Polyamides and polyesters mixed with a lithium salt interfacial tension reducing agent

专利摘要:

公开号:ES2623835T9
申请号:ES11170053.0T
申请日:2006-10-06
公开日:2017-12-12
发明作者:Paul Lewis Heater；Guliz Arf Elliott
申请人:M&G USA Corp；
IPC主号:

专利说明:

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DESCRIPTION
Polyamides and polyester mixed with a lithium salt interfacial tension reducing agent Priority and cross references
This patent application claims the benefit of the priority of the provisional US patent application. serial number 60/725085, filed on October 7, 2005, and the provisional US patent application. Serial number 60/827147, filed on September 27, 2006.
Field of the Invention
The present invention relates to the stretched wall of a container for packaging.
Background of the invention
U.S. patent applications 2002/0001684 (January 3, 2002), 20030134966 (July 13, 2003) and 20050106343 (May 19, 2005), all of which have Kim as common inventor, teach a composition of PET (A), a polyamide , nylon MXD6 (B), with cobalt octoate. Kim's series of applications teach that when the PET / MXD6 / cobalt octoate composition is injected molded into a preform (parison) and then oriented (stretched) into a blow-off bottle, the resulting bottle is turbid. Kim's requests also identify the cause of the turbidity. According to Kim, the turbidity is caused by the MXD6 domains dispersed in the PET that with the orientation have been stretched to the point that the size of the domains is larger than the wavelength of light.
Kim and colleagues teach that smaller domains reduce the turbidity caused by previously large domains. One skilled in the art knows that there are two ways to have smaller domains in the stretched bottle. One way is to reduce the size of the starting domains in the preform or parison, and the other is to orient or stretch the bottle as much as possible. The solution selected in Kim's series of requests to replace the blow injection process is the realization of the preform / parison and subsequently orient (stretch) the preform into a blown bottle with a much lower stretch process known as blowing by extrusion.
Kim's applications also teach that a container made of PET / MXD6 / cobalt octoate has a higher oxygen barrier (lower permeability index), presumably due to the well-known ability of cobalt octoate to catalyze the reaction of the nylon MXD6 with oxygen. While Kim and colleagues teach reducing the size of MXD6 domains as a way to reduce turbidity in stretched containers, it does not teach how to solve turbidity in a blow-in injection container, or how to reduce the size of domains in a blow injection container, presumably because this was already known in the state of the art prior to Kim's invention.
Document JP-2663578-B2 (October 15, 1997) by Yamamoto and colleagues identifies the same problem as Kim's requests with the same composition. Yamamoto and colleagues report that a turbid stretched blown bottle originates when a composition of polyester (A) and MXD6 nylon (B) is molded by injection forming a parison (preform) and oriented (stretching) into a bottle. Remember that Kim and colleagues teach that this turbidity is caused by large domains, and the only difference is that Kim and colleagues' bottle contains cobalt octoate.
Yamamoto and colleagues then teach that turbidity can be eliminated in the PET / MXD6 blow-injected bottle by incorporating a third polyester component (C), in which the third polyester component has 5-sodium sulfoisophthalate derived from 5-sodium acid sulfoisophthalic in its polymer chain. The copolymerization of 5-sodium sulfoisophthalic acid is shown in Table 3 of Yamamoto, with the conclusion that: when using copolymerized polyester with 5-sodium sulfoisophthalate as component (C), transparency is improved and turbidity is significantly reduced. A person skilled in the art could therefore solve the injection molded bottle with Kim stretch, which contains PET / MXD6 / cobalt octoate, adding the copolymerized polyester (C) with 5-sodium sulfoisophthalate taught by Yamamoto and colleagues. The cobalt octoate found in Kim's applications could not be removed because the container's oxygen barrier would be reduced.
U.S. Pat. No. 5,300,572 (April 5, 1994) of Tajima and colleagues teaches how to reduce the domain size of a polyamide dispersed in a polyester. Tajima and colleagues reduce the size of the polyamide domain by adding sodium sulfoisophthalic acid, either copolymerized in the polyester structural skeleton (A), or as a third component (C) which is a polyester copolymerized with sodium sulfoisophthalic acid. Since Kim's requests teach that reducing the size of the polyamide domain resolves turbidity, a person skilled in the art who wishes to make an injection molded / blow-molded bottle containing PET / MXD6 / cobalt octoate could either use PRT copolymerized with sodium sulfoisophthalate derived from sulfoisophthalic acid for component (A), as taught by Tajima and colleagues, or add a polyester
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(C) copolymerized with sodium isophthalate as taught by Yamamoto and colleagues Again, Kim and colleagues' cobalt octoate could not be eliminated, because the increased oxygen barrier of Kim and colleagues would be reduced.
WO 2005/023530 (March 17, 2005) of Mehta and colleagues teaches that a cobalt salt is essential when a preform (parison) comprising the composition of Kim and colleagues [a polyester (A), a polyamide such as MXD6 (B)], and in the presence of an ionic compatibilizer such as 5-sulfoisophthalic acid or 5-sodium sulfoisophthalate. Mehta and colleagues and Kim and colleagues use even the same cobalt salt: cobalt octoate. According to Mehta and colleagues, a large amount of yellow color originates when polyester (A) is combined with polyamide (B) in the presence of an ionic compatibilizer (C), and the use of cobalt octoate which is also taught in Kim's requests, avoid that color formation.
Although the use of cobalt can mitigate color, it inherently creates an active barrier packaging. There are other active barrier mechanisms, such as oxidation of an elemental metal in the container wall. There are, however, packaging applications that do not benefit from, and are in fact damaged by, an organic cleaner or need less powerful active packaging; There is, therefore, a need for an MXD6 / polyester ionic compatibilizer in which no cobalt is needed, to avoid damaging color formation observed by Mehta and colleagues
Summary of the invention
The present invention discloses a container wall as claimed.
An effective amount of lithium sulphonate, in particular lithium sulfoisophthalate (derived from the monolithium salt of 5-sulfoisophthalic acid), is about 0.05 to 0.1 mole percent, the optimum amount being in the range of about 0.1 to about 0.2 mole percent, the range of about 0.1 to about 1.1 mole percent being the most optimal, and from about 0.18 to about 0.74 still better, with the range of approximately 0.18 to approximately 0.6 mole percent the most optimal.
Description of the figures
Figure 1 depicts an electron microscopy (SEM) scanning photomicrograph of polyamide domains dispersed in a polyester matrix in the absence of the interfacial tension reducing agent, such as lithium sulfoisophthalate derived from sulfoisophthalic lithium acid (LiSIPA). As detailed in the test method section, the sample was prepared by extracting the polyamide with cold formic acid, and exposing the sample to an electron scanning microscope.
Figure 2 shows the graphical representation of the domain distribution corresponding to the polyester polyamide system of Figure 1.
Figure 3 depicts a photomicrograph of polyamide domains dispersed in a polyester matrix in the presence of an interfacial tension reducing agent - lithium sulfoisophthalate derived from lithium sulfoisophthalic acid (LiSIPA). As detailed below, the sample was prepared by extracting the polyamide with cold formic acid.
Figure 4 shows the graphic representation of the domain distribution corresponding to the polyester polyamide system of Figure 3.
Figure 5 represents a photograph of pellets of a crystallizable polyethylene terephthalate mixed with polyamide 6, also known as PA6 or nylon 6, with and without interfacial tension reducing agent derived from sulfoisophthalic lithium acid (LiSIPA). The impact of the interfacial tension reducing agent can easily be appreciated in the immediate clarity of the composition containing the lithium sulfoisophthalate.
Detailed description of the invention
Color formation deficiencies when mixing polyamides, polyester and interfacial tension reducing agents, can be remedied in accordance with the invention by using lithium as a metal ion in the interfacial tension reducing agent. Additionally, the deficiency of the large polyamide domains found in the stretched composition of polyamide, polyester and interfacial tension reducing agents, can be remedied when the interfacial reducing agent is a lithium salt.
The polyamide domains of the present invention exhibit a unique behavior when the article is stretched. In prior art systems, the relative increase in domain size is very close to the overall amount at which the article was stretched in the same direction. If the article was stretched 5 times in one direction, the domain could be stretched approximately 5 times in that direction. The domains of this composition do not stretch the same amount as the article. In fact, the domains have a very small amount of stretching in relation to the amount of stretching experienced by the article.
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Although it is not intended to be limited to any theory, it is conjectured that the lithium salt does not nucleate the crystallization of the polyester like the other metals (for example, sodium), and thus, the domains contract while the stretched article is cool down The reduced interfacial tension between the polyamide and the polyester coupled with the stretch characteristics, increases the dispersion of the polyamide in the polyester and the average domain size of the polymer in an unstretched portion of an article comprising the composition in less than 125 nm, with better results in at least 100 nm, even better results than when the average domain size is less than 75 nm, and the domains less than 60 nm are those of the most optimal average domain size in the unstretched portion of container wall
The stretching phenomenon can be characterized by the percentage of stretching that is defined as the stretching ratio of the polyamide domains divided by the stretching ratio of the matrix (polyester) in the same direction. Theoretically, this should be 100%, since the domains are stretched the same amount as the polyester. However, when lithium salt is used, the stretch percentage is often less than 75%, with many observations less than 50%, and in a case less than 30%. It is believed that the lower the stretch percentage, the better.
This disclosure also provides a mixture of a crystallizable polyethylene terephthalate or its polymers, a polyamide (in particular MXD6 or nylon 6) and a separate interfacial tension reducing agent to form the stretched wall of a container. The interfacial tension reducing agent could be a metal salt of sulfonated polystyrene or a metal salt of sulfonated polyester.
This disclosure provides a modified polyester, in particular a crystallizable polyethylene terephthalate or its polymers, mixed with a polyamide, in particular MXD6 or nylon-6; or a polyester, in particular polyethylene terephthalate or its copolymers, mixed with modified polyamide, in particular MXD6 to form the stretched wall of a container.
Any polyester or polyamide suitable for making a container is suitable as long as the composition comprising the polyester and the polyamide has a sufficient amount of interfacial tension reducing agent, either as a third component either incorporated in the polyester chain, or the chain of polyamide. A combination of the separate interfacial tension reducing agent and a polyester or a polyamide, or both, which is modified with an interfacial tension reducing agent is contemplated. Interfacial tension reducing agents need not be the same.
Polyesters of the invention can be prepared by polymerization procedures well known in the state of the art. Polyester polymers and copolymers can be prepared by melt phase polymerization that includes the reaction of a diol with a dicarboxylic acid, or its corresponding ester. Various copolymers of multiple diols and diacids can also be used.
In general, polyester polymers and copolymers can be prepared, for example, by melt phase polymerization that includes the reaction of a diol with a dicarboxylic acid, or its corresponding ester. Various copolymers resulting from the use of multiple diols and diacids can also be used. Polymers containing repeating units of a single chemical composition are homopolymers. Polymers with two or more chemically different repeating units in the same macromolecule are called copolymers. The diversity of the repeating units depends on the number of different types of monomers present in the initial polymerization reaction. In the case of polyester, the copolymers include reacting one or more diols with a diacid or multiple diacids, and are sometimes referred to as terpolymers. For example, in one embodiment of the present invention, m-xylylene diamine polyamide (MXD6 Grade 6007 from Mitsubixhi Gas Chemical, Japan) is dispersed in a polyethylene terephthalate copolymer comprising terephthalic acid, isophthalic acid and salt of lithium sulfoisophthalic acid
As indicated above, suitable dicarboxylic acids include those comprising from about 4 to about 40 carbon atoms. Specific dicarboxylic acids include, but are not limited to, terephthalic acid, isophthalic acid, 2,6-dicarboxylic naphthalene acid, cyclohexanedicarboxylic acid, cyclohexanediacetic acid, diphenyl-4,4'-dicarboxylic acid, 1, 3- phenylenedioxidiacetic acid, 1,2-phenylenedioxidiacetic acid, 1,4-phenylenedioxidiacetic acid, succinic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, and the like. Specific esters include, but are not limited to, phthalic esters and naphthalic diesters.
These acids or esters can be reacted with an aliphatic diol that preferably has from about 2 to about 24 carbon atoms, a cycloaliphatic diol that has from about 7 to about 24 carbon atoms, an aromatic diol that has from around 6 to about 24 carbon atoms, or an ether glycol having 4 to 24 carbon atoms. Suitable diols include, but are not limited to, ethylene glycol, 1,4-butanediol, trimethylene glycol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, diethylene glycol, resorcinol, 1,3- propanediol and hydroquinone.
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A useful polyester is a crystallizable polyester with more than 85% of its acid units derived from terephthalic acid. It is generally accepted that polyester with comonomer modification greater than 15% are difficult to crystallize. However, the invention includes polyesters that could crystallize and have a comonomer content greater than 15%.
Polyfunctional comonomers can also be used, typically in amounts from about 0.01 to about 3 mole percent. Suitable comonomers include, but are not limited to, trimellophic anhydride, trimethylpropane, pyromellophonic dianhydrolic (PMDA), and pentaerythritol. You can also use polyester forming polyamides or polyols. Mixtures of polyester and copolyester can also be useful in the present invention.
A suitable crystallizable polyester is polyethylene terephthalate (PET) or a copolymer modified with lithium sulfoisophthalate formed from diester or di-carboxylic acid of lithium sulfoisophthalate in the approximately stoichiometric reaction of 1: 1 acids, or their di- esters, with ethylene glycol. Copolymers are also suitable. The copolymers and terpolymers of interest are crystallizable polyesters comprising lithium sulfoisophthalate in combinations of isophthalic acid or its diester, 2,6 naphthalene dicarboxylic acid or its diester, and / or cyclohexane dimetanol. Optimum levels of lithium sulfoisophthalate are in the range of 0.1 and 2.0 mole percent based on the portions of acid in the polymer. Although more than 2.0 mole percent is not harmful to the intended effect, more than 2.0 mole percent gets little or no further improvement.
The amount of lithium sulphonate, in particular lithium sulfoisophthalate (derived from the monolithium salt of 5-sulfoisophthalic acid), is about 0.05 to 10.0 mole percent, the optimum amount being in the range from about 0.1 to about 2.0 mole percent, the range being from about 0.1 to about 1.1 mole percent more optimal, and about 0.18 to about 0 , 74 even better, with the range of about 0.18 to about 0.6 mole percent the most optimal range.
The esterification or polycondensation reaction of carboxylic acids or esters with glycol typically takes place in the presence of a catalyst. Suitable catalysts include, but are not limited to, antimony oxide, antimony triacetate, ethylene antimony glycolate, organomagnesium, tin oxide, titanium alkoxides, dibutyl tin dilaurate, and germanium oxide. These catalysts can be used in combination with acetates or benzoates of zinc, manganese or magnesium. Catalysts comprising antimony are preferred. Another preferred base polyester is polytrimethylene terephthalate (PTT). This can be prepared, for example, by reacting 1,3-propanediol with at least one aromatic diacid or a dialkyl ester thereof. Preferred diacids and dialkyl esters include terephthalic acid (TPA) or dimethyl terephthalate (DMT). Consequently, the PTT preferably comprises at least about 80 mole percent, either from TPA or from DMT. Other diols that can be copolymerized in such a polyester include, for example, ethylene glycol, diethylene glycol, 1,4-cyclohexane dimetanol, and 1,4-butanediol. In addition to the interfacial tension reducing agent such as sulfoisophthalic acid, other aromatic or aliphatic acids can be used simultaneously so that a copolymer includes, for example, isophthalic acid and sebacic acid.
Preferred catalysts for preparing PTT include titanium and zirconium compounds. Suitable compounds of catalytic titanium include, but are not limited to, titanium alkylates and their derivatives, complex salts of titanium, titanium complexes with hydroxycarboxylic acids, co-precipitates of titanium dioxide - silicon dioxide, and titanium dioxide containing product hydrated alkaline Specific examples include tetra- (2- ethylhexyl) -titanate, tetraestearyl titanate, diisopropoxy-bis (acetyl-acetonate) -titanium, di-n-butoxy-bis (triethanolamine) - titanium, tributylmonoacetyl titanate, triisopropyl monoacetyl titanate, tetrazoic acid titanate , alkali titanium oxalates and malonates, potassium hexafluorotitanate, and titanium complexes with tartaric acid, cfric acid or lactic acid. Preferred compounds of catalytic titanium are titanium tetrabutylate and titanium tetraisopropylate. The corresponding zirconium compounds can also be used.
The polyester of the present invention may also contain small amounts of phosphorous compounds, such as phosphates, and a catalyst such as a cobalt compound, which tends to impart a blue hue. Also, small amounts of other polymers such as polyolefins can be tolerated in the continuous matrix. While WO 2005/023530 A1 teaches the use of cobalt salts as an essence to prevent color formation, the use of cobalt salts is not necessary to reduce color formation when the interfacial tension reducing agent is salt. of lithium, in particular lithium sulfoisophthalate derived from Lithium Sulfolsophthalic Acid (LiSIPA). The molecular structure of lithium sulfoisophthalic acid is:
COOH
COOH
Lithium sulfoisophthalic acid (LiSIPA) or modified isophthalic acid of lithium salt of sulfonic acid
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As is evident from the above diagram, lithium sulfoisophthalic acid is a lithium sulphonate and comprises lithium sulfoisophthalate. Lithium sulfoisophthalate refers to the compound as it appears incorporated in the polymer chain. This is also known as a lithium sulfoisophthalic acid repeating unit. Lithium sulfoisophthalate is therefore lithium sulfoisophthalic acid minus one molecule of water, with one or more monomers (Ri and R2) in the polymer structural backbone.
COOH
p-
SO3U
COOH
The sulphonate, in this case lithium sulfoisophthalate, is the molecule between the two groups R. Again, R could be the same monomer; in the case of PET, the R's are probably the same, with the ethylene glycol portion as it reacts in the polymer chain.
Upon completion of the melt phase polymerization, the polymer can either be made in a form such as a film or part, or in bands and cut into small pieces, such as in pellets. The polymer is normally crystallized below and is subjected to a solid phase (solid state) polymerization step (SSP) to achieve the intrinsic viscosity necessary for the manufacture of certain items such as bottles. Crystallization and polymerization can be carried out in a drying reactor of an intermittent system. The solid phase polymerization can continue in the same dryer in which the polymer is subjected to high vacuum to extract the polymerization by-products.
Alternatively, crystallization and polymerization can be carried out in a solid state polymerization process in which the polymer flows from one vessel to another after its predetermined treatment in each vessel. Crystallization conditions are relative to polymer crystallization and adhesion tendencies. However, preferred temperatures range from about 100 ° C to about 235 ° C. In the case of crystallizable polyester, the solid state polymerization conditions are generally 10 ° C lower than the melting point of the polymer. In the case of non-crystallizable polyester, the solid phase polymerization temperature is generally 10 ° C below the temperature at which the polymer begins to become self-adherent. While traditional solid phase polymerization temperatures for crystallizable polymers are in the range of about 200 ° C to about 232 ° C, many operations range from about 215 ° C to about 232 ° C. Those skilled in the art will understand that the optimum temperature of solid phase polymerization is polymer specific and depends on the type and quantity of polymers of the product. However, the determination of the optimal solid phase polymerization conditions is frequently performed in the industry and can be easily done without undue experimentation.
The solid phase polymerization can be carried out for a sufficient time to raise the intrinsic viscosity to the desired level, which will depend on the application. For a typical bottle application, the preferred intrinsic viscosity (I.V.) ranges from about 0.65 to about 1.0 deciliter / gram, as determined by the method described in the method section. The time required to reach this I.V. It goes from around 8 to about 21 hours.
In one embodiment of the invention, the crystallizable polyester of the present invention may comprise recycled polyester or materials derived from the recycled polyester, such as polyester monomers, catalysts and oligomers.
The term crystallizable means that polyethylene terephthalate can become semi-crystalline, either by orientation or by induced crystallinity. The fact that the plastic is completely crystalline and that the crystalline forms are more accurately described as semi-crystalline is well known. The term semi-crystalline is well known in the state of the art and is used to describe a polymer having X-ray patterns that have characteristics of sharp features of crystalline regions and diffuse features of amorphous regions. The fact that semi-crystalline must be distinguished from the states of pure and amorphous crystalline is well known in the state of the art.
These polyamides can be in a range of average molecular weight from 2000 to 60000, measured by end group titration. These polyamides can also be described as the reaction product of amino caproic acid with itself and / or the reaction product of a dicarboxylic acid residue comprising adipic acid, isophthalic acid, terephthalic acid, 1,4-cyclohexanedicarboxylic acid, acid dicarboxylic resorcinol, or naphthalenedicarboxylic acid, or mixture thereof, with a residue of a diamine comprising m-xylylene diamine, p-xylylene diamine, hexamethylene diamine, ethylene diamine, or 1,4 cyclohexanedimethylamine, or mixture thereof.
Those skilled in the art will understand that many of the combinations are well known, commercially available polyamides. The reaction product of sebacic acid with hexamethylene diamine is nylon 6, 10, and
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The reaction product of the adipic acid and hexamethylene diamine residue is nylon 6, 6. Nylon 6, 12 is another nylon that benefits from the invention. Nylon 6 is a special type of polyamide that is made with the opening of caprolactam and the subsequent polymerization of the resulting amino caproic acid having the formula H2N- (CH2) 5- COOH. A useful polyamide is the reaction product of adipic acid and m-xylylene diamine residues, known as poly-m-xylylene adipamide. This product is commercially known as MXD6 or MXD6 nylon, and can be purchased from Mitsubishi Gas Chemical Company, Japan.
The modified polyamide could have 0.01-15 mole percent of the respective acid, or the diamine substituted by an interfacial tension modifying compound such as sulfonated isophthalic acid. U.S. Pat. No. 3,328,484 describes such modified co-polyamides.
The preferred amount of polyamide is comprised between 1 and 15 parts per 100 parts of the polyester plus polyamide, preferably between 3 and 8 parts per 100 parts of the polyester plus polyamide, with the greatest utility occurring between 4 and 7 parts of polyamide per 100 parts of polyester plus polyamide.
The preferred composition contains at least one interfacial tension reducing agent that reduces the interfacial tension between the polyester and the polyamide. In order to understand the role of the interfacial tension reducing agent, it is necessary to understand the role of the interfacial tension reducing agent in the polyester-polyamide dispersion.
The polyester-polyamide dispersion can be described as a multi-phase system consisting of a dispersed polymer and a matrix phase. The dispersed polymer is discontinuous, with very small particles scattered throughout the matrix polymer. The matrix polymer is a continuous phase, in which the polymer is not broken into discrete units, but is constantly in contact with itself. In other words, there is usually only one matrix phase, but many particles of the dispersed polymer. Technically, therefore, many phases can be considered in the dispersed component, since each particle is in its own phase. However, in that description, each particle has the same equilibrium properties as the other particle. For the purposes of the present invention, the term dispersed phase or dispersed polymer refers to all discrete particles of the discontinuous component present in the continuous phase.
It is estimated that the polyamide is dispersed in the polyester matrix forming discrete particles in the polyester. And, without linking to any theory, it is estimated that the lower dispersion of the polyester / polyamide system is due to the high interfacial tension (IFT) existing between the two polymers.
For a closed system (see “An Introduction to the Principles of Surface Chemistry”, Aveyard, R. and Haydon, D.A., 1973), the differential expression for the internal energy U of the system has been described as:
dU = dQ + dW
in which dQ is the heat absorbed by the system and dW is the change in work. The relationship with respect to dW is then isolated, which reduces the equation to:
dW = -pdV + YdA
where dV is the change in volume and y is the interfacial tension, and dA is the change in the interfacial area (the area of interaction between the two components). In the liquid-liquid system, such as that existing with the mixture of molten polyester / polyamide, there is no change in volume (dV = 0), and the equation is reduced to change in work as a function of interfacial tension and to the change in the interfacial area:
dW = YdA
The lower the interfacial tension, therefore, the larger the area of contact between the two materials. A larger interfacial contact area for a given amount of material is achieved only by creating smaller particles of the material dispersed in the matrix material. A larger interfacial contact area requires a smaller diameter, and therefore a larger number of particles. The effectiveness of the interfacial tension reducing agent can be established directly by means of the average particle size. The lower the average size of the dispersed particle, the lower the interfacial tension and the more effective the interfacial tension reducing agent.
This increase in surface area and the corresponding reduction in domain size and consequent increase in the number of domains, is estimated to increase the barrier, improve aesthetics (reduced turbidity) and also increase the amount of oxygen cleaning capacity when Polyamide has been activated to react with oxygen. Activation is often performed by exposing the polyamide to a transition metal catalyst, usually in its positive valence state.
There are other ways to increase the surface area. These include increasing the amount of shear
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During the mixing process, vary the viscosity ratios, try cross-linking or grafting of the materials. Although the inventors are familiar with all prior techniques, no technique has been as successful as the fact of directly modifying at least one of the polymers to reduce the interfacial tension between the two polymers.
The interfacial tension between two polymers in their liquid state is difficult to determine due to the high temperatures involved. One technique is to use a rotating tensiometer. However, in the absence of sophisticated equipment it is much easier to make two dispersions of polymers separately, one modified, the other unmodified, using the same amount of work (torque, spindle design, temperatures) and compare the difference in The average particle size of the dispersed material.
The immediate effect of interfacial tension reduction can be appreciated by reduced turbidity in the stretched article or by comparing the average particle size of the polyamide of an unmodified polyester-polyamide dispersion with a modified polyester-polyamide system. This test easily determines whether the interfacial tension has been reduced.
The composition should have a sufficient amount of interfacial tension reducing agent added either separately or reacted in the structural skeleton of the polyester, the polyamide or both. A combination of the separate interfacial tension reducing agent and a polyester or a polyamide, or both, which have been modified with an interfacial tension reducing agent is contemplated. Interfacial tension reducing agents do not have to be the same.
Preferably, the interfacial tension reducing agent is a co-monomer that has been reacted with the polymer. To be a co-monomer, the interfacial tension reducing agent is functionalized with at least one group that allows the interfacial tension reducing agent to react with at least one of the other polymers or polymer co-monomers of the composition.
In the case of polyester, these may be the polar co-monomers used to create PET ionomers. In the case of polyamides, the interfacial tension reducing agent may consist of the co-monomers used to create polyamide ionomers. Examples of these co-monomers are the monovalent and / or divalent salt of the respective sulphonate described in US Pat. No. 6,500,895 (B1), whose teachings are incorporated herein. Also included are the monovalent and bivalent metal salts described in the following formulas, found in Japanese patent application no. 03281246 A, whose teachings are incorporated herein.
In general, the interfacial tension reducing agent exists in the functionalized form of the XR form, where X is an alcohol, carboxylic acid or epoxy, more preferably a dicarboxylic acid or a diol, and R is -SO3U, -COOLi, - OLi , -PO3 (Li) 2, and XR is copolymerized in polyester polymer to modify the interfacial tension. The amount of X-R needed will exceed 0.01 mole percent with respect to the total number of respective moles of dicarboxylic acid or diol in the polymer. It is possible that X-R both include a diol or a carboxylic acid. In that case, the mole percentage is based on the total number of moles of diols, dicarboxylic acids or respective polymer repeating units.
The functionalized interfacial tension reducing agent may contain 2 or more R groups. R may be combined directly into the aromatic ring of X, which could be a diol, a dicarboxylic acid, or a side chain such as a methylene group.
image 1
where R is -SO3Li, -COOLi, -OLi, -PO3 (Li) 2.
In this case, the dicarboxylic acids represented by X may be in the ortho, meta or for structures. These comprise, for example, aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, orthophthalic acid, dicarboxylic naphthalene acid, dicarboxylic diphenylether acid, diphenyl-4,4-dicarboxylic acid, etc.
Aliphatic dicarboxylic acids such as oxalic acid, maloic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacid acid, etc., can be used. dicarboxylic cycloaliphatics such as cyclohexanedicarboxylic acid, and one or more species thereof. Mixtures of the dicarboxylic acids are also specifically contemplated.
X may also represent an alcohol, preferably a diol of structure:
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image2
where R is -SO3U, -COOLi, -OLi, -PO3 (Li) 2.
The diols represented by X can be used which can be, for example, aliphatic glycols such as ethylene glycol, 1,3 propanediol, 1,4-butanediol, 1,5-ppentanediol, 1,6-hexanediol, 1,9-nonanodiol , diethylene glycol, trimethylene glycol and cycloaliphatic diols such as cyclohexanediol, cyclohexanedimethyl and one or more species in combination. Among these, ethylene glycol, diethylene glycol and cyclohexanediol are preferred.
Other functionalized interfacial tension reducing agents that can be used to reduce interfacial tension include hydroxyl terminated polyethers, such as polyethylene glycol (Carbowax) and cyclic amides such as ethoxylated dimethyl hydantoin. Additionally, the polyester can be reacted with epoxy-terminated compounds, including the epoxy-terminated polyethers, to produce a polyether side chain attached to the polymer.
As used herein, the term "interfacial tension reducing agent" refers to the agent as it exists, without being incorporated into the structural skeleton of a polymer, and as having been incorporated into the structural skeleton of the polymer.
Of the metal salts, lithium, a monovalent metal, has been found to behave much better than sodium. In fact, lithium salt imparts very little or no turbidity to the polyester matrix when mixed with MXD6 and produces a dispersion with lower average domains than previously measured levels. In contrast to other systems presented in the state of the art, lithium salt has a very small turbidity increase with increased levels of MXD6, and in fact in some no increase in turbidity was measured. Also, lithium shows a drastically lower yellow color when mixed with molten polyamide, thereby eliminating the need for cobalt or zinc salt as described in WO 2005/023530 A1, whose teachings are incorporated into This memory. In fact, as described below, lithium sulfoisophthalate without any cobalt compound has a better color than sodium isophthalate mixed with the same amount of MXD6 in the presence of a cobalt salt.
Of the salt forms, di-carboxylic acid, di-ester, or pre-reacted oligomers of low molecular weight and other building blocks such as lithium sulfoisophthalate bis-hydroxyethyl ester are preferred. It is also possible that the interfacial tension reducing agent, in this case lithium sulphonate, is also produced in the form of a diol. Possible alternatives are isethionic acid. It has even been proposed to arrange the sulfonate at the end of the polyester molecule. This could be accomplished by reacting, or copolymerizing, the polyester with the sulphonated salt of benzoic acid or other monofunctional species, either in the fusion reactor or in an extruder. In this case, the interfacial tension reducing agent reacted with the structural skeleton of the polymer could be lithium sulfobenzoate. One way to describe the various lithium salts is to use the term functionalized lithium sulphonate to describe a compound in the form of R-SO3Li, where R is an aliphatic, aromatic or cyclic compound with at least one functional group that allows the salt of functionalized lithium react with the polyester or polyamide, or their respective monomers or oligomers. The functionalized lithium sulphonates included in this invention are the lithium salts of sulfonated comonomers, including aliphatic and aromatic alcohols, carboxylic acids, diols, dicarboxylic acids, and multifunctional alcohols, carboxylic acids, amines and diamines.
Sulfoisophthalic acid is a functionalized lithium sulphonate such as lithium sulfobenzoic acid.
In order for it to react in any polymer, the modifying agent must have at least one functional group. These functional groups are carboxylic acid (-COOH), alcohol (-OH), carboxylic acid ester, epoxy termination, diamine, or amine end groups.
Since a high polyester I.V. it would have two functional end groups per polymer chain, a high I.V. polyester. Containing lithium sulfoisophthalate in its structural skeleton is an interfacial tension reducing agent when mixed with polyamide and polyester without lithium sulfoisophthalate. In case the high polyester I.V. have both polymer chain ends terminated with non-functional groups, then the polyester would be considered a non-functional or non-functionalized interfacial tension reducing agent.
Non-functionalized interfacial tension reducing agents are those compounds that contain a polar group, in particular the lithium salt, but have no functional end group that allows the interfacial tension reducing agent to react with the polyester or polyamide. The sulfonated polystyrene lithium salt is an example.
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As taught in the following, the polymer is preferably modified with the interfacial tension reducing agent. This modification is made by polymerizing the interfacial tension reducing agent in the polymer chain. As taught in Example 6, the compartmentalized ball, the interfacial tension reducing agent can be incorporated into the polyester and then mixed with an unmodified polyester and polyamide to produce the composition.
The levels of interfacial tension reducing agent necessary to decrease the interfacial tension are in the range of 0.01 mole percent to 15 mole percent with respect to the total number of moles of the respective acid or diol portion. For example, a typical homopolymer polyester has 100 mole percent terephthalic acid and 100 mole percent ethylene glycol. A polyester containing 5 mole percent of the ionic co-monomer of the dicarboxylic acid could be derived from 95 moles of terephthalic acid, 5 moles of lithium sulphonate (such as sulfoisophthalic lithium acid) and 100 moles of ethylene glycol. Similarly, it may be advantageous to add another comonomer such as isophthalic acid. For example, a 2 mole percent isophthalate polymer could contain 93 moles of terephthalic acid, 2 moles of isophthalic acid, 5 moles of functionalized lithium sulphonate and 100 moles of ethylene glycol to form 100 moles of repeating unit of polymer.
In the three component mixing system, the moles of acid are the moles of acid of the modified polymer plus the moles of acid in the unmodified polymer.
Also known is the fact that di-ethylene glycol forms a site with the manufacture of polyester and about 2-3 percent of the total moles of glycol with diethylene glycol. Therefore, the composition is 97 mole percent ethylene glycol and 3 mole percent diethylene glycol.
The amount of interfacial reducing agent is determined empirically. In general, a small amount is needed and approximates a critical amount beyond which the additional amounts have no effect. In the field of surface science, this amount is known as Critical Micelle Concentration (CMC). As seen in the examples, a small amount of sulfonated material has a significant effect, but at a certain point, about 0.4 or 0.5 mole percent in the case of sulfoisophthalic lithium acid, no increased effectiveness The levels above the CMC would be a functional equivalent of the CMC since it refers to the reduction of the interfacial tension of the polyester-polyamide. In contrast to other salts, the lithium salt shows in particular an optimal level between about 0.3 and 1.0 mole percent polymer repeater unit. This can be expressed as 0.4 to 1.0 mole percent of the acid or glycol portion to which the lithium salt is fixed.
Examples of modified polyester used in the present invention are those prepared by virtually any polycondensation polymerization process. Traditional techniques can be divided into ester, acid and modified processes. In the ester process, the dimethyl ester of the acid or of the carboxylic acids is reacted with the glycol or glycols in the presence of heat, and the extracted methanol produces the bis-hydroxyethyl ester of the acids. The bis-hydroxyethyl ester is then polymerized in its liquid form by subjecting the material to vacuum and heat to extract the glycols and increase the molecular weight. A typical process could begin with these relationships: 98 moles of dimethyl terephthalate, 2 moles of dimethyl sodium sulfoisophthalate, and 220 moles of glycol, typically ethylene glycol. Of the 220 moles of glycol, 120 are excess that must be removed during the process. It should be appreciated that it is possible to obtain the sulfonated co-monomer in any of its bis- (hydroxyethyl) or dimethyl ester forms.
For clarity, the phrase copolymerized with at least X percent of a specific acid means that the compound is considered part of the polymeric acid group, such as terephthalic or isophthalic acid. This provides the reference to determine how many moles of the compound should be used. The phrase does not mean that the compound should be added to the process as an acid. For example, the sulfoisophthalic lithium acid could be copolymerized in polyethylene terephthalate as an acid, with two carboxylic end groups, the dimethyl ester of the carboxylic acid, or the bishidroxy ester of the dimethyl ester or even very low molecular weight oligomers of a glycol polymer acid in which the portions are, at least in part, the sulfoisophthalate salt.
The phrase "copolymerized acid salt" should not limit the claim to use only the acid form, but should be understood to mean that the compound is one of the acid groups of the polymer.
The phrase "copolymerized with" means that the compound has been chemically reacted with the polymer, such as in the polymer chain or as a pendant group. For example, a polyester copolymerized with lithium sulfoisophthalate, or modified by copolymerization of at least 0.01 mole percent of sulfoisophthalic lithium acid in the polyester, means that the lithium sulfoisophthalate is bound to the polymer, including the bond in the polymer chain, with at least one chemical bond. The phrases are different from how the material is incorporated in the polymer. A polyester copolymerized with lithium sulfoisophthalate, or modified by copolymerizing at least 0.01 mole percent of lithium sulfoisophthalate in polyester, refers to a polyester containing lithium sulfoisophthalate if that lithium sulfoisophthalate was incorporated using, but without limitation, sulfoisophthalic lithium acid, sulfobenzoic lithium acid, sulfoisophthalic lithium acid dimethyl ester, sulfobenzoic lithium acid methyl ester, di-alcohol
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lithium sulfoisophthalate, sulfohydroxy benzene, lithium salt of hydroxy benzene sulfonic acid, or oligomers or polymers containing lithium sulfoisophthalate.
The phrases "and derivatives" and "and their derivatives" refer to the various functionalized forms of the interfacial tension reducing agent that can be copolymerized in the polymer. For example, lithium sulfoisophthalate “and its derivatives” refers together, and without limitation, to sulfoisophthalic lithium acid, sulfoisophthalic lithium acid dimethyl ester, sulfoisophthalic lithium acid bis-hydroxyethyl ester, sulfoisophthalate di-alcohol lithium, to low molecular weight oligomers, and high IV polymers containing lithium sulfoisophthalate in the polymer chain.
The same nomenclature applies to glycol or alcohol.
In the acid process, the starting materials are di-carboxylic acids, with water being the main by-product. The charge ratio in a typical acid process is 98 moles of terephthalic acid, 2 moles of a metal sulfoisophthalic acid salt (for example, sulfoisophthalic lithium acid - LiSIPA), and 120 moles of glycols, the typical ethylene glycol. After the reaction of the glycols with the acids, the material is subjected to the same polymerization process conditions as the ester process.
Modified processes are variations of any process: combining the intermediate product in some stages. An example is to pre-polymerize the raw materials without the interfacial tension reducing agent at a low molecular weight. In the case of the examples described below, the molecular weight of the low molecular weight polyester was typically in the range of 0.096 to 0.103 dl / g having a carboxyl end group number in the range of 586 to 1740 equivalents per 1,000,000 grams of polymer. Obviously, the molecular weight could be easily varied without undue experimentation as it has been for many years by those skilled in the art when the point of addition is optimized for their additives.
Another example of a variation is to use the terephthalic acid acid process only to produce its low molecular weight intermediate product, and the ester process used to produce the bis-hydroxyethyl ester of the homopolymer sulfonated polyester. These two intermediate products are then combined and polymerized in a copolymer. Another variation consists in adding the finished modified polymer to the fusion reactor and allowing the fusion process to depolymerize the modified polymer and then form a copolymer. While the three-component system, PET, PET-ionomer, and polyamide, is not as effective as the random copolymer, the three-component system is considered a part of the invention. The copolymer is a preferred embodiment of the invention.
Another technique for manufacturing the modified polymer consists in completely trans-esterifying a modified polyester with a large number of interfacial tension reducing portions in an unmodified polyester to create a randomly structured modified copolymer. This can be done using conventional techniques that use extrusion with a long residence time and / or high temperature.
The same effect can be achieved using the multi-compartment ball technique described in WO 2005/110694, entitled "Divided Resin Balls". This could include the use of core-sheath design, in which the core is a hydrophilic polymer and the sheath is the unmodified, more hydrophobic polyester. The products are then combined in a composition during the fusion manufacturing of the article. This was the procedure used in example 6.
WO 2005/110694 entitled "Compartmentalized Resin Balls" describes the ball endowed with zones or compartmentalized as the preferred structure for the polyamide / polyester ball. The preferred ball structure is either a polyamide core with a modified polyester sheath of reduced interfacial tension, or a modified polyamide core with a polyester sheath, or both polyamide and polyester have been modified. It is understood that the core or sheath could contain some amount of another ingredient as well.
As taught in the examples of the US patent application 11/130961, this ball can be polymerized in solid phase without the expected color change. The polyamide is then mixed by fusion with the polyester when the article is manufactured, thus achieving the advantage of the invention in the article. In fact, the lowest average size of dispersed particle of 57 nm was obtained using a compartmentalized ball structure.
Other methods of incorporating similar co-monomers are listed in US Pat. No. 3,936,389, No. 3,899,470 and No. 5,178,950, and in the US Statutory Invention Registry. H1760
The polyester and polyamide are mixed by fusion and then molded by injection, granulated or formed into a film. The analysis of the dispersion at this point shows the polyamide dispersed in the polyester matrix phase. There are many techniques to analyze the properties of dispersion. The domain size of the dispersed polymer is measured in the unstretched area. The unstretched area may exist in an unstretched area of the wall, such as the thread, the neck and the sealing portions, or it may be measured on the article prior to stretching. By measuring the size of the particles dispersed in the article prior to stretching, the article produces the same value as measuring the size in the unstretched portion after
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stretching. Therefore, if the stretched wall does not have an unstretched portion, the size of the dispersed particles can be used prior to stretching. In many cases, the measurement was made on the preform or parison prior to stretching.
In one example, a fractured sample is treated with cold formic acid to extract the polyamide from PET and the sample is scanned by electron microscopy (SEM). Based on the contrast, the domains in the polyamide could easily be determined and measured (see Figures 1 and 3).
Since the molded sample is unstretched, the particles are present as spheres. The SEM image can be analyzed either manually or with various computer programs. The average particle size can then be easily calculated from the image. The average can be determined by adding the diameters of all the particles in the image and dividing by the number of particles in the image. Alternatively, a statistically significant sample size can be used instead of all domains in populations.
Similarly, a distribution analysis can be done (Figures 2 and 4), making a histogram of the number of particles corresponding to a given diameter. The data can be normalized to perform a particle density function. Such normalization could be done by taking the number of particles per area observed and multiplying next or dividing by the desired factor to normalize the result.
For example, if you want to normalize the observation of 250 particles per 100 square nanometers with respect to the number of particles per 1000 square nanometers, you could multiply 250 by 10, which is the factor of 1000 square nanometers divided by 100 square nanometers.
The interfacial tension between two polymers in their liquid state is difficult to determine due to the high temperatures involved. One technique is to use a rotating tensiometer. However, in the absence of sophisticated equipment, it is much easier to make two polymer dispersions separately, one modified, and the other unmodified, using the same amount of work (torque, spindle design, temperatures) and compare the difference The dispersed material is of medium size.
The immediate effect of the reduction in interfacial tension can be appreciated by comparing the average polyamide particle size of an unmodified polyether polyamide dispersion, with a modified polyester polyamide system. This test easily determines whether the interfacial tension has been reduced.
It has not been found that the difference in viscosity between modified and unmodified materials is a significant factor. However, this difference can be accounted for to be sure that the modified and unmodified polyester have the same fusion viscosities. Given the drastic change in particle size, the effectiveness of a particular lithium compound in reducing interfacial tension can easily be determined.
Regardless of whether the interfacial tension has been reduced, the molded part is generally not turbid. However, once the article is stretched, the spherical domains will lengthen, becoming ellipsoidal, and at least one diameter of the ellipse will be large enough to interfere with visible light. Mathematically expressed, one of the ellipse's diameters will be greater than approximately 400 nm, but less than approximately 720 nm; corresponding to the wavelength range of visible light.
Stretching occurs when the molded article, film or fiber is subjected to a force and stretched or lengthened. In general, the article is heated to a temperature below the melting point of the polymer matrix and then pulled in one or two, or in the case of a bubble, in three directions. A fiber or a type of film is an example of uni-axial stretching. A fiber is pulled in the direction of its length to be stretched. A movie will be placed on a machine that has a sequence of gears that move progressively faster, thereby stretching the film between each gear or other clamping mechanism.
In the case of bottles, biaxially oriented films, or blown films, the article is pulled in at least two directions. In the case of a blown bottle or a blown bottle with overheating or blown with stretching and overheating, pressure, such as compressed air, is introduced into the article, also known as preform or parison. The air will then expand the article so that it takes the form of the blow mold surrounding the article. Depending on the design of the article and the mold, the article will have varying degrees of stretching in both directions.
In movies, there are some techniques that simultaneously stretch the article in the machine and transverse directions. However, in industrial practice it is more common to stretch the film first in one direction and then in the other.
It is in this stretched article that the object of the invention is useful. By reducing the interfacial tension so that the particles of the dispersed polymer are extremely small, the article can be stretched to
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higher levels, and still maintain a reduced turbidity appearance because many of the stretched particles are still below 400 nm (the wavelength of light).
The amount of stretching, also known as dragging, is described as the stretching ratio. In the case of a uniaxial stretch, the ratio is the length of the stretched article divided by the length of the unstretched article, where both lengths are measured in the direction of stretching. A 50.8 mm (2 inch) sample stretched to 203.2 mm (8 inches) would have a stretch ratio of 4.
For a bi-axially stretched article, the relationship is often described as the stretch relationship in the first direction multiplied by the stretch relationship in the second direction. Thus, an article stretched 3 times in one direction and 3 times in the other direction (usually perpendicular to the first direction), has a stretch ratio of 3x3 or 9. However, an item with a stretch ratio of 2 in one direction and 4.5 in the perpendicular direction, it would also have a stretch ratio of 9.
Another technique of measuring the stretch ratio, drag ratio, or reduction ratio is to draw or describe a circle on a plane of the item, measure the area of the circle, stretch the item, and then measure the new area circumscribed by the Enlarged circumference of the old circle. The stretch ratio is then the area of the new stretched circle divided by the area of the old unstretched circle. The relationship can also be determined using the ratio of the diameters or radii.
In the case of three-dimensional stretching, the change in volume or area of a sphere could be used to approximate the stretching relationship.
Regardless of the technique used to measure the stretch ratio, stretching the molded article causes the dispersed component to stretch as well. Even if the dispersed component is not stretched, the surrounding domain of the dispersed component will lengthen. If the domain elongation has been completely filled with the dispersed material or if it is not greater than approximately 400 nm but is less than approximately 720 nm, then the stretched article will increase a Hunter Turbidity value, where turbidity is the measurement of the amount of light deviation from the transmittance direction by at least 2.5 degrees.
If enough particles have diameters between 400 and 720 nanometers, then turbidity will be detectable by the human eye. As discussed in the following, the standard deviation becomes equally as important as the average domain size.
It is evident that the diameter of the dispersed particle must be sufficiently small so that when stretched, the longest dimension of the dispersed particular and the domain encompassing the particle is less than 400 nm. For an article that stretches 3 in one direction and 3 in the other, the maximum particle size in the unstretched article must be 400 nm divided by 3, ie 133 nm. For the article stretched at 2 x 4.5, the particle size should be less than, or equal to, 400 divided by 4.5, ie 89 nm. The average target diameter of the particles dispersed in the unstretched matrix phase could then be easily expressed as 400 divided by the longest stretch dimension. For example, if the final stretch dimension were 7 x 2, then the assumption would have to consist of modifying the interfacial tension such that the average diameter of the particle in the article without stretching was 400 divided by 7, that is 57 nm. Not only is it important that the average diameter is below a certain size, but that the distribution is narrow enough to reduce the number of dispersed particles that may exist between 400-700 nm after stretching. Although reducing the average domain size is important to minimize the number of domains in the visible region, narrowing the wide distribution is also important.
Since the particles are produced according to a distribution, the average particle diameter is used. Given the ranges of stretch ratios, the average diameter of the particles dispersed in the unstretched container should be less than 125 nm, more preferably less than 100 nm, even more preferably less than 80 nm. For articles that are to be stretched with a high stretch, high stretch materials and average particle diameters of less than 90 nm should be used, the particle size smaller than 70 nm being preferred, and the size of the particles being even more preferred particle less than 60 nm, the best appearance occurring with an average particle diameter less than 50 nm.
What has been discovered is that when lithium salt is used, the domains do not follow the expected behavior. The 9 Series exam proves it. The stretch percentage that has been previously defined as the stretch ratio of the polyamide domains divided by the stretch ratio of the polyester matrix in the same direction, can be determined as follows.
The domain stretch ratio, or domain stretch ratio, is the average length of the domains after stretching in the direction of stretching measurement divided by the average length of the domains prior to stretching. Since the unstretched domain is spherical, any radio or address can be used.
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The stretch ratio of the polyester or matrix is the change in the amount by which the polyester has been stretched coinciding with the approximate area in which the domain was measured. The easiest way to measure the stretch ratio of the polyester for the calculation of the stretch percentage is to place a line of known length on the article in the approximate area where the stretch ratio of the domains is to be measured. The article is then stretched, presumably in the direction of the line and the new line length is measured next. The stretch ratio of the polyester is the length of the stretched line divided by the length of the line before the stretch. Of course, measurements must be made in the same direction of stretching.
Theoretically, the stretch percentage should be 100% (1.0), since the domains are stretched the same amount as the polyester. However, when lithium salt is used, the stretch percentage is often less than 75, with many observations less than 50%, and in a case less than 30%. It is believed that the lower the stretch percentage, the better. As shown in Series 9, the stretching percentage of the traditional sodium sulfoisophthalate interfacial tension reducing agent was 0.91 (91%), while the stretching percentage using the lithium salt was 0.71 ( 71%).
The wall thickness of the container of the present invention can be in the range of 0.01 in the case of a film up to the thickness of a preform that is usually less than 6.5 mm. In the case of the bottle, the stretched wall normally has a thickness of 0.1 to 0.9 mm. A container wall may also consist of layers of varying thickness, the thickness of the layers being usually between 0.02 and 0.2 mm. A monolayer, which is the preferred wall of the container, consists of a single layer. A monolayer of the polyester-polyamide dispersion could consist of a layer. This does not mean that the monolayer could not have a label wrapped around it. It could even be a mono-layer bottle. On the contrary, the multilayer bottle could contain at least one layer of the composition.
References to the side wall of the container and to the wall of the container of this invention also refer to the lid, the bottom and the upper sides of the container, and a film that may be wrapped around the product such as meat wraps. The wall of the container can be fully stretched or have stretched and unstretched portions. For example, a bottle blown by overheating or blown by injection stretching, is a container with a highly stretched portion in the middle of the wall, the wall successively having less stretch until the wall is no longer stretched in the neck areas and of the thread For clarity, the thread, neck and sealing portions in which the cap is applied are considered part of the wall of a container. In a bottle blown by overheating, the threads and neck area are generally unstretched. A preform or parison is also a container with at least one wall. Although it is an intermediate product, the preform is capable of containing a packaged content since it is closed at one end and open at the other.
A water activated oxygen cleaner can also be included in the composition. These oxygen cleaning compositions are well known in the literature and usually comprise particles of oxidizable metal, in particular elemental iron or aluminum, and an activation component such as a water soluble, electrolytic, acidic, non-electrolytic / acidic salt, or Lewis acids hydrolysable in water. The activation component can be either mixed or deposited on the oxidizable metal particles. The polymer composition may also contain polyamide, in particular, poly-m-xylylene adipamide (MXD6). If it is desired to only increase the passive barrier, the polyamide can be mixed without the oxygen cleaning composition.
The oxygen cleaning compositions can be added directly to the polyester or polyamide whether they are modified or not, at any stage in which one of the polymer streams is in its liquid state, such as in polymerization by fusion, granulation, formation of separate compound or fusion manufacturing operation, such as the extrusion section thereof, after which the molten mixture can be advanced directly to the article manufacturing line.
Typical values of the oxidizable metal will be between 300 and 3000 ppm by weight of the polymers of the composition.
The color and luminosity of a thermoplastic article can be observed visually, and can also be quantitatively determined by a HunterLab ColorQuest Spectrometer. This instrument uses the 1976 CIE color and brightness designation, a *, b * and L *. A coordinate * defines a color axis in which the more values are towards the red end of the color spectrum, and the less values are towards the green end.
The b * coordinate defines a second color axis, in which the more values are towards the yellow end of the visible spectrum and the less values towards the blue end of the visible spectrum.
Higher values of L * indicate an increased brightness of the material.
Examples with a cobalt compound or with a sodium sulphonate salt are provided for reasons of comparison only.
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The polyester polymers used in the present invention were manufactured by extrusion and fusion polymerization.
Example 1. Manufacture of sodium sulfonate polymer interfacially modified by fusion polymerization
A two-vessel reactor train was used to make this polymer of intermediate molecular weight at 0.5 and 2.0 mole percent sodium sulfoisophthalate. The following example demonstrates how the polymer containing 0.5 mole percent sodium isophthalate was manufactured. The same procedure was used for concentrations of 2.0 mole percent and higher in the extrusion manufacturing technique.
8933.0 grams of dimethyl terephthalate, 69.7 grams of dimethyl sodium sulfoisophthalate, 7175 grams of ethylene glycol and 261 g of manganese acetate, were added to the first vessel. The ingredients were heated at 214 ° C at a rate of 0.4 ° C per minute, and the methanol was extracted. After the extraction of 3660 ml of methanol, the ingredients were transferred to the second vessel and the batch temperature was increased to 226 ° C. 67 grams of phosphite stabilizer were added and mixed for 5 minutes. Then 140 grams of isophthalic acid were added to the batch. After stirring for 15 minutes, 77 grams of cobalt acetate, and 173 grams of glycosylated antimony oxide were added, and the vessel was placed under a vacuum of 0.13 millibars. The batch was continuously stirred and the temperature was increased to 256 ° C. The resulting polymer was discharged and granulated after reaching the desired intrinsic viscosity. The polymer produced in this particular batch had an I.V. of 0.53 dl / g, a carboxyl end group number of 14 (equivalent milligrams per gram of polymer), and a melting point of 246.9 ° C.
The molecular weight of the material was increased by polymerizing in solid phase several batches of fusion in a rotating vacuum vessel. Solid phase polymerization was carried out by placing 5 batches of fusion of the same molecular constitution in the vessel. The vessel pressure was reduced to 0.12 millibars, the temperature was set at 225 ° C, and the vessel was slowly rotated so that the material was turned therein. After 12 hours of turning, the temperature was increased to 230 ° C for 6 hours, and then increased to 235 ° C for 2 hours. The balls were then cooled and discharged. The final Intrinsic Viscosity was 0.82 dl / g. The following batches were made according to the process of Example 1, and were used in the experiments.
Table I - Properties ^ of the material produced by fusion
 Mole% of acid portions  Melting point ° C Intrinsic viscosity
 NaSIPA *  IPA * PTA *
 0.5  1.79 97.71 247 0.82
 0.5  1.79 97.71 254 0.83
 2.0  2.45 95.55 243 0.82
Note: 19 grams of sodium acetate were added to the fusion reactions producing the highest melting point. Sodium acetate suppresses the formation of di-ethylene glycol as reflected in the increased melting point.
* Although the abbreviation is for Acid, it refers to the acid portion, for example, NaSIPA refers to the sulfoisophthalic sodium acid portion that is produced as sodium sulfoisophthalate in the polymer chain.
Example 2. Manufacture of polymer modified by extrusion
25 mole percent of sodium sulfoisophthalate and 75 mole percent of modified terephthalate polymer were made using the fusion production techniques of Example 1. The polymer was then dried and fused with an extruder. double spindle in Polyester Resin Cleartuf® 8006S from M&G Polymers, LLC, USA, to achieve a polymer with 2 mole percent of SIPA. Cleartuf® Polyester Resin is 98.5 mole percent terephthalic acid, and 1.5 mole percent isophthalic copolymer of polyethylene terephthalate resin. The polymer was then polymerized in solid phase under vacuum at I.V. of 0.862 dl / g.
Another series was made in the same way. In one case, 25% of sodium sulfoisophthalate compound with 8006S to achieve a final sodium sulfoisophthalate content of 0.5 mole percent, and then mixed with 5% MXD6, Grade 6007, in one Arburg single spindle injection machine, with low shear conditions.
The 25% sulfoisophthalate compound was fused with Cleartuf 8006S® polyester, 2500 ppm of Freshblend® iron particulate oxygen cleaner (Multisorb Technologies, Incorporated, Buffalo, NY) with 5% MXD6 Grade 6007 in a machine Arburg single screw injection with low shear conditions, to achieve a final sulfoisophthalate content of 2 mole percent.
The results are presented in table II. As can be seen, the change in the type of PET or the amount of sodium sulfoisophthalate had little effect on the size of the domain. Copolymerization produced better results in all cases.
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Table II - Diameter of particles dispersed in nanometers
 PET control 8006 Reagent extrusion (example 2) Fusion polymerized random copolymer
 Diam. (nm) Def. standard Diam. (nm) Def. standard Diam. (nm) Def. standard
 0% SIPA 5% MXD6  200 76.2
 0.5 moles% NaSIPA 5% MXD6      97 36.3 78 27.5
 0.5 moles% NaSIPA 5% MXD6      97 34.1 74 22.7
 2 moles% NaSIPA 5% MXD6      100 29.1 81 26.2
 0.18 moles% LiSIPA 7% MXD6          76.93 37.28
 0.37 moles% LiSIPA 7% MXD6          67.85 34.33
 0.74 moles% LiSIPA 7% MXD6          69.73 31.37
 1.11 moles% LiSIPA 7% MXD6          77.98 39.89
 2.0 moles% LiSIPA 7% MXD6          90.6 37.46
SIPA again refers to the acid portions of this table. Example 3. Lithium sulphonate with cobalt salt
A copolyethylene terephthalate containing several amounts of lithium sulphonate in the form of lithium sulfoisophthalate derived from lithium sulfoisophthalic acid (LiSIPA) was made. The modified lithium sulfoisophthalate copolymer was manufactured by disposing 7567 grams of terephthalic acid, 157 grams of isophthalic acid, and 2974 grams of ethylene glycol in a glass of previously reacted oligomers from the previous batch. The content was maintained under a pressure of 35 psig at 262 ° C. After 35 minutes, 45.4 grams of 1% lithium mixture of lithium acetate in ethylene glycol, and 18.1 grams of mixture, 1% by weight of phosphorus, of phosphoric acid were charged into the reactor diluted in ethylene glycol. The content was kept in this vessel under stirring for 3 hours with an oil temperature of 271 ° C, increasing the temperature of the content from 248 ° C to 263 ° C, and 35 psig. During that time, the water was extracted from the glass.
After reacting for 3 hours, a portion of the content was transferred to a second vessel. The remaining amount of the first glass was about the same amount that was in the glass when the raw materials were initially loaded. Once in the second vessel, 146 grams of a 5% bis-hydroxyethyl ester of sulfoisophthalic lithium acid - 95% ethylene glycol solution and 1044 grams of ethylene were added to the material transferred from the first vessel to the second vessel. The content of the second vessel was stirred at atmospheric pressure and 244 ° C. After 30 minutes, another 146 grams of the bis-hydroxy ester of lithium sulfoisophthalic acid, and 1044 grams of ethylene glycol were added to the second vessel. After 30 minutes of mixing, 38.6 grams of 0.47 by weight cobalt acetate and cobalt acetate and ethylene glycol mixture were added to the second vessel. After 3 minutes of mixing, 206 grams of a 1% by weight antimony mixture of ethylene glycol antimony was added to the vessel. After 45 minutes, the pressure was reduced to 199 mm Hg, and after another 26 minutes, the pressure was reduced to 1.0 mm Hg. 40 minutes later, the pressure was 0.2 mm Hg and was maintained for 20 minutes before unloading the ingredients and granulating the material.
This amorphous material was combined with several other similarly produced batches, and then the solid phase was polymerized in a vacuum vessel of batch rotation at 0.1 mm Hg and 232 ° C until an I.V. of 0.802 (dl / g). The amount of lithium sulfoisophthalate was changed for the resulting mole percentages. The amount of lithium sulfoisophthalate recorded in the tables is based on the measurement of the amount of sulfur in the polymer and not on the amount charged.
The material was combined with 7% by weight of MXD6 nylon (Grade 6007, from Mitsubishi Gas Chemical, Japan) and
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It was injection molded into a preform. The preform was subjected to SEM analysis (figure 3) and compared with a similar preform with unmodified polyester (figure 1). As can be easily seen from the photomicrographs, the average polyamide particle size of the unmodified system is much larger than the particle size of the modified system. The largest particle size in the unmodified system indicates that the interfacial surface tension is higher. The analysis of the domains (figures 2 and 4) also show a much wider distribution for the unmodified system. The superiority of lithium sulfoisophthalate has also been demonstrated in Table III, which compares the change in Turbidity per mil. 2 mole percent lithium sulfoisophthalate showed almost no change in turbidity due to increasing nylon content, while 2 mole percent sodium sulfoisophthalate still shows a significant influence.
It is worth mentioning that sodium sulfoisophthalate is not preferred for stretched application, despite the claims of the prior art. The prior art exposes that sodium sulfoisophthalate is the preferred material for the three component system. What has been discovered is that sodium sulfoisophthalate gave an unacceptable turbidity, regardless of whether the stretched sample contained nylon. In contrast to sodium sulfoisophthalate in these examples, lithium sulfoisophthalate did not exhibit a relatively high inherent turbidity, thereby making it the best commercially acceptable material.
The optimal concentration and superiority of the low level of lithium sulfoisophthalate are shown in Tables III and IV. In all cases, 7% of MXD6 Grade 6007 of Mitsubichi Gas Chemical Compay was mixed by fusion with PET-lithium sulfoisophthalate, and parisons or preforms were manufactured and subsequently blown into bottles. The average particle diameter in nanometers was measured using cold formic acid tanic, followed by SEM analysis as described in the test method section.
Table III - Characterization of lithium sulfoisophthalate
 0% LiSIPA 0.18% LiSIPA with cobalt 0.37% LiSIPA with cobalt 0.5% LiSIPA without cobalt 9.74% LiSIPA with cobalt 1.11% LiSIPA with cobalt 2% LiSIPA with cobalt
 Average preform particle diameter (nm)  200 76.93 67.85 69.73 77.98 90.60
 Standard deviation of particle distribution  76.2 37.28 34.44 31.37 39.89 37.46
 Average increase in loss of I.V. during injection molding from control (without SIPA)    0.005 0.013 0.014 0.018 0.043
 Increase in preform acetaldehyde (ppm) from control      2.0 3.2 6.7 5.7
 Increase (+) or reduction (-) in color b * after 7 hours of bed drying from N2 to 150 ° C compared to control without SIPA of -0.13      -1.06 -0.50 -0.32
 Aum / b * network when small balls are converted to bottles versus control without SIPA of +4.5    -0.093 -4.50 +0.16 +1.69 3.18
 Change in Hunter turbidity per mil (%) versus control without SIPA of 0.46    -0.34 -0.39 -0.44 +0.49 -0.46
 Change in b * when pellets are converted into a bottle divided by percentage of MDX6 6007    1.97 1.81 1.32 0.69 1.72
* 1.11% LiSIPA was analyzed for nylon content and 9.5% was found instead of 7%. This variability occurs during the extrusion process. The others were analyzed for nylon content also with deviations less remote from the 7% target.
** Again, the LiSIPA in this table refers to the acid portions of the lithium sulfoisophthalate.
Example 4. Comparative Examples
Tables IV and V demonstrate the ability of the modified polyester polymer with a small amount of the comonomer to virtually eliminate the turbidity caused by mixing nylon in the polymer. 3 and 5 percent of the two polyamides (MXD6 - Grades 6001 and 6007, of Mitsubishi Gas Chemical, Japan), were mixed by fusion in preforms with Cleartuf® 8006S Polyester Resin and Turbo®® II (both available in M&G Polymers USA) and the three modified materials listed in Table I. While 8006S and Turbo® II were the controls, Turbo® was modified with approximately 5 mole percent isophthalic acid. 0.5 l bottles were blown from the preforms and turbidity was measured in each bottle (instead of in the side wall). Turbidity has been recorded in Table IV, and the change in turbidity per millimeter of the stretched wall with respect to the control without any polyamide has been recorded in Table V. The change in turbidity per millimeter in relation to the control is
Calculate by subtracting the turbidity per millimeter of the wall without nylon from the turbidity per millimeter of the wall with nylon. The more effective the material is in the reduction of interfacial tension, the lower the change in turbidity the more nylon is added. In each case, the modified polymers suppressed the turbidity caused by the addition of the nylon.
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The particle dispersion analysis was also performed on the various unstretched preforms. The results for the dispersion of 5% nylon (MXD6 Grade 6001) have been shown when it has been added to the unmodified materials, the reactive extrusion method and the fusion polymerization method. The results in Table V indicate that reactive extrusion achieves some advantages, but complete randomization does not occur. The superiority of the random copolymer is demonstrated by the fact that in each case, the diameter of the particle is significantly smaller than the particle of the others.
Table IV - Hunter Turbidity per side wall mil
 % MXD6, Grade MXD6  Turbo® II Cleartuf 8006S 2 moles% NaSIPA (PF 243 ° C) 0.5 moles% NaSIPA (PF 247 ° C) 0.5 moles% NaSIPA (PF 254 ° C) 0.18 moles% LiSIPA with cobalt 0.3 moles% LiSIPA with cobalt 0.50 moles% LiSIPA without cobalt 0.74 moles% LiSIPA with cobalt 1.11 moles% LiSIPA with cobalt 2.00 moles% LiSIPA with cobalt
 0%, 6001    0.08 0.15 0.34 0.12
 3%, 6001    0.36 0.19 0.29 0.26
 5%, 6001    0.46 0.22 0.33 0.31

 0%, 6007  0.12 0.11 0.15 0.33 0.25 0.18 0.50 0.80 0.40
 3%, 6007  0.23 0.17 0.38 0.28 0.22 0.47 0.82 0.40
 5%, 6007  0.46 0.99 0.22 0.24
 7%, 6007            0.45 0.32 0.27 0.51 0.77 0.40
* The NaSIPA or LiSIPA nomenclature in this table means the mole percent of the acidic portions of lithium sulfoisophthalate. 15 However, one skilled in the art knows that the mole percent of lithium sulfoisophthalate is equal to the mole percent of the starting monomer.
Table V - Turbidity change per millimeter in relation to control bottle with 0% nylon
 Turbo® II Cleartuf 8006S 2 moles% NaSIPA (PF 243 ° C) 0.5 moles% NaSIPA (PF 247 ° C) 0.5 moles% NaSIPA (PF 254 ° C) 0.18 moles% LiSIPA 0.37 moles% LiSIPA 0.50 moles% LiSIPA without cobalt 0.74 moles% LiSIPA 1.11 moles% LiSIPA 2.00 moles% LiSIPA
 3% 6001    0.27 0.04 -0.06 0.15
 5% 6001    0.38 0.08 -0.01 0.20

 3% 6007  0.23 0.03 0.05 0.03 0.04 0.01 0.02 0.00
 5% 6007  0.46 0.88 0.07 0.06
 7% 6007            0.12 0.07 0.09 0.03 -0.03 0.00
* The NaSIPA or LiSIPA nomenclature in this table means the mole percent of the acidic portions of lithium sulfoisophthalate. 20 However, one skilled in the art knows that the mole percent of lithium sulfoisophthalate is equal to the mole percent of the starting monomer.
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Example 5. Lithium sulphonate without cobalt salt
A polyethylene terephthalate copolymer containing 0.5 mole percent lithium sulphonate (lithium sulfoisophthalate) was prepared, in the same manner as in Example 3, except that cobalt acetate was replaced by a package of color without cobalt. The color packet was added at the beginning of the reaction and consisted of 3.03 ppm based on the production of final polymer of SB138 (Blue Solvent 138) and 1.60 ppm based on the production of final polymer of SV50 (Solvent Violet 50). Both dyes are available from Colorchem International as Amaplast Violet PC and Amaplast Blue HB. These dye levels were chosen to produce similar L *, a *, b * as cobalt acetate.
As shown in Table VI, 0.5 mole percent lithium sulphonate material had much better color with 5% MXD6 than it had the equivalent of 0.5 percent in sodium sulfonate molds with cobalt acetate In fact, it had a better color than 2 mol% sodium sulphonate when combined with MXD6 in the presence of a cobalt salt. This proves the superiority of lithium sulphonate over sodium sulphonate since a cobalt salt is not needed to control color when the material is fused with Nylon MXD6.
Table VI - Cobalt vs. no cobalt
 Nylon grade  Polymer type Nylon weight percentage Bottle b *
 0% SIPA, Cleartif® 8006S 0
 5
 6001    0
 0.5% NaSIPA, cobalt 3 13.78
 7 14.91
 0% SIPA, Cleartuf® 8006S 0 1.51
 5 15.5
 0 1.12
 Turbo II, high IPA, high clarity, PET grade bottle, without SIPA 3 10.6
 6 15.38
 6007    0 4.81
 0.5% LiSIPA, without cobalt  3 8.78
 5 11.01
 7 12.49
 0
 2.0% NaSiPA, cobalt 3 13.34
 7 15.18
* The NaSIPA or LiSIPA nomenclature in this table means the mole percent of the acidic portions of lithium sulfoisophthalate. However, one skilled in the art knows that the mole percent of lithium sulfoisophthalate is equal to the mole percent of the starting monomer.
The Hunter b * bottle is measured on a 0.5 l bottle, with a nominal wall thickness of 0.36 mm to 0.42 mm, where the bottle itself is arranged in a properly adapted machine and the light passes through of both side walls of the bottle. Thus, a bottle that has a Hunter b * color as measured on the bottle through both side walls, which is smaller than 20 units without Cobalt, is easily obtainable by means of the teachings of the present description. A bottle with a Hunter b * color of less than 15 units is also shown. A dye or color system such as a pigment or dye that reduces Hunter b * may also be present in the bottle. It is also appreciated that these bottles had less than 0.5% turbidity per millimeter.
Example 6. Lithium sulphonate with aliphatic polyamide (nylon 6)
Three samples were made demonstrating the effect of LiSIPA on nylon 6 and MXD6 mixed with nylon 6. The first mixture was 5% by weight of PA6 with 95% by weight of Cleartuf® 8006 polyethylene terephthalate of
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M&G Polymers, USA. The mixture was formed into preforms and blew into a bottle. As shown in Figure 5, the unmodified PET when mixed with PA6, was very milky white, and when it was blown in a bottle it had approximately 3% turbidity per millimeter of thickness. The resulting mixture is clear as shown in Figure 5 when the PA is mixed with 0.5 mole percent of polyethylene terephthalate modified with lithium sulfoisophthalate, and the turbidity of the bottle is 0.5% per mil. . By comparison, the turbidity of the modified polyethylene terephthalate bottle with lithium sulfoisophthalate and unmodified polyethylene terephthalate is in each case approximately 0.2 percent turbidity per millimeter without any nylon. A mixture of 1.5% by weight of PA6, 3.5% of MXD6 and 95% of polyethylene terephthalate was also made, with similar results. Turbidity for unmodified polyethylene terephthalate was approximately 1.15 percent per millimeter, while turbidity for polyethylene terephthalate modified with lithium sulfoisophthalate was 0.3 percent per mil.
Example 7. Lithium sulfoisophthalate in the nucleus-shell structure
In this series of experiments, various nucleo-shell configurations were evaluated as shown in Table V. The PET was Cleartuf 8006 and the MXD6 was grade 6007. The modified polyester contained 2.5 mole percent of lithium sulfoisophthalate of sodium sulfoisophthalate. The superiority of lithium was demonstrated again by comparing B with D and C with E. In both comparisons, lithium sulfoisophthalate had a much lower turbidity. The average domain size of the unmodified system was 200 +/- 61 nanometers, while the average domain size for the polymer modified with lithium sulfoisophthalate was 57 +/- 27 nanometers, a reduction of almost 72% The superiority of arranging the PET and the modified polyester in the same compartment instead of having the nylon and the modified polyester in the same compartment was also observed.
Table VII - Sodium and lithium sulfoisophthalate nucleo-sheath comparisons
 Core Housing L * a * b * Turbidity (%)
 TO  Control, without core 5% MXD6, 95% PET 78.46 -0.15 14.34 12.99
 B  5% MXD6 19% 2.5 moles% NaSIPA, 76% PET 79.98 -0.19 12.20 10.37
 C  5% MXD6, 5% 2.5 moles% NaSIPA 90% PET 76.05 0.01 12.93 23.36
 D  5% MXD6 19% 2.5 moles% LiSIPA, 76% PET 85.25 -0.55 7.38 4.37
 AND  5% MXD6, 5% 2.5 moles% LiSIPA 90% PET 76.85 -0.05 14.83 12.39
 F  5% MXD6 5% of 10 moles% NaSIPA, 90% PET 68.71 0.89 16.42 23.64
 G  5% MXD6, 5% 10 moles% NaSIPA 90% PET 70.46 0.52 15.41 37.79
NaSIPA and LiSIPA, refer to acidic portions as they are incorporated into the polyester structural skeleton. Example Series 9 - Demonstration of the unique stretching characteristics of lithium
The following examples demonstrate the functionality of the present invention. In Examples 1 to 3, 100 grams of polyamide pellets with the end group and the molecular weights provided in Table I, were dried separately and mixed by fusion with 1900 grams of polyester having the characteristics shown in the table. SAW. Note that the polyester of Examples 9B and 9C contains the interfacial tension reducing agent with sodium and lithium, respectively, at the mole percentages indicated, polymerized in the structural skeleton of the polymer. Example 9B is Crystar 3919/089 available in E.I. Dupont Nemours The polyester with interfacial tension reducing agent, lithium sulfoisophthalate, copolymerized in the structural skeleton used in Example 9C, was prepared as previously disclosed.
TABLE VIII
 Example 9A PET MXD6 6007 9B Na SIPA MXD6 6007 9C Li SIPA MXD6 6007
 Polyamide (% by weight of polymer components)  5 5 5
 R.V. 2.7 2.7 eg meas 2.7
 AEG (mmol / kg) 16 16 16
 CEG (mmol / kg) 68 68 68
 AEG / CEG (amino acid / acid end group ratio)
 Mn based on TEG 23810 23810 23810
 Polyester and interfacial tension reducing agent (% by weight of polymer components)  95 95 95
 PTA moles% 97.5 98.2 98.3
 IPA moles% 2.5 1.2
 LiSIPA moles% 0.5
 NaSIPA moles% 1.72
 Cobalt (ppm) 40 25
 Preform
 Domain size (nm) 71.9 47.6

 Measured shaft stretch ratio 2.91 3.36 2.73
 Hunter b * 11.83 10.59 8.3
 Thickness (mm) 0.3 0.28 0.29
 Domain size (nm) 220 93.2
 Domain stretch ratio in the ring direction 3.06 1.96
 Measured shaft stretch ratio 2.91 3.36 2.73
 Stretch percentage 92 71
 Turbidity (%) 12.09 5.7 6.1
 Turbidity / mm 40 20 21
Test methods
Intrinsic viscosity 5
The intrinsic viscosity of the intermediate molecular weight poly (ethylene terephthalate) and low crystallinity, and of the relative polymers that are soluble in 60/40 phenol / tetrachloroethane, can be determined by dissolving 0.1 grams of polymer or basic granule in 25 ml of 60/40 phenol / tetrachloroethane solution and determining the viscosity of the solution at 30 ° C +/- 0.05 relative to the solvent at the same temperature using a 10 Ubbelohde 1B viscometer. Intrinsic viscosity is calculated using the Billmeyer equation based on relative viscosity.
The intrinsic viscosity of the high molecular weight and highly crystalline poly (ethylene terephthalate) and the relative polymers that are not soluble in phenol / tetrachloroethane was determined by dissolving 0.1 grams of basic granule polymer in 25 ml of trifluoroacetic acid / 50/50 dichloromethane and determining the viscosity of the solution at 30 ° C +/- 0.05 relative to the solvent at the same temperature using a Ubbelohede Type OC viscometer. Intrinsic viscosity was calculated using the Billmeyer equation and converted using a linear regression to obtain results that are consistent with those obtained using 60/40 phenol / tetrachloroethane solvent. Linear regression is
I.V. in phenol / tetrachloroethane at 60/40 =
0.8229 x I.V. in 50/50 trifluoroacetic acid / dichloromethane + 0.0124.
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Hunter turbidity measurement
Measurements were taken through the side walls of the bottle. A HunterLab ColorQUEST Sphere Spectrophotometer System, assorted sample carriers, and green, gray and white calibration charts, and a light trap were used. The HunterLab Spectrumcolorimeter integration sphere sensor is a color and appearance measuring instrument. The light from the lamp is blurred by the sphere of integration, and is either passed through (transmitted) or reflected (reflectance) in an object to a lens. The lens collects the light and directs it to a diffraction grid that disperses it in the wavelengths of its components. The scattered light is reflected on a matrix of silicon diodes. The signals coming from the diodes pass through an amplifier to a converter, and are managed to produce the data. Turbidity data is provided by software. This is the calculated ratio of diffuse light transmittance to total light transmittance, multiplied by 100 to produce a "Turbidity in%" (0 being a transparent material, and being 100% an opaque material). Samples that are prepared either for transmittance or for reflectance should be clean and free of scratches or surface abrasion. The size of the sample must be consistent with the geometry of the opening of the sphere and, in the case of transmittance, the size of the sample is limited by the dimensions of the compartment. Each sample is tested in four different places, for example on the side wall of the bottle or a representative film area.
A Magna-Mike 8000 Hall Effect Thickness Gauge was used to measure the thickness of the side wall of the bottle.
Scattered domain analysis Scanning electron microscopy
The sample was prepared by cutting the preform or the container wall and putting the cut pieces in liquid nitrogen for five minutes. The pieces were then broken with a strong blow. A piece of the preform or wall is cut into a slice with the specified angle. The slice was placed in a 50 cc laboratory vessel, and covered with approximately 25 ml of formic acid> 96% (available as ACS reagent [64-18-6] in Fluka, Aldrich or Merck), and stirred at room temperature. The sample was extracted, after one hour the slice was taken and washed with water until the water had a neutral pH. The sample was then washed with acetone.
After washing with acetone, the sample was placed in an agar metallizing car (model A, s.n. A10S) and plated with gold in order to make it conductive. Typical conditions for the auto agar metallizer consist in using a current of 20 mA, in argon flow, for 30 seconds, using gold metal.
The coated sample was then placed in an SEM carrier and a picture was taken. A typical SEM machine is the LEO 1450 VP, s.n. 01-22, of SEM Leo Electronic Microscopy Ltd, used in the vacuum chamber mode with the acquisition system of Secondary Electronic Detection. Other details are:
EHT voltage: 20 kV
Focal length, also known as working distance or WD: 10-11 mm Point size (no dimensions): 200-300 decreasing to 80 in large magnifications Filament current: 3-3.5 A depending on the age of the filament
The dimensions and distribution of the polyamide domains were measured using Lucia M software (available in Laboratory Imaging, and can be purchased as a package with an SEM machine supplied by Nikon Japan) in automatic or manual mode. Typically, more than 250 domains were measured on 10 different photographs, increasing the number of domains analyzed per photograph with better dispersions. A statistical analysis on the domains was then carried out to determine the mean, the average value and the distribution of the domains as in Figure 4, and the frequency of domains at a given size range per unit area for each sample.

权利要求:
Claims (17)
[1]
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1. - A container wall comprising a layer with a stretched region, in which the layer comprises a polyamide that is MXD6 nylon and is dispersed in a crystallizable polymer with at least 85% of the acid acid units derived from the acid terephthalic or terephthalic acid dimethyl ester, and an interfacial tension reducing agent that is a crystallizable polyester with at least 85% units of polyester acid derived from terephthalic acid or terephthalic acid dimethyl ester and with a sulphonate salt of functionalized lithium copolymerized in its structural skeleton, in which the layer is free of cobalt compounds.
[2]
2. - The wall of claim 1, wherein the interfacial tension reducing agent is lithium sulfoisophthalate.
[3]
3. - The wall of claim 2, wherein the lithium sulfoisophthalate is present at a level in the range of 0.1 to 2.0 mole percent based on the moles of the acid units in the polyester.
[4]
4. - The wall of claim 1, wherein the interfacial tension reducing agent is lithium sulfoisophthalate present at a level in the range of 0.1 to 2.0 mole percent based on the moles of the acid units in the polyester.
[5]
5. - The wall of claim 1, wherein the interfacial tension reducing agent is lithium sulfoisophthalate present at a level in the range of 0.1 to 1.1 mole percent based on the moles of the acid units in the polyester.
[6]
6. - The wall of claim 1, wherein the average diameter of the dispersed particles is less than 100 nm, the average diameter being calculated by adding the diameters of all the particles in an SEM photograph of the wall and dividing by the number of particles in photography.
[7]
7. - The wall of claim 6, wherein the interfacial tension reducing agent is lithium sulfoisophthalate present at a level in the range of 0.1 to 2.0 mole percent based on the moles of the acid units in the polyester.
[8]
8. - The wall of claim 6, wherein the interfacial tension reducing agent is lithium sulfoisophthalate present at a level in the range of 0.1 to 1.1 mole percent based on the moles of the acid units in the polyester.
[9]
9. - The wall of claim 1, wherein the average diameter of the dispersed particles is less than 75 nm, the average diameter being calculated by adding the diameters of all the particles in a SEM photograph of the wall and dividing by the number of particles in photography.
[10]
10. - The wall of claim 9, wherein the interfacial tension reducing agent is lithium sulfoisophthalate present at a level in the range of 0.1 to 2.0 mole percent based on the moles of the acid units in the polyester.
[11]
11. - The wall of claim 9, wherein the interfacial tension reducing agent is lithium sulfoisophthalate present at a level in the range of 0.1 to 1.1 mole percent based on the moles of the acid units in the polyester.
[12]
12. - The wall of claim 1, wherein the average diameter of the dispersed particles is less than 60 nm, the average diameter being calculated by adding the diameters of all the particles in an SEM photograph of the wall and dividing by the number of particles in photography.
[13]
13. - The wall of claim 12, wherein the interfacial tension reducing agent is lithium sulfoisophthalate present at a level in the range of 0.1 to 2.0 mole percent based on the moles of the acid units in the polyester.
[14]
14. - The wall of claim 12, wherein the interfacial tension reducing agent is lithium sulfoisophthalate present at a level in the range of 0.1 to 1.1 mole percent based on the moles of the acid units in the polyester.
[15]
15. - The wall of claim 1, wherein the average diameter of the dispersed particles is less than 50 nm, the average diameter being calculated by adding the diameters of all the particles in an SEM photograph of the wall and dividing by the number of particles in photography.
[16]
16. - The wall of claim 15, wherein the interfacial tension reducing agent is lithium sulfoisophthalate present at a level in the range of 0.1 to 2.0 mole percent based on the moles of the acid units in the polyester.
[17]
17. The wall of claim 15, wherein the interfacial tension reducing agent is lithium sulfoisophthalate present at a level in the range of 0.1 to 1.1 mole percent based on the moles of the acid units in the polyester.

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引用文献:

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公开号 | 申请日 | 公开日 | 申请人 | 专利标题

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法律状态:

优先权:

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申请号 | 申请日 | 专利标题

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US72508505P| true| 2005-10-07|2005-10-07|

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US725085P|2005-10-07|

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US82714706P| true| 2006-09-27|2006-09-27|

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US827147P|2006-09-27|

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