CA2022099A1 - Barrier polymers - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE
BARRIER POLYMERS
The present invention relates to gas barriers comprising at least one layer of an amorphous polyamide derivable from a nylon salt formed from aromatic dicarboxylic acids and diamines characterised in that a) the aromatic dicarboxylic acids comprise isophthalic acid and at least one other aromatic dicarboxylic acid selected from terephthalic acid, 4,4'-dicarboxy biphenyl and 2,6-naphthalene dicarboxylic acid, and b) the diamine comprises meta-xylylene diamine, the polyamide being a barrier against oxygen and/or carbon dioxide.

Description

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Case 7198(2) BARRIER POLYMERS

This invention relates to amorphous polyamide barrier polymers and especially amorphous polyamide barrier polymers.
Barrier polymers are used in packaging containers made to protect their contents from the environment over the normal shelf life of the product. Many products, including foods, are sensitive -~
to oxygen, which can cause flavour changes or discolouration. The ingress of moisture, if allowed, could cause dry soluble powders to cake, or a loss of moisture may adversely affect the viscosity of water-based liquids or semifluids. For carbonated beverages, both the retention of carbon dioxide and protection from oxygen are important. Some containers are also required to resist oil or serve as a barrier to volatile organics.
In competition with glass and metal containers, conventional polymers such as polyolefins and nylons have been used for packaging. Their light weight, shatter resistance (as opposed to glass), ease of disposal by incineration, and lower cost (in most cases) are the advantages they confer. However, these conventional polymers, although providing fairly good resistance to moisture, are quite permeable to oxygen and organic vapours. The barrier polymers are used to overcome this defect.
The barrier polymers mainly used hitherto are ethylene-vinyl alcohol copolymers (EVOH, typically EVAL-E or F, Regd. Trade Mark), vinylidene chloride copolymers (VDC, typically Saran, Regd. Trade Mark), nitrile polymers (NP, typically Barex, Regd. Trade Mark) and amorphous polyamides (AP, typically Selar, Regd. Trade Mark).

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It has now been found that polyamides produced from an aromatic dicarboxylic acid and one or more diamines can give rise to polyamides which have particularly desirable barrier properties.
Accordingly, the present invention relates to gas barriers comprising at least one layer of an amorphous polyamide derivable from a nylon salt formed from aromatic dicarboxylic acids and ~
diamines characterised in that ~ -a) the aromatic dicarboxylic acids comprise isophthalic acid and at least one other aromatic dicarboxylic acid selected from terephthalic acid, 4,4'-dicarboxy biphenyl and 2,6-naphthalene dicarboxylic acid, and b) the diamine comprises meta-xylylene diamine, -~
the polyamide being a barrier against oxygen and/or carbon dioxide. - ~The nylon salt from which the polyamide is derivable may ;
contain upto 50 mole% of isophthalic acid and up to 90 mole% of the other aromatic dicarboxylic acid provided the total acid component is made upto 100 mole% with respect to the diamine component therein.
Similarly, the amount of meta-xylylene diamine in the diamine 20 component is at least 25 mole% and can be up to 100 mole%. However, some of the amine component may be replaced by other amines such as hexamethylene diamine or para-xylylene diamine.
Whatever the dicarboxylic acid and diamine combination used to produce the nylon salt, it should result in a melt processible amorphous polyamide. By 'melt processible' is meant that the amorphous polyamide formed should be capable of being injection moulded, blow moulded, extruded, calendered or blown into films. In -this context it is worth noting that as the meta-xylylene diamine content of the formulation to produce the polyamide is increased, the isophathalic acid content should also be increased in order to maintain the melt processibility of the polyamide formed.
Specific examples of amorphous polyamides which can be used as gas barriers according to the present invention are polyamides derivable from a nylon salt having one of the following formulations in moles %:

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a) isophthalic acidtterephthalic acid/metaxylylene diamine (50/50/lOO), -b) isophthalic acid/terphthalic acid/hexamethylene diamine/meta-xylylene diamine (50/50/50/50) and c) isophthalic acid/terephthalic acid/hexamethylene diamine/meta-xylylene diamine (50/50/30/70) -The nylon salt for instance can be prepared by mixing an equimolar proportion of the diacid and diamine in water and heating ~-to form an aqueous solution.
Prior to heatinB the salt concentrations can be modified to give equimolar amounts of each component by adjustment of solution pH. The solution so formed can be decolourised over e.g. activated ~ ;~
charcoal. The resultant purified solution can then be cooled to precipitate the nylon salt.
The nylon salt can be polymerised to a higher molecular weight polyamide by charging the salt into a reactor and heating the -~
contents optionally in the presence of a catalyst.
To accelerate the rate of polycondensation, a catalyst or mixture of catalysts can be added to the nylon salt feedstock prior to feeding thereof into the polycondensation reactor. Typical catalysts include polyphosphoric acid, ammonium hypophosphite, metal hypophosphites and the like. In the present process, the preferred catalyst is ammonium hypophosphite blended into the salt at a level of 0.025 - 1.05X by weight, preferably at a level of 0.1% by weight. Optionally, a second catalyst may be added, providing additional benefits in terms of colour stability. This second catalyst, added in addition to ammonium hypophosphite, is preferably ~;
sodium hypophosphite added at a level of between 0.1 and l.0% by weight and specifically 0.5%.
At elevated temperatures e.g. 200-350C, polymerisation occurs - -~
and upon cooling the desired polyamide of high molecular weight is formed. The reaction mixt~re is cooled and the polyamide collected and sent for further processing.
The polyamides used as gas barrier materials in the present invention suitably have 2 ~ $ ~

a) a number average molecular weight in the range 15,000 to 40,000, preferably 25,000 to 35,000, ~ -~
b) an inherent viscosity in the range 1.0 to 2.0 dlg-~
c) a glass transition temperature in the range 120C to 210C, and d) oxygen gas permeability at 100% relative humidity (RH) in the range from 0.1 x 10-13 to 20 x 10-13 cm3(STP)cm/cm2scmHg.
The barrier polyamides thus formed could be used in both flexible and rigid packaging where the ingress of oxygen into the packaging, resulting in deterioration of the product packaged, is undesirable. Examples of products where oxygen exposure is undesirable include foodstuffs and many chemicals. In addition it is expected that the polyamites will also have good resistance to carbon dioxide permeation hence they would be a good packaging material for carbonated beverages where both the retention of carbon ~;~
dioxide and proteGtion from oxygen ingress are important.
The polyamides are readily mouldable into many different forms which include bottles, drums, trays, boxes, films and pipes. The products can be produced on conventional extrusion and injection equipment designed to process nylon or polyolefin resins. Processes that can be used include blown film, cast film, sheet and blow moulding, injectlon moulding and extrusion. The polyamide can either be used as a monolayer or as multilayer structure (e.g. of upto 9 layers) of the polyethylene terephthalate (PET)/polyamide/(PET) type although other layers such as, for 25 example, polyethylene, polypropylene, polystyrene, polyvinyl -chloride, ethylene-vinyl acetate copolymer, polybutylene terephthalate or even conventional semi-crystalline nylons such as nylon-6 and nylon-6,6 can also be used in combination with polyamides of the present invention. Adhesive or tie layers may be required between the polymer layers to form a cohesive multilayer structure.
Using multilayer composites can have advantages over monolayer composites. For example, it is possible to calculate the minimum thickness of the barrier resin required for protection of the product to be packaged against oxygen. However, this calculated ~?~

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thickness may be too thin to give the container the necessary mechanical strength. Use of cheaper outer layers can give the container the necessary mechnical strength whilst keeping the cost of the package down. The outer layers may also give other -~
advantages over monolayers. For example, if polyethylene is used then lower water vapour transmission rates will be experienced.
The main advantage of the barrier polyamides of the present invention over existing barrier resins is the improvement in resistance to oxygen permeation with increasing humidity so that as 100% relative humidity (RH) is approached, the present polyamides have permeability co-efficients which are significantly lower than and, in some cases, the lowest of all the existing commercial barrier resins known. The present polyamides are also naturally ~ ~-transparent due to their amophorus structure and have excellent 15 optical properties. High temperature resistance and toughness are ~-additional advantages.
The present invention is further illustrated with reference to the following Examples~
Examples All the examples given below utilised similar preparative techniques which are detailed below:
Abbreviations used:
IPA : isophthalic acid TPA : terephthalic acid HMD : hexamethylene diamine MXD : m-xylylene diamine AHP : ammonium hypophosphite (catalyst) BA : benzoic acid (chain stopper) IV : inherent viscosity OTR : oxygen transmission rate IPA/HMD nylon salt : hexamethylene diammonium isophthalate TPA/HMD nylon salt : hexamethylene diammonium terephthalate IPA/MXD nylon salt : m-xylylene diammonium isophthalate TPA/MXD nylon salt : m-xylylene diammonium terephthalate .

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Raw Materials used~
isophthalic acid ex Amoco Chemicals, IPA-220 grade terephthalic acid (polymerisation grade) ex ICI, hexamethylene diamine (60Z w/w aqueous solution) ex ICI
m-xylylene diamine (99%) ex Akzo Chemie AHP ex Ubichem Ltd BA (Gold Label) ex Aldrich Chemicals, Activated carbon SX Plus ex Norit UK Ltd.
All chemicals were used as received with no further purification.
Preparation of NYlon Salt -~
Diacid and diamine were dissolved in distilled water in ~-equimolar quantities at 95C. A saturated solution at this temperature was prepared for all nylon salts except for the -preparation of IPA/HMD and IPA/MXD salts where concentrations of 15 125% w/w and 30% w/w were used respectively. The solution pH was adjusted to the stoichiometric pH; then the solution was d~colourised using SX-Plus activated carbon until the difference in % transmission between solution and distilled water measured at 480nm was less than 0.5%. The solution was then cooled to 25~C and -the salt precipitated using propan-2-ol, (99%, ex BDH Ltd). The salt was then filtered, washed with fresh propan-2-ol and dried under vacuum at 65C to <0.5% wt moisture.
General PolYmerisation Procedure All polycondensations were carried out in 500ml 3-necked round-bottomed flasks. A Techne SBL-l fluidised sandbath was used to heat the reaction flask and the temperature of the reaction charge was monitored u~ing a NiCr/NiAl thermocouple. A
fractionating column was attached to the reaction flask to allow the removal of water from the reaction flask whilst minimising diamine losses. An overhead mechanically-powered agitator was used to stir the reaction mixture.
The nylon salts (produced as described above) were first charged to the reaction flask along with the other ingredients. A
small quantity of excess diamine (0.5 mol%) was added to the reaction charge to compensate the diamine losses which occur during ::

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the polymerisation so that stoichiometry was maintained throughout.
The reaction charge was initially heated to 130C during which the bulk of the water was removed. The temperature was maintained at 130C for 1 hour. The reaction temperature was then raised to 275C
over a period of 2 hours. Polymerisation was carried out at 275C
for a total of 3 hours.
A nitrogen blanket (white spot) was maintained over the rsaction mixture during the heating and until the product had cooled to 25C.
Inherent viscosities (IV's) were measured by initially dissolving 0.15g of the polymer in 100ml of 98.0Z sulphuric acid (BDH Ltd, England, AnalaR grade) overnight and the solution flow time was measured in BS/U ASTM D445 type D viscometers suspended in a viscometer bath controlled at 25 +~_ 0.01C. The inherent viscosity is calculated from IV-[loge(t/tO)]/C where C =
concentration in gdl-l, t - solution flowtime in seconds and to ~
solvent flowtime in seconds. No corrections were made for kinetic energy or end effects.
Glass transition temperatures (tg's) were measured by differential scanning calorimetry (DSC). The DSC used was manufactured by Mettler, model DSC30 coupled to a TClOA processor (also ex Mettler). A heating rate of 10C min~l was used with a nitrogen purge rate through the DSC cell of 50cm3 min~l. A 5mg sample size was used.
OxYRen Permeabilitv Testin~
All oxygen permeability co-efficients were measured using OX-TRAN 1000 oxygen transmission rate test apparatus as manufactured by Modern Controls Inc., Minneapolis, USA. The measurements were carried out in accordance with ASTM te~t method D-3985-81, which was designed around the OX-TRAN equipment, except for two operating parameters. Firstly a test temperature of 25C was used instead of the stipulated 23C in the method. Secondly in addition to measurements at 0% relative humidity as specified in the test method, permeability co-efficients close to 100% relative humidity were also measured. The relative humidity was maintained at close 2 ~ ~ 2 ~

to lOOX by bubbling the test gates through bubbler tubes filled with glass beads and water. All other operating parameters and procedures were as specified in D-3985-81 (ASTM).
All films were prepared from the polyamide in pellet form for testing by compression moulding at 270C using a 25-ton hydraulic press manufactured by George E. Moore and Son Ltd. The pellets were pressed between mirror finished nickel electroplated steel sheets using a suitable release agent preferably Frekote 700 (ex Hysol, A
and IP Division) to within the thickness range 100-300 micrometers and if uniform thickness across the sheet +/_ 10 micrometers.
A schematic representation of the test apparatus used is given in the accompanying Figure 1. A brief description of the test procedure as detailed in ASTN D-3982-ôl is as follows. lOcm x lOcm test films were clamped into special 50cm2 diffusion cells. Both ~;~
sides of the film were initially purged with an oxygen-free carrier gas preferably 98Z nitrogen with 2Z hydrogen although the accuracy of the mixture was not critical. This was done to remove residual ;
oxygen from the sample. When a stable zero had been established, oxygen (99.9% purity) was then introduced into the upper half of the diffusion cell. Carrier gas continued to flow through the lower half of the cell carrying any oxygen which had diffused through the film to a coulometric detector. The test was continued until a stable equilibrium oxygen transmission rate value was reached. Each sample was tested in duplicate.

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Example 1 ~ -Monomer formulation: IPA/TPA/MXD
~ 50/ 50/100 mol %
Reaction charge: IPA/MXD nylon salt 60.4g TPA/MXD nylon salt 60.4g AHP 0.12g; 0.1 % wt BA 0.24g; 0.5 mol %
water 100ml ;~
The product formed was water-white with an IV = 1.34 dlg-10 OTR at 0% RH : 1.3 x 10~13cm3 (STP)cm/cm2scmHg OTR at lOOZ RH : 0.3 c 10~13cm3 (STP)cm/cm2scmHg ExamPle 2 Monomer formulation: IPA/TPA/HMD/MXD
~ 50/ 50/ 50/ 50 mol %
Reaction charge: TPA/HMD nylon salt 56.4g IPA/MXD nylon salt 60.4g water: 100 ml AHP 0.12g; 0.1 Z wt BA 0.24 g; 0.5 mol %
An amorphous, water-white polymer with tg - 166C and IV - 1.64 dlg-l was produced OTR at 0%RH : 17 x 10~13cm3 (STP)cm/cm2scmHg OTR at 100%RH : 5.5 x 10~13cm3 (STP)cm/cm2scmHg Example 3 Monomer formulation: IPA/TPA/HMD/MXD
- 50/ 50/ 30/ 70 mol %
Reaction charge: TPA/HMD nylon salt 33.84g IPA/MXD nylon salt 60.4g TPA/MXD nylon salt 24.16g AHP 0.12g; 0.1 % wt BA 0.24g; 0.5 mol Z
water lOOml The product formed was water-white, amorphous with a tg = 178C and an IV = 1.29 dlg-l OTR at 0%RH : 3.1 x 10~13cm3 (STP)cm/cm2scmHg 35 OTR at lOO~RH : 2.5 x 10~13cm3 (STP)cm/cm2scmHg `'c'.."', ''''' ' . ~ ~-2Q~2~

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Table 1 Çomparison of OTR's with commerciallv available barrier resins ' .

Comp. Relative Humidity Test Resins 0% ca.100X ;
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A Eval-F (HIBAR*FILM, ex Dow 0.08 5.1 23~ F) B MXD-6 (NYREF* 6001, ex 0.5 0.9 -SOLVAY) Comparative C PVDC (SARAN* X05253.25, ex _ 0.68 Data on Dow) known art D Nitrile Plastic (BAREX* 210 4.1 4.4 resins. ex BP America) E Polyamide (TROG~MID* T, ex 54 20 Chemische Warke H~ls AG) F Polyamide (SELAR* PA3426, 18.7 6.1 ex DU PONT) Example 1 IPA/TPA/MXD (50/50/lOOmol%) 1.3 0.3 `~ ~;
Polyamides 2 IPA/TPA/HMD/MXD (50/50/50/ 17 5.5 of the 50mol%) 25 present 3 IPA/TPA/HMD/MXD (50/50/30/ 3.1 2.5 invention 70mol%) *Regd. Trade Mark.
Units: 10~13cm3 (STP) cm/cm2scmHg 30 All resins measured using modified test ASTM D-3985-81 as described in the text.

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Claims (4)

1. Gas barriers comprising at least one layer of an amorphous polyamide derivable from a nylon salt formed from aromatic dicarboxylic acids and diamines characterised in that a) the aromatic dicarboxylic acids comprise isophthalic acid and at least one other aromatic dicarboxylic acid selected from terephthalic acid, 4,4'-dicarboxy biphenyl and 2,6-naphthalene dicarboxylic acid, and b) the diamine comprises meta-xylylene diamine, the polyamide being a barrier against any substantial diffusion of oxygen and/or carbon dioxide therethrough.

2. Gas barriers according to Claim 1 characterised in that a) the dicarboxylic acid has upto 50 mole% of isophthalic acid and upto 90 mole% of at least one other aromatic dicarboxylic acid provided that the total acid component is made upto 100 mole% with respect to the diamine component and b) the diamine has at least 25 mole% and upto 100 mole% of metaxylylene diamine, some of the amine being optionally replaced by a diamine selected from hexamethylene diamine and para-xylylene diamine.

3. Gas barriers according to Claim 1 wherein the polyamide is derivable from a nylon salt having one of the following formulations in moles %:
a) isophthalic acid/terephthalic acid/metaxylylene diamine (50/50/100), b) isophthalic acid/terephthalic acid/hexamethylene diamine/meta-xylylene diamine (50/50/50/50) and c) isophthalic acid/terephthalic acid/hexamethylene diamine/meta-xylylene diamine (50/50/30/70).

4. Gas barriers according to Claim 1 characterised in that the amorphous polyamide has a) a number average molecular weight from 15,000 to 40,000, b) an inherent viscosity in the range of 1.0 to 2.0 dl/g, c) a glass transition temperature in the range from 120 to 210°C
and d) an oxygen permeability at 100% relative humidity in the range of 0.1 x 10-13 to 20 x 10-13 cm3 (STP)cm/cm2 scmHg.