ITMI961265A1 - PROCESS PERFECTED FOR THE PRODUCTION OF POLYESTER RESINS - Google Patents
PROCESS PERFECTED FOR THE PRODUCTION OF POLYESTER RESINS Download PDFInfo
- Publication number
- ITMI961265A1 ITMI961265A1 IT96MI001265A ITMI961265A ITMI961265A1 IT MI961265 A1 ITMI961265 A1 IT MI961265A1 IT 96MI001265 A IT96MI001265 A IT 96MI001265A IT MI961265 A ITMI961265 A IT MI961265A IT MI961265 A1 ITMI961265 A1 IT MI961265A1
- Authority
- IT
- Italy
- Prior art keywords
- acid
- units
- moles
- copolymers
- naphthalindicarboxylic
- Prior art date
Links
- 229920001225 polyester resin Polymers 0.000 title description 4
- 239000004645 polyester resin Substances 0.000 title description 4
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 18
- 229920001577 copolymer Polymers 0.000 claims description 13
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 10
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 7
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 6
- -1 Polyethylene Polymers 0.000 claims description 3
- 239000004698 Polyethylene Substances 0.000 claims description 3
- 230000003750 conditioning effect Effects 0.000 claims description 3
- 229920000573 polyethylene Polymers 0.000 claims description 3
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 claims description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- 230000004888 barrier function Effects 0.000 description 6
- 229920001897 terpolymer Polymers 0.000 description 6
- 125000003118 aryl group Chemical group 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 238000006068 polycondensation reaction Methods 0.000 description 3
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 238000010102 injection blow moulding Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 150000002531 isophthalic acids Chemical class 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- OJURWUUOVGOHJZ-UHFFFAOYSA-N methyl 2-[(2-acetyloxyphenyl)methyl-[2-[(2-acetyloxyphenyl)methyl-(2-methoxy-2-oxoethyl)amino]ethyl]amino]acetate Chemical compound C=1C=CC=C(OC(C)=O)C=1CN(CC(=O)OC)CCN(CC(=O)OC)CC1=CC=CC=C1OC(C)=O OJURWUUOVGOHJZ-UHFFFAOYSA-N 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 150000003504 terephthalic acids Chemical class 0.000 description 1
- 150000000000 tetracarboxylic acids Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Polyesters Or Polycarbonates (AREA)
Description
La presente invenzione riguarda resine poliestere aromatiche dotate di elevata cristallinità e di proprietà barriera ai gas notevolmente superiori a quelle delle resine poliestere aromatiche convenzionali. The present invention relates to aromatic polyester resins having high crystallinity and gas barrier properties which are considerably higher than those of conventional aromatic polyester resins.
Le resine dell'invenzione sono costituite da copolimeri polietilentereftalici comprendenti unità derivanti da acido tereftalico, acido isoftalico e acido 2,6-naftalindicarbossilico in cui le unità da acido isoftalico e naftalindicarbossilici sono comprese tra 5 e 15 in moli ed il rapporto molare tra le unità da acido isoftalico e acido naftalindicarbossilico è compreso da 1 :3 a 3: 1 ed in cui il contenuto di dietilene glicole (DEG) è inferiore a 3% in moli, preferibilmente inferiore a 2% in moli. The resins of the invention consist of polyethylene terephthalic copolymers comprising units deriving from terephthalic acid, isophthalic acid and 2,6-naphthalindicarboxylic acid in which the isophthalic and naphthalindicarboxylic acid units are between 5 and 15 in moles and the molar ratio between the units from isophthalic acid and naphthalindicarboxylic acid is comprised from 1: 3 to 3: 1 and in which the content of diethylene glycol (DEG) is lower than 3% by moles, preferably lower than 2% by moles.
Un copoiimero di particolare interesse è costituito dal terpolimero contenente 88% in moli di unità derivanti da acido tereftalico 3-6%, preferibilmente 4,5%, in moli di unità da acido isoftalico e 6-9% , preferibilmente 7,5 %, in moli di unità da acido 2,6-naftalindicarbossilico. Il contenuto di dietilene glicole in questi copolimeri è preferibilmente inferiore a 2%. A copolymer of particular interest is constituted by the terpolymer containing 88% by moles of units deriving from terephthalic acid 3-6%, preferably 4.5%, in moles of units from isophthalic acid and 6-9%, preferably 7.5%, in moles of units of 2,6-naphthalene carboxylic acid. The diethylene glycol content in these copolymers is preferably less than 2%.
Il livello di cristallinità di questi terpolimeri può arrivare al 60% 0 più. La velocità di cristallizzazione è pure elevata. Ciò viene ottenuto mediante condizionamento termico dei film e degli oggetti formati a temperatura comprese tra 160°C e 215°C per un tempo sufficiente ad ottenere l'aumento della cristallinità (generalmente da 10 secondi a 5 minuti). The crystallinity level of these terpolymers can reach 60% or more. The crystallization rate is also high. This is achieved by thermal conditioning of the films and of the formed objects at a temperature between 160 ° C and 215 ° C for a time sufficient to obtain the increase in crystallinity (generally from 10 seconds to 5 minutes).
Queste caratteristiche di cristallinità sono eccezionali in un terpolimero ad elevato contenuto di comononieri. These crystallinity characteristics are exceptional in a terpolymer with a high content of comononiers.
Estrapolando i livelli di cristallinità per questi terpolimeri da correlazioni con il po lieti lentereftalato (PET) si ricavano valori inferiori a quelli reali. Ad esempio la cristallinità dei copolimeri binari 88/12 contenenti unità da acido tereftalico e acido isoftaiico o acido 2,6-naftalindicarbossilico è significativamente inferiore a quella dei terpolimeri dell'invenzione. Extrapolating the crystallinity levels for these terpolymers from correlations with polyethylene lenterephthalate (PET) yields lower than real values. For example, the crystallinity of binary copolymers 88/12 containing units of terephthalic acid and isophthaic acid or 2,6-naphthalindicarboxylic acid is significantly lower than that of the terpolymers of the invention.
Le proprietà di barriera ai gas dei film ottenuti dai copolimeri è eccelente. A confronto, bottiglie (1.5 I. , 48g) ottenute da PET e da terpolimero T/I/N 88:4.5:7.5% in moli presentano le seguenti proprietà (T = acido tereftalico, 1= acido isoftalico, N=acido 2,6nafta!indicarbossilico): The gas barrier properties of the films obtained from the copolymers are excellent. In comparison, bottles (1.5 I., 48g) obtained from PET and from terpolymer T / I / N 88: 4.5: 7.5% by moles have the following properties (T = terephthalic acid, 1 = isophthalic acid, N = acid 2, 6nafta! Indicarboxylic):
PET T/l/N Viscosità intrinseca(dl/g) 0.81 0.81 Temp. di transizione vetrosa(°C) 78.1 81.2 Temperatura di fusione(°C) 246 223 Entalpia di fusione(J/g) 11.3 10.2 Cristailinità % PET T / l / N Intrinsic viscosity (dl / g) 0.81 0.81 Glass transition temperature (° C) 78.1 81.2 Melting temperature (° C) 246 223 Enthalpy of melting (J / g) 11.3 10.2 Chrystailinity%
di spaila 25.7 24.1 parete laterale 25.7 24.3 fondo 26 20.6 Barriera aH'ossigeno(ml/bottiglia/giorno) 0.795 0.652 Percentuale di miglioramento — 18 spail 25.7 24.1 side wall 25.7 24.3 bottom 26 20.6 Oxygen barrier (ml / bottle / day) 0.795 0.652 Percentage of improvement - 18
Nel caso dei film, il miglioramento della barriera all'ossigeno può arrivare a 25% e più. In the case of films, the oxygen barrier improvement can reach 25% and more.
I copolimeri dell'invenzione vengono prodoti secondo i metodi convenzionali utilizzati per le resine poliestere aromatiche. The copolymers of the invention are produced according to the conventional methods used for aromatic polyester resins.
Si può partire dagli acidi e policondensarli con il glicole etilenico o dall'estere dimetilico dell’acido 2,6-naftalindicarbossilico che viene transesterificato dapprima con glicole etilenico ed il diestere ottenuto viene poi policondensato con gli acidi tereftalico e isoftalico. You can start from the acids and polycondensate them with ethylene glycol or the dimethyl ester of 2,6-naphthalindicarboxylic acid which is first transesterified with ethylene glycol and the diester obtained is then polycondensed with terephthalic and isophthalic acids.
La viscosità dei copolimeri dopo policondensazione è in genere compresa tra 0.5 e 0.7 dl/g; piò essere aumentata mediante reazioni di policondensazione allo stato solido, operando secondo i metodi convenzionali. The viscosity of the copolymers after polycondensation is generally between 0.5 and 0.7 dl / g; it can be increased by solid state polycondensation reactions, operating according to conventional methods.
La cinetica di policondensazione allo stato solido può essere migliorata aggiungendo ai copolimeri, preferibilmente nel fuso, ima dianidride di un acido tetracarbossilico, preferibilmente aromatico, in quantità da 0.01 a 2% in peso. The solid state polycondensation kinetics can be improved by adding to the copolymers, preferably in the melt, a dianhydride of a tetracarboxylic acid, preferably aromatic, in an amount from 0.01 to 2% by weight.
La dianidride piromellitica è il composto preferito. Pyromellitic dianhydride is the preferred compound.
Le resine dell'invenzione sono particolarmente adatte alla preparazione di film e di contenitori (bottiglie per acqua minerale) mediante injection blow molding, per sterilizzazioni ad alte temperature e per applicazioni dove sono richieste proprietà barriera ai gas. The resins of the invention are particularly suitable for the preparation of films and containers (bottles for mineral water) by means of injection blow molding, for sterilization at high temperatures and for applications where gas barrier properties are required.
Si è trovato e ciò costituisce un ulteriore aspetto del trovato, che al fine di aumentare la cristallinità delle pareti dei contenitori e dei film e stabilizzare gli stessi dimensionalmente, è opportuno sottoporre i contenitori ed i film a condizionamento termico a temperature comprese tra 160°C e 215°C per una durata sufficiente ad ottenere i risultati desiderati. It has been found and this constitutes a further aspect of the invention, that in order to increase the crystallinity of the walls of the containers and of the films and stabilize them dimensionally, it is appropriate to subject the containers and films to thermal conditioning at temperatures between 160 ° C and 215 ° C for a duration sufficient to obtain the desired results.
La viscosità intrinseca viene misurata in soluzione di 0.5 g di polimero in 100 mi di una miscela 60/40 in peso di fenolo e tetracloroetano a 25 °C operando secondo la norma ASTM 4603/86. The intrinsic viscosity is measured in a solution of 0.5 g of polymer in 100 ml of a 60/40 by weight mixture of phenol and tetrachloroethane at 25 ° C operating according to the ASTM 4603/86 standard.
Le proprietà barriere all'ossigeno sono state determinate secondo ASTM D 3985-81 utilizzando lo strumento OX TRAN 100. Oxygen barrier properties were determined according to ASTM D 3985-81 using the OX TRAN 100 instrument.
Claims (6)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IT96MI001265A IT1284052B1 (en) | 1996-06-21 | 1996-06-21 | PROCESS PERFECTED FOR THE PRODUCTION OF POLYESTER RESINS |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IT96MI001265A IT1284052B1 (en) | 1996-06-21 | 1996-06-21 | PROCESS PERFECTED FOR THE PRODUCTION OF POLYESTER RESINS |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| ITMI961265A0 ITMI961265A0 (en) | 1996-06-21 |
| ITMI961265A1 true ITMI961265A1 (en) | 1997-12-21 |
| IT1284052B1 IT1284052B1 (en) | 1998-05-08 |
Family
ID=11374459
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| IT96MI001265A IT1284052B1 (en) | 1996-06-21 | 1996-06-21 | PROCESS PERFECTED FOR THE PRODUCTION OF POLYESTER RESINS |
Country Status (1)
| Country | Link |
|---|---|
| IT (1) | IT1284052B1 (en) |
-
1996
- 1996-06-21 IT IT96MI001265A patent/IT1284052B1/en active IP Right Grant
Also Published As
| Publication number | Publication date |
|---|---|
| IT1284052B1 (en) | 1998-05-08 |
| ITMI961265A0 (en) | 1996-06-21 |
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