CN101166783A - Polyester composition with enhanced gas barrier, articles made therewith, and methods - Google Patents
Polyester composition with enhanced gas barrier, articles made therewith, and methods Download PDFInfo
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- CN101166783A CN101166783A CNA2005800495323A CN200580049532A CN101166783A CN 101166783 A CN101166783 A CN 101166783A CN A2005800495323 A CNA2005800495323 A CN A2005800495323A CN 200580049532 A CN200580049532 A CN 200580049532A CN 101166783 A CN101166783 A CN 101166783A
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- dihydroxy naphthlene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/008—Additives improving gas barrier properties
Abstract
A polyester composition with enhanced gas barrier properties comprises a polyester and an organic gas barrier enhancing additive having the chemical formula OH-AR-OH, wherein AR is substituted or unsubstituted naphthalene. Articles with enhanced gas barrier and methods for making gas barrier enhanced polyesters and articles are disclosed.
Description
Technical field
The present invention relates to polyester and polyester article.Especially, the present invention relates to the polyester that in the application such as packed drink, uses, wherein the gas barrier or the Oxygen scavenging performance that improve of expectation.
Background technology
Polyethylene terephthalate and copolyesters thereof (hereinafter being referred to as " PET ") are widely used in the container of making carbonated soft drink, fruit juice, water and analogue, and this is because they have the excellent combination of transparency, machinery and capacity for air resistance.Although they have these ideal features, PET has limited the packing that PET is applied to reduced size to the capacity for air resistance deficiency of oxygen and carbonic acid gas, and the quick product of packing oxygen, for example food, beer, fruit juice and tea product.In packaging industry, exist extensively clear and definite demand in the hope of further improving the capacity for air resistance of PET.
PET has limited the high relatively rate of permeation of carbonic acid gas and has used less pet container packing carbonated soft drink.At room temperature, the infiltration rate scope of carbonic acid gas by pet container is 3-14cc/ days or the loss speed of 1.5-2% weekly, and this depends on the size of container.Less container has bigger S/V, thereby causes higher relative loss speed.For this reason, pet container is at present only as bigger container package carbonated soft drink, and metal tin and Glass Containers are less carbonated soft drink container selection.
Many technology or been have have been researched and developed, to improve PET stopping to little gas molecule.For example, researched and developed outside or the coated inside that improves the gas barrier of pet container.The blocking layer that this coating layer is normally very high, it or inorganic or organic, and the diffusion of the gas that slows down.Yet, implement this technical requirements coating apparatus, described coating apparatus does not use in making packed drink usually.Therefore require significant capital investment, the energy usage quantity of increase and the ground space that increases.In crowded many drink packs workshop, additional space is not the scheme of selecting.
Also researched and developed the laminated vessel that between two-layer or more multi-layered pet layer, accompanies high blocking layer.Implement this technology and also require significant capital investment, and the delamination of container floor influences outward appearance, block and the mechanical property of container.
PET or polymkeric substance barrier additive with inherent barrier properties are preferred solutions.Any in this solution all do not require extra capital investment, therefore do not have other technology inherent limitation.Also can add barrier additive in the Shooting Technique process, this will provide greater flexibility for downstream process.
L.M.Robeson and J.A.Faucher are at J.Polymer Science, and Part B7 discloses some additives and can be incorporated in the polymkeric substance among the 35-40 (1969), increase its modulus and capacity for air resistance by anti-plasticizing mechanism.These goods disclose and have utilized additive and polycarbonate, polyvinyl chloride, polyphenylene oxide and polyethylene oxide.
In WO01/12521, people such as Plotzker have proposed to use the additive that is selected from 4-hydroxybenzoate and the associated molecule to increase the capacity for air resistance of PET.The patent application of this announcement discloses the barrier additive of following structure:
HO-Ar-COOR、HO-Ar-COOR1COO-AR-OH、HO-AR-CONHR、HO-AR-CO-NHR3-COO-AR-OH、HO-AR-CONHR2NHCO-AR-OH
In aforementioned structure, AR is selected from and replaces or unsubstituted phenylene or naphthylidene.R1, R2 and R3 are selected from C1-C6 alkyl, phenyl and naphthyl.
Disclosed aforementioned additive provides the only moderate improvement of PET block in this area, for best example, under the situation that adopts 5wt% load level, to stopping of oxygen little 2.1 times (X).Yet, under this load level, the remarkable decline of significant degraded of PET experience and intrinsic viscosity (IV).Although reduce the degraded that content of additive will reduce PET, it also can reduce barrier improvement factor so greatly, so that there is not the benefit of reality when using these additives in packing carbonated soft drink or the quick food of oxygen.In addition, can not for example use PET in the beverage container at blow-molded container with significantly low IV.And the PET of low IV makes container have poor mechanical property, for example creep and shock of a fall etc.Again further, the pet container of being made by the PET that hangs down IV has poor stress cracking resistance, and this is non-required in container application.
With other component modification PET or with its blend, to improve the gas barrier of PET.Example comprises Polyethylene Naphthalate (PEN)/PET multipolymer or blend, the PET of isophthalic acid ester (IPA) modification, and with poly-ethylene m-phthalate (PEI) or polymeric amide, the PET of nylon blending and with the PET of resorcinol based diols modification for example.Realize that for the PET multipolymer 2X or higher appropriateness stop raising, modification (modification) common 10-20wt or mol% greater than whole comonomers.When modified PET arrived this high level, the stretch characteristic of PET sharply changed, and the result can not use normal pet container preform design in the manufacturing of container.Tensile preform and final container are very difficult to make to use the pet container preform of these PET copolymer molding routines will cause fully, if not impossible words.Even can make this container, but it does not demonstrate improved barrier properties and demonstrates the physicals of deterioration, and it can not be used to pack carbonated soft drink as a result.United States Patent (USP) 5888598 and 6150450 discloses the pet container preform of the redesign with thicker sidewall, with the stretch ratio of compensation increase.Yet the mould that this thicker preform will be looked for novelty, described new die require extra capital investment and with lower throughput rate manufacturing, this is because need long time cooling of cost and heating than the heavy-walled preform.In addition, PET and polymeric amide, for example blend yellowing of nylon and form mist degree, and do not resemble the conventional PET transparent.
To the product of oxygen sensitive, for example food, beverage and medicine in the presence of oxygen with deterioration and corruption.In order to prevent that oxygen from entering product, researched and developed different oxygen scavenger technologies.These oxygen scavenqers are called as barrier technique initiatively.They are different from passive barrier technique and are, the latter is only worked improving aspect the stopping of little gas molecule.United States Patent (USP) #5021515 discloses the multilayer nylon based oxygen scavenger.United States Patent (USP) #5744056 discloses a kind of oxygen scavenging compositions, and it can be incorporated in the sidewall of bottle in the mode of individual layer.Similarly, United States Patent (USP) #5700554 discloses a kind of oxygen scavenging compositions.Compare with the multilayer oxygen scavenqer, monolayer oxygen scavenger provides extra benefit to be, monolayer oxygen scavenger except stopping that oxygen enters in the container, also can with the oxygen reaction in the container top space.Therefore, monolayer oxygen scavenger can prevent the dioxygen oxidation product because of headspace.Yet disclosed oxygen scavenging compositions all contains transition metal as catalyzer in these and other similar patent.Transition metal can cause the PET degraded and cause the PET variable color.In addition, in some countries, some transition metal also produce environment and rules worry.
Therefore, this area still needs to improve the barrier properties of PET in the hope of using in the application of the block that requires to improve, for example be used to pack soda pop and quick beverage of oxygen and food, its mode will not cause that PET significantly degrades, have no significant effect the stretch ratio of PET, do not comprise transition metal, and allow to use existing PET preform mould.
Summary of the invention
Contain the polymer blend (wherein AR replaces or unsubstituted naphthalene) that makes the organic additive that gas barrier improves that polyester and chemical formula are OH-AR-OH by providing, the invention solves above-described demand the gas barrier PET that improves.
According to special embodiment, the polyester in polymer blend comprises poly-(ethylene glycol terephthalate) base co-polymer (PET multipolymer).In required embodiment, based on 100mol% diacid component and 100mol% diol component, polyester comprise the diacid component modification less than 20% and/or the diol component modification less than 10% PET multipolymer.The organic additive that employing improves gas barrier, this embodiment will provide acceptable gas barrier, although the modification degree of diacid or glycol is low, if there is any modification.Under situation about being not wishing to be bound by theory, think that embodiments more of the present invention have gas barrier capability, and another embodiment has bigger oxygen scavenging capacity, perhaps has gas barrier and oxygen scavenging capacity simultaneously.
According to another embodiment, the present invention includes the method that improves the polymer blend gas barrier, described polymer blend comprises polyester, is that the organic additive that gas barrier is improved of OH-AR-OH mixes mutually with chemical formula, wherein AR replaces or unsubstituted naphthalene.According to embodiment preferred, polyester is the PET multipolymer.
According to an embodiment again, the present invention includes a kind of goods, described goods comprise that polyester and chemical formula are the organic additive that gas barrier is improved of OH-AR-OH, wherein AR replaces or unsubstituted naphthalene.According to special embodiment, goods are containers and in other embodiment preferred, are the tensile blow-molded containers.In preferred embodiments, polyester is the PET multipolymer.
According to an embodiment again, the present invention includes the method for making the goods that gas barrier improves, this method comprises the steps: that blending polyester and chemical formula are the organic additive that gas barrier is improved of OH-AR-OH, wherein AR replaces or unsubstituted naphthalene.In special embodiment, polyester is the PET multipolymer.In addition, in another embodiment, goods are stretch blow molded containers.
Special embodiment of the present invention provides gas barrier to improve and especially to the polyester of the block raising of carbonic acid gas and oxygen, for example the PET multipolymer.This makes embodiments more of the present invention be particularly suitable for packing carbonated soft drink and quick beverage of oxygen and food.Special embodiment will realize the gas barrier of this raising, keep acceptable physicals simultaneously.
According to following detailed description, accompanying drawing and claim, other purpose of the present invention, feature and advantage will become apparent.
Description of drawings
Fig. 1 is according to embodiment of the present invention, the synoptic diagram of the system of the pet container that the manufacturing gas barrier improves.
Fig. 2 is the cross-section elevation according to the mold container preform of embodiment of the present invention manufacturing.
Fig. 3 is according to embodiment of the present invention, the cross-section elevation of the blow-molded container of being made by the preform of Fig. 2.
Fig. 4 is the sectional view according to the packed drink of embodiment of the present invention manufacturing.
Specific embodiments
The present invention includes gas barrier or oxygen scavenging capacity or polymer blend that these two all improves, improve the method for polymer blend gas barrier or oxygen scavenging capacity, contain the goods of this polymer blend and make the method for this goods.Just as described in more detail below, embodiment of the present invention provide a kind of polymer blend and with the goods of its manufacturing, it demonstrates the gas barrier or the oxygen scavenging capacity of raising, keeps physicals simultaneously.
The present invention can be applicable on any polyester, and is suitable for wherein wishing the purposes of high gas barrier.Suitable polyester comprises those that are suitable for packing quick beverage of carbonic acid or noncarbonated beverage products and oxygen or foods prods.The suitable polyester of Shi Yonging comprises PET multipolymer, Polyethylene Naphthalate (PEN), poly-ethylene m-phthalate and analogue in embodiments of the invention.The PET multipolymer is particularly useful, and this is because they are used for many barrier applications, for example in film and the container.Suitable containers includes, but not limited to bottle, bucket, carafe, water cooler and analogue.
The PET multipolymer that is suitable for using in embodiments of the invention comprises having from the diol component of the repeating unit of ethylene glycol with from the dibasic acid component of the repeating unit of terephthalic acid.It is desirable to, in some embodiments, based on the dibasic acid component of 100mol% and the diol component of 100mol%, the PET multipolymer has less than 20% dibasic acid component modification and/or less than 10% diol component modification.This PET multipolymer is well-known.
According to embodiment of the present invention, suitable organic gas stops that improving additive is that chemical formula is those of OH-AR-OH, and wherein AR replaces or unsubstituted naphthalene.Suitable additive comprises, but is not limited to, 1, and 2-dihydroxy naphthlene, 1,3-dihydroxy naphthlene, 1,5-dihydroxy naphthlene, 1,6-dihydroxy naphthlene and 2,6-dihydroxy naphthlene.1, the 5-dihydroxy naphthlene is degraded under the polyester melt processing temperature, is not preferred additives therefore, but can uses under lower melt processing temperature.Do not enumerate 2,7 dihydroxy naphthalene, this is because it has even lower degradation temperature, and is not suitable for the additive as PET.
Organic gas is stopped that improving additive compound joins in the polyester with the consumption of the capacity for air resistance that is enough to improve polyester.According to embodiment of the present invention, polyester is present in the polymer blend with the consumption of the 99.9%-90% of polymer blend weight and organic additive that gas barrier improves is present in the polymer blend with the consumption of the 0.1%-about 10% of polymer blend weight.According to another embodiment of the invention, the PET multipolymer is present in the polymer blend with the consumption of the 99.9%-about 95% of polymer blend weight and additive is present in the polymer blend with the consumption of about 0.1%-about 5% of polymer blend weight.The embodiment again according to the present invention, PET multipolymer are present in the polymer blend with the consumption of about 9 % of about 99.9%-of polymer blend weight and additive is present in the polymer blend with the consumption of about 0.1%-about 3% of polymer blend weight.
Polyester (comprising the PET multipolymer) has the free volume between polymer chain.As known to those skilled in the art, the free volume amount in the polyester such as the PET multipolymer determines its stopping gas molecule.Free volume is low more, and gaseous diffusion is low more and high more to stopping of gas molecule.In some embodiments, think that additive to small part is arranged in the polyester free volume between the polyester chain, and after melt, when the cooling blend to room temperature following time, in free volume, harden.Because there are two hydroxyls in additive, so it can react with polyester chain and cause that intrinsic viscosity (IV) descends, although the reactivity of hydroxyl is very low in additive of the present invention.Therefore, when additive and polyester fondant blend, additive can part with pet reaction and form the mixture of polyester/dihydroxy naphthalene copolymer, polyester and additive.For example,, during the 3-dihydroxy naphthlene, think additive, and form the part of polyester backbone to small part and pet reaction when additive is 1.According to special embodiment, polyester comprises poly-(ethylene glycol terephthalate) base co-polymer (PET multipolymer), can be based on the diol component of 100mol% dibasic acid component and 100mol%, the PET multipolymer has less than 20% dibasic acid component modification with less than 10% diol component modification, with at least a portion additive and PET copolymer reaction, so that diol component comprises the additive of the about 5mol% of 0.1-.
Additive can be incorporated in the polyester according to different modes.For example, under lower load level, promptly be less than or equal under the 3wt%, additive can directly be incorporated in the polyester in the Shooting Technique process.Can be in the vibrin manufacturing process premix, perhaps can be incorporated in the molten polyester, in melt polymerization process, discharge polyester afterwards.Under higher load level, promptly more than or equal under the 3wt%, additive can with the polyester premix, be melt extruded and solid state polymerized to required IV.Solid mixt can be injection molded into the container preform then, just as described in more detail below.
In some embodiments, wish to reduce the potential impact of any residual polycondensation catalyst in the polyester.These catalyzer comprise catalyzer commonly used, for example contain the compound and the analogue of antimony, titanium, tin, and by the P contained compound inactivation.P contained compound comprise organic and mineral compound the two.Example includes, but not limited to phosphoric acid, polyphosphoric acid and three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester, three single nonyl phenyl phosphites.Typically add these additives with consumption less than 2000ppm.
As mentioned above, polymer blend of the present invention can be used for making the goods of wherein wishing the gas barrier of raising.In brief,, above-described polymer blend is configured as required goods, thereby makes this goods by the ordinary method such as melt forming.Suitable melt forming technology includes, but not limited to injection moulding, extrudes, thermoforming and compression moulding.
Especially, embodiment of the present invention are suitable for making the container that is used for packaging application in carbonic acid and industry of non-carbonated soft drink and foodstuffs industry.The common manufacture method that forms these containers comprises the injection moulded containers preform, then by single hop, two sections and compound blowing manufacturing system, makes container by this preform.This method is that those skilled in the art is known, and discloses the suitable preform and the example of structure of container in United States Patent (USP) 5888598, and its disclosure is specially introduced by reference in its entirety at this.
More particularly, become blowable geometric format, thereby form the container preform by the injection moulding polyester.In die cavity, hold this preform then and maybe can blow form with required volume of a container structure, and by in the space of die cavity, blowing this preform with pressurized air, thereby make it to expand.
According to embodiment of the present invention, commercially available equipment (it is used to make the single-use PET beverage container of thin-walled) can be used for making container.In addition, also business equipment can be used, for example employed equipment in the pet container can be recharged at the heavy-walled of making routine.
According to embodiment of the present invention, can be by the cylindrical injection moulding preform with open top end and neck shape bottleneck (neckfinish), blowing suitable containers.This preform can have along the right cylinder side basically, and the taper of uniform thickness shoulder forms part, form part with the bottom of preferred champagne design, but comprise and have bottom cup-shaped (base cup) or pin shape (footed) design, for example domed bottom of petal-shaped design.In preferred embodiments, preform is unbodied, and substantial transparent and being injection molding.
According to the preferred embodiments of the invention, in the blowing device of the container preform has upper die part with being placed on (its engagement neck shape bottleneck), intermediate mold part (it has the internal chamber that forms the container side wall shape) and lower mould part (it has the outside recessed vault upper surface partly that forms container bottom).Reheat stretch blow mold process according to standard, at first the preform of reheat injection moulding places in the blow mold to the temperature (about 70-130 ℃) that is suitable for stretching and being orientated, and inserts the axial tension rod then in upper, open end, and moving down, so that axial tension preform.Subsequently or simultaneously, expanding gas is incorporated into the inside of preform, part is formed on outward radial expansion shoulder, sidewall and bottom, so that contact with the internal surface of mould part.The container of gained blowing has the neck shape bottleneck identical with preform and external screw-thread and minimum neck flange (neck flange).The rest part experience of bottle expands, although degree changes.Lid under can removing is contained on the upper, open end of container.Lid comprises the basic component with internal whorl, and described inner striped meshes external screw-thread on neck shape bottleneck.
Fig. 1 shows the system 10 of being made rigid container preform 12 (shown in Figure 2) and rigid container 14 (shown in Figure 3) according to an embodiment of the present invention by preform.As shown in Figure 1, solid PET copolymer pellets 20 and the organic additive that gas barrier is improved, for example dimethyl terephthalate (DMT) 22 joins in feeder or the hopper 24, and described feeder or hopper 24 carry each component in the hot melt forcing machine 26 of fusion within it of each component and blend.Hot melt forcing machine 26 is extruded the PET multipolymer and organic gas stops the molten mixture that improves additive in injection moulding apparatus 28 then, forms preform 12.The cooling preform also takes out from injection moulding apparatus 28, and be transported in the blowing device 30, is final rigid container 14 at this blowing preform 12.
As mentioned above, in the production of preform melt residence time preferably less than 3 minutes and about 120 seconds of 100-more preferably from about.Melt temperature is desirably about 300 ℃ and more desirably be about 290 ℃ of about 270-of 270-.When the PET multipolymer with make the organic additive that stops raising enter melt extruder 26 in and when beginning fusion, melt residence time begin and the fused blend is being expelled to form preform 12 in the injection mold after termination.
Forward Fig. 2 to, show polyester container preform 12.By injection moulding PET base resin, make this preform 12, and this preform is included in its lower end and ends at neck finish 112 in the cap colalr gasket (capping flange) 114.Below 114, have cylindrical part 116 at cap colalr gasket usually, described cylindrical part 116 ends in the outer radius portion 118 that increases gradually, so that the wall thickness of increase is provided.Below 118, there is the main part 120 that prolongs in part.
But the preform 12 that blowing is shown in Figure 2 forms the container 14 shown in Fig. 3 and 4.Container 14 comprises shell 124 and at the base 136 of container bottom, described shell 124 comprises the neck finish 126 of determining mouth 128, cap colalr gasket 130 in the neck finish bottom is from the tapered section 132 that cap colalr gasket extends, the main part 134 of extending in the tapered section bottom.For most of parts, container 14 height diaxial orientations, but neck shape bottleneck 126 is not orientated.Use container 14 to make the beverage 138 of packing suitably, as shown in Figure 4.The beverage 138 of packing comprises beverage such as the carbonated soda beverage that places in the container 14 and the stopper 140 that seals this container finish 128.
The beverage 138 of preform 12, container 14 and packing only is to use the application example of preform of the present invention.Be to be understood that and use method and apparatus manufacturing of the present invention to have the preform and the container of various structures.
More than described the present invention and further set forth the present invention by the following examples, but described embodiment shall not be construed as the dielectric imposed limits that the scope of the invention is had any way.On the contrary, understand with will be clear that, go to various other embodiments and modification and equivalence for help, after the explanation of reading herein, described various other embodiments and modification thereof and equivalence itself can be advised to some extent and not break away from the scope of the present invention and claims those skilled in the art.
Embodiment 1
Commercially available polyester container grade resin is as contrast.Dibasic acid component has terephthalic acid and the 2.8mol% m-phthalic acid of 97.2mol% in the polymer blend (PET), and diol component has the ethylene glycol of 97.2-97.3mol% and the glycol ether of 2.7-2.8mol%.In vacuum drying oven, 140 ℃ down dry PET spend the night to moisture level less than 50ppm.In vacuum drying oven, the listed additive of dry table 1 spends the night under 70 ℃, to remove the moisture of absorption.Before injection moulding, the different additive of hybrid PET and 5wt%.Laboratory scale Arburg unit chamber injection moulding machine is used for injection moulding.Use the 24.5g preform to make the 500ml container.Adopt the SidelSBO2/3 blow moulding machine, this preform of blowing is made the profiling container of acceptable 500ml.Use the instrument of Macon2/60 model then, under 22.2 ℃ and 50% relative humidity (RH), adopting purge rates on a side is the 99%N of 10ml/min
2/ 1%H
2With on opposite side, adopt air, the oxygen transmission rate of measuring vessel.The result is as shown in table 1.Barrier improvement factor (BIF) is defined as the oxygen transmission rate of contrast and the ratio of additive packing.BIF compares with contrast, stops measuring of raising degree.
Table 1 under the additive load of 5wt%, the oxygen transmission rate of contrast and additive container
Table 1
| Additive | Oxygen transmission rate (cc/pkg/ days) | Barrier improvement factor (BIF) |
| The PET contrast | 0.046 | 1.00 |
| 1, the 5-dihydroxy naphthlene | 0.0097 | 4.74 |
| 1, the 6-dihydroxy naphthlene | 0.005 | 9.20 |
| 2, the 6-dihydroxy naphthlene | 0.0064 | 7.19 |
With listed resin and the additive of embodiment 1 the same dry table 2, mix and injection moulding.Use the additive load of the alternative 5wt% of additive load of 3wt%.Use the 24.5g preform to make the 500ml container.Adopt the SidelSBO2/3 blow moulding machine, this preform of blowing is made the profiling container of acceptable 500ml.Use the instrument of Macon2/60 model then, under 22.2 ℃ and 50%RH, adopting purge rates on a side is the 99%N of 10ml/min
2/ 1%H
2With on opposite side, adopt air, the oxygen transmission rate of measuring vessel.Table 2 shows the result.
Table 2 under the additive load of 3wt%, the oxygen transmission rate of contrast and additive container
| Additive | Oxygen transmission rate (cc/pkg/ days) | Barrier improvement factor (BIF) |
| The PET contrast | 0.046 | 1.0 |
| 1, the 6-dihydroxy naphthlene | 0.008 | 5.75 |
| 2, the 6-dihydroxy naphthlene | 0.008 | 5.75 |
Embodiment 3
With 1 of the PET resin of embodiment 1 the same dry commercially available carbonated soft drink grade and 3wt%, the 3-dihydroxy naphthlene mixes and injection moulding.Use this preform of 24.5g, make the 500ml container.Adopt the SidelSBO2/3 blow moulding machine, this preform of blowing is made the profiling container of acceptable 500ml.Then the sidewall of bottle is cut into 2 inches * 2 inches square and be installed in the Mocon Permeatran, to measure the transmitance of carbonic acid gas.For the transmitance of carbonic acid gas, also use the PET control film.Table 3 shows the result.
The carbonic acid gas transmitance of table 3 contrast and additive films
| Additive | CO 2Transmitance (cc/mil/100in 2/ day) | Barrier improvement factor (BIF) |
| The PET contrast | 29.1 | 1.0 |
| 3wt%1, the 3-dihydroxy naphthlene | 13.7 | 2.12 |
Embodiment 4
With 1 of the PET resin of embodiment 1 the same dry commercially available carbonated soft drink grade and 5wt%, 3-dihydroxy naphthlene additive mixes and injection moulding.Use this preform of 24.5g, make the 500ml container.Adopt the SidelSBO2/3 blow moulding machine, this preform of blowing is made the profiling container of acceptable 500ml.Use the instrument of Macon2/60 model then, under 22.2 ℃ and 50%RH, adopting purge rates on a side is the 99%N of 10ml/min
2/ 1%H
2With on opposite side, adopt air, the oxygen transmission rate of measuring vessel.Table 4 shows the result.
The oxygen transmission rate of table 4 contrast and additive container
| Additive | Oxygen transmission rate (cc/pkg/ days) | Barrier improvement factor (BIF) |
| The PET contrast | 0.046 | 1.00 |
| 5wt%1, the 3-dihydroxy naphthlene | 0.0000 | NA |
Surprisingly, 5wt%1,3-dihydroxy naphthlene obtain unexpected low oxygen transmission rate.Oxygen transmission rate is too low, so that can't be detected by metering facility.This clearly illustrates that the effect of oxygen scavenqer.Compare with the oxygen scavenging compositions of prior art, this oxygen scavenging compositions has additional benefits and is that it does not contain any transition metal.
Embodiment 5 (Comparative Examples)
With embodiment 1 the same drying, mixing and casting resin and additive.Use two kinds of correlated additives.A kind of being selected from from premolding additive register best among the WO01/12521,4-methyl hydroxybenzoate.The height that another kind is selected from U.S. Patent No. 6320014 stops comonomer, 1, and the 3-dihydroxy-benzene.At first, add additive with 5wt% then with 3wt%.When adding with 5wt%, 1,3-dihydroxy-benzene generation excessive degradation.This excessive degradation can cause that I V significantly descends, and the result can not make acceptable container.Use the 24.5g preform to make the 500ml container.Adopt the SidelSBO2/3 blow moulding machine, this preform of blowing is made the profiling container of acceptable 500ml.Use the instrument of Macon2/60 model then, under 22.2 ℃ and 50%RH, adopting purge rates on a side is the 99%N of 10ml/min
2/ 1%H
2With on opposite side, adopt air, the oxygen transmission rate of measuring vessel.Table 5 shows the result.
Table 5: the comparison oxygen transmission rate of contrast and additive container
| Additive | Load | Oxygen transmission rate (cc/pkg/ days) | Barrier improvement factor (BIF) |
| The PET contrast | 0.046 | 1.00 | |
| 1, the 3-dihydroxy-benzene | 3wt％ | 0.034 | 1.35 |
| The 4-methyl hydroxybenzoate | 5wt％ | 0.023 | 2.00 |
| The 4-methyl hydroxybenzoate | 3wt％ | 0.03 | 1.53 |
Data according to table 5 can find out that embodiment of the present invention have the much higher gas barrier of making than with conventional barrier additive of container.
Should be appreciated that above stated specification relates to particular of the present invention and can make many variations to it under the situation of the scope of the invention that does not break away from following claim definition.
Claims (33)
1. polymer blend, it comprises:
Polyester; With
Chemical formula is the organic additive that gas barrier is improved of OH-AR-OH, and wherein AR replaces or unsubstituted naphthalene.
2. the polymer blend of claim 1, wherein polyester is present in the polymer blend with the consumption of the about 90wt% of about 99.9wt%-of polymer blend and additive is present in the polymer blend with the consumption of the about 10wt% of about 0.1wt%-of polymer blend.
3. the polymer blend of claim 1, wherein additive is selected from 1,2-dihydroxy naphthlene, 1,3-dihydroxy naphthlene, 1,5-dihydroxy naphthlene, 1,6-dihydroxy naphthlene and 2,6-dihydroxy naphthlene.
4. the polymer blend of claim 1, wherein additive is 1, the 3-dihydroxy naphthlene.
5. the polymer blend of claim 1, wherein polyester comprises based on the dibasic acid component of 100mol% and the diol component meter of 100mol%, its dibasic acid component modification less than 20% and/or the diol component modification less than poly-(ethylene glycol terephthalate) base co-polymer (PET multipolymer) of 10%.
6. the polymer blend of claim 5, wherein the PET multipolymer is present in the polymer blend with the consumption of the about 90wt% of about 99.9 wt%-of polymer blend and additive is present in the polymer blend with the consumption of the about 10wt% of about 0.1wt%-of polymer blend.
7. the polymer blend of claim 5, wherein the PET multipolymer is present in the polymer blend with the consumption of the about 95wt% of about 99.9 wt%-of polymer blend and additive is present in the polymer blend with the consumption of the about 5wt% of about 0.1wt%-of polymer blend.
8. the polymer blend of claim 5, wherein the PET multipolymer is present in the polymer blend with the consumption of the about 97wt% of about 99.9wt%-of polymer blend and additive is present in the polymer blend with the consumption of the about 3wt% of about 0.1wt%-of polymer blend.
9. the polymer blend of claim 5, wherein additive is selected from 1,2-dihydroxy naphthlene, 1,3-dihydroxy naphthlene, 1,5-dihydroxy naphthlene, 1,6-dihydroxy naphthlene and 2,6-dihydroxy naphthlene.
10. the polymer blend of claim 1, wherein polyester has free volume and at least a portion additive not with pet reaction and be positioned at the free volume of polyester.
11. the polymer blend of claim 1, wherein polyester comprises poly-(ethylene glycol terephthalate) base co-polymer (PET multipolymer), with based on the dibasic acid component of 100mol% and the diol component of 100mol%, this PET multipolymer has less than 20% dibasic acid component modification with less than 10% diol component modification, with at least a portion additive and PET copolymer reaction, so that diol component comprises the additive of the about 5mol% of 0.1-.
12. improve the method for polymer blend gas barrier or gas clean-up ability, this method comprises that blending polyester and chemical formula are the organic additive that gas barrier is improved of OH-AR-OH, wherein AR replaces or unsubstituted naphthalene.
13. the method for claim 12, wherein polyester is present in the polymer blend with the consumption of the about 90wt% of about 99.9wt%-of polymer blend and additive is present in the polymer blend with the consumption of the about 10wt% of about 0.1wt%-of polymer blend.
14. the method for claim 12, wherein additive is selected from 1,2-dihydroxy naphthlene, 1,3-dihydroxy naphthlene, 1,5-dihydroxy naphthlene, 1,6-dihydroxy naphthlene and 2,6-dihydroxy naphthlene.
15. the method for claim 12, wherein additive is 1, the 3-dihydroxy naphthlene.
16. the method for claim 12, wherein polyester comprises based on the dibasic acid component of 100mol% and the diol component meter of 100mol%, its dibasic acid component modification less than 20% and the diol component modification less than poly-(ethylene glycol terephthalate) base co-polymer (PET multipolymer) of 10%.
17. the method for claim 16, wherein the PET multipolymer is present in the polymer blend with the consumption of the about 90wt% of about 99.9wt%-of polymer blend and additive is present in the polymer blend with the consumption of the about 10wt% of about 0.1wt%-of polymer blend.
18. the method for claim 16, wherein the PET multipolymer is present in the polymer blend with the consumption of the about 95wt% of about 99.9wt%-of polymer blend and additive is present in the polymer blend with the consumption of the about 5wt% of about 0.1wt%-of polymer blend.
19. the method for claim 16, wherein the PET multipolymer is present in the polymer blend with the consumption of the about 97wt% of about 99.9 wt%-of polymer blend and additive is present in the polymer blend with the consumption of the about 3wt% of about 0.1wt%-of polymer blend.
20. the method for claim 16, wherein additive is selected from 1,2-dihydroxy naphthlene, 1,3-dihydroxy naphthlene, 1,5-dihydroxy naphthlene, 1,6-dihydroxy naphthlene and 2,6-dihydroxy naphthlene.
21. the method for claim 12, wherein polyester has free volume and at least a portion additive not with pet reaction and be positioned at the free volume of polyester.
22. the method for claim 12, wherein polyester comprises poly-(ethylene glycol terephthalate) base co-polymer (PET multipolymer), with based on the dibasic acid component of 100mol% and the diol component of 100mol%, this PET multipolymer has less than 20% dibasic acid component modification with less than 10% diol component modification, with at least a portion additive and PET copolymer reaction, so that diol component comprises the additive of the about 5mol% of 0.1-.
23. a container, described container comprises polymer blend, and described polymer blend comprises:
Polyester; With
Chemical formula is the organic additive that gas barrier is improved of OH-AR-OH, and wherein AR replaces or unsubstituted naphthalene.
24. the container of claim 23, wherein container is a stretch blow molded containers, and described stretch blow molded containers comprises bottom, opening end mouth and extends to the main body of opening end mouth from the bottom.
25. the container of claim 23, wherein polyester is present in the polymer blend with the consumption of the about 90wt% of about 99.9wt%-of polymer blend and additive is present in the polymer blend with the consumption of the about 10wt% of about 0.1wt%-of polymer blend.
26. the container of claim 23, wherein additive is selected from 1,2-dihydroxy naphthlene, 1,3-dihydroxy naphthlene, 1,5-dihydroxy naphthlene, 1,6-dihydroxy naphthlene and 2,6-dihydroxy naphthlene.
27. the container of claim 23, wherein polyester comprises based on the dibasic acid component of 100mol% and the diol component meter of 100mol%, its dibasic acid component modification less than 20% and the diol component modification less than poly-(ethylene glycol terephthalate) base co-polymer (PET multipolymer) of 10%.
28. the container of claim 27, wherein the PET multipolymer is present in the polymer blend with the consumption of the about 90wt% of about 99.9wt%-of polymer blend and additive is present in the polymer blend with the consumption of the about 10wt% of about 0.1wt%-of polymer blend.
29. the container of claim 27, wherein the PET multipolymer is present in the polymer blend with the consumption of the about 95wt% of about 99.9wt%-of polymer blend and additive is present in the polymer blend with the consumption of the about 5wt% of about 0.1wt%-of polymer blend.
30. the container of claim 27, wherein the PET multipolymer is present in the polymer blend with the consumption of the about 97wt% of about 99.9wt%-of polymer blend and additive is present in the polymer blend with the consumption of the about 3wt% of about 0.1wt%-of polymer blend.
31. the container of claim 27, wherein additive is selected from 1,2-dihydroxy naphthlene, 1,3-dihydroxy naphthlene, 1,5-dihydroxy naphthlene, 1,6-dihydroxy naphthlene and 2,6-dihydroxy naphthlene.
32. the container of claim 23, wherein polyester has free volume and at least a portion additive not with pet reaction and be positioned at the free volume of polyester.
33. the container of claim 23, wherein polyester comprises poly-(ethylene glycol terephthalate) base co-polymer (PET multipolymer), with based on the dibasic acid component of 100mol% and the diol component of 100mol%, this PET multipolymer has less than 20% dibasic acid component modification with less than 10% diol component modification, with at least a portion additive and PET copolymer reaction, so that diol component comprises the additive of the about 5mol% of 0.1-.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/US2005/013226 WO2006112840A1 (en) | 2005-04-19 | 2005-04-19 | Polyester composition with enhanced gas barrier, articles made therewith, and methods |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101166783A true CN101166783A (en) | 2008-04-23 |
Family
ID=34965956
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2005800495323A Pending CN101166783A (en) | 2005-04-19 | 2005-04-19 | Polyester composition with enhanced gas barrier, articles made therewith, and methods |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP1902092A1 (en) |
| JP (1) | JP2008537006A (en) |
| CN (1) | CN101166783A (en) |
| WO (1) | WO2006112840A1 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ES2678249T3 (en) | 2011-09-12 | 2018-08-09 | Plastipak Packaging, Inc. | PET bottles with a monolayer barrier to carbon dioxide |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4474918A (en) * | 1983-05-31 | 1984-10-02 | Eastman Kodak Company | Thermoplastic polyester compositions having improved barrier properties |
| US4574148A (en) * | 1985-06-21 | 1986-03-04 | Eastman Kodak Company | Polyester resins capable of forming containers having improved gas barrier properties |
| US5039780A (en) * | 1988-11-08 | 1991-08-13 | Mitsui Petrochemical Industries, Ltd. | Copolyester having gas-barrier property |
| US6489386B1 (en) * | 1999-08-12 | 2002-12-03 | E. I. Du Pont De Nemours And Company | Method and composition for improving gas barrier properties of polymeric containers and films |
| AUPR005000A0 (en) * | 2000-09-12 | 2000-10-05 | Polymers Australia Pty Limited | Polyster resins with improved properties |
-
2005
- 2005-04-19 CN CNA2005800495323A patent/CN101166783A/en active Pending
- 2005-04-19 EP EP05735791A patent/EP1902092A1/en not_active Withdrawn
- 2005-04-19 JP JP2008507607A patent/JP2008537006A/en not_active Withdrawn
- 2005-04-19 WO PCT/US2005/013226 patent/WO2006112840A1/en active Application Filing
Also Published As
| Publication number | Publication date |
|---|---|
| JP2008537006A (en) | 2008-09-11 |
| EP1902092A1 (en) | 2008-03-26 |
| WO2006112840A1 (en) | 2006-10-26 |
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Open date: 20080423 |