WO2006016875A1

WO2006016875A1 - Delamination-resistant multilayer container, preform and method of manufacture

Info

Publication number: WO2006016875A1
Application number: PCT/US2004/022212
Authority: WO
Inventors: Philip D. Bourgeois
Original assignee: Continental Pet Technologies, Inc.
Priority date: 2004-07-09
Filing date: 2004-07-09
Publication date: 2006-02-16
Also published as: DE112004002912T5; CA2573057A1; AU2004322268B2; AU2004322268A1; GB2430912A; GB2430912B; BRPI0418947A; GB0701187D0

Abstract

A plastic container or preform includes a multilayer wall having at least one layer of polyester resin, at least one layer of barrier resin, and an adhesion-promoting material blended with the barrier resin and/or the polyester resin to promote bonding between the barrier and polyester layers. The adhesion-promoting material includes an organometallic coupling agent based upon titanium, zirconium or aluminum. The organometallic coupling agent preferably has an amino end group with an affinity for carboxylic end groups in the polyester, and preferably is selected from the group consisting of neopentyl(diallyl)oxy, tri(N-ethylenediamino) ethyl titanate, zirconate and aluminate. Coupling agents based upon titanium and zirconium are particularly preferred for containers and preforms having a clear (non-colored) wall.

Description

DELAMINATION-RESISTANT MULTILAYER CONTAINER, PREFORM AND

METHOD OF MANUFACTURE

The present invention is directed to multilayer plastic containers and preforms,

and to methods of manufacturing such containers and preforms.

Background and Summary of the Invention

Multilayer plastic containers and preforms typically include one or more layers

of plastic resin such as polyethylene terephthalate (PET) alternating with one or more layers of

barrier resin such as nylon or ethylene vinyl alcohol (EVOH) to resist transmission of gas, water

vapor and/or fiavorants, including odorants and essential oils, through the container wall. An

important property of containers of this type is interlaminar adhesion to resist delamination

between or among the various layers during filling and handling of the containers by the

container manufacturer and the product packager, and during use of the container by the

consumer. Various techniques have been proposed for increasing interlaminar adhesion, which

generally result in a decrease in barrier properties, an increase in manufacturing cost and/or an

increase in other undesirable container properties such as haze in the container wall. It is

therefore a general object of the present invention to provide a multilayer container, a container

preform and a method of manufacture having improved adhesion characteristics between the

layers of the container (and preform) wall without significantly affecting container cost or other

parameters of manufacture.

A plastic container in accordance with one presently preferred aspect of the

invention includes a multilayer wall having at least one layer of polyester resin, at least one layer

of barrier resin, and an adhesion-promoting material blended with the barrier resin and/or the polyester resin to promote bonding between the barrier and polyester layers. In the preferred

embodiments of the invention, the adhesion-promoting material is blended with the barrier resin.

The adhesion-promoting material includes an organometallic coupling agent based upon

titanium, zirconium or aluminum. The organometallic coupling agent preferably has an amino

end group with an affinity for the carboxylic end group of the polyester, and preferably is selected

from the group consisting of neopentyl(diallyl)oxy, tri(N-ethylenediamino) ethyl titanate,

zirconate and aluminate. Coupling agents based upon titanium and zirconium are particularly

preferred for containers having a clear (non-colored) wall.

The polyester resin preferably is selected from the group consisting of PET,

polyethylene naphthalate (PEN), blends and copolymers of PET and PEN, and process regrind

that consists essentially of PET, PEN, or blends or copolymers of PET and PEN. The barrier

resin preferably is selected from the group consisting of EVOH₅ nylon, acrylonitrile copolymers,

blends of EVOH and nylon, nanocomposites of EVOH or nylon and clay, blends of EVOH and

an ionomer, acrylonitrile, cyclic olefin copolymers, polyglycolic acid (PGA), and blends thereof.

EVOH a nd m eta-xylylenediamine ( MXD) n ylon a re p articularly p referred. A ctive o xygen

absorbing barrier resins also may be employed in combination with or in place of the listed

passive barrier resins.

Other aspects of the invention include a plastic container preform, methods of

making a plastic container and a preform, a barrier resin blend, a method of processing a barrier

resin and a multilayer article in accordance with the invention. Brief Description of the Drawings

The invention, together with additional objects, features, advantages and aspects

thereof, will be best understood from the following description, the appended claims and the

accompanying drawings, in which:

FIGS. 1 to 4 are graphic illustrations of test results on containers fabricated in

accordance with exemplary embodiments of the invention,

FIGS. 5 A and 5B are schematic diagrams of a container preform in accordance

with one aspect of the invention, and

FIGS. 6 A and 6B are schematic diagrams of aplastic container in accordance with

another aspect of the invention.

Detailed Description of Preferred Embodiments

The Ken-React Reference Manual, published by Kenrich Petrochemicals, 2^nd

edition 1993, Bulletin KR 0401, is incorporated herein by reference.

Containers and preforms in accordance with the present invention have a

multilayer wall with at least one layer of polyester resin alternating with at least one layer of

barrier resin. (Additional layers not germane to the present invention may also be included, such

as post consumer resin layers.) For example, a three-layer container or preform may have a wall

with layers in the sequence polyesterΛarrier/polyester. A five-layer container or preform may

have wall layers in the sequence polyeste^arrier/polyester/barrier/polyester. The barrier layer

or layers may extend throughout the bottom wall and the sidewall of the container or preform,

or may be confined to a portion of the sidewall, for example. The barrier layers may or may not

extend into the finish of the container or preform. FIGS. 6 A and 6B are schematic illustrations

of a five-layer container in accordance with the invention, the size and geometry being for

illustrative purposes only. All exemplary test containers (and preforms) are five-layer containers (and preforms) ofthe type illustrated in FIGS. 6Aand 6B (and FIGS. 5A and5B). In accordance

with one aspect ofthe present invention, an organometallic coupling agent based upon titanium,

zirconium or aluminum is blended in each barrier layer and/or each polyester layer to promote

adhesion between the barrier and polyester layers.

The polyester resin preferably is selected from the group consisting of PET, PEN,

blends and copolymers of PET and PEN, and process regrind that consists essentially of PET,

PEN, or blends or copolymers of PET and PEN. In the examples discussed in the present

application, the polyester resin was PET.

The barrier resin is a thermoplastic material that has a low gas and/or water vapor

transmission rate, and/or exhibits a high barrier to transmission of flavorants including odorants

and essential oils. The following materials are preferred: EVOH, nylon (including amorphous

nylon and semicrystalline nylon such as MXD6), acrylonitrile copolymers, blends of EVOH and

nylon, blends of EVOH and an ionomer, cyclic olefin copolymers, PGA, nanocomposites of

EVOH or nylon and clay, and blends thereof. EVOH and nylon are particularly preferred.

MXD6 nylon and EVOH were employed as barrier resins in the examples discussed in this application.

The organometallic coupling agents employed in the present invention preferably,

although not necessarily, are marketed by Kenrich Petrochemicals Inc. of Bayonne, New Jersey.

Coupling agents that are amino functionalized - i.e., that include, an amino end group - are

preferred. Such amino end groups in the coupling agent have an affinity for polyester, carbonyl

and acid end groups in the structural resin layers. Neopentyl(diallyl)oxy, tri(N-ethylenediamino)

ethyl titanate marketed under the trade designation LICA-44 and neopentyl(diallyl)oxy, tri(N-

ethylenediamino) ethyl zirconate marketed under the trade designation NZ-44 are particularly

preferred. Corresponding organometallic coupling agents based upon aluminum can tint the wall of a clear (non-colored) plastic container, but may be employed where the container is

intentionally colored and such tinting would not be an issue. Other coupling agents marketed by

Kenrich and having amino end groups include isopropyl tri(N-ethylenediamino) ethyl titanate

(KR-44), neopentyl (diallyl)oxy, tri(m-amino) phenyl titanate (LICA-97),

dineopentyl(diallyl)oxy, diparamino beneoyl zirconate (NZ-37) and neopentyl(diallyl)oxy, tri(m-

amino)phenyl zirconate (NZ-97). NZ-44 and LICA- 44 coupling agents were employed in the

examples discussed in this application.

It is currently preferred that the coupling agent be blended with the barrier resin.

Because the barrier resin layers form a relatively small percentage by weight of the overall

preform or container, a lesser quantity of coupling agent is required than if the coupling agent

were blended with the polyester resin. However, the coupling agent could be blended with the

polyester resin, or with both the polyester resin and the barrier resin, in accordance with the

broadest aspects of the invention.

The organometallic coupling agent typically is in the form of a liquid, and

preferably is blended with the barrier resin material prior to forming the multilayer container.

In the tests described in this application, the liquid coupling agent additive was blended with

particles of the barrier material (MXD6 or EVOH) at room temperature before feeding the blend

to the extruder. This blending could also be done by master batch concentration by the barrier

material supplier. The coupling agent acts as a melt phase modifier during the manufacturing

process, which c an 1 ower t he p rocessing t emperature and/or p ermit u se o f h igher i ntrinsic

viscosity (IV) barrier resins. Higher IV barrier resins tend to have better barrier properties, and

thus the present invention facilitates improved barrier properties of the resin without increasing

the thickness of the barrier resin layer. The following Table 1 shows plaque screening test results

on MXD6 barrier material without coupling agent (control), or blended with either LICA-44 or NZ-44 coupling agent, or blended with LICA- 12 (neopentyl(diallyl)oxy, tri(dioctyl)phosphato

titanate) or NZ- 12 (neopentyl(diallyl)oxy, tri(dioctyl)phosphato zirconate) coupling agents also

supplied by Kenrich:

Table 1

The plaques were made by injection molding at the processing temperatures indicated in the

Table. Theplaques were stepped plaques 6.25 in (158.75 mm) long by 1.75 in (44.45 mm) wide.

The plaques had five equal sections of stepped thicknesses of 0.16 in (4.06 mm), 0.13 in (3.3

mm), 0.10 in (2.54 mm), 0.07 in (1.78 mm) and 0.04 in (1 mm). The visual tests consisted of

observation whether the plaque mold had completely filled. The control sample required a

processing temperature of 26O⁰C to fill the plaque mold completely, while the samples with

coupling agents required a processing temperature of only 23O⁰C to fill the plaque mold

completely. It will also be noted that LICA-12 and NZ- 12 coupling agents, which have

phosphate end groups rather than amino end groups, also achieved the reduced processing

temperature, although these additives would not be preferred for promoting adhesion to polyester

layers because of the absence of the amino end groups.

Table 1 also indicates the relative viscosities (RV) and intrinsic viscosities (FV)

of the base resin and the plaques. These viscosities were measured in a Viscotek model Y501C viscometer employing standard dilute solution viscometry techniques. Relative viscosities were

measured at the "low" range of the equipment. Intrinsic viscosities were measured as described

in the equipment manual with use of the Solomon-Gatesman equation. Resin viscosities were

measured at 3O⁰C in 60:40 Phenol: 1,1, 2,2 Tetrachloroethane. Thus, as shown in Table 1, the

coupling agents permitted the processing temperature to be lowered 30°C and still make good

plaques. The control (MXD6 without coupling agent) could not be processed at temperatures

below 26O⁰C in the equipment employed. (The same Arburg Model 320-210-500 molding

equipment was employed for all tests.) There were no significant differences among the intrinsic

viscosities of the blends and the control, demonstrating that there was no degradation of the

polymer molecular weight.

The following Table 2 demonstrates the increase in barrier properties employing

an MXD6 barrier resin of higher intrinsic viscosity (IY), which was enabled by blending the

barrier resin with the coupling agent. Li test containers of Table 2, the containers with MXD6

barrier resin were of the five-layer construction of FIGS, 6A and 6B, with the total weight

percentages of barrier resin (blended with coupling agent) being 3 %, such that each barrier layer

was approximately 1.5 wt % of the total container weight. That is, the NZ-44 coupling agent was

0.5 wt % of the total barrier resin, and the blend of coupling agent and barrier resin was 3 wt%

of the containers.

Table 2

* Measured @ 3O⁰C in 60:40 Phenol : 1,1,2,2 Tetrachloroethane employing the Viscotek equipment and techniques discussed above.

** 28mm 500 ml beverage containers were filled at 3.0 gas volumes of C O₂ by chemical carbonation techniques and were capped with 28 mm closures. These closures were polypropylene closures with ethylene vinyl acetate (EVA) liners as disclosed in U.S. Patent 5,306,542. After being allowed to equilibrate for 14 days at 68F/50% RH storage, the total container CO₂ transmission rate was measured by placing the container within a sealed vessel with a known capture volume. The sealed vessel had two ports through which nitrogen carrier gas flowed in through one of the ports and exited the vessel from the other port. The exit port was directed to a Mocon C-IV CO₂ test machine used for detecting the amount of CO₂. The quantity of CO₂ was measured for a period of time, from which the CO₂ transmission rate was determined.

The process of container manufacture preferably involves manufacture of a

preform, followed by blow molding the preform to form the container. In the examples discussed

in this application, the preform was formed in a sequential injection molding operation of a type

illustrated in U.S. Patents 4,550,043, 4,609,516, 4,710,118 and 4,954,376. FIGS. 5A and 5B are

a schematic illustrations of a preform in accordance with the invention, the size and geometry

being for illustrative purposes only. However, the preform can also be formed in a simultaneous

injection molding operation of a type illustrated in U.S. Patents 4,990,301 and 5,098,274, an

over-molding operation of a type illustrated in U.S. Patent 6,428,737, a compression molding

operation of a type illustrated in U.S. published application 2002/0098310 using a mold charge

that includes the polyester resin and the barrier resin/coupling agent blend, or in a coextrusion operation that produces a hollow tube having alternate layers of polyester resin and barrier resin

blend. These specific citations are merely exemplary.

The amount of coupling agent blended with the barrier resin preferably does not

exceed about 4% by weight of the blend. The amount of coupling agent more preferably does

not exceed about 1.5% by weight of the blend. All percentages in this application are by weight

unless otherwise indicated.

The presently preferred coupling agents identified above are well suited for the

chemistries of the disclosed barrier and polyester resins. The chemical functionalities of the

coupling agents do not affect the processability or barrier properties of the barrier material, other

than acting as a melt phase modifier as discussed above. The preferred organometallic coupling

agents promote bonding between the polyester and barrier resin layers while the materials are in

contact at elevated melt temperatures; it was difficult to separate the layers of apreform after the

preform had cooled. While not being bound by any particular theory or mechanism, one theory

is that the bonding between the polyester resin layers and the barrier resin layers promoted by the

organometallic coupling agents includes covalent bonding, ionic bonding and/or polar bonding

depending upon the type of barrier resin employed.

FIGS. 1-4 illustrate delamination test results on various container samples

constructed in accordance with the present invention. Each container had a five-layer wall of

PET/MXD6/PET/MXD6/PET configuration (FIGS. 1-3B) or PET/EVOH/PET/EVOH/PET

configuration (FIG. 4). In all tests, the containers were experimental containers constructed for

comparison purposes only. The tests were arbitrarily devised to obtain differentiation in data,

and do not reflect anyperformance specification or conditions of use. hi each figure, the ordinate

indicates the percentage of containers in which delamination was observed by visual inspection

as a result of the test, while the abscissa indicates the container structure, specifically the total amount of barrier material by weight and the amount of NZ- 44 or LICA 44 coupling agent

employed. With the exception of the amount and type of coupling agent (NZ-44 or LICA-44),

and the type of barrier resin employed (EVOH or MXD6), all containers in each test were

identical.

FIG. 1 illustrates the results of drop tests performed on twenty-four ounce non-

round containers having a rounded rectangular cross section. The containers were filled with

water, in which a blue dye was added to facilitate visual identification of delaminations where

they occurred. The barrier layers totaled 1.5% of the containers by weight, with the percentages

of NZ-44 or LICA-44 indicated in FIG. 1 (and in FIGS. 2A-4) being percentages of the total

barrier layers -e.g., 0.20% of the 1.5% barrier layer or 0.003 % coupling agent based upon the

total weight of the container. The filled containers were dropped onto a cement base from a

height of three feet so that the containers impacted on their bottoms, and then were examined

for delamination. As shown in FIG. 1, approximately 22% of the containers showed

delamination without the NZ-44 or LICA-44 coupling agent in the barrier layers. The containers

having MXD6 blended with 0.2 % LICA-44 showed delamination in 10% of the containers. The

percentage of containers showing delamination progressively decreased in container have 0.20%,

0.35% and 0.50% NZ-44. The last column in FIG. 1 shows delamination in 5% of containers

when NZ-44 in the amount of 0.50% by weight was mixed with the MXD6 barrier material. This

percentage of NZ-44 zirconate coupling agent was then employed in subsequent tests (FIGS .2 A-

4).

FIGS. 2 A and 2B illustrate side-impact test results on 400 ml cylindrical

carbonated beverage containers. This side-impact testing involved a single impact against the

container sidewall with a steel wedge and with the container clamped in stationary position. The

energy of the impact was approximately 3.3 joules. FIG. 2 A illustrates test results with the containers filled with water, and FIG. 2B illustrates test results with the containers filled with

water and carbonated at 3.0 GV (gas volumes). The barrier resin layers totaled 3% by weight of

the containers. In the samples having a coupling agent, the coupling agent was in the amount of

0.50% of the total barrier resin layers. Both FIGS. 2A and 2B show significant percentages of

containers without the coupling agents of the present invention exhibiting delamination after

testing, while containers in which the coupling agent was blended with the barrier resin exhibited

no delamination after testing.

FIGS. 3 A and 3B illustrate the results of drop tests on highly embossed 500 ml

cylindrical beverage containers. These embossments were decorative design details molded into

the container walls, and tend to act as stress concentrators and promote delamination in the

container walls. In both of the tests of FIG. 3 A and 3B, the containers were filled with water and

dropped onto a cement base to impact on their bottoms. FIG. 3 A illustrates the results of a three-

foot drop. The containers containing MXD6 barrier material exhibited delamination in 6% of

the containers, while the containers having MXD6 with 0.50% NZ-44 in the barrier layers

exhibited no delamination. The drop height was then increased to six feet, with the results being

illustrated in FIG. 3B. The containers without coupling agents exhibited delamination in 42%

of the containers, while the containers with coupling agent exhibited delamination in only about

8 % of the containers . The coupling agent/barrier resin blend constituted 3 % of the total container

weight in the tests of FIGS . 3 A and 3B .

FIG. 4 illustrates the results of a three- foot drop test on eight ounce cylindrical

containers having 5% EVOH (or EVOH blended with coupling agent) as the barrier layer. In the

three-foot drop test, in which the water-filled container was dropped onto its base as described

above in connection with FIG. 1, FIG. 4 shows that there was a 20% reduction in delamination

when the coupling agent was blended with the barrier material. In a side-impact test, in which the water-filled container was impacted on its sidewall as described above in connection with

FIG. 2A, the containers showed no delamination both with and without the coupling agent.

There have thus been disclosed a multilayer container, a multilayer preform, a

barrier resin blend for use in a multilayer container, a method of making a multilayer preform or

container, and a multilayer plastic article of manufacture that fully satisfy all of the objects and

aims previously set forth. The container, barrier blend and method of manufacture have been

disclosed in conjunction with a number of exemplary embodiments thereof, and several

modifications and variations have been discussed. Other modifications and variations will

readily suggest themselves to persons of ordinary skill in the art. For example, the invention in

its broadest aspects can also be applied to other articles of manufacture having multilayer walls,

particularly walls with one or more barrier layers, such as container closures and liners, or films

or sheets for later thermoforming, without departing from the scope of the invention in its

broadest aspects. The invention is intended to embrace all such modifications aid variations as

fall within the spirit and broad scope of the appended claims.

Claims

1.

A plastic container having a multilayer wall that includes:

at least one layer of polyester resin,

at least one layer of barrier resin, and

an adhesion-promoting material blended with said barrier resin and/or said

polyester resin to promote bonding between said barrier and polyester layers, said adhesion-

promoting material including an organometallic coupling agent based upon titanium, zirconium

or aluminum.

2.

The container set forth in claim 1 wherein said organometallic coupling agent

includes an amino end group.

3.

The container set forth in claim 2 wherein said organometallic coupling agent is

selected from the group consisting of: neopentyl(diallyl)oxy, tri(N-ethylenediamine) ethyl

titanate, zirconate and aluminate.

4.

The container set forth in claim 3 wherein said coupling agent consists essentially

of neopentyl(diallyl)oxy, tri(N-ethylenediamine) ethyl titanate or zirconate.

5.

The container set forth in claim 1 wherein said polyester resin is selected from the

group consisting of: PET, PEN, blends or copolymers of PET and PEN, and process regrind

consisting essentially of PET, PEN, or blends or copolymers of PET and PEN.

6.

The container set forth in claim 1 wherein said barrier resin is selected from the

group consisting of: EVOH, nylon, acrylonitrile copolymers, blends of EVOH and nylon,

nanocomposites of EVOH or nylon and clay, blends of EVOH and an ionomer, acrylonitrile,

cyclic olefin copolymers, polyglycolic acid, and blends thereof.

7.

A plastic container having a multilayer wall that includes:

at least one layer of polyester resin selected from the, group consisting of PET,

PEN, blends or copolymers of PET and PEN, and process regrind that consists essentially of

PET, PEN, or blends or copolymers of PET and PEN,

at least one layer of barrier resin selected from the group consisting of EVOH,

nylon, acrylonitrile copolymers, blends of EVOH and nylon, nanocomposites of EVOH or nylon

and clay, blends of EVOH and an ionomer, acrylonitrile, cyclic olefin copolymers, polyglycolic

acid, and blends thereof, and

an organometallic coupling agent blended in said at least one layer of barrier resin

to promotebondingbetween said barrier and polyester layers, said organometallic coupling agent

having an amino end group that has an affinity for carboxylic end groups in the polyester resin and being selected from the group consisting of neopentyl(diallyl)oχy, tri(N-ethylenediamine) ethyl titanate, zirconate and aluminate.

8.

The container set forth in claim 7 wherein said coupling agent is selected from the

group consisting of neopentyl(diallyl)oxy, tri(N-ethylenediamine) ethyl titanate, zirconate and aluminate.

9.

The container set forth in claim 8 wherein said coupling agent consists essentially

of neopentyl(diallyl)oxy, tri(N-etliylenediamine) ethyl titanate or zirconate.

10.

A barrier resin blend for use in a layered plastic container, said barrier resin blend including:

a barrier resin to resist transmission of gas, water vapor or flavorants, and

an organometallic coupling agent based on titanium, zirconium or aluminum, said

coupling agent having an amino end group to promote bonding between said barrier resin and

adjacent layers in a container.

11.

The barrier resin blend set forth in claim 10 wherein said organometallic coupling

agent is selected from the group consisting of: neopentyl(diallyl)oxy, tri(N-ethylenediamine)

ethyl titanate, zirconate and aluminate.

12.

The barrier resin blend set forth in claim 11 wherein said coupling agent consists

essentially of neopentyl(diallyl)oxy, tri(N-ethylenediarnine) ethyl titanate or zirconate.

13.

The barrier resin blend set forth in claim 10 wherein said barrier resin is selected

from the group consisting of: EVOH, nylon, acrylonitrile copolymers, blends of EVOH and

nylon, nanocomposites of EVOH or nylon and clay, blends of EVOH and an ionomer,

acrylonitrile, cyclic olefin copolymers, polyglycolic acid, and blends thereof.

14.

A method of making a multilayer plastic container that includes:

(a) blending an organometallic coupling agent based on titanium, zirconium

or aluminum with a barrier resin, and

(b) forming a preform in which the blend formed in step (a) is in layers

alternating with layers of polyester resin, and in which said coupling agent promotes bonding

between said barrier resin and said polyester resin.

15.

The process set forth in claim 14 further including: (c) blow molding the preform

formed in step (b) into a hollow plastic container,

16.

The method set forth in claim 14 wherein said step (b) is carried out while said

blend formed in said step (a) and said polyester resin are in melt phase.

17.

The method set forth in claim 16 wherein said step (b) is carried out by a process

selected from the group consisting of simultaneously injection molding said polyester resin and

said barrier resin blend, sequentially inj ection molding said polyester resin and said barrier resin

blend, overmolding sequential layers of said polyester resin and said barrier resin blend,

compression molding a mold charge that includes said polyester resin and said barrier resin

blend, and extruding a hollow tube that includes alternate layers of said polyester resin and said barrier resin blend.

18.

The method set forth in claim 14 wherein said coupling agent has an amino end group.

19.

The method set forth in claim 18 wherein said organometallic coupling agent is

titanate, zirconate and aluminate.

20.

The method set forth in claim 19 wherein said coupling agent consists essentially

of neopentyl(diallyl)oxy, tri(N-ethylenediamine) ethyl titanate or zirconate.

21.

The method set forth in claim 18 wherein said polyester resin is selected from the

consisting essentially of PET, PEN, or blends or copolymers of PET and PEN.

22.

The method set forth in claim 18 wherein said barrier resin is selected from the

iianocomposites of EVOH or nylon and clay, blends of EVOH and an ionomer, acrylonitrile,

cyclic olefin copolymers, polyglycolic acid, and blends thereof.

23.

A preform for blow molding a plastic container having a multilayer wall, which

, includes:

at least one layer of polyester resin,

at least one layer of barrier resin, and

an adhesion-promoting material blended with said barrier resin and/or said

or aluminum.

24.

The preform set forth in claim 23 wherein said organometallic coupling agent

includes an amino end group.

25.

The preform set forth in claim 24 wherein said organometallic coupling agent is

titanate, zirconate and aluminate.

26.

The preform set forth in claim 25 wherein said coupling agent consists essentially

of neopentyl(diallyl)oxy, tri(N-ethylenediamine) ethyl titanate or zirconate.

27.

1 The preform set forth in claim 23 wherein said polyester resin is selected from the

2 group consisting of: PET, PEN, blends or copolymers of PET and PEN, and process regrind

3 consisting essentially of PET, PEN, or blends or copolymers of PET and PEN.

28.

1 The preform set forth in claim 23 wherein said barrier resin is selected from the

2 group consisting of: EVOH, nylon, acrylonitrile copolymers, blends of EVOH and nylon,

^•3 nanocomposites of EVOH or nylon and clay, blends of EVOH and an ionomer, acrylonitrile,

4 cyclic olefin copolymers, polyglycolic acid, and blends thereof.

29.

1 A preform for blow molding a plastic container having a multilayer wall, which

2 includes:

3 at least one layer of polyester resin selected from the group consisting of PET,

4 PEN, blends or copolymers of PET and PEN, and process regrind that consists essentially of

5 PET, PEN, or blends or copolymers of PET and PEN,

6 at least one layer of barrier resin selected from the group consisting of EVOH,

7 nylon, acrylonitrile copolymers, blends of EVOH and nylon, nanocomposites of EVOH or nylon

8 and clay, blends of EVOH and an ionomer, acrylonitrile, cyclic olefin copolymers, polyglycolic

9 acid, and blends thereof, and

0 an organometallic coupling agent blended in said at least one layer of barrier resin

1 to promote bonding between said barrier and polyester layers, said organometallic coupling agent

2 having an amino end group that has an affinity for carboxylic end groups in the polyester resin and being selected from the group consisting of neopentyl(diallyl)oxy, tri(N-ethylenediamine)

ethyl titanate, zirconate and aluminate.

30.

The preform set forth in claim 29 wherein said coupling agent is selected from the

group consisting of neopentyl(diallyl)oxy, tri(N-ethylenediamine) ethyl titanate, zirconate and

aluminate.

31. The preform set forth in claim 30 wherein said coupling agent consists essentially

of neopentyl(diallyl)oxy, tri(N-ethylenediamine) ethyl titanate or zirconate.

32.

a barrier resin to resist transmission of gas, water vapor or flavorants, and

an organometallic coupling agent based on titanium, zirconium or aluminum, said

coupling agent functioning as a melt phase modifier to said barrier resin and lowering the

temperature required to process said barrier resin in melt phase.

33.

The barrier resin blend set forth in claim 32 wherein said organometallic coupling

agent is selected from the group consisting of: neopentyl(diallyi)oxy, tri(N-ethylenediamine)

ethyl titanate, zirconate and aluminate.

34.

The barrier resin blend set forth in claim 33 wherein said coupling agent consists

essentially of neopentyl(diallyl)oxy, tri(N-ethylenediamine) ethyl titanate or zirconate.

35.

The barrier resin blend set forth in claim 32 wherein said barrier resin is selected

nylon, nanocomposites of EVOH or nylon and clay, blends of EVOH and an ionomer,

acrylonitrile, cyclic olefin copolymers, polyglycolic acid, and blends thereof.

36.

A method of processing a barrier resin having a predetermined intrinsic viscosity,

which includes:

(a) processing said barrier resin in melt phase, and

(b) blending said barrier resin prior to or during said step (a) with a melt phase

modifier that includes an organometallic coupling agent based upon titanium, zirconium or

aluminum to reduce the temperature required in said step (a) to process said barrier resin in melt

phase.

37.

The method set forth in claim 36 wherein said organometallic coupling agent is

selected from the group consisting of: neopentyl(diallyl)oxy₅ tri(N-ethylenediamine) ethyl 3 titanate, zirconate and aluminate, and neopentyl(diallyl)oxy, tri(dioctyl)phosphato titanate,

4. zirconate and aluminate.

38.

1 The method set forth in claim 30 wherein said organometallic coupling agent is

2 selected from the group consisting of: neopentyl(diallyl)oxy, tri(N-ethylenediamine) ethyl

3 titanate or zirconate, and neopentyl(diallyl)oxy, tri(dioctyl)phosphato zirconate or titanate.

4 ^{• ■}

5 39.

6 A plastic article of manufacture having a multilayer wall that includes:

7 at least one layer of polyester resin,

8 at least one layer of barrier resin, and

9 an adhesion-promoting material blended with said barrier resin to promote

0 bonding between said barrier and polyester layers, said adhesion-promoting material including

1 an organometallic coupling agent based upon titanium, zirconium or aluminum.

40.

1 The article set forth in claim 39 wherein said organometallic coupling agent

2 includes an amino end group.

41.

1 The article set forth in claim 40 wherein said organometallic coupling agent is

3 titanate, zirconate and aluminate.

42.

The article set forth in claim 41 wherein said coupling agent consists essentially

of neopentyl(diallyl)oxy, tri(N-ethylenediamine) ethyl titanate or zirconate.

43.

. The article set forth in claim 39 wherein said polyester resin is selected from the

consisting essentially of PET, PEN, or blends or copolymers of PET and PEN.

44.

The article set forth in claim 39 wherein said barrier resin is selected from the

cyclic olefin copolymers, polyglycolic acid, and blends thereof.