) Title: HIGH MOLECULAR WEIGHT COPOLYESTER RESINS HAVING LOW MELTING POINTS (57) Abstract Copolyethylene terephthalate containing from 10 to 25 by weight of the resin of units deriving from isophthalic acid, having intrinsic viscosity higher than 0.85 dl/g, melting point lower than 220 °C and crystallization properties such as to solidify from the melt to the amorphous form also by low cooling rate (1 °C/min).
A
WO 92/17519 PCT/EP92/00669 1 High molecular weight copolyester resinshaving low melting points The present invention relates to high molecular weight copolyester resins having low melting points and peculiar crystallization behaviour and the process for preparing the resins.
It is well known that the molecular weight of the polyester resins can be increased by solid state polycondensation reaction.
The possibility however to upgrade polyester resins having low melting points, e.g. lower than 220*C presents serious process difficulties due to the sticking problems on the walls of the reactor caused by the high upgrading temperatures used.
The known solid state polycondensation processes need high upgrading temperature due to the low kinetic of the upgrading reactions. Usually, the solid state polycondensation reactions of polyester resins are performed by temperatures higher than 180*C; mainly higher than 195 0 C (see page 3295 of Journal of Applied Polym. Cs.
28 3289 3300, 1989).
The possibility of preparing polyster resins with low melting points and having sufficiently high values of the intrinsic viscosity, which are particularly suitable for extrusion blow applications, is a not yet solved problem.
In Applicant's previous pending European application No. 89119049.8 a solid state upgrading process. is described in which the resin is upgraded at temperatures higher than 170°C and in general in the range of 170'C 220°C, using a dianhydride of an aromatic tetracarboxylic acid.
The resins subjected to upgrading comprise copolyethylenterephtalates (6OPETs). Amongs the COPETs use is exemplified .of copolimers containing at most 10% in FT a lamols of units deriving from isophtalic acid on the total of the acid units. Except tie melting point of the resin after upgrading and intrinsic viscosity values no other indications are given regarding the upgraded polymer.
It has now been found that it is possible to upgrade polyester resins having melting points lower than 220°C without having sticking problems and that the upgraded resin presents valuable properties particularly from the viewpoint of the crystallization behaviour.
The resins subjected to upgrading are the copolyethylenterephthalates containing from 10 to 25% by weight on the total resin weight of units deriving from isophtalic acid (COPETs).
According to the present invention, there is 0.85 dl/g, melting point lower than 220 C and solidifying from the melt to amorphous solid at a cooling rate not less than 1 0 C/min.
The present invention also provides formed articles obtained from the copolyethylenterephthalates of the present invention.
4 25 The present invention also provides bottles obtained Sby blow molding the copolyethylenterephthalates of the 1 present invention.
40i d 20 soidfyn fro th ett mrhusslda oln WO 92/17519 PCT/EP92/00669 I 7-7-7 WO 92/17519 PCT/EP92/00669 2 of the acid units. Except the melting point o the resin after upgrading and intrinsic viscosity vaues no other indications are given regarding the up ?ded polymer.
It has now been found that it s possible to upgrade polyester resins having meltin oints lower than 220*C without having sticking pro ems and that the upgraded resin presents valuable poperties particularly from the viewpoint of the crys lization behaviour.
The resins subjected to upgrading are the copolyethylent ephtalates containing from 10 to 25% by weight on e total resin weight of units deriving from According to the process of the present invention, the COPET is upgraded at temperature lower than 170"C and higher than the TG of the resin, preferably comprised between 130° and 160°C using an upgrading additive selected from the group consisting of the dianhydrides of aromatic, aliphatic cycloaliphatic tetracarboxylic acids.
Unexpectedly, the upgraded COPETs present, besides the high IV values (higher than 0.85 dl/g) and molding points lower than 220 0 C, other valuable properties.
In particular the crystallization behaviour of the resins is remarkable from the view point of the molding applications, because the resin does not show any cristallinity also by slow cooling from the melt; the COPETs give clear, transparent amorphous solids also by very slow cooling rate, e.g. 1°C/min.
It is worthwhile to note that the resin crystall izes when heated in the solid state for instance at 150*C for mins.
Another interesting property of the resin is its gel-free characteristic.
Part-icularly interesting is the COPET containing about 15% wYeight of the resin of isophtalic acid units, i WO 92/17519 PCT/EP92/00669 3 melting point of 212*C. This COPET gives clear highly transparent amorphous solid by cooling its melt also at very slow cooling rate (1*C/min). Pyromellitic dianhydride is the preferred upgrading compound.
Other suitable dianhydrides are the dianhydrides of 1, 2, 3, 4-cyclobutanetetracarboxylicacid, 3,4-dicarboxy-l,2,3,4-tetrahydro-l-naphthalenesuccinic acid and 3,3',44' benzophenone tetracarboxylic acid.
The preferred dianhydride from the cycloaliphatic acids is 1,2,3,4 cyclobutantetracarboxylic acid dianhydride.
Interesting results are also obtainable with the dianhydride of 3,4 dicarboxy 1,2,3,4 tetrahydro-l-naphtalenesuccinic acid and bicyclo (2,2,2) oct-7-ene 2,3,5,6 tetracarboxylic acid.
The preferred concentration of the additive with respect to the polyester resin is 0,05-1% by weight.
The solid state upgrading process comprises the steps of blending the COPET resin in a molten state with the upgrading additive, converting the melt into granules, crystallizing the granulate at temperatures higher than the TG of the resin but lower than 180°C and then upgrading the crystallized resin at a temperature comprised in the range from the TG of the resin and 180°C, particularly from 130* and 170 "C.
The process is preferably carried out in continuous way using continuous crystallizers and upgrading reactors where the chips can move counter currently with a stream of a heated gas, e.g. air, nitrogen and carbon dioxide.
Apparatus suitable for the crystallization and upgrading steps can be those described in USP 4,064,112 and 4,161,578 whose description is herewith enclosed for reference.
The recycling of the inert gas streams can be carried out according to European application 86830340.5 whose I -7-C L WO 92/17519 PCT/EP92/00669 description is herewith enclosed for reference.
The blending of the polyester resin with the additive is carried out in an equipment capable to perform reactive extrusion such as corotating or counter rotating intermeshing or not intermeshing twin screw extruder with or without venting capability at a temperature between 2000 and 350*C, depending on the melting point of the polyester.
A counter rotating non intermeshing twin screw extruder vented or not vented is preferred.
The use of such kind of extruder allows to perform a good distribution of the additive in the melt and to avoid problems of local high concentrations of the additive due to its high reactivity.
The extruder may be directly fed with molten COPET from a plant in which the COPET is produced by polycondensation in the molten state.
The extruder may also be fed with solid COPET granulates produced in another plant.
The extruder is preferably connected to a high vacuum oil seal pump to maintain a vacuum higher than 2 torr for the devolatilization of the reactive blend and for obtaining a resin with a low content of acetaldehyde. However, the blending could be also performed without the use of vacuum.
The residence time in the extruder could be comprised between 10 and 120 sec., preferably 15-30 sec.
To avoid random local concentration of additive in the melt it is advisable to dilute the additive with crystallised PET powder (1 part of additive to 5 parts of PET powder). This procedure will ensure a homogeneous odistribution of PMDAt in the melt leading to a better reproducibility of the end product intrinsic viscosity and inhibitinig the gel formation.
The dianhydri de could be also diluted using blends of i .4 WO 92/17519 PCT/EP92/00669 the dianhydride and crystallized PET-chips (1 part additive to 10 parts PET chips). The dilution could be performed in a fanned blender using about 0,1% of polyethylenglycol or polycaprolactone, as adhesives, and using blending temperature at about 150 0
C.
The reactive melt coming out of the twin screw extruder is continuously pallettized using an underwater pelletizer or a strand pelletizer system.
According to another aspect of this invention, the new COPETs may be modified by blending with polymers like polybutylenterephtalate, polycarbonate, polycaprolactone, polyester elastomers, phenoxy resins in amount up to about by weight of the total resins, directly before the extrusion processing. The addition has the effect of improving the mechanical properties of the composition as well as the processing conditions without sacrifying the transparency of the end product.
Analytical Procedures The intrinsic viscosity was determined on a solution of 0.5 g of COPET in 100 ml of 60/40 mixture by weight of phenol and tetrachloroethane at 25"C according to ASTM D 4603 86.
The acetaldehyde content was determined with a gas chromatographic method according to ASTM D 4526-85, using a Perkin Elmer 8700 gas chromatograph. (Perkin Elmer model HS 101).
The extraction conditions were 150°C for 90 min.
SExample 1 Kg/h random COPET melt (15% isophtaiic acid in weight, melting point 212 0 C, IV 0.75 dl/g) having a content of 110 ppm acetaldehyde were fed continuously from the finisher of PET melt polycondensation pilot plant to a counter rotating not intermeshing 30 mm twin screw extruder with venting capability.
220 g/h of a mixture of 20% weight of pyromellitic
F
i 1 1 ^i .1 1 I- I I WO 92/17519 PCT/EP92/00669 6 acid dianhydride in crystallized COPET powder (IV: 0.75 dl/g, 15% weight isophtalic acid) were fed to the extruder using a gravimetric feeder.
The test conditions were as follows: pyromellitic acid dianhydride in the COPET melt 0.15% by weight screw speed: 415 RPM ratio length/diameter 24 average residence time: 18 25 sec.
barrel temperature: 235°C product melt temperature: 290°C vacuum: 1 5 torr A die with double holes was used as extruder die (Diameter: 7 mm).
A strand pelletizer was used to obtain the COPETchips which had a cylindrical shape with a diameter of 3 mm and a length of 5 mm, and with an intrinsic viscosity IV 0.85 0.01 dl/g.
The COPET chips had an acetaldehyde content of 5 8 ppm. During the test period, the IV of the product was constant over the period of 2 weeks.
The melting point of the product was 212*C.
The COPET-chips were then fed continuously to a solid state upgrading pilot plant using the apparatus and the inert gas ricycling conditions set forth in European application EP 86830340.5.
The crystallization temperature was 150*C and the residence time was 40 min.
The temperature of the solid state upgrading reactor was 150°C and the residence time was 12 h.
The IV of the upgraded products was 0,94 0,02 dl/g.
The product was free from gel, with acetaldehyde content of 0.60 ppm.
In comparison, there was no upgrading of COPET not containing pyromellitic dianhydride (starting IV 0.75 i :t WO 92/17519 PCT/EP92/00669 7 1/g) using the same conditions for crystallization and upgrading as in this example.
The crystallization behaviour of the COPET in comparison with standard PET is shown in figure 1.
Fig. 1 shows the crystallization kinetic of COPET prepared according to this example in comparison with standard bottle grade polyethyleneterephthalate. The crystallization kinetic was determined under isothermal conditions at 120C.
It is interesting that although this COPET is crystallizing in the solid state (150*C/40 min), its melt does not bring about any crystallization by cooling, and gives a clear transparent amorphous solid also by very slow cooling rate.
Table 1 shows the data relating to crystallization by cooling of COPET of example 1 in comparison to standard
PET.
All the crystallization data are obtained by DSC measurements performed with Mettler Thermal Analyzer YC 11.
Fig. 2 reports the DSC curves of COPET versus the cooling rate of the melt, starting from a rate of changing then to 5 and 3*C/min curves A, B, and C respectively. Curve 1 refers to standard PET cooled to a rate of 10°C/min wherein the increase of the heat of crystallization is 11.8 J/g.
TABLE 1 2 Heat of melting of PET samples crystallized with different cooling rates.
Heats are in joule/gram.
u ,B 1 1 1 1 1 1 i I I I I SAMPLE QUENCHING COOLING RATE (deg/min) I I 10 5 3 COPET 2.1 N N N STANDARD PET 30.0 34.1 (c) f I f N no crystallization a) crystallization during melting 1.6 J/g b) crystallization during melting 29.1 J/g c) crystallization during melting 12.2 J/g Example 2 Kg/h random COPET melt (15% isophthalic acid in weight, melting point 212 0 C, IV 0.75 dl/g) having a content of 110 ppm acetaldehyde were fed continuously from the finisher of a PET melt polycondensation pilot plant to a counter rotating not intermeshing 30 mm twin screw extruder with venting capability.
220 g/h of a mixture of 20% weight of 1, 2, 3, 4-cyclobutanetetracarboxylic acid- dianhydride in crystallized COPET powder (IV: 0.75 dl/g, 15% weight isophthalic acid) were fed into the extruder using a gravimetric feeder. The test conditions were as follows: Cyclobutane tetracarboxylic acid dianhydride in the COPET melt 0.15% by weight Screw speed: 415 RPM Ratio length-diameter 24 Average residence time: 18 25 sec.
Barrel temperature: 235°C Produst melt temperature: 290*C Vacuum: 1 5 to~t-.
A die with double holes was used as extruder die (Diameter: 7 mm).
A strand pelletizer was used to obtain the COPETchips which had a cylindrical shape with a diameter of 3 i ir a I:1.
1 ii ii: 1 i I '3 The COPET chips had an acetaldehyde content of 6 9 ppm. During the test period, the IV of the product was constant over a period of 2 weeks.
The masting point of the product was 212 0
C.
The mbdified COPET-chips were then fed continuously into a solid state polycondensation pilot plant using the apparatus and the inert gas recycling conditions described in European application EP 86830340.5.
The crystallization temperature was 150°C and the residence time in the crystallizer was 40 min. The solid state temperature in the reactor was 150°C and the residence time was 10 h. The IV of the upgraded product was 0,965 dl/g. The product was free from gel, with an acetaldehyde content of 0.60 ppm.
In comparison, there was no upgrading of COPET not containing the dianhydride (starting IV 0.75 dl/g), using the same conditions for crystallization and upgrading as in this example.
Example 3 The same COPET was used as in Example 1, but in the form of crystallized COPET granules of IV 0.75 dl/g.
The crystallized COPET chips were dried and fed into the twin screw.
The IV of the product was 0.845 0.02 dl/g.
The same conditions were used as in Example 1; only the average residence time was about 25 sec.
The solid state conditions were 1300 1400C in the cryCtallizer and 140°C in the polyaddition reactor. The residence time in the reactor was 10 hours. The chips intrinsic viscosity was 0.92 0,015 dl/g. The acetaldehyd content was 0.67 ppm.
xample 4 The following table reports the extrusion blow i 1 1 1 1 1 i
I
la^^ a~i 1 1 4 IS (i 1'I 1\ WO 92/17519 PCT/EP92/00669 -f moulding conditions tion of the bottles mould: head: screw length: screw size: screw type: article: volume: output: parison length: production: cycle: temperature barrel: profile head: die: and the apparatus used for the producup to 1500 ml: rotative distributor 2 moulds PET covered mono parison 24 L/D 65 mm standard PVC round bottle up to 1500 ml 50.4 Kg/h (depends on the bottle volume) up to 40 cm 960 bottles/hour 8.0 seconds 250C 280 0
C
2900C The COPET was dried to a content of water less 0.005% using dried air with Dew point between 30°C The following table gives the blowing conditions the results obtained using the COPET of example 1.
than and and ,I I I r l RESIN BARREL HEAD/ DIE BOTTLE/ HOURS BOTTLE I OUTPUT SCEW IACA DROP TEMP. I WEIGHT ISPEED TEST C No. gr j Kg/h rp I ppa I c COPET 230 270 280--?60 42 j 1 j 50.4 48 13.6 62 I I I I I I ACA= acetaldefiyde Example This example describes the extrusion blowing of COPET produced according to example and mixed before blowing with'polybutylenterephthalate (General Electric) (PBT); IV 1 -v i
B
j!
.I
j
-A
WO 92/17519 PCT/EP92/00669 11 1.220 dl/g in amount of 3,5% by weight.
This mixture was dried and blowed according to the general description of example 4.
The following table gives the blowing conditions and the results obtained.
I I I I I I I I I RESIN BARREL HEAD DIE BOTTLE HOURS BOTTLE OUTPUT SCPEW ACA DROP TEMP. i EIGHT SPEED TEST "C No. gr Kg/h rpm ppm j c COPET 240 280 300 960 42 1 50.4 52 3.7 I I 1 I I I I Example 6 This example describes the extrusion blowing of COPET of example 1 and mixed before blowing with 5% by weight of polycarbonate (Dow Chem.).
This mixture was then dried and blowed according to the general description of example 4.
The following table reports the conditions and the obtained results.
j--j j RESIN BARREL HEAD DIE BOTTLE HOURS "OTTLE OUTPUT SCREW ACA I DROP STEMP. W EIGHT SPEED I TEST 'C No. gr Kg/h rpa pp ca COPET 20 20 3I I 94 I ICOPET 1 240 290 300 960 i 42 1 j 50.4 52 I3.7 I I 1I I I I.II I Example 7 S This example describes the extrusion blowing of COPET of example 1 mixed before blowing with 5% by weight of phenoxy resin (Union Carbide).
v This mixture was dried and blowed according to the general description of example 4.
The 'following table reports the conditions and the results obtained.
-U
RESIN BARREL HEAD DIE IBOTTLE HOURS fBOTTLE OUTPUT ISCREW ACA DROP ITEMP. WEIGHT SPEED I TESTI ac N o. I gr Kg/h Irpm pp cm ICOPET 1240 280 300 960 4t2 50. 1550 15.11 691
Claims (9)
1. Copolyethylenterephthalate containing from 10 to by weight of the resin of units deriving from isophthalic acid, having intrinsic viscosity higher than 0.85 dl/g, melting point lower than 220 C and solidifying from the melt to amorphous solid at a cooling rate not less than l°C/min.
2. Copolyethylenterephthalate according to claim 1, containing about 15% by weight of the resin of units from isophthalic acid.
3. Copolyethylenterephthalate according to any one of claims 1 and 2, free from gel.
4. Copolyethylenterephthalate according to any one of claims 1 to 3, obtained with a process comprising the steps of blending in the molten state a 20 copolyethylenterephthalate with intrinsic viscosity less than 0.85 dl/g with 0.05 1% by weight of a dianhydride of an aliphatic, cycloaliphatic, aromatic tetracarboxylic acid, pelletizing the melt, crystallizing and then upgrading the resin at temperatures higher than TG and 25 lower than 170 0 C.
5. Copolyethylenterephthalate according to any one of claims 1 to 4, mixed with 1 20% by weight of a polymer selected from polycarbonate, polybutylenterephthalate, epoxy resins.
6. Formed articles obtained from the copolyethylentere- phthalate of any one of the previous claims.
7. Bottles obtained by blow molding the copolyethylen- terephthalates of any one of the claims 1 to 4.,
8. A copolyethylenterephthalate according to claim 1, substantially as herein described with reference to any one of the embodiments of the Examples. i I
9. Formed phthalates reference to -14- articles obtained from copolyethylentere- substantially as herein described with any one of the embodiments of the Examples. Bottles obtained by blow molding copolyethylentere- phthalates substantially as herein described with reference to any one of the embodiments of the Examples. DATED 15 JUNE 1994 I i 1 I II( I I I I I 1 1 1 II,, I r II I I I 1 t III I 111(11 1 PHILLIPS ORMONDE FITZPATRICK Attorneys for M. G. RICERCHE S.p.A. A 7885Z ,oH r a r h a .1
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
ITMI910885A IT1245599B (en) | 1991-03-29 | 1991-03-29 | COPOLYESTER RESINS WITH HIGH MOLECULAR WEIGHT AND LOW MELTING POINT |
ITMI91A0885 | 1991-03-29 | ||
PCT/EP1992/000669 WO1992017519A1 (en) | 1991-03-29 | 1992-03-26 | High molecular weight copolyester resins having low melting points |
Publications (2)
Publication Number | Publication Date |
---|---|
AU1434392A AU1434392A (en) | 1992-11-02 |
AU652233B2 true AU652233B2 (en) | 1994-08-18 |
Family
ID=11359372
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
AU14343/92A Ceased AU652233B2 (en) | 1991-03-29 | 1992-03-26 | High molecular weight copolyester resins having low melting points |
Country Status (17)
Country | Link |
---|---|
EP (1) | EP0531485A1 (en) |
JP (1) | JPH05507760A (en) |
CN (1) | CN1066856A (en) |
AU (1) | AU652233B2 (en) |
BR (1) | BR9204821A (en) |
CA (1) | CA2083279A1 (en) |
FI (1) | FI925418A (en) |
HU (2) | HU9203750D0 (en) |
IL (1) | IL101330A0 (en) |
IT (1) | IT1245599B (en) |
MX (1) | MX9201413A (en) |
NO (1) | NO924542L (en) |
PT (1) | PT100318A (en) |
TR (1) | TR27173A (en) |
TW (1) | TW203066B (en) |
WO (1) | WO1992017519A1 (en) |
ZA (1) | ZA922247B (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
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AU653392B2 (en) * | 1991-03-29 | 1994-09-29 | Sinco Engineering S.P.A. | Block copolyester resins |
Families Citing this family (15)
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IT1245598B (en) * | 1991-03-29 | 1994-09-29 | M & G Ricerche Spa | PROCESS FOR THE PRODUCTION OF HIGH MOLECULAR WEIGHT POLYESTER RESINS |
IT1245597B (en) * | 1991-03-29 | 1994-09-29 | M & G Ricerche Spa | PROCESS FOR THE PRODUCTION OF HIGH MOLECULAR WEIGHT POLYESTER RESINS |
IT1251953B (en) * | 1991-10-18 | 1995-05-27 | M & G Ricerche Spa | PROCEDURE FOR THE PRODUCTION OF HIGH MOLECULAR WEIGHT POLYESTER RESINS. |
IT1252223B (en) * | 1991-12-16 | 1995-06-05 | M & G Ricerche Spa | CELLULAR POLYESTER RESINS AND THEIR PREPARATION PROCEDURE |
JPH07507831A (en) * | 1992-06-15 | 1995-08-31 | アライド−シグナル・インコーポレーテッド | Improved methods of making extended chain polyesters and block or graft copolyesters |
IT1256600B (en) * | 1992-10-15 | 1995-12-12 | POLYMERIC ALLOYS FROM POLYESTER RESINS AND PROCEDURE FOR THEIR PREPARATION | |
EP0606663A1 (en) * | 1993-01-12 | 1994-07-20 | Agfa-Gevaert N.V. | Method of manufacturing a photographic reflective support |
IT1269192B (en) * | 1994-01-20 | 1997-03-21 | Enichem Spa | PROCEDURE FOR THE PREPARATION OF REUSABLE BOTTLES CONSTITUTED BY A MIXTURE OF PET AND PC |
IT1307930B1 (en) * | 1999-01-26 | 2001-11-29 | Sinco Ricerche Spa | TRANSPARENT ARTICLES IN POLYESTER RESIN (MG32). |
US7935399B2 (en) * | 2004-09-02 | 2011-05-03 | Grupo Petrotemex, S.A. De C.V. | Low melting polyester polymers |
CN102177189B (en) * | 2008-08-07 | 2016-01-27 | 英威达技术有限公司 | Preparation has the method for the polyester of low acetaldehyde content and regeneration rate |
CN106280296A (en) * | 2016-08-05 | 2017-01-04 | 上海金发科技发展有限公司 | A kind of PET/PC resin combination of high fluidity and preparation method thereof |
CN106280297A (en) * | 2016-08-05 | 2017-01-04 | 上海金发科技发展有限公司 | A kind of PBT resin and low-melting point PET resin combination and preparation method thereof |
CN106243641A (en) * | 2016-08-05 | 2016-12-21 | 上海金发科技发展有限公司 | A kind of glass fiber reinforcement PBT/PET resin combination of high fluidity low melting point and preparation method thereof |
CN114479030B (en) * | 2020-11-11 | 2024-03-26 | 中国石油化工股份有限公司 | PBT copolyester with high glass transition temperature and low melting point and application thereof |
Citations (3)
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AU1423392A (en) * | 1991-03-29 | 1992-11-02 | Sinco Engineering S.P.A. | Process for the production of high molecular weight polyester resins |
AU631265B2 (en) * | 1989-10-13 | 1992-11-19 | M&G Luxembourg S.A. | Process for the continuous production of high molecular weight polyester resin |
AU643609B2 (en) * | 1991-03-29 | 1993-11-18 | M. & G. Ricerche S.P.A. | Process for the production of high molecular weight polyester resins |
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US2965613A (en) * | 1954-03-02 | 1960-12-20 | Goodyear Tire & Rubber | Copolyesters |
GB1239751A (en) * | 1967-05-23 | 1971-07-21 | ||
GB1489430A (en) * | 1973-11-12 | 1977-10-19 | Gen Electric | Solid phase polymerization of polybutylene terephthalate |
FR2295999A1 (en) * | 1974-12-26 | 1976-07-23 | Rhone Poulenc Textile | GOOD FLAME RESISTANCE POLYESTER ARTICLES AND METHOD OF OBTAINING THEIR |
US4161578A (en) * | 1978-05-12 | 1979-07-17 | Bepex Corporation | Process for solid phase polymerization of polyester |
JPS5523125A (en) * | 1978-08-07 | 1980-02-19 | Toray Ind Inc | Copolymerized polyethylene terephthalate composition |
US4234708A (en) * | 1979-04-23 | 1980-11-18 | Celanese Corporation | Extrusion grade polyethylene iso/terephthalate copolymer |
US4569882A (en) * | 1983-12-15 | 1986-02-11 | Hideo Watase | Thermoplastic synthetic resin-covered metal wire |
EP0174265A3 (en) * | 1984-09-07 | 1987-09-09 | The Goodyear Tire & Rubber Company | Solid state polymerization process |
-
1991
- 1991-03-29 IT ITMI910885A patent/IT1245599B/en active IP Right Grant
-
1992
- 1992-03-22 IL IL92101330A patent/IL101330A0/en unknown
- 1992-03-26 HU HU9203750A patent/HU9203750D0/en unknown
- 1992-03-26 WO PCT/EP1992/000669 patent/WO1992017519A1/en not_active Application Discontinuation
- 1992-03-26 AU AU14343/92A patent/AU652233B2/en not_active Ceased
- 1992-03-26 CA CA002083279A patent/CA2083279A1/en not_active Abandoned
- 1992-03-26 BR BR9204821A patent/BR9204821A/en not_active Application Discontinuation
- 1992-03-26 EP EP92906945A patent/EP0531485A1/en not_active Withdrawn
- 1992-03-26 JP JP92506528A patent/JPH05507760A/en active Pending
- 1992-03-26 HU HU9203750A patent/HUT64988A/en unknown
- 1992-03-27 ZA ZA922247A patent/ZA922247B/en unknown
- 1992-03-27 TR TR00305/92A patent/TR27173A/en unknown
- 1992-03-27 MX MX9201413A patent/MX9201413A/en unknown
- 1992-03-27 PT PT100318A patent/PT100318A/en not_active Application Discontinuation
- 1992-03-28 CN CN92102952A patent/CN1066856A/en active Pending
- 1992-03-28 TW TW081102405A patent/TW203066B/zh active
- 1992-11-25 NO NO92924542A patent/NO924542L/en unknown
- 1992-11-27 FI FI925418A patent/FI925418A/en not_active Application Discontinuation
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
AU631265B2 (en) * | 1989-10-13 | 1992-11-19 | M&G Luxembourg S.A. | Process for the continuous production of high molecular weight polyester resin |
AU1423392A (en) * | 1991-03-29 | 1992-11-02 | Sinco Engineering S.P.A. | Process for the production of high molecular weight polyester resins |
AU643609B2 (en) * | 1991-03-29 | 1993-11-18 | M. & G. Ricerche S.P.A. | Process for the production of high molecular weight polyester resins |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
AU653392B2 (en) * | 1991-03-29 | 1994-09-29 | Sinco Engineering S.P.A. | Block copolyester resins |
Also Published As
Publication number | Publication date |
---|---|
AU1434392A (en) | 1992-11-02 |
IL101330A0 (en) | 1992-11-15 |
HU9203750D0 (en) | 1993-03-29 |
ITMI910885A1 (en) | 1992-09-29 |
CA2083279A1 (en) | 1992-09-30 |
NO924542D0 (en) | 1992-11-25 |
ZA922247B (en) | 1992-12-30 |
CN1066856A (en) | 1992-12-09 |
NO924542L (en) | 1993-01-27 |
FI925418A0 (en) | 1992-11-27 |
IT1245599B (en) | 1994-09-29 |
HUT64988A (en) | 1994-03-28 |
MX9201413A (en) | 1993-02-01 |
TR27173A (en) | 1994-11-10 |
EP0531485A1 (en) | 1993-03-17 |
JPH05507760A (en) | 1993-11-04 |
ITMI910885A0 (en) | 1991-03-29 |
WO1992017519A1 (en) | 1992-10-15 |
BR9204821A (en) | 1993-07-13 |
PT100318A (en) | 1993-07-30 |
FI925418A (en) | 1992-11-27 |
TW203066B (en) | 1993-04-01 |
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