CN101133122A

CN101133122A - Transparent, oxygen-scavenging compositions and articles prepared therefrom

Info

Publication number: CN101133122A
Application number: CNA2006800065090A
Authority: CN
Inventors: W·R·黑尔; T·J·佩科里尼; M·E·斯图尔特; M·E·罗杰斯; S·A·吉利亚姆; M·D·克利夫顿; M·D·谢尔比
Original assignee: Eastman Chemical Co
Current assignee: Eastman Chemical Co
Priority date: 2005-03-02
Filing date: 2006-03-02
Publication date: 2008-02-27
Anticipated expiration: 2026-03-02
Also published as: CN101132910A; CN101132909A; CN101133124A; CN101132910B; CN101133122B; CN101133123B; CN101132909B; CN101133123A

Abstract

Disclosed is a process for the preparation of shaped articles such as, for example, sheeting, films, tubes, bottles, preforms and profiles, having high transparency and low haze comprising immiscible blends of one or more thermoplastic polymers selected from polyesters, polycarbonates, and polyarylates, and a copolyamide or a transamidized, homogeneous blend of a least two polyamides. The components of the immiscible blend which have refractive indices which differ by about 0.006 to about -0.0006. The small difference in the refractive indices enable the incorporation of regrind into the polymer composition to produce transparent shaped articles. These articles may have one or more layers and can exhibit improved excellent barrier properties and good melt processability while retaining excellent mechanical properties. Metal catalysts can be incorporated into the compositions to produce shaped articles having oxygen-scavenging properties.

Description

Transparent oxygen-scavenging compositions and goods prepared therefrom

The cross reference of related application

The application requires the rights and interests of U.S. Provisional Application sequence number of submitting on March 2nd, 2,005 60/657,746 and the U.S. Provisional Application sequence number of submitting on March 2nd, 2,005 60/657,747, and it is attached to herein in full by reference for each.

Invention field

The present invention relates to transparent oxygen scavenging polymer composition.More specifically, the present invention relates to immiscible blend polymer, described immiscible blend polymer comprises the homogeneous blend of oxide catalyst, at least a thermoplastic polymer and copolyamide or at least two kinds of polymeric amide, wherein, the absolute value of the out of phase refringence of described unmixing blend is little.The present invention also relates to comprise the moulded products of described oxygen-scavenging compositions.

Background of invention

Many products (particularly food) are to existence and the dehydration or the suction sensitivity of oxygen.The interior product of packing with this susceptibility is easy to go bad because of contacting the oxygen or the moisture absorption.The wrapping material of limit food product class article contact oxygen help for example to keep the quality of foodstuff article and reduce corrupt.Therefore the use of this class barrier packaging can make the longer time of article inventory and therefore reduce the cost and the loss of restocking.The effort that is intended to address this problem has made the oxygen barrier material and/or has been used widely in wrapping material every wet stock.Many polymer materialss have been known and can be used as oxygen barrier or every wet stock.For example, typically comprise polyethylene and polypropylene every wet stock.Representational oxygen barrier material comprises the blend of ethylene-vinyl alcohol copolymer (" EVOH "), polyvinyl alcohol (" PVOH "), polymeric amide (nylon) and these materials.Poly-(vinylidene chloride), vinyl chloride copolymer and vinylidene chloride-methyl acrylate copolymer also are useful every wet and oxygen barrier material.

But these conventional barrier materials cost an arm and a leg and have unsettled constitutional features or an other defect, make to be difficult to fully from barrier material Production and Packaging material or to produce undesirable.For example, though EVOH has superior oxygen barrier, not effectively every wet stock.Other barrier materials are when using it as wrapping material fully, and price is very expensive.For avoiding these problems, use multilayered structure to become convention, wherein, the amount of expensive barrier material can reduce to skim and be used in combination low-cost polymkeric substance as structural sheet on the barrier layer one or both sides.The use of multilayered structure also helps to avoid degenerating by structural sheet protection barrier layer.But the production possible price costliness of multilayer product.In addition, multi-layer articles may be difficult to reclaim, because different polymeric constituents is difficult to separate.In addition, the blend of the polymer waste of recovery or " again pulverize material " and unworn polymkeric substance often because of virgin material with pulverize the incompatible of material again and can cause mist degree unsatisfactory or opacity.

The shortcoming of conventional separating polymer also can be overcome by the blend that uses separating polymer and another polymkeric substance.Regrettably, as mentioned above, many blends of separating polymer and other thermoplastic polymers all are unmixings, opaque or muddy.Such blend can not be satisfactory for the application (for example beverage container) that requires the transparency.

Polyester polymers is usually used in the packaging application as poly-(ethylene glycol terephthalate) (" PET ").PET has many its character that become useful wrapping material that make, and comprises acceptable carbonic acid gas barrier for the soft drink that contains many portions of foods in being packaged in bottle.But for the soft drink that is packaged in the bottle, the carbonic acid gas barrier of PET also need improve, and its oxygen barrier also need be improved in addition, because of its be not be well suited for packing oxygen quick property product such as beer, citrus products, based on the product of tomato and the meat of sterile packed.The barrier property of poly-((ethylene naphthalate)) (" PEN ") is 3-10 a times of PET, but price is also more expensive.

Can use multilayered structure to improve the barrier properties for gases of PET.For example, have excellent oxygen barrier (also claiming " passive obstruct ") or oxygen and remove the laminate structure that the polymkeric substance of (also claiming " initiatively intercepting ") character can be made up of various polymkeric substance with the PET combinations produce.But the productive expense of these multilayered structures is high.The blend of separating polymer and PET also has been used to improve the oxygen barrier of packing, but as mentioned above, and its transparency is usually poor and be unsuitable for many packaging application.The transparency difference of blend also makes it be difficult in the future, and the processing waste recovery of autohemagglutination compound blend is used for unworn polymkeric substance.

Copolyester film and extrusion-blown modling (" EBM ") bottle often has ideal toughness, and it often replaces PET to be used for extrusion-blown modling and film is used.These often use need with the suitable barrier of barrier of orientation PET.But regrettably, the barrier of copolyesters is not as orientation PET.By producing multilayered structure to improve total barrier to the thin barrier films of the center of thicker body construction coextrusion.But for the purpose of economy, EBM and membrane method usually require the material of pulverizing again (being flash and scrap stock) of high level (at the most 80%) is reprocessed.Regrettably, common barrier material and copolyesters unmixing, the blend of these separating polymers and polyester often show the mist degree of height and the transparency of difference.Therefore, when being added in the main stor(e)y (primary layer) again, the level of haze of whole membrane structure will increase to unacceptable level when waste material polymkeric substance (pulverizing material again).

It is economic also reclaiming efficiently that good blend polymer passive and/or initiatively barrier is provided, and this is the needs of this area.Such blend should be transparent, and containing provides height oxygen barrier, water proof and every the thermoplasticity and the separating polymer of carbonic acid gas, and can be used for wherein having added the high-caliber goods formation method of pulverizing material again economically.In addition, need can be used to produce economically multi-layer product and also can bear barrier material and the thermoplastic polymer composition that high level is pulverized material again with high transparent.

Summary of the invention

Polymer composition with high transparent and high barrier can be prepared through the unmixing blend of the homogeneous blend of acid amides exchange by one or more thermoplastic polymers and copolyamide or two kinds of polymeric amide at least, wherein, the refringence between polyamide component and thermoplastic polymer components is about 0.006-about-0.0006.Therefore, the invention provides a kind of polymer composition, described polymer composition comprises the unmixing blend of following component:

(i) first component, described first component comprises at least a thermoplastic polymer that is selected from polyester, polycarbonate, polyarylester and its homogeneous blend; With

(ii) second component, described second component comprise the homogeneous blend of at least two kinds of polymeric amide through the acid amides exchange;

Wherein, second component (ii) is about 0.006-pact-0.0006 with the refringence (RI (second component)-RI (first component)) of first component (i), and the percent transmittancy of blend is at least 75%, and mist degree is below 10%.

First component comprises at least a thermoplastic polymer that is selected from the homogeneous blend of polyester, polycarbonate, polyarylester and these polymkeric substance, and second component comprises the blend of at least two kinds of polymeric amide, described at least two kinds of polymeric amide acid amides exchange and produced homogeneous blend.We have found that the polymeric amide that the specific refractory power of first and second components can be by selecting at least two kinds of aliphatic series with different levels and aromatic moieties also makes these polymeric amide generation acid amides exchanges form homogeneous blends and tight coupling.Therefore, the homogeneous blend of thermoplastic polymer and polymeric amide can be used to the specific refractory power of " adjusting " second component and first component in its required scope, so that refringence is about 0.006-about-0.0006.For example, polyester can be used as first component with the homogeneous blend that comprises the polycarbonate of dihydroxyphenyl propane residue, and first polymeric amide that comprises the residue of m-xylene diamine and hexanodioic acid can be used as separating polymer with second aliphatic polyamide through the homogeneous blend that acid amides exchanges.When therefore specific refractory power mated, described first and second components formed transparent unmixing blend, and described blend is suitable for preparing the high transparent moulded products that can be used in many packaging application.Also can prepare multi-layer product by the method for knowing in multiple this area.For example, first and second components can be from the melt coextrusion or are injected altogether and form independent layer, but or each self-forming of layer in follow-up method (for example lamination), be incorporated into together again.

Second component also can comprise copolyamide, and the ratio of its aromatics and aliphatic dicarboxylic acid and diamines residue can be through changing so that the specific refractory power of first and second components is closely mated.Therefore, another aspect of the invention is polymer composition, described polymer composition comprises the unmixing blend of following component:

(ii) second component, described second component comprises copolyamide;

Another aspect of the invention is the polymer composition that makes by the method that comprises the following component of melt blending:

Composition of the present invention has excellent barrier.Oxygen barrier can strengthen to produce oxygen-scavenging compositions by add transition-metal catalyst such as cobalt, manganese, iron, ruthenium, copper, nickel, palladium and platinum in blend.Therefore, the present invention also provides oxygen-scavenging compositions, and described oxygen-scavenging compositions comprises:

(A) unmixing blend, described insoluble blend comprises:

Wherein, second component (ii) is about 0.006-pact-0.0006 with the refringence (RI (second component)-RI (first component)) of first component (i), and the percent transmittancy of blend is at least 75%, and mist degree is below 10%; With

(B) at least a periodic table of elements 3-12 family, the metal in 4-6 cycle of being selected from.Typical metal catalyst is cobalt, manganese and iron.

Blend of the present invention can be used for producing transparent moulded products, and it has improved barrier, melt processable and excellent mechanical property, and it can be by adding a high proportion of material preparation of pulverizing again in unworn polymkeric substance.That these moulded products can be single or multiple lift and can be used in many packaging application.Therefore, the present invention also provides the method that forms moulded products, and described method comprises:

(A) melt blending

Wherein, first component (i) (ii) forms the unmixing blend with second component, the refringence of second component and first component (RI (second component)-RI (first component)) is about 0.006-pact-0.0006, and the percent transmittancy of blend is at least 75%, and mist degree is below 10%;

(B) form moulded products;

(C) recovery comprises first and second components (i) of blend and polymer waste composition (ii);

(D) pulverize described polymer waste composition and pulverize material again to produce polymkeric substance;

(E) the described polymer waste composition of optionally drying; With

(F) merge described polymkeric substance and pulverize material again and (ii) with first and second components (i) of step (A).The example of moulded products that can be by method of the present invention preparation includes but not limited to sheet, film, pipe, bottle or parison.Moulded products can by extrude, calendering, thermoforming, blowing, extrusion-blown modling, injection moulding, compression moulding, curtain coating, drawing-off, tentering or blowing produce.

Moulded products can have one or more layers that comprise the unmixing blend of first and second components maybe can have the wherein a plurality of layers of first and second components in independent layer.The present invention also provides multilayer formed article, and described multilayer formed article comprises:

(i) the first layer, described the first layer comprise at least a thermoplastic polymer that is selected from polyester, polycarbonate, polyarylester and its homogeneous blend; With

The (ii) second layer, the described second layer comprise the homogeneous blend of at least two kinds of polymeric amide through the acid amides exchange;

Wherein, the second layer (ii) and the refringence of the first layer (i) (RI (second layer)-RI (the first layer)) be about 0.006-pact-0.0006, and the percent transmittancy of moulded products is at least 75%, mist degree is below 10%.

The present invention also provides the method that forms multilayer formed article, and described method comprises:

(i) heating comprises about Tg+100 ℃ to about Tg+300 ℃ the temperature of first component of at least a thermoplastic polymer that is selected from polyester, polycarbonate, polyarylester and its homogeneous blend to described first component;

(ii) heating comprises copolyamide or at least two kinds of polymeric amide through second component of the homogeneous blend of acid amides exchange about Tg+100 ℃ to about Tg+300 ℃ temperature to described second component;

(iii) form the moulded products of described first and second components in independent layer;

(iv) reclaim the waste material of first and second components;

(waste material of v) pulverizing described first and second components is pulverized material again to produce;

(vi) described the pulverizing again of optionally drying expected; With

(vii) merge described pulverize again material and step (i) and first component (ii), second component or its combination;

Wherein, step (ii) second component and the refringence (RI (second component)-RI (first component)) of first component of step (i) be about 0.006-pact-0.0006, and the percent transmittancy of blend is at least 75%, mist degree is below 10%.Described pulverize again material can be added to first or the second layer in and can account for about 60% weight of about 5-of goods.

Describe in detail

Polymer composition with high transparent and good barrier can be by one or more thermoplastic polymers and the unmixing blend preparation of at least two kinds of polymeric amide through the homogeneous blend of acid amides exchange, wherein, the refringence between polyamide blend and thermoplastic polymer is about 0.006-about-0.0006.The percent transmittancy of described blend is at least 75%, and mist degree is below 10%.In general embodiment, the invention provides polymer composition, described polymer composition comprises the unmixing blend of following component:

Wherein, second component (ii) is about 0.006-pact-0.0006 with the refringence (RI (second component)-RI (first component)) of first component (i), and the percent transmittancy of blend is at least 75%, and mist degree is below 10%.Described thermoplastic polymer and polymeric amide can be selected from multiple polymers.The specific refractory power of second component and first component can be by second component the selection of polymeric amide and ratio or the thermoplastic polymer by blend first component form homogeneous blend and regulate, making difference is about 0.006-pact-0.0006.Novel compositions of the present invention can be used to produce the moulded products with one or more layers, for example sheet, film, pipe, bottle and parison.Moulded products can by extrude, calendering, thermoforming, blowing, extrusion-blown modling, injection moulding, compression moulding, curtain coating, drawing-off, tentering or blowing produce.Can prepare unmixing blend wherein is present in one or more layers or first and second components are present in multi-layer product in the independent layer.Because the refringence of first and second components is little, keep the good transparency so in the moulded products that composition of the present invention makes, can be incorporated into quite a large amount of material of pulverizing again.The transparency of these moulded products that produced and barrier make it be specially adapted to packaging application.

Unless point out in addition, otherwise the number average of amount, character such as molecular weight, reaction conditions etc. of used all expression compositions is interpreted as being term " about " in all cases and modifies in this specification sheets and claims.Correspondingly, unless point out in addition, the numerical parameter of listing in following specification sheets and subsidiary claims is approximation, and it can be according to the character of acquisition required for the present invention and different.On the bottom line, each numerical parameter should be understood according to the number and the conventional rounding-off method of employing of given significant figure at least.In addition, the scope that provides in the disclosure and claims is intended to clearly comprise entire area rather than end points only.What for example, provide is intended to disclose all marks between all integers between 0 and 10 (as 1,2,3,4 etc.), 0 and 10 (as 1.5,2.3,4.57,6.1113 etc.) and end points 0 and 10 for the scope of 0-10.The scope relevant with chemical substituting group is as " C ₁-C ₅Hydrocarbon " also be intended to clearly comprise and disclose C ₁And C ₅Hydrocarbon and C ₂, C ₃And C ₄Hydrocarbon.

Though illustrating the numerical range and the parameter of broad range of the present invention is approximation, the numerical value that provides in the specific embodiment is accurate as far as possible.But any numerical value all contains the error that certain standard deviation in measuring because of its each must cause inherently.

Unless spell out in addition in the context, used singulative " ", " a kind of " and " being somebody's turn to do " all contains its plural object in this specification sheets and subsidiary claims.For example, mention that " polymkeric substance " or " moulded products " is intended to comprise the processing or the making of multiple polymers or goods.Mention that composition contains or comprise that " a kind of " composition or " a kind of " polymkeric substance are intended to comprise respectively other compositions or other polymkeric substance except that specified polymkeric substance.

Get rid of unless in claims, have clearly; otherwise " comprise " or " containing " or " comprising " refers to that specified at least compound, element, particle or method steps etc. are present in composition or goods or the method; but do not get rid of the existence of other compounds, catalyzer, material, particle, method steps etc., even if other such compounds, material, particle, method steps etc. have and specified identical functions.

Should also be understood that mentioning of one or more method stepss do not get rid of the existence of additive method step before or after the whole described step or the existence of the method steps between these steps that spell out.In addition, the mark of method steps or composition is the means that make things convenient for of discrete activity of sign or composition, unless point out in addition, described mark can any sequence arrangement.

The term of using herein " polyester " is intended to comprise equal polyester, copolyesters and three-element copolymerized ester.Generally speaking, the synthetic polymer that makes for the polycondensation by one or more two functional carboxylic acid and one or more two senses oxy-compound of polyester.Usually, described two functional carboxylic acid are dicarboxylic acid or hydroxycarboxylic acid, and described two sense oxy-compound are dibasic alcohol such as ethylene glycol and glycol.In the present invention, described two functional carboxylic acid can be aliphatic series or cycloaliphatic dicarboxylic acid's (as hexanodioic acid) or aromatic dicarboxylic acid (as terephthalic acid).Described two sense oxy-compound can be cycloaliphatic diol (as 1,4 cyclohexane dimethanol), straight or branched aliphatic diol (as 1, the 4-butyleneglycol) or aromatic diol (as quinhydrones).

The term of using herein " polymeric amide " is intended to comprise the synthetic polymer that makes by one or more two functional carboxylic acid and one or more two functional amines' polycondensation or the ring-opening polymerization by lactan, and can comprise homopolymer and multipolymer.For example, described two functional carboxylic acid can be dicarboxylic acid such as hexanodioic acid or m-phthalic acid, and described two functional amines can be diamines such as hexanediamine or m-xylene diamine.The term of using herein " copolyamide " is interpreted as the polymeric amide that finger comprises the repeating unit of at least two kinds of chemistry unique (chemically distinct).For example, MXD6 nylon is not copolyamide, because it only contains a kind of chemical different repeating unit that contains the residue of hexanodioic acid and m-xylene diamine.On the contrary, (hexamethylene adipamide)-(6I hexamethylene isoterephalamide) multipolymer that makes by the hexanediamine and the condensation of hexanodioic acid and m-phthalic acid has two repeating units that chemistry is different, promptly contains the repeating unit and another repeating unit that contains the residue of hexanediamine and m-phthalic acid of the residue of hexanediamine and hexanodioic acid.

In this article, term " polycarbonate " is defined as the condensation product in carbonate source and glycol source, for 200% mole total monomeric unit or 100% mole " repeating unit ", carbonate component contains 100% mole carbonate unit, and diol component contains 100% mole diol units.In one embodiment of the invention, the polycarbonate of described first component part is based on 4, the polycarbonate of 4 '-isopropylidene biphenol (being commonly referred to bisphenol-a polycarbonate).The straight or branched polycarbonate can be derived from dihydroxyphenyl propane and can be by the preparation of the method known in this area widely for available among the present invention, and for example United States Patent (USP) 3,030, disclosing in 335 and 3,317,466.Can be used among the present invention and have the example of commercially available bisphenol-a polycarbonate to comprise can to have bought with trade(brand)name LEXAN  from General Electric Company and can be from Bayer, the material that Inc. has bought with trade(brand)name MAKROLON .

The term of using herein " polyarylester " refers to the polyester that the polycondensation by one or more two functional aromatics dicarboxylic acid and one or more dihydric phenols makes.For example, typical aromatic dicarboxylic acid is terephthalic acid and m-phthalic acid, and typical aromatics diphenol is dihydroxyphenyl propane and quinhydrones.

The used term of polymkeric substance of the present invention herein " residue " refers to be incorporated into any organic structure in the polymkeric substance by corresponding monomeric polycondensation or ring-opening reaction.The term of using herein " repeating unit " refers to the shortest sequence of the monomer residue that can repeatedly find in polymkeric substance.For example, in polyester, repeating unit is the organic structure that contains dicarboxylic acid residue and diol residue or pass through carbonyl acyloxy bonded hydroxycarboxylic acid residue.In polymeric amide, repeating unit is the organic structure that contains dicarboxylic acid and diamines residue, lactan or pass through amide group bonded amino-acid residue.

Should also be understood that those skilled in the art can derive from any derivative of described parent monomeric compound self or described parent compound obtains and various polyester of the present invention, polymeric amide, residue that polycarbonate is relevant with polyarylester.For example, the dicarboxylic acid of indication and amino-acid residue can be derived from dicarboxylic acid or amino acid monomer or its relevant carboxylic acid halides, ester, salt, acid anhydrides or its mixture and obtained in the polymkeric substance of the present invention.Therefore, the term of using herein " dicarboxylic acid " or " amino acid " be intended to comprise dicarboxylic acid and with the polycondensation method of glycol production high molecular weight polyesters or polymeric amide in any dicarboxylic acid derivatives of available, comprise carboxylic acid halides, ester, half ester, salt, half salt, acid anhydrides, mixed acid anhydride or its mixture that it is relevant." hydroxycarboxylic acid " be intended to comprise aliphatic series and cyclic aliphatic hydroxycarboxylic acid and monohydroxy-monocarboxylic acid and in the polycondensation method of producing high molecular weight polyesters or ring-opening reaction its any derivative of available, comprise carboxylic acid halides, ester, cyclic ester (comprising dimer such as lactic acid lactide), salt, acid anhydrides, mixed acid anhydride or its mixture that it is correlated with.Equally, " amino acid " be intended to comprise aliphatic series, aromatics and cyclic aliphatic amino acid and in the polycondensation method of producing superpolyamide or ring-opening reaction its any derivative of available, comprise carboxylic acid halides, acid amides, cyclic amide (lactan), salt, acid anhydrides, mixed acid anhydride or its mixture that it is relevant.In addition, term " diamines " is intended to comprise diamines and its relevant salt, acid amides or its any other derivative of available in the preparation of polymeric amide.

Used term " limiting viscosity " (I.V.) is interpreted as referring to comprising the viscosimetric analysis value that the solvent of the tetrachloroethane of the phenol of 60% weight and 40% weight obtains with the every 100ml of 0.5 gram polymkeric substance under 25 ℃ among the application.

The term of using herein " specific refractory power " (abbreviating " RI " as) refers to the detecting refractive index value by well-known standard method acquisition in this area.The specific refractory power that provides herein ties up to the wavelength of 633nm down with 2010 type Metricon Prism Coupler ^TMRefractometer (can buy) from Metricon Inc. measure and with three orthogonal directionss (extrude or stretch, laterally and thickness direction) mean value of the specific refractory power that records provides.The statement of using in the context of composition of the present invention, method and moulded products " refringence " always is meant the value that specific refractory power obtained that deducts the component (being commonly referred to " first component " or " the first layer " in the multi-layer product in this article) that contains polyester, polycarbonate or polyarylester from the specific refractory power of the component that contains polymeric amide or copolyamide (being commonly referred to " second component " or " second layer " the multi-layer product in this article).Therefore, by the present invention, refringence (" ARI ") should be calculated as follows:

Δ RI=RI (second component or layer)-RI (first component or layer)

For a person skilled in the art will be clearly, refringence can be positive number or negative.

The term of using herein " % mist degree " refers to the haze value (% mist degree=100* diffuse transmission/total transmission) that records with the common software (version 3 .8) of HunterLabUltraScan Sphere 8000 colourimeters (Hunter Associates Laboratory Inc., Reston produces) by Hunter by ASTM method D1003.The mensuration program of specific refractory power provides in an embodiment.For composition of the present invention, mist degree is by becoming composition molding or curtain coating thick sheet or film and by the program determination described in the embodiment below 1/8 inch.For moulded products (comprising multilayer formed article), mist degree can (promptly 1 * 1cm) also by the program determination of describing herein by goods being cut out thick fritter below 1/8 inch.

The term second-order transition temperature of using herein (" Tg ") refers to dsc (" DSC "), the Tg value that records with the scanning speed of common 20 ℃/min.The example of DSC instrument is TA Instruments 2920 type differential scanning calorimeter.

Composition of the present invention comprises first component, and described first component comprises the thermoplastic polymer that one or more are selected from polyester, polycarbonate, polyarylester and its homogeneous blend.The term of using herein " thermoplastic polymer " is intended to refer to that is to say its obvious meaning that it will be appreciated by those skilled in the art that, and is softening and get back to the polymkeric substance of its initial conditions when cool to room temperature when being heated.Described first component can comprise the blend (condition is that described blend is a homogeneous blend) that single thermoplastic polymer maybe can comprise two or more polymkeric substance.Term of using herein " homogeneous blend " and term " mixable " synonym are intended to refer to that described blend has single homogeneous phase, and this is indicated by single composition Tg peak.For example, can be used to " plasticising " described second polymkeric substance with mixable first polymkeric substance of second polymkeric substance, as United States Patent (USP) 6,211, shown in 309.Homogeneous blend can pass through two or more polymer formation of simple blend, or can form by the transesterify or the acid amides exchange of two or more polymkeric substance under the situation of polycondensate such as polyester or polymeric amide.On the contrary, the blend that the term of using herein " immiscible " refers to have at least two random blended phases and shows more than one Tg.Some polymkeric substance may unmixings but are compatible with each other.About can miscible and immiscible blend polymer and be used for Polymer Blends (polymkeric substance closes and mixes thing) the 1st and 2 volumes that other universal descriptions of the various analytical procedures of its sign can edit at D.R.Paul and C.B.Bucknall (2000, John Wiley﹠amp; Sons finds in Inc.).

Described first component can comprise the thermoplastic polymer that one or more are selected from polyester, polycarbonate, polyarylester and its homogeneous blend.For example, described first component can comprise polyester, described polyester comprises (a) diacid residues, the modification of at least a 2-20 of containing the carbon atom that the residue of described diacid residues comprises at least 80% mole of accounting for total diacid residues at least a dicarboxylic acid that is selected from terephthalic acid, m-phthalic acid, naphthalic acid and 1,4 cyclohexanedicarboxylic acid and 0-are about 20% mole is with the residue of dicarboxylic acid; (b) diol residue, described diol residue comprises at least 80% mole at least a ethylene glycol, 1 that is selected from that accounts for the diol residue total mole number, 4-cyclohexanedimethanol, neopentyl glycol, Diethylene Glycol, 1, ammediol, 1,4-butyleneglycol and 2,2,4,4-tetramethyl--1, at least a residue that contains the modification of 3-16 carbon with glycol that the residue of the glycol of 3-cyclobutanediol and 0-are about 20% mole.The ring glycol that contains cis and trans-isomer(ide) can be used as pure cis or trans-isomer(ide) or uses as the mixture of cis and trans-isomer(ide).

For example, described diacid residues can comprise one or more residues that is selected from the dicarboxylic acid of terephthalic acid, m-phthalic acid or its combination, described diol residue comprises one or more residues that is selected from the glycol of 1,4 cyclohexane dimethanol, neopentyl glycol, ethylene glycol and its combination.For example, in one embodiment, described diacid residues can comprise the residue of terephthalic acid and m-phthalic acid.To be higher than m-phthalic acid be favourable to the concentration of terephthalic acid in the polyester, because the polyester of gained provides higher shock strength to polymkeric substance.For example, described diacid residues can comprise about 100% mole terephthalic acid residue of about 60-and the about 40% mole isophthalic acid residues of 0-, and described diol residue can comprise about 100% mole 1,4 cyclohexane dimethanol residue.Other examples of dicarboxylic acid content comprise the terephthalic acid that about 80-is about 100% mole and the m-phthalic acid of 0-20% mole, and about 100% mole terephthalic acid.

Other representational polyester that can be used as the thermoplastic polymer of component (i) comprise the polyester that contains following diacid residues and diol residue: (a) diacid residues comprises the terephthalic acid residue of 80-100% mole, diol residue comprises about 90% mole 1,4 cyclohexane dimethanol residue of about 50-and the about 50% mole neopentyl glycol residue of about 10-; (b) diacid residues comprises 100% mole terephthalic acid residue, and diol residue comprises about 40% mole 1,4 cyclohexane dimethanol residue of about 10-and the about 90% mole glycol residue of 60-; (c) diacid residues comprises 100% mole terephthalic acid residue, and diol residue comprises about 90% mole glycol residue of about 10-about 99% mole 1,4 cyclohexane dimethanol residue, 0-and the about 25% mole Diethylene Glycol residue of about 1-; (d) diacid residues comprises 100% mole terephthalic acid residue, and diol residue comprises about 90% mole 1,4 cyclohexane dimethanol residue of about 50-and the about 50% mole glycol residue of 10-.

In another embodiment, described dicarboxylic acid can be selected from terephthalic acid and m-phthalic acid, and described glycol is selected from 1,4 cyclohexane dimethanol and ethylene glycol.For example, in a composition, described dicarboxylic acid is a terephthalic acid, and described glycol is a 1,4 cyclohexane dimethanol.And in another embodiment, described diacid residues can comprise at least 95% mole terephthalic acid residue, described diol residue can comprise the about 40% mole 1,4 cyclohexane dimethanol residue of about 10-, Diethylene Glycol residue and the about 89% mole glycol residue of about 35-that about 1-is about 25% mole.

If desired, described polyester also can comprise about 20% mole one or more of 0-and contain the residue of modifications of 2-20 carbon atom with diacid.For example, other aromatic dicarboxylic acids that contain about 16 carbon atoms of 8-that available 0-is about 30% mole, the cycloaliphatic dicarboxylic acid who contains about 16 carbon atoms of 8-, the aliphatic dicarboxylic acid that contains about 16 carbon atoms of about 2-or its mixture.Modification includes but not limited to 4 with the example of carboxylic acid, 4 '-biphenyl dicarboxylic acid, 1,4-naphthalic acid, 1,5-naphthalic acid, 2,6-naphthalic acid, 2,7-naphthalic acid, 4,4 '-hydroxy-benzoic acid, anti--4, one or more in 4 '-toluylene dioctyl phthalate, oxalic acid, propanedioic acid, succsinic acid, pentanedioic acid, hexanodioic acid, pimelic acid, suberic acid, nonane diacid and the sebacic acid.

In another embodiment, described polyester can comprise about 99% mole 1,4 cyclohexane dimethanol residue and the about 1% mole glycol residue of about 99-of about 1-that accounts for the diol residue total mole number.The typical molecular fraction of 1,4 cyclohexane dimethanol residue comprises about 40% mole, 50% mole of about 25% mole of about 10% mole of about 1-, about 1-, about 1-or higher and 100% mole in the polyester of the present invention.For example, in another embodiment, described dicarboxylic acid is a 1,4 cyclohexanedicarboxylic acid, and described glycol is a 1,4 cyclohexane dimethanol.In yet another embodiment, described polyester can comprise the residue of 1,4 cyclohexane dimethanol unit and neopentyl glycol.And in another embodiment, described polyester can comprise 1,4 cyclohexane dimethanol unit and 2,2,4,4-tetramethyl--1, the residue of 3-cyclobutanediol.

The diol component of polyester also can be by the about 20% mole at least a residue modification that contains the modification of 3-16 carbon with glycol of 0-.Modification comprises that with other scopes of glycol load is not limited to about 10% mole and be lower than 5% mole of 0-.Modification can be selected from 1 with glycol, 2-propylene glycol, 1, ammediol, 1,4-butyleneglycol, 1,5-pentanediol, 1,6-hexylene glycol, 1,4 cyclohexane dimethanol, terephthalyl alcohol, neopentyl glycol, polyoxyethylene glycol, polytetramethylene glycol and 2,2,4,4-tetramethyl--1, one or more in the 3-cyclobutanediol.The example of polyalkylene glycol comprises poly-(butyleneglycol) (" PTMG ") and poly-(ethylene glycol) (" PEG ") of molecular weight about at the most 2,000.For example, described diol component can be with the about 10% mole polyoxyethylene glycol of 0-or polytetramethylene glycol modification to strengthen elastomeric properties.In another embodiment, described diol residue can comprise about 90% mole glycol residue of about 10-about 99% mole 1,4 cyclohexane dimethanol residue, 0-and the about 25% mole Diethylene Glycol residue of about 1-.Described polyester also can contain the residue of about at the most 5% mole of accounting for acid or diol component, about 0.1-is about 2.0% mole usually polyfunctionality branching agent, the compound deriving of self-contained at least three carboxyls of described polyfunctionality branching agent and/or hydroxyl obtains, to form branched polyester.The example of this compounds comprises trimellitic acid or acid anhydrides, trimesic acid, pyromellitic acid acid anhydride, trimethylolethane, TriMethylolPropane(TMP), trimer acid etc.Skilled person in the art will appreciate that final composition can reach by the various resins of blend or by direct reactor copolymerization.The latter is an ideal reducing to greatest extent aspect the composition variability, but economic certainty often makes blend more economical efficient.

Other examples of polyester are to contain 100% mole terephthalic acid residue accounting for total diacid residues and arbitrary following diol residue to form those of (based on total diol residue): 1,4 cyclohexane dimethanol residue that (i) about 1-is about 5% mole and the about 95% mole glycol residue of about 99-; 1,4 cyclohexane dimethanol residue that (ii) about 29-is about 33% mole and the about 67% mole glycol residue of about 71-; 1,4 cyclohexane dimethanol residue that (iii) about 45-is about 55% mole and the about 45% mole glycol residue of about 55-; 1,4 cyclohexane dimethanol residue that (iv) about 60-is about 65% mole and the about 35% mole glycol residue of about 40-; (1,4 cyclohexane dimethanol residue that v) about 79-is about 83% mole and the about 17% mole glycol residue of about 21-; (vi) about 100% mole 1,4 cyclohexane dimethanol residue.

The limiting viscosity of described polyester (I.V.) value is usually in the scope of the about 1.4dL/g of about 0.4dL/g-.I.V. other examples of scope comprise about 1.0dL/g of about 0.65dL/g-and the about 0.85dL/g of about 0.7dL/g-.As previously mentioned, limiting viscosity is 25 ℃ of solvent mensuration that comprise down the tetrachloroethane of the phenol of 60% weight and 40% weight with the every 100ml of 0.5 gram polymkeric substance.

But the polymkeric substance of polymkeric substance crystalline of the present invention, hemicrystalline or amorphous.The term of using herein " hemicrystalline " refers to that polymkeric substance contains two phases: orderly crystallization phases and unordered amorphous phase.Polymkeric substance with hypocrystalline form had not only shown crystalline melt temperature (Tm) but also had shown second-order transition temperature (Tg) and can separate with " amorphous " polyidal field, and the latter only shows second-order transition temperature.

Polyester used among the present invention is usually from dicarboxylic acid and glycol preparation, and the two is incorporated in the polyester polymers with the basic ratio reaction that equates and with its corresponding residue.Therefore, contain the sour residue (100% mole) and the diol residue (100% mole) of mol ratio such as basic from the derive polyester that obtains of dicarboxylic acid of the present invention and diol residue, so that the total mole number of repeating unit equals 100% mole.Therefore the molecular fraction that provides in the disclosure can be based on the total mole number of sour residue, the total mole number of diol residue or the total mole number of repeating unit.For example, the copolyesters that contains 30% mole the terephthalic acid that accounts for total sour residue means that described copolyesters has 30% mole terephthalic acid residue in 100% mole total sour residue.Therefore, in per 100 equimolar acid residues 30 moles of terephthalic acid residues are arranged.For an example, the copolyesters that contains 30% mole the 1,4 cyclohexane dimethanol that accounts for total diol residue means that described copolyesters has 30% mole 1,4 cyclohexane dimethanol residue in 100% mole total diol residue again.Therefore, in per 100 moles of diol residue 30 moles of 1,4 cyclohexane dimethanol residues are arranged.When diol component is mainly ethylene glycol, the copolyesters of the terephthalic acid of using herein, ethylene glycol and 1,4 cyclohexane dimethanol can be described as " PET ", when diol component is mainly 1, during the 4-cyclohexanedimethanol, can be described as " PCT ", when the ratio of ethylene glycol and 1,4 cyclohexane dimethanol greater than 1 the time, can be described as " PETG ", when the ratio of ethylene glycol and 1,4 cyclohexane dimethanol less than 1 the time, can be described as " PCTG ".

Polyester of the present invention is easy to prepare with typical polycondensation condition from suitable dicarboxylic acid, ester, acid anhydrides or salt and suitable glycol or diol mixture.Therefore, the dicarboxylic acid component of polyester of the present invention can derive from dicarboxylic acid, its corresponding ester or its mixture and obtains.The example of the ester of available dicarboxylic acid comprises dimethyl ester, dipropyl, diisopropyl ester, dibutylester and diphenyl ester etc. among the present invention.

Polyester of the present invention prepares by program well known to those skilled in the art.Preparation can be continuous, semicontinuous and batch mode of operation carry out and can use multiple type of reactor.The example of suitable type of reactor includes but not limited to stirred pot, continuously stirring jar, slurry, tubular type, scraped film type, falling film type or extrusion reaction device.The polyester conditioned disjunction of the available routine of reaction of glycol and dicarboxylic acid is undertaken by the fusion phase method, but have enough crystalline those can by fusion mutually then process for solid state polycondensation carry out.For example, by transesterification reaction (promptly from dicarboxylic acid component ester-formin) preparation polyester the time, reaction process can comprise for two steps.In the first step, diol component and dicarboxylic acid component (for example dimethyl terephthalate (DMT)) were reacting about 0.5-about 8 hours under the about 150 ℃-Yue 250 ℃ high temperature and the pressure of about 0.0kPa gauge pressure-Yue 414kPa gauge pressure (60 pound per square inches, " psig ") usually.The temperature of preferred transesterification reaction keeps about 4 hours of about 1-in about 180 ℃-Yue 230 ℃ scope and the preferred pressure scope is about 103kPa gauge pressure (15psig)-Yue 276kPa gauge pressure (40psig).Afterwards, heating is to form polyester and to remove glycol under higher temperature and decompression for reaction product, and under these conditions, glycol is easy to evaporation and removes from system.This second step (or condensation polymerization step) was continued about 6 hours of about 0.1-or preferably about 0.2-about 2 hours under the temperature of higher vacuum and about 230 ℃-Yue 350 ℃ usually, preferred about 250 ℃-Yue 310 ℃, most preferably from about 260 ℃-Yue 290 ℃, the polymkeric substance that has the required polymerization degree until acquisition; The polymerization degree is determined by limiting viscosity.Condensation polymerization step can be carried out under the decompression in about 53kPa (400 holder)-Yue 0.013kPa (0.1 holder) scope.All use in two stages stir or suitable condition to guarantee to conduct heat fully and the Surface Renewal of reaction mixture.The speed of reaction in two stages can be by suitable catalyzer such as alkoxy titanium compound, alkali metal hydroxide and alcoholate, organic carboxyl acid salt, Alkyzin compound, metal oxide etc. be improved.Also can use and United States Patent (USP) 5,290, similar three stage production sequences described in 631 are particularly when having adopted the mix monomer charging of acid and ester.

For the transesterification reaction of guaranteeing diol component and dicarboxylic acid component is driven to fully, need to use the about 2.5 moles diol component of about 1.05-sometimes to 1 mole dicarboxylic acid component.But the ratio that skilled person in the art will appreciate that diol component and dicarboxylic acid component is usually by the structures shape of the reactor of the process that reacts therein.

By the direct esterification method promptly when dicarboxylic acid component's sour form prepares polyester, polyester is by dicarboxylic acid or dicarboxylic acid mixture and diol component or the production of diol component mixture reaction.Be reflected at about 7kPa gauge pressure (1psig)-Yue 1379kPa gauge pressure (200psig), preferably be lower than that to carry out to produce mean polymerisation degree under the pressure of 689kPa (100psig) be the low-molecular-weight polyester product of about 1.4-about 10.The temperature that adopts in the direct esterification reaction process usually in about 180 ℃-Yue 280 ℃ scope, more preferably from about 220 ℃-Yue 270 ℃ scope.This low-molecular weight polymer can pass through polycondensation polymerized then.

Thermoplastic polymer of the present invention also can comprise polyarylester.Polyarylester obtains by the polymerization of dihydric phenol and dicarboxylic acid.The example that can be used for the polyarylester in composition of the present invention, method and the moulded products is seen and is set forth in United States Patent (USP) 4,598,130,5,034,502 and 4,374,239.The example that can be used to prepare the dihydric phenol of described polyarylester is bis-phenol such as two (4-hydroxy phenyl) methane, 2, two (4-hydroxy phenyl) propane (" dihydroxyphenyl propane "), 2 of 2-, two (the 4-hydroxy-3-methyl phenyl) propane, 4 of 2-, two (4-hydroxy phenyl) heptane, 2 of 4-, two (the 4-hydroxyls-3 of 2-, the 5-dichlorophenyl) propane, 2, two (4-hydroxyl-3, the 5-dibromo phenyl) propane of 2-; Binary phenolic ether such as two (4-hydroxy phenyl) ether, two (3,5-two chloro-4-hydroxy phenyls) ether; Dihydroxybiphenyl such as p, p '-dihydroxybiphenyl, 3,3 '-two chloro-4,4 '-dihydroxybiphenyl; Dihydroxyl aryl sulfone such as two (4-hydroxy phenyl) sulfone, two (3,5-dimethyl-4-hydroxy phenyl) sulfone; Dihydroxy-benzene such as Resorcinol; Quinhydrones; The dihydroxy-benzene that halo and alkyl replace is as 1,4-dihydroxyl-2,5-dichlorobenzene, 1,4-dihydroxyl-3-methylbenzene; With dihydroxyl diphenyl sulfoxide such as two (4-hydroxy phenyl) sulfoxide and two (3,5-two bromo-4-hydroxy phenyls) sulfoxide.Multiple other dihydric phenols are also available, and are as United States Patent (USP) 2,999, disclosed in 835,3,028,365 and 3,153,008.From above-mentioned dihydric phenol and halogen-containing dihydric phenol as 2, two (3, the 5-two chloro-4-hydroxy phenyls) propane and 2 of 2-, the multipolymer that two (3,5-two bromo-4-hydroxy phenyls) the propane copolymerization of 2-make also suits.Also can adopt two or more different dihydric phenols or dihydric phenol and glycol, with the polyester of hydroxyl or acid blocked or with the multipolymer of diprotic acid and the blend of any above-mentioned materials.Suitable dicarboxylic acid include but not limited to aromatic dicarboxylic acid (as phthalic acid, m-phthalic acid, terephthalic acid, phthalic acid, neighbour-,-and right-phenylene-diacetic acid) and polynuclear aromatic acid (as diphenic acid and 1, the 4-naphthalic acid).

Other examples that can be used for the polyarylester among the present invention comprise between dihydroxyphenyl propane (2, two (4-hydroxy phenyl) propane of 2-) and 50: 50/those polymkeric substance that the polymerization of terephthaldehyde's acid mixture obtains.Some described polymkeric substance can trade(brand)name " U-Polymer U-100 " have been bought (can buy from Unitika America Corporation) from the market.Other examples are based on tetramethyl-dihydroxyphenyl propane, 4, the polyarylester of 4 '-dihydroxy benaophenonel and 5-tertiary butyl isophthaloyl dichloro.

Polyarylester of the present invention can be by well-known any ester formation prepared in reaction in this area, and for example the alkaline aqueous solution of solution by under agitation mixing aromatics dicarboxylic dihydrazides dihalo-/organic solvent and bis-phenol is so that the interfacial polymerization of these substance reactions; Solution polymerization by aromatics dicarboxylic dihydrazides dihalo-and the bis-phenol reaction in the presence of disacidify agent such as pyridine in the organic solvent; Melt polymerization by aromatic dicarboxylic acid diphenyl ester and bis-phenol reaction; By the melt polymerization of aromatic dicarboxylic acid, diphenyl carbonate and bis-phenol reaction, by the melt polymerization of aromatic dicarboxylic acid and bisphenol diacetate reaction and the polymerization of reacting by aromatic dicarboxylic acid and bisphenol diacetate.The example for preparing the method for polyarylester is disclosed in United States Patent (USP) 5,034, in 502,4,321,355 and 4,374,239.The limiting viscosity of polyarylester of the present invention is generally the about 1.1dL/gm of about 0.5-.

In addition, described polyester, polycarbonate and polyarylester also can comprise one or more following substances: oxidation inhibitor, melt strength improving agent, branching agent (as glycerine, trimellitic acid and acid anhydrides), chain propagation agent, fire retardant, filler, acid scavenger, dyestuff, tinting material, pigment, antisticking agent, FLOW IMPROVERS, impact modifying agent, static inhibitor, processing aid, releasing agent, softening agent, surface slip agent, stablizer, wax, UV absorption agent, white dyes, lubricant, pinningadditives, whipping agent, static inhibitor, nucleator etc.Can add tinting material (also claiming toning agent sometimes) to give polyester ideal neutralc tint and/or brightness.One or more processing aids that the preferred polyester composition can comprise about 30% weight of 0-flow with the surface properties and/or the enhancing that change composition.The representational example of processing aid comprises lime carbonate, talcum, clay, mica, zeolite, wollastonite, kaolin, diatomite, TiO ₂, NH ₄Cl, silica, calcium oxide, sodium sulfate and calcium phosphate.Can use titanium dioxide and other pigment or dyestuff, with the whiteness of for example controlling diaphragm or make colored goods.Also can apply static inhibitor or other coatings to product surface.

Second component of composition of the present invention (ii) comprises the homogeneous blend of at least two kinds of polymeric amide through the acid amides exchange.Usually, described homogeneous blend comprises the about 10 kinds of different polymeric amide of 2-.In another embodiment, described homogeneous blend can comprise 2-4 kind polymeric amide.By the present invention, fusing point is lower than about 300 ℃ polymeric amide and can be used as at least a polymeric amide.In another embodiment, can use fusing point to be lower than about 275 ℃, second-order transition temperature and be higher than about 25 ℃ polymeric amide.Usually, the I.V. of described polymeric amide between the about 2.0dL/g of about 0.3dL/g-, preferred 0.5dL/g at least.

For composition of the present invention, it is favourable to produce homogeneous blend that the acid amides permutoid reaction takes place between the polymeric amide.The term of using herein " exchanges through acid amides " and term " acid amides exchange " and " acid amides permutoid reaction " synonym, refers to the process of exchange amido between two kinds of different polymeric amide.Acid amides permutoid reaction between two or more polymeric amide can realize by making polymeric amide contact under about 270 ℃ usually-Yue 350 ℃ high temperature.Other examples of acid amides permutoid reaction temperature are about 280 ℃-Yue 350 ℃ and about 290 ℃-Yue 340 ℃.Acid amides permutoid reaction between polymeric amide is by the appearance indication of blend single glass transition temperature (" Tg "), and Tg adopts standard method well known to those skilled in the art (described in ASTM method D3418) to measure with dsc (" DSC ").Polymeric amide can be directly under these temperature or heating together in the presence of the thermoplastic polymer of first component (i).For example, the exchange of the contact of polymeric amide and acid amides can take place by first and second components of melt blending during extruding or other high temperature process by polymer composition and its component.In another embodiment, polymeric amide can be in independent container heating together, and then with the first component melts blend.

First and second polymeric amide of second component can be selected from multiple polymeric amide.For mating the specific refractory power of first component better, preferred but inessential at least a polymeric amide comprises aromatic moieties.In one embodiment, can to comprise number-average molecular weight be partially aromatic polymeric amide and aliphatic polyamide below 7000 to described polymeric amide.The combination of this class polymeric amide is also included within the scope of the present invention.The partially aromatic polymeric amide comprises amido linkage between at least one aromatic ring and at least one non-aromatic species.Though Wholly aromatic polyamide is generally liquid crystal, fusing point is lower than this resinoid blend of 300 ℃ and can be used among the present invention.When using the homogeneous blend of polymeric amide, the quick acid amides exchange of aliphatic nylon and aromatics or partially aromatic polymeric amide (acid amides-acid amides exchange) can be regulated the specific refractory power of polyamide blend by the ratio that changes aliphatic polyamide and aromatics or partially aromatic polymeric amide.This technology can be mated the specific refractory power of homogeneous phase polyamide blend with thermoplastic polymer one or more polyester as first component.The bibliography of acid amides permutoid reaction can be referring to Y.Takeda, et.al., Polymer, 1992vol.33, pg.3394.

By the present invention, described second component can be the homogeneous blend of two or more polymeric amide (for example first polymeric amide and second polymeric amide) through acid amides exchange, and the selection of polymeric amide makes the specific refractory power that second component has and the refringence (RI (second component)-RI (first component)) of first component be about 0.006-pact-0.0006.For mating the specific refractory power of first component, aromatics and aliphatic residue that first and second polymeric amide contain different amounts are favourable.For example, second component (ii) can comprise the homogeneous blend of first polymeric amide and second polymeric amide, and described first polymeric amide comprises aromatic moieties, and described second polymeric amide comprises aliphatic residue.Diamines about polymeric amide of the present invention refers to that with the term " aliphatic series " that the dicarboxylic acid monomer uses monomeric carboxyl or amino are not connected by virtue nuclear herein.For example, hexanodioic acid does not contain virtue nuclear in its skeleton (carbon atom chain that promptly connects hydroxy-acid group), so it is " aliphatic series ".On the contrary, term " aromatics " refers to that dicarboxylic acid or diamines contain virtue nuclear in its skeleton, terephthalic acid or 1 for example, 4-m-xylene diamine.The representative example of aromatic poly be comprise at least 70% mole comprise diamines such as m-xylene diamine or comprise m-xylene diamine and at the most 30% p dimethylamine's benzene dimethylamine mixture residue and contain those polymeric amide of residue of the aliphatic dicarboxylic acid of 6-10 carbon atom.Therefore, term " aliphatic series " is intended to comprise aliphatic series and cyclo-aliphatic structure as containing the straight or branched of forming carbon atom or circular permutation diamines, diacid, lactan, amino alcohol and the aminocarboxylic acid as skeleton, described structure (promptly the containing carbon-to-carbon triple bond) of saturated or alkane character, undersaturated but (promptly containing non-aromatics carbon-to-carbon double bond) or acetylene series.Therefore, in the context of specification sheets of the present invention and claims, aliphatic being intended to comprises straight chain and branched structure (being referred to herein as " aliphatic series ") and ring texture (being referred to herein as " alicyclic " or " cyclic aliphatic ").But the aromatic substituent on any skeleton that may be connected in aliphatic series or cycloaliphatic diol or diacid or hydroxycarboxylic acid do not got rid of in term " aliphatic series ".

The weight percent percentage of first and second polymeric amide that exist in the homogeneous blend of acid amides exchange can be about 1: in about 50: 1 scope of 50-(based on the gross weight of second component).Other examples of weight percent percentage are 1: about 20: 1 of 20-and about 1: about 10: 1 of 10-.

The example that can be used for the polymeric amide in the homogeneous blend of the present invention comprises that comprising one or more is selected from m-phthalic acid, terephthalic acid, cyclohexane cyclohexanedimethanodibasic, m-xylene diamine, p dimethylamine, 1,3-hexanaphthene dimethylamine, 1, contains the polymeric amide of residue of the aliphatic diamine of 4-12 carbon atom at 4-hexanaphthene dimethylamine, the aliphatic diacid that contains 6-12 carbon atom, aliphatic amino acid that contains 6-12 carbon atom or lactan.Can use the diacid and the diamines of other formation polymeric amide that are widely known by the people.Described polymeric amide also can contain a spot of three-functionality-degree or four functionality comonomers such as trimellitic acid 1,2-anhydride, pyromellitic acid dianhydride or known in the art other form the polyacid and the polyamines of polymeric amide.

The example of partially aromatic polymeric amide includes but not limited to: poly-(m xylylene adipamide) (also claiming " MXD6 " nylon in this article), poly-(6I hexamethylene isoterephalamide), (hexamethylene adipamide)-(6I hexamethylene isoterephalamide) multipolymer, (hexamethylene adipamide)-(hexamethylene terephthalamide) multipolymer and (6I hexamethylene isoterephalamide)-(hexamethylene terephthalamide) multipolymer.In one embodiment, described partially aromatic polymeric amide is poly-(m xylylene adipamide).In one embodiment, the number-average molecular weight of described partially aromatic polymeric amide can be below 7000.The representative example of aliphatic polyamide comprises poly-(2-Pyrrolidone) (nylon 4,6; CAS numbers 44,299-2), poly-decyl amide (nylon 6; CAS numbers 18,111-0), poly-(2-piperidone) (nylon 5; CAS 24938-57-6), poly-(7-aminoheptylic acid) (nylon 7; CAS 25035-01-2), poly-(pelargonamide) (nylon 9; CAS 25748-72-5), poly-(11-aminoundecanoic acid) (Ni Long11; CAS 25035-04-5), poly-(12-aminolauric acid) (nylon 12; CAS 24937-16-4), poly-(hexanedioyl quadrol) (nylon 2,6), nylon 46 (nylon 4,6; CAS 50327-22-5), polyhexamethylene adipamide (nylon 6,6; CAS numbers 42,917-1), (nylon 6,9; CAS numbers 18,806-9), poly-(sebacoyl hexanediamine) (nylon 6,10; CAS 9008-66-6), poly-(undecane two acyl hexanediamines) (nylon 6,11), poly-(dodecane two acyl hexanediamines) (nylon 6,12; CAS 24936-74-1), poly-(hexanedioyl octamethylenediamine) (nylon 8,6), hexanodioic acid-decamethylene diamine multipolymer (nylon 10,6; CAS 26123-27-3), poly-dodecanoyl decamethylene diamine (nylon 10,12), poly-(hexanedioyl dodecane diamines) (nylon 12,6) and poly-(sebacoyl dodecane diamines) (nylon 12,8).

For example, second component (ii) can comprise homogeneous blend, described homogeneous blend comprises first polymeric amide and second polymeric amide, described first polymeric amide comprises the residue of m-xylene diamine and hexanodioic acid, and described second polymeric amide comprises the aliphatic series or the cyclic aliphatic residues of monomers of at least a diacid of selecting oneself, pimelic acid, suberic acid, nonane diacid, sebacic acid, undecane diacid, dodecanedioic acid, hexanolactam, butyrolactam, the amino undecane diacid of 11-, m-phthalic acid and hexanediamine.For example, described first polymeric amide can comprise MXD6 nylon, and its commodity can have been bought from Mitsubishi Corporation.In another embodiment, described second polymeric amide can comprise at least a polymeric amide that is selected from nylon 4, nylon 6, nylon 9, Ni Long11, nylon 12, nylon 6,6, nylon 5,10, nylon 6,12, nylon 6,11, nylon 10,12 and its combination.And in another embodiment, described second polymeric amide can comprise nylon 6, nylon 6,6 or its blend.

Described second component also can comprise single copolyamide, and wherein, the selection of the composition of monomer residue should make the specific refractory power of its specific refractory power and first component closely mate.Therefore, in another embodiment, the invention provides a kind of polymer composition, described polymer composition comprises the unmixing blend of following component:

(ii) second component, described second component comprises copolyamide;

Wherein, second component (ii) is about 0.006-pact-0.0006 with the refringence (RI (second component)-RI (first component)) of first component (i), and the percent transmittancy of blend is at least 75%, and mist degree is below 10%.For example, described copolyamide can contain the residue of m-xylene diamine, p dimethylamine or its combination; And at least a terephthalic acid, m-phthalic acid, hexanodioic acid, pimelic acid, suberic acid, nonane diacid, sebacic acid, undecane diacid, dodecanedioic acid, hexanolactam, butyrolactam, 11-amino-undecane diacid and 1, the residues of monomers of 6-hexanediamine of being selected from.In another embodiment, described copolyamide can comprise the about 100% mole m-xylene diamine residue of about 15-of accounting for 100% mole of total diamines residue content and account for one or more about 15% mole aliphatic series of the about 85% mole hexanodioic acid residue of about 15-of 100% mole of total diacid residue content and about 85-or cycloaliphatic dicarboxylic acid's residue, described aliphatic series or cycloaliphatic dicarboxylic acid are selected from pimelic acid, suberic acid, nonane diacid, sebacic acid, undecane diacid, dodecanedioic acid and 1,4 cyclohexanedicarboxylic acid.Should be understood that the homogeneous blend of the polymeric amide of mentioning and the various embodiments of copolyamide can combine with any embodiment of polyester previously discussed herein.

Can be separately or include but not limited to comprise the about 100% mole p dimethylamine's residue of about 15-of accounting for 100% mole of total diamines residue and the copolyamide of hexanodioic acid residue as other examples that the part with the homogeneous blend of another polymeric amide is used for the copolyamide of composition of the present invention.The typical amount of the hexanodioic acid residue that can exist in these copolyamides can account for about 75% mole of about 85% mole of about 5-of diacid residues total mole number, about 20-about 80% mole and about 25-.Remaining dicarboxylic acid residue can comprise the residue that contains the aliphatic dicarboxylic acid (as pimelic acid, suberic acid, nonane diacid, sebacic acid, undecane diacid, dodecanedioic acid or 1,4 cyclohexanedicarboxylic acid) of 7-12 carbon atom from one or more.In another embodiment, described polyamic acid also can comprise the residue from m-phthalic acid and terephthalic acid.

Except that the m-xylene diamine residue, copolyamide of the present invention also can comprise other diamines or lactan residue.For example, described copolyamide can comprise at least 15% mole or at least about 20% mole m-xylene diamine residue, remaining diamines residue comprises the residue of one or more aliphatic series or aromatic diamine.For example, described copolyamide can comprise about 80% mole or about 85% mole 1 that accounts for diamines residue total mole number, 6-hexanediamine residue.Also can use the p dimethylamine, 1 of different amounts, 3-hexanaphthene dimethylamine or 1,4-hexanaphthene dimethylamine.Equally, described copolyamide can comprise the residue of the lactan (as hexanolactam or based on the lactan of γ-An Jidingsuan or 11-amino-undeeanoic acid) of 90% mole of about 10% mole of accounting for the repeating unit total mole number-Yue or about 10% mole-Yue 70% mole.In another embodiment, copolyamide of the present invention can comprise about 15% mole-Yue 85% mole, about 20-about 80% mole or the about 75% mole of residue from m-xylene diamine of about 25-that accounts for diamines residue total mole number, remaining diamines residue comprises the residue from one or more diamines such as aliphatic diamine (particularly 1,6-hexanediamine).In this embodiment, described diamines residue also can comprise other micro-diamines such as p dimethylamine or cycloaliphatic diamine as 1,3-hexanaphthene dimethylamine or 1, the residue of one or more in the 4-hexanaphthene dimethylamine.In addition, described polymeric amide can be chosen wantonly and contain (instead of part hexanodioic acid) and contain the aliphatic series of 7-12 carbon atom or aromatic dicarboxylic acid (as pimelic acid, suberic acid, nonane diacid, sebacic acid, undecane diacid, dodecanedioic acid, 1 from one or more, 4-cyclohexane cyclohexanedimethanodibasic or m-phthalic acid) residue, its amount can be about 15% mole-Yue 85% mole, and optional terephthalic acid with trace exists.Described polymeric amide also can comprise lactan such as hexanolactam or based on the residue of the lactan of gamma-amino-butyric acid or 11-aminoundecanoic acid, its amount accounts for about 10% mole-Yue 90% mole or about 10% mole-70% mole of repeating unit total mole number.

And in another embodiment, copolyamide of the present invention can comprise about 15% mole-Yue 90% mole of residue from hexanodioic acid, and all the other diacid residues comprise the about 85% mole isophthalic acid residues of about 10-that accounts for the dicarboxylic acid residue total mole number.Other examples of hexanodioic acid and isophthalic acid residues content comprise about 75% mole of about 20-80% mole and about 25-.In this embodiment, described polymeric amide can choose wantonly comprise the trace from one or more aliphatic dicarboxylic acids that contain 7-12 carbon atom (as pimelic acid, suberic acid, nonane diacid, sebacic acid, undecane diacid, dodecanedioic acid or 1, the 4-cyclohexane cyclohexanedimethanodibasic) residue, its terephthalic acid that can choose wantonly with trace exists.Optional described polymeric amide can comprise the m-xylene diamine residue.The example of m-xylene diamine residue concentration comprises about 80% mole of about 90% mole of about 15-, about 20-about 85% mole or about 25-.Remaining residue can comprise the residue from one or more aliphatic diamines (as 1, the 6-hexanediamine), one or more aromatic diamines (as the p dimethylamine).Equally, described copolyamide also can comprise lactan such as hexanolactam or based on the residue of the lactan of gamma-amino-butyric acid or 11-amino-undeeanoic acid, its amount accounts for about 10% mole-Yue 90% mole or about 10% mole-70% mole of repeating unit total mole number.

And in another embodiment, copolyamide of the present invention can comprise one or more lactan such as hexanolactam or based on the residue of the lactan of gamma-amino-butyric acid or 11-amino-undeeanoic acid, its amount accounts for about 10% mole-Yue 90% mole or about 10% mole-70% mole or about 15% mole-Yue 60% mole of repeating unit total mole number.About 20% mole-Yue 80% mole amount that one or more residues that contain the aliphatic dicarboxylic acid (as pimelic acid, suberic acid, nonane diacid, sebacic acid, undecane diacid, dodecanedioic acid or 1,4 cyclohexanedicarboxylic acid) of 7-12 carbon atom also can account for the repeating unit total mole number exists.For example, described copolyamide can comprise the residue from m-phthalic acid or terephthalic acid.In this embodiment, described copolyamide can comprise the about 15% mole-Yue 85% mole of residue from m-xylene diamine that accounts for diamines residue total mole number.Other examples of m-xylene diamine content for about 20-about 80% mole with about 75% mole of about 25-.Remaining diamines residue can comprise one or more aliphatic diamines as 1, the residue of 6-hexanediamine.In this embodiment, described diamines residue also can comprise other diamines of trace such as p dimethylamine or cycloaliphatic diamine as 1,3-hexanaphthene dimethylamine or 1, the residue of one or more in the 4-hexanaphthene dimethylamine.Choose wantonly and can use p dimethylamine, 1,3-hexanaphthene dimethylamine or 1, one or more in the 4-hexanaphthene dimethylamine micro-ly.

Another embodiment of the present invention is a polymer composition, and described polymer composition is made up of the unmixing blend of following component substantially:

(i) first component, described first component is made up of at least a thermoplastic polymer that is selected from polyester, polycarbonate, polyarylester and its homogeneous blend substantially; With

(ii) second component, described second component are made up of through the homogeneous blend of acid amides exchange at least two kinds of polymeric amide substantially;

Wherein, second component (ii) is about 0.006-pact-0.0006 with the refringence (RI (second component)-RI (first component)) of first component (i), and the percent transmittancy of blend is at least 75%, and mist degree is below 10%.The statement of using herein " substantially by ... form " be intended to contain composition for unmixing blend (promptly recording at least two composition Tg peaks) with DSC, and described composition has first component and second component, described first component contains polyester, polycarbonate, polyarylester or its homogeneous blend, and described second component contains the homogeneous blend of at least two kinds of polymeric amide through the acid amides exchange.In this embodiment, described composition is interpreted as and gets rid of any composition that may substantially change the essential property of indication composition.For example, composition can contain other components of compatibility of % mist degree, percent transmittancy or the blend of the specific refractory power that do not change component, blend.For example, should not comprise the compatibility that can change composition and the expanding material of specific refractory power in the present embodiment.Equally, second component that contains the copolyamide of the copolymerization by constituent monomers should be excluded, because such copolyamide is considered to have and the homogeneous blend different character of two kinds of polymeric amide through the acid amides exchange at least, and is also like this even if the molecular fraction of monomer residue equates.

Equally, another embodiment of the present invention is an oxygen-scavenging compositions, and described oxygen-scavenging compositions is made up of following component substantially:

(A) the unmixing blend of forming by following component substantially:

(i) first component, described first component is made up of at least a thermoplastic polymer that is selected from polyester, polycarbonate, polyarylester and its homogeneous blend substantially;

(B) at least a periodic table of elements 3-12 family, the metal in 4-6 cycle of being selected from;

Wherein, the refringence absolute value of described first component and second component is below 0.008, and the percent transmittancy of moulded products is at least 75%, and mist degree is below 10%.In this embodiment, described composition is interpreted as and gets rid of any composition that may substantially change the essential property (as the specific refractory power of component, % mist degree, percent transmittancy, the compatibility of blend or the oxygen scavenging of composition of blend) of indication composition.For example, except that copolyamide or polymeric amide through the blend of acid amides exchange oxygen-scavenging composition such as diene, polyethers or in the right claim the listed component adding of the organic compound of any easy oxidation all should be excluded.

Polymeric amide used among the present invention is usually from dicarboxylic acid and the basic geometric ratio prepared in reaction of diamines, or from the ring-opening polymerization preparation of lactan, and is incorporated in the polyamide polymer with its corresponding residue.Therefore the polymeric amide that is derived from dicarboxylic acid and diamines residue of the present invention contains the sour residue (100% mole) and the diamines residue (100% mole) of mol ratio such as basic, so that the total mole number of repeating unit equals 100% mole.Therefore the molecular fraction that provides in the disclosure can be calculated based on the total mole number of sour residue, the total mole number of diol residue or the total mole number of repeating unit.For example, polymeric amide or the copolyamide that contains 30% mole the terephthalic acid that accounts for total sour residue means that described copolyamide has 30% mole terephthalic acid residue in 100% mole total sour residue.Therefore, in per 100 equimolar acid residues 30 moles of terephthalic acid residues are arranged.For an example, the copolyamide that contains 30% mole the m-xylene diamine that accounts for total diamines residue means that described copolyamide has 30% mole m-xylene diamine residue in 100% mole total diamines residue again.Therefore, in per 100 moles of diamines residues 30 moles of m-xylene diamine residues are arranged.

Any method known in the art all can be used to produce described polymeric amide.But common original position certainly of described polymeric amide or diacid-two amine compound that makes in independent step prepare by melt phase polymerization.In arbitrary method all with diacid and diamines as starting raw material.Perhaps can use the ester-formin of diacid, preferred dimethyl ester.If what use is ester, then reaction must be carried out being converted into acid amides until ester under quite low temperature (80-120 ℃ usually).Heated mixt is to polymerization temperature then.With regard to polycaprolactam, hexanolactam or 6-aminocaprolc acid can be used as starting raw material, and polymerization can pass through the adding catalysis of hexanodioic acid/hexanediamine salt, obtain nylon 6/66 copolymer like this.When using diacid-two amine compound, mixture is through being heated to fusion and stirring until balance.

Molecular weight is by diacid-diamines ratio control.Excessive diamines produces the end amino of higher concentration.For oxygen-scavenging compositions, it is to be favourable below the 20mmole/kg that adjusting diacid-diamines ratio makes the concentration of end amido.If diacid-two amine compound prepares in independent step, then excessive diamines adds before polymerization.Polymerization can be carried out under barometric point or elevated pressure.

For having the gratifying transparency and low haze, second component of described unmixing blend and the refringence of first component are generally about 0.006-about-0.0006, that is to say that (RI (second component)-RI (first component)) is about 0.006-about-0.0006.Other examples of refringence absolute value for about 0.005-approximately-0.0006, about 0.004-approximately-0.0006, about-0.0006, the about 0.005-about-0.0005 of about 0.003-and about 0.004-about-0.0005.But skilled person in the art will appreciate that acceptable refringence depends on blend composition, particle diameter, specific refractory power, wavelength and grain pattern, as Biangardi etc., Die Angew.Makromole.Chemie is described in 183,221 (1990).

Unmixing blend of the present invention has the excellent transparency, and it is at least 75% by the percent transmittancy that ASTM method D1003 records, and mist degree is below 10%.Other examples of percent transmittancy are at least 77%, at least 80% and at least 85%.Other examples of the revealable haze value of blend of the present invention are below 9%, below 7%, below 5% and below 3%.For composition of the present invention, mist degree is by becoming composition molding or curtain coating thick sheet or film and by the program determination described in the embodiment below 1/8 inch.For moulded products (comprising multilayer formed article), mist degree can be by cutting out goods thick fritter (promptly 1 * 1cm) and by the program determination that provides among the embodiment below 1/8 inch.

Described first component also can comprise the homogeneous blend of one or more polymkeric substance.For example, described first component can comprise first polyester and the homogeneous blend that is selected from one or more polymkeric substance of polycarbonate, second polyester and polyarylester.Described polyester can be any as described in this article polyester.For example, first component can comprise polyester and the homogeneous blend that comprises the polycarbonate of dihydroxyphenyl propane residue.

Described polycarbonate can comprise about 10% mole one or more of the dihydroxyphenyl propane residue of the about 90-100% mole that accounts for the diol residue total mole number and 0-and contain the residue of the modification of 2-16 carbon atom with aliphatic diol or dihydric phenol.Representational example comprises two (4-hydroxy phenyl) methane, 2, two (4-hydroxy phenyl) propane (" dihydroxyphenyl propane "), 2 of 2-, two (the 4-hydroxy-3-methyl phenyl) propane, 4 of 2-, two (4-hydroxy phenyl) heptane, 2 of 4-, two (the 4-hydroxyls-3 of 2-, the 5-dichlorophenyl) propane, 2, two (4-hydroxyl-3, the 5-dibromo phenyl) propane of 2-; Binary phenolic ether such as two (4-hydroxy phenyl) ether, two (3,5-two chloro-4-hydroxy phenyls) ether; Dihydroxybiphenyl such as p, p '-dihydroxybiphenyl, 3,3 '-two chloro-4,4 '-dihydroxybiphenyl; Dihydroxyl aryl sulfone such as two (4-hydroxy phenyl) sulfone, two (3,5-dimethyl-4-hydroxy phenyl) sulfone; Dihydroxy-benzene such as Resorcinol; Quinhydrones; The dihydroxy-benzene that halo and alkyl replace is as 1,4-dihydroxyl-2,5-dichlorobenzene, 1,4-dihydroxyl-3-methylbenzene; With dihydroxyl diphenyl sulfoxide such as two (4-hydroxy phenyl) sulfoxide and two (3,5-two bromo-4-hydroxy phenyls) sulfoxide.Multiple other dihydric phenols are also available, and are as United States Patent (USP) 2,999, disclosed in 835,3,028,365 and 3,153,008.From above-mentioned dihydric phenol and halogen-containing dihydric phenol as 2, two (3, the 5-two chloro-4-hydroxy phenyls) propane and 2 of 2-, the multipolymer that two (3,5-two bromo-4-hydroxy phenyls) the propane copolymerization of 2-make also suits.Also can adopt two or more different dihydric phenols or dihydric phenol and glycol, with the polyester of hydroxyl or acid blocked or with the multipolymer of diprotic acid and the blend of any above-mentioned materials.Suitable dicarboxylic acid include but not limited to aromatic dicarboxylic acid (as phthalic acid, m-phthalic acid, terephthalic acid, phthalic acid, neighbour-,-and right-phenylene-diacetic acid) and polynuclear aromatic acid (as diphenic acid and 1, the 4-naphthalic acid).

The representative example of aliphatic diol comprises the dihydroxyl alkyl oxide (as the dihydroxy ethyl ether of dihydroxyphenyl propane) of ethylene glycol, propylene glycol, butyleneglycol, pentanediol, hexylene glycol, heptanediol, ethohexadiol, neopentyl glycol, aryl-alkyl diol (as Benzenediol, xylyl alcohol), dihydric phenol etc.Other examples of aliphatic diol are more high-molecular weight aliphatic dihydroxy compound such as polyoxyethylene glycol, polyphenyl glycol, polypropylene glycol, polytetramethylene glycol, poly-sulfo-glycol, poly-aralkyl ethers two pure and mild multipolymer polyether glycols.Other representative example of dihydric phenol and aliphatic diol are seen and are set forth in United States Patent (USP) 3,030,335 and 3,317,466.Polycarbonate also can comprise one or more branching agents as four phenolic compound, three-(4-hydroxy phenyl) ethane, pentaerythritol triacrylate with as United States Patent (USP) 6,160, and 082,6,022,941,5,262,511,4,474, the residue of disclosed other compounds in 999 and 4,286,083.Other suitable branching agents are mentioned hereinafter.In other examples, described polycarbonate comprises at least 95% mole the dihydroxyphenyl propane residue that accounts for the diol residue total mole number.

The limiting viscosity of the polycarbonate of blend of the present invention part is preferably at least about 0.3dL/g, more preferably 0.5dL/g at least.The polycarbonate of blend of the present invention part by ASTM method D1238 in the melt flow index that records with the load of 1.2kg under 300 ℃ the temperature preferably between 1 and 20, more preferably between 2 and 18.

The method for preparing polycarbonate is well-known in this area.Can be used among the present invention and straight or branched polycarbonate disclosed herein is not limited to or is bound by described polycarbonate type or its production method.Usually make dihydric phenol such as dihydroxyphenyl propane and phosgene reaction, use simultaneously optional single functionality compound as chain terminator and three-functionality-degree or more the compound of high functionality as branching or linking agent.The reactive carboxylic acid halides of single functionality, difunctionality and three-functionality-degree also can be used in the preparation of polycarbonate as end-caps (single functionality), comonomer (difunctionality) or branching agent (three-functionality-degree or higher).

For example, well-known melt polymerization, solution polymerization or interfacial polymerization preparation in available this area of polycarbonate part of blend of the present invention.Suitable method comprises makes carbonate source and glycol react the sufficiently long time to form the step of polycarbonate under the pressure of about 0 ℃-315 ℃ temperature and about 0.1-760mmHg.Can be used for commodity polycarbonate among the present invention usually by making aromatic diol and carbonate source (as phosgene, dibutyl carbonate or diphenyl carbonate) reaction, in polycarbonate, to introduce 100% mole carbonate unit and 100% mole diol units preparation.Other representative example of producing the method for polycarbonate are seen and are set forth in United States Patent (USP) 5,498,688,5,494,992 and 5,489,665.

The blend of polyester and polycarbonate can be prepared by a method comprising the following steps: make polycarbonate and sufficiently long time of polyester blend to form transparent blend composition under about 25 ℃-350 ℃ temperature.Suitable conventional blending technology comprises scorification and solution preparation.Other suitable blending technologies comprise dry blend/or extrude.

The present composition that wherein contains unmixing and homogeneous blend can and can be used as thermoplastic composition and the formation that is used for film and individual layer and multi-layer product by any method known in the art preparation.Except that the various blend component of physical blending, the homogeneous phase polyester blend can be by the transesterification reaction preparation of polyester components.Equally, the homogeneous blend of polymeric amide can be by the acid amides permutoid reaction preparation of polyamide component.

Melt-blending process be included under the temperature that is enough to fusion first component and second component part various polymkeric substance of blend and with the postcooling blend to the temperature that is enough to produce transparent blends.The term of using herein " fusion " includes but not limited to only softening polymkeric substance.The example of the melting mixing method of generally knowing in the polymer arts is seen and is set forth in Mixing and Compounding ofPolymers (I.Manas-Zloczower ﹠amp; Z.Tadmor eds., Carl Hanser Verlagpublisher, N.Y.1994).

Solution preparation be included in suitable organic solvent as first component of the suitable w/w ratio of dissolving in 70/30 mixture of methylene dichloride or methylene dichloride and hexafluoroisopropanol with second component, mix as described in solution and the precipitation by blend or the evaporation by solvent from solution, separate blend composition.The formulations prepared from solutions blending method is generally to know in the polymer arts.

Melt-blending process is a preferred method of producing blend composition of the present invention.Melt-blending process is more economical, safer than solution method, and the latter need use volatile solvent.Melt-blending process is providing also more effective aspect the transparent blends.Can also can prepare by of the present invention any transparent blends of solution blending preparation by scorification.But blends more of the present invention can not prepare by solution preparation by the scorification preparation.Provide any blend method of transparent blends of the present invention all to suit.Those skilled in the art will determine to produce the suitable blend method of transparent blends of the present invention.

These of the present composition first and second components can be for example by using single screw rod or twin screw extruder melt compounded.It also can be by the preparation of blend in solution.As described in other components also can add as stablizer, fire retardant, tinting material, lubricant, releasing agent, impact modifying agent etc. in the mixing material.For example, described composition can be by melt extruding productions such as compounding first component and second component and any other composition component such as metal catalyst, pigment, toning agent, filler.Described composition can be by do mixing each thermoplastic polymer and polyamide component solid particulate or pellet, then suitable mixing device as forcing machine, mixing roll mill etc. in mixture formation as described in the melt blending.When polymeric amide when the homogeneous blend of acid amides exchange is used as second component, to process under the temperature that the acid amides permutoid reaction takes place between the polymeric amide will be favourable will making.Usually, these temperature are in about 270 ℃-Yue 350 ℃ temperature range.Other examples of acid amides permutoid reaction temperature are about 280 ℃-Yue 350 ℃ and about 290 ℃-Yue 340 ℃.The time that blend continues should produce the unmixing blend of good distribution.It can easily be determined by those skilled in the art.If desired, described composition can and be cut into pellet so that further processing through cooling, it can be extruded into film, sheet, parison and other profiled members, can be injection molding or compression moulding forms various moulded products, or it can be formed film and optional by the method single shaft known in this area or biaxial stretch-formed.

The amount of first and second components can change widely in the unmixing blend.For example, the unmixing blend of this novel compositions can comprise first component of about 99% weight of about 5-that accounts for composition total weight and second component of about 1% weight of about 95-.The nonrestrictive representative example of other of the weight percentage of first and second components comprises first component of about 99% weight of about 50-and second component, first component of about 99% weight of about 60-and second component and first component of about 99% weight of about 70-and second component of about 1% weight of about 30-of about 1% weight of about 40-of about 1% weight of about 50-.

The present invention also provides the composition by the method preparation that comprises the following component of melt blending:

Wherein, second component (ii) is about 0.006-pact-0.0006 with the refringence (RI (second component)-RI (first component)) of first component (i), and the percent transmittancy of blend is at least 75%, and mist degree is below 10%.Described composition comprises the various embodiments and the arbitrary combination thereof of polyester, polycarbonate, polyarylester, homogeneous blend and polymeric amide as previously mentioned.For example, second component of composition can comprise the homogeneous blend of at least two kinds of polymeric amide through acid amides exchange, and wherein, the acid amides permutoid reaction can be finished being generally to contact under the about 270 ℃-Yue 350 ℃ high temperature by making polymeric amide.Other examples of acid amides permutoid reaction temperature are about 280 ℃-Yue 350 ℃ and about 290 ℃-Yue 340 ℃.

As previously mentioned, component homogeneous blend (ii) can comprise first polymeric amide and second polymeric amide, and first polymeric amide comprises aromatic moieties, and second polymeric amide comprises aliphatic residue.For example, the typical polyamides that can be used as second polymeric amide includes but not limited to nylon 4, nylon 6, nylon 9, Ni Long11, nylon 12, nylon 6,6, nylon 5,10, nylon 6,12, nylon 6,11, nylon 10,12 and its combination.Except that aforementioned polyester, described first component can comprise polyester and the homogeneous blend that comprises the polycarbonate of dihydroxyphenyl propane residue.

Another aspect of the invention is the method for preparing transparent, oxygen-scavenging compositions, described method comprises:

(A) select first component, described first component comprises at least a thermoplastic polymer that is selected from polyester, polycarbonate, polyarylester and its homogeneous blend;

(B) determine the specific refractory power of first component;

(C) provide second component, described second component comprises

(i) have the copolyamide of certain aliphatic series and aromatic moieties mol ratio, wherein the selection of aliphatic series and aromatic moieties mol ratio should be able to produce the second component specific refractory power that satisfies following formula:

0.006 〉=RI (second component)-RI (first component) 〉=-0.0006

Or;

(ii) first and second polymeric amide are through the homogeneous blend of acid amides exchange, and at least a described polymeric amide has aromatic moieties, and wherein the selection of the weight percentage of first and second polymeric amide should be able to produce the second component specific refractory power that satisfies following formula:

0.006 〉=RI (second component)-RI (first component) 〉=-0.0006

Wherein RI is a specific refractory power; With

(D) melt blending first and second components with produce percent transmittancy at least 75%, mist degree is the blend below 10%.

Described method comprises the various embodiments and the arbitrary combination thereof of polyester, polycarbonate, polyarylester, homogeneous blend, copolyamide and polymeric amide as previously mentioned.Described method comprises first component of selecting can be polyester, polycarbonate, polyarylester or its homogeneous blend.The specific refractory power of first component can be determined with method well known to those skilled in the art.Can comprise single copolyamide or at least two kinds of polymeric amide through second component of the homogeneous blend of acid amides exchange through regulating specific refractory power with tight coupling first component, the suitable mixture (under copolyamide situation) of described adjusting by selecting aromatics and aliphatic monomers or the polyamide compound by selecting to contain required aromatics and aliphatic residue mixture when using the homogeneous blend of polymeric amide (if) realization.Various polymeric amide or the specific refractory power of copolyamide and the aromatics that selection will provide targeted refractive index of different aromatic moieties of measuring and aliphatic residue can be determined or contain by drafting to the selection of the adequate rate of monomer or polymeric amide by for example repetition test in other embodiments: aliphatic residue mol ratio or polymeric amide weight percentage are than determining.The first and second component melt blendable.When second component comprised at least two kinds of polymeric amide through the homogeneous blend of acid amides exchange, it was desirable carrying out the melt blending step under to acid amides exchange process efficient temperature.Typical acid amides permutoid reaction temperature range as previously mentioned.

The specific refractory power that also can mate second component by the selection of thermoplastic polymer.Therefore, another aspect of the invention is the method for preparing transparent, oxygen-scavenging compositions, described method comprises:

(A) select second component, described second component comprises

(i) has the copolyamide of certain aliphatic series and aromatic moieties mol ratio; Or

(ii) first and second polymeric amide are through the homogeneous blend of acid amides exchange, and at least a described polymeric amide has aromatic moieties;

(B) determine the specific refractory power of second component;

(C) provide first component, described first component comprises at least a thermoplastic polymer that is selected from polyester, polycarbonate, polyarylester and its homogeneous blend, and wherein the selection of polyester, polycarbonate, polyarylester or its homogeneous blend should be able to produce the first component specific refractory power that satisfies following formula:

0.006 〉=RI (second component)-RI (first component) 〉=-0.0006

Wherein RI is a specific refractory power; With

(D) melt blending first and second components with produce percent transmittancy at least 75%, mist degree is the blend below 10%.Should also be understood that aforesaid method also comprises the arbitrary combination of the various embodiments of polyester, polycarbonate, polyarylester, homogeneous blend, copolyamide, polymeric amide as previously mentioned.

For an example, the thermoplastic polymer blend of carrying out for second component and first component of about 0.006-about-0.0006 for the acquisition refringence can illustrate with the polycarbonate/polyester blend for example.For example, make can be by changing the specific refractory power (RI) that polycarbonate/PCTG ratio is regulated polycarbonate/PCTG blend for the complete miscibility of the polycarbonate of dihydroxyphenyl propane and PCTG.By regulating the polycarbonate ratio, about 0.006-that the specific refractory power of first component of the present invention can be matched to the specific refractory power of second component that comprises the polymeric amide separating polymer makes an appointment with in-0.0006.For example, if obtained transparent blends by following operation, then polymkeric substance can be confirmed as the suitable modification polymer of homogeneous phase polyester/polycarbonate blend noted earlier: 1) described modification polymer of blend and the blend that contains polycarbonate and polyester portion that has existed, or 2) described modification polymer of blend and polycarbonate part before adding polyester portion, or 3) described modification polymer of blend and polyester portion before adding the polycarbonate part, or 4) the described modification polymer of mixing before blend, polycarbonate part and polyester portion are in together.

Transparent blends of the present invention still can pass through to add modification polymer, and modification is to produce the high-performance blend, and described high-performance blend is not necessarily transparent in addition.For example, polymeric amide is as the nylon 6 from DuPont, 6, poly-(ether-imide) is as the ULTEM poly-(ether-imide) from General Electric, polyphenylene oxide is as poly-(2,6-dimethyl phenylate) or poly-(phenylate)/polystyrene blend (as the NORYL resin from General Electric), polyester, polyphenylene sulfide, polyphenylene sulfide/sulfone, poly-(ester-carbonic ether) is as LEXAN 3250 poly-(ester-carbonic ether) (General Electric), except that from the polycarbonate the LEXAN polycarbonate of General Electric, polyarylester such as ARDEL D100 polyarylester (Amoco), polysulfones, polysulfones ether, poly-(ether-ketone) or aromatic dihydroxy compound can be used as blend properties-correcting agent to change character or to reduce flammable.Some aromatic dihydroxy compounds that are used for preparing these polymkeric substance are at United States Patent (USP) 3,030,335 and United States Patent (USP) 3,317,466 in have open.

The copolyamide of the present composition or polymeric amide homogeneous blend can play the effect of separating polymer and therefore improve the barrier of whole composition.The term of using herein " separating polymer " refers to have one or more polymkeric substance of following character: (1) is below the 2gm-mils/100sq in/24hr with ASTM method F1249 in the water-permeable that records under 38 ℃; (2) be 5cc (STP)-below the mils/100sq in/24hrs-atm with ASTM method D3985 in the oxygen-permeable that records under 23 ℃; Or (3) saturating carbonic acid gas of recording under 23 ℃ with ASTM method D1434 is 25cc (STP)-below the mils/100sq in/24hrs-atm.

Barrier can strengthen the reaction of one or more polymeric amide in described catalyst oxygen and the composition to produce oxygen-scavenging compositions by adding metal catalyst.Therefore the present invention also provides oxygen-scavenging compositions, and described oxygen-scavenging compositions comprises:

(A) unmixing blend, described insoluble blend comprises:

(B) at least a periodic table of elements 3-12 family, the metal in 4-6 cycle of being selected from.

Except that the homogeneous blend of more than one polymeric amide, for other embodiments of the present invention, oxygen-scavenging compositions of the present invention also can contain foregoing single copolyamide.Therefore, the present invention also provides oxygen-scavenging compositions, and described oxygen-scavenging compositions comprises:

(A) unmixing blend, described insoluble blend comprises:

(ii) second component, described second component comprises copolyamide;

Should also be understood that described oxygen-scavenging compositions comprises the arbitrary combination of the various embodiments of described first and second components of preamble, polyester, polycarbonate, polyarylester, homogeneous blend, copolyamide and polymeric amide.

Oxygen-scavenging compositions of the present invention can contain a kind of 1984 editions periodic table of elements 3-12 families, metal in 4-6 cycle that is selected from International Union of Pure and Applied Chemistry's promulgation.Typical oxide catalyst comprises the transition-metal catalyst of change between at least two kinds of oxidation state easily.Available metal example comprises copper, nickel, cobalt, iron, manganese and its combination.Effectively any catalytic amount all can use in Catalytic Oxygen is removed, but metal uses with the amount of the about 1000ppm of about 10ppm-usually.Other scopes of metal concentration comprise the about 750ppm of about 50ppm-that accounts for the oxygen-scavenging compositions gross weight, the about 500ppm of about 10-, the about 500ppm of about 50ppm-and the about 300ppm of about 50-.Described metal usually can its metal simple-substance self, with the metal complex that contains organic part, use with oxide compound or with metal-salt.The example of the counterion of metal-salt includes but not limited to chlorion, acetate moiety, methyl ethyl diketone root, stearate radical, palm acid group, 2 ethyl hexanoic acid root, neodecanoic acid root, sad or cycloalkanes acid group and its mixture.Described metal-salt also can be ionomer, adopts the polymkeric substance counterion in this case.Such ionomer is well-known in this area.

In one example, described metal catalyst is cobalt or compound such as the cobalt salt that contains cobalt.Cobalt can be+2 or+3 oxidation state.Other examples of metal catalyst are the rhodium of+2 oxidation state and the copper of+2 oxidation state.Metal can salt form (for example easily with carboxylate salt such as cobalt octoate, cobaltous acetate or new cobalt decanoate) add.The amount of being given is calculated based on the weight of blend polymer and to be added to metal in the composition but not its compound weight.Under the situation of cobalt as described metal, typical amount is 50ppm or 60ppm or 75ppm or 100ppm or 125ppm at least at least at least at least at least.Catalyzer can pure state or is added in carrier (as liquid or wax) in other equipment of forcing machine or article of manufacture, or its can with the enriched material of polyamide polymer in, with the enriched material of polyester polymers in or with the enriched material of unmixing blend in add.Described carrier and described first and second components can be reactive or for non-reacted, volatility or nonvolatile carrier fluid all can adopt.Metal catalyst can add at a plurality of some places in the preparation oxygen-scavenging compositions process with by multiple blend method.Useful especially method is in the later stage of the final blend composition of preparation polymeric amide to be contacted with transition metal, even late to forming in the preceding final fusion step of goods, so that the oxygen of polymeric amide is removed active not initiation too early.In some cases, as when cobalt provides as transition metal, may preferably in the process of blend first and second components, add cobalt, rather than for example in the process of preparation thermoplastic polymer, add.

For example, in one embodiment, first component of described oxygen-scavenging compositions can comprise to contain and has the polyester of the arbitrary combination of monomer residue as previously mentioned.For example, described polyester can comprise (a) diacid residues, the modification of at least a 2-20 of containing the carbon atom that the residue of described diacid residues comprises at least 80% mole of accounting for the total diacid residue at least a dicarboxylic acid that is selected from terephthalic acid, m-phthalic acid, naphthalic acid and 1,4 cyclohexanedicarboxylic acid and 0-are about 20% mole is with the residue of dicarboxylic acid; (b) diol residue, described diol residue comprises at least 80% mole at least a ethylene glycol, 1 that is selected from that accounts for the diol residue total mole number, 4-cyclohexanedimethanol, neopentyl glycol, Diethylene Glycol, 1, ammediol, 1,4-butyleneglycol and 2,2,4,4-tetramethyl--1, at least a residue that contains the modification of 3-16 carbon with glycol that the residue of the glycol of 3-cyclobutanediol and 0-are about 20% mole.In another embodiment, described diacid residues can comprise the terephthalic acid residue and the about 40% mole isophthalic acid residues of 0-of about 60-100% mole, and described diol residue can comprise about 100% mole 1,4 cyclohexane dimethanol residue.In another embodiment, described diacid residues can comprise the about 100% mole terephthalic acid residue who accounts for the diacid residues total mole number.Other specific exampless that can be used as the polyester of first component comprise the polyester that comprises following residue: (i) 1,4 cyclohexane dimethanol residue that the terephthalic acid residue that about 80-is about 100% mole and Yue 50-are about 90% mole and the about 50% mole neopentyl glycol residue of about 10-; 1,4 cyclohexane dimethanol residue that (ii) about 100% mole terephthalic acid residue and Yue 10-are about 40% mole and the about 90% mole glycol residue of 60-; The Diethylene Glycol residue that the glycol residue that 1,4 cyclohexane dimethanol residue, the 0-that (iii) about 100% mole terephthalic acid residue and Yue 10-are about 99% mole is about 90% mole and about 1-are about 25% mole.Described polyester yet can comprise at least a residue that is selected from the branching agent of trimellitic acid, trimellitic acid 1,2-anhydride and pyromellitic acid dianhydride as previously mentioned of the about 0.1-2% mole that accounts for the total diacid residue.

Described first component also can comprise the homogeneous blend of at least a polyester and at least a polycarbonate.The polycarbonate that can be used in these homogeneous blends is described in front.

Described homogeneous blend or copolyamide through the acid amides exchange can comprise foregoing any polymeric amide, as various nylon.But it will be favourable that the copolyamide of oxygen-scavenging compositions or polymeric amide homogeneous blend comprise the residue of m-xylene diamine, p dimethylamine or its combination.For example, second component can comprise the homogeneous blend of first polymeric amide and second polymeric amide, and described first polymeric amide comprises the residue of m-xylene diamine and hexanodioic acid, and described second polymeric amide comprises nylon 6, nylon 6,6 or its blend.As another example, this homogeneous blend can be incorporated in the unmixing blend with first component of homogeneous blend that comprises polyester and comprise the polycarbonate of dihydroxyphenyl propane residue.For obtaining best oxygen scavenging, it also is favourable that copolyamide or polymeric amide homogeneous blend contain the following free amine group of 20mmoles/kg.The concentration of free amine group can be with technology well known to those skilled in the art as determining by titration.

In another example, oxygen-scavenging compositions comprises the copolyamide of m-xylene diamine adipic acid ester.Compare with the composition that only contains m-xylene diamine adipic acid ester homopolymer, can obtain having the oxygen-scavenging compositions of improved oxygen scavenging through the use of the m-xylene diamine adipic acid ester of modification (wherein, some hexanodioic acid residues or some m-xylene diamine residues or in the two some replace for other residues).Other polymeric amide separating polymers also can be used as the part of oxygen-scavenging compositions as described herein.

Aforementioned composition of the present invention can be used to make moulded products such as sheet, film, pipe, precast billet, bottle or parison.This based article can by any method well known to those skilled in the art as extrude, calendering, thermoforming, blowing, extrusion-blown modling, injection moulding, compression moulding, curtain coating, drawing-off, tentering or blowing form.

For example, composition of the present invention can become moulded products such as film by any fabrication techniques known in the art.The formation of film can be by melt extruding (as United States Patent (USP) 4,880, described in 592) or obtaining by compression moulding (as United States Patent (USP) 4,427, described in 614) or by any other suitable method.For example, film can be by well-known casting films, blown film and extrusion coated technology production, and the latter comprises and being expressed on the matrix.Such matrix also can comprise tack coat.The film useful binders thermal caking that produces by melt curtain coating or blowing or be sealed on the matrix.Described composition can become the single or multiple lift film by any fabrication techniques known in the art.For example, the single or multiple lift film can be by well-known casting films, blown film or extrusion coated technology production, and the latter comprises and being expressed on the matrix.Representational matrix comprises film, sheet and weaving and nonwoven fabric.The single or multiple lift film useful binders thermal caking that produces by melt curtain coating or blowing or be sealed on the matrix.

For example, described composition can form film with conventional blown film device.Film deposition system can be in this area and is known as a kind of of " blown film " device and contains the circular die that is used for film bubble blown film, and by described die head, composition is squeezed and forms film " film bubble ".The formation film finally caves in described " film bubble ".

Described composition also can be used to form moulded products by extrusion-blown modling and injection moulding stretching-blowing.Injection moulding process softens copolyamide or homogeneous phase polyamide blend in the barrel of heating, mould, the cooling die of injection sealing bring out curing and make molded precast billet leave mould under high pressure when it melts.Production and the thermal stretch again-blowing subsequently of these precast billet that moulding compound is very suitable for precast billet form the final doleiform with required character.The suitable orientation temperature of injection moulding precast billet in being heated to 100 ℃ of-150 ℃ of scopes, drawn-blowing then.Back one method comprise by mechanical means as the mode that pushes away with core rod insert for the first time axial tension heat precast billet, blow high-pressure air (500psi at the most) then and stretch with hoop.Made the blow molded bottle of diaxial orientation like this.Typical blow-up ratio is in the 5/1-15/1 scope.

The transparency of its excellence of composition of the present invention and low haze allow to add quite a large amount of polymer wastes or " pulverizing material again " makes transparent moulded products.The term of using herein " is pulverized material again " and is interpreted as to have its generally accepted meaning in this area, i.e. reclaim and be ground into more short grained polymer waste in the own product formation method.Usually, pulverize material again and sell, it is used in the unessential moulded products to add wherein the transparency of goods with waste material.For the bottle and the film that use in some moulded products such as the packaging application, low haze and high transparent are key characters.The production of these goods (particularly multi-layer product) produces a large amount of polymer wastes inherently, and it can not turn back in the goods formation method usually, and reason is to form unacceptable level of haze.Because the tight coupling of the first and second component specific refractory poweres, therefore, but from composition of the present invention with pulverize the adding production low haze of expecting, transparent moulded products again.

Therefore, another aspect of the invention is the method that forms moulded products, described method comprises:

(A) melt blending

Wherein, first component (i) and second component (ii) form the unmixing blend, the refringence of second component and first component (RI (second component)-RI (first component)) is about 0.006-pact-0.0006, and the percent transmittancy of blend is at least 75%, and mist degree is below 10%;

(B) form moulded products;

(E) the described polymer waste composition of optionally drying; With

(F) merge described polymkeric substance and pulverize material again and (ii) with first and second components (i) of step (A).

Therefore the inventive method allows to add polymer waste and pulverizes material again and keep low haze and high transparent in moulded products.Should also be understood that aforesaid method comprises the various embodiments of aforementioned first and second components, polyester, polycarbonate, polyarylester, homogeneous blend, copolyamide, polymeric amide, oxygen-scavenging compositions and its arbitrary combination.

For example, as previously mentioned, the unmixing blend that forms from first and second components also can comprise at least a periodic table of elements 3-12 family, the metal in 4-6 cycle of being selected from.The example of metal comprises copper, nickel, cobalt, iron, manganese and its combination.Usually, metal exists with the amount of the about 500ppm weight metal of about 10-that accounts for the moulded products gross weight.Preferred metal is a cobalt.

The moulded products of the inventive method can form by any method that known in the art and front have been described.For example, moulded products can by extrude, calendering, thermoforming, blowing, extrusion-blown modling, injection moulding, compression moulding, curtain coating, drawing-off, tentering or blowing produce.

Although method of the present invention can be used to prepare any moulded products, producible representative article is sheet, film, precast billet, pipe and bottle.These goods can have individual layer or contain about 7 layers of 2-.Pulverize material again and can be incorporated in one or more these layers, described one or more layers can comprise the material of pulverizing again of the about 50-100% weight that accounts for described one or more layers of weight.Other examples that can be present in the material level of pulverizing again in the moulded products are about 95% weight of 5-, about 60% weight of about 10-, about 50% weight of about 15-and about 30% weight of about 20-.

Moulded products can comprise multilayer, and wherein one or more described layers comprise the unmixing blend of first and second components or wherein first component and second component are present in the independent layer.Therefore, another aspect of the invention is multilayer formed article, described multilayer formed article comprises:

Described moulded products can comprise the various embodiments of aforementioned first and second components, polyester, polycarbonate, polyarylester, homogeneous blend, copolyamide, polymeric amide, oxygen-scavenging compositions, moulded products and its arbitrary combination.

Multilayer formed article can by extrude, calendering, thermoforming, blowing, extrusion-blown modling, injection moulding, compression moulding, curtain coating, drawing-off, tentering or blowing produce.Because the tight coupling of first and second layers specific refractory poweres, described multi-layer product also can comprise the material of pulverizing again of the mixture that contains first and second layers, and it can be added in the combination of the first layer, the second layer or first and second layers.Usually, pulverize about 5% weight-Yue 60% weight that material accounts for the multi-layer product gross weight again.Other examples of pulverizing the weight percentage of material in the moulded products again are about 10% weight-Yue 40% weight and about 20% weight-Yue 30% weight that accounts for the goods gross weight.

Depend on its desired use, multi-layer product can have about 7 layers of 2-.For example, as previously mentioned, moulded products can be sheet, film, pipe, bottle or precast billet.Also can be lamination layer structure.For example, moulded products can have the laminate structure of ABA, ABABA, ABCBA or ACBCA representative, its middle level A comprises the first layer (i), layer B comprises the second layer (ii), layer C comprises pulverizing material again, and the described material package of pulverizing again contains first and second layers (i) and waste material mixture (ii), consumes polyester or polycarbonate or its combination that acquisition is reclaimed in the back.Depend on the composition of pulverizing material again, the refringence of layer B and layer C (RI (layer B)-RI (layer C)) may be favourable for about 0.006-about-0.0006 with the transparency of maintenance goods with in conjunction with pulverizing the ability of expecting again.

In another embodiment, layer A can comprise the second layer (ii), and layer B comprises the first layer (i), and layer C comprises first and second layers (i) and waste material mixture (ii), polyester or polycarbonate or its combination that obtains reclaimed in the consumption back.

In addition, the second layer of this novel multi-layer goods (ii) also can comprise at least a periodic table of elements 3-12 family, the metal in 4-6 cycle of being selected from.The example of metal comprises copper, nickel, cobalt, iron, manganese and its combination.Usually, metal exists with the amount of the about 500ppm weight metal of about 10-that accounts for the moulded products gross weight.Preferred metal is a cobalt.

And in another embodiment, multilayer formed article of the present invention also can comprise at least one other layer, and described other layers comprise the material of pulverizing again of about 100% weight of about 50-that accounts for described layer gross weight.Contain described other layers of pulverizing material again and also can comprise at least a periodic table of elements 3-12 family, the metal in 4-6 cycle of being selected from.The example of metal comprises copper, nickel, cobalt, iron, manganese and its combination.Usually, the amount of metal accounts for the about 500ppm weight of about 10-of described moulded products gross weight.Preferred metal is a cobalt.

As previously mentioned, described multilayer formed article can comprise the various embodiments of moulded products, thermoplastic polymer, polymeric amide, unmixing blend, homogeneous blend and oxygen-scavenging compositions as previously mentioned.For example, described at least a thermoplastic polymer can comprise the straight or branched polyester, the modification of at least a 2-20 of containing the carbon atom that the residue of described polyester comprises at least 80% mole of accounting for the total diacid residue at least a dicarboxylic acid that is selected from terephthalic acid, m-phthalic acid, naphthalic acid and 1,4 cyclohexanedicarboxylic acid and 0-are about 20% mole is with the residue of dicarboxylic acid; (b) diol residue, described diol residue comprises at least 80% mole at least a ethylene glycol, 1 that is selected from that accounts for the diol residue total mole number, 4-cyclohexanedimethanol, neopentyl glycol, Diethylene Glycol, 1, ammediol, 1,4-butyleneglycol and 2,2,4,4-tetramethyl--1, at least a residue that contains the modification of 3-16 carbon with glycol that the residue of the glycol of 3-cyclobutanediol and 0-are about 20% mole; And described one or more separating polymers comprise the homogeneous blend of first polymeric amide and second polymeric amide, and described first polymeric amide comprises the residue of m-xylene diamine and hexanodioic acid, and described second polymeric amide comprises nylon 6, nylon 6,6 or its blend.For example, described thermoplastic polymer can comprise branched polyesters.In a further example, described thermoplastic polymer also comprises polyester and the homogeneous blend that comprises the polycarbonate of dihydroxyphenyl propane residue.

Multilayer formed article of the present invention can be by any method preparation well known to those skilled in the art.For example, moulded products can form also and can use the typical method explanation of producing multilayer film by coextrusion especially by the film forming any routine techniques of shape (comprise lamination, extrude lamination, be total to injection, stretching-blowing and coextrusion blowing).For example, first and second components and any optional layer are transported in the forcing machine hopper of same quantity, and each forcing machine is respectively handled one or more layers material.Usually, for composition of the present invention, each is heated to about Tg+100 ℃ to about Tg+300 ℃ temperature first and second components before extruding and in the process, and wherein Tg is the second-order transition temperature of first and second components that record of dsc.Melt-flow from each forcing machine is transported in the pure road coextrusion die head.In the time of in die head, layer through and put and merge, the single multilayer film as polymer materials occurs from die head then.After leaving die head, film is cast onto on the casting roller of first controlled temperature, and through first roller, to the roller of second controlled temperature, the temperature of second roller is low than first roller usually then.The roller of controlled temperature is controlled the rate of cooling of leaving the die head caudacoria to a great extent.In other method, film deposition system can be and is known as a kind of of blown film device in this area and contains the many material road circular die that is used for film bubble blown film, and by described die head, film composition is squeezed and forms film bubble, and described film steeps the formation film that finally caves in.The coextrusion method that forms film and sheet laminate is widely known by the people.Perhaps each layer can form sheet earlier then at heat and pressure and have or the situation lower floor that do not have an intermediary adhesive layer is pressed on together.

The transparency of composition of the present invention and low haze also allow to add quite a large amount of polymer wastes or " pulverizing material again " and make multilayer, transparent moulded products.Therefore, the present invention also provides the method that forms multilayer formed article, and described method comprises:

(iv) reclaim the waste material of first and second components;

(vi) described the pulverizing again of optionally drying expected; With

Wherein, step (ii) second component and the refringence (RI (second component)-RI (first component)) of first component of step (i) be about 0.006-pact-0.0006, and the percent transmittancy of blend is at least 75%, mist degree is below 10%.Described method can comprise the various embodiments of aforementioned first and second components, polyester, polycarbonate, polyarylester, homogeneous blend, copolyamide, polymeric amide, oxygen-scavenging compositions, moulded products, goods formation method and its arbitrary combination.

The inventive method allows to add quite a large amount of material of pulverizing again in moulded products and keeps low haze and high transparent.The described mixture of expecting to comprise usually step (i) and first and second components (ii) of pulverizing again, it produces as waste material in goods formation method, but any polymer materials is all available, as long as the refringence of its specific refractory power and second component is about 0.006-about-0.0006.The material of pulverizing again of procedure can with first component of step (i), step (ii) second component or the combination of first and second components merge.Pulverize about 5% weight-Yue 60% weight that material can account for the moulded products gross weight again.Its other representative example of pulverizing material content again of the moulded products of method of the present invention are about 10% weight-Yue 40% weight of moulded products and about 20% weight-Yue 30% weight of moulded products.

Depend on its desired use, the multi-layer product of present method can have about 7 layers of 2-.For example, as previously mentioned, multilayer formed article can be sheet, film, pipe, bottle or precast billet.Lamination layer structure also can.For example, moulded products can have the laminate structure of ABA, ABABA, ABCBA or ACBCA representative, its middle level A comprises first component of step (i), layer B comprises step second component (ii), layer C comprises pulverizing material again, and the described material package of pulverizing again contains the waste material mixture from step (i) and first and second components (ii), polyester or polycarbonate or its combination that acquisition is reclaimed in the consumption back.Depend on the composition of pulverizing material again, the refringence of layer B and layer C (RI (layer B)-RI (layer C)) may be favourable for about 0.006-about-0.0006 with the transparency of maintenance goods with in conjunction with pulverizing the ability of expecting again.

In another embodiment, layer A can comprise step second component (ii), layer B comprises first component of step (i), and layer C comprises waste material mixture, the consumption back of step (i) and first and second components (ii) and reclaim polyester or polycarbonate or its combination that obtains.

In addition, the step of novel multi-layer goods of the present invention second component (ii) also can comprise at least a periodic table of elements 3-12 family, the metal in 4-6 cycle of being selected from.The example of available metal comprises copper, nickel, cobalt, iron, manganese and its combination.Usually, metal exists with the amount of the about 500ppm weight metal of about 10-that accounts for the moulded products gross weight.Preferred metal is a cobalt.

And in another embodiment, the step of method of the present invention (iii) also can comprise at least one other layer of formation, and described other layers comprise the material of pulverizing again of about 100% weight of about 50-that accounts for described layer gross weight.Contain described other layers of pulverizing material again and also can comprise at least a periodic table of elements 3-12 family, the metal in 4-6 cycle of being selected from.The example of metal comprises copper, nickel, cobalt, iron, manganese and its combination.Usually, metal exists with the amount of the described metal of the about 500ppm weight of about 10-that accounts for described moulded products gross weight.Preferred metal is a cobalt.

As previously mentioned, described multilayer formed article can comprise the various embodiments of moulded products, thermoplastic polymer, polymeric amide, unmixing blend, homogeneous blend and oxygen-scavenging compositions as previously mentioned.For example, described at least a thermoplastic polymer can comprise polyester, the modification of at least a 2-20 of containing the carbon atom that the residue of described polyester comprises at least 80% mole of accounting for the total diacid residue at least a dicarboxylic acid that is selected from terephthalic acid, m-phthalic acid, naphthalic acid and 1,4 cyclohexanedicarboxylic acid and 0-are about 20% mole is with the residue of dicarboxylic acid; (b) diol residue, described diol residue comprises at least 80% mole at least a ethylene glycol, 1 that is selected from that accounts for the diol residue total mole number, 4-cyclohexanedimethanol, neopentyl glycol, Diethylene Glycol, 1, ammediol, 1,4-butyleneglycol and 2,2,4,4-tetramethyl--1, at least a residue that contains the modification of 3-16 carbon with glycol that the residue of the glycol of 3-cyclobutanediol and 0-are about 20% mole; And described one or more separating polymers comprise the homogeneous blend of first polymeric amide and second polymeric amide, and described first polymeric amide comprises the residue of m-xylene diamine and hexanodioic acid, and described second polymeric amide comprises nylon 6, nylon 6,6 or its blend.For example, described thermoplastic polymer can comprise branched polyesters.In a further example, described thermoplastic polymer also comprises polyester and the homogeneous blend that comprises the polycarbonate of dihydroxyphenyl propane residue.

In addition, another embodiment of the present invention is for forming the method for multilayer formed article, and described method comprises:

(A) heating first component is to polyester that it comprised or about Tg+100 ℃ to about Tg+300 ℃ temperature of polycarbonate, described first component comprises (i) at least a polyester, described polyester comprises: (a) diacid residues, described diacid residues comprise account for the total diacid residue at least about 95% mole terephthalic acid residue; (b) diol residue, described diol residue comprise at least 95% mole at least a residue that is selected from the glycol of ethylene glycol and 1,4 cyclohexane dimethanol that accounts for the diol residue total mole number; (ii) at least a polycarbonate, described polycarbonate comprises the residue of dihydroxyphenyl propane; Or (iii) its homogeneous blend;

(B) heating second component is to about 290 ℃ temperature, described second component comprises the polymeric amide that contains diamines and the diacid residues homogeneous blend through the acid amides exchange, described polymeric amide comprises about 100% mole m-xylene diamine residue that accounts for total diamines residue and the about 100% mole hexanodioic acid residue that accounts for the total diacid residue, and at least a polymeric amide is selected from nylon 6 and nylon 6,6;

(C) form the moulded products of described first and second components in independent layer;

(D) waste material of recovery first and second components;

(E) waste material of pulverizing described first and second components is pulverized material again to produce;

(F) the described material of pulverizing again of optionally drying; With

(G) merge described pulverize again material and step (A) and first component (B), second component or its combination;

Wherein, the refringence of first component of second component of step (B) and step (B) (RI (second component)-RI (first component)) is about 0.006-pact-0.0006, and the percent transmittancy of blend is at least 75%, and mist degree is below 10%.Described method can comprise the various embodiments of aforementioned first and second components, polyester, polycarbonate, polyarylester, homogeneous blend, copolyamide, polymeric amide, oxygen-scavenging compositions, moulded products, goods formation method and its arbitrary combination.

As previously mentioned, pulverize again material can comprise first and second components (i) and mixture (ii) and can with first component (i), second component (ii) or its combination merging.Pulverize about 5% weight-Yue 60% weight that material can account for the moulded products gross weight again.Its other representative example of pulverizing material content again of the moulded products of method of the present invention are about 10% weight-Yue 40% weight of moulded products and about 20% weight-Yue 30% weight of moulded products.

The polyester of present method can comprise to contain at least about 95% mole terephthalic acid residue's the diacid residues and the glycol that can have a certain limit and form.For example, described polyester can comprise the diol residue that contains the about 95% mole glycol residue of the about 5% mole 1,4 cyclohexane dimethanol residue of about 1-and about 99-.Other examples that the glycol of the polyester of present method is formed include but not limited to: the diol residue that (i) comprises the about 67% mole glycol residue of the about 33% mole 1,4 cyclohexane dimethanol residue of about 39-and about 71-; The diol residue that (ii) comprises the about 45% mole glycol residue of the about 55% mole 1,4 cyclohexane dimethanol residue of about 45-and about 55-; The diol residue that (iii) comprises the about 35% mole glycol residue of the about 65% mole 1,4 cyclohexane dimethanol residue of about 60-and about 40-; The diol residue that (iv) comprises the about 17% mole glycol residue of the about 83% mole 1,4 cyclohexane dimethanol residue of about 79-and about 21-; (the diol residue that v) comprises about 100% mole 1,4 cyclohexane dimethanol residue.Described polyester also can comprise at least a residue that is selected from the branching agent of trimellitic acid, trimellitic acid 1,2-anhydride and pyromellitic acid dianhydride of the about 0.1-2% mole that accounts for the total diacid residue.

In a further example, described thermoplastic polymer also can comprise polyester and the homogeneous blend that comprises the polycarbonate of dihydroxyphenyl propane residue.Polyester and polycarbonate respectively can be straight or branched.

In addition, the step of novel method of the present invention second component (ii) also can comprise at least a periodic table of elements 3-12 family, the metal in 4-6 cycle of being selected from.The example of available metal comprises copper, nickel, cobalt, iron, manganese and its combination.Usually, metal exists with the amount of the about 500ppm weight metal of about 10-that accounts for the moulded products gross weight.Preferred metal is a cobalt.

And in another embodiment, the step of method of the present invention (C) also can comprise at least one other layer of formation, and described other layers comprise the material of pulverizing again of about 100% weight of about 50-that accounts for described layer gross weight.Contain described other layers of pulverizing material again and also can comprise at least a periodic table of elements 3-12 family, the metal in 4-6 cycle of being selected from.The example of metal comprises copper, nickel, cobalt, iron, manganese and its combination.Usually, metal exists with the amount of the described metal of the about 500ppm weight of about 10-that accounts for described moulded products gross weight.Preferred metal is a cobalt.

Moulded products of the present invention also can pass through stretch orientation, and it can improve the barrier of goods.As previously mentioned, may need in polymer composition of the present invention, to add other conventional additives or modification polymer.For example can add oxidation inhibitor, light and heat stablizer, dyestuff, static inhibitor, lubricant, sanitas, processing aid, surface slip agent, antisticking agent, pigment, fire retardant, whipping agent etc.Can use more than one additive.Additive can be any desired amount exist, but be no more than about 20% weight of moulded products gross weight usually, preferably be no more than 10% weight.

The polymer composition that makes thus, oxygen-scavenging compositions and moulded products also can comprise about at the most 30% weight, preferably be lower than about 20% weight some be derived from the platy shaped particle of at least a layered silicate material to improve its barrier.Described platy shaped particle can a kind of at least ammonium compound modification of week.The amount of platy shaped particle can be determined by the residual ash of measuring polymkeric substance-platy shaped particle composition when pressing ASTM D5630-94 processing.The improvement of barrier properties for gases improves with the increase of platy shaped particle concentration in the composition usually.Though about 0.01% the platy shaped particle amount of being low to moderate promptly provides improved barrier (especially when good dispersion and time) in order, but the composition that contains at least about the platy shaped particle of 0.5% weight is preferred, improves because it demonstrates ideal aspect barrier properties for gases.

Usually layered silicate material is the fine and close coacervate of platy shaped particle, and it closely is laminated in together as card.The thickness of platy shaped particle of the present invention is lower than about 2nm, and diameter is in the about 5000nm scope of about 10-.With regard to purpose of the present invention, described measuring only refers to platy shaped particle and do not comprise any other dispersing auxiliary and the compound for treating that ammonium compound maybe may be used.Suitable platy shaped particle is derived from layered silicate material, and layered silicate material is generally free-pouring powder, its cation exchange capacity (CEC) between about 0.3 and about 3meq/g between, preferably between about 0.8 and about 1.5meq/g between.The example of suitable layered silicate material comprises mica group stratiform phyllosilicate, comprises clay, smectic clays, sodium montmorillonite, sodium hectorite, wilkinite, nontronite, beidellite, chromium neck stone (volonsloite), saponite, sauconite, magadiite (magadite), fibrous morphology crystals, synthetic sodium hectorite etc.The clay of this character can comprise Southern Clay Products andNanocor from a plurality of companies, and Inc. has bought.Most preferred platy shaped particle is derived from sodium bentonite or sodium montmorillonite.Such clay is easy to buy in the U.S., is celebrated with Wyoming type montmorillonite, also can buy from world's elsewhere, and comprising can be from Kunimine Industries, the Kunipia clay that Inc. has bought.

Layered silicate material is usually through handling to improve its dispersion in polymer composition.Known in the art have many useful clay treatment methods, and these are handled also can be before adding layered silicate material in composition of the present invention, afterwards or use in the process and do not depart from scope of the present invention.The example of useful processing includes but not limited to handle with silane compound, swelling agent, polymkeric substance and oligopolymer, dispersing auxiliary, organic cation salt and its combination.

The example of the useful processing of carrying out with silane compound comprises that those disclosed is handled among the international publication number WO93/11190.The example of useful silane compound comprises (3-glycidyl ether oxygen base propyl group)-Trimethoxy silane, 2-methoxyl group (polyoxyethylene) propyl group seven methyl trisiloxanes, octadecyl dimethyl (3-trimethoxy-silylpropyl) ammonium chloride etc.

The example of the useful processing of carrying out with swelling agent comprises well-known oligopolymer in this area.Handle typical polymers and the oligopolymer that clay uses and comprise United States Patent (USP) 5,552, those disclosed in 469 and 5,578,672.Many dispersing auxiliaries are known, and covering scope is material widely, comprise water, alcohol, ketone, aldehyde, chlorinated solvent, varsol, aromatic solvent etc. and its combination.

Embodiment

General introduction: the present invention further specifies by the following examples.The second-order transition temperature of polyester, polymeric amide and blend (Tg) is measured under the scanning speed of 20 ℃/min with TA Instruments2920 type differential scanning calorimeter (DSC) by ASTM method D3418.Heat-drawn wire is pressed ASTM method D648 and is measured, and the Izod notched Izod impact strength is undertaken by ASTM method D256.Flexural property is pressed ASTM method D790 and is measured.The tensile property of blend is pressed ASTM method D638 and is measured down at 23 ℃.The limiting viscosity of polyester concentration with 0.5g/100mL in the phenol/tetrachloroethane of 60/40 (w/w) is measured down at 25 ℃.The glycol content of the polyester portion of these blends proton nuclear magnetic resonance spectroscopy ( ¹H NMR) measures.The compatibility of the blend determine with dsc method of press mold and moulded product.

Haze value is pressed ASTM method D1003 (% mist degree=100* diffuse transmission/total transmission) and is measured by the common software (version 3 .8) of Hunter with HunterLab UltraScan Sphere 8000 colourimeters (Hunter Associates LaboratoryInc., Reston produces).The calibration of this instrument and operation are undertaken by the HunterLab user manual.Diffuse transmission (% transmission) thus eliminate straight-through light path and obtain by on the opposite side of sample port integrating sphere, placing ligh trap.Only scattering is determined greater than the light of 2.5 degree.Total transmission comprise directly by the light of sample and by sample scattering to transmitter from axle light.Sample is placed in the exit end of ball so that can be used to scattering from solid sphere inside from axle light.The transparency adopts range estimation and mist degree method of masurement to measure.For blend of the present invention and various composition, mist degree by composition is formed thick below 1/8 inch sheet, film or plate and measure by said procedure.For moulded products (comprising multilayer formed article), (promptly 1 * 1cm) also by above-described program determination by goods being cut out thick fritter below 1/8 inch for mist degree.

Specific refractory power Metricon Prism Coupler ^TM2010 type refractometers (can buy) from MetriconInc. under 633nm, measure and with three orthogonal directionss (extrude or stretch, laterally and thickness direction) mean value of the specific refractory power that records provides.Alignment films goes up at TM Long film pulling device (with manufacturer's name) and produces the sample of this film pulling device single shaft or biaxial stretch-formed press mold, blown film or extruded film.The operation of film pulling device based on be the motion of two pull bars under the effect of hydraulic drive bar that is mutually the right angle.Film pulling device has the fixed pull bar relative with the pull bar of each motion.Motion that these are relative and steady brace form the diaxon be mutually the right angle to (four limits of membrane sample are fixed thereon), and sample promptly stretches with four or seven times of any stretch ratios to original size at the most along such axle, specifically depends on used machine.Sample places the clamp on the machine and heats before stretching, if necessary.Equipment is output as the stress-elongation data (if necessary) of stretched film under the experimental temperature.

The oxygen-permeable MOCON of film, Inc.Minneapolis, the Ox-Tran oxygen flow tester that MN produces is measured.Oxygen-permeable is calculated from known area, film thickness, the oxygen partial pressure difference of film both sides and the stable state transmission rates that records that is tried film.For having the initiatively sample of oxygen scavenging capacity, flux is not to measure under real stable state, changes because transmission rates can change in time because of the efficient of oxygen cleaning reaction slowly.But under these circumstances, seeing through of oxygen often considered to be in the pseudostationary attitude in the oxygen flow test process.The active oxygen that comprises is in the following embodiments removed in the sample, does not almost have or do not have the obvious change of elimination efficiency in the mensuration process, and oxygen-permeable is calculated from the pseudostationary attitude transmission rates that records.

Comparative examples 1-12: listed copolyesters in terephthalic acid, ethylene glycol and 1,4 cyclohexane dimethanol (CHDM) preparation table 1.The amount of CHDM provides in table 1 in the polyester.Embodiment F contains 100% CHDM (0% ethylene glycol), but 26% mole acid moieties is m-phthalic acid rather than terephthalic acid.

Table 1

Polyester	CHDM in the polyester (% mole)	Tg	The specific refractory power of polyester
Polyester	CHDM in the polyester (% mole)	Tg	The specific refractory power of polyester	A	1.5	81	1.5708
B	31	83	1.5644	A	1.5	81	1.5708

C	50	84	1.5593
C	50	84	1.5593	D	62	86	1.5573
E	81	91	1.5547	D	62	86	1.5573
E	81	91	1.5547	F	100	88	1.5519

Copolyesters and MXD66121 polymeric amide (contain 100% mole m-xylene diamine and 100% mole hexanodioic acid, can buy from Mitsubishi Corporation) are 70 ℃ of following dried overnight.These copolyesters each with the MXD6 bag of 1,3 and 5% weight mix and be transported to rotating speed 90rpm, temperature setting (℃) in following 1.5 inches single screw extrusion machines of Sterling to form blend:

1 district	2 districts	3 districts	4 districts	5 districts
1 district	2 districts	3 districts	4 districts	5 districts	240	250	260	260	260

Blend is 70 ℃ of following dried overnight, is injection molded into 1/8 inch thick 4 then on Toyo 90 injection moulding machines under 270 ℃ " square plate.The specific refractory power that records MXD6 is 1.5824.The result that gained haze value and nylon specific refractory power deduct polyester specific refractory power gained provides in table 2:

Table 2

Embodiment	Polyester type	Polyester (% weight)	MXD6 (% weight)	The % mist degree	Total transmission (%)	RI (nylon)-RI (polyester)
Embodiment	Polyester type	Polyester (% weight)	MXD6 (% weight)	The % mist degree	Total transmission (%)	RI (nylon)-RI (polyester)	C-1	A	99	1	5.2	82.8	0.0116
C-2	A	97	3	14.3	81.6	0.0116	C-1	A	99	1	5.2	82.8	0.0116
C-2	A	97	3	14.3	81.6	0.0116	C-3	A	95	5	29.8	82.0	0.0116
C-4	B	99	1	5.1	79.5	0.0180	C-3	A	95	5	29.8	82.0	0.0116
C-4	B	99	1	5.1	79.5	0.0180	C-5	B	97	3	22.4	70.7	0.0180
C-6	B	95	5	42.9	62.4	0.0180	C-5	B	97	3	22.4	70.7	0.0180
C-6	B	95	5	42.9	62.4	0.0180	C-7	C	99	1	8.5	80.7	0.0231
C-8	C	97	3	31.0	70.4	0.0231	C-7	C	99	1	8.5	80.7	0.0231
C-8	C	97	3	31.0	70.4	0.0231	C-9	C	95	5	50.7	62.6	0.0231
C-10	D	99	1	11.5	77.6	0.0251	C-9	C	95	5	50.7	62.6	0.0231
C-10	D	99	1	11.5	77.6	0.0251	C-11	D	97	3	59.0	63.3	0.0231
C-12	D	95	5	81.6	53.5	0.0231	C-11	D	97	3	59.0	63.3	0.0231

Embodiment 13-24,27-29,31-32,34-36,38 and comparative examples 25-26,30,33,36-37 and 39: nylon 6 (can buy with Zytel  7335F) and MXD6 (trade mark 6121) from DuPont 120 ℃ dry 48 hours and mix down with various ratio bags.Then the polymeric amide bag is mixed thing be transported to rotating speed 90rpm, temperature (℃) in following 1.5 inches single screw extrusion machines of Sterling to form homogeneous blend through the acid amides exchange, this can be indicated by the single composition Tg of each blend peak.The Tg value provides in table 3.

1 district	2 districts	3 districts	4 districts	5 districts
1 district	2 districts	3 districts	4 districts	5 districts	250	270	300	300	300

Part through the blend of nylon of acid amides exchange or MXD6 120 ℃ of following dried overnight, then or on Toyo 90 injection moulding machines in being injection molded into 1/8 inch thick sample under 240 ℃ or under 240 ℃, being extruded into the thick film of 15mil.The preparation of film is undertaken by following extrusion method: used forcing machine is the Killian forcing machine of conventional 2.54cm diameter, and L: D (length-to-diameter ratio) is 24: 1, is equipped with compression ratio and is 3: 1 and with the feed worm of spiral Maddock mixing zone.Use conventional feed piece in the 15.24cm of routine hanger-style die, to transmit melt.2-roller casting films downstack configuration is adopted in the quenching of melt.These films stretch 4 times in 95 ℃ of lower edge each side on TM-Long then.The character of these films provides in table 3 before stretching, and the character after the stretching provides in table 3A.Should point out that the oxygen-permeable of table among the 3A ties up under 30 ℃ and 50% the relative humidity and use 100%O ₂Record as test gas.

Film character before table 3-stretches

Embodiment	MXD6 (% weight)	Nylon 6 (% weight)	Tg (℃)	Oxygen-permeable (cc ^＊mil/ 100in ^2＊day ^＊atm)	Thickness (mil)	Specific refractory power
Embodiment	MXD6 (% weight)	Nylon 6 (% weight)	Tg (℃)	Oxygen-permeable (cc ^＊mil/ 100in ^2＊day ^＊atm)	Thickness (mil)	Specific refractory power	13	100	0	88	0.533	15.003	1.5824
14	95	5	87	0.440	15.000	1.5772	13	100	0	88	0.533	15.003	1.5824
14	95	5	87	0.440	15.000	1.5772	15	90	10	83	0.100	14.465	1.5739
16	87	13	83	0.063	14.498	1.5724	15	90	10	83	0.100	14.465	1.5739
16	87	13	83	0.063	14.498	1.5724	17	85	15	81	0.413	14.065	1.5717
18	75	25	77	1.266	15.260	1.5655	17	85	15	81	0.413	14.065	1.5717
18	75	25	77	1.266	15.260	1.5655	19	73	27	76	1.060	14.065	1.5641
20	70	30	75	1.317	14.535	1.5617	19	73	27	76	1.060	14.065	1.5641
20	70	30	75	1.317	14.535	1.5617	21	65	35	72	1.334	14.755	1.5599

Embodiment	MXD6 (% weight)	Nylon 6 (% weight)	Tg (℃)	Oxygen-permeable (cc ^＊mil/ 100in ^2＊day ^＊atm)	Thickness (mil)	Specific refractory power
Embodiment	MXD6 (% weight)	Nylon 6 (% weight)	Tg (℃)	Oxygen-permeable (cc ^＊mil/ 100in ^2＊day ^＊atm)	Thickness (mil)	Specific refractory power	22	62	38	72	0.740	16.385	1.5575
23	60	40	70	0.709	14.630	1.5536	22	62	38	72	0.740	16.385	1.5575
23	60	40	70	0.709	14.630	1.5536	24	0	100	44			1.5318

Film character after table 3A-stretches

Embodiment	MXD6 (% weight)	Nylon 6 (% weight)	Oxygen-permeable (cc ^＊mil/(100in ^2＊day ^＊atm)	Thickness (mil)
Embodiment	MXD6 (% weight)	Nylon 6 (% weight)	Oxygen-permeable (cc ^＊mil/(100in ^2＊day ^＊atm)	Thickness (mil)	13	100	0	0.230	0.900
14	95	5	0.238	0.930	13	100	0	0.230	0.900
14	95	5	0.238	0.930	15	90	10	0.263	0.850
16	87	13	0.340	0.860	15	90	10	0.263	0.850
16	87	13	0.340	0.860	17	85	15	0.325	0.820
18	75	25	0.499	0.900	17	85	15	0.325	0.820
18	75	25	0.499	0.900	19	73	27	1.402	0.885
20	70	30	0.622	0.880	19	73	27	1.402	0.885
20	70	30	0.622	0.880	21	65	35	0.215	0.970
22	62	38	0.847	1.095	21	65	35	0.215	0.970
22	62	38	0.847	1.095	23	60	40	0.982	0.995
24	0	100			23	60	40	0.982	0.995
24	0	100

For producing embodiment and the comparative examples shown in the table 4, part is through blend or MXD6 dried overnight between 70-120 ℃ of acid amides exchange, and is compound with the polyester of table 1 then.Polyester is dried overnight between 70-120 ℃.These polyester of table 1 each with the table 3 of 10% weight selected through acid amides exchange blend or the MXD6 bag mix and be transported to rotating speed 90rpm, temperature setting (℃) in following 1.5 inches single screw extrusion machines of Sterling to form the unmixing blend:

1 district	2 districts	3 districts	4 districts	5 districts
1 district	2 districts	3 districts	4 districts	5 districts	240	260	280	280	280

Blend is 70 ℃ of following dried overnight, is injection molded into 1/8 inch thick 4 then on Toyo 90 injection moulding machines under 270 ℃ " square plate.The result that gained haze value and nylon specific refractory power deduct polyester specific refractory power gained provides in table 4.

Be to produce embodiment 38 and comparative examples C-39, from table 3 embodiment 20 through the blend of acid amides exchange 70 ℃ of following dried overnight, polyester A or the C bag with table 1 mixes then.Polyester is dried overnight between 70-120 ℃ also.The mixed thing of bag is injection molded into 1/8 inch thick 4 then under 270 ℃ on Toyo 90 injection moulding machines " square plate.The result that the specific refractory power of gained haze value and MXD6 or blend of nylon deducts the specific refractory power gained of polyester provides in table 4.

Table 4-polyester blend and homogeneous phase MXD6/ blend of nylon

Embodiment	Polyester type	The blend embodiment of table 3	CHDM in the polyester (% mole)	MXD6 blend (% weight)	Nylon 6 blends (% weight)	The % mist degree	The total transmission of %	RI (nylon)-RI (polyester)
Embodiment	Polyester type	The blend embodiment of table 3	CHDM in the polyester (% mole)	MXD6 blend (% weight)	Nylon 6 blends (% weight)	The % mist degree	The total transmission of %	RI (nylon)-RI (polyester)	C-25	A	13	1.5	100	0	28.1	71.1	0.0116
C-26	A	14	1.5	95	5	13.5	76.0	0.0064	C-25	A	13	1.5	100	0	28.1	71.1	0.0116
C-26	A	14	1.5	95	5	13.5	76.0	0.0064	27	A	15	1.5	90	10	6.3	77.8	0.0031
28	A	16	1.5	87	13	6.9	78.1	0.0016	27	A	15	1.5	90	10	6.3	77.8	0.0031
28	A	16	1.5	87	13	6.9	78.1	0.0016	29	A	17	1.5	85	15	7.7	77.9	0.0009
C-30	B	17	31	85	15	21.3	81.8	0.0073	29	A	17	1.5	85	15	7.7	77.9	0.0009
C-30	B	17	31	85	15	21.3	81.8	0.0073	31	B	18	31	75	25	5.0	86.5	0.0011
32	B	19	31	73	27	8.5	85.4	-0.0003	31	B	18	31	75	25	5.0	86.5	0.0011
32	B	19	31	73	27	8.5	85.4	-0.0003	C-33	B	20	31	70	30	16.2	84.1	-0.0027
34	C	20	50	70	30	4.1	86.8	0.0024	C-33	B	20	31	70	30	16.2	84.1	-0.0027
34	C	20	50	70	30	4.1	86.8	0.0024	36	C	21	50	65	35	8.3	84.5	0.0006
C-36	C	22	50	62	38	13.6	82.8	-0.0018	36	C	21	50	65	35	8.3	84.5	0.0006
C-36	C	22	50	62	38	13.6	82.8	-0.0018	C-37 38 C-39	C C A	23 20 20	50 50 3.5	60 70 70	40 30 30	19.3 3.7 33.0	80.2 86.3 69.9	-0.0057 0.0024 -0.0091

Embodiment 40: in this predictability embodiment, adopted the synthetic route of the polymeric amide with suitable specific refractory power rather than two kinds of polymeric amide of blend as among the top embodiment 13-24.Any method known in the art all can be used to produce these direct synthetic polymeric amide.But common original position certainly of such polymeric amide or diacid-two amine compound that makes in independent step prepare by melt phase polymerization.In arbitrary method all with diacid and diamines as starting raw material.Perhaps can use the ester-formin of diacid, preferred dimethyl ester.If what use is ester, then reaction must be carried out being converted into acid amides until ester under quite low temperature (80-120 ℃ usually).Heated mixt is to polymerization temperature then.For this predictability embodiment, institute's synthetic polymeric amide is poly-(pimeloyl m-xylene diamine), and it is synthetic from diamines m-xylene diamine and diacid pimelic acid.This polymeric amide is pressed copolyesters A blend in the table 1 of disclosed method and 90% weight among the embodiment 25-39 then.The refringence of these copolyesters A and poly-(pimeloyl m-xylene diamine) is expected to be 0.0034 and be expected to be transparent.The haze value that the gained blend is estimated is that percent transmittancy is higher than 75% below 10%.

Embodiment 42-43 and 47-49 and comparative examples 41,44-46 and 50-53.The unitary film of blend and oxygen-scavenging compositions: prepared some MXD6/N6 through the blend of acid amides exchange and in table 5, provide by the mode of discussing among the top embodiment 13-24.Listed refractive index value is to record by the 15mil film of the mode of discussing among the top embodiment 13-24 to these acid amides exchange blends in the table 5.These acid amides exchange MXD6/N6 pre-compositions of 3% weight or 5% weight or the some copolyesters bags in MXD6 and the table 1 are mixed.These blend of pellets are then 60 ℃ of-70 ℃ of following dried overnight, are transported to then in rotating speed 95rpm, temperature 1.0 inches single screw extrusion machines of Killian as shown in table 7 to form the thick film of nominal 30mil by this unmixing blend.All haze values that contain the film of pure MXD6 are higher than 10%.Wherein the refractive index match to 0.006 of the specific refractory power of blend of nylon and corresponding polyester is transparent (mist degree≤10%) to the film in-0.0006 scope.

Table 5-homogeneous phase MXD6-nylon 6 mixing thing

Nylon	Composition	Specific refractory power	Tg (℃)
Nylon	Composition	Specific refractory power	Tg (℃)	W-	Acid amides exchange MXD6/23% weight nylon 6 pre-compositions	1.5650	78
X-	Acid amides exchange MXD6/30% weight nylon 6 pre-compositions	1.5617	75	W-		1.5650	78
X-		1.5617	75	Y-	Acid amides exchange MXD6/41% weight nylon 6 pre-compositions	1.5528	70
Z-	Acid amides exchange MXD6/50% weight nylon 6 pre-compositions	1.5472	66	Y-		1.5528	70
Z-		1.5472	66	MXD6	MXD6	1.5824	88

Adding contains the enriched material of new cobalt decanoate to produce oxygen-scavenging compositions in two films.Being prepared as follows of this enriched material.Independent C kind polyester and new cobalt decanoate (are lozenge form and with Cobalt Ten-Cem ^TM22.5% supply (can buy from OMG Corp.)) charging is transported to the 57mm twin screw extruder and melt blending under about 235 ℃ barrel set point.Molten polymer is with diameter about 0.08 " wire-form leave forcing machine, the quenching of wire rod water and be cut into be about 0.125 " pellet.The ratio of polyester and polymeric amide and enriched material (by weight) is 93.5: 5: 1.5, and in the enriched material cobalt concentration of metal level to make the cobalt in the final blend film be about 140-150ppm.The sample that contains cobalt shows excellent oxygen scavenging capacity.These samples (being contained in after extruding for 1 week on the Ox-Tran penetration testing instrument) average apparent perviousness in 6 months under these conditions are lower than 0.15cc (STP) ^*Mil/100in ²/ day/atm.

Table 6-30mil unitary film result

Embodiment	Polyester	Nylon	Melt temperature	The % mist degree	Total transmission (%)	RI (nylon)-RI (polyester)	Oxygen-permeable ^*
Embodiment	Polyester	Nylon	Melt temperature	The % mist degree	Total transmission (%)	RI (nylon)-RI (polyester)	Oxygen-permeable ^*	C-41	B	3％MXD6	250℃	22.72	88.1	0.0180
42	B	3％W	250℃	1.13	90.5	0.0006		C-41	B	3％MXD6	250℃	22.72	88.1	0.0180
42	B	3％W	250℃	1.13	90.5	0.0006		43	C		250℃	0.47	90.8	n/a	25.06
C-44	C	3％MXD6	250℃	35.90	87.8	0.0231		43	C		250℃	0.47	90.8	n/a	25.06
C-44	C	3％MXD6	250℃	35.90	87.8	0.0231		C-45	C	5％MXD6	280℃	53.57	87.7	0.0231	13.62
C-46	C	5％MXD6+ Co	280℃	34.12	86.2	0.0231	0.20	C-45	C	5％MXD6	280℃	53.57	87.7	0.0231	13.62
C-46	C	5％MXD6+ Co	280℃	34.12	86.2	0.0231	0.20	47	C	3％X	250℃	1.00	90.7	0.0024
48	C	5％X	280℃	0.98	90.6	0.0024	20.70	47	C	3％X	250℃	1.00	90.7	0.0024
48	C	5％X	280℃	0.98	90.6	0.0024	20.70	49	C	5％X+Co	280℃	1.10	90.4	0.0024	0.09
C-50	E	3％MXD6	290℃	27.12	85.6	0.0277		49	C	5％X+Co	280℃	1.10	90.4	0.0024	0.09
C-50	E	3％MXD6	290℃	27.12	85.6	0.0277		C-51	E	3％Y	290℃	2.99	90.8	-0.0019
C-52	F	3％MXD6	250℃	64.06	87.9	0.0305		C-51	E	3％Y	290℃	2.99	90.8	-0.0019
C-52	F	3％MXD6	250℃	64.06	87.9	0.0305		C-53	F	3％Z	250℃	2.28	92.3	-0.0047

^*Be contained on the instrument after 15 days under the relative humidity of 23 ℃ and about 60-80% and test the apparent perviousness (mean values of every composition 2 films, 3 mensuration of every film) that gas records as the upstream with air.

The material of pulverizing again of embodiment 56 and comparative examples 54-55-multilayer film is by exchanging MXD6/30% weight N6 blend " X " the layer layer preparation multilayer film of the polyester C of two 15mil of coextrusion on every side at 4mil thick MXD6 layer or acid amides.This is called as " ABA " structure, and wherein " A " layer is outer, and " B " layer is an internal layer.Using Killian 1 " forcing machine extrudes skin from polyester C under 265 ℃ temperature.Using 0.75 " the Killian forcing machine extrudes internal layer under the temperature of 285 ℃ (for MXD6) and 275 ℃ (exchanging MXD6/30% weight nylon 6 mixing things " X " for acid amides).For simulating these multilayer films as pulverizing the again utilization of material in single layer structure again, these multilayer films are pulverized then and are done mixed with 50/50 ratio with other polyester C pellet.Should do mix thing then 70 ℃ dry down and at Killian 1 " under 240 ℃ temperature, be extruded into the film of 20mil on the forcing machine.Haze value provides in table 7.Its haze value of the film of all coextrusion all is lower than 2%.But pulverized and during with pure polyester " C " blend when these films, contain the haze value that C/MXD6 pulverizes the film of material blend again and increase to more than 10%, to pulverize the film maintenance of material more transparent and contain " C/X ".

Table 7

	30mil ABA co-extruded films (4mil B layer)			20mil unitary film from the co-extruded films generation of 50% " C " pellet and 50% through pulverizing
	30mil ABA co-extruded films (4mil B layer)						Embodiment	Material	Mist degree (%)	Total transmission (%)	Mist degree (%)	Total transmission (%)	RI (nylon)-RI (polyester)
C-54 C-55 56	C C/MXD6/C C/X/C	0.12 1.49 0.62	91.5 91.1 91.2	0.09 16.44 0.37	91.5 87.3 91.5	n/a 0.0231 0.0022	Embodiment	Material	Mist degree (%)	Total transmission (%)	Mist degree (%)	Total transmission (%)	RI (nylon)-RI (polyester)

Embodiment and contrast implement 57 and 58.Multilayer film bonding: by the layer preparation ABA film of the polyester C of two 15mil of coextrusion around thick MXD6 layer of 4mil or acid amides exchange MXD6/30% weight N6 blend " X " layer.In this embodiment, the nylon 6 that uses in the acid amides exchange blend is Zytel 7301.Using Killian 1 " forcing machine extrudes the skin of polyester C under 265 ℃ temperature.Using 0.75 " the Killian forcing machine extrudes internal layer under the temperature shown in the table 8.The bonding MXD6 that is better than of acid amides exchange MXD6/30% weight N6 blend " X " and polyester C.In addition, when the internal layer melt temperature increases to 280 ℃-285 ℃, obtain improved bonding between acid amides exchange MXD6/30% weight N6 blend and polyester C.MXD6 is bonding not to show any temperature dependency.

Table 8

Embodiment	Material	" B " layer melt temperature	Average stripping strength
Embodiment	Material	" B " layer melt temperature	Average stripping strength	C-57	C/MXD6/C	270℃ 280℃ 285℃	g/mm 1.74 1.7 1.88
58	C/X/C	270℃ 280℃ 285℃	4.33 4.42 7.14	C-57	C/MXD6/C	270℃ 280℃ 285℃	g/mm 1.74 1.7 1.88

Claims

1. oxygen-scavenging compositions, described oxygen-scavenging compositions comprises:

(A) unmixing blend, described unmixing blend comprises:

Wherein, described second component (ii) is about 0.006-pact-0.0006 with the refringence (RI (second component)-RI (first component)) of described first component (i), and the percent transmittancy of described blend is at least 75%, and mist degree is below 10%; With

2. the oxygen-scavenging compositions of claim 1, wherein said second component (ii) are the homogeneous blends of at least two kinds of polymeric amide through the acid amides exchange, and described homogeneous blend is by forming described at least two kinds of polymeric amide contact under about 290 ℃-Yue 340 ℃ temperature.

3. the oxygen-scavenging compositions of claim 2, wherein said contact is by melt blending or extrude and carry out.

4. described second component that the oxygen-scavenging compositions of claim 2, described oxygen-scavenging compositions comprise described first component (i) of about 99% weight of about 5-that accounts for its gross weight and about 1% weight of about 95-(ii).

5. described second component that the oxygen-scavenging compositions of claim 4, described oxygen-scavenging compositions comprise described first component (i) of about 99% weight of about 50-that accounts for its gross weight and about 1% weight of about 50-(ii).

6. described second component that the oxygen-scavenging compositions of claim 5, described oxygen-scavenging compositions comprise described first component (i) of about 99% weight of about 70-that accounts for its gross weight and about 1% weight of about 30-(ii).

7. the oxygen-scavenging compositions of claim 1, wherein said second component (ii) are about 0.005-pact-0.0006 with the refringence (RI (second component)-RI (first component)) of described first component (i).

8. the oxygen-scavenging compositions of claim 1, wherein said at least a thermoplastic polymer comprises polyester, described polyester comprises: (a) diacid residues, the modification of at least a 2-20 of containing the carbon atom that the residue of described diacid residues comprises at least 80% mole of accounting for total diacid residues at least a dicarboxylic acid that is selected from terephthalic acid, m-phthalic acid, naphthalic acid and 1,4 cyclohexanedicarboxylic acid and 0-are about 20% mole is with the residue of dicarboxylic acid; (b) diol residue, described diol residue comprises at least 80% mole at least a ethylene glycol, 1 that is selected from that accounts for the diol residue total mole number, 4-cyclohexanedimethanol, neopentyl glycol, Diethylene Glycol, 1, ammediol, 1,4-butyleneglycol and 2,2,4,4-tetramethyl--1, at least a residue that contains the modification of 3-16 carbon with glycol that the residue of the glycol of 3-cyclobutanediol and 0-are about 20% mole.

9. the oxygen-scavenging compositions of claim 8, wherein said modification is selected from 4 with dicarboxylic acid, 4 '-biphenyl dicarboxylic acid, 1,4-naphthalic acid, 1,5-naphthalic acid, 2,6-naphthalic acid, 2,7-naphthalic acid, 4,4 '-hydroxy-benzoic acid, anti--4,4 '-toluylene dioctyl phthalate, oxalic acid, propanedioic acid, succsinic acid, pentanedioic acid, hexanodioic acid, pimelic acid, suberic acid, nonane diacid and sebacic acid; Described modification is selected from 1 with glycol, 2-propylene glycol, 1, ammediol, 1,4-butyleneglycol, 1,5-pentanediol, 1,6-hexylene glycol, 1,4 cyclohexane dimethanol, terephthalyl alcohol, neopentyl glycol, polyoxyethylene glycol, Diethylene Glycol, polytetramethylene glycol and 2,2,4,4-tetramethyl--1,3-cyclobutanediol.

10. the oxygen-scavenging compositions of claim 8, wherein said diacid residues comprises one or more residues that is selected from the dicarboxylic acid of terephthalic acid, m-phthalic acid or its combination, described diol residue comprises one or more residues that is selected from the glycol of 1,4 cyclohexane dimethanol, neopentyl glycol, ethylene glycol and its combination.

11. the oxygen-scavenging compositions of claim 8, described composition also comprise at least a residue that is selected from the branching agent of trimellitic acid, trimellitic acid 1,2-anhydride and pyromellitic acid dianhydride of the about 0.1-2% mole that accounts for the total diacid residue.

12. the oxygen-scavenging compositions of claim 8, wherein said diacid residues comprise the terephthalic acid residue and the about 40% mole isophthalic acid residues of 0-of about 60-100% mole, described diol residue comprises about 100% mole 1,4 cyclohexane dimethanol residue.

13. the oxygen-scavenging compositions of claim 8, wherein said diacid residues comprises 100% mole terephthalic acid residue.

14. the oxygen-scavenging compositions of claim 8, wherein said diacid residues comprises the terephthalic acid residue of 80-100% mole, described diol residue comprises about 90% mole 1,4 cyclohexane dimethanol residue of about 50-and the about 50% mole neopentyl glycol residue of about 10-.

15. the oxygen-scavenging compositions of claim 8, wherein said diacid residues comprises 100% mole terephthalic acid residue, and described diol residue comprises the 1,4 cyclohexane dimethanol residue and the about 90% mole glycol residue of 60-of about 40% weight of about 10-.

16. the oxygen-scavenging compositions of claim 13, wherein said diol residue comprise about 90% mole glycol residue of about 10-about 99% mole 1,4 cyclohexane dimethanol residue, 0-and the about 25% mole Diethylene Glycol residue of about 1-.

17. the oxygen-scavenging compositions of claim 13, wherein said diol residue comprise about 90% mole 1,4 cyclohexane dimethanol residue of about 50-and the about 50% mole glycol residue of about 10-.

18. an oxygen-scavenging compositions, described oxygen-scavenging compositions comprises:

(A) unmixing blend, described unmixing blend comprises:

(ii) second component, described second component comprises copolyamide;

19. the oxygen-scavenging compositions of claim 18, wherein said copolyamide comprises the residue and at least a terephthalic acid, m-phthalic acid, hexanodioic acid, pimelic acid, suberic acid, nonane diacid, sebacic acid, undecane diacid, dodecanedioic acid, hexanolactam, butyrolactam, 11-amino-undecane diacid and 1, the residues of monomers of 6-hexanediamine of being selected from of m-xylene diamine, p dimethylamine or its combination.

20. the oxygen-scavenging compositions of claim 19, wherein said copolyamide comprises the about 100% mole m-xylene diamine residue of about 15-of accounting for 100% mole of total diamines residue content and accounts for one or more about 15% mole aliphatic series of the about 85% mole hexanodioic acid residue of about 15-of 100% mole of total diacid residue content and about 85-or cycloaliphatic dicarboxylic acid's residue, described aliphatic series or cycloaliphatic dicarboxylic acid are selected from pimelic acid, suberic acid, nonane diacid, sebacic acid, undecane diacid, dodecanedioic acid and 1,4 cyclohexanedicarboxylic acid.

21. the oxygen-scavenging compositions of claim 20, wherein said copolyamide comprise the following end amido of 20mmole/kg.

22. the oxygen-scavenging compositions of claim 20, wherein said first component (i) comprises polyester, described polyester comprises: (a) diacid residues, the modification of at least a 2-20 of containing the carbon atom that the residue of described diacid residues comprises at least 80% mole of accounting for total diacid residues at least a dicarboxylic acid that is selected from terephthalic acid, m-phthalic acid, naphthalic acid and 1,4 cyclohexanedicarboxylic acid and 0-are about 20% mole is with the residue of dicarboxylic acid; (b) diol residue, described diol residue comprises at least 80% mole at least a ethylene glycol, 1 that is selected from that accounts for the diol residue total mole number, 4-cyclohexanedimethanol, neopentyl glycol, Diethylene Glycol, 1, ammediol, 1,4-butyleneglycol and 2,2,4,4-tetramethyl--1, at least a residue that contains the modification of 3-16 carbon with glycol that the residue of the glycol of 3-cyclobutanediol and 0-are about 20% mole.

23. the oxygen-scavenging compositions of claim 1, wherein said second component (ii) comprises homogeneous blend, and described homogeneous blend comprises first polymeric amide and second polymeric amide, and described first polymeric amide comprises aromatic moieties, and described second polymeric amide comprises aliphatic residue.

24. the oxygen-scavenging compositions of claim 23, wherein said homogeneous blend comprises first polymeric amide and second polymeric amide, described first polymeric amide comprises the residue of m-xylene diamine and hexanodioic acid, and described second polymeric amide comprises the aliphatic series or the cyclic aliphatic residues of monomers of at least a diacid of selecting oneself, pimelic acid, suberic acid, nonane diacid, sebacic acid, undecane diacid, dodecanedioic acid, hexanolactam, butyrolactam, the amino undecane diacid of 11-, m-phthalic acid and hexanediamine.

25. the oxygen-scavenging compositions of claim 23, wherein said second polymeric amide comprise at least a nylon 4, nylon 6, nylon 9, Ni Long11, nylon 12, nylon 6,6, the nylon 5 of being selected from, 10, nylon 6,12, the polymeric amide of nylon 6,11, nylon 10,12 and its combination.

26. the oxygen-scavenging compositions of claim 25, wherein said second polymeric amide comprises nylon 6, nylon 6,6 or its blend.

27. the oxygen-scavenging compositions of claim 25, wherein said homogeneous blend comprise the following end amido of 20mmole/kg.

28. the oxygen-scavenging compositions of claim 1, wherein said metal are selected from copper, nickel, cobalt, iron, manganese and its combination.

29. the oxygen-scavenging compositions of claim 28, described composition contain the described metal of the about 500ppm weight of about 10-that accounts for its gross weight.

30. the oxygen-scavenging compositions of claim 29, it comprises the described metal of the about 300ppm of about 50-.

31. the oxygen-scavenging compositions of claim 27, wherein said metal is a cobalt, described at least a thermoplastic polymer comprises polyester, described polyester comprises: (a) diacid residues, the modification of at least a 2-20 of containing the carbon atom that the residue of described diacid residues comprises at least 80% mole of accounting for total diacid residues at least a dicarboxylic acid that is selected from terephthalic acid, m-phthalic acid, naphthalic acid and 1,4 cyclohexanedicarboxylic acid and 0-are about 20% mole is with the residue of dicarboxylic acid; (b) diol residue, described diol residue comprises at least 80% mole at least a ethylene glycol, 1 that is selected from that accounts for the diol residue total mole number, 4-cyclohexanedimethanol, neopentyl glycol, Diethylene Glycol, 1, ammediol, 1,4-butyleneglycol and 2,2,4,4-tetramethyl--1, at least a residue that contains the modification of 3-16 carbon with glycol that the residue of the glycol of 3-cyclobutanediol and 0-are about 20% mole.

32. the oxygen-scavenging compositions of claim 31, wherein said diacid residues comprises one or more residues that is selected from the dicarboxylic acid of terephthalic acid, m-phthalic acid or its combination, described diol residue comprises one or more residues that is selected from the glycol of 1,4 cyclohexane dimethanol, neopentyl glycol, ethylene glycol and its combination.

33. the oxygen-scavenging compositions of claim 31, wherein said diacid residues comprises the terephthalic acid residue and the about 40% mole isophthalic acid residues of 0-of about 60-100% mole, described diol residue comprises about 100% mole 1,4 cyclohexane dimethanol residue.

34. the oxygen-scavenging compositions of claim 31, wherein said diacid residues comprises 100% mole terephthalic acid.

35. the oxygen-scavenging compositions of claim 31, wherein said diacid residues comprises the terephthalic acid residue of 80-100% mole, described diol residue comprises about 90% mole 1,4 cyclohexane dimethanol residue of about 50-and the about 50% mole neopentyl glycol residue of about 10-.

36. the oxygen-scavenging compositions of claim 31, wherein said diacid residues comprises 100% mole terephthalic acid, and described diol residue comprises the 1,4 cyclohexane dimethanol and the about 90% mole ethylene glycol of 60-of about 40% weight of about 10-.

37. the oxygen-scavenging compositions of claim 31, wherein said diol residue comprise about 90% mole glycol residue of about 10-about 99% mole 1,4 cyclohexane dimethanol residue, 0-and the about 25% mole Diethylene Glycol residue of about 1-.

38. the oxygen-scavenging compositions of claim 31, wherein said diol residue comprise about 90% mole 1,4 cyclohexane dimethanol residue of about 50-and the about 50% mole glycol residue of about 10-.

39. the oxygen-scavenging compositions of claim 31, wherein said at least a thermoplastic polymer also comprise described polyester and the homogeneous blend that comprises the polycarbonate of dihydroxyphenyl propane residue.

40. the oxygen-scavenging compositions of claim 39, wherein said polyester and described polycarbonate are side chains.

41. the oxygen-scavenging compositions of claim 40, wherein said polyester also comprise at least a residue that is selected from the branching agent of trimellitic acid, trimellitic acid 1,2-anhydride and pyromellitic acid dianhydride of the about 0.1-2% mole that accounts for the total diacid residue.

42. the oxygen-scavenging compositions of claim 39, wherein said diacid residues comprises one or more residues that is selected from the dicarboxylic acid of terephthalic acid, m-phthalic acid or its combination, described diol residue comprises one or more residues that is selected from the glycol of 1,4 cyclohexane dimethanol, neopentyl glycol, ethylene glycol and its combination.

43. the oxygen-scavenging compositions of claim 39, wherein said diacid residues comprises the terephthalic acid residue and the about 40% mole isophthalic acid residues of 0-of about 60-100% mole, described diol residue comprises about 100% mole 1,4 cyclohexane dimethanol residue.

44. the oxygen-scavenging compositions of claim 39, wherein said diacid residues comprises 100% mole terephthalic acid.

45. the oxygen-scavenging compositions of claim 39, wherein said diacid residues comprises the terephthalic acid of 80-100% mole, and described diol residue comprises about 90% mole 1,4 cyclohexane dimethanol of about 50-and the about 50% mole neopentyl glycol of about 10-.

46. the oxygen-scavenging compositions of claim 39, wherein said diacid residues comprises 100% mole terephthalic acid, and described diol residue comprises about 40% mole 1,4 cyclohexane dimethanol of about 10-and the about 90% mole ethylene glycol of 60-.

47. the oxygen-scavenging compositions of claim 44, wherein said diol residue comprise the about 99% mole 1,4 cyclohexane dimethanol of about 10-, ethylene glycol and the about 25% mole Diethylene Glycol of about 1-that 0-is about 90% mole.

48. the oxygen-scavenging compositions of claim 44, wherein said diol residue comprise about 90% mole 1,4 cyclohexane dimethanol of about 50-and the about 50% mole ethylene glycol of about 10-.

49. a moulded products, described moulded products comprise in the claim 2,8,25 or 46 each oxygen-scavenging compositions.

50. the moulded products of claim 49, described moulded products by extrude, calendering, thermoforming, blowing, extrusion-blown modling, injection moulding, compression moulding, curtain coating, drawing-off, tentering or blowing produce.

51. the moulded products of claim 50, described moulded products are sheet, film, pipe, precast billet or bottle.

52. the moulded products of claim 51, described moulded products are bottle.

53. the moulded products of claim 51, described moulded products has the 2-7 layer.