CN101132910B

CN101132910B - Transparent and multi-layer articles and preparation method thereof

Info

Publication number: CN101132910B
Application number: CN200680006991.8A
Authority: CN
Inventors: W·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: 2014-04-30
Anticipated expiration: 2026-03-02
Also published as: CN101133124A; CN101133122B; CN101132909B; CN101133122A; CN101132909A; CN101133123A; CN101133123B; CN101132910A

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 polyarylester, 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

The transparent article of multilayer and production method thereof

The cross reference of related application

The application requires the U.S. Provisional Application sequence number 60/657,746 submitted on March 2nd, 2005 and in 60/657,747 the rights and interests that on March 2nd, 2005 submits to, the content of described application is incorporated herein by reference.

Invention field

The present invention relates to transparent multilayer formed article and production method thereof.More particularly, the present invention relates to transparent multi-layer product, wherein at least one deck contains polyester, Merlon, polyarylate or its homogeneous blend, and another layer contains copolyamide or polyamide homogeneous blend.The difference of the refractive index absolute value of these layers is little.The invention further relates to a kind of method of producing transparent multilayer formed article, wherein can recycle leftover pieces polymer abrasive again.

Background of invention

Many products (particularly food) are responsive to the loss of the existence of oxygen and water or absorption.The packaging product with this sensitiveness is easily deteriorated because being exposed to oxygen or moisture absorption.For example, the packaging material that contact with oxygen for limit food product can help to keep the quality of food article and reduce rotten.Therefore, the use of this barrier package keeps the longer operating period of goods, thereby reduces cost and the waste storing again.For the effort addressing this problem makes to be widely used oxygen obstruction agent and/or moisture barrier (protection against the tide) agent in packaging material.The known barrier of doing oxygen or moisture for many polymeric materials.For example, typical moisture barrier agent comprises polyethylene and polypropylene.Representational oxygen obstruction agent comprises polyethylene/vinyl base alcohol (" EVOH "), polyvinyl alcohol (" PVOH "), polyamide (nylon), and the blend of these materials.Polyvinylidene chloride, vinyl chloride copolymer and vinylidene chloride/methyl acrylate copolymer are also as moisture and oxygen obstruction agent.

But these conventional barrier materials are expensive, and there is unsettled architectural feature or other defect, only cause being difficult to by gas barrier manufacture of materials packaging material or form unwanted packaging material.For example, although EVOH has excellent oxygen barrier property, can not be used as moisture barrier agent.It is disadvantageously expensive when other barrier material is used alone as packaging material.For fear of these problems, in common practice, use sandwich construction, wherein the amount of expensive barrier material can reduce to thin layer, and with using together with the cheap polymer of structure sheaf on one or both sides at barrier layer.The use of sandwich construction also helps protection barrier layer to avoid deteriorated by structure sheaf.But the production of multi-layered product is expensive.In addition, multi-layer product is difficult aspect recycling, because different polymers compositions is difficult to separation.In addition, the polymer leftover pieces that reclaim or " grinding again " material are caused to unsatisfied mist degree or opacity conventionally with raw polymer blend, this is because raw material and the again incompatibility of abrasive.

The shortcoming of conventional barrier polymer also can be by overcoming with the blend of barrier polymer and another kind of polymer.As mentioned above, disadvantageously, many blends of barrier polymer and other thermoplastic polymer are unmixability, and are opaque or muddy.These blends are applied to need transparent purposes, for example container for drink unsatisfactorily.

In packaging applications, conventionally use polyester polymers, for example PET (" PET ").PET have many can be for the performance of packaging material, comprise acceptable carbon dioxide barrier properties for the soft drink in packaging in thering is multiduty bottle.But, for in compared with bottle and the soft drink of packing in its oxygen obstruction agent need to improve the carbon dioxide barrier properties of PET, this barrier can not perform well in packing oxysensible product, for example the meat products of beer, orange product, the product based on tomato and aseptic packaging.PEN (" PEN ") as barrier than the effective 3-10 of PET doubly, still more expensive.

Sandwich construction can be for improvement of the gas barrier characteristic of PET.The polymer for example with excellent oxygen-barrier property (also referred to as " passive obstruct ") or removing performance (also referred to as " initiatively intercepting ") can combine with PET, makes the laminate structures being comprised of each single kind polymer.But the production of these sandwich constructions is expensive.The blend of barrier polymer and PET also, for improvement of the oxygen barrier property of packing, still as mentioned above, conventionally has the poor transparency, and is not suitable for many packaging applications.The poor production leftover pieces that are difficult to autohemagglutination compound blend in future that also make of the transparency of blend are recycled in raw polymer.

(" EBM ") bottle of copolyester film and extrusion-blown modling need to have toughness conventionally, and conventionally replaces PET to be used for extrusion-blown modling and film purposes.These purposes conventionally need to the comparable barrier property of orientation PET.But unfortunately, the barrier property of copolyesters is poorer than orientation PET.Sandwich construction can by by thin Obstruct membrane coextrusion to the center of thicker body construction to improve overall barrier.But for the purpose of economy, EBM and membrane process require the abrasive again (being leftover pieces) of high-load (the highest by 80%) to reprocess conventionally.Unfortunately, typical barrier material can not be miscible with copolyesters, and the blend of these barrier polymer and polyester shows high-caliber mist degree and the poor transparency conventionally.So when leftover pieces polymer (again abrasive) is recycled initiation layer, the mist degree of whole membrane structure is increased to unacceptable level.

Can provide good passive and/or initiatively barrier property, blend polymer economic and can Efficient Cycle are that this area is needed.These blends should be transparent, contain thermoplasticity and barrier polymer (this polymer can provide the high barrier to oxygen, water and carbon dioxide), and can in the product forming process of abrasive, use economically introducing high-load again.In addition, need barrier and thermoplastic polymer composition, it can be economically for the production of the multi-layer product with high transparent, and can tolerate the abrasive again of high-load.

Summary of the invention

The polymer composition with high transparent and high obstructing performance can be prepared by the homogeneous phase of one or more thermoplastic polymers and copolyamide or at least two kinds of polyamide, the unmixability blend that turns acyl amination blend, and wherein the difference of the refractive index between polyamide component and thermoplastic polymer components is approximately 0.006 to approximately-0.0006.Therefore, the invention provides a kind of polymer composition, the unmixability blend that it comprises following component:

(i) the first component that comprises at least one thermoplastic polymer, described thermoplastic polymer is selected from polyester, Merlon, polyarylate and their homogeneous blend; With

(ii) homogeneous phase that comprises at least two kinds of polyamide, turn the second component of acyl amination blend;

Wherein the difference of the refractive index of second component (ii) and the first component (i) is that RI (second component)-RI (the first component) is approximately 0.006 to approximately-0.0006, and the percent transmission that described unmixability blend has is at least 75%, mist degree is 10% or less.

The first component comprises at least one thermoplastic polymer, it is selected from the homogeneous blend of polyester, Merlon, polyarylate and these polymer, and the blend that second component comprises at least two kinds of polyamide, described polyamide has been turned acyl amination to make homogeneous blend.We have found that by selection and have the aliphatic series of different content and at least two kinds of polyamide of aromatic moieties and these polyamide are turned to acyl amination to form homogeneous blend, the refractive index of the first and second components can closely be mated.Therefore, the homogeneous blend of thermoplastic polymer and polyamide can be for designing the refractive index of second component and the first component in their required scopes, and the difference that makes refractive index is approximately 0.006 to approximately-0.0006.For example, polyester and can be used as the first component containing the homogeneous blend of the Merlon of bisphenol-A residue, the turning acyl amination homogeneous blend and can be used as barrier polymer of the first polyamide of the residue that comprises m-xylene diamine and adipic acid and the second aliphatic polyamide.When refractive index is so mated, the first and second components form transparent unmixability blend, and it is applicable to preparation can be for the high transparent moulded products of many packing purposes.Sandwich construction also can be prepared by many methods well known in the art.For example, the first and second components can or be injected into each independent layer altogether from melt coextrusion, or these layers can each self-forming and for example, combine in follow-up technique (laminated).

Second component also can comprise copolyamide, the ratio of the aromatics that it has and aliphatic dicarboxylic acid and diamines residue can change with closely with the refractive index matched of the first and second components.Therefore, another aspect of the present invention is a kind of polymer composition, the unmixability blend that it comprises following component:

(ii) second component that comprises copolyamide;

Another aspect of the present invention is a kind ofly by comprising, following component to be carried out to the polymer composition that comprises unmixability blend prepared by the method for melt blending:

(ii) homogeneous phase that comprises at least two kinds of polyamide turns the second component of acyl amination blend;

The barrier property of compositions display excellence of the present invention.Oxygen barrier property can be by for example producing deoxidizing compositions in cobalt, manganese, iron, ruthenium, copper, nickel, palladium and platinum introducing blend by transition-metal catalyst.Therefore, the present invention further provides a kind of deoxidizing compositions, it comprises:

(A) the unmixability blend that comprises following component:

Wherein difference RI (the second component)-RI (the first component) of the refractive index of second component (ii) and the first component (i) is approximately 0.006 to approximately-0.0006, and the percent transmission that described unmixability blend has is at least 75%, mist degree is 10% or less; With

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

Blend of the present invention is for the production of transparent moulded products, and it has improved barrier property, melt processability and excellent mechanical property, and can in raw polymer, with a high proportion of abrasive again, prepare.These moulded products can have single or multiple lift, and have many packaging applications.Therefore, the present invention further provides a kind of method that forms moulded products, comprising:

(A) following component is carried out melt blended:

(ii) homogeneous phase that comprises copolyamide or at least two kinds of polyamide turns the second component of acyl amination blend;

Wherein the first component (i) and second component (ii) form unmixability blend, difference RI (the second component)-RI (the first component) of the refractive index of second component (ii) and the first component (i) is approximately 0.006 to approximately-0.0006, and the percent transmission that described unmixability blend has is at least 75%, mist degree is 10% or less;

(B) form moulded products;

(C) the first and second components (i) that recovery comprises blend and leftover pieces polymer composition (ii);

(D) leftover pieces polymer composition is ground to prepare polymer abrasive again;

(E) optionally, leftover pieces polymer composition is dried; With

(F) by polymer again abrasive with the first and second components (i) in step (A) with (ii), mix.The example of the moulded products that can prepare by the inventive method is including, but not limited to sheet material, film, pipe, bottle or section bar.Moulded products can be by extruding, calendering, thermoforming, blowing, extrusion-blown modling, injection moulding, compression molding, casting, drawing-off (drafting), tentering (tentering) or foaming are produced.

Moulded products can have the layer of one or more unmixability blends that contain the first and second components; Maybe can have multilayer, wherein the first and second components are in minute other layer.The present invention also provides a kind of moulded products of multilayer, and it comprises:

(i) ground floor that comprises at least one thermoplastic polymer, described thermoplastic polymer is selected from polyester, Merlon, polyarylate and their homogeneous blend; With

(ii) homogeneous phase that comprises at least two kinds of polyamide turns the second layer of acyl amination blend;

Wherein difference RI (the second layer)-RI (ground floor) of the refractive index of the second layer (ii) and ground floor (i) is approximately 0.006 to approximately-0.0006, and the percent transmission that described moulded products has is at least 75%, mist degree is 10% or less.

The present invention also provides a kind of method that forms multilayer formed article, comprising:

(i) the first component that comprises at least one thermoplastic polymer is heated to the Tg+100 ℃ of temperature of Tg+300 ℃ to the approximately first component of the approximately first component, wherein said thermoplastic polymer is selected from polyester, Merlon, polyarylate and their homogeneous blend;

(ii) second component is heated to the Tg+100 ℃ of temperature of Tg+300 ℃ to about second component of about second component, the homogeneous phase that wherein second component comprises copolyamide or at least two kinds of polyamide turns acyl amination blend;

(iii) be formed on the moulded products in minute other layer with the first and second components;

(iv) reclaim the leftover pieces of the first and second components;

(v) leftover pieces of the first and second components are ground to prepare abrasive again;

(vi) optionally, abrasive is dried again; With

(vii) will be again first component, second component or its mixture of abrasive with step (i) and (ii) combine;

Wherein difference RI (the second component)-RI (the first component) of the refractive index of the second component in step (ii) and the first component in step (i) is approximately 0.006 to approximately-0.0006, and the percent transmission that described moulded products has is at least 75%, mist degree is 10% or less.Described abrasive again can be introduced into first or the second layer in, and can account for approximately 5-approximately 60 % by weight of these goods.

Detailed description of the present invention

The polymer composition with high transparent and excellent barrier properties can be from a kind of unmixability blend preparation, the homogeneous phase that described unmixability blend comprises one or more thermoplastic polymers and at least two kinds of polyamide turns acyl amination blend, and wherein the difference of the refractive index between polyamide blend and thermoplastic polymer is approximately 0.006 to approximately-0.0006.The percent transmission that described unmixability blend has is at least 75%, and mist degree is 10% or less.In general embodiment, the invention provides a kind of polymer composition, the unmixability blend that it comprises following component:

Wherein difference RI (the second component)-RI (the first component) of the refractive index of second component (ii) and the first component (i) is approximately 0.006 to approximately-0.0006, and the percent transmission that described unmixability blend has is at least 75%, mist degree is 10% or less.Thermoplastic polymer and polyamide can be selected from various polymer.Can by select second component polyamide ratio or by the thermoplastic polymer blend of the first component is formed to the refractive index that homogeneous blend regulates second component and the first component, obtain approximately 0.006 to approximately-0.0006 refractive index difference.New compositions of the present invention can be for the production of having one or more layers moulded products, for example sheet material, film, pipe, bottle and section bar.Moulded products can be by extruding, calendering, thermoforming, blowing, extrusion-blown modling, injection moulding, compression molding, casting, drawing-off, tentering or foaming are produced.Can produce multi-layer product, wherein unmixability blend is present in one or more layers, or the first and second components are in different layers.Because the refractive index difference of the first and second components is little, so the moulded products of being produced by the present composition can be introduced the abrasive again of significant quantity and keep the good transparency.The transparency of these moulded products that make and barrier property make them be used in particular for packing purposes.

Except as otherwise noted, in description and claims for representing that all numerals of the amount, performance such as molecular weight, reaction condition etc. of component should be understood to be modified by term " about " in all cases.Therefore, unless indicated to the contrary, the digital parameters occurring in following description and appended claims represents about implication, can change according to the performance of wanting required for the present invention.On minimum level, each digital parameters should at least be considered recorded precise figure and adopt the common technology analysis of rounding up.In addition, at the Range Representation described in disclosure and claims book, comprise concrete gamut and be not only end points.For example, the Range Representation of 0-10 discloses: all integers between 0 and 10, such as 1,2,3,4 etc.; All marks between 0-10, such as 1.5,2.3,4.57,6.1113 etc.; With end points 0 and 10.Equally, the scope relevant with chemical substituting group, for example " C ₁-C ₅hydrocarbon ", represent particularly including with C is disclosed ₁and C ₅hydrocarbon and C ₂, C ₃and C ₄hydrocarbon.

Although setting digital scope and the parameter of wide region of the present invention is about implication, the numerical value occurring in specific embodiment as far as possible accurately records.But any numerical value itself contains some error, this inevitable standard deviation owing to finding in its corresponding experiment detects causes.

Singulative " one " used, the plural form that " a kind of " and " described " comprises them in description and appended claims, except as otherwise noted.For example, " polymer " or " moulded products " means processing or the preparation that comprises multiple polymers or goods.For the composition that contains or comprise " a kind of " component or " a kind of " polymer, mean and except described component, also correspondingly comprise other component or other polymer.

Term " comprises " or " containing " or " comprising " represents that at least described compound, element, particle or processing step etc. are present in said composition or goods or method; but do not get rid of the existence of other compound, catalyst, material, particle, processing step etc.; even if these other compounds, catalyst, material, particle, processing step etc. have and described those identical effects, unless clearly got rid of in the claims.

It is to be further understood that while mentioning one or more processing step and be not precluded within additional technical steps before or after the described step of combination or the existence of the middle process step between those clearly defined steps.In addition, the numbering of processing step or component is for determining the usual manner of different activities or component, and illustrated numbering can be according to any order arrangement, except as otherwise noted.

At term used herein " polyester ", represent to comprise homopolymerization polyester, copolyester and ternary polymerization polyester.Generally speaking, polyester is to carry out synthetic polymer prepared by polycondensation reaction by one or more bifunctional carboxylic acids and one or more difunctionality hydroxy compounds.Conventionally, bifunctional carboxylic acid is dicarboxylic acids or hydroxycarboxylic acid, and difunctionality hydroxy compounds is dihydroxylic alcohols, for example dihydroxylic alcohols and glycol.In the present invention, bifunctional carboxylic acid can be aliphatic series or cycloaliphatic dicarboxylic acid, for example adipic acid; Or aromatic dicarboxylic acid, for example terephthalic acid (TPA).Difunctionality hydroxy compounds can be cycloaliphatic diol, for example 1,4-CHDM; The aliphatic diol of straight chain or branching, for example BDO; Or aromatic diol, for example quinhydrones.

At term used herein " polyamide ", represent to comprise by one or more bifunctional carboxylic acids and one or more bifunctional amines' polycondensation reaction or by the prepared synthetic polymer of ring-opening polymerisation of lactams, and can comprise homopolymers and copolymer.For example, bifunctional carboxylic acid can be dicarboxylic acids, for example adipic acid or M-phthalic acid; Bifunctional amine can be diamines, for example hexamethylene diamine or m-xylene diamine.Term used herein " copolyamide " is interpreted as the polyamide that expression contains at least 2 chemically different repetitives.For example, MXD6 nylon is not copolyamide, because it only contains single chemically different repetitive of planting, the residue that this repetitive contains adipic acid and m-xylene diamine.By contrast, hexamethylene adipamide/6I hexamethylene isoterephalamide the copolymer prepared from the condensation of adipic acid and M-phthalic acid by hexamethylene diamine has two kinds at chemically different repetitives, that is to say the repetitive of a kind of repetitive of the residue that contains hexamethylene diamine and adipic acid and the another kind of residue that contains hexamethylene diamine and M-phthalic acid.

Herein, term " Merlon " is defined as the condensation product of carbonate source compound and glycol source compound, there is the carbonate component that contains 100 % by mole of carbonate units and the diol component that contains 100 % by mole of diol units, for 200 % by mole of monomeric units or 100 % by mole " repetitive " altogether.In one embodiment of the invention, the polycarbonate unit of the first component is based on 4, and the Merlon of 4 '-isopropylidene biphenol, is commonly referred to bisphenol-a polycarbonate.The various straight chains that can use in the present invention or branching polycarbonate can be derived from bisphenol-As, and can prepare by means commonly known in the art, for example, be disclosed in US patent No. ' s3, in 030,335 and 3,317,466.The example of the bisphenol-a polycarbonate that can use in the present invention and can obtain from business comprises can be from General Electric Company with trade name

the material of selling, and can be from Bayer Inc with trade name

the material of selling.

At term used herein " polyarylate ", be interpreted as the polyester that expression is prepared by the polycondensation reaction of one or more difunctionality dicarboxylic acids and one or more dihydric phenols.For example, typical aromatic dicarboxylic acid is terephthalic acid (TPA) and M-phthalic acid, and typical aromatics dihydric phenol is bisphenol-A and quinhydrones.

The term using when mentioning polymer of the present invention herein " residue " represents anyly by relating to polycondensation or the ring-opening reaction of corresponding monomer, to be introduced into the organic structure in polymer.In term used herein " repetitive " expression, can in polymer, repeat the shortest sequence of the monomer residue of discovery.For example, in polyester, repetitive is to have dicarboxylic acid residue and diol residue, or the organic structure of the hydroxycarboxylic acid residue closing via ketonic oxygen base key.In polyamide, repetitive is the organic structure having via dicarboxylic acids and diamines residue, lactams or the amino acid residue of amide group bonding.

Those skilled in the art also can understand residue relevant in various polyester of the present invention, polyamide, Merlon and polyarylate can be derivative or derivative from any derivative of parent compound from parent monomeric compound itself.For example, the dicarboxylic acids of mentioning in polymer of the present invention and amino acid residue can be derived from dicarboxylic acids or amino acid monomer or its relevant carboxylic acid halides, ester, salt, acid anhydrides or its mixtures.Therefore, terminology used here " dicarboxylic acids " or " amino acid " are intended to comprise any derivative of dicarboxylic acids and dicarboxylic acids, comprise corresponding carboxylic acid halides, ester, half ester, salt, half salt, acid anhydrides, mixed acid anhydride or its mixture, for react the polycondensating process of preparing high molecular weight polyesters or polyamide with glycol." hydroxycarboxylic acid " is intended to comprise hydroxycarboxylic acid and monohydroxy monocarboxylic acid and any its derivative of aliphatic series and cyclic aliphatic, comprise that its corresponding carboxylic acid halides, ester, cyclic ester (comprise dimer, lactic acid lactide for example), salt, acid anhydrides, mixed acid anhydride or its mixture, for polycondensating process or ring-opening reaction to prepare high molecular weight polyesters.Similarly, " amino acid " is intended to comprise amino acid and any derivative thereof of aliphatic series, aromatics and cyclic aliphatic, comprise its corresponding carboxylic acid halides, acid amides, cyclic amides (lactams), salt, acid anhydrides, mixed acid anhydride or derivatives thereof, for polycondensating process or ring-opening reaction to prepare superpolyamide.In addition, term " diamines " be intended to comprise diamines with and relevant salt, acid amides or their any other derivative, for the preparation of polyamide.

When using term " intrinsic viscosity " (I.V.) in this application, it should be understood that the viscosity measuring at 25 ℃ of solvents that contain 60 % by weight phenol and 40 % by weight tetrachloroethanes that use 0.5g polymer/100ml.

At term used herein " refractive index " (referred to as " RI "), represent the refractive index measured value obtaining according to standard method well known in the art.Herein, the refractive index of record is with Metricon Prism Coupler under 633nm wavelength ^tM2010 type refractometers (from MetriconInc.) are measured, and be recorded as three orthogonal directions (extrude or draw direction, laterally and thickness direction) mean value of the upper refractive index of measuring.In the content about composition of the present invention, method and moulded products, term used " refractive index poor " always means that the refractive index of the component (here conventionally referred to as " second component " or " second layer " in multi-layer product) that contains polyamide or copolyamide by use deducts the value that the refractive index of the component (here conventionally referred to as " the first component " or " ground floor " in multi-layer product) that contains polyester, Merlon or polyarylate obtains.Therefore,, according to the present invention, poor (" the Δ RI ") of refractive index should calculate according to following formula:

Δ RI=RI (second component or the second layer)-RI (the first component or ground floor)

To those skilled in the art, the difference of refractive index can be obviously positive number or negative.

At term used herein " mist degree % ", represent to use HunterLab UltraScan Sphere 8000 colorimeters (by Hunter Associates LaboratoryInc., to be manufactured according to ASTM method D1003, Reston, Va) haze value (mist degree %=100 * diffused transmission/total transmission) that adopts Hunter ' s Universal Software (3.8 editions) to measure.The method of measuring refractive index provides in an embodiment.For composition of the present invention, mist degree and percent transmission are by composition molding or casting to be become to thickness be 1/8 inch or less sheet or film and measure mist degree according to the operation of describing in embodiment and measure.For moulded products, comprise multilayer formed article, mist degree and percent transmission can be by being cut into goods 1/8 inch of thickness or less fritter (that is, 1 * 1cm) and measuring mist degree according to the operation of describing in embodiment and measure.

(" the Tg value that DSC ") measures, adopts the sweep speed of 20 ℃/min conventionally at term used herein " glass transition temperature " (" Tg "), to represent to use differential scanning calorimetry.The example of DSC instrument is TA Instruments 2920 differential scanning calorimeters.

Composition of the present invention comprises the first component, and it contains one or more and is selected from following thermoplastic polymer: polyester, Merlon, polyarylate and their homogeneous blend.At term used herein " thermoplastic polymer ", represent to there is the general implication that those of ordinary skills understand, namely when being exposed to the polymer that returns to its original state when softening and working as cool to room temperature when hot.The first component can contain single thermoplastic polymer of planting, or the blend of two or more polymer, and condition is that described blend is homogeneous blend.At term used herein " homogeneous blend ", be the synonym of term " compatibility ", and be intended to represent that described blend has single homogeneous phase, by single compositing dependence Tg, represented.For example, the first polymer that can be miscible with second polymer can be for " plasticising " second polymer, as United States Patent (USP) 6,211, described in 309.Homogeneous blend can be by simply two or more polyblends being formed, or for example, form by two or more polymer being carried out to ester exchange or turn acyl amination condensation polymer (polyester or polyamide) in the situation that.On the contrary, at term used herein " unmixability ", represent to show the phase of at least two random mixing, and show the blend of more than one Tg.Some polymer can be unmixability, but can be compatible with each other.About the further universal description of compatibility and unmixability blend and various phenetic analysis technology can at Polymer Blends the 1st and 2 volumes, (D.R.Paul and C.B.Bucknall edit, 2000, John Wiley & Sons, Inc) in find.

The first component can contain one or more thermoplastic polymers, is selected from polyester, Merlon, polyarylate and their homogeneous blend.For example, the first component can contain polyester, this polyester comprises (a) diacid residues, it contains and is selected from terephthalic acid (TPA), M-phthalic acid, naphthalenedicarboxylic acid and 1 based at least 80 % by mole of diacid residues total amount meters, the residue of at least one dicarboxylic acids in 4-cyclohexane cyclohexanedimethanodibasic, and at least one of 0 to approximately 20 % by mole has the residue of the modification dicarboxylic acids of 2-20 carbon atom; (b) diol residue, it contains and is selected from ethylene glycol, 1 based at least 80 % by mole of diol residue total amount meters, 4-cyclohexanedimethanol, neopentyl glycol, diethylene glycol (DEG), 1, ammediol, BDO and 2,2,4,4-tetramethyl-1, the residue of at least one glycol in 3-cyclobutane glycol, and at least one of 0 to approximately 20 % by mole has the residue of the modification glycol of 3-16 carbon atom.The cyclic diols that contains cis and transisomer can be used as pure along or transisomer or use as the mixture of genial transisomer.

For example, diacid residues can comprise the residue that is selected from one or more dicarboxylic acids in terephthalic acid (TPA), M-phthalic acid or its combination, diol residue comprises the residue that is selected from one or more glycol in 1,4-CHDM, neopentyl glycol, ethylene glycol and combination thereof.In one embodiment, for example, diacid residues can contain the residue of terephthalic acid (TPA) and M-phthalic acid.The concentration of terephthalic acid (TPA) in polyester is favourable higher than M-phthalic acid, and this is because the polyester of gained provides larger impact strength to described blend.For example, diacid residues can be containing the terephthalic acid residue of approximately 100 % by mole of the 60-of having an appointment and the isophthalic acid residues of 0 to approximately 40 % by mole, and diol residue can be containing having an appointment the 1,4-CHDM residue of 100 % by mole.The example of other dicarboxylic acids content comprises the terephthalic acid (TPA) of approximately 100 % by mole of about 80-and the M-phthalic acid of 0-20 % by mole, and the terephthalic acid (TPA) of approximately 100 % by mole.

Other representative polyester that can be used as thermoplastic polymer in component (i) comprises the polyester that comprises following residue: the diacid residues that (a) contains 80-100 % by mole of terephthalic acid residue, and the diol residue that contains have an appointment approximately 90 % by mole of 1,4-CHDM residues of 50-and approximately 50 % by mole of neopentyl glycol residues of about 10-; (b) diacid residues that contains 100 % by mole of terephthalic acid residues, and the diol residue that contains have an appointment approximately 40 % by mole of 1,4-CHDM residues of 10-and approximately 90 % by mole of glycol residues of 60-; (c) diacid residues that contains 100 % by mole of terephthalic acid residues, and the diol residue that contains have an appointment approximately 99 % by mole of 1,4-CHDM residues of 10-, approximately 90 % by mole of glycol residues of 0-and approximately 25 % by mole of diethylene glycol (DEG) residues of about 1-; (d) diacid residues that contains 100 % by mole of terephthalic acid residues, and the diol residue that contains have an appointment approximately 90 % by mole of 1,4-CHDM residues of 50-and approximately 50 % by mole of glycol residues of about 10-.

In another example, dicarboxylic acids can be selected from terephthalic acid (TPA) and M-phthalic acid, and glycol is selected from 1,4-CHDM and ethylene glycol.In a composition, for example, dicarboxylic acids is that terephthalic acid (TPA) and glycol are 1,4-CHDMs.In another example, diacid residues can comprise the terephthalic acid residue of at least 95 % by mole, and diol residue can comprise the glycol residue of approximately 89 % by mole of the diethylene glycol (DEG) residue of approximately 25 % by mole of the 1,4-CHDM residues of approximately 40 % by mole of about 10-, about 1-and about 35-.

If necessary, polyester can further comprise one or more of 0 to approximately 20 % by mole and has the residue of the modification diacid of 2-20 carbon atom.For example, can use 0 to approximately 30 % by mole other aromatic dicarboxylic acid with 8 to approximately 16 carbon atoms, have 8 to approximately 16 carbon atoms cycloaliphatic dicarboxylic acid, there is aliphatic dicarboxylic acid or its mixture of approximately 16 carbon atoms of about 2-.The example of modified carboxylic acid is including, but not limited to 4,4 '-biphenyl dicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 4,4 '-p-methoxybenzoic acid, trans-4, one or more in 4 '-Stilbene dicarboxylic acids, oxalic acid, malonic acid, butanedioic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid and decanedioic acid.

In another embodiment, polyester can contain the glycol residue of approximately 1 % by mole of 1,4-CHDM residue, the about 99-of approximately 99 % by mole of approximately 1-based on diol residue total mole number meter.For the 1,4-CHDM residue for polyester of the present invention, its molar ratio generally includes approximately 10 % by mole of about 1-, approximately 25 % by mole of about 1-, and approximately 40 % by mole of about 1-, 50 % by mole and larger, and 100 % by mole.In another embodiment, for example, dicarboxylic acids is Isosorbide-5-Nitrae-cyclohexane cyclohexanedimethanodibasic, and glycol is 1,4-CHDM.In another example, polyester can contain the residue of 1,4-CHDM unit and neopentyl glycol.In another example, polyester can contain the residue of 1,4-CHDM unit and TMCD.

The diol component of polyester also can be modified as at least one of 0 to approximately 20 % by mole and have the residue of the modification glycol of 3-16 carbon atom.Other scope of modification glycol is including, but not limited to 0 to approximately 10 % by mole, and is less than 5 % by mole.Modification glycol can be selected from following one or more: 1,2-propane diols, 1, ammediol, BDO, 1,5-PD, 1,6-hexylene glycol, 1,4-cyclohexanedimethanol, to penylene glycol, neopentyl glycol, polyethylene glycol, polytetramethylene glycol and 2,2,4,4-tetramethyl-1,3-cyclobutane glycol.The example of PAG comprises that molecular weight mostly is approximately 2000 polytetramethylene glycol (" PTMG ") and polyethylene glycol (" PEG ") most.Diol component for example can be with the polyethylene glycol of 0 to approximately 10 % by mole or polytetramethylene glycol modification to improve elasticity.In another example, diol residue can be containing the diethylene glycol (DEG) residue of approximately 25 % by mole of the 1,4-CHDM residue of approximately 99 % by mole of the 10-of having an appointment, the glycol residue of 0 to approximately 90 % by mole and about 1-.Based on acid or diol component meter, polyester also can contain approximately 2.0 % by mole of approximately 5 % by mole at most, common about 0.1-from thering is the residue of multifunctional branching agent of the compound deriving of at least three carboxyls and/or hydroxyl, thereby form branched polyester.The example of these compounds comprises trimellitic acid or trimellitic anhydride, 1,3,5-benzenetricarboxylic acid, 1,2,4,5-pyromellitic anhydride, trimethylolethane, trimethylolpropane, trimer acid etc.Those skilled in the art can understand final composition can by the various resins of blend or by directly in reactor copolymerization obtain.For the changeability that makes to form minimizes, the latter is favourable, but economic cause makes blend method conventionally, is that more cost is effective.

Another example of polyester is 100 % by mole of terephthalic acid residues containing based on diacid residues total amount meter, any with in following diol residue composition based on diol residue total amount meter: (i) glycol residue of approximately 95 % by mole of the 1,4-CHDM residue of approximately 5 % by mole of about 1-and about 99-; (ii) glycol residue of approximately 67 % by mole of the 1,4-CHDM residue of approximately 33 % by mole of about 29-and about 71-; (iii) glycol residue of approximately 45 % by mole of the 1,4-CHDM residue of approximately 55 % by mole of about 45-and about 55-; (iv) glycol residue of approximately 35 % by mole of the 1,4-CHDM residue of approximately 65 % by mole of about 60-and about 40-; (v) glycol residue of approximately 17 % by mole of the 1,4-CHDM residue of approximately 83 % by mole of about 79-and about 21-; (vi) the 1,4-CHDM residue of approximately 100 % by mole.

The intrinsic viscosity of polyester (I.V.) value is conventionally in the scope of the about 1.4dL/g of about 0.4-.I.V. other example of scope comprises the about 1.0dL/g of about 0.65-and the about 0.85dL/g of about 0.7-.As mentioned above, intrinsic viscosity is to use the solvent that contains 60 % by weight phenol and 40 % by weight tetrachloroethanes of 0.5g polymer/100ml to measure at 25 ℃.

Polymer of the present invention can be crystallinity, hemicrystalline or unbodied polymer.At term used herein " hemicrystalline ", represent that this polymer contains two-phase: orderly crystalline phase and unordered amorphous phase.There is the rheol polymer of hemicrystalline and show crystalline melt temperature (Tm) and glass transition temperature (Tg), and can be different from " amorphous " polymer that only shows glass transition temperature.

Polyester used is normally prepared from dicarboxylic acids and glycol in the present invention, and they are according to substantially equal ratio reaction and introduce in polyester polymers as corresponding residue.So the sour residue (100 % by mole) and the diol residue (100 % by mole) that contain basic equimolar ratio example from dicarboxylic acids of the present invention and the derivative polyester of diol residue, make the total mole number of repetitive equal 100 % by mole.So, total mole number, the total mole number of diol residue or the total mole number meter of repetitive that can be based on sour residue at molar percentage provided herein.For example, the copolyesters containing based on 30 % by mole of terephthalic acid (TPA)s of sour residue total amount meter represents that this copolyesters contains the terephthalic acid residue of 30 % by mole who accounts for 100 % by mole of sour residues.Therefore, in every 100 equimolar acid residues, there is the terephthalic acid residue of 30 moles.In another example, the copolyesters containing based on 30 % by mole of 1,4-CHDMs of diol residue total amount meter represents that this copolyesters contains the 1,4-CHDM residue of 30 % by mole that accounts for 100 % by mole of diol residue total amounts.Therefore, in every 100 moles of diol residue, there is the 1,4-CHDM residue of 30 moles.At terephthalic acid (TPA) used herein, ethylene glycol and 1, the copolyesters of 4-cyclohexanedimethanol can be called " PET " when diol component is mainly ethylene glycol, when diol component is mainly 1, during 4-cyclohexanedimethanol, can be called " PCT ", when ethylene glycol and 1, the ratio of 4-cyclohexanedimethanol is greater than at 1 o'clock can be called " PETG ", and can be called " PCTG " when the ratio of ethylene glycol and 1,4-CHDM is less than 1.

Polyester of the present invention can adopt conventional polycondensation reaction condition preparation from suitable dicarboxylic acids, ester, acid anhydrides or salt and suitable glycol or diol mixture.Therefore, the dicarboxylic acid component of polyester of the present invention can be derived from dicarboxylic acids, its corresponding ester or their mixture.The example of the ester of the dicarboxylic acids using in the present invention comprises dimethyl esters, dipropyl, diisopropyl ester, dibutyl ester and diphenyl etc.

Polyester of the present invention can be by well known to a person skilled in the art prepared by method.Polyester can be prepared by continuous, semicontinuous and batch mode of operation, and can use various types of reactors.Suitable type of reactor is for example including, but not limited to stirred tank, continuous stirred tank, slurry phase reactor, tubular reactor, scraper-type film reactor, falling film reactor or extrusion reaction device.The reaction of glycol and dicarboxylic acids can be used conventional polyester conditioned disjunction to be undertaken by melt method, can be by melt but have the polyester of enough degree of crystallinity, then by solid phase polycondensation technology, prepare.For example, when preparing polyester by ester exchange reaction, while being prepared by dicarboxylic acid component's ester-formin, reaction method can comprise two steps.In a first step, diol component and dicarboxylic acid component (for example dimethyl terephthalate (DMT)) react about 0.5-approximately 8 hours at approximately 250 ℃ of high temperature, common about 150-under the pressure of the about 414kPa gauge pressure of about 0.0kPa-(60 pounds/square inch, " psig ").Preferably, for the temperature of ester exchange reaction, be at approximately 230 ℃ of about 180-approximately 1～approximately 4 hour, simultaneously preferred pressure limit is that about 103kPa gauge pressure (15psig) is to about 276kPa gauge pressure (40psig).Then, product adds thermosetting polyester under high temperature and decompression, eliminates glycol simultaneously, and glycol is easy under these conditions volatilization and removes from system.Second step or condensation polymerization step are at high vacuum and approximately 350 ℃ of common about 230-, approximately 310 ℃ of preferred about 250-, most preferably from about continue about 0.1-approximately 6 hours at the temperature of approximately 290 ℃ of 260-or preferred about 0.2-approximately 2 hours, until obtain the polymer with the required degree of polymerization (measuring by intrinsic viscosity).Condensation polymerization step can be carried out at about 53kPa (400 holder) to the decompression in about 0.013kPa (0.1 holder) scope.In two stages, all use stir or suitable condition to guarantee enough heat transfers and the Surface Renewal of reactant mixture.The reaction rate in two stages improves by suitable catalyst, for example alkoxy titanium compound, alkali metal hydroxide and alkoxide, the salt of organic carboxyl acid, Alkyzin compound, metal oxide etc.Also can use and United States Patent (USP) 5,290, similar three stage production methods described in 631, particularly when being used the mix monomer charging of acid and ester.

In order to ensure diol component and dicarboxylic acid component's ester exchange reaction, carry out completely, sometimes wish to use with respect to 1 moles of dicarboxylic acids component the diol component of approximately 2.5 moles of about 1.05-.But the ratio that those skilled in the art can understand diol component and dicarboxylic acid component is decided by the reactor design of carrying out reaction process conventionally.

Prepare the process of polyester (from sour form of the dicarboxylic acid component) by direct ester exchange, by the mixture of dicarboxylic acids or dicarboxylic acids and the mixture of diol component or diol component, react to prepare polyester.Reaction in about 7kPa gauge pressure (1psig) to about 1379kPa gauge pressure (200psig), be preferably less than under the pressure of 689kPa gauge pressure (100psig) and carry out producing the low molecular weight polyester product that average degree of polymerization is about 1.4-approximately 10.Approximately 280 ℃ of the normally about 180-of temperature using in direct ester exchange reaction, more preferably from about 220-is approximately 270 ℃.Then this low-molecular weight polymer can pass through polycondensation polymerized.

Thermoplastic polymer of the present invention also can contain polyarylate.Polyarylate obtains by dihydric phenol and dicarboxylic acids polymerization.The example of the polyarylate that can use in the present composition, method and moulded products is United States Patent (USP) 4,598, those that describe in 130,5,034,502 and 4,374,239.Can for the preparation of the dihydric phenol of polyarylate, be for example bis-phenol, two (4-hydroxy phenyl) methane for example; 2,2-bis-(4-hydroxy phenyl) propane (" bisphenol-A "); 2,2-bis-(4-hydroxy-3-methyl phenyl) propane; 4,4-bis-(4-hydroxy phenyl) heptane; 2,2-bis-(4-hydroxyl-3,5-dichlorophenyl) propane; 2,2-bis-(4-hydroxyl-3,5-dibromo phenyl) propane; Binary phenolic ether, for example two (4-hydroxy phenyl) ether, two (the chloro-4-hydroxy phenyl of 3,5-bis-) ether; Dihydroxybiphenyl class, p for example, p '-dihydroxybiphenyl, 3,3 '-bis-is chloro-4,4 '-dihydroxybiphenyl; Dihydroxy aryl sulfone, for example two (4-hydroxy phenyl) sulfone; Two (3,5-dimethyl-4-hydroxy phenyl) sulfone; Dihydroxy benzenes class, for example resorcinol; Quinhydrones; The dihydroxy benzenes class that halo and alkyl replace, Isosorbide-5-Nitrae-dihydroxy-2 for example, 5-dichloro-benzenes, Isosorbide-5-Nitrae-dihydroxy-3-methylbenzene; With dihydroxy diphenyl sulfoxide, two (4-hydroxy phenyl) sulfoxide for example; With two (the bromo-4-hydroxy phenyl of 3,5-bis-) sulfoxide.Many other dihydric phenols also can be used, for example, be disclosed in United States Patent (USP) 2,999, in 835,3,028,365 and 3,153,008.Also suitable is the copolymer obtaining from above-mentioned dihydric phenol and halogen-containing dihydric phenol copolymerization, and halogen-containing dihydric phenol is for example 2,2-bis-(the chloro-4-hydroxy phenyl of 3,5-bis-) propane and 2,2--bis-(the bromo-4-hydroxy phenyl of 3,5-bis-) propane.Also can use two or more different dihydric phenols, or dihydric phenol and glycol, with the copolymer forming by the polyester of hydroxyl or acid blocked or with binary acid and the blend of any above-mentioned any material.Suitable dicarboxylic acids is including, but not limited to aromatic dicarboxylic acid, for example phthalic acid, M-phthalic acid, terephthalic acid (TPA), phthalic acid, o-, m-and p-phenylene oxalic acid, and polynuclear aromatic carboxylic acid, for example diphenic acid and Isosorbide-5-Nitrae-naphthalenedicarboxylic acid.

Can comprise for the other example of polyarylate of the present invention from bisphenol-A (2,2-bis-(4-hydroxy phenyl) propane) and/those polymer that terephthalic acid (TPA) (50: 50) polymerization of mixtures obtains.Some polymer obtain (from Unitika AmericaCorporation, obtaining) with trade name " U-Polymer U-100 ".Other example is based on tetramethyl bisphenol-A, 4, the polyarylate of 4 '-dihydroxy benzophenone and 5-tert-butyl group m-phthaloyl chloride.

Polyarylate of the present invention can be prepared by the reaction of any formation polyester well known in the art, and for example by aromatic dicarboxylic acid dihalide, the solution in organic solvent under agitation mixes with the alkaline aqueous solution of bis-phenol so that interfacial polymerization is carried out in these material reactions; By aromatic dicarboxylic acid dihalide, for example, under the existence of deacidification reagent (pyridine), in organic solvent, react and carry out polymerisation in solution with bis-phenol; By aromatic dicarboxylic acid diphenyl, react with bis-phenol and carry out melting (melt) polymerization; By aromatic dicarboxylic acid, dipheryl carbonate base ester, react and carry out melt polymerization with bis-phenol; By aromatic dicarboxylic acid, react and carry out melt polymerization with bisphenol diacetate; With by aromatic dicarboxylic acid, react and carry out polymerization with bisphenol diacetate.The example of preparing the method for polyarylate is disclosed in United States Patent (USP) 5,034, in 502,4,321,355 and 4,374,239.Polyarylate of the present invention has the intrinsic viscosity of the about 1.1dL/gm of about 0.5-conventionally.

In addition, polyester, Merlon and polyarylate can further contain one or more following components: antioxidant, melt strength reinforcing agent, branching agent (glycerine for example, trimellitic acid and acid anhydrides), chain extender, fire retardant, filler, plumper, dyestuff, colouring agent, pigment, antiblocking agent, flow improving agent, (resisting) impact modifying agent, antistatic additive, processing aid, demoulding additive, plasticizer, antiseize paste, stabilizing agent, wax, UV absorbent, fluorescent whitening agent, lubricant, locking agent (pinning additive), blowing agent, antistatic additive, nucleator etc.Can add colouring agent (being sometimes referred to as toner) to adjust and/or brightness to give required Natural color to polyester.Preferably, one or more processing aids that polymer blend can contain 0 to approximately 30 % by weight are to change the surface property of composition and/or to improve mobile.The representative example of processing aid comprises calcium carbonate, talcum, clay, mica, zeolite, wollastonite, kaolin, diatomite, TiO ₂, NH ₄cl, silica, calcium oxide, sodium sulphate and calcium phosphate.Can comprise and use titanium dioxide and other pigment or dyestuff with the whiteness of controlling diaphragm or produce articles colored.Antistatic additive or other coating also can be applied on product surface.

What the second component of the present composition (ii) contained at least two kinds of polyamide turns acyl amination homogeneous blend.Conventionally, homogeneous blend will contain 2 to approximately 10 kinds of different polyamide.In another example, homogeneous blend can contain 2-4 kind polyamide.According to the present invention, fusing point can be used as at least one polyamide lower than the polyamide of approximately 300 ℃.In another example, can use fusing point lower than approximately 275 ℃ and glass transition temperature the polyamide higher than approximately 25 ℃.Conventionally, the I.V. of polyamide is the about 2.0dL/g of about 0.3-, preferably 0.5dL/g at least.

For composition of the present invention, advantageously between polyamide, there is turning acyl amination to produce homogeneous blend.At term used herein, " turn acyl amination " and represent and the term implication that " to turn amidated " identical with " turning amidation ", represent a kind of method that exchanges acylamino-between two kinds of different polyamide.The amidated that turns between two or more polyamide can be by having contacted polyamide at the temperature of approximately 350 ℃ of high temperature, common about 270-.Other example that turns amidated temperature is approximately 340 ℃ of approximately 350 ℃ of about 280-and about 290-.The existence of amidated by the single glass transition temperature for blend (" Tg ") that turn between polyamide represents, by differential scanning calorimetry, (" DSC ") is used and well known to a person skilled in the art standard technique mensuration Tg value, for example ASTM method D3418.Polyamide can directly heat together at these temperature or under the thermoplastic polymer of the first component (i) exists.For example, the contact of polyamide and subsequently turn amidated can by extrude or other high temperature process of polymer composition and component thereof during the first and second component melts blend are carried out.In another example, polyamide can be together in independent vessel in heating, then with the first component melts blend.

The first of second component and the second polyamide can be selected from the polyamide of wide region.In order to mate better the refractive index of the first component, what wish (but unnecessary) is that at least one polyamide comprises aromatic moieties.In an example, it is 7000 or less partially aromatic polyamide and aliphatic polyamide that polyamide can contain number-average molecular weight.The combination of these polyamide is also included within the scope of the invention.Partially aromatic polyamide contains the amido link between at least one aromatic ring and at least one non-aromatic material.Although whole aromatic polyamides is liquid crystal liquid crystal property normally, these fusing points can be for the present invention lower than the blend of the resin of 300 ℃.When using the homogeneous blend of polyamide, aliphatic nylon reacts with the acyl amination that turns fast of aromatics or partially aromatic polyamide the refractive index that (exchange of acid amides-acid amides) allows to design by the ratio between adjusting aliphatic polyamide and aromatics or partially aromatic polyamide polyamide blend.This technology can make the thermoplastic polymer (for example one or more polyester) of refractive index with first component of homogeneous phase polyamide blend mate.About turning acyl amination reaction, can be referring to Y.Takeda etc., Polymer, 1992 the 33rd volumes, 3394 pages.

According to the present invention, second component can be two or more polyamide turn acyl amination homogeneous blend, for example select the first polyamide and the second polyamide, making difference RI (the second component)-RI (the first component) of the refractive index of second component and the first component is approximately 0.006 to approximately-0.0006.In order to mate the refractive index of the first component, advantageously the first and the second polyamide have aromatics and the aliphatic residue of different amounts.For example, second component (ii) can be a kind of homogeneous blend, and it comprises containing the first polyamide of aromatic moieties with containing the second polyamide of aliphatic residue.About diamines and the dicarboxylic acid monomer of polyamide of the present invention, term used herein " aliphatic series " represents that carboxyl or the amino of monomer do not connect by aromatic kernel.For example, adipic acid does not contain fragrant core in its main chain (chain that connects the carbon atom of hydroxy-acid group); Therefore be " aliphatic series ".By contrast, term " aromatics " represents that dicarboxylic acids or diamines contain the fragrant core in main chain, for example terephthalic acid (TPA) or Isosorbide-5-Nitrae-m-xylene diamine.The representative example of aromatic polyamides is those polyamide, its contain at least 70 % by mole containing the residue of diamines, benzene dimethylamine or containing the benzene dimethylamine mixture of m-xylene diamine for example; With maximum 30% p dimethylamine with there is the aliphatic dicarboxylic acid of 6-10 carbon atom.So, term " aliphatic series " is intended to comprise aliphatic series and cyclo-aliphatic structure, for example diamines, diacid, lactams, amino alcohol and amino carboxylic acid, it contains as the straight chain of main chain or branched chain, or the annular arrangement of composition carbon atom, these carbon atoms can be (that is, the containing carbon-to-carbon triple bond) of saturated or alkane character, undersaturated (that is, containing non-aromatic carbon-to-carbon double bond) or acetylene series.Therefore,, in description of the present invention and claims, aliphatic series is intended to comprise chain structure (being called " aliphatic series ") and the circulus (being called " cyclic aliphatic " or " alicyclic ") of straight chain and branching.But any aromatic substituent that can be connected with the main chain of aliphatic series or cycloaliphatic diol or diacid or hydroxycarboxylic acid do not got rid of in term " aliphatic series ".

The percentage by weight of first and second kinds of polyamide that exist in turning the homogeneous blend of acyl amination can be in the scope of approximately 1: 50 to approximately 50: 1, the gross weight meter based on second component.Other example of percentage by weight is approximately 1: 20 to approximately 20: 1 and approximately 1: 10 to approximately 10: 1.

The example of the polyamide that can use in homogeneous blend of the present invention comprises and contains the polyamide that one or more are selected from following residue: M-phthalic acid, terephthalic acid (TPA), cyclohexane cyclohexanedimethanodibasic, m-xylene diamine (also referred to as " m-benzene dimethylamine "), p dimethylamine's (also referred to as " p-benzene dimethylamine "), 1,3-cyclohexane (two) methyl amine, 1,4-cyclohexane (two) methyl amine, the aliphatic diacid with 6-12 carbon atom, aliphatic amino acid or the lactams with 6-12 carbon atom, have the aliphatic diamine of 4-12 carbon atom.Can use other to become known for forming diacid and the diamines of polyamide.Polyamide also can contain a small amount of trifunctional or four sense comonomers, for example polyacid and the polyamines of trimellitic anhydride, PMDA or other formation polyamide well known in the art.

The example of partially aromatic polyamide is including, but not limited to xylylene adipamide (referred to herein as " MXD6 " nylon) between poly-, poly-1,6-hexylidene terephthalamide, 1,6-hexylidene adipamide/1, benzenedicarboxamide copolymer between 6-hexylidene, 1,6-hexylidene adipamide/1,6-hexylidene terephthalamide copolymer, with benzenedicarboxamide/1 between 1,6-hexylidene, 6-hexylidene terephthalamide copolymer.In one embodiment, partially aromatic polyamide be poly-between xylylene adipamide.In one embodiment, partially aromatic polyamide can have 7000 or less number-average molecular weight.The representative example of aliphatic polyamide comprises poly-(2-Pyrrolidone) (nylon 4,6; CAS No.44,299-2); Polycaprolactam (nylon 6; CAS No.18,111-0), poly-(2-piperidones) (nylon 5; CAS No.24938-57-6); Poly-(7-aminoheptylic acid) (nylon 7; CAS No.25035-01-2); Nylon 9 (nylon 9; CAS No.25748-72-5); Poly-(the amino hendecanoic acid of 11-) (nylon 11; CAS No.25035-04-5); Poly-(12-aminolauric acid) (nylon 12; CAS No.24937-16-4); Poly-ethylidene adipamide (nylon 2,6); Polytetramethylene adipamide (nylon 4,6, CAS No.50327-22-5); Poly-1,6-hexylidene adipamide (nylon 6,6, CAS No.42,917-1), (nylon 6,9, CASNo.18,806-9) poly-1,6-hexylidene decanediamide (nylon 6,10, CAS No.9008-66-6), poly-1,6-hexylidene undecanoic amide (nylon 6,11) poly-1,6-hexylidene dodecane acid amides (nylon 6,12, CAS No.24936-74-1), poly-eight methylene adipamides (nylon 8,6); Adipic acid-decamethylene diamine copolymer (nylon 10,6, CAS No.26123-27-3), poly-decamethylene dodecane acid amides (nylon 10,12), poly-ten dimethylene adipamides (nylon 12,6); With poly-ten dimethylene decanediamides (nylon 12,8 (10)).

For example, second component (ii) can contain a kind of homogeneous blend, the first polyamide that it contains the residue that comprises m-xylene diamine and adipic acid, with the second polyamide of the residue that comprises at least one aliphatic series or cyclic aliphatic monomer, wherein aliphatic series or cyclic aliphatic monomer are select oneself diacid, pimelic acid, suberic acid, azelaic acid, decanedioic acid, heneicosanedioic acid, dodecanedioic acid, caprolactam, butyrolactam, the amino heneicosanedioic acid of 11-, M-phthalic acid and hexamethylene diamine.The first polyamide for example can comprise MXD6 nylon, and it can obtain from Mitsubishi Corporation.In another example, the second polyamide can comprise at least one and be selected from following polyamide: nylon 4, nylon 6, nylon 9, nylon 11, nylon 12, nylon 6,6, nylon 5,10, nylon 6,12, nylon 6,11, nylon 10,12; And their combination.In another example, the second polyamide can comprise nylon 6, nylon 6,6 or its blend.

Second component also can comprise single copolyamide of planting, and wherein selects the composition of monomer residue, obtains the refractive index of closely mating with the refractive index of the first component.Therefore, in another embodiment, the invention provides a kind of polymer composition, the unmixability blend that it comprises following component:

(ii) second component that comprises copolyamide;

Wherein difference RI (the second component)-RI (the first component) of the refractive index of second component (ii) and the first component (i) is approximately 0.006 to approximately-0.0006, and the percent transmission that described unmixability blend has is at least 75%, mist degree is 10% or less.For example, copolyamide can be m-xylene diamine, p dimethylamine's residue or its combination; Be selected from the residue of following monomer with at least one: terephthalic acid (TPA), M-phthalic acid, adipic acid, pimelic acid, suberic acid, azelaic acid, decanedioic acid, heneicosanedioic acid, dodecanedioic acid, caprolactam, butyrolactam, 11-amino-heneicosanedioic acid and 1,6-hexa-methylene (hexylidene) diamines.In another example, copolyamide can comprise the m-xylene diamine residue based on approximately 100 % by mole of 100 % by mole of about 15-of diamines residue total content meter, with approximately 15 % by mole of adipic acid residue based on approximately 85 % by mole of 100 % by mole of about 15-of diacid residues total content meter and about 85-be selected from one or more following aliphatic series or cycloaliphatic dicarboxylic acid's residue: pimelic acid, suberic acid, azelaic acid, decanedioic acid, heneicosanedioic acid, dodecanedioic acid and Isosorbide-5-Nitrae-cyclohexane cyclohexanedimethanodibasic.It should be understood that the various embodiments of the homogeneous blend of polyamide mentioned in this article and copolyamide can with above-mentioned any embodiment combination about polyester.

Can in the present composition, use separately or as other example of the copolyamide of the part with the homogeneous blend of another kind of polyamide including, but not limited to such copolyamide, it comprises the m-xylene diamine residue based on approximately 100 % by mole of 100 % by mole of about 15-of diamines residue total content meter, and adipic acid residue.The amount of the adipic acid residue that can exist in these copolyamides is approximately 85 % by mole of approximately 5-based on diacid residues total mole number meter normally, approximately 75 % by mole of approximately 80 % by mole of about 20-and about 25-.Remaining dicarboxylic acid residue can comprise the residue from one or more with the aliphatic dicarboxylic acid of 7-12 carbon atom, for example pimelic acid, suberic acid, azelaic acid, decanedioic acid, heneicosanedioic acid, dodecanedioic acid or Isosorbide-5-Nitrae-cyclohexane cyclohexanedimethanodibasic.In another example, polyamic acid also can comprise the residue from M-phthalic acid and terephthalic acid (TPA).

Copolyamide of the present invention also can comprise other diamines or the lactams residue except m-xylene diamine residue.For example, copolyamide can comprise at least 15 % by mole or at least about the m-xylene diamine residue of 20 % by mole, and the residue that remaining diamines residue comprises one or more aliphatic series or aromatic diamine.For example, copolyamide can comprise 1 of approximately 80 % by mole or approximately 85 % by mole, the residue of 6-hexamethylene diamine, the total mole number meter based on diamines residue.Also can use the p dimethylamine, 1 of various amounts, 3-cyclohexane two (methyl amine) or Isosorbide-5-Nitrae-cyclohexane two (methyl amine).Similarly, copolyamide can comprise for example residue of caprolactam of lactams, or the residue of the lactams based on the amino hendecanoic acid of GABA or 11-, its amount is approximately 70 % by mole of approximately 90 % by mole of about 10-or about 10-, the total mole number meter based on repetitive.In another embodiment, copolyamide of the present invention can be containing the residue from m-xylene diamine of have an appointment approximately 75 % by mole of approximately 85 % by mole of 15-, approximately 80 % by mole of about 20-or about 25-, total mole number meter based on diamines residue, and remaining diamines residue comprises the residue from one or more diamines, aliphatic diamine and particularly 1 for example, 6-hexamethylene diamine.In this embodiment, diamines residue can further contain the residue of other a small amount of diamines, and for example p dimethylamine, or cycloaliphatic diamine is following one or more for example: 1,3-cyclohexane two (methyl amine) or Isosorbide-5-Nitrae-cyclohexane two (methyl amine).In addition, replace a part of adipic acid, polyamide can optionally comprise from one or more and has the aliphatic series of 7-12 carbon atom or the residue of aromatic dicarboxylic acid, for example pimelic acid, suberic acid, azelaic acid, decanedioic acid, heneicosanedioic acid, dodecanedioic acid, 1,4-cyclohexane cyclohexanedimethanodibasic or M-phthalic acid, it can exist with the amount of approximately 85 % by mole of about 15-, optionally contains a small amount of terephthalic acid (TPA).Polyamide also can contain the residue of lactams, the residue of caprolactam for example, or the residue of the lactams based on GABA or the amino hendecanoic acid of 11-, its amount is approximately 90 % by mole of about 10-or about 10-70 % by mole, the total mole number meter based on repetitive.

In another embodiment, can comprise the residue from adipic acid of approximately 90 % by mole of about 15-according to copolyamide of the present invention, the isophthalic acid residues that remaining diacid residues comprises approximately 85 % by mole of about 10-, based on dicarboxylic acid residue total mole number meter.Other example of adipic acid and isophthalic acid residues content comprises about 20-80 % by mole, and approximately 75 % by mole of about 25-.In this embodiment, polyamide can optionally comprise and a small amount of from one or more, has the residue of the aliphatic dicarboxylic acid of 7-12 carbon atom, for example pimelic acid, suberic acid, azelaic acid, decanedioic acid, heneicosanedioic acid, dodecanedioic acid or 1,4-cyclohexane cyclohexanedimethanodibasic, optionally has a small amount of terephthalic acid (TPA).Optionally, polyamide can comprise m-xylene diamine residue.The example of m-xylene diamine residue concentration comprises approximately 80 % by mole of approximately 90 % by mole of about 15-, approximately 85 % by mole of about 20-or about 25-.Remaining residue can contain one or more aliphatic diamines, and for example 1,6-hexamethylene diamine; One or more aromatic diamines, for example p dimethylamine.Similarly, copolyamide also can comprise the residue of lactams, for example residue of caprolactam, or the residue of the lactams based on GABA or the amino hendecanoic acid of 11-, its amount is approximately 70 % by mole of approximately 90 % by mole of about 10-or about 10-, the total mole number meter based on repetitive.

In another example, copolyamide of the present invention can comprise the residue of one or more lactams, the residue of caprolactam for example, or the residue of the lactams based on GABA or the amino hendecanoic acid of 11-, its amount is approximately 60 % by mole of approximately 90 % by mole of about 10-or approximately 70 % by mole of about 10-or about 15-, the total mole number meter based on repetitive.One or more have aliphatic dicarboxylic acid (for example pimelic acid, suberic acid, azelaic acid, decanedioic acid, heneicosanedioic acid, the dodecanedioic acid or 1 of 7-12 carbon atom, 4-cyclohexane cyclohexanedimethanodibasic) residue also can exist with the amount of approximately 80 % by mole of about 20-, the total mole number meter based on repetitive.For example, copolyamide can comprise the residue from M-phthalic acid or terephthalic acid (TPA).In this embodiment, copolyamide can comprise the residue from m-xylene diamine of approximately 85 % by mole of about 15-, the total mole number meter based on diamines residue.Other example of m-xylene diamine residue content is approximately 75 % by mole of approximately 80 % by mole of about 20-and about 25-.Remaining diamines residue can comprise the residue of one or more aliphatic diamines, and for example 1,6-hexamethylene diamine.In this embodiment, diamines residue can further contain the residue of other a small amount of diamines, for example p dimethylamine, or the residue of cycloaliphatic diamine, for example, below one or more: 1,3-cyclohexane two (methyl amine) or Isosorbide-5-Nitrae-cyclohexane two (methyl amine).Optionally, can use a small amount of following one or more: p dimethylamine, 1,3-cyclohexane two (methyl amine) or Isosorbide-5-Nitrae-cyclohexane two (methyl amine).

Another embodiment of the invention is a kind of polymer composition, and it is comprised of the unmixability blend of following component substantially:

(i) the first component substantially being formed by least one thermoplastic polymer, described thermoplastic polymer is selected from polyester, Merlon, polyarylate and their homogeneous blend; With

(ii) substantially by the homogeneous phase of at least two kinds of polyamide, turn the second component that acyl amination blend forms;

Wherein difference RI (the second component)-RI (the first component) of the refractive index of second component (ii) and the first component (i) is approximately 0.006 to approximately-0.0006, and the percent transmission that described unmixability blend has is at least 75%, mist degree is 10% or less.Term used herein " substantially by ... form " represent to comprise such composition, it is unmixability blend, there are at least 2 compositing dependence Tg that measured by DSC, and have the first component that contains polyester, Merlon, polyarylate or its homogeneous blend, and the homogeneous phase that contains at least two kinds of polyamide turns the second component of acyl amination blend.In this embodiment, composition is interpreted as any component of the essence performance that does not comprise the composition that can significantly change this term indication.For example, composition can comprise other component of compatibility of mist degree %, percent transmission or the blend of the refractive index that can not change component, blend.For example, in this embodiment, eliminating is added to bulking agent, it can change compatibility and the refractive index of composition.Similarly, the second component that contains the copolyamide of preparing by described constituent monomers copolymerization will be excluded, because this copolyamide turns the different performance of acyl amination blend by being considered to have from the homogeneous phase of at least two kinds of polyamide, even if the molar percentage of monomer residue is identical.

Similarly, another embodiment of the invention is a kind of deoxidizing compositions, and it is substantially composed of the following components:

(A) unmixability blend composed of the following components substantially:

(ii) substantially by the second component that acyl amination homogeneous blend forms that turns of at least two kinds of polyamide;

(B) at least one is selected from the capable metal of the periodic table of elements 3-12 4-6 of family;

In this embodiment, composition is interpreted as any component of the essence performance that does not comprise the composition that can significantly change this term indication, the refractive index that described essence performance is for example component, the mist degree % of blend, percent transmission, the compatibility of blend or the deoxygenation performance of composition.For example, in this embodiment by the deoxygenation component acyl amination blend that turns of get rid of adding except copolyamide or polyamide, for example diene, polyethers or any easy oxidation and different described in claim organic compounds.

In the present invention polyamide used normally from dicarboxylic acids and diamines according to substantially equal ratio reaction preparation, or prepare by the ring-opening polymerisation of lactams, and introduce in polyamide polymer as corresponding residue.So the sour residue (100 % by mole) and the diamines residue (100 % by mole) that contain basic equimolar ratio example from dicarboxylic acids of the present invention and the derivative polyamide of diamines residue, make the total mole number of repetitive equal 100 % by mole.So, total mole number, the total mole number of diamines residue or the total mole number meter of repetitive that can be based on sour residue at molar percentage provided herein.For example, the polyamide or the copolyamide that contain based on 30 % by mole of terephthalic acid (TPA)s of sour residue total amount meter represent that this copolyamide contains the terephthalic acid residue of 30 % by mole who accounts for 100 % by mole of sour residues.Therefore, in every 100 equimolar acid residues, there is the terephthalic acid residue of 30 moles.In another example, the copolyamide containing based on 30 % by mole of m-xylene diamines of diamines residue total amount meter represents that this copolyamide contains the m-xylene diamine residue of 30 % by mole that accounts for 100 % by mole of diamines residues.Therefore, in every 100 moles of diamines residues, there is the m-xylene diamine residue of 30 moles.

Any method well known in the art can be for the production of polyamide.Polyamide is prepared by the melt polymerization of diacid-diamine complexe conventionally, and diacid-diamine complexe can original position (at the scene) or prepared in independent step.In either method, diacid and diamines are as parent material.Or, can use the ester-formin of diacid, preferably dimethyl esters.If use ester, reaction must be carried out at lower temperature, and common 80-120 ℃, until ester is converted to acid amides.Then this mixture is heated to polymerization temperature.The in the situation that of polycaprolactam, caprolactam or 6-aminocaprolc acid can be used as raw material, and polymerization can carry out catalysis by adding adipic acid/hexamethylene diamine salt, obtain nylon 6/66 copolymer.When using diacid-diamine complexe, this mixture is heated to melting and stirs until balance.

Molecular weight is by the proportion control of diacid-diamines.Excessive diamines produces the amino end group of higher concentration.For deoxidizing compositions, advantageously regulate diacid-diamines ratio so that amine-terminated concentration is 20 mMs/kg or less.If prepare diacid-diamine complexe in independent step, before polymerization, add excessive diamines.Polymerization can be carried out under atmospheric pressure or the pressure raising.

In order to show the gratifying transparency and low haze, it is approximately 0.006 to approximately-0.0006 refractive index that the second component of unmixability blend and the first component have difference conventionally, that is, RI (second component)-RI (the first component) is approximately 0.006 to approximately-0.0006.Other example of the difference of refractive index absolute value is approximately 0.005 to approximately-0.0006, and approximately 0.004 to approximately-0.0006, and approximately 0.003 to approximately-0.0006, and approximately 0.005 to approximately-0.0005, and approximately 0.004 to approximately-0.0005.But, it will be understood to those of skill in the art that acceptable refractive index difference depends on the composition of blend, particle diameter, refractive index, wavelength and grain structure, as Biangardi etc., Die Angew.Maromole.Chemie, described in 183,221 (1990).

Unmixability blend of the present invention has the transmissivity % being measured by ASTM method D1003 of the excellent transparency and at least 75%, and 10% or less mist degree.Other example of transmissivity % is at least 77%, at least 80% and at least 85%.Other example of the haze value that blend of the present invention is shown is 9% or less, 7% or less, 5% or less and 3% or less.For composition of the present invention, mist degree is by composition molding or casting to be become to thickness be 1/8 inch or thinner sheet or film and measure mist degree according to the method for describing in embodiment and determine.For moulded products (comprising multilayer formed article), mist degree can be by goods to be cut into thickness be 1/8 inch or thinner fritter (i.e. 1 * 1cm) and measure mist degree according to the method for describing in embodiment and determine.

The first component also can contain the homogeneous blend of one or more polymer.For example, the first component can contain the first polyester and one or more are selected from the homogeneous blend of the polymer in Merlon, the second polyester and polyarylate.Polyester can be any polyester described here.The homogeneous blend of the Merlon that for example, the first component can contain polyester and contain bisphenol-A residue.

Merlon can contain the residue bisphenol-A of approximately 90-100 % by mole based on diol residue total mole number meter, and one or more of 0 to approximately 10 % by mole have modification aliphatic diol or the dihydric phenol of 2-16 carbon atom.Representative example comprises two (4-hydroxy phenyl) methane; 2,2-bis-(4-hydroxy phenyl) propane (" bisphenol-A "); 2,2-bis-(4-hydroxy-3-methyl phenyl) propane; 4,4-bis-(4-hydroxy phenyl) heptane; 2,2-bis-(4-hydroxyl-3,5-dichlorophenyl) propane; 2,2-bis-(4-hydroxyl-3,5-dibromo phenyl) propane; Binary phenolic ether, two (4-hydroxy phenyl) ether for example, two (the chloro-4-hydroxy phenyl of 3,5-bis-) ether; Dihydroxybiphenyl, p for example, p '-dihydroxybiphenyl, 3,3 '-bis-is chloro-4,4 '-dihydroxybiphenyl; Dihydroxy aryl sulfone, for example two (4-hydroxy phenyl) sulfone; Two (3,5-dimethyl-4-hydroxy phenyl) sulfone; Dihydroxy benzenes, resorcinol for example, quinhydrones; The dihydroxy benzenes that halo and alkyl replace, Isosorbide-5-Nitrae-dihydroxy-2 for example, 5-dichloro-benzenes, Isosorbide-5-Nitrae-dihydroxy-3-methylbenzene; With dihydroxy diphenyl sulfoxide, two (4-hydroxy phenyl) sulfoxide for example; With two (the bromo-4-hydroxy phenyl of 3,5-bis-) sulfoxide.Many other dihydric phenols also can be used, for example, be disclosed in United States Patent (USP) 2,999, in 835,3,028,365 and 3,153,008.Also suitable is the copolymer obtaining from above-mentioned dihydric phenol and halogen-containing dihydric phenol copolymerization, and halogen-containing dihydric phenol is for example 2,2-bis-(the chloro-4-hydroxy phenyl of 3,5-bis-) propane and 2,2-bis-(the bromo-4-hydroxy phenyl of 3,5-bis-) propane.Also can use two or more different dihydric phenols, or dihydric phenol and glycol, with by the polyester of hydroxyl or acid blocked or the copolymer that forms with the blend of binary acid and any above-mentioned any material.Suitable dicarboxylic acids is including, but not limited to aromatic dicarboxylic acid, for example phthalic acid, M-phthalic acid, terephthalic acid (TPA), phthalic acid, o-, m-and p-phenylene oxalic acid, and polynuclear aromatic carboxylic acid, for example diphenic acid and Isosorbide-5-Nitrae-naphthalenedicarboxylic acid.

The representative example of aliphatic diol comprises ethylene glycol, propandiols, butanediol class, pentanediol class, heptandiol class, ethohexadiol class, neopentyl glycol; Alkylaryl glycol, styrene glycol for example, xylylene glycols; The dihydroxy alkyl ether of dihydric phenol, such as dihydroxy ethyl ether of bisphenol-A etc.Other example of aliphatic diol is the aliphatic dihydroxy compound of HMW, for example polyethylene glycol, polystyrene glycol, polypropylene glycol, polytetramethylene glycol, poly-sulphur glycol, polyoxyethylene alkyl aryl base ether glycol and PTMEG copolymer.The other representative example of dihydric phenol and aliphatic diol is described in United States Patent (USP) 3,030, in 335 and 3,317,466.Merlon can further contain the residue of one or more branching agents, four phenolic compounds for example, three-(4-hydroxy phenyl) ethane, pentaerythritol triacrylate and at United States Patent (USP) 6,160,082,6,022,941,5,262,511,4,474, disclosed other compound in 999 and 4,286,083.Other suitable branching agent is in following description.In another example, the bisphenol-A residue that Merlon contains at least 95 % by mole, the total mole number meter based on diol residue.

The intrinsic viscosity of the Merlon part of blend of the present invention is preferably at least about 0.3dL/g, more preferably 0.5dL/g at least.The melt flow index of the Merlon part of blend of the present invention is 1-20 preferably, more preferably 2-18, according to ASTM method D1238 the temperature of 300 ℃ with use the weight measurement of 1.2kg.

The method of preparing Merlon is well known in the art.Can use in the present invention and disclosed straight or branched Merlon is not subject to Merlon type or its production method in this article restriction or constraint.Conventionally, dihydric phenol (for example bisphenol-A) reacts in the situation that using optional monofunctional compound as chain terminating agent and using trifunctional or higher functional compound as branching agent or crosslinking agent with phosgene.The active carboxylic acid halides of simple function, difunctionality and trifunctional also can be used as and stop compound (simple function), comonomer (difunctionality) or branching agent (trifunctional or more high functionality) in the preparation of Merlon.

For example, the Merlon of blend of the present invention part can be prepared by melt polymerization well known in the art, polymerisation in solution or interfacial polymerization technology.Suitable method comprises makes carbonate source compound and glycol react the time that is enough to form Merlon under the pressure of the temperature of about 0-315 ℃ and about 0.1-760mmHg.In the present invention the operable Merlon that can obtain from business conventionally by make aromatic diol and carbonate source compound for example phosgene, dibutyl carbonate or dipheryl carbonate base ester react to obtain, thereby the carbonate unit of 100 % by mole is introduced in Merlon with together with the diol units of 100 % by mole.Other representative example of preparing the method for Merlon is described in United States Patent (USP) 5,498, in 688,5,494,992 and 5,489,665.

The blend of polyester and Merlon can be prepared by the following method: polyester and Merlon part are enough to form the time of transparent blends composition the temperature blend of about 25-350 ℃.Suitable conventional blending technology comprises melt process and solution manufacturing method.Other suitable blending technology comprises dry blend and/or extrudes.

Composition of the present invention (comprising wherein contained unmixability and homogeneous blend) can be prepared by any method well known in the art, and is used as thermoplastic composition and is used to form film and individual layer and multi-layer product.Except the various components of blend are carried out physical blending, homogeneous phase polyester blend can be prepared by the ester exchange reaction of polyester components.Similarly, the homogeneous blend of polyamide can be prepared by the acyl amination reaction that turns of polyamide component.

Melt blended method comprises is being enough to make blend at the temperature of the first component and second component partial melting by polymer, then described blend is cooled to be enough to produce the temperature of transparent blends.At term used herein " melting " including, but not limited to softening polymer only.The example of the known melt mixed method of polymer arts be described in Mixing and Compounding ofPolymers (I.Manas-Zloczower and Z.Tadmor edit, Carl Hanser Verlag publishing house, N.Y.1994) in.

Solution manufacturing method comprises the first component of suitable w/w ratio and second component is dissolved in to suitable organic solvent for example in 70/30 mixture of carrene or carrene and hexafluoroisopropanol, solution is mixed, and by precipitation blend or by evaporating solvent and from solution separated blend composition.Solution blending process is that polymer arts is known.

Melt blended method is the method for optimizing for the preparation of blend composition of the present invention.Melt blended method is more more economical and safer than using the solution methods of volatile solvent.Melt blended method is also more effective providing aspect transparent blends.Any transparent blends of the present invention that can prepare by solution blending also can be prepared by melt process.But blends more of the present invention can be prepared by melt process, but can not prepare by solution methods.It is suitable that any blend method of transparent blends of the present invention can be provided.Those skilled in the art can determine the suitable blend method for the preparation of transparent blends of the present invention.

Described the first component and the second component of composition can mix with melt form, for example, by using single screw rod or double screw extruder to carry out.They also can be prepared by blend in solution.Also can in formula, introduce other component, such as stabilizing agent, fire retardant, colouring agent, lubricant, releasing agent, impact modifying agent etc.For example, composition can mix to produce with the melt extrusion of any other composition component such as metallic catalyst, dyestuff, toner, filler etc. via the first component and second component.Said composition can be by being dry mixed the solid particle of every kind of thermoplastic polymer and polyamide component or pellet, then this mixture being carried out to melt blended formation in suitable mixing apparatus such as extruder, roll mixer etc.When polyamide turn acyl amination homogeneous blend when the second component, advantageously at the temperature that turns acyl amination reaction that can cause between polyamide, process.Conventionally, these temperature are approximately 350 ℃ of about 270-.Other example that turns acyl amination reaction temperature is approximately 340 ℃ of approximately 350 ℃ of about 280-and about 290-.Blend carries out producing the time of the unmixability blend of fine dispersion.This can easily be determined by those skilled in the art.If necessary, can be by said composition cooling and be cut into pellet for further processing, can film extrusion, sheet material, section bar and other profile member, injection moulding or compression moulding form various moulded products, maybe can form film and optionally carry out by means commonly known in the art single shaft or biaxial stretch-formed.

In unmixability blend, the amount of the first and second components can change in wide region.For example, the unmixability blend of new compositions of the present invention can contain the second component of the first component and about 95-approximately 1 % by weight of 5-approximately 99 % by weight of having an appointment, the gross weight meter based on said composition.Other non-limiting representative example of the percentage by weight of the first and second components comprises the second component of the first component and about 50-approximately 1 % by weight of about 50-approximately 99 % by weight, the first component of about 60-approximately 99 % by weight and the second component of about 40-approximately 1 % by weight, the first component of about 70-approximately 99 % by weight and the second component of about 30-approximately 1 % by weight.

The present invention also provides a kind of composition that comprises unmixability blend, and it is by comprising that following component is carried out to melt blended method to be prepared:

Wherein difference RI (the second component)-RI (the first component) of the refractive index of second component (ii) and the first component (i) is approximately 0.006 to approximately-0.0006, and the percent transmission that described unmixability blend has is at least 75%, mist degree is 10% or less.Said composition comprises the various embodiments of above-mentioned polyester, Merlon, polyarylate, homogeneous blend and polyamide and their any combination.For example, the homogeneous phase that the second component of said composition can comprise at least two kinds of polyamide turns acyl amination blend, and its transfer acyl amination reaction can be by polyamide has at high temperature been contacted, approximately 350 ℃ of normally about 270-.Other example that turns acyl amination reaction temperature is approximately 340 ℃ of approximately 350 ℃ of about 280-and about 290-.

The homogeneous blend of component (ii) can comprise containing the first polyamide of aromatic moieties with containing the second polyamide of aliphatic residue, as previously mentioned.For example, can be as the typical polyamides of the second polyamide including, but not limited to nylon 4, nylon 6, nylon 9, nylon 11, nylon 12, nylon 6,6, nylon 5,10, nylon 6,12, nylon 6,11, nylon 10,12; And their combination.Except aforementioned polyester, the first component can comprise polyester and contain the homogeneous blend of the Merlon of bisphenol-A residue.

Another aspect of the present invention is a kind of method of preparing transparent, oxygen-scavenging compositions, comprising:

(A) the first component that comprises at least one thermoplastic polymer, described thermoplastic polymer is selected from polyester, Merlon, polyarylate and their homogeneous blend;

(B) determine the refractive index of the first component;

(C) provide the second component that comprises following component:

(i) there is the copolyamide of aliphatic series and aromatic moieties mol ratio, wherein select the mol ratio of aliphatic series and aromatic moieties to be met the second component refractive index of following formula:

0.006 >=RI (second component)-RI (the first component) >=-0.0006, or

(ii) homogeneous phase of first and second kinds of polyamide turns acyl amination blend, and at least one polyamide has aromatic moieties, wherein selects the percentage by weight of first and second kinds of polyamide to be met the second component refractive index of following formula:

0.006 >=RI (second component)-RI (the first component) >=-0.0006;

Wherein RI is refractive index; With

(D) the first and second components are carried out melt blended, obtain percent transmission and be 75% and mist degree be 10% or less unmixability blend.

Method of the present invention comprises the various embodiments of above-mentioned polyester, Merlon, polyarylate, homogeneous blend, copolyamide and polyamide and their any combination.Method of the present invention comprises selects the first component, and it can be polyester, Merlon, polyarylate or their homogeneous blend.The refractive index of the first component can be used the method for well known to a person skilled in the art to determine.Second component can comprise single plant copolyamide or at least two kinds of polyamide turn acyl amination homogeneous blend, the in the situation that of copolyamide, pass through to select the suitable mixture of aromatics and aliphatic monomers, or in the situation that use the polyamide compound of the desired mixt that the homogeneous blend of polyamide contains aromatics and aliphatic residue by selection, be designed to closely mate with the refractive index of the first component.The selection of the proper ratio of monomer or polyamide can for example be determined with proofreading and correct by experiment, or in another example, by being figure by containing different amount aromatic moieties and the various polyamide of aliphatic residue or the refractive index of copolyamide, and select to obtain the aromatics of target refractive index: the mol ratio of aliphatic residue or the weight percent of polyamide are recently determined.The first and second components can be carried out melt blended.When second component contain at least two kinds of polyamide turn acyl amination homogeneous blend time, advantageously to turning acyl amination, reacting and at effective temperature, carrying out melt blended step.Typically turn acyl amination temperature range as previously mentioned.

Also can select thermoplastic polymer with the refractive index of coupling second component.Therefore, another aspect of the present invention is a kind of method of preparing transparent, oxygen-scavenging compositions, comprising:

(A) second component that selection comprises following component:

(i) there is the copolyamide of aliphatic series and aromatic moieties mol ratio,

(ii) homogeneous phase of first and second kinds of polyamide turns acyl amination blend, and wherein at least one polyamide has aromatic moieties;

(B) determine the refractive index of second component;

(C) provide the first component that comprises at least one thermoplastic polymer, described thermoplastic polymer is selected from polyester, Merlon, polyarylate and their homogeneous blend, wherein selects polyester, Merlon, polyarylate and their homogeneous blend to be met the first component refractive index of following formula:

0.006 >=RI (second component)-RI (the first component) >=-0.0006,

Wherein RI is refractive index; With

(D) the first and second components are carried out melt blended, obtain percent transmission at least 75% and mist degree be 10% or less unmixability blend.Should be understood that in addition, said method also comprises any combination of the various embodiments of above-mentioned polyester, Merlon, polyarylate, homogeneous blend, copolyamide, polyamide.

In an example, can illustrate thermoplastic polymer blend be take and obtained second component and the first component that the difference of refractive index is approximately 0.006 to approximately-0.0006 with particular reference to polycarbonate/polyester blend.For example, make can be by regulating the refractive index that recently designs Merlon/PCTG blend (RI) of Merlon/PCTG for the Merlon of bisphenol-A and the complete miscibility of PCTG.By regulating the ratio of Merlon, the refractive index of the present invention's the first component can the refractive index in the second component with comprising polyamide barrier polymer differs in approximately 0.006 to approximately-0.0006 scope.For example, if transparent blends forms as follows: 1) carry out blend by polymer-modified with the blend that contains Merlon and polyester portion that be pre-existing in, or 2) by polymer-modified, before introducing polyester portion, carry out blend with Merlon part, or 3) by polymer-modified, before introducing Merlon part, carry out blend with polyester portion, or 4) polymer-modified, Merlon part were mixed together with polyester portion before blend, can determine that polymer is the suitable polymer-modified of above-mentioned homogeneous phase polyester/polycarbonate blend.

Transparent blends of the present invention can still carry out modification by polymer-modified introducing is produced to performance blend, and this can not must be transparent.For example, polyamide is for example from the nylon 6 of DuPont, 6, PEI is for example from the ULTEM PEI of General Electric, polyphenylene oxide for example gathers (2, 6-dimethyl phenylate) or polyphenyl ether/styrene blend for example from the NORYL resin of General Electric, polyester, polyphenylene sulfide, polyphenylene sulfide/sulfone, polyestercarbonate is LEXAN 3250 polyestercarbonates (General Electric) for example, the Merlon from General Electric except LEXAN Merlon, polyarylate is ARDELD100 polyarylate (Amoco) for example, polysulfones, polysulfones ether, polyether-ketone or aromatic dihydroxy compound, can be as blend modifier to improve performance or to reduce flammable.Some aromatic dihydroxy compounds for the preparation of these polymer are disclosed in United States Patent (USP) 3,030,335 and United States Patent (USP) 3,317,466.

The copolyamide of the present composition or polyamide homogeneous blend can be used as barrier polymer, and can therefore improve the barrier property of whole composition.Term used herein " barrier polymer " represents to have the polymer of one or more following performances: (1) water permeability is 2gm-mils/100 square inch/24 hour or less, according to ASTM method F1249 in 38 ℃ of mensuration; (2) oxygen permeability is 5cc (STP)-mils/100 square inch/24 hour-atm or less, according to ASTM method D3985 in 23 ℃ of mensuration; Or (3) carbon dioxide permeability is 25cc (STP)-mils/100 square inch/24 hour-atm or less, according to ASTM method D1434 in 23 ℃ of mensuration.

Barrier property can improve by introducing metallic catalyst, obtains the deoxidizing compositions of one or more polyamide reactions in a kind of energy catalytic oxygen and composition.So, the present invention further provides a kind of deoxidizing compositions, it comprises:

(A) the unmixability blend that comprises following component:

(ii) second component that turns acyl amination homogeneous blend that comprises at least two kinds of polyamide;

(B) at least one is selected from the capable metal of the periodic table of elements 3-12 4-6 of family.

Except the homogeneous blend of one or more polyamide, deoxidizing compositions of the present invention also can comprise above-mentioned single copolyamide of planting of describing for other embodiment of the present invention.Therefore, the present invention also provides a kind of deoxidizing compositions, and it comprises:

(A) the unmixability blend that comprises following component:

(ii) second component that comprises copolyamide;

Should be understood that in addition, deoxidizing compositions also comprises any combination of the various embodiments of above-mentioned the first and second components, polyester, Merlon, polyarylate, homogeneous blend, copolyamide and polyamide.

Deoxidizing compositions of the present invention can comprise and is selected from a kind of metal that the periodic table of elements 3-12 4-6 of family is capable, as 1984 editions periodic table of elements of Internation Union of Pure and Applied Chemistry.Typical oxidation catalyst comprises transition-metal catalyst, and it can change between at least two kinds of oxidation state.The example of operable metal comprises copper, nickel, cobalt, iron, manganese and its combination.Can use the effectively catalyst of any amount of catalytic deoxidation, but the consumption of metal is the about 1000ppm of about 10-conventionally.Other scope of metal concentration comprises the about 750ppm of about 50ppm-, the about 500ppm of about 10-, the about 500ppm of about 50-, and about 50-300ppm, the gross weight meter based on deoxidizing compositions.Metal is usually used as metal element itself, as the metal complex that contains organic ligand, used as oxide or as slaine.The example of the counter ion counterionsl gegenions of slaine is including, but not limited to chlorion, acetate, acetylacetone,2,4-pentanedione acid group, stearate radical, palm acid group, 2 ethyl hexanoic acid root, neodecanoic acid root, sad or cycloalkanes acid group and their mixture.Slaine can be also from aggressiveness, uses in this case polymeric counter-ions.These are well known in the art from aggressiveness.

In an example, metallic catalyst is cobalt or the compound that contains cobalt, for example cobalt salt.Cobalt can in+2 or+3 oxidation state.Other example of metallic catalyst is rhodium and the copper in+2 oxidation state in+2 oxidation state.Metal can add with the form of salt, usually used as carboxylate, and for example cobalt octoate, cobalt acetate or new cobalt decanoate.The amount recording is gross weight based on blend polymer for adding metal in composition but not its compound weight is measured.At cobalt as metal in the situation that, consumption is 50ppm at least normally, or 60ppm at least, or 75ppm at least, or 100ppm at least, or 125ppm at least.Catalyst can be separately or in carrier (for example liquid or wax) join in the equipment of extruder or other article of manufacture, or can the concentrate with polyamide polymer, with the concentrate of polyester polymers or with the concentrate of unmixability blend in add.Carrier can be can or can not be with the first and second component reaction, and can use volatility or nonvolatile vehicle liquid.Metallic catalyst can be during the preparation of deoxidizing compositions at various point with add by various blending methods.Useful especially approach is the later stage in the preparation of final blend composition to make polyamide together with transition metal, even to the final melt step before forming goods, makes can not causing too early except oxygen activity of polyamide evening.In some cases, for example, when cobalt is used as transition metal, preferably during the first and second component blend, adds cobalt, rather than for example during preparing thermoplastic polymer, add.

In one embodiment, for example, the first component of deoxidizing compositions can contain the polyester of any combination with above-mentioned monomer residue.For example, polyester can contain (a) diacid residues, its contain based at least 80 % by mole of diacid residues total amount meter be selected from terephthalic acid (TPA), M-phthalic acid, naphthalenedicarboxylic acid and 1, the residue of at least one dicarboxylic acids in 4-cyclohexane cyclohexanedimethanodibasic, and at least one of 0 to approximately 20 % by mole has the residue of the modification dicarboxylic acids of 2-20 carbon atom; (b) diol residue, it contains and is selected from ethylene glycol, 1 based at least 80 % by mole of diol residue total mole number meters, 4-cyclohexanedimethanol, neopentyl glycol, diethylene glycol (DEG), 1, ammediol, BDO and 2,2,4,4-tetramethyl-1, the residue of at least one glycol in 3-cyclobutane glycol, and at least one of 0 to approximately 20 % by mole has the residue of the modification glycol of 3-16 carbon atom.In another example, diacid residues can comprise the terephthalic acid residue of about 60-100 % by mole and the isophthalic acid residues of 0 to approximately 40 % by mole, and diol residue can comprise the 1,4-CHDM residue of approximately 100 % by mole.In another example, diacid residues can contain the terephthalic acid residue of approximately 100 % by mole based on diacid residues total mole number meter.Can comprise as other object lesson of the polyester of the first component the polyester containing following residue: (i) terephthalic acid residue of approximately 100 % by mole of about 80-and Yue the neopentyl glycol residue of approximately 50 % by mole of the 1,4-CHDM residue of approximately 90 % by mole of 50-and about 10-; (ii) terephthalic acid residue of approximately 100 % by mole and the Yue glycol residue of approximately 90 % by mole of the 1,4-CHDM of approximately 40 % by mole of 10-and about 60-; (iii) terephthalic acid residue of approximately 100 % by mole and Yue the diethylene glycol (DEG) residue of approximately 25 % by mole of the glycol residue of approximately 90 % by mole of 1,4-CHDM, the 0-of approximately 99 % by mole of 10-and about 1-.Polyester also can further comprise at least one of based on diacid residues total amount meter approximately 0.1-2 % by mole and be selected from the residue of the branching agent in above-mentioned trimellitic acid, trimellitic anhydride and PMDA.

The first component also can contain the homogeneous blend of at least one polyester and at least one Merlon.The Merlon that can use in these homogeneous blends is being described above.

Turn acyl amination homogeneous blend or copolyamide and can contain any above-mentioned polyamide, for example various nylon.But, the residue that advantageously copolyamide in deoxidizing compositions or polyamide homogeneous blend contain m-xylene diamine, p dimethylamine or its combination.For example, second component can contain homogeneous blend, and described homogeneous blend comprises following component: contain the first polyamide of m-xylene diamine residue and adipic acid residue, and contain the second polyamide of nylon 6, nylon 6,6 or its blend.As another example, this homogeneous blend can be in unmixability blend with containing polyester with there is first combination of components of homogeneous blend of the Merlon of bisphenol-A residue.For optimum deoxygenation performance, also wish that the homogeneous blend of copolyamide or polyamide contains 20 mMs/kg or free amine group still less.The concentration of free amine group can be determined by the technology of well known to a person skilled in the art, for example, by titration.

In another example, the copolyamide that deoxidizing compositions contains m-xylene diamine adipate ester.Compare with the composition that only contains m-xylene diamine adipate ester homopolymers, the use of Modifer adipate ester (wherein a part of adipic acid residue or a part of m-xylene diamine residue or the two a part are replaced by other residue) has obtained having the deoxidizing compositions of improved deoxygenation performance.Other polyamide barrier polymer also can be as a part for deoxidizing compositions as described herein.

The above-mentioned present composition can be for the production of moulded products, for example sheet material, film, pipe, precast body, bottle or section bar.These goods can for example be extruded by well known to a person skilled in the art that any method forms, calendering, thermoforming, blowing, extrusion-blown modling, injection moulding, compression molding, casting, drawing-off, tentering or foaming.

For example, composition of the present invention can be by well known to a person skilled in the art that any technology makes moulded products, for example film.The formation of film can realize by melt extrusion, as United States Patent (USP) 4,880, described in 592; Or by compression moulding, as United States Patent (USP) 4,427, described in 614; Or by any other suitable method.For example, film can be produced by known casting films, blown film and Extrusion Coating technology, and Extrusion Coating technology comprises and being expressed on base material.This base material also can comprise tack coat.The film of producing by melt curtain coating or blowing can be used adhesive hot adhesion or be sealed on base material.Said composition can be made single or multiple lift film by technology well known in the art.For example, single or multiple lift film can be produced by known casting films, blown film and Extrusion Coating technology, and Extrusion Coating technology comprises and being expressed on base material.Representative base material comprises film, sheet material, weaves and supatex fabric.The single or multiple lift film of producing by melt curtain coating or blowing can be used adhesive hot adhesion or be sealed on base material.

For example, said composition can be used conventional film blowing device to form film.Film-forming apparatus can be in this area, to be called those of " blown film " equipment, comprises the annular die head for the film that froths, and makes composition be forced through this die head and forms film " bubble "." bubble " finally subsides and forms film.

Said composition also can be for forming moulded products by extrusion-blown modling and injection drawing blow.Shooting Technique is softening by copolyamide or homogeneous phase polyamide blend in the cylinder of heating, in melting, it is under high pressure expelled in the mould of sealing, and mold cools down is curing to cause, and from the mould molding precast body of being hit by a bullet out.Moulding compound is also highly suitable for producing precast body and subsequently these precast body reheatstretch blows is become to have the final doleiform shape of desired properties.The precast body of injection moulding is heated at the proper orientation temperature within the scope of 100-150 ℃, then carries out stretch-blow.First a kind of rear method comprise by mechanical device hot precast body stretched (for example, by stretching with core rod plug-in unit) along axial direction, be then blown into pressure-air (the highest 500psi) thus in circumferential (hoop) direction, stretching.By this way, make the blow molded bottle of biaxial orientation.Typical blowing is than in 5/1 to 15/1 scope.

The excellent transparency of the present composition and low haze make it possible to prepare transparent moulded products in the situation that introduce leftover pieces polymer or " abrasive again " of significant quantity.At term used herein " abrasive again ", be interpreted as to there is the generally accepted implication in this area, namely from product forming process, reclaim and grind to form more short grained leftover pieces polymer.Conventionally, then abrasive sells as leftover pieces, and for introducing moulded products, wherein the transparency of these goods has nothing to do to its application.The bottle and the film that for specific moulded products, for example in packaging applications, use, low haze and high transparent are important features.The production itself of these goods, particularly multi-layer product produces a large amount of leftover pieces polymer, conventionally owing to forming the mist degree of unacceptable degree, can not return to product forming process again.Because the tight coupling of the first and second components aspect refractive index can be produced from composition of the present invention the transparent moulded products with low haze comprising abrasive again.

So another aspect of the present invention is a kind of method that forms moulded products, comprising:

(A) following component is carried out melt blended:

Wherein difference RI (the second component)-RI (the first component) of the refractive index of second component (ii) and the first component (i) is approximately 0.006 to approximately-0.0006, and the percent transmission that described unmixability blend has is at least 75%, mist degree is 10% or less;

(B) form moulded products;

(E) optionally, leftover pieces polymer composition is dried; With

(F) by polymer again abrasive with the first and second components (i) in step (A) with (ii), mix.

Therefore, the inventive method allow by leftover pieces polymer again abrasive introduce in moulded products, keep low haze and high transparent simultaneously.Should be further understood that, said method comprises the various embodiments of above-mentioned the first and second components, polyester, Merlon, polyarylate, homogeneous blend, copolyamide, polyamide, deoxidizing compositions and its any combination.

For example, as mentioned above, the unmixability blend forming from the first and second components can further comprise and is selected from least one metal that the periodic table of elements 3-12 4-6 of family is capable.The example of metal comprises copper, nickel, cobalt, iron, manganese and its combination.The described metal of the amount of the metal about 500ppm of normally about 10-(weight), the gross weight meter based on moulded products.Preferred metal is cobalt.

The moulded products of the inventive method can form by well known in the art and previously described method.For example, moulded products can be by extruding, calendering, thermoforming, blowing, extrusion-blown modling, injection moulding, compression molding, casting, drawing-off, tentering or foaming produce.

Although the inventive method can be for the production of any moulded products, the representative example that can produce is sheet material, film, precast body, pipe and bottle.These goods can have individual layer or contain 2 to approximately 7 layers.Abrasive can be introduced in one or more layers of these layers again, and these layers can be containing the abrasive again of the 50-100 % by weight of having an appointment, the weighing scale based on one or more layers.Other example of the content of abrasive again that can exist in moulded products is 5 to approximately 95 % by weight, about 10-60 % by weight, about 15-approximately 50 % by weight, and about 20-approximately 30 % by weight.

Moulded products can comprise multilayer, and wherein one or more layers comprises the first and second components as unmixability blend, or wherein the first component and second component are present in independent layer.Therefore, another aspect of the present invention is a kind of moulded products of multilayer, and it comprises:

(ii) second layer that turns acyl amination homogeneous blend that comprises at least two kinds of polyamide;

Wherein difference RI (the second layer)-RI (ground floor) of the refractive index of the second layer (ii) and ground floor (i) is approximately 0.006 to approximately-0.0006, and the percent transmission that described moulded products has is at least 75%, mist degree is 10% or less.This moulded products can comprise various embodiments and its any combination of above-mentioned the first and second components, polyester, Merlon, polyarylate, homogeneous blend, copolyamide, polyamide, deoxidizing compositions, moulded products.

Multilayer formed article can be by extruding, calendering, thermoforming, blowing, extrusion-blown modling, injection moulding, compression molding, casting, drawing-off, tentering or foaming are produced.Because tight coupling between the refractive index of first and second layers, so the abrasive again of the mixture that multi-layer product can further contain first and second layers, it can be introduced in the combination of ground floor, the second layer or first and second layers.Conventionally, then abrasive is approximately 5-approximately 60 % by weight of multi-layer product, the gross weight meter based on goods.Other example of the percentage by weight of abrasive in moulded products is approximately 10-approximately 40 % by weight and about 20-approximately 30 % by weight of goods gross weight again.

According to desired use, multi-layer product can have 2 to approximately 7 layers.For example, as mentioned above, moulded products can be sheet material, film, pipe, bottle or precast body.Complicated layer structure is also possible.For example, moulded products can have the layer structure being represented by ABA, ABABA, ABCBA or ACBCA, its middle level A comprises ground floor (i), layer B comprises the second layer (ii), layer C comprises abrasive again, polyester or Merlon or its combination that described abrasive again contains leftover pieces first and second layers of (i) and mixture (ii), by the rear recovery of consumption, obtained.According to the composition of abrasive again, advantageously the difference RI of the refractive index of layer B and layer C (layer B)-RI (layer C) is approximately 0.006 to approximately-0.0006, thereby keeps the transparency of goods and introduce the ability of abrasive again.

In another embodiment, layer A can comprise the second layer (ii), layer B can comprise ground floor (i), polyester or Merlon or its combination that layer C can comprise leftover pieces first and second layers of (i) and mixture (ii), by the rear recovery of consumption, be obtained.

In addition, the second layer of novel multi-layer goods of the present invention (ii) can further contain and is selected from least one metal that the periodic table of elements 3-12 4-6 of family is capable.The example of metal comprises copper, nickel, cobalt, iron, manganese and its combination.The described metal of the amount of the metal about 500ppm of normally about 10-(weight), the gross weight meter based on moulded products.Preferred metal is cobalt.

In another embodiment, multilayer formed article of the present invention can further comprise at least one additional layer, and it is containing the abrasive again of 50-approximately 100 % by weight of having an appointment, the gross weight meter based on this layer.The additional layer that contains again abrasive can further contain and is selected from least one metal that the periodic table of elements 3-12 4-6 of family is capable.The example of metal comprises copper, nickel, cobalt, iron, manganese and its combination.The described metal of the amount of the metal about 500ppm of normally about 10-(weight), the gross weight meter based on moulded products.Preferred metal is cobalt.

As mentioned above, this multilayer formed article can comprise the various embodiments of above-mentioned moulded products, thermoplastic polymer, polyamide, unmixability blend, homogeneous blend and deoxidizing compositions.For example, at least one thermoplastic polymer can comprise straight or branched polyester, it contains and is selected from terephthalic acid (TPA), M-phthalic acid, naphthalenedicarboxylic acid and 1 based at least 80 % by mole of diacid residues total amount meters, the residue of at least one dicarboxylic acids in 4-cyclohexane cyclohexanedimethanodibasic, and at least one of 0 to approximately 20 % by mole has the residue of the modification dicarboxylic acids of 2-20 carbon atom; (b) diol residue, it contains and is selected from ethylene glycol, 1 based at least 80 % by mole of diol residue total mole number meters, 4-cyclohexanedimethanol, neopentyl glycol, diethylene glycol (DEG), 1, ammediol, BDO and 2,2,4,4-tetramethyl-1, the residue of at least one glycol in 3-cyclobutane glycol, and at least one of 0 to approximately 20 % by mole has the residue of the modification glycol of 3-16 carbon atom; Contain homogeneous blend with one or more barrier polymer, this homogeneous blend contains containing the first polyamide of m-xylene diamine residue and adipic acid residue with containing the second polyamide of nylon 6, nylon 6,6 or its blend.For example, thermoplastic polymer can contain branched polyester.In another example, thermoplastic polymer further contains polyester and contains the homogeneous blend of the Merlon of bisphenol-A residue.

Multilayer formed article of the present invention can be by well known to a person skilled in the art that any method produces.For example, moulded products can form by any conventional art that is used to form film, comprises lamination, extrusion laminate, injection, stretch-blow and coextrusion blowing altogether, and can illustrate with particular reference to the typical method of preparing multilayer film by coextrusion.For example, the first and second components and any optional layer are added in the feed hopper of similarity number object extruder, and each extruder is processed the material for one or more layers.Conventionally, for composition of the present invention, before extruding and during, the first and second components are heated to the temperature of about Tg+100 ℃ to about Tg+300 ℃ separately, wherein Tg is first or the glass transition temperature of second component, by differential scanning calorimetry, measures.Melting charge stream from each extruder is added in many times of single co-extrusion outlet molds.In the time of in mouth mould, these layers intersect and combine, and then from mouth mould, as single polymeric material multilayer film, take out.After leaving mouthful mould, film curtain coating, to the casting roller of first controlled temperature, through first roller, then arrives on the casting roller of second controlled temperature, and this roller is conventionally low than the temperature of first roller.The roller of controlled temperature has been controlled the cooldown rate of film after leaving mouthful mould to a great extent.In another method, film-forming apparatus can be to be called in the prior art those of film blowing device, and comprises the many times of annular die heads for the film that froths, and composition is forced through this die head and forms film bubble.Bubble finally subsides and forms film.The coextrusion method that is used to form film and laminate film is also known.Or each layer can first form sheet material, then under heat and pressure, in the situation that being with or without intermediary adhesive layer, be laminated together.

The transparency of the present composition and low haze also make it possible in the situation that introduce the leftover pieces polymer of significant quantity or the transparent moulded products that " abrasive again " prepares multilayer.So the present invention also provides a kind of method that forms the moulded products of multilayer, comprising:

(ii) second component is heated to Tg+100 ℃ of about second component to the temperature of Tg+300 ℃ of about second component, what wherein second component comprised copolyamide or at least two kinds of polyamide turns acyl amination homogeneous blend;

(iii) in minute other layer, form the moulded products with the first and second components;

(iv) reclaim the leftover pieces of the first and second components;

(vi) optionally, abrasive is dried again; With

(vii) first component, second component or its mixture of abrasive with step (i) and (ii) mixes again;

Wherein difference RI (the second component)-RI (the first component) of the refractive index of second component (ii) and the first component (i) is approximately 0.006 to approximately-0.0006, and the percent transmission that described moulded products has is at least 75%, mist degree is 10% or less.The method can comprise various embodiments and its any combination of above-mentioned the first and second components, polyester, Merlon, polyarylate, homogeneous blend, copolyamide, polyamide, deoxidizing compositions, moulded products, product molding method.

The inventive method allows the abrasive again of significant quantity to introduce in moulded products, keeps low haze and high transparent simultaneously.Abrasive is generally comprised within product molding process as the step (i) of leftover pieces generation and the mixture of the first and second components (ii) again, but can use any polymeric material, as long as the refractive index of its refractive index and second component differs approximately 0.006 to approximately-0.0006.The abrasive again of the inventive method can merge with the first component, the second component of step (ii) or the combination of the first and second components of step (i).Abrasive can be approximately 5-approximately 60 % by weight of moulded products again, the gross weight meter based on moulded products.Other representative example of the content of abrasive again in moulded products of the present invention is approximately 10-approximately 40 % by weight of moulded products and approximately 20-approximately 30 % by weight of moulded products.

According to desired use, multi-layer product of the present invention can have 2 to approximately 7 layers.For example, as mentioned above, multilayer formed article can be sheet material, film, pipe, bottle or precast body.Complicated layer structure is also possible.For example, moulded products can have the layer structure being represented by ABA, ABABA, ABCBA or ACBCA, the first component that its middle level A comprises step (i), the second component that layer B comprises step (ii), layer C comprises abrasive again, and described abrasive again contains from the mixture of step (i) and the first and second components of leftover pieces (ii), from polyester or Merlon or its combination of reclaiming after consumption.According to the composition of abrasive again, advantageously the difference RI of the refractive index of layer B and layer C (layer B)-RI (layer C) is approximately 0.006 to approximately-0.0006, thereby keeps the transparency of goods and introduce the ability of abrasive again.

In another embodiment, layer A can comprise the second component of step (ii), the first component that layer B comprises step (i), layer C comprises step (i) and the first and second component mixtures of leftover pieces (ii), by after consuming, reclaims polyester or Merlon or its combination obtaining.

In addition, the second component of the step of novel multi-layer goods of the present invention (ii) can further contain and is selected from least one metal that the periodic table of elements 3-12 4-6 of family is capable.The example of operable metal comprises copper, nickel, cobalt, iron, manganese and its combination.The described metal of the amount of the metal about 500ppm of normally about 10-(weight), the gross weight meter based on moulded products.Preferred metal is cobalt.

In another embodiment, the step of the inventive method (iii) may further include and forms at least one additional layer, and it is containing the abrasive again of 50-approximately 100 % by weight of having an appointment, the gross weight meter based on this layer.The additional layer that contains again abrasive can further contain and is selected from least one metal that the periodic table of elements 3-12 4-6 of family is capable.The example of metal comprises copper, nickel, cobalt, iron, manganese and its combination.The described metal of the amount of the metal about 500ppm of normally about 10-(weight), the gross weight meter based on moulded products.Preferred metal is cobalt.

As mentioned above, this multilayer formed article can comprise the various embodiments of above-mentioned moulded products, thermoplastic polymer, polyamide, unmixability blend, homogeneous blend and deoxidizing compositions.For example, at least one thermoplastic polymer can comprise polyester, it contains and is selected from terephthalic acid (TPA), M-phthalic acid, naphthalenedicarboxylic acid and 1 based at least 80 % by mole of diacid residues total amount meters, the residue of at least one dicarboxylic acids in 4-cyclohexane cyclohexanedimethanodibasic, and at least one of 0 to approximately 20 % by mole has the residue of the modification dicarboxylic acids of 2-20 carbon atom; (b) diol residue, it contains and is selected from ethylene glycol, 1 based at least 80 % by mole of diol residue total amount meters, 4-cyclohexanedimethanol, neopentyl glycol, diethylene glycol (DEG), 1, ammediol, BDO and 2,2,4,4-tetramethyl-1, the residue of at least one glycol in 3-cyclobutane glycol, and at least one of 0 to approximately 20 % by mole has the residue of the modification glycol of 3-16 carbon atom; Contain a kind of homogeneous blend with one or more barrier polymer, this homogeneous blend contains containing the first polyamide of m-xylene diamine residue and adipic acid residue with containing the second polyamide of nylon 6, nylon 6,6 or its blend.For example, thermoplastic polymer can contain branched polyester.In another example, thermoplastic polymer further contains polyester and contains the homogeneous blend of the Merlon of bisphenol-A residue.

Another embodiment of the invention is a kind of method that forms multilayer formed article, comprising:

(A) the first component is heated to the Tg+100 ℃ of temperature of Tg+300 ℃ to the approximately first component of the approximately first component, wherein said the first component contains (i) at least one polyester that contains following residue: (a) diacid residues, contains the terephthalic acid residue at least about 95 % by mole based on diacid residues total amount meter; (b) diol residue, contains the residue that is selected from least one glycol in ethylene glycol and 1,4-CHDM at least about 95 % by mole based on diol residue total mole number meter; (ii) at least one Merlon that contains bisphenol-A residue; Or (iii) their homogeneous blend;

(B) second component is heated to the Tg+100 ℃ of temperature of Tg+300 ℃ to about second component of about second component, wherein second component comprises a kind of acyl amination homogeneous blend that turns, it comprises: the polyamide that contains diamines and diacid residues, and this polyamide contains m-xylene diamine residue and the adipic acid residue based on approximately 100 % by mole of diacid residues total amount meters based on approximately 100 % by mole of diamines residue total amount meters; Be selected from the polyamide of nylon 6 and nylon 6,6 with at least one;

(C) in minute other layer, form the moulded products with the first and second polymer compositions;

(D) reclaim the leftover pieces of the first and second components;

(E) leftover pieces of the first and second components are ground to prepare abrasive again;

(F) optionally, abrasive is dried again; With

(G) first component, second component or its mixture of abrasive with step (A) and (B) mixes again;

Wherein difference RI (the second component)-RI (the first component) of the refractive index of the first component of the second component of step (B) and step (A) is approximately 0.006 to approximately-0.0006, and the percent transmission that described moulded products has is at least 75%, mist degree is 10% or less.The method can comprise various embodiments and its any combination of above-mentioned the first and second components, polyester, Merlon, polyarylate, homogeneous blend, copolyamide, polyamide, deoxidizing compositions, moulded products, product molding method.

As mentioned above, then abrasive can comprise the first and second components (i) and mixture (ii), and can merge with the combination of the first component (i), second component (ii) or the first and second components.Abrasive can be approximately 5-approximately 60 % by weight of moulded products again, the gross weight meter based on moulded products.Other representative example of the content of abrasive again in moulded products of the present invention comprises approximately 10-approximately 40 % by weight of moulded products and approximately 20-approximately 30 % by weight of moulded products.

The polyester of the inventive method can comprise containing the diacid residues at least about 95 % by mole of terephthalic acid residues, and can have the glycol composition of certain limit.For example, polyester can comprise diol residue, the glycol residue that its 1,4-CHDM residue containing approximately 5 % by mole of the 1-of having an appointment and about 99-are approximately 95 % by mole.Other example forming for the glycol of the polyester of the inventive method including, but not limited to: (i) containing the diol residue of have an appointment approximately 33 % by mole of 1,4-CHDM residues of 29-and approximately 67 % by mole of glycol residues of about 71-; (ii) contain the diol residue of have an appointment approximately 55 % by mole of 1,4-CHDM residues of 45-and approximately 45 % by mole of glycol residues of about 55-; (iii) contain the diol residue of have an appointment approximately 65 % by mole of 1,4-CHDM residues of 60-and approximately 35 % by mole of glycol residues of about 40-; (iv) contain the diol residue of have an appointment approximately 83 % by mole of 1,4-CHDM residues of 79-and approximately 17 % by mole of glycol residues of about 21-; (v) contain the diol residue of the 100 % by mole of 1,4-CHDM residues of having an appointment.Polyester can further comprise the residue that is selected from least one branching agent in trimellitic acid, trimellitic anhydride and PMDA of about 0.1-2 % by mole, the total amount meter based on diacid residues.

In another embodiment, thermoplastic polymer can further comprise polyester and containing the homogeneous blend of the Merlon of bisphenol-A residue.Every kind of polyester and Merlon can be straight or brancheds.

In addition, the second component in the step of novel method of the present invention (ii) can further contain and is selected from least one metal that the periodic table of elements 3-12 4-6 of family is capable.The example of operable metal comprises copper, nickel, cobalt, iron, manganese and its combination.The described metal of the amount of the metal about 500ppm of normally about 10-(weight), the gross weight meter based on moulded products.Preferred metal is cobalt.

In another embodiment, the step of the inventive method (C) may further include and forms at least one additional layer, and it is containing the abrasive again of 50-approximately 100 % by weight of having an appointment, the gross weight meter based on this layer.The additional layer that contains again abrasive can further contain and is selected from least one metal that the periodic table of elements 3-12 4-6 of family is capable.The example of metal comprises copper, nickel, cobalt, iron, manganese and its combination.The described metal of the amount of the metal about 500ppm of normally about 10-(weight), the gross weight meter based on moulded products.Preferred metal is cobalt.

Moulded products of the present invention can further be orientated by stretching, and this can improve the barrier property of goods.As mentioned above, can wish in other conventional additives or polymer-modified introducing polymer composition of the present invention.For example, can add antioxidant, light and heat stabilizing agent, dyestuff, antistatic additive, lubricant, anticorrisive agent, processing aid, antiseize paste, antiblocking agent, pigment, fire retardant, blowing agent etc.Can use more than a kind of additive.Additive can be used with the amount of any hope, but is conventionally no more than approximately 20 % by weight of moulded products gross weight, is preferably no more than 10 % by weight.

Polymer composition, deoxidizing compositions and moulded products prepared therefrom also can contain maximum approximately 30 % by weight, be preferably less than approximately 20 % by weight from the derivative particular die pellet of at least one layered silicate material to improve their barrier property.Described small pieces pellet can be with at least one ammonium compounds modification.The amount of described small pieces pellet can be determined by measure the residual ash of polymer-small pieces pellet composition when processing according to ASTM D5630-94.The improvement of barrier properties for gases improves along with the increase of described small pieces pellet concentration in composite conventionally.Although be low to moderate the described small pieces pellet of approximately 0.01 % by weight, can improve barrier property (especially when fine dispersion and sequence), but preferably have the composition at least about small pieces pellet described in 0.5 % by weight, this is because they are presented at the required improvement effect of gas permeability aspect.

The dense agglomerate of the normally described small pieces pellet of layered silicate material, they are together tightly packed as the card.Small pieces pellet of the present invention has and is less than the thickness of about 2mm and the diameter of the about 5000nm of about 10-.For the object of the invention, measure only for small pieces pellet, rather than ammonium compounds or any dispersing aid that other may use and processing compound.Suitable small pieces pellet comes from layered silicate material, and it is free flowing powder normally, has the cation exchange capacity (CEC) of the about 3meq/g of about 0.3-, the about 1.5meq/g of preferred about 0.8-.Suitable layered silicate material for example comprises mica type stratiform phyllosilicate, comprises clay, smectic type clay, montmorillonite sodium, hectorite sodium, bentonite, nontronite, beidellite, volonsloite, talcum powder, sauconite, magadite, kenyaite, synthetic li-montmorillonite etc.The clay of this character can be from comprising that the various companies of Southern Clay Products and Nanocor Inc. obtain.Most preferred small pieces pellet is derivative for bentonite sodium or montmorillonite sodium.These clays can obtain as Wyoming type montmorillonite in the U.S., and other place in the world comprises the Kunipia clay obtaining from Kunimine IndustriesInc..

Layered silicate material processes to improve the dispersion in polymer composition conventionally.Many useful clay treatment are well known in the art, these process also can be in layered silicate material be introduced to the present composition before, afterwards or during carry out, and do not depart from scope of the present invention.The example of useful processing is including, but not limited to the processing of carrying out with silane compound, swelling agent, polymer and oligomer, dispersing aid, organic cation salt and its combination.

With the example of the useful processing of silane compound, being included in those disclosed in international publication WO93/11190 processes.Useful silane compound comprises (3-glycidoxy propyl group) trimethoxy silane, 2-methoxyl group (polyoxyethylene) propyl group heptamethyltrisiloxane, octadecyl dimethyl (3-trimethoxy-silylpropyl) ammonium chloride etc.

With the example of the useful processing of swelling agent, comprise oligomer well known in the art.For the treatment of the polymer of clay and the representative example of oligomer, comprise United States Patent (USP) 5,552,469 and 5,578,672 those disclosed.Many dispersing aiies are known, comprise the material of wide region, comprise water, alcohol, ketone, aldehyde, chlorinated solvent, hydrocarbon solvent, arsol etc. or its combination.

Embodiment

General description: further describe the present invention by following examples.The glass transition temperature of polyester, polyamide and blend (Tg) is used TA Instruments2920 differential scanning calorimeter (DSC) to measure by ASTM method D3418, and sweep speed is 20 ℃/min.By ASTM method D648, measure heat deflection temperature, according to ASTM method D256, measure breach (izod) impact strength.According to ASTM method D790, measure flexural property.According to ASTM method D638 in 23 ℃ of tensile properties of measuring blends.In 60/40 (wt/wt) phenol/tetrachloroethanes with the concentration of 0.5g/100mL in 25 ℃ of intrinsic viscosities of measuring polyester.Glycol content in the polyester portion of these blends by proton magnetic resonance (PMR) spectrum ( ¹h NMR) measure.The compatibility of blend is measured by the means of differential scanning calorimetry of press mold and moulded work.

Haze value is used HunterLab UltraScan Sphere 8000 colorimeters (by Hunter AssociatesLaboratory Inc. by ASTM method D1003 (% mist degree=100 * diffuse transmissivity/total transmittance), Reston, VA., produce) adopt Hunter ' s Universal Software (3.8 editions) to measure.The correction of instrument and operation are carried out according to HunterLab user's manual.Diffuse transmissivity obtains by ligh trap being placed on to the opposite side of the whole spheroid of sample part, thus the path of removing direct light.Only measure the light that is greater than 2.5 degree scatterings.Total transmittance comprises to be measured directly through the light of sample and the off-axis light that is arrived sensor by sample scattering.Sample is placed on to the exit position of ball, making can scattering from the off-axis light of whole balls inside.Transparency is by range estimation and haze measurement.For blend of the present invention and various composition, mist degree and percent transmission are by composition to be formed to sheet material, film or thickness be 1/8 inch or less plate and measure mist degree according to said procedure and measure.For moulded products, comprise multilayer formed article, mist degree and percent transmission are by being 1/8 inch or less goods are cut into small pieces (i.e. 1 * 1cm) and measure mist degree according to said procedure and measure by thickness.

Refractive index is at Metricon Prism Coupler for 633nm ^tM2010 type refractometers (being obtained by Metricon Inc.) are measured, record value be 3 orthogonal directions (extrude or draw direction, laterally and thickness direction) mean value of the upper refractive index of measuring.Alignment films is produced (for the producer) on the long film tensilometer of TM, wherein the sample of press mold, blown film or extruded film is carried out to single shaft or biaxial stretch-formed.Upper two stretching rods of rod that the operation of film tensilometer is based on hydro powered are with the movement in rectangular direction each other.There is fixing stretching rod on the stretching rod opposite of moving at each.These are paired relatively moves and fixing stretching rod (four of junctional membrane sample edges thereon) forms rectangular two axles each other, sample is stretched to four times or seven times of original size according to any draw ratio along these axles, this depends on machine used.Sample is placed in the fixture on machine, and heating before stretching if necessary.The output valve of this equipment is that stress is to the elongation rate data under experimental temperature (if necessary) and stretched film.

The oxygen permeability of film is used Ox-Tran Oxygen Permeation Instruments (by MOCON, Inc., Minneapoils, MN. production) to measure.Oxygen permeability is by the known area of film in experiment, film thickness, calculate along the oxygen partial pressure stable state transmissivity poor and that measure of film.In the situation that show the initiatively sample of deoxygenation, the flow of measurement is not completely in stable state, and this is because transmissivity can change over time and lentamente along with deoxygenation reaction efficiency.But, in these cases, oxygen permeability is considered to be in infiltration conventionally measure during in pseudostationary state.In the active oxygen scavenger sample comprising in following examples, elimination efficiency is obviously changes little or not variation during measuring, and calculates permeability from the pseudostationary state transmissivity of measuring.

Comparative example 1-12: the copolyesters of listing in table 1 is prepared by terephthalic acid (TPA), ethylene glycol and 1,4-CHDM (CHDM).CHDM amount in polyester is listed in table 1.Embodiment F contains 100% CHDM (0% ethylene glycol), and the acid moieties of 26 % by mole is the M-phthalic acid that replaces terephthalic acid (TPA).

Table 1

Polyester	CHDM in polyester (% by mole)	Tg	The refractive index of polyester
				A	1.5	81	1.5708
B	31	83	1.5644
				C	50	84	1.5593
C	62	86	1.5573
				E	81	91	1.5547
F	100	88	1.5519

Copolyesters and MXD6 6121 polyamide (contain 100 % by mole of meta-xylenes and 100 % by mole of adipic acids, from Mitsubishi Corporation, obtain) are 70 ℃ of dried overnight.MXD6 pocket type (bag) blend of every kind of these copolyesters and 1,3 and 5 % by weight, and add 90rpm following Temperature Setting (℃) 1.5 inches of single screw extrusion machines of Sterling in, form blend.

Region 1	Region 2	Region 3	Region 4	Region 5
					240	250	260	260	260

Blend, in 70 ℃ of dried overnight, is then injection molded into 4 square plates of 1/8 inch on Toyo 90 injection machines in 270 ℃.The refractive index of MXD6 is measured as 1.5824.The haze value of gained and deduct the results are shown in table 2 of polyester refractive index from nylon refractive index:

Table 2

Embodiment 13-24,27-29,31-32,34-36,38 and comparative example 25-26,30,33,36-37 and 39: using nylon 6 (from DuPont as 7335F obtains) and MXD6 (6121 grades) at 120 ℃, be dried 48 hours, and carry out pocket type blend according to various ratios.Then polyamide pocket type blend is added the setting in following condition of 90rpm (℃) 1.5 inches of single screw extrusion machines of Sterling in, form the blend that homogeneous phase turns acyl amination, by exist single compositing dependence Tg value to prove for every kind of blend.Tg value is listed in table 3.

Region 1	Region 2	Region 3	Region 4	Region 5
					250	270	300	300	300

The part that turns acyl amination blend of nylon or MXD6, in 120 ℃ of dried overnight, is then injection molded into the sample of 1/8 inch or at 240 ℃ of films that are extruded into 15 mil thick in 240 ℃ on Toyo 90 injection machines.These films are prepared by following expressing technique: extruder used is conventional 2.54cm diameter Killian extruder, and (length: ratio diameter) is 24: 1 is equipped with that to have compression ratio be 3: 1 and reverse the feed worm of maddock mixing section to L: D.Conventional feed zone is for the rack-style mouth mould to conventional 15.24cm diameter by melt Conveying.Two roller casting films downstack structures are used for melt quenching.Then these films stretch in each direction in 95 ℃ on TM-Long 4x.The performance of these films before stretching is listed in table 3, and the performance after stretching is listed in table 3A.It should be noted, the oxygen permeability at table in 3A under 30 ℃ and 50% relative humidity with 100% oxygen as detection gasmetry.

Film properties before table 3-stretches

Film properties after table 3A-stretches

In order to obtain embodiment listed in table 4 and comparative example, the part that turns acyl amination blend or MXD6,70-120 ℃ of dried overnight, is then mixed with the polyester of table 1.Polyester is 70-120 ℃ of dried overnight.By these polyester in table 1 separately with table 3 in 10 % by weight selected turn acyl amination blend or MXD6 blend, and add 90rpm following Temperature Setting (℃) 1.5 inches of single screw extrusion machines of Sterling in, form unmixability blend.

Region 1	Region 2	Region 3	Region 4	Region 5
					240	260	280	280	280

These blends, 70 ℃ of dried overnight, are then injection molded into 4 square plates of 1/8 inch on Toyo 90 injection machines in 270 ℃.The haze value of gained and deduct the results are shown in table 4 of polyester refractive index from nylon refractive index.

In order to obtain embodiment 38 and comparative example C-39, by from embodiment in table 3 20 turn acyl amination blend 70 ℃ of dried overnight, then with table 1 in polyester A or C carry out pocket type blend.These polyester are also 70-120 ℃ of dried overnight.Then these pocket type blends are injection molded into 4 square plates of 1/8 inch on Toyo 90 injection machines in 270 ℃.The haze value of gained and deduct the results are shown in table 4 of polyester refractive index from the refractive index of MXD6 or blend of nylon.

Table 4-has the polyester blend of homogeneous phase MXD6/ nylon 6 Blends

Embodiment 40, in this prediction embodiment, use the synthetic route of the polyamide obtain having suitable refractive index to replace the method for the two kinds of polyamide of blend in above-described embodiment 13-24.Any method known in the art can be for the production of these direct synthetic polyamide.These polyamide are prepared by diacid-diamine complexes by melt polymerization conventionally, and the latter can original position prepare or prepare in independent step.In either method, diacid and diamines are as raw material.Or, can use the ester-formin of diacid, preferably dimethyl esters.If use ester, reaction must be carried out at a lower temperature, and 80-120 ℃ normally, until ester is converted to acid amides.Then this mixture is heated to polymerization temperature.For this prediction embodiment, synthetic polyamide is poly-sub-meta-xylene base heptanedioyl amine, and it is synthetic with the pimelic acid as diacid by the m-xylene diamine as diamines.This polyamide is then according to the copolyesters A blend in the table 1 of disclosed method and 90 % by weight in embodiment 25-39.The difference of estimating the refractive index between these copolyesters A and poly-sub-meta-xylene base heptanedioyl amine is 0.0034, and estimates it is transparent.The blend of estimating gained has the haze value that is less than 10% and the transmissivity that is greater than 75%.

Embodiment 42-43 and 47-49 and comparative example 41,44-46 and 50-53.The monofilm of blend and deoxidizing compositions: according to the mode that provides described in above-described embodiment 13-24 and in table 5, prepare several MXD6/N6 and turn acyl amination blend.In table 5, listed refractive index value is to measure on these turn 15 mil film of acyl amination blend according to the mode described in above-described embodiment 13-24.These of 3 % by weight or 5 % by weight turn the pre-blend of acyl amination MXD6/N6 or MXD6 and according to table 6, carry out pocket type blend from several copolyesters of table 1.These granular blends, then 60-70 ℃ of dried overnight, are then added in 95rpm and 1.0 inches of single screw extrusion machines of the Killian under table 7 temp. displaying function, thereby by unmixability blend, are formed the film of nominal 30 mil thick.All films that contain pure MXD6 have the haze value that is greater than 10%.Those films that wherein refractive index of blend of nylon and the refractive index of corresponding polyester are mated in 0.006 to-0.0006 scope are transparent (mist degree≤10%).

The homogeneous blend of table 5MXD6-nylon 6

In order to prepare deoxidizing compositions, the concentrate that contains new cobalt decanoate is added in two kinds of these films.This concentrate is prepared as follows.C type polyester and new cobalt decanoate (are usingd to the form of lozenge as Cobalt Ten-Cem ^tM22.5% supply, from OMG Corp.) different feeds add in 57mm double screw extruder, and carry out melt blended at the barrel set point of approximately 235 ℃.The polymer of melting is discharged from extruder with the form of the line material with approximately 0.08 inch diameter, and water quenching, is cut into the pellet of approximately 0.125 inchage.Polyester: polyamide: the ratio of concentrate (weight ratio) is 93: 5: 1.5, and the concentration of cobalt metal in this concentrate makes this ratio obtain the cobalt of about 140-150ppm in final blend film.The sample that contains cobalt shows excellent deoxygenation ability.These samples are placed a week after extruding on Ox-Tran permeability apparatus, and the average apparent permeability having under these conditions in 6 months is 0.15cc (STP) * mil * 100in ²/ sky/atm.

The result of table 6-30 mil monofilm

^*be placed on instrument uses air to record as upstream detection gas under 23 ℃ and about 60-80% relative humidity apparent permeability after upper 15 day (every kind of average two films of composition, and every kind of film is measured 3 permeability)

The abrasive again of embodiment 56 and comparative example 54-55-multilayer film: multilayer film by MXD6 or turn acyl amination MXD6/30 % by weight N6 blend " X " 4 mil thickness layer around the polyester C layer of two-layer 15 mil thick of coextrusion prepare.This is called " ABA " structure, and wherein " A " layer is outer, and " B " layer is internal layer.Killian 1 " extruder is for extruding skin from polyester C at the temperature of 265 ℃.0.75 " Killian extruder for extruding internal layer from MXD6 with under the temperature of 275 ℃ from turning acyl amination MXD6/30 % by weight N6 blend " X " at the temperature of 285 ℃.In order to simulate these multilayer films as the recycling of abrasive in single layer structure again, then these multilayer films are ground and be dry mixed according to 50/50 ratio with other polyester C pellet.Be dry mixed thing then 70 ℃ dry, and 1 " in the temperature of 240 ℃, be extruded into the film of 20 mils on Killian extruder.Haze value is listed in table 7.The film of coextrusion all has the haze value that is less than 2%.But, when these films grind and during with pure polyester " C " blend again, contain C/MXD6 again the haze value of the film of grinding and mixing thing be increased to higher than 10%.It is transparent that the film that contains " C/X " abrasive keeps.

Table 7

Embodiment and comparative example 57 and 58.Multilayer film bonding: ABA film by MXD6 or turn acyl amination MXD6/30 % by weight N6 blend " X " 4 mil thickness layer around the polyester C layer of two-layer 15 mil thick of coextrusion prepare.In turning acyl amination blend, nylon 6 used is Zytel 7301 in this embodiment.Killian 1 " extruder is outer for extrude polyester C at the temperature of 265 ℃.0.75 " Killian extruder for extruding internal layer at the temperature shown in table 8.Turn acyl amination MXD6/30 % by weight N6 blend " X " and demonstrate the better cohesive to polyester C than MXD6.In addition,, when internal layer melt temperature is elevated to 285 ℃ from 280 ℃, turns acyl amination MXD6/30 % by weight N6 blend the cohesive of polyester C is improved.The cohesive of MXD6 does not demonstrate any temperature dependency.

Table 8

The transparent article of multilayer and production method thereof

The cross reference of related application

Invention field

Background of invention

Summary of the invention

Wherein the difference of the refractive index of second component (ii) and the first component (i) is that RI (second component)-RI (the first component) is approximately 0.006 to approximately-0.0006, and the percent transmission that described blend has is at least 75%, mist degree is 10% or less.

(ii) second component that comprises copolyamide;

Another aspect of the present invention is a kind ofly by comprising, following component to be carried out to polymer composition prepared by the method for melt blending:

(A) the unmixability blend that comprises following component:

Wherein difference RI (the second component)-RI (the first component) of the refractive index of second component (ii) and the first component (i) is approximately 0.006 to approximately-0.0006, and the percent transmission that described blend has is at least 75%, mist degree is 10% or less; With

(A) following component is carried out melt blended:

Wherein the first component (i) and second component (ii) form unmixability blend, difference RI (the second component)-RI (the first component) of the refractive index of second component (ii) and the first component (i) is approximately 0.006 to approximately-0.0006, and the percent transmission that described blend has is at least 75%, mist degree is 10% or less;

(B) form moulded products;

(E) optionally, leftover pieces polymer composition is dried; With

(iv) reclaim the leftover pieces of the first and second components;

(vi) optionally, abrasive is dried again; With

Wherein difference RI (the second component)-RI (the first component) of the refractive index of the second component in step (ii) and the first component in step (i) is approximately 0.006 to approximately-0.0006, and the percent transmission that described blend has is at least 75%, mist degree is 10% or less.Described abrasive again can be introduced into first or the second layer in, and can account for approximately 5-approximately 60 % by weight of these goods.

Detailed description of the present invention

The polymer composition with high transparent and excellent barrier properties can be from a kind of unmixability blend preparation, the homogeneous phase that described unmixability blend comprises one or more thermoplastic polymers and at least two kinds of polyamide turns acyl amination blend, and wherein the difference of the refractive index between polyamide blend and thermoplastic polymer is approximately 0.006 to approximately-0.0006.The percent transmission that described blend has is at least 75%, and mist degree is 10% or less.In general embodiment, the invention provides a kind of polymer composition, the unmixability blend that it comprises following component:

Wherein difference RI (the second component)-RI (the first component) of the refractive index of second component (ii) and the first component (i) is approximately 0.006 to approximately-0.0006, and the percent transmission that described blend has is at least 75%, mist degree is 10% or less.Thermoplastic polymer and polyamide can be selected from various polymer.Can by select second component polyamide ratio or by the thermoplastic polymer blend of the first component is formed to the refractive index that homogeneous blend regulates second component and the first component, obtain approximately 0.006 to approximately-0.0006 refractive index difference.New compositions of the present invention can be for the production of having one or more layers moulded products, for example sheet material, film, pipe, bottle and section bar.Moulded products can be by extruding, calendering, thermoforming, blowing, extrusion-blown modling, injection moulding, compression molding, casting, drawing-off, tentering or foaming are produced.Can produce multi-layer product, wherein unmixability blend is present in one or more layers, or the first and second components are in different layers.Because the refractive index difference of the first and second components is little, so the moulded products of being produced by the present composition can be introduced the abrasive again of significant quantity and keep the good transparency.The transparency of these moulded products that make and barrier property make them be used in particular for packing purposes.

the material of selling, and can be from Bayer Inc with trade name

the material of selling.

At term used herein " polyarylate ", it is the polyester of preparing by the polycondensation reaction of one or more difunctionality dicarboxylic acids and one or more dihydric phenols.For example, typical aromatic dicarboxylic acid is terephthalic acid (TPA) and M-phthalic acid, and typical aromatics dihydric phenol is bisphenol-A and quinhydrones.

At term used herein " mist degree % ", represent to use HunterLab UltraScan Sphere 8000 colorimeters (by Hunter Associates LaboratoryInc., to be manufactured according to ASTM method D1003, Reston, Va) haze value (mist degree %=100 * diffused transmission/total transmission) that adopts Hunter ' s Universal Software (3.8 editions) to measure.The method of measuring refractive index provides in an embodiment.For composition of the present invention, mist degree is by composition molding or casting to be become to thickness be 1/8 inch or less sheet or film and measure mist degree according to the operation of describing in embodiment and measure.For moulded products, comprise multilayer formed article, mist degree can be by goods to be cut into thickness be 1/8 inch or less fritter (that is, 1 * 1cm) and measure mist degree according to the operation of describing in embodiment and measure.

Thermoplastic polymer of the present invention also can contain polyarylate.Polyarylate obtains by dihydric phenol and dicarboxylic acids polymerization.The example of the polyarylate that can use in the present composition, method and moulded products is United States Patent (USP) 4,598, those that describe in 130,5,034,502 and 4,374,239.Can for the preparation of the dihydric phenol of polyarylate, be for example bis-phenol, two (4-hydroxy phenyl) methane for example; 2,2-bis-(4-hydroxy phenyl) propane (" bisphenol-A "); 2,2-bis-(4-hydroxy-3-methyl phenyl) propane; 4,4-bis-(4-hydroxy phenyl) heptane; 2,2-bis-(4-hydroxyl-3,5-dichlorophenyl) propane; 2,2-bis-(4-hydroxyl-3,5-dibromo phenyl) propane; Binary phenolic ether, for example two (4-hydroxy phenyl) ether, two (the chloro-4-hydroxy phenyl of 3,5-bis-) ether; Dihydroxybiphenyl class, p for example, p '-dihydroxybiphenyl, 3,3 '-bis-is chloro-4,4 '-dihydroxybiphenyl; Dihydroxy aryl sulfone, for example two (4-hydroxy phenyl) sulfone; Two (3,5-dimethyl-4-hydroxy phenyl) sulfone; Dihydroxy benzenes class, for example resorcinol; Quinhydrones; The dihydroxy benzenes class that halo and alkyl replace, Isosorbide-5-Nitrae-dihydroxy-2 for example, 5-dichloro-benzenes, Isosorbide-5-Nitrae-dihydroxy-3-methylbenzene; With dihydroxy diphenyl sulfoxide, two (4-hydroxy phenyl) sulfoxide for example; With two (the bromo-4-hydroxy phenyl of 3,5-bis-) sulfoxide.Many other dihydric phenols also can be used, for example, be disclosed in United States Patent (USP) 2,999, in 835,3,028,365 and 3,153,008.Also suitable is the copolymer obtaining from above-mentioned dihydric phenol and halogen-containing dihydric phenol copolymerization, and halogen-containing dihydric phenol is for example 2,2-bis-(the chloro-4-hydroxy phenyl of 3,5-bis-) propane and 2,2-bis-(the bromo-4-hydroxy phenyl of 3,5-bis-) propane.Also can use two or more different dihydric phenols, or dihydric phenol and glycol, with the copolymer forming by the polyester of hydroxyl or acid blocked or with binary acid and the blend of any above-mentioned any material.Suitable dicarboxylic acids is including, but not limited to aromatic dicarboxylic acid, for example phthalic acid, M-phthalic acid, terephthalic acid (TPA), phthalic acid, o-, m-and p-phenylene oxalic acid, and polynuclear aromatic carboxylic acid, for example diphenic acid and Isosorbide-5-Nitrae-naphthalenedicarboxylic acid.

(ii) second component that comprises copolyamide;

Wherein difference RI (the second component)-RI (the first component) of the refractive index of second component (ii) and the first component (i) is approximately 0.006 to approximately-0.0006, and the percent transmission that described blend has is at least 75%, mist degree is 10% or less.For example, copolyamide can be m-xylene diamine, p dimethylamine's residue or its combination; Be selected from the residue of following monomer with at least one: terephthalic acid (TPA), M-phthalic acid, adipic acid, pimelic acid, suberic acid, azelaic acid, decanedioic acid, heneicosanedioic acid, dodecanedioic acid, caprolactam, butyrolactam, 11-amino-heneicosanedioic acid and 1,6-hexa-methylene (hexylidene) diamines.In another example, copolyamide can comprise the m-xylene diamine residue based on approximately 100 % by mole of 100 % by mole of about 15-of diamines residue total content meter, with approximately 15 % by mole of adipic acid residue based on approximately 85 % by mole of 100 % by mole of about 15-of diacid residues total content meter and about 85-be selected from one or more following aliphatic series or cycloaliphatic dicarboxylic acid's residue: pimelic acid, suberic acid, azelaic acid, decanedioic acid, heneicosanedioic acid, dodecanedioic acid and Isosorbide-5-Nitrae-cyclohexane cyclohexanedimethanodibasic.It should be understood that the various embodiments of the homogeneous blend of polyamide mentioned in this article and copolyamide can with above-mentioned any embodiment combination about polyester.

Wherein difference RI (the second component)-RI (the first component) of the refractive index of second component (ii) and the first component (i) is approximately 0.006 to approximately-0.0006, and the percent transmission that described blend has is at least 75%, mist degree is 10% or less.Term used herein " substantially by ... form " represent to comprise such composition, it is unmixability blend, there are at least 2 compositing dependence Tg that measured by DSC, and have the first component that contains polyester, Merlon, polyarylate or its homogeneous blend, and the homogeneous phase that contains at least two kinds of polyamide turns the second component of acyl amination blend.In this embodiment, composition is interpreted as any component of the essence performance that does not comprise the composition that can significantly change this term indication.For example, composition can comprise other component of compatibility of mist degree %, percent transmission or the blend of the refractive index that can not change component, blend.For example, in this embodiment, eliminating is added to bulking agent, it can change compatibility and the refractive index of composition.Similarly, the second component that contains the copolyamide of preparing by described constituent monomers copolymerization will be excluded, because this copolyamide turns the different performance of acyl amination blend by being considered to have from the homogeneous phase of at least two kinds of polyamide, even if the molar percentage of monomer residue is identical.

(A) unmixability blend composed of the following components substantially:

Wherein the first component and second component have absolute value and differ 0.008 or less refractive index, and moulded products has at least 75% transmissivity, and mist degree is 10% or less.In this embodiment, composition is interpreted as any component of the essence performance that does not comprise the composition that can significantly change this term indication, the refractive index that described essence performance is for example component, the mist degree % of blend, percent transmission, the compatibility of blend or the deoxygenation performance of composition.For example, in this embodiment by the deoxygenation component acyl amination blend that turns of get rid of adding except copolyamide or polyamide, for example diene, polyethers or any easy oxidation and different described in claim organic compounds.

The present invention also provides a kind of composition, and it is by carrying out melt blended preparation by following component:

Wherein difference RI (the second component)-RI (the first component) of the refractive index of second component (ii) and the first component (i) is approximately 0.006 to approximately-0.0006, and the percent transmission that described blend has is at least 75%, mist degree is 10% or less.Said composition comprises the various embodiments of above-mentioned polyester, Merlon, polyarylate, homogeneous blend and polyamide and their any combination.For example, the homogeneous phase that the second component of said composition can comprise at least two kinds of polyamide turns acyl amination blend, and its transfer acyl amination reaction can be by polyamide has at high temperature been contacted, approximately 350 ℃ of normally about 270-.Other example that turns acyl amination reaction temperature is approximately 340 ℃ of approximately 350 ℃ of about 280-and about 290-.

(B) determine the refractive index of the first component;

(C) provide the second component that comprises following component:

0.006 >=RI (second component)-RI (the first component) >=-0.0006, or

0.006 >=RI (second component)-RI (the first component) >=-0.0006;

Wherein RI is refractive index; With

(D) the first and second components are carried out melt blended, obtain percent transmission and be 75% and mist degree be 10% or less blend.

(A) second component that selection comprises following component:

(B) determine the refractive index of second component;

0.006 >=RI (second component)-RI (the first component) >=-0.0006,

Wherein RI is refractive index; With

(D) the first and second components are carried out melt blended, obtain percent transmission at least 75% and mist degree be 10% or less blend.Should be understood that in addition, said method also comprises any combination of the various embodiments of above-mentioned polyester, Merlon, polyarylate, homogeneous blend, copolyamide, polyamide.

Transparent blends of the present invention can still carry out modification by polymer-modified introducing is produced to performance blend, and this can not must be transparent.For example, polyamide is for example from the nylon 6 of DuPont, 6, PEI is for example from the ULTEM PEI of General Electric, polyphenylene oxide for example gathers (2, 6-dimethyl phenylate) or polyphenyl ether/styrene blend for example from the NORYL resin of General Electric, polyester, polyphenylene sulfide, polyphenylene sulfide/sulfone, polyestercarbonate is LEXAN 3250 polyestercarbonates (General E1ectric) for example, the Merlon from General Electric except LEXAN Merlon, polyarylate is ARDELD100 polyarylate (Amoco) for example, polysulfones, polysulfones ether, polyether-ketone or aromatic dihydroxy compound, can be as blend modifier to improve performance or to reduce flammable.Some aromatic dihydroxy compounds for the preparation of these polymer are disclosed in United States Patent (USP) 3,030,335 and United States Patent (USP) 3,317,466.

(A) the unmixability blend that comprises following component:

(ii) second component that comprises copolyamide;

(A) following component is carried out melt blended:

Wherein difference RI (the second component)-RI (the first component) of the refractive index of second component (ii) and the first component (i) is approximately 0.006 to approximately-0.0006, and the percent transmission that described blend has is at least 75%, mist degree is 10% or less;

(B) form moulded products;

(E) optionally, leftover pieces polymer composition is dried; With

(iv) reclaim the leftover pieces of the first and second components;

(vi) optionally, abrasive is dried again; With

Wherein difference RI (the second component)-RI (the first component) of the refractive index of second component (ii) and the first component (i) is approximately 0.006 to approximately-0.0006, and the percent transmission that described blend has is at least 75%, mist degree is 10% or less.The method can comprise various embodiments and its any combination of above-mentioned the first and second components, polyester, Merlon, polyarylate, homogeneous blend, copolyamide, polyamide, deoxidizing compositions, moulded products, product molding method.

(A) the first component is heated to the Tg+100 ℃ of temperature of Tg+300 ℃ to about polyester or Merlon of about polyester or Merlon, wherein said the first component contains (i) at least one polyester that contains following residue: (a) diacid residues, contains the terephthalic acid residue at least about 95 % by mole based on diacid residues total amount meter; (b) diol residue, contains the residue that is selected from least one glycol in ethylene glycol and 1,4-CHDM at least about 95 % by mole based on diol residue total mole number meter; (ii) at least one Merlon that contains bisphenol-A residue; Or (iii) their homogeneous blend;

(B) second component is heated to the temperature of approximately 290 ℃, wherein second component comprises a kind of acyl amination homogeneous blend that turns, it comprises: the polyamide that contains diamines and diacid residues, and this polyamide contains m-xylene diamine residue and the adipic acid residue based on approximately 100 % by mole of diacid residues total amount meters based on approximately 100 % by mole of diamines residue total amount meters; Be selected from the polyamide of nylon 6 and nylon 6,6 with at least one;

(D) reclaim the leftover pieces of the first and second components;

(F) optionally, abrasive is dried again; With

Wherein difference RI (the second component)-RI (the first component) of the refractive index of the first component of the second component of step (B) and step (A) is approximately 0.006 to approximately-0.0006, and the percent transmission that described blend has is at least 75%, mist degree is 10% or less.The method can comprise various embodiments and its any combination of above-mentioned the first and second components, polyester, Merlon, polyarylate, homogeneous blend, copolyamide, polyamide, deoxidizing compositions, moulded products, product molding method.

Embodiment

Haze value is used HunterLab UltraScan Sphere 8000 colorimeters (by Hunter AssociatesLaboratory Inc. by ASTM method D1003 (% mist degree=100 * diffuse transmissivity/total transmittance), Reston, VA., produce) adopt Hunter ' s Universal Software (3.8 editions) to measure.The correction of instrument and operation are carried out according to HunterLab user's manual.Diffuse transmissivity (% transmittance) obtains by ligh trap being placed on to the opposite side of the whole spheroid of sample part, thus the path of removing direct light.Only measure the light that is greater than 2.5 degree scatterings.Total transmittance comprises to be measured directly through the light of sample and the off-axis light that is arrived sensor by sample scattering.Sample is placed on to the exit position of ball, making can scattering from the off-axis light of whole balls inside.Transparency is by range estimation and haze measurement.For blend of the present invention and various composition, mist degree is by composition to be formed to sheet material, film or thickness be 1/8 inch or less plate and measure mist degree according to said procedure and measure.For moulded products, comprise multilayer formed article, mist degree is by being 1/8 inch or less goods are cut into small pieces (i.e. 1 * 1cm) and measure mist degree according to said procedure and measure by thickness.

The oxygen permeability of film is used Ox-Tran Oxygen Permeation Instruments (by MOCON, Inc., Minneapoils, MN production) to measure.Oxygen permeability is by the known area of film in experiment, film thickness, calculate along the oxygen partial pressure stable state transmissivity poor and that measure of film.In the situation that show the initiatively sample of deoxygenation, the flow of measurement is not completely in stable state, and this is because transmissivity can change over time and lentamente along with deoxygenation reaction efficiency.But, in these cases, oxygen permeability is considered to be in infiltration conventionally measure during in pseudostationary state.In the active oxygen scavenger sample comprising in following examples, elimination efficiency is obviously changes little or not variation during measuring, and calculates permeability from the pseudostationary state transmissivity of measuring.

Table 1

Region 1	Region 2	Region 3	Region 4	Region 5
					240	250	260	260	260

Table 2

Embodiment 13-24,27-29,31-32,34-36,38 and comparative example 25-26,30,33,36-37 and 39: using nylon 6 (from DuPont as

7335F obtains) and MXD6 (6121 grades) at 120 ℃, be dried 48 hours, and carry out pocket type blend according to various ratios.Then polyamide pocket type blend is added the setting in following condition of 90rpm (℃) 1.5 inches of single screw extrusion machines of Sterling in, form the blend that homogeneous phase turns acyl amination, by exist single compositing dependence Tg value to prove for every kind of blend.Tg value is listed in table 3.

Region 1	Region 2	Region 3	Region 4	Region 5
					250	270	300	300	300

Film properties before table 3-stretches

Film properties after table 3A-stretches

Region 1	Region 2	Region 3	Region 4	Region 5
					240	260	280	280	280

Table 4-has the polyester blend of homogeneous phase MXD6/ nylon 6 Blends

The homogeneous blend of table 5MXD6-nylon 6

The result of table 6-30 mil monofilm

Table 7

Table 8

Claims

1. a method that forms multilayer formed article, comprising:

(i) the Tg+100 ℃ of temperature of Tg+300 ℃ to described the first component that the first component that comprises at least one thermoplastic polymer is heated to described the first component, wherein said thermoplastic polymer is selected from polyester, Merlon, polyarylate and their homogeneous blend;

(ii) second component is heated to Tg+100 ℃ of described second component to the temperature of Tg+300 ℃ of described second component, what wherein second component comprised copolyamide or at least two kinds of polyamide turns acyl amination homogeneous blend;

(iii) be formed on the moulded products in minute other layer with described the first component and second component;

(iv) reclaim the leftover pieces of the first component and second component;

(v) the leftover pieces of described the first component and second component are ground to prepare abrasive again;

(vi) optionally, described abrasive is again dried; With

(vii) by described abrasive again and step, the mixture of described the first component in (i) of described second component in (ii) of described the first component in (i), step or step and the step described second component in (ii) mixes;

The difference RI(second component of the refractive index of the described second component of step in (ii) and step described the first component in (i) wherein) be-RI(the first component) 0.006 to-0.0006, and the percent transmission that described moulded products has is at least 75%, mist degree is 10% or less.

According to described in the process of claim 1 wherein again abrasive containing described the first component (i) and (ii) and the mixture of second component in steps.

3. according to the method for claim 2, wherein said abrasive again and step described the first component in is (i) mixed.

4. according to the method for claim 2, the 5-60 % by weight that wherein said abrasive is again described moulded products, the gross weight meter based on described moulded products.

5. according to the method for claim 4, the 10-40 % by weight that wherein said abrasive is again described moulded products.

6. according to the method for claim 5, the 20-30 % by weight that wherein said abrasive is again described moulded products.

7. according to the process of claim 1 wherein that the homogeneous blend of step component is (ii) effectively to cause that by least two kinds of polyamide described in making at the temperature that turns acyl amination, contact forms.

8. according to the method for claim 7, wherein saidly effectively cause that the temperature that turns acyl amination is 290 ℃-340 ℃.

According to the process of claim 1 wherein the formation of described moulded products by extruding, calendering, thermoforming, blowing, extrusion-blown modling, injection moulding, compression molding, casting, drawing-off, tentering or foaming carry out.

10. according to the method for claim 9, wherein said moulded products is sheet material, film, pipe, bottle or precast body.

11. according to the method for claim 9, and the formation of wherein said moulded products is undertaken by extruding.

12. according to the method for claim 9, and wherein said moulded products has 2-7 layer.

13. according to the method for claim 12, wherein said moulded products has the layer structure being represented by ABA, ABABA or ABCBA, its middle level A comprises step the first component (i), layer B comprises step second component (ii), layer C comprises abrasive again, and described abrasive is again containing the mixture of the leftover pieces of described the first component (i) and the leftover pieces of step described second component (ii) in steps or this mixture and polyester by circulation obtains after consumption or the combination of Merlon.

14. according to the process of claim 1 wherein the difference RI(second component of refractive index of described second component (ii) of step and step described the first component (i))-RI(the first component) be 0.005 to-0.0006.

15. according to the method for claim 1, wherein step described at least one thermoplastic polymer (i) comprises polyester, this polyester contains: (a) diacid residues, it contains and is selected from terephthalic acid (TPA), M-phthalic acid, naphthalenedicarboxylic acid and 1 based at least 80 % by mole of diacid residues total amount meters, the residue of at least one dicarboxylic acids in 4-cyclohexane cyclohexanedimethanodibasic, and at least one of 0 to 20 % by mole has the residue of the modification dicarboxylic acids of 2-20 carbon atom; (b) diol residue, it contains and is selected from ethylene glycol, 1 based at least 80 % by mole of diol residue total mole number meters, 4-cyclohexanedimethanol, neopentyl glycol, diethylene glycol (DEG), 1, ammediol, BDO and 2,2,4,4-tetramethyl-1, the residue of at least one glycol in 3-cyclobutane glycol, and at least one of 0 to 20 % by mole has the residue of the modification glycol of 3-16 carbon atom.

16. according to the method for claim 15, wherein said modification dicarboxylic acids is selected from 4,4 '-biphenyl dicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, NDA, 2,7-naphthalenedicarboxylic acid, 4,4 '-p-methoxybenzoic acid, trans-4,4 '-Stilbene dicarboxylic acids, oxalic acid, malonic acid, butanedioic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid and decanedioic acid; Described modification glycol is selected from 1,2-propane diols, 1, ammediol, BDO, 1,5-PD, 1,6-hexylene glycol, 1,4-cyclohexanedimethanol, paraxylene glycol, neopentyl glycol, polyethylene glycol, diethylene glycol (DEG), polytetramethylene glycol and 2,2,4,4-tetramethyl-1,3-cyclobutane glycol.

17. according to the method for claim 15, the residue that wherein said diacid residues contains one or more dicarboxylic acids that are selected from terephthalic acid (TPA), M-phthalic acid or its combination, the residue that described diol residue contains one or more glycol that are selected from 1,4-CHDM, neopentyl glycol, ethylene glycol and its combination.

18. according to the method for claim 15, wherein said polyester further comprise based on 0.1-2 % by mole of diacid residues total amount meter at least one be selected from the residue of the branching agent in trimellitic acid, trimellitic anhydride and PMDA.

19. according to the method for claim 15, the isophthalic acid residues of the terephthalic acid residue that wherein said diacid residues contains 60-100 % by mole and 0 to 40 % by mole, the 1,4-CHDM residue that described diol residue contains 100 % by mole.

20. according to the method for claim 15, the terephthalic acid residue that wherein said diacid residues contains 100 % by mole.

21. according to the method for claim 15, the terephthalic acid residue that wherein said diacid residues contains 80-100 % by mole, the 1,4-CHDM residue that described diol residue contains 50-90 % by mole and the neopentyl glycol residue of 10-50 % by mole.

22. according to the method for claim 15, the terephthalic acid residue that wherein said diacid residues contains 100 % by mole, the 1,4-CHDM residue that described diol residue contains 10-40 % by mole and the glycol residue of 60-90 % by mole.

23. according to the method for claim 21, the 1,4-CHDM residue that wherein said diol residue contains 10-99 % by mole, the glycol residue of 0 to 90 % by mole and the diethylene glycol (DEG) residue of 1-25 % by mole.

24. according to the method for claim 21, the ethylene glycol of the 1,4-CHDM that wherein said diol residue contains 50-90 % by mole and 10-50 % by mole.

25. according to the method for claim 24, wherein said polyester further comprise based on 0.1-2 % by mole of diacid residues total amount meter at least one be selected from the residue of the branching agent in trimellitic acid, trimellitic anhydride and PMDA.

26. according to the process of claim 1 wherein that the described second component during step (ii) comprises copolyamide, the residue that this copolyamide comprises m-xylene diamine, p dimethylamine or its combination; With the residue that is selected from least one following monomer: the amino heneicosanedioic acid of terephthalic acid (TPA), M-phthalic acid, adipic acid, pimelic acid, suberic acid, azelaic acid, decanedioic acid, heneicosanedioic acid, dodecanedioic acid, caprolactam, butyrolactam, 11-and 1,6-hexamethylene diamine.

27. according to the process of claim 1 wherein that the described second component during step (ii) comprises a kind of homogeneous blend, and described homogeneous blend contains containing the first polyamide of aromatic moieties with containing the second polyamide of aliphatic residue.

28. according to the method for claim 27, and wherein said homogeneous blend comprises the first polyamide, the residue that it comprises m-xylene diamine and adipic acid; Contain and be selected from least one following aliphatic series or the residue of cyclic aliphatic monomer with described the second polyamide: adipic acid, pimelic acid, suberic acid, azelaic acid, decanedioic acid, heneicosanedioic acid, dodecanedioic acid, caprolactam, butyrolactam, the amino decane diacid of 11-and hexamethylene diamine.

29. according to the method for claim 27, and wherein said the second polyamide contains and is selected from least one following polyamide: nylon 4, nylon 6, nylon 9, nylon 11, nylon 12, nylon 6,6, nylon 5,10, nylon 6,12, nylon 6,11, nylon 10,12; And their combination.

30. according to the method for claim 29, and wherein said the second polyamide contains nylon 6, nylon 6,6 or its blend.

31. according to the method for claim 30, wherein said at least one thermoplastic polymer comprises polyester, this polyester contains: (a) diacid residues, it contains and is selected from terephthalic acid (TPA), M-phthalic acid, naphthalenedicarboxylic acid and 1 based at least 80 % by mole of diacid residues total amount meters, the residue of at least one dicarboxylic acids in 4-cyclohexane cyclohexanedimethanodibasic, and at least one of 0 to 20 % by mole has the residue of the modification dicarboxylic acids of 2-20 carbon atom; (b) diol residue, it contains and is selected from ethylene glycol, 1 based at least 80 % by mole of diol residue total mole number meters, 4-cyclohexanedimethanol, neopentyl glycol, diethylene glycol (DEG), 1, ammediol, BDO and 2,2,4,4-tetramethyl-1, the residue of at least one glycol in 3-cyclobutane glycol, and at least one of 0 to 20 % by mole has the residue of the modification glycol of 3-16 carbon atom.

32. according to the method for claim 31, the residue that wherein said diacid residues contains one or more dicarboxylic acids that are selected from terephthalic acid (TPA), M-phthalic acid or its combination, the residue that described diol residue contains one or more glycol that are selected from 1,4-CHDM, neopentyl glycol, ethylene glycol and its combination.

33. according to the method for claim 31, the isophthalic acid residues of the terephthalic acid residue that wherein said diacid residues contains 60-100 % by mole and 0 to 40 % by mole, the 1,4-CHDM residue that described diol residue contains 100 % by mole.

34. according to the method for claim 31, the terephthalic acid (TPA) that wherein said diacid residues contains 100 % by mole.

35. according to the method for claim 31, the terephthalic acid (TPA) that wherein said diacid residues contains 80-100 % by mole, the neopentyl glycol of the 1,4-CHDM that described diol residue contains 50-90 % by mole and 10-50 % by mole.

36. according to the method for claim 31, the terephthalic acid (TPA) that wherein said diacid residues contains 100 % by mole, the ethylene glycol of the 1,4-CHDM that described diol residue contains 10-40 % by mole and 60-90 % by mole.

37. according to the method for claim 31, the 1,4-CHDM that wherein said diol residue contains 10-99 % by mole, the ethylene glycol of 0 to 90 % by mole and the diethylene glycol (DEG) of 1-25 % by mole.

38. according to the method for claim 31, the ethylene glycol of the 1,4-CHDM that wherein said diol residue contains 50-90 % by mole and 10-50 % by mole.

39. according to the method for claim 38, wherein said polyester further comprise based on 0.1-2 % by mole of diacid residues total amount meter at least one be selected from the residue of the branching agent in trimellitic acid, trimellitic anhydride and PMDA.

40. according to the method for claim 31, and wherein said at least one thermoplastic polymer further contains described polyester and contains the homogeneous blend of the Merlon of bisphenol-A residue.

41. according to the method for claim 40, and wherein said polyester and described Merlon are branching.

42. according to the method for claim 40, wherein said polyester further comprise based on 0.1-2 % by mole of diacid residues total amount meter at least one be selected from the residue of the branching agent in trimellitic acid, trimellitic anhydride and PMDA.

43. according to the method for claim 40, the residue that wherein said diacid residues contains one or more dicarboxylic acids that are selected from terephthalic acid (TPA), M-phthalic acid or its combination, the residue that described diol residue contains one or more glycol that are selected from 1,4-CHDM, neopentyl glycol, ethylene glycol and its combination.

44. according to the method for claim 40, the isophthalic acid residues of the terephthalic acid residue that wherein said diacid residues contains 60-100 % by mole and 0 to 40 % by mole, the 1,4-CHDM residue that described diol residue contains 100 % by mole.

45. according to the method for claim 40, the terephthalic acid (TPA) that wherein said diacid residues contains 100 % by mole.

46. according to the method for claim 40, the terephthalic acid (TPA) that wherein said diacid residues contains 80-100 % by mole, the neopentyl glycol of the 1,4-CHDM that described diol residue contains 50-90 % by mole and 10-50 % by mole.

47. according to the method for claim 40, the terephthalic acid (TPA) that wherein said diacid residues contains 100 % by mole, the ethylene glycol of the 1,4-CHDM that described diol residue contains 10-40 % by mole and 60-90 % by mole.

48. according to the method for claim 40, the 1,4-CHDM that wherein said diol residue contains 10-99 % by mole, the ethylene glycol of 0 to 90 % by mole and the diethylene glycol (DEG) of 1-25 % by mole.

49. according to the method for claim 40, the ethylene glycol of the 1,4-CHDM that wherein said diol residue contains 50-90 % by mole and 10-50 % by mole.

50. according to the method for claim 28, and wherein said second component further contains and is selected from least one metal that the periodic table of elements 3-12 4-6 of family is capable.

51. according to the method for claim 50, and wherein said metal is selected from copper, nickel, cobalt, iron, manganese and its combination.

52. according to the method for claim 51, wherein contains the described metal of 10-500ppm by weight, the gross weight meter based on described moulded products.

53. according to the method for claim 52, and wherein said metal is cobalt.

54. according to the method for claim 52, and wherein said homogeneous blend contains 20 mMs/kg or amine end groups still less.

55. form at least one deck additional layer according to the process of claim 1 wherein that step (iii) further comprises, the described abrasive again that described additional layer contains 50-100 % by weight, the gross weight meter based on described layer.

56. according to the method for claim 55, wherein said at least one deck additional layer contain 10-500ppm by weight at least one be selected from the metal in copper, nickel, cobalt, iron, manganese and its combination, the gross weight meter based on described moulded products.

57. according to the method for claim 56, and wherein said metal is cobalt.

The multilayer formed article that 58. methods by any one in claim 1,4,13,15,26,31,40,53 or 56 are produced.

The multilayer formed article that 59. methods according to claim 1 form, it comprises:

(i) the ground floor that comprises at least one thermoplastic polymer, described thermoplastic polymer is selected from polyester, Merlon, polyarylate and their homogeneous blend; With

(ii) the second layer that turns acyl amination, homogeneous blend that comprises at least two kinds of polyamide;

The difference RI(second layer of the refractive index of the wherein said second layer and described ground floor) be-RI(ground floor) 0.006 to-0.0006, and the percent transmission that described moulded products has is at least 75%, mist degree is 10% or less.

60. according to the moulded products of claim 59, and it further comprises a kind of abrasive again, the mixture that described abrasive again contains described ground floor and the second layer.

61. according to the moulded products of claim 60, abrasive again described in wherein said ground floor or the described second layer contain.

62. according to the moulded products of claim 60, the 5-60 % by weight that wherein said abrasive is again described moulded products, the gross weight meter based on described moulded products.

63. according to the moulded products of claim 62, the 10-40 % by weight that wherein said abrasive is again described moulded products, the gross weight meter based on described moulded products.

64. according to the moulded products of claim 63, the 20-30 % by weight that wherein said abrasive is again described moulded products, the gross weight meter based on described moulded products.

65. according to the moulded products of claim 59, and wherein the described homogeneous blend of the second layer is effectively to cause that by least two kinds of polyamide described in making at the temperature that turns acyl amination, contact forms.

66. according to the moulded products of claim 65, and wherein said temperature is 290 ℃-340 ℃.

67. according to the moulded products of claim 59, and wherein said moulded products has 2-7 layer.

68. according to the moulded products of claim 59, wherein said moulded products by extruding, calendering, thermoforming, blowing, extrusion-blown modling, injection moulding, compression molding, casting, drawing-off, tentering or foam production.

69. according to the moulded products of claim 68, and wherein said moulded products is sheet material, film, pipe, bottle or precast body.

70. according to the moulded products of claim 67, wherein said moulded products has the layer structure being represented by ABA, ABABA, ABCBA or ACBCA, its middle level A comprises described ground floor, layer B comprises the described second layer, layer C comprises abrasive again, the mixture of the leftover pieces that described abrasive again contains described ground floor and the leftover pieces of the described second layer, the polyester or Merlon or its combination that by the rear circulation of consumption, are obtained.

71. according to the moulded products of claim 59, the difference RI(second layer of the refractive index of the wherein said second layer and described ground floor)-RI(ground floor) be 0.005 to-0.0006.

72. according to the moulded products of claim 59, wherein said at least one thermoplastic polymer comprises polyester, this polyester contains: (a) diacid residues, it contains and is selected from terephthalic acid (TPA), M-phthalic acid, naphthalenedicarboxylic acid and 1 based at least 80 % by mole of diacid residues total amount meters, the residue of at least one dicarboxylic acids in 4-cyclohexane cyclohexanedimethanodibasic, and at least one of 0 to 20 % by mole has the residue of the modification dicarboxylic acids of 2-20 carbon atom; (b) diol residue, it contains and is selected from ethylene glycol, 1 based at least 80 % by mole of diol residue total mole number meters, 4-cyclohexanedimethanol, neopentyl glycol, diethylene glycol (DEG), 1, ammediol, BDO and 2,2,4,4-tetramethyl-1, the residue of at least one glycol in 3-cyclobutane glycol, and at least one of 0 to 20 % by mole has the residue of the modification glycol of 3-16 carbon atom.

73. according to the moulded products of claim 72, wherein said modification dicarboxylic acids is selected from 4,4 '-biphenyl dicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, NDA, 2,7-naphthalenedicarboxylic acid, 4,4 '-p-methoxybenzoic acid, trans-4,4 '-Stilbene dicarboxylic acids, oxalic acid, malonic acid, butanedioic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid and decanedioic acid; Described modification glycol is selected from 1,2-propane diols, 1, ammediol, BDO, 1,5-PD, 1,6-hexylene glycol, 1,4-cyclohexanedimethanol, paraxylene glycol, neopentyl glycol, polyethylene glycol, diethylene glycol (DEG), polytetramethylene glycol and 2,2,4,4-tetramethyl-1,3-cyclobutane glycol.

74. according to the moulded products of claim 72, the residue that wherein said diacid residues contains one or more dicarboxylic acids that are selected from terephthalic acid (TPA), M-phthalic acid or its combination, the residue that described diol residue contains one or more glycol that are selected from 1,4-CHDM, neopentyl glycol, ethylene glycol and its combination.

75. according to the moulded products of claim 72, wherein said polyester further comprise based on 0.1-2 % by mole of diacid residues total amount meter at least one be selected from the residue of the branching agent in trimellitic acid, trimellitic anhydride and PMDA.

76. according to the moulded products of claim 72, the isophthalic acid residues of the terephthalic acid residue that wherein said diacid residues contains 60-100 % by mole and 0 to 40 % by mole, the 1,4-CHDM residue that described diol residue contains 100 % by mole.

77. according to the moulded products of claim 72, the terephthalic acid residue that wherein said diacid residues contains 100 % by mole.

78. according to the moulded products of claim 72, the terephthalic acid residue that wherein said diacid residues contains 80-100 % by mole, the 1,4-CHDM residue that described diol residue contains 50-90 % by mole and the neopentyl glycol residue of 10-50 % by mole.

79. according to the moulded products of claim 72, the terephthalic acid residue that wherein said diacid residues contains 100 % by mole, the 1,4-CHDM residue that described diol residue contains 10-40 % by mole and the glycol residue of 60-90 % by mole.

80. according to the moulded products of claim 77, the 1,4-CHDM residue that wherein said diol residue contains 10-99 % by mole, the glycol residue of 0 to 90 % by mole and the diethylene glycol (DEG) residue of 1-25 % by mole.

81. according to the moulded products of claim 77, the ethylene glycol of the 1,4-CHDM that wherein said diol residue contains 50-90 % by mole and 10-50 % by mole.

82. 1 moulded products according to Claim 8, wherein said polyester further comprise based on 0.1-2 % by mole of diacid residues total amount meter at least one be selected from the residue of the branching agent in trimellitic acid, trimellitic anhydride and PMDA.

The multilayer formed article that 83. methods according to claim 1 form, it comprises:

(ii) the second layer that comprises copolyamide;

84. 3 moulded products according to Claim 8, the residue that wherein said copolyamide comprises m-xylene diamine, p dimethylamine or its combination; With the residue that is selected from least one following monomer: the amino heneicosanedioic acid of terephthalic acid (TPA), M-phthalic acid, adipic acid, pimelic acid, suberic acid, azelaic acid, decanedioic acid, heneicosanedioic acid, dodecanedioic acid, caprolactam, butyrolactam, 11-and 1,6-hexamethylene diamine.

85. 4 moulded products according to Claim 8, wherein said copolyamide comprises the m-xylene diamine residue based on 15-100 % by mole of 100 % by mole of diamines residue total content meter, with adipic acid residue based on 15-85 % by mole of 100 % by mole of diacid residues total content meter and 85-15 % by mole be selected from one or more following aliphatic series or cycloaliphatic dicarboxylic acid's residue: pimelic acid, suberic acid, azelaic acid, decanedioic acid, heneicosanedioic acid, dodecanedioic acid and Isosorbide-5-Nitrae-cyclohexane cyclohexanedimethanodibasic.

86. 5 moulded products according to Claim 8, wherein said thermoplastic polymer comprises polyester, this polyester contains: (a) diacid residues, it contains and is selected from terephthalic acid (TPA), M-phthalic acid, naphthalenedicarboxylic acid and 1 based at least 80 % by mole of diacid residues total amount meters, the residue of at least one dicarboxylic acids in 4-cyclohexane cyclohexanedimethanodibasic, and at least one of 0 to 20 % by mole has the residue of the modification dicarboxylic acids of 2-20 carbon atom; (b) diol residue, it contains and is selected from ethylene glycol, 1 based at least 80 % by mole of diol residue total mole number meters, 4-cyclohexanedimethanol, neopentyl glycol, diethylene glycol (DEG), 1, ammediol, BDO and 2,2,4,4-tetramethyl-1, the residue of at least one glycol in 3-cyclobutane glycol, and at least one of 0 to 20 % by mole has the residue of the modification glycol of 3-16 carbon atom.

87. according to the moulded products of claim 59, and wherein the described homogeneous blend in the second layer contains containing the first polyamide of aromatic moieties with containing the second polyamide of aliphatic residue.

88. 7 moulded products according to Claim 8, wherein the described homogeneous blend of the second layer comprises the first polyamide, the residue that it comprises m-xylene diamine and adipic acid; Contain and be selected from least one following aliphatic series or the residue of cyclic aliphatic monomer with described the second polyamide: adipic acid, pimelic acid, suberic acid, azelaic acid, decanedioic acid, heneicosanedioic acid, dodecanedioic acid, caprolactam, butyrolactam, the amino decane diacid of 11-and hexamethylene diamine.

89. 7 moulded products according to Claim 8, wherein said the second polyamide contains and is selected from least one following polyamide: nylon 4, nylon 6, nylon 9, nylon 11, nylon 12, nylon 6,6, nylon 5,10, nylon 6,12, nylon 6,11, nylon 10,12; And their combination.

90. 9 moulded products according to Claim 8, wherein said the second polyamide contains nylon 6, nylon 6,6 or its blend.

91. according to the moulded products of claim 90, wherein said at least one thermoplastic polymer comprises polyester, this polyester contains: (a) diacid residues, it contains and is selected from terephthalic acid (TPA), M-phthalic acid, naphthalenedicarboxylic acid and 1 based at least 80 % by mole of diacid residues total amount meters, the residue of at least one dicarboxylic acids in 4-cyclohexane cyclohexanedimethanodibasic, and at least one of 0 to 20 % by mole has the residue of the modification dicarboxylic acids of 2-20 carbon atom; (b) diol residue, it contains and is selected from ethylene glycol, 1 based at least 80 % by mole of diol residue total mole number meters, 4-cyclohexanedimethanol, neopentyl glycol, diethylene glycol (DEG), 1, ammediol, BDO and 2,2,4,4-tetramethyl-1, the residue of at least one glycol in 3-cyclobutane glycol, and at least one of 0 to 20 % by mole has the residue of the modification glycol of 3-16 carbon atom.

92. according to the moulded products of claim 91, the residue that wherein said diacid residues contains one or more dicarboxylic acids that are selected from terephthalic acid (TPA), M-phthalic acid or its combination, the residue that described diol residue contains one or more glycol that are selected from 1,4-CHDM, neopentyl glycol, ethylene glycol and its combination.

93. according to the moulded products of claim 91, the isophthalic acid residues of the terephthalic acid residue that wherein said diacid residues contains 60-100 % by mole and 0 to 40 % by mole, the 1,4-CHDM residue that described diol residue contains 100 % by mole.

94. according to the moulded products of claim 91, the terephthalic acid (TPA) that wherein said diacid residues contains 100 % by mole.

95. according to the moulded products of claim 91, the terephthalic acid (TPA) that wherein said diacid residues contains 80-100 % by mole, the neopentyl glycol of the 1,4-CHDM that described diol residue contains 50-90 % by mole and 10-50 % by mole.

96. according to the moulded products of claim 91, the terephthalic acid (TPA) that wherein said diacid residues contains 100 % by mole, the ethylene glycol of the 1,4-CHDM that described diol residue contains 10-40 % by mole and 60-90 % by mole.

97. according to the moulded products of claim 91, the 1,4-CHDM that wherein said diol residue contains 10-99 % by mole, the ethylene glycol of 0 to 90 % by mole and the diethylene glycol (DEG) of 1-25 % by mole.

98. according to the moulded products of claim 91, the ethylene glycol of the 1,4-CHDM that wherein said diol residue contains 50-90 % by mole and 10-50 % by mole.

99. according to the moulded products of claim 98, wherein said polyester further comprise based on 0.1-2 % by mole of diacid residues total amount meter at least one be selected from the residue of the branching agent in trimellitic acid, trimellitic anhydride and PMDA.

100. according to the moulded products of claim 91, and wherein described at least one thermoplastic polymer of ground floor further contains described polyester and containing the homogeneous blend of the Merlon of bisphenol-A residue.

101. according to the moulded products of claim 100, and wherein said polyester and described Merlon are branching.

102. according to the moulded products of claim 101, wherein said polyester further comprise based on 0.1-2 % by mole of diacid residues total amount meter at least one be selected from the residue of the branching agent in trimellitic acid, trimellitic anhydride and PMDA.

103. according to the moulded products of claim 100, the residue that wherein said diacid residues contains one or more dicarboxylic acids that are selected from terephthalic acid (TPA), M-phthalic acid or its combination, the residue that described diol residue contains one or more glycol that are selected from 1,4-CHDM, neopentyl glycol, ethylene glycol and its combination.

104. according to the moulded products of claim 100, the isophthalic acid residues of the terephthalic acid residue that wherein said diacid residues contains 60-100 % by mole and 0 to 40 % by mole, the 1,4-CHDM residue that described diol residue contains 100 % by mole.

105. according to the moulded products of claim 100, the terephthalic acid (TPA) that wherein said diacid residues contains 100 % by mole.

106. according to the moulded products of claim 100, the terephthalic acid (TPA) that wherein said diacid residues contains 80-100 % by mole, the neopentyl glycol of the 1,4-CHDM that described diol residue contains 50-90 % by mole and 10-50 % by mole.

107. according to the moulded products of claim 100, the terephthalic acid (TPA) that wherein said diacid residues contains 100 % by mole, the ethylene glycol of the 1,4-CHDM that described diol residue contains 10-40 % by mole and 60-90 % by mole.

108. according to the moulded products of claim 100, the 1,4-CHDM that wherein said diol residue contains 10-99 % by mole, the ethylene glycol of 0 to 90 % by mole and the diethylene glycol (DEG) of 1-25 % by mole.

109. according to the moulded products of claim 100, the ethylene glycol of the 1,4-CHDM that wherein said diol residue contains 50-90 % by mole and 10-50 % by mole.

110. 8 moulded products according to Claim 8, the wherein said second layer further contains and is selected from least one metal that the periodic table of elements 3-12 4-6 of family is capable.

111. according to the moulded products of claim 110, and wherein said metal is selected from copper, nickel, cobalt, iron, manganese and its combination.

112. according to the moulded products of claim 111, and it contains the described metal of 10-500ppm by weight, the gross weight meter based on described moulded products.

113. according to the moulded products of claim 112, and wherein said metal is cobalt.

114. according to the moulded products of claim 113, and wherein the described homogeneous blend of the second layer contains 20 mMs/kg or amine end groups still less.

115. according to the moulded products of claim 60, and wherein said moulded products further comprises at least one deck additional layer, the described abrasive again that described additional layer contains 50-100 % by weight, the gross weight meter based on described layer.

116. according to the moulded products of claim 115, wherein said at least one deck additional layer contain 10-500ppm by weight at least one be selected from the metal in copper, nickel, cobalt, iron, manganese and its combination.

117. according to the moulded products of claim 116, and wherein said metal is cobalt.