CN101193979A - Transparent deoxidizing compositions comprising polymer containing a cyclobutanediol and articles prepared therefrom - Google Patents

Transparent deoxidizing compositions comprising polymer containing a cyclobutanediol and articles prepared therefrom Download PDF

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Publication number
CN101193979A
CN101193979A CNA2006800205700A CN200680020570A CN101193979A CN 101193979 A CN101193979 A CN 101193979A CN A2006800205700 A CNA2006800205700 A CN A2006800205700A CN 200680020570 A CN200680020570 A CN 200680020570A CN 101193979 A CN101193979 A CN 101193979A
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Prior art keywords
residue
acid
tetramethyl
component
cyclobutanediol
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Chinese (zh)
Inventor
W·R·黑尔
T·J·佩科里尼
M·E·斯图尔特
M·E·罗杰斯
S·A·吉列姆
M·D·克利夫顿
E·D·克劳福德
D·S·波特
G·W·康奈尔
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Eastman Chemical Co
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Eastman Chemical Co
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/62—Plastics recycling; Rubber recycling

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  • Compositions Of Macromolecular Compounds (AREA)
  • Polyesters Or Polycarbonates (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Containers Having Bodies Formed In One Piece (AREA)
  • Laminated Bodies (AREA)
  • External Artificial Organs (AREA)
  • Materials For Medical Uses (AREA)

Abstract

Disclosed are oxygen-scavenging polymer compositions having high transparency and low haze comprising immiscible blends of at least one polyester comprising 2,2,4,4-tetramethyl-l ,3-cyclobutanediol, a copolyamide or a transamidized, homogeneous blend of a least two polyamides, and a metal catalyst. 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. The blends of the present invention are useful in producing shaped articles such as, for example, sheeting, films, tubes, bottles, preforms and profiles. These articles may have one or more layers and can exhibit improved excellent barrier properties and good melt processability while retaining excellent mechanical properties.

Description

The transparent deoxidizing compositions that contains the polyester that comprises cyclobutanediol reaches by its goods of making
The cross reference of related application
The application is the U.S. Patent application of submitting on February 27th, 2,006 11/363,374 part continuation application, this U.S. Patent application has required the U.S. Provisional Application 60/657,746 submitted on March 2nd, 2005 and the interests of the U.S. Provisional Application 60/657,747 submitted on March 2nd, 2005.The application further requires in the U.S. Provisional Application 60/691 of submission on June 17th, 2005 based on 35 U.S.C. § 119 (e), 567, the U.S. Provisional Application of submitting on October 28th, 2,005 60/731,454, the U.S. Provisional Application of submitting on October 28th, 2,005 60/731,389, the U.S. Provisional Application of submitting on November 22nd, 2,005 60/739,058 and the U.S. Provisional Application 60/738 submitted on November 22nd, 2005,869, the U.S. Provisional Application of submitting on December 15th, 2,005 60/750,692, the U.S. Provisional Application of submitting on December 15th, 2,005 60/750,693, the U.S. Provisional Application of submitting on December 15th, 2,005 60/750,682 and the U.S. Provisional Application 60/750 submitted on December 15th, 2005,547 right of priority, all these files mode is by reference all incorporated this paper into.
Technical field
The present invention relates to transparent deoxygenation (oxygen-scavenging) polymer composition.In particular, the present invention relates to comprise oxide catalyst, at least aly comprise 2,2,4,4-tetramethyl--1, the immiscible polymer adulterant of the even adulterant of the polyester of 3-cyclobutanediol and copolyamide or at least two kinds of polymeric amide, wherein the difference of the out of phase specific refractory power absolute value of this non-miscible adulterant is very little.The invention still further relates to the moulded products that comprises this deoxidizing compositions.
Background technology
Many products, particularly foodstuff products are responsive for the existence of oxygen and the loss or the absorption of water.Wrapped product with this susceptibility is easily because of contacting with oxygen or adsorbing the moisture deterioration.The wrapping material that restriction oxygen contacts with food article for example, help to keep the quality of food article and reduce rotten.Therefore, use such barrier package the goods of storage can be kept more of a specified duration, thereby reduce again carrying cost and waste.Oxygen obstruction agent and/or moisture barrier agent have been caused in wrapping material, generally using for addressing this problem the trial of carrying out.Known many polymeric materials can serve as the barrier agent of oxygen or moisture.For example, typical moisture barrier agent comprises polyethylene and polypropylene.Representational oxygen obstruction agent comprises the adulterant of poly-(ethylene-vinyl alcohol) (" EVOH "), poly-(vinyl alcohol) (" PVOH "), polymeric amide (nylon) and these materials.Poly-(vinylidene chloride), vinyl chloride copolymer and vinylidene chloride-methyl acrylate copolymer also can be used for moisture barrier agent and oxygen obstruction agent.
Yet these traditional barrier materials are expensive, and have unsettled structural performance or other and make and be difficult to construct wrapping material separately or it constructs unfavorable shortcoming with barrier material.For example, though EVOH has superior oxygen barrier property, it can not be effective as the moisture barrier agent.Other barrier material is expensive hangs back to making us, and is difficult to be used alone as wrapping material.For avoiding these problems, use following multilayered structure to become common practice in the practice: in this multilayered structure, the amount of expensive barrier material can be reduced to skim, and uses as the cheap polymkeric substance of structural sheet is collaborative with being positioned on these barrier layer one or both sides.Use multilayered structure to protect barrier layer to avoid damaging by structural sheet.But the production of multilayer product may be expensive.And multi-layer product may have difficulties in regeneration, because different polymeric constituents is difficult to separate.And, the waste of polymeric that reclaims or " regrowth (regrind) " usually mixed with novel polymer can cause unfavorable turbidity or opaqueness, because novel material and regrowth are incompatible.
The shortcoming of conventional obstructive polymkeric substance also can overcome by the adulterant that uses barrier polymer and another kind of polymkeric substance.Unfortunately, as mentioned above, many adulterants of barrier polymer and other thermoplastic polymer are immiscible, and are opaque or muddy.This adulterant is not satisfied for the purposes such as the beverage container of the needs transparency.
Polyester polymers such as polyethylene terephthalate (" PET ") generally are used to pack purposes.PET has many its performances that can be used as wrapping material that make, and comprises acceptable carbon dioxide barrier properties the soft drink in being packaged in the bottle that contains multiple composition (servings).But, for being packaged in, needing to improve carbonic acid gas barrier and the oxygen-barrier property thereof of PET than the soft drink in the ampoule, it is not suitable for the meat of the oxysensible product of packing such as beer, Citrus product, tomato based product and sterile packed.PEN (" PEN ") as barrier agent doubly than the effective 3-10 of PET, but it is expensive more.
Multilayered structure can be used to improve the gas-barrier characteristic of PET.For example, the polymkeric substance with excellent oxygen-barrier property (being also referred to as " passive barrier ") or deoxygenation performance (being also referred to as " initiatively barrier ") can combine with PET and be used to make the layered structure of being made up of multiple independent polymkeric substance.But the production of these multilayered structures is too expensive.The adulterant of barrier polymer and PET can also be used to improve the oxygen-barrier property of packing, and still, as mentioned above, it usually has the poor transparency, and is not suitable for many packing purposes.The transparency difference of adulterant can make that also being difficult to from polymer blend regeneration makes waste material and join in the novel polymer.
Copolyesters film and extrusion blow (" EBM ") bottle is an ideal through the toughness aspect of being everlasting, and generally is used for substituting PET in extrusion blow and thin film application.These purposes usually need can with orientation PET suitable barrier.Yet unfortunately, the barrier property of copolyesters is poorer than orientation PET.Multilayered structure can be by the following manner manufacturing: the central authorities to thicker body structure extrude barrier film jointly to improve whole barrier.But for the purpose of saving, EBM and thin-film technique need be reprocessed the regrowth (that is, flash (flash) and tankage (trim)) of high level (up to 80%) usually.Unfortunately, typical barrier material and copolyesters are immiscible, and the adulterant of these barrier polymer and polyester often shows high-caliber turbidity and very poor cleanliness.Therefore, when with waste of polymeric (that is, regrowth) when being added back in the initiation layer, the turbidity level of whole membrane structure is elevated to unacceptable level.
In the art, need such polymer blend: its provide good passive and/or initiatively barrier property, be economical and can regenerate effectively.This adulterant should be transparent, and the thermoplasticity barrier polymer that provides the high barrier of oxygen, water and carbonic acid gas is provided, and can be used to add the goods forming technology of high-level regrowth economically.And, need can be used in and make the multi-layer product that has high-clarity and can tolerate high-caliber regrowth economically.
Summary of the invention
Polymer composition with high-clarity and high obstructing performance can be prepared by non-miscible adulterant of following substances: the even adulterant of the commentaries on classics acyl amination (transamidize) of one or more thermoplastic polymers and copolyamide or at least two kinds of polymeric amide, wherein the difference between the specific refractory power of polyamide component and thermoplastic polymer components is about 0.006 to about-0.0006.Therefore, the invention provides a kind of polymer composition, it comprises non-miscible adulterant of following substances:
(i) comprise at least a first component that is selected from the thermoplastic polymer of polyester, polycarbonate, polyarylester and even adulterant thereof;
Second component of even adulterant that (ii) comprises the commentaries on classics acyl amination of at least two kinds of polymeric amide;
Wherein second component (ii) with the refringence of first component (i), RI (second component)-RI (first component) is about 0.006 to approximately-0.0006, the percent transmittance of this non-miscible adulterant is at least 75%, turbidity is 10% or lower.
In another aspect of this invention, first component comprises and contains terephthalic acid, 2,2,4,4-tetramethyl--1, the polyester of 3-cyclobutanediol and 1,4 cyclohexane dimethanol residue (residue).Therefore, the present invention also provides a kind of polymer composition, and it comprises non-miscible adulterant of following substances:
(i) contain at least a first component that comprises the polyester of following residue:
(a) diacid residues, based on all diacid residues, it comprises that about 70 to about 100mol% terephthalic acid residue, 0 arrives at least a modified aromatic family's dicarboxylic acid residue of about 30mol% and 0 to about 10mol% at least a modified aliphatic dicarboxylic acid residue, wherein this modified aromatic family dicarboxylic acid has 20 carbon atoms at the most, and this modified aliphatic dicarboxylic acid has 16 carbon atoms at the most; With
(b) diol residue, based on all diol residue, it comprises that about 1 arrives 2,2,4 of about 99mol%, 4-tetramethyl--1,3-cyclobutanediol residue and about 1 arrives the 1,4 cyclohexane dimethanol residue of about 99mol%; And
Second component of even adulterant that (ii) comprises the commentaries on classics acyl amination of at least two kinds of polymeric amide;
Wherein second component (ii) with the refringence of first component (i), RI (second component)-RI (first component) is about 0.006 to approximately-0.0006, the percent transmittance of this non-miscible adulterant is at least 75%, turbidity is 10% or lower.
First component comprises at least a thermoplastic polymer that is selected from the even adulterant of polyester, polycarbonate, polyarylester and these polymkeric substance, and second component comprises that at least two kinds have been changeed the adulterant of acyl amination with the polymeric amide that produces even adulterant.We have found that the polymeric amide by selecting at least two kinds of aliphatics with different levels and aromatic residue also changes acyl aminations to form even adulterant with these polymeric amide, the specific refractory power of first and second components can be mated nearly.Therefore, the even adulterant of thermoplastic polymer and polymeric amide can be used to make the specific refractory power of second component and first component to reach in the required scope, is about 0.006 to about-0.0006 thereby make the difference between the specific refractory power.For example, comprise that the polyester of dihydroxyphenyl propane residue and the even adulterant of polycarbonate can be used as first component, and comprise that the even adulterant of the commentaries on classics acyl amination of first polymeric amide of m-xylene diamine and hexanodioic acid residue and second fatty polyamide can be used as barrier polymer.Therefore when refractive index match, first and second components form transparent non-miscible adulterant, and it is applicable to that preparation can be used for the high-clarity molded article of multiple packing purposes.Multi-layer product also can be by kinds of processes preparation known in the art.For example, can be with first and second components from molten mass coextrusion (coextrude) or be injected to independent layer altogether, perhaps these layers can form independently and put together in subsequently technology such as lamination.
Second component also can comprise the copolyamide with a certain proportion of aromatic series and aliphatic dicarboxylic acid and diamines residue, this ratio can change in case with the specific refractory power close match of first and second components.Therefore, another aspect of the present invention is a kind of polymer composition, and it comprises non-miscible adulterant of following substances:
(i) comprise at least a first component that is selected from the thermoplastic polymer of polyester, polycarbonate, polyarylester and even adulterant thereof;
Second component that (ii) comprises copolyamide;
Wherein said second component (ii) with the refringence of first component (i), RI (second component)-RI (first component) is about 0.006 to approximately-0.0006, and the percent transmittance of this non-miscible adulterant is at least 75%, turbidity is 10% or lower.In another embodiment, first component comprises and contains terephthalic acid, 2,2,4,4-tetramethyl--1, the polyester of 3-cyclobutanediol and 1,4 cyclohexane dimethanol residue.Therefore, the invention provides a kind of polymer composition, it comprises non-miscible adulterant of following substances:
(i) comprise first component of at least a polyester, this polyester comprises:
(a) diacid residues, based on all diacid residues, it comprises at least a modified aliphatic dicarboxylic acid residue of 16 carbon atoms at the most that has of about terephthalic acid residue of 70 to about 100mol%, 0 to about 30mol% at least a modified aromatic family's dicarboxylic acid residue with 20 carbon atoms at the most and 0 to about 10mol%; And
(b) diol residue, based on all diol residue, it comprises that about 1 arrives 2,2,4 of about 99mol%, 4-tetramethyl--1,3-cyclobutanediol residue and about 1 arrives the 1,4 cyclohexane dimethanol residue of about 99mol%; And
Second component that (ii) comprises copolyamide;
Wherein second component (ii) with the refringence of first component (i), RI (second component)-RI (first component) is about 0.006 to approximately-0.0006, the percent transmittance of this non-miscible adulterant is at least 75%, turbidity is 10% or lower.
Another aspect of the present invention is a kind of polymer composition for preparing by the technology that comprises following substances fusion fusion:
(i) comprise at least a first component that is selected from the thermoplastic polymer of polyester, polycarbonate, polyarylester and even adulterant thereof; With
Second component of even adulterant that (ii) comprises the commentaries on classics acyl amination of at least two kinds of polymeric amide;
Wherein second component (ii) with the refringence of first component (i), RI (second component)-RI (first component) is about 0.006 to approximately-0.0006, the percent transmittance of said composition is at least 75%, turbidity is 10% or lower.In still another aspect of the invention, first component comprises and contains terephthalic acid, 12,2,4,4-tetramethyl--1, the polyester of the residue of 3-cyclobutanediol and 1,4 cyclohexane dimethanol.Therefore, the present invention also provides a kind of polymer composition for preparing by the technology that comprises following substances fusion fusion:
(i) comprise first component of at least a polyester, this polyester comprises:
(a) diacid residues, based on all diacid residues, it comprises at least a modified aliphatic dicarboxylic acid residue of 16 carbon atoms at the most that has of about terephthalic acid residue of 70 to about 100mol%, 0 to about 30mol% at least a modified aromatic family's dicarboxylic acid residue with 20 carbon atoms at the most and 0 to about 10mol%; And
(b) diol residue, based on all diol residue, it comprises that about 1 arrives 2,2,4 of about 99mol%, 4-tetramethyl--1,3-cyclobutanediol residue and about 1 arrives the 1,4 cyclohexane dimethanol residue of about 99mol%; And
Second component of even adulterant that (ii) comprises the commentaries on classics acyl amination of at least two kinds of polymeric amide;
Wherein second component (ii) with the refringence of first component (i), RI (second component)-RI (first component) is about 0.006 to approximately-0.0006, the percent transmittance of said composition is at least 75%, turbidity is 10% or lower.
The barrier property of composition exhibiting excellence of the present invention.Oxygen barrier property can improve to produce deoxidizing compositions by add transition-metal catalyst such as cobalt, manganese, iron, ruthenium, copper, nickel, palladium and platinum to adulterant.Therefore, the present invention further provides a kind of deoxidizing compositions, it comprises:
(A) comprise non-miscible adulterant of following substances:
(i) comprise at least a first component that is selected from the thermoplastic polymer of polyester, polycarbonate, polyarylester and even adulterant thereof;
Second component of even adulterant that (ii) comprises the commentaries on classics acyl amination of at least two kinds of polymeric amide;
Wherein said second component (ii) with the refringence of first component (i), RI (second component)-RI (first component) is about 0.006 to approximately-0.0006, the percent transmittance of said composition is at least 75%, turbidity is 10% or lower; And
(B) at least a 3-12 family of the periodic table of elements, the metal that 4-6 is capable of being selected from.
Typical metal catalyst includes but not limited to cobalt, manganese and iron.First component of non-miscible adulterant can comprise and contains terephthalic acid, 2,2,4,4-tetramethyl--1, the polyester of the residue of 3-cyclobutanediol and 1,4 cyclohexane dimethanol.Therefore, another embodiment of the invention is a kind of deoxidizing compositions, and it comprises:
(A) comprise non-miscible adulterant of following substances:
(i) comprise first component of at least a polyester, this polyester comprises:
(a) diacid residues, based on all diacid residues, it comprises at least a modified aliphatic dicarboxylic acid residue of 16 carbon atoms at the most that has of about terephthalic acid residue of 70 to about 100mol%, 0 to about 30mol% at least a modified aromatic family's dicarboxylic acid residue with 20 carbon atoms at the most and 0 to about 10mol%; And
(b) diol residue, based on all diol residue, it comprises that about 1 arrives 2,2,4 of about 99mol%, 4-tetramethyl--1,3-cyclobutanediol residue and about 1 arrives the 1,4 cyclohexane dimethanol residue of about 99mol%; And
Second component of even adulterant that (ii) comprises the commentaries on classics acyl amination of at least two kinds of polymeric amide;
Wherein said second component (ii) with the refringence of first component (i), RI (second component)-RI (first component) is about 0.006 to approximately-0.0006, the percent transmittance of said composition is at least 75%, turbidity is 10% or lower; And
(B) at least a 3-12 family of the periodic table of elements, the metal that 4-6 is capable of being selected from.
Adulterant of the present invention can be used for producing have improved barrier property, the transparent formed articles of melt processable and excellent mechanical property, these goods can use a high proportion of regenerated polymer/novel polymer to prepare.These molded articles can have single or multiple lift, and can have a lot of packing purposes.Therefore, the present invention further provides a kind of method that forms molded article, it comprises:
(A) with following substances fusion fusion:
(i) comprise at least a first component that is selected from the thermoplastic polymer of polyester, polycarbonate, polyarylester and even adulterant thereof;
Second component of even adulterant that (ii) comprises the commentaries on classics acyl amination of copolyamide or at least two kinds of polymeric amide;
Wherein first component (i) and second component (ii) form non-miscible adulterant, the refringence of described second component and first component, RI (second component)-RI (first component) is about 0.006 to about-0.0006, the percent transmittance of this non-miscible adulterant is at least 75%, and turbidity is 10% or lower;
(B) form molded article;
(C) recovery comprises first and second components (i) of fusion and waste of polymeric composition (ii);
(D) the waste of polymeric composition is ground to produce polymer recycled thing;
(E) randomly, dry this waste of polymeric composition; With
(F) with first and second components (i) in polymer recycled thing and the step (A) and (ii) merging.In another example, first component can comprise and contains terephthalic acid, 2,2,4,4-tetramethyl--1, the polyester of the residue of 3-cyclobutanediol and 1,4 cyclohexane dimethanol.Therefore, the present invention also comprises a kind of method that forms molded article, and it comprises:
(A) with following substances fusion fusion:
(i) comprise first component of at least a polyester, this polyester comprises:
(a) diacid residues, based on all diacid residues, it comprises at least a modified aliphatic dicarboxylic acid residue of 16 carbon atoms at the most that has of about terephthalic acid residue of 70 to about 100mol%, 0 to about 30mol% at least a modified aromatic family's dicarboxylic acid residue with 20 carbon atoms at the most and 0 to about 10mol%; And
(b) diol residue, based on all diol residue, it comprises that about 1 arrives 2,2,4 of about 99mol%, 4-tetramethyl--1,3-cyclobutanediol residue and about 1 arrives the 1,4 cyclohexane dimethanol residue of about 99mol%; And
Second component of even adulterant that (ii) comprises the commentaries on classics acyl amination of copolyamide or at least two kinds of polymeric amide;
Wherein first component (i) and second component (ii) form non-miscible adulterant, the refringence of described second component and first component, RI (second component)-RI (first component) is about 0.006 to about-0.0006, the percent transmittance of this non-miscible adulterant is at least 75%, and turbidity is 10% or lower;
(B) form molded article;
(C) recovery comprises first and second components (i) of fusion and waste of polymeric composition (ii);
(D) the waste of polymeric composition is ground to produce polymer recycled thing;
(E) randomly, dry this waste of polymeric composition; With
(F) with first and second components (i) in polymer recycled thing and the step (A) and (ii) merging.
The example of molded article that can be by method of the present invention preparation includes but not limited to sheet material, film, pipeline, bottle or profile (profile).Molded article can by extruding, calendering (calendering), thermoforming, blowing, extrusion blow,, compression moulding, curtain coating, drawing-off (draft), tentering (tenter) or prepare.
Molded article can have one or more layers non-miscible adulterant that comprises first and second components, perhaps can have wherein first component and second component multilayer in layer independently.Therefore, the present invention also provides a kind of multilevel shaping goods, and it comprises:
(i) comprise at least a the first layer that is selected from the thermoplastic polymer of polyester, polycarbonate, polyarylester and even adulterant thereof; And
The second layer of even adulterant that (ii) comprises the commentaries on classics acyl amination of at least two kinds of polymeric amide;
Wherein the second layer (ii) and the refringence of the first layer (i), RI (second layer)-RI (the first layer) is about 0.006 to approximately-0.0006, the percent transmittance of this molded article is at least 75%, turbidity is 10% or lower.On the other hand, described the first layer can comprise and contains terephthalic acid, 2,2,4,4-tetramethyl--1, the polyester of the residue of 3-cyclobutanediol and 1,4 cyclohexane dimethanol.Therefore, another embodiment of the invention is a kind of multilevel shaping goods, and it comprises:
(i) comprise the first layer of at least a polyester, this polyester comprises:
(a) diacid residues, based on all diacid residues, it comprises at least a modified aliphatic dicarboxylic acid residue of 16 carbon atoms at the most that has of about terephthalic acid residue of 70 to about 100mol%, 0 to about 30mol% at least a modified aromatic family's dicarboxylic acid residue with 20 carbon atoms at the most and 0 to about 10mol%; And
(b) diol residue, based on all diol residue, it comprises that about 1 arrives 2,2,4 of about 99mol%, 4-tetramethyl--1,3-cyclobutanediol residue and about 1 arrives the 1,4 cyclohexane dimethanol residue of about 99mol%; And
The second layer of even adulterant that (ii) comprises the commentaries on classics acyl amination of at least two kinds of polymeric amide;
Wherein the second layer (ii) and the refringence of the first layer (i), RI (second layer)-RI (the first layer) is about 0.006 to approximately-0.0006, and the percent transmittance of this molded article is at least 75%, turbidity is 10% or lower.
The present invention further provides a kind of method that forms the multilevel shaping goods, it comprises:
(i) will comprise that at least a first component that is selected from the thermoplastic polymer of polyester, polycarbonate, polyarylester and even adulterant thereof is heated to about Tg+100 ℃ to about Tg+300 ℃ temperature of this first component;
To comprise that (ii) second component of even adulterant of the commentaries on classics acyl amination of copolyamide or at least two kinds of polymeric amide is heated to about Tg+100 ℃ to about Tg+300 ℃ temperature of this second component;
(iii) form described first and second components independently the layer in molded article;
(iv) reclaim useless first and second components;
(first and second components of v) will giving up grind to produce regrowth;
(vi) randomly, dry described regrowth; With
(vii) regrowth and step (i) and first component (ii), second component or its combination are merged;
Wherein step second component (ii) and the refringence of first component of step (i), RI (second component)-RI (first component) is about 0.006 to approximately-0.0006, and the percent transmittance of this molded article is at least 75%, and turbidity is 10% or lower.In another example, described first component can comprise and contains terephthalic acid, 2,2,4,4-tetramethyl--1,3-cyclobutanediol and 1, the polyester of the residue of 3-cyclohexanedimethanol.Therefore, another aspect of the present invention is a kind of method that forms the multilevel shaping goods, and it comprises:
(i) first component is heated to about Tg+100 ℃ to about Tg+300 ℃ temperature of this first component, this first component comprises at least a polyester, and this polyester comprises:
(a) diacid residues, based on all diacid residues, it comprises at least a modified aliphatic dicarboxylic acid residue of 16 carbon atoms at the most that has of about terephthalic acid residue of 70 to about 100mol%, 0 to about 30mol% at least a modified aromatic family's dicarboxylic acid residue with 20 carbon atoms at the most and 0 to about 10mol%; And
(b) diol residue, based on all diol residue, it comprises that about 1 arrives 2,2,4 of about 99mol%, 4-tetramethyl--1,3-cyclobutanediol residue and about 1 arrives the 1,4 cyclohexane dimethanol residue of about 99mol%;
To comprise that (ii) second component of even adulterant of the commentaries on classics acyl amination of copolyamide or at least two kinds of polymeric amide is heated to about Tg+100 ℃ to about Tg+300 ℃ temperature of this second component;
(iii) form described first and second components independently the layer in molded article;
(iv) reclaim useless first and second components;
(first and second components of v) will giving up grind to produce regrowth;
(vi) randomly, dry described regrowth; With
(vii) regrowth and step (i) and first component (ii), second component or its combination are merged;
Wherein step second component (ii) and the refringence of first component of step (i), RI (second component)-RI (first component) is about 0.006 to approximately-0.0006, and the percent transmittance of this molded article thing is at least 75%, turbidity is 10% or lower.Regrowth can join first or the second layer in, and can be these goods about 5 to about 60wt%.
Embodiment
Polymer composition with high-clarity and good barrier performance can be by the non-miscible adulterant preparation of one or more thermoplastic polymers with the even adulterant of the commentaries on classics acyl amination of at least two kinds of polymeric amide, and wherein the refringence between polyamide compounds and the thermoplastic polymer is about 0.006 to about-0.0006.The percent transmittance of this non-miscible adulterant is at least 75%, and turbidity is 10% or lower.In a general embodiment, the invention provides the polymer composition of the non-miscible adulterant that comprises following substances:
(i) comprise at least a first component that is selected from the thermoplastic polymer of polyester, polycarbonate, polyarylester and even adulterant thereof;
Second component of even adulterant that (ii) comprises the commentaries on classics acyl amination of at least two kinds of polymeric amide;
Wherein second component (ii) with the refringence of first component (i), RI (second component)-RI (first component) is about 0.006 to approximately-0.0006, and the percent transmittance of this non-miscible adulterant is at least 75%, turbidity is 10% or lower.Thermoplastic polymer and polymeric amide can be selected from multiple polymers.For example, first component can comprise and contains terephthalic acid, 2,2,4,4-tetramethyl--1, the polyester of the residue of 3-cyclobutanediol and 1,4 cyclohexane dimethanol.The selection of the polymeric amide by second component and ratio or mix by the thermoplastic polymer with first component and to form even adulterant, the refringence of second component and first component can be adjusted to provides about 0.006 to-0.0006 difference approximately.Novel composition of the present invention can be used for producing molded article such as sheet material, film, pipeline, bottle and the profile with one or more layers.Molded article can prepare by extruding, calendering, thermoforming, blowing, extrusion blow, injection moulding, compression moulding, curtain coating, drawing-off, tentering or blowing.Can prepare such multi-layer product: wherein non-miscible adulterant is present in one or more layers, and perhaps first and second components are arranged in independently layer.Because the refringence of first and second components is very little, can comprise that by the molded article of preparation of compositions of the present invention a large amount of regrowths keep good transparency simultaneously.The transparency of the molded article of these preparations and barrier property make them be specially adapted to pack purposes.
Unless otherwise indicated, all numerals that are expressed as component, character such as molecular weight, reaction conditions etc. all can be understood to be in all situations and modified by term " approximately " in specification sheets and claims.Therefore, unless explanation in contrast, the numerical parameter of listing in specification sheets below and the appended claims all is the desirable properties that can will obtain according to the present invention and the approximation that changes.At least, each numerical parameter should can be analyzed according to the significant figure of being reported and by using the general method of rounding at least.In addition, the described scope of disclosure and claims of the present invention means and specifically comprises entire area and end points not just.For example, 0 to 10 the scope of being recited as means and discloses: all numerals between 0 and 10 as 1,2,3,4 etc., all marks between 0 and 10 are as 1.5,2.3,4.57,6.1113 etc., and end points 0 and 10.Equally, relevant with chemical substituted radical scope is as " C 1To C 5Hydrocarbon " mean and specifically comprise and disclose C 1And C 5Hydrocarbon and C 2, C 3And C 4Hydrocarbon.
Although numerical range and the parameter listed at wide region of the present invention are approximations, the numerical value of listing in specific embodiment is as far as possible accurately reported.Yet any numerical value all comprises some error that causes because of the standard deviation of finding inherently in its experimental measurement separately.
Unless regulation clearly in addition in context, otherwise the singulative that uses in specification sheets of the present invention and the claims " ", " a kind of " and " being somebody's turn to do " include its plural parameter.For example, mentioning that a kind of " polymkeric substance " or one " molded article " means comprises processing or prepares multiple (individual) polymkeric substance or goods.Mentioning that the composition that contains or comprise " a kind of " composition or " a kind of " polymkeric substance means except specified also comprises other composition or other polymkeric substance respectively the sort of.
For " comprising ", " containing " or " comprising "; be meant in the present invention in described composition or goods or method and have specified compound, element, particle or method steps etc. at least; but do not get rid of the existence of other compound, catalyzer, material, particle, method steps etc.; even these other compounds, material, particle, method steps etc. have with specified those and have identical function, unless get rid of clearly in the claims.
It is also understood that and mention that there is other method steps in one or more method stepss or inserts method steps between clear and definite specified those steps before or after being not precluded within described step combination.And, be a kind of method easily of discerning discrete actives or composition with method steps or composition numbering, unless otherwise indicated, described numbering can be with any series arrangement.
Here employed term " polyester " means and comprises equal polyester, copolyesters and three polyester.Usually, polyester is the synthetic polymer that the polycondensation by one or more two functional groups and/or polyfunctional group carboxylic acid and one or more two functional groups and/or polyfunctional group oxy-compound prepares.Typically, two functional group's carboxylic acids are dicarboxylic acid or hydroxycarboxylic acid, and two functional group's oxy-compound are dibasic alcohol such as glycol (glycol) and glycol (diol).Equally, polyester of the present invention can contain branched monomer, and this monomer can contain the combination of 3 or more a plurality of hydroxy-acid group, hydroxyl or hydroxy-acid group and hydroxyl.Therefore, employed here term " diacid " or " dicarboxylic acid " also mean and comprise and can be used as branched monomeric polyfunctional carboxylic acids such as trimellitic acid.Similarly, employed here " glycol " or " glycol " also mean and comprise and can be used as branched monomeric multifunctional hydroxy compounds such as tetramethylolmethane.In the present invention, two senses or polyfunctional carboxylic acids can be aliphatics or alicyclic dicarboxylic acid such as hexanodioic acid, perhaps aromatic dicarboxylic acid such as terephthalic acid.Two sense oxy-compound can be alicyclic diol such as 1,4 cyclohexane dimethanol, and the straight or branched aliphatic diol is as 1,4-butyleneglycol, perhaps aromatic diol such as quinhydrones.
Polyester used in the present invention is incorporated into by the reaction of equal proportion basically and with its corresponding residue normally that dicarboxylic acid in this polyester polymers and glycol prepare.Therefore, contain the sour residue (100mol%) and the diol residue (100mol%) of first-class substantially molar ratio, make the total mole number of repeating unit equal 100mol% derived from the polyester of dicarboxylic acid of the present invention and diol residue.Therefore, the molar percentage that provides of disclosure of the present invention can be based on the total mole number of sour residue, the total mole number of diol residue or the total mole number of repeating unit.For example, based on all sour residues, the copolyesters that contains the 30mol% terephthalic acid is meant, is the sour residue of 100mol% based on total amount, and this copolyesters contains the 30mol% terephthalic acid residue.Therefore, in every 100mol acid residue, there is the 30mol terephthalic acid residue.In another example, based on all diol residue, contain 30mol%1, the copolyesters of 4-cyclohexanedimethanol is meant, is the diol residue of 100mol% based on total amount, this copolyesters contains 30mol%1,4-cyclohexanedimethanol residue.Therefore, in every 100mol diol residue, there is the 1,4 cyclohexane dimethanol residue of 30mol.When diol component mainly was ethylene glycol, the copolyesters of employed here terephthalic acid, ethylene glycol and 1,4 cyclohexane dimethanol can be called as " PET "; When diol component mainly was 1,4 cyclohexane dimethanol, this copolyesters can be called as " PCT "; When the ratio of ethylene glycol and 1,4 cyclohexane dimethanol greater than 1 the time, this copolyesters can be called as " PETG "; And when the ratio of ethylene glycol and 1,4 cyclohexane dimethanol less than 1 the time, this copolyesters can be called as " PCTG ".
Here employed term " polymeric amide " means the synthetic polymer that the polycondensation that comprises by one or more two functional carboxylic acid and one or more two functional amines or the ring-opening polymerization by lactan prepare, and can comprise homopolymer and multipolymer.For example, two functional carboxylic acid can be dicarboxylic acid such as hexanodioic acid or m-phthalic acid, and two functional amines can be diamines such as hexanediamine or m-xylene diamine.Here employed term " copolyamide " is understood that to mean the polymeric amide that comprises at least two kinds of chemically different repeating units.For example, MXD6 nylon is not copolyamide, because it only contains the repeating unit of a kind of chemically identification (chemically distinct), this repeating unit contains the residue of hexanodioic acid and m-xylene diamine.On the contrary, have two chemically different repeating units by hexanediamine with poly-(the hexa-methylene adipamide-be total to-isophthaloyl amine) of the condensation prepared of hexanodioic acid and m-phthalic acid, that is the repeating unit and the another kind of repeating unit that contains hexanediamine and isophthalic acid residues that, contain hexanediamine and hexanodioic acid residue.
The term here " polycarbonate " is defined as the condensation product in carbonate source and glycol source, for 200mol% monomeric unit or 100mol% " repeating unit " altogether, this condensation product has the carbonic ether composition that contains the 100mol% carbonate unit and contains the diol component of 100mol% diol units.In an embodiment of the invention, the carbonate moiety of first component is based on 4,4 '-polycarbonate of isopropylidene dihydric phenol, it is commonly called bisphenol-a polycarbonate.Can be used for multiple straight or branched polycarbonate of the present invention can be derived from dihydroxyphenyl propane, and can be according to method preparation well known in the art, as United States Patent (USP) 3,030, and 335 and 3,317,446 disclosed methods.Can be used for the present invention and can the commercial polycarbonate that obtains comprise can derive from GeneralElectric Company with trade(brand)name LEXAN The material of selling and can derive from Bayer, the commodity of Inc. are called MAKROLON Material.
Here employed term " polyarylester " is understood that to mean the polyester by the polycondensation preparation of one or more two senses aromatic dicarboxylic acids and one or more dihydric phenols.For example, typical aromatic dicarboxylic acid is terephthalic acid and m-phthalic acid, and typical fragrant diphenol is dihydroxyphenyl propane and quinhydrones.
Here the term " residue " that polymkeric substance employed and of the present invention is relevant is meant by relating to corresponding monomeric polycondensation or ring-opening reaction and joins any organic structure in the polymkeric substance.Here employed term " repeating unit " is meant the shortest sequence that can repeat the monomer residue found in polymkeric substance.For example, in polyester, repeating unit is the organic structure with dicarboxylic acid residue and diol residue or hydroxycarboxylic acid residue that connects by carbonyl oxygen base group.In polymeric amide, repeating unit is the organic structure with dicarboxylic acid and diamines residue, lactan or amino-acid residue that connects by amide group.
Those skilled in the art it is also understood that the residue relevant with polyarylester with various polyester of the present invention, polymeric amide, polycarbonate can be derived from any derivative of parent monomeric compound self or parent compound.For example, relating to the dicarboxylic acid of polymkeric substance of the present invention can be derived from dicarboxylic acid or amino acid monomer or its relevant carboxylic acid halides, ester, salt, acid anhydrides or their mixture with amino-acid residue.Therefore, here employed term " dicarboxylic acid " or " amino acid " mean and comprise that the process that can be used for carrying out polycondensation with glycol with preparation high molecular weight polyesters, polymeric amide, polycarbonate or the dicarboxylic acid of polyarylester and any derivative of dicarboxylic acid, comprises carboxylic acid halides, ester, half ester, salt, half salt, acid anhydrides, mixed acid anhydride or their mixture that it is relevant.Term " hydroxyl is calculated " means and comprises and can be used in polycondensation process or the open loop reflection comprising carboxylic acid halides, ester, cyclic ester (comprising dipolymer such as lactic acid lactide), salt, acid anhydrides, mixed acid anhydride or its mixture that it is relevant to make aliphatics and alicyclic hydroxycarboxylic acid and monohydroxy-monocarboxylic acid and composition thereof of high molecular weight polyesters.Similarly, " amino acid " means and comprises and can be used for polycondensation process or ring-opening reaction aliphatics, aromatic series and alicyclic amino acid and any derivative thereof with the preparation superpolyamide, comprise carboxylic acid halides, acid amides, cyclic amide (lactan), salt, acid anhydrides, mixed acid anhydride or their mixture that it is relevant.In addition, term " diamines " mean comprise the diamines that can be used for preparing polymeric amide with and relevant salt, acid amides or its any other derivative.
As long as term " logarithmic viscosity number " (I.V.) uses in this application, it is appreciated that the viscosity measurement value that is meant that the 0.5g polymkeric substance obtains in 25 ℃ of every 100ml solvents of use, contains 60wt% phenol and 40wt% tetrachloroethane in this solvent.
Here employed term " specific refractory power " (being abbreviated as " RI " in this article) is meant the refractive index measurements that obtains according to method well known in the art.The specific refractory power that this paper reported is to use Metricon Prism Coupler under the 633nm wavelength TMModel 2010 refractometers (can available from Metricon Inc.) are measured, and are reported as the mean value of going up the specific refractory power of measuring at three orthogonal directionss (extruding or draw direction, laterally and thickness direction).Here the employed phrase " refringence " relevant with composition, method and molded article typically refers to by the specific refractory power from the component (being commonly referred to " second layer " of " second component " or multi-layer product in this article) that contains polymeric amide or copolyamide and deducts the value that the specific refractory power of the component (being commonly referred to " the first layer " of " first component " or multi-layer product in this article) that contains polyester, polycarbonate or polyarylester obtains.Therefore, according to the present invention, refringence (" Δ RI ") should be calculated according to following formula:
Δ RI=RI (second component or the second layer)-RI (first component or the first layer)
For a person skilled in the art, the apparent refractive index difference can be positive number or negative.
Here employed term " % turbidity " is meant according to ASTM method D1003, uses the Hunter Associates Laboratory of Virginia Reston, HunterLabUltraScan Sphere 8000 colorimeters that Inc. makes, uses Hunter ' s Universal Software (3.8 editions) and the turbidity value (% turbidity=100* diffuse transmission/total transmission) determined.Here employed term " percent transmittance " and term " per-cent transmittance " synonym.The method of measuring specific refractory power provides in an embodiment.For composition of the present invention, turbidity and percent transmittance are (promptly, the % transmissivity) measure by following method: it is 1/8 inch or lower sheet material or film that composition molding or curtain coating are become thickness, and measures turbidity and percent transmittance according to the described method of embodiment.For molded article, comprise the multilevel shaping goods, turbidity and percent transmittance can be measured by following method: the sub-fraction (that is, 1 * 1cm) of downcutting these goods, the thickness of this cutting-out part is 1/8 inch or lower, and measures turbidity according to method as herein described.
Here employed term second-order transition temperature (" Tg ") is meant and uses differential scanning calorimetric (" DSC "), uses the Tg value of the scan rate measurement of 20 ℃/min usually.An example of DSC equipment is TA Instrumetns 2920 differential scanning calorimeters.
Composition of the present invention comprises that containing one or more is selected from polyester, polycarbonate, polyarylester and even first component of the thermoplastic polymer of adulterant thereof.Here employed term " thermoplastic polymer " means that it has general sense understood by one of ordinary skill in the art, that is, softening and be returned to the polymkeric substance of its original state during at cool to room temperature when being exposed to when hot.First component can comprise single thermoplastic polymer, perhaps can comprise the adulterant of two or more polymkeric substance, and condition is that this adulterant is even adulterant.Here employed term " evenly adulterant " and term " solvable mixing " synonym, and mean that this adulterant of expression has homogeneous single phase, shown in single as it, the relevant Tg with composition.For example, as United States Patent (USP) 6,211, shown in 309, can be used to make second polymkeric substance " to become mouldable " with miscible first polymkeric substance of second polymkeric substance.Evenly adulterant can form by two or more polymkeric substance of simple blending, and perhaps in the situation of condensation polymer such as polyester or polymeric amide, transesterify or transmidation by two or more polymkeric substance form.On the contrary, employed here term " non-miscible " is meant such adulterant: it shows that at least two random blended also show above a Tg mutually.Some polymkeric substance is immiscible, but still compatible with each other.About solvable mixed immiscible polymer adulterant with and the further general remark of the various analytical technologies of feature can be at PoymerBlends the 1st and 2 volumes, D.R.Paul and C.B.Bucknall edit, 2000, John Wiley﹠amp; Sons finds among the Inc..
First component can comprise that one or more are selected from the thermoplastic polymer of polyester, polycarbonate, polyarylester and even adulterant thereof.For example, first component can comprise and contains following polyester:
(a) diacid residues, based on all diacid residues, it comprises that 80mol%'s at least is selected from terephthalic acid, m-phthalic acid, naphthalic acid and 1, at least a modification dicarboxylic acid residue with 2-20 carbon atom of at least a dicarboxylic acid residue of 4-cyclohexane dicarboxylic acid and 0-20mol%; And
(b) diol residue, based on all diol residue, it comprises that 80mol%'s at least is selected from ethylene glycol, 1,4-cyclohexanedimethanol, neopentyl glycol, glycol ether, 1, ammediol, 1,4-butyleneglycol and 2,2,4,4-tetramethyl--1, at least a modification diol residue of at least a diol residue of 3-cyclobutanediol and 0-20mol% with 3-16 carbon atom.The cyclic diols that contains cis and trans-isomer(ide) can be used as pure cis or trans-isomer(ide) use, and the mixture that perhaps can be used as cis and trans-isomer(ide) uses.
For example, diacid residues can comprise that one or more are selected from the residue of the dicarboxylic acid of terephthalic acid, m-phthalic acid or its combination, and diol residue comprises that one or more are selected from 1,4-cyclohexanedimethanol, neopentyl glycol, ethylene glycol, 2,2,4,4-tetramethyl--1, the residue of the glycol of 3-cyclobutanediol and combination thereof.In one embodiment, for example, diacid residues can comprise the residue of terephthalic acid and m-phthalic acid.To be higher than the concentration of m-phthalic acid be favourable to the concentration of terephthalic acid in polyester, because the polyester that obtains provides bigger shock strength for adulterant.For example, diacid residues can comprise that about 60 arrive the terephthalic acid residue of about 100mol% and 0 to about 40mol% isophthalic acid residues, and diol residue can comprise the 1,4 cyclohexane dimethanol residue of about 100mol%.Other example of dicarboxylic acid content comprises that about 80 isophthalic acid residues to the terephthalic acid residues of about 100mol% and 0 to 20mol%, about 95 arrive the terephthalic acid residue of about 100mol% and the terephthalic acid residue of about 100mol%.
Other the representative polyester that can be used as the thermoplastic polymer of component (i) comprises and contains following polyester: (a) comprise about terephthalic acid residue's of 80 to about 100mol% diacid residues and comprise that about 50 to about 90mol% 1,4 cyclohexane dimethanol residues and about 10 arrive the diol residue of the neopentyl glycol residue of about 50mol%; (b) comprise 100mol% the terephthalic acid residue diacid residues and comprise that about 10 arrive the diol residue of the glycol residue of about 90mol% to the 1,4 cyclohexane dimethanol residues of about 40mol% and 60; (c) comprise about 100mol% terephthalic acid diacid residues and comprise that about 10 arrive the diol residue of the glycol ether residue of about 25mol% to the 1,4 cyclohexane dimethanol residues of about 99mol%, 0 to about 90mol% glycol residue and about 1; (d) comprise 100mol% terephthalic acid diacid residues and comprise that about 50 arrive the diol residue of the ethylene glycol of about 50mol% to the 1,4 cyclohexane dimethanols of about 90mol% and about 10.
In another embodiment, first component can comprise at least a terephthalic acid, 2,2,4 that contains, 4-tetramethyl--1, the polyester of the residue of 3-cyclobutanediol and 1,4 cyclohexane dimethanol.For example, this polyester can comprise (a) diacid residues, based on all diacid residues, it comprises about terephthalic acid residue of 70 to about 100mol%, 0 to about 30mol% at least a residue with modified aromatic family dicarboxylic acid of 20 carbon atoms at the most and 0 to about 10mol% at least aly has a residue of the modified aliphatic dicarboxylic acid of 16 carbon atoms at the most; And (b) diol residue, based on all diol residue, it comprise about 1 to about 99mol% 2,2,4,4-tetramethyl--1,3-cyclobutanediol and about 1 arrives the residue of the 1,4 cyclohexane dimethanol of about 99mol%.Other representative example that can be used for the polyester of first component includes but not limited to following polyester: based on all diacid residues, it comprise 70 to about 100mol% terephthalic acid residue, 0 to about 30mol% at least aly have a residue of the modified aromatic family dicarboxylic acid of 20 carbon atoms at the most; With 0 to about 10mol% at least aly have a modified aliphatic dicarboxylic acid of 16 carbon atoms at the most, and any in forming of following diol residue: (i) about 5 to about 60mol% 2,2,4,4-tetramethyl--1,3-cyclobutanediol residue and about 40 arrives the 1,4 cyclohexane dimethanol residue of about 95mol%; (ii) about 15 arrive 2,2,4 of about 40mol%, 4-tetramethyl--1, and 3-cyclobutanediol residue and about 60 arrives the 1,4 cyclohexane dimethanol residue of about 85mol%; (iii) about 20 arrive 2,2,4 of about 30mol%, 4-tetramethyl--1, and 3-cyclobutanediol residue and about 70 arrives the 1,4 cyclohexane dimethanol residue of about 80mol%; (iv) about 20 arrive 2,2,4 of about 25mol%, 4-tetramethyl--1, and 3-cyclobutanediol residue and about 75 arrives the 1,4 cyclohexane dimethanol residue of about 80mol%.
In another example, dicarboxylic acid can be selected from terephthalic acid and m-phthalic acid, and glycol is selected from 1,4 cyclohexane dimethanol and ethylene glycol.In a composition, for example, dicarboxylic acid is a terephthalic acid, and glycol is a 1,4 cyclohexane dimethanol.In another example, diacid residues can comprise the terephthalic acid residue of 95mol% at least, and diol residue can comprise that about 10 to about 40mol% 1,4 cyclohexane dimethanol residue, about 1 arrives the glycol ether residue of about 25mol% and about 35 to about 89mol% glycol residue.
If desired, polyester may further include 0 to about 30mol% one or more contain the residue of the modification diacid of 2 to 20 carbon atoms.For example, can use 0 to about 30mol% contain 8 other aromatic dicarboxylic acids, contain 8 alicyclic dicarboxylic acids, contain and have an appointment 2 to the aliphatic dicarboxylic acid of about 16 carbon atoms or their mixture to about 16 carbon atoms to about 16 carbon atoms.The example of modified aromatic family dicarboxylic acid includes but not limited to one or more in following: 4,4 '-diphenyl dicarboxylic acid, m-phthalic acid, 1,4-naphthalic acid, 1,5-naphthalic acid, 2,6-naphthalic acid, 2,7-naphthalic acid, 4,4 '-oxybenzene formic acid and trans-4,4 '-the Stilbene dicarboxylic acid.The example of modified aliphatic dicarboxylic acid includes but not limited to one or more in following: oxalic acid, propanedioic acid, Succinic Acid, pentanedioic acid, hexanodioic acid, pimelic acid, suberic acid, nonane diacid and sebacic acid.For example, the diacid component of polyester can with 0 to about 10mol% at least aly have at the most that the modified aliphatic dicarboxylic acid of 16 carbon atoms comes modification.
In another embodiment, based on all diol residue, polyester can comprise that about 1 arrives the 1,4 cyclohexane dimethanol of about 99mol% and about 99 to about 1mol% glycol residue.The typical molar percentage that is used for the 1,4 cyclohexane dimethanol residue of polyester of the present invention comprises about 1 to about 10mol%, about 1 to about 25mol%, about 1 to about 40mol%, 50mol% or more and 100mol%.In another embodiment, for example, dicarboxylic acid is 1, the 4-cyclohexane dicarboxylic acid, and glycol is a 1,4 cyclohexane dimethanol.In another example, polyester can comprise the residue of 1,4 cyclohexane dimethanol unit and neopentyl glycol.In another example, polyester can comprise 1,4 cyclohexane dimethanol unit and 2,2,4,4-tetramethyl--1, the residue of 3-cyclobutanediol.
The diol component of polyester can also come modification with the modification glycol of at least a 3-16 of having carbon atom of 0 to about 20mol%.Other scope of modification glycol includes but not limited to 0 to about 10mol% and be less than 5mol%.The modification glycol can be selected from one or more in following: 1,2-propylene glycol, 1, ammediol, 1,4-butyleneglycol, 1,5-pentanediol, 1,6-hexylene glycol, 1,4-cyclohexanedimethanol, terephthalyl alcohol, neopentyl glycol, polyoxyethylene glycol, polytetramethylene glycol and 2,2,4,4-tetramethyl--1, the 3-cyclobutanediol.The example of polyalkylene glycol comprises that molecular weight is up to about 2,000 polytetramethylene glycol (" PTMG ") and polyoxyethylene glycol (" PEG ").Diol component, for example, can be with 0 to about 10mol% polyoxyethylene glycol or polytetramethylene glycol modification, so that strengthen elastic behavior.In another example, diol residue can comprise that about 10 to about 99mol% 1,4 cyclohexane dimethanol residue, 0 arrives the glycol residue of about 90mol% and about 1 to about 25mol% glycol ether residue.Total amount based on diacid or diol residue, polyester can also contain 5mol% at the most, be generally about 0.01 to about 2.0mol% or be more typically about 0.01 to about 1mol% multifunctional collateralization agent (branching agent) with the formation branched polyesters, and this multifunctional collateralization agent derives from the compound with at least three carboxyls and hydroxyl.The example of this compound comprises trimellitic acid, trimellitic acid 1,2-anhydride and pyromellitic acid dianhydride, glycerine, Sorbitol Powder, 1,2,6-hexanetriol, tetramethylolmethane, tartrate, citric acid, trimethylolethane and trimesic acid etc.It will be appreciated by those skilled in the art that final composition can realize by the various resins of blending or by direct reactor copolymerization.For reduce forming variability as far as possible, the latter is an ideal, and more cost is effective but economic necessity usually makes blending.
Other example of polyester is based on all diacid residues and contains those that the terephthalic acid residue of the 100mol% that has an appointment and any one following diol residue form: based on all diol residue, (i) about 1 to about 5mol% 1,4 cyclohexane dimethanol residue and about 99 arrives the glycol residue of about 95mol%; (ii) about 29 to about 33mol% 1,4 cyclohexane dimethanol residue and about 71 arrives the glycol residue of about 67mol%; (iii) about 45 to about 55mol% 1,4 cyclohexane dimethanol residue and about 55 arrives the glycol residue of about 45mol%; (iv) about 60 to about 65mol% 1,4 cyclohexane dimethanol residue and about 40 arrives the glycol residue of about 35mol%; (v) about 79 to about 83mol% 1,4 cyclohexane dimethanol residue and about 21 arrives the glycol residue of about 17mol%; (the vi) 1,4 cyclohexane dimethanol residue of about 100mol%; (vii) about 5 arrive 2,2,4 of about 60mol%, 4-tetramethyl--1, and 3-cyclobutanediol residue and about 40 arrives the 1,4 cyclohexane dimethanol residue of about 95mol%; (viii) about 15 arrive 2,2,4 of about 40mol%, 4-tetramethyl--1, and 3-cyclobutanediol residue and about 60 arrives the 1,4 cyclohexane dimethanol residue of about 85mol%; (ix) about 20 to about 30mol% 2,2,4,4-tetramethyl--1,3-cyclobutanediol residue and about 70 arrives the 1,4 cyclohexane dimethanol residue of about 80mol%; And (x) about 20 to about 25mol% 2,2,4,4-tetramethyl--1,3-cyclobutanediol residue and about 75 arrives the 1,4 cyclohexane dimethanol residue of about 80mol%.
It is believed that, some has specific monomer and forms, comprising of logarithmic viscosity number and second-order transition temperature by terephthalic acid and ester or their composition, 1,4-cyclohexanedimethanol and 2,2,4,4-tetramethyl--1, the composition of the polyester that the 3-cyclobutanediol forms, in high impact, stability to hydrolysis, toughness, chemical resistant properties, good color and transparency, long crystallization half-life, low ductility for brittle transition temperature, lower proportion, and one or more aspects of thermoforming ability, be better than polyester known in the art and polycarbonate.The thermotolerance that it is believed that these compositions is similar to polycarbonate, and remains machinable on standard industry equipment.
In another aspect of this invention, for example, the Tg that can be used for the polyester of composition of the present invention, method and molded article can be at least one in the following ranges: 60-200 ℃; 60-190 ℃; 60-180 ℃; 60-170 ℃; 60-160 ℃; 60-155 ℃; 60-150 ℃; 60-145 ℃; 60-140 ℃; 60-138 ℃; 60-135 ℃; 60-130 ℃; 60-125 ℃; 60-120 ℃; 60-115 ℃; 60-110 ℃; 60-105 ℃; 60-100 ℃; 60-95 ℃; 60-90 ℃; 60-85 ℃; 60-80 ℃; 60-75 ℃; 65-200 ℃; 65-190 ℃; 65-180 ℃; 65-170 ℃; 65-160 ℃; 65-155 ℃; 65-150 ℃; 65-145 ℃; 65-140 ℃; 65-138 ℃; 65-135 ℃; 65-130 ℃; 65-125 ℃; 65-120 ℃; 65-115 ℃; 65-110 ℃; 65-105 ℃; 65-100 ℃; 65-95 ℃; 65-90 ℃; 65-85 ℃; 65-80 ℃; 65-75 ℃; 70-200 ℃; 70-190 ℃; 70-180 ℃; 70-170 ℃; 70-160 ℃; 70-155 ℃; 70-150 ℃; 70-145 ℃; 70-140 ℃; 70-138 ℃; 70-135 ℃; 70-130 ℃; 70-125 ℃; 70-120 ℃; 70-115 ℃; 70-110 ℃; 70-105 ℃; 70-100 ℃; 70-95 ℃; 70-90 ℃; 70-85 ℃; 70-80 ℃; 70-75 ℃; 75-200 ℃; 75-190 ℃; 75-180 ℃; 75-170 ℃; 75-160 ℃; 75-155 ℃; 75-150 ℃; 75-145 ℃; 75-140 ℃; 75-138 ℃; 75-135 ℃; 75-130 ℃; 75-125 ℃; 75-120 ℃; 75-115 ℃; 75-110 ℃; 75-105 ℃; 75-100 ℃; 75-95 ℃; 75-90 ℃; 75-85 ℃; 75-80 ℃; 80-200 ℃; 80-190 ℃; 80-180 ℃; 80-170 ℃; 80-160 ℃; 80-155 ℃; 80-150 ℃; 80-145 ℃; 80-140 ℃; 80-138 ℃; 80-135 ℃; 80-130 ℃; 80-125 ℃; 80-120 ℃; 80-115 ℃; 80-110 ℃; 80-105 ℃; 80-100 ℃; 80-95 ℃; 80-90 ℃; 80-85 ℃; 85-200 ℃; 85-190 ℃; 85-180 ℃; 85-170 ℃; 85-160 ℃; 85-155 ℃; 85-150 ℃; 85-145 ℃; 85-140 ℃; 85-138 ℃; 85-135 ℃; 85-130 ℃; 85-125 ℃; 85-120 ℃; 85-115 ℃; 85-110 ℃; 85-105 ℃; 85-100 ℃; 85-95 ℃; 85-90 ℃; 90-200 ℃; 90-190 ℃; 90-180 ℃; 90-170 ℃; 90-160 ℃; 90-155 ℃; 90-150 ℃; 90-145 ℃; 90-140 ℃; 90-138 ℃; 90-135 ℃; 90-130 ℃; 90-125 ℃; 90-120 ℃; 90-115 ℃; 90-110 ℃; 90-105 ℃; 90-100 ℃; 90-95 ℃; 95-200 ℃; 95-190 ℃; 95-180 ℃; 95-170 ℃; 95-160 ℃; 95-155 ℃; 95-150 ℃; 95-145 ℃; 95-140 ℃; 95-138 ℃; 95-135 ℃; 95-130 ℃; 95-125 ℃; 95-120 ℃; 95-115 ℃; 95-110 ℃; 95-105 ℃; 95-100 ℃; 100-200 ℃; 100-190 ℃; 100-180 ℃; 100-170 ℃; 100-160 ℃; 100-155 ℃; 100-150 ℃; 100-145 ℃; 100-140 ℃; 100-138 ℃; 100-135 ℃; 100-130 ℃; 100-125 ℃; 100-120 ℃; 100-115 ℃; 100-110 ℃; 105-200 ℃; 105-190 ℃; 105-180 ℃; 105-170 ℃; 105-160 ℃; 105-155 ℃; 105-150 ℃; 105-145 ℃; 105-140 ℃; 105-138 ℃; 105-135 ℃; 105-130 ℃; 105-125 ℃; 105-120 ℃; 105-115 ℃; 105-110 ℃; 110-200 ℃; 110-190 ℃; 110-180 ℃; 110-170 ℃; 110-160 ℃; 110-155 ℃; 110-150 ℃; 110-145 ℃; 110-140 ℃; 110-138 ℃; 110-135 ℃; 110-130 ℃; 110-125 ℃; 110-120 ℃; 110-115 ℃; 115-200 ℃; 115-190 ℃; 115-180 ℃; 115-170 ℃; 115-160 ℃; 115-155 ℃; 115-150 ℃; 115-145 ℃; 115-140 ℃; 115-138 ℃; 115-135 ℃; 110-130 ℃; 115-125 ℃; 115-120 ℃; 120-200 ℃; 120-190 ℃; 120-180 ℃; 120-170 ℃; 120-160 ℃; 120-155 ℃; 120-150 ℃; 120-145 ℃; 120-140 ℃; 120-138 ℃; 120-135 ℃; 120-130 ℃; 125-200 ℃; 125-190 ℃; 125-180 ℃; 125-170 ℃; 125-165 ℃; 125-160 ℃; 125-155 ℃; 125-150 ℃; 125-145 ℃; 125-140 ℃; 125-138 ℃; 125-135 ℃; 127-200 ℃; 127-190 ℃; 127-180 ℃; 127-170 ℃; 127-160 ℃; 127-150 ℃; 127-145 ℃; 127-140 ℃; 127-138 ℃; 127-135 ℃; 130-200 ℃; 130-190 ℃; 130-180 ℃; 130-170 ℃; 130-160 ℃; 130-155 ℃; 130-150 ℃; 130-145 ℃; 130-140 ℃; 130-138 ℃; 130-135 ℃; 135-200 ℃; 135-190 ℃; 135-180 ℃; 135-170 ℃; 135-160 ℃; 135-155 ℃; 135-150 ℃; 135-145 ℃; 135-140 ℃; 140-200 ℃; 140-190 ℃; 140-180 ℃; 140-170 ℃; 140-160 ℃; 140-155 ℃; 140-150 ℃; 140-145 ℃; 148-200 ℃; 148-190 ℃; 148-180 ℃; 148-170 ℃; 148-160 ℃; 148-155 ℃; 148-150 ℃; Be higher than 148-200 ℃; Be higher than 148-190 ℃; Be higher than 148-180 ℃; Be higher than 148-170 ℃; Be higher than 148-160 ℃; Be higher than 148-155 ℃; 150-200 ℃; 150-190 ℃; 150-180 ℃; 150-170 ℃; 150-160; 155-190 ℃; 155-180 ℃; 155-170 ℃; With 155-165 ℃..
In another aspect of this invention, the diol component of polyester of the present invention includes but not limited to any one in the combination of following ranges: 2,2,4 of 1-99mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 1-99mol%; 2,2,4 of 1-95mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 5-99mol%; 2,2,4 of 1-90mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 10-99mol%; 2,2,4 of 1-85mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 15-99mol%; 2,2,4 of 1-80mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 20-99mol%; 2,2,4 of 1-75mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 25-99mol%; 2,2,4 of 1-70mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 30-99mol%; 2,2,4 of 1-65mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 35-99mol%; 2,2,4 of 1-60mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 40-99mol%; 2,2,4 of 1-55mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 45-99mol%; 2,2,4 of 1-50mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 50-99mol%; 2,2,4 of 1-45mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 55-99mol%; 2,2,4 of 1-40mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 60-99mol%; 2,2,4 of 1-35mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 65-99mol%; 2,2,4 of 1-30mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 70-99mol%; 2,2,4 of 1-25mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 75-99mol%; 2,2,4 of 1-20mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 80-99mol%; 2,2,4 of 1-15mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 85-99mol%; 2,2,4 of 1-10mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 90-99mol%; And 1-5mol% 2,2,4,4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 95-99mol%.
In another aspect of this invention, the diol component of polyester of the present invention includes but not limited to any one in the combination of following scope: 0.01 to being less than 2,2 of 5mol%, 4,4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 95-99.99mol%; 0.01 to 2,2,4 of 4.5mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 95.5-99.99mol%; 0.01 to 2,2,4 of 4mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 96-99.99mol%; 0.01 to 2,2,4 of 3.5mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 96.5-99.99mol%; 0.01 to 2,2,4 of 3mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 97-99.99mol%; 0.01 to 2,2,4 of 2.5mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 97.5-99.99mol%; 0.01 to 2,2,4 of 2mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 98-99.99mol%; 0.01 to 2,2,4 of 1.5mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 98.5-99.99mol%; 0.01 to 2,2,4 of 1mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 99-99.99mol%; And 0.01 to 0.5mol% 2,2,4,4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 99.5-99.99mol%.
In another aspect of this invention, diol component can include but not limited to any one in the combination of following scope: 5 to 99mol% 2,2,4,4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 1-95mol%; 5 arrive 2,2,4 of 95mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 5-95mol%; 5 arrive 2,2,4 of 90mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 10-95mol%; 5 arrive 2,2,4 of 85mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 15-95mol%; 5 arrive 2,2,4 of 80mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 20-95mol%; 5 arrive 2,2,4 of 75mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 25-95mol%; 5 arrive 2,2,4 of 70mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 30-95mol%; 5 arrive 2,2,4 of 65mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 35-95mol%; 5 arrive 2,2,4 of 60mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 40-95mol%; 5 arrive 2,2,4 of 55mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 45-95mol%; And 5 to 50mol% 2,2,4,4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 50-95mol%.
In another aspect of this invention, diol component can include but not limited to any one in the combination of following scope: 5 to being less than 2,2,4 of 50mol%, 4-tetramethyl--1,3-cyclobutanediol and more than 50 to 95mol% 1,4 cyclohexane dimethanol; 2,2,4 of 5-45mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 55-95mol%; 2,2,4 of 5-40mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 60-95mol%; 2,2,4 of 5-35mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 65-95mol%; 5 to being less than 2,2,4 of 35mol%, 4-tetramethyl--1,3-cyclobutanediol and more than 65 to 95mol% 1,4 cyclohexane dimethanol; 2,2,4 of 5-30mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 70-95mol%; 2,2,4 of 5-25mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 75-95mol%; 2,2,4 of 5-20mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 80-95mol%; 2,2,4 of 5-15mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 85-95mol%; 2,2,4 of 5-10mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 90-95mol%; More than 5 to being less than 2,2,4 of 10mol%, 4-tetramethyl--1,3-cyclobutanediol and be less than 90 to 1,4 cyclohexane dimethanols more than 95mol%; 2,2,4 of 5.5mol%-9.5mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 94.5mol%-90.5mol%; And 6-9mol% 2,2,4,4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 94-91mol%;
In another aspect of this invention, the diol component of polyester of the present invention can include but not limited at least one in the combination of following scope: 2,2,4 of 10-99mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 1-90mol%; 2,2,4 of 10-95mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 5-90mol%; 2,2,4 of 10-90mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 10-90mol%; 2,2,4 of 10-85mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 15-90mol%; 2,2,4 of 10-80mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 20-90mol%; 2,2,4 of 10-75mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 25-90mol%; 2,2,4 of 10-70mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 30-90mol%; 2,2,4 of 10-65mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 35-90mol%; 2,2,4 of 10-60mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 40-90mol%; 2,2,4 of 10-55mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 45-90mol%; 2,2,4 of 10-50mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 50-90mol%; 10 to being less than 2,2,4 of 50mol%, 4-tetramethyl--1,3-cyclobutanediol and more than 50 to 90mol% 1,4 cyclohexane dimethanol; 2,2,4 of 10-45mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 55-90mol%; 2,2,4 of 10-40mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 60-90mol%; 2,2,4 of 10-35mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 65-90mol%; 10 to being less than 2,2,4 of 35mol%, 4-tetramethyl--1,3-cyclobutanediol and more than 65 to 90mol% 1,4 cyclohexane dimethanol; 2,2,4 of 10-30mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 70-90mol%; 2,2,4 of 10-25mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 75-90mol%; 2,2,4 of 10-20mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 80-90mol%; And 10-15mol% 2,2,4,4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 85-90mol%.
In another aspect of this invention, diol component can include but not limited at least one in the combination of following scope: 2,2,4 of 14-99mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 1-86mol%; 2,2,4 of 14-95mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 5-86mol%; 2,2,4 of 14-90mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 10-86mol%; 2,2,4 of 14-85mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 15-86mol%; 2,2,4 of 14-80mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 20-86mol%; 2,2,4 of 14-75mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 25-86mol%; 2,2,4 of 14-70mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 30-86mol%; 2,2,4 of 14-65mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 35-86mol%; 2,2,4 of 14-60mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 40-86mol%; 2,2,4 of 14-55mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 45-86mol%; 2,2,4 of 14-50mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 50-86mol%; 14 to being less than 2,2,4 of 50mol%, 4-tetramethyl--1,3-cyclobutanediol and more than 50 to 86mol% 1,4 cyclohexane dimethanol; 2,2,4 of 14-45mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 55-86mol%; 2,2,4 of 14-40mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 60-86mol%; 2,2,4 of 14-35mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 65-86mol%; 2,2,4 of 14-30mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 70-86mol%; 2,2,4 of 14-24mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 76-86mol%; And 14-25mol% 2,2,4,4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 75-86mol%.
In another aspect of this invention, the ethylene glycol component of polyester of the present invention can include but not limited at least one in the combination of following scope: 2,2,4 of 15-99mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 1-85mol%; 2,2,4 of 15-95mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 5-85mol%; 2,2,4 of 15-90mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 10-85mol%; 2,2,4 of 15-85mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 15-85mol%; 2,2,4 of 15-80mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 20-85mol%; 2,2,4 of 15-75mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 25-85mol%; 2,2,4 of 15-70mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 30-85mol%; 2,2,4 of 15-65mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 35-85mol%; 2,2,4 of 15-60mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 40-85mol%; 2,2,4 of 15-55mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 45-85mol%; 2,2,4 of 15-50mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 50-85mol%; 15 to being less than 2,2,4 of 50mol%, 4-tetramethyl--1,3-cyclobutanediol and more than 50 to 85mol% 1,4 cyclohexane dimethanol; 2,2,4 of 15-45mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 55-85mol%; 2,2,4 of 15-40mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 60-85mol%; 2,2,4 of 15-35mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 65-85mol%; 2,2,4 of 15-30mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 70-85mol%; 2,2,4 of 15-25mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 75-85mol%; And 15-24mol% 2,2,4,4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 76-85mol%.
In another aspect of this invention, the diol component of polyester of the present invention can include but not limited at least one in the combination of following scope: 2,2,4 of 20-99mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 1-80mol%; 2,2,4 of 20-95mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 5-80mol%; 2,2,4 of 20-90mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 10-80mol%; 2,2,4 of 20-85mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 15-80mol%; 2,2,4 of 20-80mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 20-80mol%; 2,2,4 of 20-75mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 25-80mol%; 2,2,4 of 20-70mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 30-80mol%; 2,2,4 of 20-65mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 35-80mol%; 2,2,4 of 20-60mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 40-80mol%; 2,2,4 of 20-55mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 45-80mol%; 2,2,4 of 20-50mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 50-80mol%; 20 to being less than 2,2,4 of 50mol%, 4-tetramethyl--1,3-cyclobutanediol and more than 50 to 80mol% 1,4 cyclohexane dimethanol; 2,2,4 of 20-45mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 55-80mol%; 2,2,4 of 20-40mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 60-80mol%; 2,2,4 of 20-35mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 65-80mol%; 2,2,4 of 20-30mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 70-80mol%; And 20-25mol% 2,2,4,4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 75-80mol%.
In another aspect of this invention, the diol component of polyester of the present invention can include but not limited at least one in the combination of following scope: 2,2,4 of 25-99mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 1-75mol%; 2,2,4 of 25-95mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 5-75mol%; 2,2,4 of 25-90mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 10-75mol%; 2,2,4 of 25-85mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 15-75mol%; 2,2,4 of 25-80mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 20-75mol%; 2,2,4 of 25-75mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 25-75mol%; 2,2,4 of 25-70mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 30-75mol%; 2,2,4 of 25-65mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 35-75mol%; 2,2,4 of 25-60mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 40-75mol%; 2,2,4 of 25-55mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 45-75mol%; 2,2,4 of 25-50mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 50-75mol%; 25 to being less than 2,2,4 of 50mol%, 4-tetramethyl--1,3-cyclobutanediol and more than 50 to 75mol% 1,4 cyclohexane dimethanol; 2,2,4 of 25-45mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 55-75mol%; 2,2,4 of 25-40mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 60-75mol%; 2,2,4 of 25-35mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 65-75mol%; And 25-30mol% 2,2,4,4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 70-75mol%.
In another aspect of this invention, the diol component of polyester of the present invention can include but not limited at least one in the combination of following scope: 2,2,4 of 30-99mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 1-70mol%; 2,2,4 of 30-95mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 5-70mol%; 2,2,4 of 30-90mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 10-70mol%; 2,2,4 of 30-85mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 15-70mol%; 2,2,4 of 30-80mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 20-70mol%; 2,2,4 of 30-75mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 25-70mol%; 2,2,4 of 30-70mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 30-70mol%; 2,2,4 of 30-65mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 35-70mol%; 2,2,4 of 30-60mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 40-70mol%; 2,2,4 of 30-55mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 45-70mol%; 2,2,4 of 30-50mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 50-70mol%; 30 to being less than 2,2,4 of 50mol%, 4-tetramethyl--1,3-cyclobutanediol and more than 50 to 70mol% 1,4 cyclohexane dimethanol; 2,2,4 of 30-45mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 55-70mol%; 2,2,4 of 30-40mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 60-70mol%; 2,2,4 of 30-35mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 65-70mol%.
In another aspect of this invention, the diol component of polyester of the present invention can include but not limited at least one in the combination of following scope: 2,2,4 of 35-99mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 1-65mol%; 2,2,4 of 35-95mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 5-65mol%; 2,2,4 of 35-90mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 10-65mol%; 2,2,4 of 35-85mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 15-65mol%; 2,2,4 of 35-80mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 20-65mol%; 2,2,4 of 35-75mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 25-65mol%; 2,2,4 of 35-70mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 30-65mol%; 2,2,4 of 35-65mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 35-65mol%; 2,2,4 of 35-60mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 40-65mol%; 2,2,4 of 35-55mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 45-65mol%; 2,2,4 of 35-50mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 50-65mol%; 35 to being less than 2,2,4 of 50mol%, 4-tetramethyl--1,3-cyclobutanediol and more than 50 to 65mol% 1,4 cyclohexane dimethanol; 2,2,4 of 35-45mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 55-65mol%; 2,2,4 of 35-40mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 60-65mol%.
In another aspect of this invention, the diol component of polyester of the present invention can include but not limited at least one in the combination of following scope: 2,2,4 of 40-99mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 1-60mol%; 2,2,4 of 40-95mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 5-60mol%; 2,2,4 of 40-90mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 10-60mol%; 2,2,4 of 40-85mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 15-60mol%; 2,2,4 of 40-80mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 20-60mol%; 2,2,4 of 40-75mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 25-60mol%; 2,2,4 of 40-70mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 30-60mol%; 2,2,4 of 40-65mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 35-60mol%; 2,2,4 of 40-60mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 40-60mol%; 2,2,4 of 40-55mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 45-60mol%; 40 to being less than 2,2,4 of 50mol%, 4-tetramethyl--1,3-cyclobutanediol and more than 50 to 60mol% 1,4 cyclohexane dimethanol; 2,2,4 of 40-50mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 50-60mol%; And 40-45mol% 2,2,4,4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 55-60mol%.
In another aspect of this invention, the diol component of polyester of the present invention can include but not limited at least one in the combination of following scope: 2,2,4 of 45-99mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 1-55mol%; 2,2,4 of 45-95mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 5-55mol%; 2,2,4 of 45-90mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 10-55mol%; 2,2,4 of 45-85mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 15-55mol%; 2,2,4 of 45-80mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 20-55mol%; 2,2,4 of 45-75mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 25-55mol%; 2,2,4 of 45-70mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 30-55mol%; 2,2,4 of 45-65mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 35-55mol%; 2,2,4 of 45-60mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 40-55mol%; More than 45 to 55mol% 2,2,4,4-tetramethyl--1,3-cyclobutanediol and 45 is to the 1,4 cyclohexane dimethanol that is less than 55mol%; 2,2,4 of 45-55mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 45-55mol%; And 45-50mol% 2,2,4,4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 50-60mol%.
In another aspect of this invention, the diol component of polyester of the present invention can include but not limited at least one in the combination of following scope: more than 50 to 99mol% 2,2,4,4-tetramethyl--1,3-cyclobutanediol and 1 is to the 1,4 cyclohexane dimethanol that is less than 50mol%; More than 50 to 95mol% 2,2,4,4-tetramethyl--1,3-cyclobutanediol and 5 is to the 1,4 cyclohexane dimethanol that is less than 50mol%; More than 50 to 90mol% 2,2,4,4-tetramethyl--1,3-cyclobutanediol and 10 is to the 1,4 cyclohexane dimethanol that is less than 50mol%; More than 50 to 85mol% 2,2,4,4-tetramethyl--1,3-cyclobutanediol and 15 is to the 1,4 cyclohexane dimethanol that is less than 50mol%; More than 50 to 80mol% 2,2,4,4-tetramethyl--1,3-cyclobutanediol and 20 is to the 1,4 cyclohexane dimethanol that is less than 50mol%; More than 50 to 75mol% 2,2,4,4-tetramethyl--1,3-cyclobutanediol and 25 is to the 1,4 cyclohexane dimethanol that is less than 50mol%; More than 50 to 70mol% 2,2,4,4-tetramethyl--1,3-cyclobutanediol and 30 is to the 1,4 cyclohexane dimethanol that is less than 50mol%; More than 50 to 65mol% 2,2,4,4-tetramethyl--1,3-cyclobutanediol and 35 is to the 1,4 cyclohexane dimethanol that is less than 50mol%; More than 50 to 60mol% 2,2,4,4-tetramethyl--1,3-cyclobutanediol and 40 is to the 1,4 cyclohexane dimethanol that is less than 50mol%.
In another aspect of this invention, the diol component of polyester of the present invention can include but not limited at least one in the combination of following scope: 2,2,4 of 55-99mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 1-45mol%; 2,2,4 of 55-95mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 5-45mol%; 2,2,4 of 55-90mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 10-45mol%; 2,2,4 of 55-85mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 15-45mol%; 2,2,4 of 55-80mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 20-45mol%; 2,2,4 of 55-75mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 25-45mol%; 2,2,4 of 55-70mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 30-45mol%; 2,2,4 of 55-65mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 35-45mol%; And 55-60mol% 2,2,4,4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 40-45mol%.
In another aspect of this invention, the diol component of polyester of the present invention can include but not limited at least one in the combination of following scope: 2,2,4 of 60-99mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 1-40mol%; 2,2,4 of 60-95mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 5-40mol%; 2,2,4 of 60-90mo1%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 10-40mol%; 2,2,4 of 60-85mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 15-40mol%; 2,2,4 of 60-80mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 20-40mol%; 2,2,4 of 60-75mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 25-40mol%; And 60-70mol% 2,2,4,4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 30-40mol%.
In another aspect of this invention, the diol component of polyester of the present invention can include but not limited at least one in the combination of following scope: 2,2,4 of 65-99mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 1-35mol%; 2,2,4 of 65-95mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 5-35mol%; 2,2,4 of 65-90mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 10-35mol%; 2,2,4 of 65-85mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 15-35mol%; 2,2,4 of 65-80mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 20-35mol%; 2,2,4 of 65-75mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 25-35mol%; And 65-70mol% 2,2,4,4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 35-40mol%.
In another aspect of this invention, the diol component of polyester of the present invention can include but not limited at least one in the combination of following scope: 2,2,4 of 70-99mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 1-30mol%; 2,2,4 of 70-95mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 5-30mol%; 2,2,4 of 70-90mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 10-30mol%; 2,2,4 of 70-85mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 15-30mol%; 2,2,4 of 70-80mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 20-30mol%; And 70-75mol% 2,2,4,4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 25-30mol%.
In another aspect of this invention, the diol component of polyester of the present invention can include but not limited at least one in the combination of following scope: 2,2,4 of 75-99mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 1-25mol%; 2,2,4 of 75-95mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 5-25mol%; 2,2,4 of 75-90mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 10-25mol%; And 75-85mol% 2,2,4,4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 15-25mol%.
In another aspect of this invention, the diol component of polyester of the present invention can include but not limited at least one in the combination of following scope: 2,2,4 of 80-99mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 1-20mol%; 2,2,4 of 80-95mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 5-20mol%; And 80-90mol% 2,2,4,4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 10-20mol%.
In another aspect of this invention, the diol component of polyester of the present invention can include but not limited at least one in the combination of following scope: 2,2,4 of 37-80mol%, 4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 20-63mol%; 40 to being less than 2,2,4 of 45mol%, 4-tetramethyl--1,3-cyclobutanediol and more than 55 to 60mol% 1,4 cyclohexane dimethanol; More than 45 to 55mol% 2,2,4,4-tetramethyl--1,3-cyclobutanediol and 45 is to the 1,4 cyclohexane dimethanol that is less than 55mol%; And 46-55mol% 2,2,4,4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 45-54mol%; And 46-65mol% 2,2,4,4-tetramethyl--1, the 1,4 cyclohexane dimethanol of 3-cyclobutanediol and 35-54mol%.
In another aspect of this invention, wherein the molar percentage based on diol component equals 100mol%, 2,2,4,4-tetramethyl--1, the molar percentage of 3-cyclobutanediol is 0.01 to being less than 5mol%, and wherein the existence of CHDM is chosen wantonly, and the diol component that can be used for polyester of the present invention includes but not limited at least one in the combination of following scope: 0.01 to being less than 2,2 of 5mol%, 4,4-tetramethyl--1,3-cyclobutanediol residue, the glycol residue more than 0.01 to 95mol% and 0 arrive the 1,4 cyclohexane dimethanol of 99.98mol%; 0.01 to being less than 2,2,4 of 5mol%, 4-tetramethyl--1,3-cyclobutanediol residue, glycol residue and 0.01 to 99.98mol% 1,4 cyclohexane dimethanol more than 0.01 to 94.99mol%; 0.01 to being less than 2,2,4 of 5mol%, 4-tetramethyl--1,3-cyclobutanediol residue, glycol residue and 5 to 99.98mol% 1,4 cyclohexane dimethanol more than 0.01 to 90mol%; 0.01 to being less than 2,2,4 of 5mol%, 4-tetramethyl--1,3-cyclobutanediol residue, glycol residue and 10 to 99.98mol% 1,4 cyclohexane dimethanol more than 0.01 to 85mol%; 0.01 to being less than 2,2,4 of 5mol%, 4-tetramethyl--1,3-cyclobutanediol residue, glycol residue and 15 to 99.98mol% 1,4 cyclohexane dimethanol more than 0.01 to 80mol%; 0.01 to being less than 2,2,4 of 5mol%, 4-tetramethyl--1,3-cyclobutanediol residue, glycol residue and 20 to 99.98mol% 1,4 cyclohexane dimethanol more than 0.01 to 75mol%; 0.01 to being less than 2,2,4 of 5mol%, 4-tetramethyl--1,3-cyclobutanediol residue, glycol residue and 25 to 99.98mol% 1,4 cyclohexane dimethanol more than 0.01 to 70mol%; Glycol residue more than 0.01 to 65mol% and 30 arrives the 1,4 cyclohexane dimethanol of 99.98mol%; 0.01 to being less than 2,2,4 of 5mol%, 4-tetramethyl--1,3-cyclobutanediol residue, glycol residue and 35 to 99.98mol% 1,4 cyclohexane dimethanol more than 0.01 to 60mol%; 0.0l to being less than 2,2,4 of 5mol%, 4-tetramethyl--1,3-cyclobutanediol residue, glycol residue and 40 to 99.98mol% 1,4 cyclohexane dimethanol more than 0.01 to 55mol%; 0.01 to being less than 2,2,4 of 5mol%, 4-tetramethyl--1,3-cyclobutanediol residue, glycol residue and 45 to 99.98mol% 1,4 cyclohexane dimethanol more than 0.01 to 50mol%; 0.01 to being less than 2,2,4 of 5mol%, 4-tetramethyl--1,3-cyclobutanediol residue, glycol residue and 50 to 99.98mol% 1,4 cyclohexane dimethanol more than 0.01 to 45mol%; 0.01 to being less than 2,2,4 of 5mol%, 4-tetramethyl--1,3-cyclobutanediol residue, glycol residue and 55 to 99.98mol% 1,4 cyclohexane dimethanol more than 0.01 to 40mol%; 0.01 to being less than 2,2,4 of 5mol%, 4-tetramethyl--1,3-cyclobutanediol residue, glycol residue and 60 to 99.98mol% 1,4 cyclohexane dimethanol more than 0.01 to 35mol%; 0.01 to being less than 2,2,4 of 5mol%, 4-tetramethyl--1,3-cyclobutanediol residue, glycol residue and 65 to 99.98mol% 1,4 cyclohexane dimethanol more than 0.01 to 30mol%; 0.01 to being less than 2,2,4 of 5mol%, 4-tetramethyl--1,3-cyclobutanediol residue, glycol residue and 70 to 99.98mol% 1,4 cyclohexane dimethanol more than 0.01 to 25mol%; 0.01 to being less than 2,2,4 of 5mol%, 4-tetramethyl--1,3-cyclobutanediol residue, glycol residue and 75 to 99.98mol% 1,4 cyclohexane dimethanol more than 0.01 to 20mol%; 0.01 to being less than 2,2,4 of 5mol%, 4-tetramethyl--1,3-cyclobutanediol residue, glycol residue and 80 to 99.98mol% 1,4 cyclohexane dimethanol more than 0.01 to 15mol%; 0.01 to being less than 2,2,4 of 5mol%, 4-tetramethyl--1,3-cyclobutanediol residue, glycol residue and 85 to 99.98mol% 1,4 cyclohexane dimethanol more than 0.01 to 10mol%; 0.01 to being less than 2,2,4 of 5mol%, 4-tetramethyl--1,3-cyclobutanediol residue, glycol residue and 90 to 99.98mol% 1,4 cyclohexane dimethanol more than 0.01 to 5mol%; 0.01 to being less than 2,2,4 of 5mol%, 4-tetramethyl--1,3-cyclobutanediol residue, glycol residue and 90 to 99.98mol% 1,4 cyclohexane dimethanol more than 0.01 to 5mol%.
Diol component can also contain 2,2,4 of one of following scope, 4-tetramethyl--1,3-cyclobutanediol residue: 0.01-4.5mol%; 0.01-4mol%; 0.01-3.5mol%; 0.01-3mol%; 0.01-2.5mol%; 0.01-2.0mol%; 0.01-2.5mol%; 0.01-2mol%; 0.01-1.5mol%; 0.01-1.0mol%; And 0.01-0.5mol%.Remaining diol component can be the 1,4 cyclohexane dimethanol and the ethylene glycol of any amount, as long as the total amount of diol component equals 100mol%.
Except the glycol of listing above, the polyester that can be used for polymer blend of the present invention can be by 1, ammediol, 1,4-butyleneglycol or the preparation of its mixture.It is contemplated that, by 1, ammediol, 1, the composition of the present invention of 4-butyleneglycol or its mixture preparation one of can have in the Tg scope as herein described at least, logarithmic viscosity number scope as herein described one of at least, and/or glycol as herein described or two acid ranges one of at least.In addition or another kind of the selection be, by 1, ammediol or 1, the polyester of 4-butyleneglycol or the preparation of its mixture can also be by the 1,4 cyclohexane dimethanol preparation that is at least one of following amount: 0.1-99mol%; 0.1-90mol%; 0.1-80mol%; 0.1-70mol%; 0.1-60mol%; 0.1-50mol%; 0.1-40mol%; 0.1-35mol%; 0.1-30mol%; 0.1-25mol%; 0.1-20mol%; 0.1-15mol%; 0.1-10mol%; 0.1-5mol%; 1-99mol%; 1-90mol%; 1-80mol%; 1-70mol%; 1-60mol%; 1-50mol%; 1-40mol%; 1-35mol%; 1-30mol%; 1-25mol%; 1-20mol%; 1-15mol%; 1-10mol%; 1-5mol%; 5-80mol%; 5-70mol%; 5-60mol%; 5-50mol%; 5-40mol%; 5-35mol%; 5-30mol%; 5-25mol%; 5-20mol%; And 5-15mol%; 5-10mol%; 10-99mol%; 10-90mol%; 10-80mol%; 10-70mol%; 10-60mol%; 10-50mol%; 10-40mol%; 10-35mol%; 10-30mol%; 1 0-25mol%; 10-20mol%; 10-15mol%; 20-99mol%; 20-95mol%; 20-80mol%; 20-70mol%; 20-60mol%; 20-50mol%; 20-40mol%; 20-35mol%; 20-30mol%; And 20-25mol%.
Polyester has logarithmic viscosity number (I.V.) value in about 0.1dL/g arrives the scope of about 1.4dL/g usually.I.V. other example of scope comprises that about 0.65dL/g arrives about 0.85dL/g to about 1.0dL/g and about 0.7dL/g.As previously mentioned, logarithmic viscosity number uses every 100ml solvent 0.5g polymkeric substance to measure at 25 ℃, and this solvent comprises the phenol of 60wt% and the tetrachloroethane of 40wt%.For embodiments of the present invention, can be used for polyester of the present invention can show in the following logarithmic viscosity number (in 60/40 (wt/wt) phenol/tetrachloroethane with the concentration of 0.5g/100ml 25 ℃ of mensuration) one of at least: 0.10-1.2dL/g; 0.10-1.1dL/g; 0.10-1dL/g; 0.10 arrive less than 1dL/g; 0.10-0.98dL/g; 0.10-0.95dL/g; 0.10-0.90dL/g; 0.10-0.85dL/g; 0.10-0.80dL/g; 0.10-0.75dL/g; 0.10 arrive less than 0.75dL/g; 0.10-0.72dL/g; 0.10-0.70dL/g; 0.10 arrive less than 0.70dL/g; 0.10-0.68dL/g; 0.10 arrive less than 0.68dL/g; 0.10-0.65dL/g; 0.10-0.6dL/g; 0.10-0.55dL/g; 0.10-0.5dL/g; 0.10-0.4dL/g; 0.10-0.35dL/g; 0.20-1.2dL/g; 0.20-1.1dL/g; 0.20-1dL/g; 0.20 arrive less than 1dL/g; 0.20-0.98dL/g; 0.20-0.95dL/g; 0.20-0.90dL/g; 0.20-0.85dL/g; 0.20-0.80dL/g; 0.20-0.75dL/g; 0.20 arrive less than 0.75dL/g; 0.20-0.72dL/g; 0.20-0.70dL/g; 0.20 arrive less than 0.70dL/g; 0.20-0.68dL/g; 0.20 arrive less than 0.68dL/g; 0.20-0.65dL/g; 0.20-0.6dL/g; 0.20-0.55dL/g; 0.20-0.5dL/g; 0.20-0.4dL/g; 0.20-0.35dL/g; 0.35-1.2dL/g; 0.35-1.1dL/g; 0.35-1dL/g; 0.35 arrive less than 1dL/g; 0.35-0.98dL/g; 0.35-0.95dL/g; 0.35-0.90dL/g; 0.35-0.85dL/g; 0.35-0.80dL/g; 0.35-0.75dL/g; 0.35 arrive less than 0.75dL/g; 0.35-0.72dL/g; 0.35-0.70dL/g; 0.35 arrive less than 0.70dL/g; 0.35-0.68dL/g; 0.35 arrive less than 0.68dL/g; 0.35-0.65dL/g; 0.40-1.2dL/g; 0.40-1.1dL/g; 0.40-1dL/g; 0.40 arrive less than 1dL/g; 0.40-0.98dL/g; 0.40-0.95dL/g; 0.40-0.90dL/g; 0.40-0.85dL/g; 0.40-0.80dL/g; 0.40-0.75dL/g; 0.40 arrive less than 0.75dL/g; 0.40-0.72dL/g; 0.40-0.70dL/g; 0.40 arrive less than 0.70dL/g; 0.40-0.68dL/g; 0.40 arrive less than 0.68dL/g; 0.40-0.65dL/g; Greater than 0.42 to 1.2dL/g; Greater than 0.42 to 1.1dL/g; Greater than 0.42 to 1dL/g; Arrive less than 1dL/g greater than 0.42; Greater than 0.42 to 0.98dL/g; Greater than 0.42 to 0.95dL/g; Greater than 0.42 to 0.90dL/g; Greater than 0.42 to 0.85dL/g; Greater than 0.42 to 0.80dL/g; Greater than 0.42 to 0.75dL/g; Arrive less than 0.75dL/g greater than 0.42; Greater than 0.42 to 0.72dL/g; Greater than 0.42 to 0.70dL/g; Arrive less than 0.70dL/g greater than 0.42; Greater than 0.42 to 0.68dL/g; Arrive less than 0.68dL/g greater than 0.42; With greater than 0.42 to 0.65dL/g.
For embodiments of the present invention, can be used for polyester of the present invention can show in the following logarithmic viscosity number (in 60/40 (wt/wt) phenol/tetrachloroethane with the concentration of 0.5g/100ml 25 ℃ of mensuration) one of at least: 0.45-1.2dL/g; 0.45-1.1dL/g; 0.45-1dL/g; 0.45-0.98dL/g; 0.45-0.95dL/g; 0.45-0.90dL/g; 0.45-0.85dL/g; 0.45-0.80dL/g; 0.45-0.75dL/g; 0.45-less than 0.75dL/g; 0.45-0.72dL/g; 0.45-0.70dL/g; 0.45-less than 0.70dL/g; 0.45-0.68dL/g; 0.45-less than 0.68dL/g; 0.45-0.65dL/g; 0.50-1.2dL/g; 0.50-1.1dL/g; 0.50-1dL/g; 0.50-less than 1dL/g; 0.50-0.98dL/g; 0.50-0.95dL/g; 0.50-0.90dL/g; 0.50-0.85dL/g; 0.50-0.80dL/g; 0.50-0.75dL/g; 0.50-less than 0.75dL/g; 0.50-0.72dL/g; 0.50-0.70dL/g; 0.50-less than 0.70dL/g; 0.50-0.68dL/g; 0.50-less than 0.68dL/g; 0.50-0.65dL/g; 0.55-1.2dL/g; 0.55-1.1dL/g; 0.55-1dL/g; 0.55-less than 1dL/g; 0.55-0.98dL/g; 0.55-0.95dL/g; 0.55-0.90dL/g; 0.55-0.85dL/g; 0.55-0.80dL/g; 0.55-0.75dL/g; 0.55-less than 0.75dL/g; 0.55-0.72dL/g; 0.55-0.70dL/g; 0.55-less than 0.70dL/g; 0.55-0.68dL/g; 0.55-less than 0.68dL/g; 0.55-0.65dL/g; 0.58-1.2dL/g; 0.58-1.1dL/g; 0.58-1dL/g; 0.58-less than 1dL/g; 0.58-0.98dL/g; 0.58-0.95dL/g; 0.58-0.90dL/g; 0.58-0.85dL/g; 0.58-0.80dL/g; 0.58-0.75dL/g; 0.58-less than 0.75dL/g; 0.58-0.72dL/g; 0.58-0.70dL/g; 0.58-less than 0.70dL/g; 0.58-0.68dL/g; 0.58-less than 0.68dL/g; 0.58-0.65dL/g; 0.60-1.2dL/g; 0.60-1.1dL/g; 0.60-1dL/g; 0.60-less than 1dL/g; 0.60-0.98dL/g; 0.60-0.95dL/g; 0.60-0.90dL/g; 0.60-0.85dL/g; 0.60-0.80dL/g; 0.60-0.75dL/g; 0.60-less than 0.75dL/g; 0.60-0.72dL/g; 0.60-0.70dL/g; 0.60-less than 0.70dL/g; 0.60-0.68dL/g; 0.60-less than 0.68dL/g; 0.60-0.65dL/g; 0.65-1.2dL/g; 0.65-1.1dL/g; 0.65-1dL/g; 0.65-less than 1dL/g; 0.65-0.98dL/g; 0.65-0.95dL/g; 0.65-0.90dL/g; 0.65-0.85dL/g; 0.65-0.80dL/g; 0.65-0.75dL/g; 0.65-less than 0.75dL/g; 0.65-0.72dL/g; 0.65-0.70dL/g; 0.65-less than 0.70dL/g; 0.68-1.2dL/g; 0.68-1.1dL/g; 0.68-1dL/g; 0.68-less than 1dL/g; 0.68-0.98dL/g; 0.68-0.95dL/g; 0.68-0.90dL/g; 0.68-0.85dL/g; 0.68-0.80dL/g; 0.68-0.75dL/g; 0.68-less than 0.75dL/g; 0.68-0.72dL/g; Greater than 0.76dL/g-1.2dL/g; Greater than 0.76dL/g-1.1dL/g; Greater than 0.76dL/g-1dL/g; Greater than 0.76dL/g-less than 1dL/g; Greater than 0.76dL/g-0.98dL/g; Greater than 0.76dL/g-0.95dL/g; Greater than 0.76dL/g-0.90dL/g; Greater than 0.80dL/g-1.2dL/g; Greater than 0.80dL/g-1.1dL/g; Greater than 0.80dL/g-1dL/g; Greater than 0.80dL/g-less than 1dL/g; Greater than 0.80dL/g-1.2dL/g; Greater than 0.80dL/g-0.98dL/g; Greater than 0.80dL/g-0.95dL/g; Greater than 0.80dL/g-0.90dL/g.
For containing 2,2,4,4-tetramethyl--1, the polyester of the present invention of 3-cyclobutanediol, cis/trans 2,2,4,4-tetramethyl--1, the mol ratio of 3-cyclobutanediol can change to its mixture from pure substance form separately.In some embodiments, cis and/or trans 2,2,4,4-tetramethyl--1, the molar percentage of 3-cyclobutanediol is: more than the cis of 50mol% be less than the trans of 50mol%; Perhaps more than the cis of 55mol% be less than the trans of 45mol%; Perhaps 30 trans to the cis of 70mol% and 70 to 30%; Perhaps 40 to 60mol% cis and 60 arrives the trans of 40mol%; Perhaps 50 cis to 70mol% trans and 50 to 30%; Perhaps 50 trans to the cis of 70mol% and 50 to 30%; Perhaps 60 to 70mol% cis and 30 arrives the trans of 40mol%; Perhaps more than the cis of 70mol% be less than the trans of 30mol%; Cis and trans 2,2,4 wherein, 4-tetramethyl--1, the summation of the molar percentage of 3-cyclobutanediol equals 100mol%.The mol ratio of cis/trans 1,4 cyclohexane dimethanol can change in 50/50 to 0/100 scope, for example between 40/60 to 20/80.
It is contemplated that, except as otherwise noted, composition of the present invention can have in the logarithmic viscosity number scope as herein described one of at least with the monomer scope of composition as herein described in one of at least.It is also conceivable that except as otherwise noted, composition of the present invention can have in the Tg scope as herein described one of at least with the monomer scope of composition as herein described one of at least.It is also conceivable that except as otherwise noted, composition of the present invention can have in the logarithmic viscosity number as herein described one of at least, in the Tg scope as herein described one of at least and the monomer scope of composition as herein described one of at least.
In some embodiments, terephthalic acid or its ester such as dimethyl terephthalate (DMT) or terephthalic acid residue's mixture and ester thereof can be configured for forming the dicarboxylic acid component that can be used for polyester of the present invention partly or entirely.In some embodiments, the terephthalic acid residue can serve as the dicarboxylic acid component that is used to form polyester of the present invention partly or entirely, its concentration is 70mol% at least, for example 80mol%, 90mol%, 95mol% at least at least at least, at least 99mol%, perhaps even 100mol%.In some embodiments, can use the terephthalic acid of higher amount, so that produce polyester than high impact.For the purpose of the disclosure of invention, term " terephthalic acid " and " dimethyl terephthalate (DMT) " can be exchanged use in this article.In one embodiment, dimethyl terephthalate (DMT) be used to prepare the dicarboxylic acid component that can be used for polyester of the present invention partly or entirely.In all embodiments, can use terephthalic acid and/or the dimethyl terephthalate (DMT) and/or its mixture: the 70-100mol% of following ranges; Perhaps 80-100mol%; Perhaps 90-100mol% or 99-100mol%; Perhaps 100mol%.
Except terephthalic acid, the dicarboxylic acid component who can be used for polyester of the present invention can also be contained at the most 30mol%, 20mol%, 10mol%, 5mol% or the modified aromatic family dicarboxylic acid of 1mol% at the most at the most at the most at the most.Another embodiment contains the modified aromatic family dicarboxylic acid of 0mol%.Therefore, if exist, it is contemplated that the amount of one or more modified aromatic family dicarboxylic acid can comprise for example 0.01-30mol%, 0.01-20mol%, 0.01-10mol%, 0.01-5mol% and 0.01-1mol% in the scope of aforementioned any endpoint value.In one embodiment, can be used for modified aromatic of the present invention family dicarboxylic acid and include but not limited to have those of 20 carbon atoms at the most, it can be straight chain, contraposition or symmetric.The example that can be used for modified aromatic of the present invention family dicarboxylic acid include but not limited to m-phthalic acid, 4,4 '-diphenyl dicarboxylic acid, 1,4-naphthalic acid, 1,5-naphthalic acid, 2,6-naphthalic acid, 2,7-naphthalic acid and trans-4,4 '-Stilbene dicarboxylic acid and their ester.In one embodiment, modified aromatic family dicarboxylic acid is a m-phthalic acid.
Can be used for polyester of the present invention carboxyl acid component can also with 10mol% at the most, for example at the most 5mol% or at the most one or more of 1mol% contain the aliphatic dicarboxylic acid modification of 2-16 carbon atom, as propanedioic acid, succsinic acid, pentanedioic acid, hexanodioic acid, pimelic acid, suberic acid, nonane diacid and dodecanedioic acid.Some embodiment can also comprise 0.01mol% or more, for example 0.1mol% or more, 1mol% or more, 5mol% or more or 10mol% or more one or more modified aliphatic dicarboxylic acid.Another embodiment contains the modified aliphatic dicarboxylic acid of 0mol%.Therefore, if exist, it is contemplated that the amount of one or more modified aliphatic dicarboxylic acid can comprise for example 0.01-10mol% and 0.1-10mol% in the scope of aforementioned any endpoint value.Total mol% of dicarboxylic acid component is 100mol%.
Terephthalate and other modification dicarboxylic acid or its corresponding ester and/or salt can be used to replace dicarboxylic acid.The suitable example of dicarboxylic ester includes but not limited to dimethyl ester, diethyl ester, dipropyl, diisopropyl ester, dibutylester and diphenyl ester.In one embodiment, ester be selected from following one of at least: methyl esters, ethyl ester, propyl ester, isopropyl ester and phenyl ester.
1,4 cyclohexane dimethanol can be cis, trans or their mixture, and for example the ratio of cis/trans is 60: 40 to 40: 60.In another embodiment, anti-form-1, the 4-cyclohexanedimethanol can exist with the amount of 60-80mol%.
The diol component that can be used for the polyester portion of polymer blend of the present invention can contain 25mol% or still less one or more are not 2,2,4,4-tetramethyl--1, the modification glycol of 3-cyclobutanediol or 1,4 cyclohexane dimethanol; In one embodiment, can be used for polyester of the present invention and can contain one or more modification glycol that are less than 15mol%.In another embodiment, can be used for polyester of the present invention and can contain 10mol% or one or more modification glycol still less.In another embodiment, can be used for polyester of the present invention and can contain 5mol% or one or more modification glycol still less.In another embodiment, can be used for polyester of the present invention and can contain 3mol% or one or more modification glycol still less.In another embodiment, can be used for the modification glycol that polyester of the present invention can contain 0mol%.Some embodiment can also contain 0.01mol% or more, for example 0.1mol% or more, 1mol% or more, 5mol% or more or 10mol% or more one or more modification glycol.Therefore, if exist, it is contemplated that the amount of one or more modification glycol can comprise for example 0.01-15mol% and 0.1-10mol% in the scope of aforementioned any endpoint value.
Can be used for modification glycol of the present invention and be meant except that 2,2,4,4-tetramethyl--1, the glycol outside 3-cyclobutanediol and the 1,4 cyclohexane dimethanol, it can contain 2-16 carbon atom.The example of suitable modification glycol includes but not limited to ethylene glycol, 1,2-propylene glycol, 1, ammediol, neopentyl glycol, 1,4-butyleneglycol, 1,5-pentanediol, polyoxyethylene glycol, glycol ether, polytetramethylene glycol, 1,6-hexylene glycol, terephthalyl alcohol or their mixture.An embodiment of modification glycol is an ethylene glycol.Other modification glycol includes but not limited to 1, ammediol and 1,4-butyleneglycol.In another embodiment, do not make spent glycol as the modification glycol.In another embodiment, do not use 1, ammediol and 1, the 4-butyleneglycol is as the modification glycol.In another embodiment, do not use 2 as the modification glycol.
Can be used for the residue that the polyester of polymer blend of the present invention and/or polycarbonate can contain one or more cladodification monomers (being also referred to as the cladodification agent) of 0 to about 10mol%, this cladodification monomer has 3 or more a plurality of carboxyl substituent, hydroxyl substituent or their combination.Other example that may reside in the molar percentage of the cladodification agent in polyester of the present invention or the polycarbonate is: respectively based on the glycol of polyester and/or polycarbonate or the integral molar quantity of diacid residues, the about 5mol% of about 0.05-, the about 1mol% of about 0.01-, about 0.01-are about 0.7, about 0.01-about 0.5 and the about 0.7mol% of about 0.1-.In some embodiments, cladodification monomer or cladodification agent can add in the polymerization process of polyester.Therefore, polyester of the present invention can be a straight or branched.Polycarbonate of the present invention also can be a straight or branched.In some embodiments, cladodification monomer or cladodification agent can before the polymerization process of polycarbonate and/or among and/or add afterwards.
The monomeric example of cladodification includes but not limited to polyfunctional acid or polyfunctional alcohol such as trimellitic acid, trimellitic acid 1,2-anhydride, pyromellitic dianhydride, TriMethylolPropane(TMP), glycerine, tetramethylolmethane, citric acid, tartrate, 3-hydroxyl pentanedioic acid, glycerine, Sorbitol Powder, 1,2,6-hexanetriol, trimethylolethane and/or trimesic acid etc.In one embodiment, the cladodification monomer residue can comprise 0.01-1mol% one or more be selected from following residue one of at least: trimellitic acid 1,2-anhydride, pyromellitic dianhydride, glycerine, Sorbitol Powder, 1,2,6-hexanetriol, tetramethylolmethane, trimethylolethane and/or trimesic acid.The cladodification monomer can be with as United States Patent (USP) 5,654,347 and 5,696,176 described enriched material forms be added in the pet reaction mixture or with the polyester blending.
Show long crystallization half-life (for example, more than 5 minutes) owing to can be used for some polyester of the present invention at 170 ℃, it can produce container injection blow goods, injection drawing blow goods, extrusion blow goods and extrusion stretching blow-molded article.Polyester of the present invention can be " amorphous " or hemicrystalline.In one aspect, can be used for some polyester of the present invention and can have low relatively degree of crystallinity.Therefore, can be used for some polyester of the present invention and can have unbodied basically form, represent that this polyester comprises unordered substantially polymer areas.
In one embodiment, " amorphous " polyester can have under 170 ℃ the crystallization half-life more than 5 minutes, perhaps under 170 ℃ more than 10 minutes, perhaps under 170 ℃ more than 100 minutes.In an embodiment of the invention, crystallization half-life under 170 ℃ more than 1,000 minute.In yet another embodiment of the present invention, the crystallization half-life that can be used for polyester of the present invention under 170 ℃ more than 10,000 minutes.Here can measure by well known to a person skilled in the art method the crystallization half-life of employed polyester.For example, the crystallization half-life of polyester, t 1/2, can measure by following manner: go up the light transmission of measurement at the hot microscope carrier (stage) of controlled temperature as the sample of the function of time via laser apparatus and photodetector.This measurement can be by being exposed to temperature T with polymkeric substance Max, it is cooled to temperature required carrying out then.Then, sample can remain on temperature required by hot microscope carrier, measures the transmission as the function of time simultaneously.At first, sample can visually be clarifying and have high light transmission, become opaque then when the sample crystallization.Be that light transmission is the time of initial light transmission and final light transmission intermediate value crystallization half-life.T MaxBe defined as crystal region (if having crystal region) the required time of fusion that makes sample.Sample can be heated to T MaxBefore measuring, adjust this sample in crystallization half-life.The absolute T of each composition MaxTemperature is different.For example, PCT can be heated to above certain temperature of 290 ℃ so that the crystal region fusion.
Polymkeric substance of the present invention can be crystalline, hemicrystalline or unbodied polymkeric substance.Here employed term " hypocrystalline " is meant that polymkeric substance contains two-phase: orderly crystallization phases and unordered amorphous phase.Polymkeric substance with hypocrystalline form shows crystalline melt temperature (Tm) and second-order transition temperature (Tg) simultaneously, and can make a distinction with " amorphous " polymkeric substance that only shows second-order transition temperature.
Polyester of the present invention can use typical polycondensation condition from suitable dicarboxylic acid, ester, acid anhydrides or salt, and suitable glycol or diol mixture and prepare.As previously mentioned, the dicarboxylic acid component of polyester of the present invention can be derived from dicarboxylic acid, its corresponding ester or their mixture.The example that can be used for the ester of dicarboxylic acid of the present invention comprises dimethyl ester, dipropyl, diisopropyl ester, dibutylester and diphenyl ester etc.In one embodiment, for example, terephthalic acid can be used as starting material.In another example, dimethyl terephthalate (DMT) can be used as starting material.In another embodiment, the mixture of terephthalic acid and terephthaldehyde's diphenyl phthalate can be as starting material and/or as intermediate material.
Polyester of the present invention is by well known to a person skilled in the art the method preparation.They can prepare by successive, semi-continuous and batch-wise operator scheme, and can utilize various type of reactor.The example of suitable type of reactor includes but not limited to stirred-tank reactor, continuous stirred tank reactor, slurry reactor, tubular reactor, commentaries on classics membrane reactor, falling film reactor or extruding reaction device.The reaction of two pure and mild dicarboxylic acid can use conventional polyester condition to carry out, perhaps can be undertaken by the fusion phase method, but have enough degree of crystallinity those can by fusion mutually then the technology of solid phase polycondensation carry out.For example, when preparing polyester by transesterification reaction, promptly when dicarboxylic acid component's ester-formin prepared polyester, reaction method can comprise for two steps.In the first step, diol component and dicarboxylic acid component such as dimethyl terephthalate (DMT) are reacted about 0.5 down and are arrived about 8 hours being generally about 150 ℃ of pressure to about 250 ℃ high temperature and about 0.0kPa to about 414kPa gauge pressure (60 pounds/square inch, " psig ").The temperature range of preferred transesterification reaction is about 180 ℃ to about 230 ℃, and time range is about 1 to about 4 hours, and the preferred pressure scope is that about 103kPa gauge pressure (15psig) is to about 276kPa gauge pressure (40psig) simultaneously.Then, reaction product is at higher temperature and more be heated under the low pressure, has eliminated the polyester of glycol with formation, and this glycol is evaporated easily under these conditions and removes from system.This second step, perhaps condensation polymerization step, high vacuum and be generally 230 ℃ to about 350 ℃, preferred about 250 ℃ to about 310 ℃, most preferably from about 260 ℃ proceeded about 0.1 to about 6 hours under about 290 ℃ temperature or preferably about 0.2 arrive about 2 hours, when acquisition detects by logarithmic viscosity number, have the polymkeric substance of required extent of polymerization.Condensation polymerization step can be carried out under the lower pressure of about 0.013kPa (0.1torr) at about 53kpa (400torr).Stirring well-known in the art or suitable hybrid technology can be used for this two-stage, to guarantee the Surface Renewal of heat passage fully and reaction mixture.The speed of response of this two-stage can be by appropriate catalyst such as alkoxy titanium compound, alkali metal hydroxide and alkoxide, organic carboxyl acid salt, Alkyzin compound, metal oxide etc. be enhanced.Also can use and United States Patent (USP) 5,290,631 described three grades of similar production methods are particularly when adopting the mix monomer charging of acid and ester.
For driving is finished by the diol component of transesterification reaction and dicarboxylic acid component's reaction, the 1mol dicarboxylic acid component need use about 1.05 to about 2.5mol diol component sometimes.But diol component and dicarboxylic acid component's the ratio of it will be understood to those of skill in the art that is normally determined by the DESIGN OF REACTOR of the process of reacting.
Reacting by direct esterification in the process for preparing polyester, that is, when dicarboxylic acid component's sour form prepared polyester, polyester was to prepare by the mixture reaction that makes dicarboxylic acid or dicarboxylic acid mixture and diol component or diol component.This is reflected at about 7kPa gauge pressure (1psig) to about 1379kPa gauge pressure (200psig), preferably be lower than under the pressure of 689kpa (100psig) and carry out, and obtains mean polymerisation degree and be about 1.4 to about 10 low-molecular-weight polyester product.Normally about 180 ℃ to about 280 ℃ of the temperature range that adopts in the direct esterification reaction process, more preferably from about 220 ℃ to about 270 ℃.Then, this low-molecular weight polymer can the polymerization by polycondensation.
Thermoplastic polymer of the present invention can also comprise polyarylester.Polyarylester is that the polymerization by dihydric phenol and dicarboxylic acid obtains.The example that can be used for the polyarylester in composition of the present invention, method and the molded article is at United States Patent (USP) 4,598, describes in 130,5,034,502 and 4,374,239.The example that can be used for preparing the dihydric phenol of polyarylester is bis-phenol such as two (4-hydroxyphenyl) methane, 2, two (4-hydroxyphenyl) propane (" bisphenol-A "), 2 of 2-, two (4-hydroxyl-3-tolyl) propane, 4 of 2-, two (4-hydroxyphenyl) heptane, 2 of 4-, two (the 4-hydroxyls-3 of 2-, the 5-dichlorophenyl) propane, 2, two (4-hydroxyl-3, the 5-dibromo phenyl) propane of 2-; For example two (4-hydroxyphenyl) ethers of binary phenolic ether, two (3,5-two chloro-4-hydroxyphenyl) ether; Dihydroxybiphenyl such as p, p '-dihydroxybiphenyl, 3,3 '-two chloro-4,4 '-dihydroxybiphenyl; Dihydroxyl aryl sulfone such as two (4-hydroxyphenyl) sulfone, two (3,5-dimethyl-4-hydroxyphenyl) sulfone; Dihydroxy-benzene such as Resorcinol; Quinhydrones; The dihydroxy-benzene that halogen replaces and alkyl replaces, as 1,4-dihydroxyl-2,5-dichlorobenzene, 1,4-dihydroxyl-3-toluene; And dihydroxybiphenyl sulfoxide such as two (4-hydroxyphenyl) sulfoxide and two (3,5-two bromo-4-hydroxyphenyl) sulfoxide.Multiple other dihydric phenol also can use, and for example United States Patent (USP) 2,999, those disclosed in 835,3,028,365 and 3,153,008.By above-mentioned dihydric phenol and halogen-containing dihydric phenol as 2, two (3, the 5-two chloro-4-hydroxyphenyl) propane and 2 of 2-, two (3,5-two bromo-4-hydroxyphenyl) propane copolymerization of 2-and the multipolymer for preparing also is suitable.Dihydric phenol that can also two or more are different or dihydric phenol use with the polyester of the multipolymer of glycol and hydroxyl or acid blocked or with the adulterant of diprotic acid and above-mentioned any material.Suitable dicarboxylic acid include but not limited to aromatic dicarboxylic acid such as phthalic acid, m-phthalic acid, terephthalic acid, phthalic acid, neighbour, and to phenylene-diacetic acid; And polynuclear aromatic is sour as diphenic acid and 1,4-naphthalene diacid.
Other example that can be used for polyarylester of the present invention comprise by between dihydroxyphenyl propane (2, two (4-hydroxyphenyl) propane of 2-) and 50: 50/condensation of terephthaldehyde's acid mixture and obtain those.Some polymkeric substance is commercially available with trade(brand)name " U-Polymer U-100 " (can derive from Unitaka America Corporation).Other example be based on tetramethyl-dihydroxyphenyl propane, 4,4 '-dihydroxyl-benzophenone and 5-tert-butyl isophthalic acid dichloride (isophthalic acid dichloride).
Polyarylester of the present invention can form reaction by any polyester well known in the art and prepare, for example, the solution of aromatic dicarboxylic acid dichloride (dicarboxylic acid dihalide) in organic solvent is under agitation mixed with the alkaline aqueous solution of bis-phenol so that the interfacial polymerization of these substance reactions; The solution polymerization that aromatic dicarboxylic acid dichloride and bis-phenol are reacted in the presence of de-acidying agent such as pyridine; Make the melt polymerization of aromatic dicarboxylic acid diphenyl ester and bis-phenol reaction; Make the melt polymerization of aromatic dicarboxylic acid, diphenyl carbonate and bis-phenol reaction; Make the melt polymerization of aromatic dicarboxylic acid and bisphenol diacetate reaction; And the polymerization that makes aromatic dicarboxylic acid and bisphenol diacetate reaction.The example of method that is used to prepare polyarylester is at United States Patent (USP) 5,034, and is open in 502,4,321,355 and 4,374,239.Polyarylester of the present invention has usually and is about 0.5 to the logarithmic viscosity number of 1.1dL/gm.
In addition, polyester, polycarbonate and polyarylester may further include one or more in following: antioxidant, the melt strength toughener, cladodification agent (for example, glycerine, trimellitic acid and acid anhydrides), chain extension agent, fire retardant, filler, acid scavenger, dyestuff, tinting material, pigment, anti, flow enhancing agent, impact modifier, static inhibitor, processing aid, demoulding additive, softening agent, slip(ping)agent (slip), stablizer, wax, the UV absorption agent, white dyes, lubricant, closed (pinning) additive, pore forming material, anti-clean electric agent, nucleator or the like.Tinting material is sometimes referred to as toning agent, can be added into so that give neutralc tint and/or the brightness that polyester needs.Preferred this polymer blend can comprise that one or more processing aids of 0 to about 30wt% flow with the surface properties and/or the raising that change said composition.The representative example of processing aid comprises lime carbonate, talcum, clay, mica, zeolite, wollastonite, kaolin, diatomite, TiO 2, NH 4Cl, silica, calcium oxide, sodium sulfate and calcium phosphate.Multiple pigment or dyestuff can be used for, and for example, prepare articles colored.Anti-clean electric agent or other coating also can be applied to the surface of article.
Second component of composition of the present invention (ii) comprises the even adulterant of the commentaries on classics acyl amination of at least two kinds of polymeric amide.Usually, this even adulterant comprises 2 to about 10 kinds of different polymeric amide.In another example, this even adulterant can comprise 2 to 4 kinds of polymeric amide.According to the present invention, show that the polymeric amide that is lower than about 300 ℃ fusing point can be used as at least a polymeric amide.In another example, can use fusing point to be lower than about 275 ℃ and glass transition temperature and be higher than about 25 ℃ polymeric amide.Usually, this polymeric amide has about 0.3dL/g to the I.V. of about 2.0dL/g, preferably 0.5dL/g at least.
For composition of the present invention, transmidation advantageously takes place to produce uniform adulterant between polymeric amide.Here employed term " the commentaries on classics amide groupization " is defined as with term and " changes amide groupization " and " transmidation " synonym, and is meant the process of exchange amide group between two kinds of different polymeric amide.Therefore, employed polymeric amide " changeing the adulterant of amide groupization " is such adulterant here: wherein polyamide component has exchanged is enough to make this adulterant to become the amide group of the amount of even adulterant.Transmidation between two or more polymeric amide can be by making under about 350 ℃ high temperature multiple polymeric amide contact realize being generally about 270 ℃.Other example of the temperature of transmidation is about 280 ℃ to about 350 ℃ and about 290 ℃ to about 340 ℃.Transmidation between the polymeric amide shows by following manner: when using the method mensuration that well known to a person skilled in the art described in standard technique such as the ASTM method D3418 by dsc (" DSC "), there is single glass transition temperature (" Tg ") in this adulterant.Polymeric amide can be under these temperature directly heating together, perhaps can heating down at the thermoplastic polymer of first component (i).For example, make polymeric amide contact and therefore change amide groupization can be by in the process of the extruding of polymer composition and component thereof or other pyroprocessing, the first and second component melt-mixing being carried out.In another example, polymeric amide can heat in independent container together, mixes with first component melts then.
First and second polymeric amide of second component can be selected from multiple polymeric amide.In order to mate the specific refractory power of first component better, desirable but optional be that at least a polymeric amide comprises aromatic moieties.In an example, polymeric amide can comprise that number-average molecular weight is 7,000 or the polymeric amide and the fatty polyamide of part aromaticity still less.The combination of this polymeric amide is also included within the scope of the present invention.The polymeric amide of part aromaticity is included in the amido linkage between at least one aromatic ring and at least one the non-aromaticity species.Although the polymeric amide of complete aromaticity is liquid crystal normally, the adulterant that this fusing point is lower than 300 ℃ resin can be used for the present invention.When using the even adulterant of polymeric amide, the rapid commentaries on classics amide groupization of the polymeric amide of aliphatics nylon and aromaticity or part aromaticity (acid amides-acid amides exchange) allows to adjust by the ratio of the polymeric amide of regulating fatty polyamide and aromaticity or part aromaticity the specific refractory power of polyamide compounds.This technology makes the specific refractory power of uniform polyamide compounds to be complementary with thermoplastic polymer one or more polyester as first component.The reference of transmidation can be found Polymer, 1992vol.33,3394 pages in the work of Y.Takeda etc.
According to the present invention, second component can be the even adulterants of two or more polymeric amide as the commentaries on classics amide groupization of first polymeric amide and second polymeric amide, and this first polymeric amide and second polymeric amide are chosen as the second component specific refractory power that provides such: the refringence of second and first component (RI (second component)-RI (first component)) is about 0.006 to about-0.0006.For the specific refractory power with first component is complementary, advantageously first and second polymeric amide have the aromatics and the aliphatic residue of different amounts.For example, second component (ii) can comprise first polymeric amide that contains aromatic moieties and the even adulterant that contains second polymeric amide of aliphatic residue.Here employedly be meant monomeric carboxyl or amino be not connected by aromatic proton about the diamines of polymeric amide of the present invention and dicarboxylic acid monomer's term " aliphatics ".For example, hexanodioic acid does not comprise aromatic proton in its main chain, that is, carbon atom chain connects hydroxy-acid group; Therefore, it is " aliphatics ".On the contrary, term " aromatics " is meant that dicarboxylic acid or diamines contain aromatic proton in main chain, terephthalic acid or 1 for example, 4-mphenylenediamine.The representative example of aromatic poly is to comprise comprising diamines such as m-xylene diamine or containing the residue and 30% the p dimethylamine and have the aromatic poly of those polymeric amide of the aliphatic dicarboxylic acid of 6 to 10 carbon atoms at the most of the benzene dimethylamine mixture of m-xylene diamine of 70mol% at least.Therefore, term " aliphatics " is meant and comprises aliphatics and alicyclic structure simultaneously, for example, contain diamines, diacid, lactan, amino alcohol and the aminocarboxylic acid of the composition carbon atom of straight or branched or circular permutation as main chain, this composition carbon atom can be in itself saturated or alkane, undersaturated (promptly, the carbon-to-carbon double bond that contains non-aromatics) or (that is, the containing carbon-to-carbon triple bond) of acetylene series.Therefore, in the context of specification sheets of the present invention and claims, aliphatics is meant chain structure (referring to " aliphatics " here) and the ring structure (referring to " alicyclic " or " cyclic aliphatic " here) that comprises straight chain and side chain.Yet the aromatic substituent on any main chain that can be coupled to aliphatics or alicyclic diol or diacid or hydroxycarboxylic acid do not represented to get rid of in term " aliphatics ".
Based on the gross weight of second component, the weight percent that is present in first and second polymeric amide in the even adulterant that changes amide groupization can be about 1: 50 to about 50: 1 usually.Other example of weight percent is 1: 20 to about 20: 1 and about 1: 10 to about 10: 1.
The example that can be used for the polymeric amide in the even adulterant of the present invention comprises and comprises the polymeric amide that one or more are selected from following residue: m-phthalic acid, terephthalic acid, cyclohexane dicarboxylic acid, m-xylene diamine (being also referred to as m-xylylenediamine here), p dimethylamine's (being also referred to as " right-benzene dimethylamine " here), 1,3-hexanaphthene (two) methylamine, 1,4-hexanaphthene (two) methylamine, have 6 to 12 carbon atoms aliphatic diacid, have 6 aliphatic amino acid or lactan, have the aliphatie diamine of 4 to 12 carbon atoms to twelve carbon atom.Can use other diacid and the diamines of common known formation polymeric amide.Polymeric amide can also contain other polyacid and the polyamines of small amount of trifunctional or four sense comonomers such as trimellitic acid 1,2-anhydride, pyromellitic dianhydride or formation polymeric amide well known in the art.
The example of the polymeric amide of part aromaticity includes but not limited to: gather (an inferior xylylene hexanediamide) (being called " MXD6 " nylon here), poly-(hexa-methylene isophthaloyl amine), gather (hexamethylene adipamide-be total to-isophthaloyl amine), gather (hexamethylene adipamide-be total to-terephthaloyl amine) and poly-(hexa-methylene isophthaloyl amine-be total to-terephthaloyl amine).In one embodiment, the polymeric amide of part aromaticity is poly-(an inferior xylylene hexanediamide).In one embodiment, the number-average molecular weight of the polymeric amide of part aromaticity can be for 7000 or still less.The representative example of fatty polyamide comprises poly-(2-Pyrrolidone) (nylon 4,6; CAS No.44,299-2); Poly-decyl amide (nylon 6; CAS No.18,111-0), poly-(2-piperidone) (nylon 5, CASNo.24938-57-6); Poly-(7-aminoheptylic acid) (nylon 7; CAS No.25035-01-2); Poly-(pelargonamide) (nylon 9; CAS No.25748-72-5); Poly-(11-aminoundecanoic acid) (Ni Long11; CASNo.25035-04-5); Poly-(12-aminolauric acid) (nylon 12, CAS No.24937-16-4); Poly-(ethylidene hexanediamide) (nylon 2,6); Polytetramethylene adipoyl diamines (nylon 4,6; CASNo.50327-22-5); Polyhexamethylene hexanediamide (nylon 6,6; CAS No.42,917-1), (nylon 6,9; CAS No.18,806-9) poly-(hexa-methylene-sebacoyl diamines (sebacamide)) (nylon 6,10; CAS No.9008-66-6), poly-(hexa-methylene-undecane two acid diamides (undecanamide)) (nylon 6,11) poly-(hexa-methylene dodecane two acid diamides (dodecamide)) (nylon 6,12; CAS No.24936-74-1), poly-(decamethylene hexanediamide) (nylon 8,6); Hexanodioic acid-decamethylene diamine multipolymer (nylon 10,6; CAS No.26123-27-3); Poly-decamethylene-dodecane two acid diamides (nylon 10,12); Poly-(ten dimethylene hexanediamides) (nylon 12,6); And poly-(ten dimethylene sebacoyl diamines) nylon 12,8).
For example, second component (ii) can comprise the even adulterant that contains first polymeric amide and second polymeric amide, wherein this first polymeric amide contains the residue of m-xylene diamine and hexanodioic acid, and second polymeric amide contains at least one diacid of selecting oneself, pimelic acid, suberic acid, nonane diacid, 11 carbon diacid, dodecanedioic acid, hexanolactam, butyrolactam, the amino 11 carbon diacid of 11-and the aliphatics of hexanediamine or the residue of alicyclic monomer.First polymeric amide for example can comprise the MXD6 nylon that obtains from Mitsubishi Corporation by commercial sources.In another example, second polymeric amide can comprise that at least one is selected from the polymeric amide of nylon 4, nylon 6, nylon 9, Ni Long11, nylon 12, nylon 6,6, nylon 5,10, nylon 6,12, nylon 6,11, nylon 10,12 and combination thereof.In another example, second polymeric amide can comprise nylon 6, nylon 6,6 or its mixture.
Second component can also comprise single copolyamide, wherein select monomer residue composition so that the specific refractory power of its specific refractory power and first component closely mate.Therefore, in another embodiment, the invention provides a kind of polymer composition, it comprises non-miscible adulterant of following material:
(i) comprise at least a first component that is selected from the thermoplastic polymer of polyester, polycarbonate, polyarylester and even adulterant thereof; And
Second component that (ii) comprises copolyamide;
Wherein second component (ii) with the refringence of first component (i), RI (second component)-RI (first component) is about 0.006 to approximately-0.0006, and the transmittance percentage of this non-miscible adulterant is at least 75%, turbidity is 10% or lower.In another embodiment, first component can comprise and contains terephthalic acid, 2,2,4,4-tetramethyl--1, the polyester of the residue of 3-cyclobutanediol and 1,4 cyclohexane dimethanol.Therefore, another embodiment of the invention is a kind of polymer composition, and it comprises non-miscible adulterant of following material:
(i) contain first component of at least a polyester, this polyester contains:
(a) diacid residues, based on all diacid residues, it comprises at least a modified aliphatic dicarboxylic acid residue of 16 carbon atoms at the most that has of about terephthalic acid residue of 70 to about 100mol%, 0 to about 30mol% at least a modified aromatic family's dicarboxylic acid residue with 20 carbon atoms at the most and 0 to about 10mol%; And
(b) diol residue, based on all diol residue, it comprises that about 1 arrives 2,2,4 of about 99mol%, 4-tetramethyl--1,3-cyclobutanediol residue and about 1 arrives the 1,4 cyclohexane dimethanol residue of about 99mol%; And
Second component that (ii) comprises copolyamide;
Wherein second component (ii) with the refringence of first component (i), RI (second component)-RI (first component) is about 0.006 to approximately-0.0006, and the transmittance percentage of this non-miscible adulterant is at least 75%, turbidity is 10% or lower.For example, copolyamide can comprise the residue of m-xylene diamine, p dimethylamine or its combination; And at least a terephthalic acid, m-phthalic acid, hexanodioic acid, pimelic acid, suberic acid, nonane diacid, sebacic acid, 11 carbon diacid, dodecanedioic acid, hexanolactam, butyrolactam, 11-amino-11 carbon diacid and 1, the residues of monomers of 6-hexanediamine of being selected from.In another example, copolyamide can comprise based on total amount be 100mol% the diamines residue about 15 to about 100mol% m-xylene diamine residue; With based on total amount be 100mol% diacid residues about 15 arrive one or more aliphatics of about 15mol% or alicyclic dicarboxylic acid's residue to about 85mol% hexanodioic acid residue and about 85, wherein this aliphatics or alicyclic dicarboxylic acid are selected from pimelic acid, suberic acid, nonane diacid, sebacic acid, 11 carbon diacid, dodecanedioic acid and 1,4-cyclohexane dicarboxylic acid.The numerous embodiments that should be appreciated that the even adulterant of polymeric amide described here and copolyamide can combine with any embodiment of the polyester of above being discussed.
In composition of the present invention, can use separately or include but not limited to contain based on total amount and arrive about 100mol% m-xylene diamine residue and hexanodioic acid residue as about 15 of the diamines residue of 100mol% as other example of the copolyamide that uses with the part of the even adulterant of another kind of polymeric amide.May reside in the typical amount of the hexanodioic acid residue in these copolyamides,, be about 5 to about 85mol%, about 20 to about 80mol% and about 25 to about 75mol% based on the diacid residues total amount.All the other dicarboxylic acid residue can comprise from one or more having the aliphatic dicarboxylic acid of 7-12 carbon atom such as pimelic acid, suberic acid, nonane diacid, sebacic acid, 11 carbon diacid, dodecanedioic acid or 1,4-cyclohexane dicarboxylic acid.In another example, polyamic acid can also comprise the residue from m-phthalic acid and terephthalic acid.
Except that the m-xylene diamine residue, copolyamide of the present invention can also comprise other diamines or lactan residue.For example, copolyamide can comprise 15mol% at least or at least about the m-xylene diamine residue of 20mol%, all the other diamines residues comprise the residue of one or more aliphatics or aromatic diamine.For example, based on the integral molar quantity of diamines residue, copolyamide can comprise 1 of about 80mol% or about 85mol%, 6-hexanediamine residue.Can also use the p dimethylamine, 1 of different amounts, 3-hexanaphthene dimethylamine or 1,4-hexanaphthene dimethylamine.Similarly, copolyamide can comprise lactan such as hexanolactam or based on the residue of the lactan of γ-An Jidingsuan or 11-aminoundecanoic acid, and its amount arrives about 90mol% or the about 70mol% of about 10mol% for the about 10mol% based on the integral molar quantity of repeating unit.In another embodiment, copolyamide of the present invention can comprise the m-xylene diamine residue that arrives about 75mol% based on about 15mol% of the integral molar quantity of diamines residue to about 85mol%, about 20 to about 80mol% or about 25, remaining diamines residue comprises one or more diamines such as aliphatie diamine, the particularly residue of 1,6 hexanediamine.In this embodiment, the diamines residue may further include the residue of a spot of other following diamines, for example one or more in p dimethylamine or cyclic aliphatie diamine such as the following material: hexanaphthene dimethylamine or 1,4-hexanaphthene dimethylamine.In addition, polymeric amide can comprise randomly that one or more aliphatics with 7-12 carbon atom or aromatic dicarboxylic acid residue are with the instead of part hexanodioic acid, this dicarboxylic acid is pimelic acid, suberic acid, nonane diacid, sebacic acid, 11 carbon diacid, dodecanedioic acid, 1 for example, 4-cyclohexane dicarboxylic acid or m-phthalic acid, it can exist to the amount of about 85mol% with about 15mol%, randomly has a small amount of terephthalic acid.Polymeric amide can also comprise lactan such as hexanolactam or based on the residue of the lactan of γ-An Jidingsuan or 11-aminoundecanoic acid, and its amount arrives about 90mol% or about 10mol% to 70mol% for the about 10mol% based on the integral molar quantity of repeating unit.
In another embodiment, integral molar quantity based on dicarboxylic acid residue, can comprise that according to copolyamide of the present invention about 15mol% arrives the hexanodioic acid residue of about 90mol% at the most, remaining diacid residues comprises about 10 to about 85mol% isophthalic acid residues.Other example of hexanodioic acid and isophthalic acid residues content comprises about 20 to 80mol% and about 25 to about 75mol%.In this embodiment, polymeric amide can randomly comprise the residue of one or more aliphatic dicarboxylic acids that have 7-12 carbon atom on a small quantity, this dicarboxylic acid is pimelic acid, suberic acid, nonane diacid, sebacic acid, 11 carbon diacid, dodecanedioic acid or 1 for example, the 4-cyclohexane dicarboxylic acid randomly has a small amount of terephthalic acid.Randomly, this polymeric amide can comprise the m-xylene diamine residue.The example of m-xylene diamine residue concentration comprises about 15 to about 90mol% or about 25 to about 85mol% or about 25 to about 80mol%.All the other residues can comprise one or more aliphatie diamines as 1, the residue of 6-hexanediamine or one or more aromatic diamines such as p dimethylamine's residue.Similarly, copolyamide also can comprise lactan such as hexanolactam or based on the residue of the lactan of γ-An Jidingsuan or 11-aminoundecanoic acid, and its amount arrives about 70mol% for the about 10mol% based on the integral molar quantity of repeating unit to about 90mol% or about 10mol%.
In another example, copolyamide of the present invention can comprise one or more lactan such as hexanolactam or based on the residue of the lactan of γ-An Jidingsuan or 11-aminoundecanoic acid, based on the integral molar quantity of repeating unit, its amount arrives about 60mol% to about 90mol% or about 10mol% to about 70mol% or about 15mol% for about 10mol%.Have one or more aliphatic dicarboxylic acids of 7-12 carbon atom such as pimelic acid, suberic acid, nonane diacid, sebacic acid, 11 carbon diacid, dodecanedioic acid or 1, the amount of the residue of 4-cyclohexane dicarboxylic acid also can be based on about 20mol% of integral molar quantity of repeating unit to about 80mol%.For example, copolyamide can comprise m-phthalic acid or terephthalic acid residue.In this embodiment, based on the integral molar quantity of diamines residue, copolyamide can comprise the residue of about 15mol% to the m-xylene diamine of about 85mol%.Other example of m-xylene diamine content is about 20 to about 80mol% and about 25 to about 75mol%.Remaining diamines residue can comprise one or more diamines aliphatie diamines as 1, the residue of 6-hexanediamine.In this embodiment, the diamines residue may further include a spot of other diamines residue, for example one or more in p dimethylamine or cyclic aliphatie diamine such as the following material: 1, and 3-hexanaphthene dimethylamine or 1,4-hexanaphthene dimethylamine.Randomly, can use a spot of p dimethylamine, 1,3-hexanaphthene dimethylamine or 1, one or more in the 4-hexanaphthene dimethylamine.
Another embodiment of the invention is a polymer composition, and it is made up of non-miscible adulterant of following material basically:
(i) first component of forming by at least a thermoplastic polymer that is selected from polyester, polycarbonate, polyarylester and even adulterant thereof basically; And
(ii) second component of forming by the even adulterant of the commentaries on classics amide groupization of at least two kinds of polymeric amide basically;
Wherein second component (ii) with the refringence of first component (i), RI (second component)-RI (first component) is about 0.006 to approximately-0.0006, and the transmittance percentage of this non-miscible adulterant is at least 75%, turbidity is 10% or lower.In another aspect of this invention, first component is basically by containing terephthalic acid, 2,2,4,4-tetramethyl--1, the polyester composition of the residue of 3-cyclobutanediol and 1,4 cyclohexane dimethanol.Therefore, the present invention also provides a kind of polymer composition, and it is made up of non-miscible adulterant of following material basically:
(i) first component of forming by at least a polyester that comprises following substances basically:
(a) diacid residues, based on all diacid residues, it comprises about 70 to about 100mol% terephthalic acid residue; 0 to about 30mol% at least a modified aromatic family dicarboxylic acid residue with 20 carbon atoms at the most; And 0 to about 10mol% have an at least a modified aliphatic dicarboxylic acid residue of 16 carbon atoms at the most; And
(b) diol residue, based on all diol residue, its basically by about 1 to about 99mol% 2,2,4,4-tetramethyl--1,3-cyclobutanediol residue and about 1 is to the 1,4 cyclohexane dimethanol residue of about 99mol% composition; And
(ii) second component of forming by the even adulterant of the commentaries on classics amide groupization of at least two kinds of polymeric amide basically;
Wherein second component (ii) with the refringence of first component (i), RI (second component)-RI (first component) is about 0.006 to approximately-0.0006, and the transmittance percentage of this non-miscible adulterant is at least 75%, turbidity is 10% or lower.Here employed phrase " basically by ... form " be meant and comprise such composition: said composition is non-miscible adulterant, promptly, comprise at least two kinds of materials, when its Tg when the dsc measurement is relevant with composition, and said composition has first component that contains polyester, polycarbonate, polyarylester or its even adulterant and contains second component of even adulterant of the commentaries on classics amide groupization of at least two kinds of polymeric amide.In this embodiment, said composition is understood that not comprise any composition that will substantially change the essential property of this phrase indication composition.For example, composition can comprise other component of miscibility of % turbidity, % transmittance or non-miscible adulterant of the specific refractory power that can not change component, non-miscible adulterant.For example, this embodiment does not comprise that adding can change the compatilizer of the miscibility and the specific refractory power of composition.Similarly, second component that does not comprise the copolyamide of the interpolymerization preparation that contains by constituent monomers, because this copolyamide is considered to have the different character of even adulterant with the commentaries on classics amide groupization of at least two kinds of polymeric amide, even the molecular fraction of monomer whose residue equates.
Be used for polymeric amide of the present invention usually by the dicarboxylic acid and the diamines preparation of equal proportion reaction basically, perhaps the ring-opening polymerization by lactan prepares, and incorporates in the polyamide polymer with its corresponding residue.Therefore, the polymeric amide from dicarboxylic acid and diamines residue of the present invention contains the sour residue (100mol%) and the diamines residue (100mol%) of first-class substantially mol ratio, so the integral molar quantity of repeating unit equals 100mol%.Therefore, molecular fraction provided by the invention can be based on the integral molar quantity of sour residue, the integral molar quantity of diamines residue or the integral molar quantity of repeating unit.For example, contain in the sour residue based on the polymeric amide of the 30mol% terephthalic acid of total acid residue or the 100mol% altogether that copolyamide is meant at this copolyamide and contain the 30mol% terephthalic acid residue.Therefore, in per 100 equimolar acid residues, 30 moles of terephthalic acid residues are arranged.In another example, contain the m-xylene diamine residue that contains 30mol% in the diamines residue of the 100mol% altogether that the copolyamide based on the 30mol% m-xylene diamine of total diamines residue is meant at this copolyesters.Therefore, in per 100 moles of diamines residues, 30 moles of m-xylene diamine residues are arranged.
Any method well known in the art can be used for producing this polymeric amide.The polymeric amide preparation of the melt phase polymerization by diacid-two amine compound usually, this diacid-two amine compound can in-situ preparing or are prepared in independent step.In any one method, diacid and diamines are as initial substance.Perhaps, can use the ester-formin of diacid, preferred dimethyl ester.If the use ester, then reaction must be carried out under low relatively temperature, is generally 80 to 120 ℃, is converted into acid amides up to ester.Then, mixture is heated to polymerization temperature.Under the situation of polycaprolactam, hexanolactam or 6-aminocaprolc acid can be used as starting material, and the addition of hexanodioic acid/hexanediamine salt that polymerization can be by producing nylon 6/66 copolymer comes catalysis.When using diacid-two amine compound, mixture is heated to fusing and stirs up to balance.
Molecular weight is controlled by the ratio of diacid-diamines.The excessive terminal amino group that then produces higher concentration of diamines.For deoxidizing compositions, advantageously regulate the ratio of diacid-diamines so that the concentration of the terminal amine group that is produced is 20mmol/kg or lower.If diacid-two amine compound is to prepare in independent step, then excessive diamines adds before polymerization.Polymerization can be carried out under normal atmosphere or high pressure.
For showing satisfied transparency and low turbidity, second component of non-miscible adulterant and first component have usually and differ about 0.006 to-0.0006 specific refractory power approximately, that is, RI (second component)-RI (first component) is about 0.006 to approximately-0.0006.Other example of the difference of specific refractory power absolute value is about 0.005 to approximately-0.0006, about 0.004 to approximately-0.0006, about 0.003 to approximately-0.0006, about 0.005 to approximately-0.0005, about 0.004 to approximately-0.0005.Yet the difference that it will be understood to those of skill in the art that acceptable specific refractory power depends on composition, particle diameter, specific refractory power, wavelength and the grain pattern of adulterant, as described in Biangardi etc., and Die Angew.Makromole.Chemie, 183,221 (1990).
Non-miscible adulterant of the present invention has outstanding transparency, and has at least 75% % transmissivity (measuring by ASTM method D1003) and 10% or lower turbidity.According to this method, the % turbidity value is calculated by the % transmittance values.Other example of % transmissivity is at least 77%, at least 80% and at least 85%.Other example of the turbidity value that adulterant of the present invention can show be 9% or lower, 7% or lower, 5% or lower and 3% or lower.For composition of the present invention, turbidity is measured by following method: it is 1/8 inch or lower sheet material or film that said composition molding or curtain coating are become thickness, and measures turbidity according to the method described in the embodiment.For molded article, comprise the multilevel shaping goods, turbidity can be measured by following manner: downcutting thickness from this goods is 1/8 inch or lower sub-fraction (that is, 1 * 1cm), and measure turbidity according to providing method among the embodiment.
Described first component can also comprise the even adulterant of one or more polymkeric substance.For example, first component can comprise that first polyester and one or more are selected from the even adulterant of the polymkeric substance of polycarbonate, second polyester and polyarylester.Polyester can be any polyester as described herein.For example, first component can comprise polyester and the even adulterant that contains the polycarbonate of dihydroxyphenyl propane residue.
Polycarbonate can comprise based on one or more of about 90 to 100mol% dihydroxyphenyl propane residue of the integral molar quantity of diol residue and 0 to about 10mol% having the modified aliphatic glycol of 2 to 16 carbon or the residue of dihydric phenol.Representative example comprises two (4-hydroxyphenyl) methane, 2, two (4-hydroxyphenyl) propane (" bisphenol-A "), 2 of 2-, two (the 4-hydroxy-3-methyl phenyl) propane, 4 of 2-, two (4-hydroxyphenyl) heptane, 2 of 4-, two (the 4-hydroxyls-3 of 2-, the 5-dichlorophenyl) propane, 2, two (4-hydroxyl-3, the 5-dibromo phenyl) propane of 2-; Binary phenolic ether such as two (4-hydroxyphenyl) ether, two (3,5-two chloro-4-hydroxyphenyl) ether; Dihydroxybiphenyl such as p, p '-dihydroxybiphenyl, 3,3 '-two chloro-4,4 '-dihydroxybiphenyl; Dihydroxyl aryl sulfone such as two (4-hydroxyphenyl) sulfone, two (3,5-dimethyl-4-hydroxyphenyl) sulfone; Dihydroxy-benzene such as Resorcinol; Quinhydrones; The dihydroxy-benzene that halogen and alkyl replace is as 1,4-dihydroxyl-2,5-dichlorobenzene, 1,4-dihydroxyl-3-methylbenzene; And dihydroxyl diphenyl sulfoxide such as two (4-hydroxyphenyl) sulfoxide and two (3,5-two bromo-4-hydroxyphenyl) sulfoxide.Multiple other diphenol also is an available, and for example United States Patent (USP) 2,999,835,3,028,365 and 3,153,008 disclosed those.The suitable multipolymer that also has by above-mentioned dihydric phenol and halogen-containing dihydric phenol copolymerization, this halogen-containing dihydric phenol for example 2, two (3, the 5-two chloro-4-hydroxyphenyl) propane and 2 of 2-, 2-pair of (3,5-two bromo-4-hydroxyphenyl) propane.Can also use two or more different dihydric phenols, the adulterant of the perhaps multipolymer of the multipolymer of the polyester of the multipolymer of dihydric phenol and glycol, dihydric phenol and hydroxyl or acid blocked or dihydric phenol and diprotic acid, and any above-mentioned substance.Suitable dicarboxylic acid includes but not limited to aromatic dicarboxylic acid such as phthalic acid, m-phthalic acid, terephthalic acid, phthalic acid, phthalic acid, a phenylene-diacetic acid and to phenylene-diacetic acid, and polynuclear aromatic acid is as diphenic acid and 1, the 4-naphthalic acid.
The representative example of aliphatic diol comprises ethylene glycol, propylene glycol, butyleneglycol, pentanediol, hexylene glycol, heptanediol, ethohexadiol, neopentyl glycol, arylalkyl glycol such as styrene glycol and xylyl alcohol, the dihydroxyl alkyl oxide of dihydric phenol such as dihydroxyl ether of dihydroxyphenyl propane or the like.Other example of aliphatic diol is that the higher aliphatics dihydroxy compound of molecular weight such as polyoxyethylene glycol, polyphenyl are for ethylene glycol, polypropylene glycol, polytetramethylene glycol, poly-mercaptoethanol (polythioglycol), poly-aryl alkyl ethers glycol and multipolymer polyether glycol.The other representative example of dihydric phenol and aliphatic diol is a United States Patent (USP) 3,030,335 and 3,317, and those described in 466.Polycarbonate may further include the residue of one or more cladodification agent, this cladodification agent is as four oxybenzene compounds, three (4-hydroxyphenyl) ethane, pentaerythritol triacrylate and 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 cladodification agent is as described below.In another example, polycarbonate contains the dihydroxyphenyl propane residue based on the 95mol% at least of diol residue integral molar quantity.
According to the logarithmic viscosity number of the polycarbonate of adulterant of the present invention part preferably at least about 0.3dL/g, more preferably 0.5dL/g at least.According to the melt flow of polycarbonate of the present invention part 1-20 preferably, more preferably 2-18, it is the weight measurement of using 1.2kg according to ASTM method D1238 under 300 ℃ temperature.
The preparation method of polycarbonate is well known in the art.Disclosed herein and polycarbonate that can be used for straight or branched of the present invention is not subjected to the restriction of polycarbonate type or its production method.Usually, dihydric phenol such as dihydroxyphenyl propane and phosgene by use optional as chain terminator monofunctional compound and react as the trifunctional or the more polyfunctional compound of cladodification agent or linking agent.The reactive carboxylic acid halides of simple function, two senses and trifunctional also can be used for the preparation of polycarbonate as end-caps (simple function), comonomer (two is functional) or cladodification agent (trifunctional or higher).
For example, the polycarbonate of adulterant of the present invention part can prepare in melt, in solution or by interfacial polymerization technology well known in the art.Suitable method comprises the steps: under about 0 ℃ to 315 ℃ temperature, arrives under the pressure of 760mmHg about 0.1, makes the reaction of carbonate source and glycol be enough to form the time of polycarbonate.Can be used for commercial polycarbonate of the present invention normally by following manner preparation: make aromatic diol and carbonate source such as phosgene, dibutyl carbonate or diphenyl carbonate reaction, so that add the carbonate unit of 100mol% and with the diol units introducing polycarbonate of 100mol%.Produce other representative example such as the United States Patent (USP) 5,498,688,5,494,992 and 5,489 of the method for polycarbonate, described in 665.
The adulterant of polyester and polycarbonate can be by the preparation of following method: this method is included under about 25 ℃ to 350 ℃ temperature the time that polycarbonate and polyester portion fusion is enough to form transparent clear adulterant composition.Suitable conventional fusion technology comprises method of fusion and solution preparation.Other suitable fusion technology comprises does fusion and/or extrusion process.
The composition of the present invention that wherein contains non-miscible even adulterant can prepare by any method well known in the art, and can be used as thermoplastic composition and be used to form film and individual layer and multi-layer product.Except each the component physics fusion with adulterant, polyester blend can be by the transesterification preparation of polyester components uniformly.Similarly, the even adulterant of polymeric amide can be by the transmidation preparation of polyamide component.
Fusion fusion method comprises polymkeric substance fusion under the temperature that is enough to melt first component and second component part, then this adulterant is cooled to be enough to produce the temperature of transparent blends.Here employed term " fusion " includes but not limited to only softening polymkeric substance.(I.Manas-Zloczower ﹠amp described in the example of known fusion fusion method such as the Mixing and Compounding of Polymers in the polymer arts; Z.Tadmor eds., Carl Hanser Verlag press, N.Y.1994).
Solution preparation comprises first component of suitable w/w ratio and second components dissolved in 70/30 adulterant of appropriate organic solvent such as methylene dichloride or methylene dichloride and hexafluoroisopropanol, this solution of fusion, and by precipitating adulterant or by evaporating solvent the adulterant composition being separated from solution.Formulations prepared from solutions fusion method is known in the polymer arts.
Fusion fusion method is preferred for producing blend composition of the present invention.Fusion fusion method is than the more economical and safety of solution method that needs to use volatile solvent.Fusion fusion method also can more effectively provide transparent blends.Can also can prepare by of the present invention any transparent blends of solution blending preparation by melting method.Yet some can not prepare by solution preparation by the adulterant of the present invention of scorification preparation.It is any that the fusion method of transparent blends of the present invention is provided is suitable.Those skilled in the art can determine to produce the suitable fusion method of transparent blends of the present invention.
These of composition first and second components can be for example by using single screw rod or twin-screw extruder be mixed in melt (compound).They also can prepare by fusion in solution.Other component such as stablizer, fire retardant, tinting material, lubricant, releasing agent, impact modifier or the like also can join in this prescription.For example, composition can be mixed by the melt extruded of first component and second component and any other composition component such as metal catalyst, dyestuff, toning agent, filler etc. and produce.Composition can form by following manner: the solid particulate or the pill of every kind of thermoplastic polymer and polyamide component are done fusion, then with mixture fusion fusion in suitable mixing device such as extrusion machine, mixing roll mill etc.When wishing that produce in situ contains second component of even adulterant of commentaries on classics amide groupization of polymeric amide (, in the presence of first component), advantageously will carry out under the temperature of transmidation causing between the polymeric amide taking place.Usually, these temperature are about 270 ℃ to about 350 ℃.Other example of the temperature of transmidation is about 280 ℃ to about 350 ℃ and about 290 ℃ to about 340 ℃.Fusion carries out accessing for some time of non-miscible adulterant of good distribution.This can easily be determined by those skilled in the art.If desired; composition can cool off and cut into pill with further processing; it can be squeezed into film, sheet material, profile and other drip moldings; injection molding or pressing mold form multiple molded article, and perhaps it can form film also randomly by mode single shaft well known in the art or biaxial stretch-formed.
The amount of first and second components in this non-miscible adulterant can change to a great extent.For example, non-miscible adulterant of novel compositions of the present invention can comprise based on about 5 of composition total weight and arrives second component of about 1wt% to first component of about 99wt% and about 95.The unrestriced representative example of other of first and second components comprises that about 50 arrive first component of about 99wt% and about 50 to about 1wt% second component, first component of about 60 about 99wt% and about 40 arrives second component of about 1wt%, and second component of about 70 to about 99wt% first components and about 30 to about 1wt%.
The present invention also provides a kind of composition for preparing by the method that comprises fusion fusion following substances:
(i) comprise at least a first component that is selected from the thermoplastic polymer of polyester, polycarbonate, polyarylester and even adulterant thereof; And
Second component of even adulterant that (ii) comprises the commentaries on classics amide groupization of at least two kinds of polymeric amide;
Wherein second component (ii) with the refringence of first component (i), RI (second component)-RI (first component) is about 0.006 to approximately-0.0006, and the transmittance percentage of said composition is at least 75%, turbidity is 10% or lower.Of the present invention aspect another, first component comprises and contains terephthalic acid, 2,2,4,4-tetramethyl--1, the polyester of the residue of 3-cyclobutanediol and 1,4 cyclohexane dimethanol.Therefore, the present invention also provides a kind of polymer composition for preparing by the method that comprises fusion fusion following substances:
(i) contain first component of at least a polyester, this polyester contains:
(a) diacid residues, based on all diacid residues, it comprises at least a modified aliphatic dicarboxylic acid residue of 16 carbon atoms at the most that has of about terephthalic acid residue of 70 to about 100mol%, 0 to about 30mol% at least a modified aromatic family's dicarboxylic acid residue with 20 carbon atoms at the most and 0 to about 10mol%; And
(b) diol residue, based on all diol residue, it comprises that about 1 arrives 2,2,4 of about 99mol%, 4-tetramethyl--1,3-cyclobutanediol residue and about 1 arrives the 1,4 cyclohexane dimethanol residue of about 99mol%; And
Second component of even adulterant that (ii) comprises the commentaries on classics amide groupization of at least two kinds of polymeric amide;
Wherein second component (ii) with the refringence of first component (i), RI (second component)-RI (first component) is about 0.006 to approximately-0.0006, and the transmittance percentage of said composition is at least 75%, turbidity is 10% or lower.Said composition comprises the various embodiments of above-mentioned polyester, polycarbonate, polyarylester, its even adulterant and polymeric amide and any combination thereof.For example, second component of said composition can comprise the even adulterant of the commentaries on classics amide groupization of at least two kinds of polymeric amide, and wherein transmidation can contact under about 350 ℃ high temperature and finishes being generally about 270 ℃ by making polymeric amide.Other example of the temperature of transmidation is about 280 ℃ to about 350 ℃ and about 290 ℃ to about 340 ℃.
Second component even adulterant (ii) can comprise first polymeric amide that contains aromatic moieties and second polymeric amide that contains aliphatic residue as described above.For example, can include but not limited to nylon 4, nylon 6, nylon 9, Ni Long11, nylon 12, nylon 6,6, nylon 5,10, nylon 6,12, nylon 6,11, nylon 10,12 and combination thereof as the typical polymeric amide of second polymeric amide.Except that above-mentioned polyester, first component can comprise polyester and contain the even adulterant of the polycarbonate of dihydroxyphenyl propane residue.
Another aspect of the present invention is a kind of method for preparing transparent polymer blend, and this method comprises:
(A) select to comprise at least a first component that is selected from the thermoplastic polymer of polyester, polycarbonate, polyarylester and even adulterant thereof;
(B) measure the specific refractory power of this first component;
(C) provide second component that comprises following substances
(i) have the copolyamide of the aliphatics and the aromatic moieties of certain mol proportion, wherein the mol ratio of aliphatics and aromatic moieties is chosen as and makes the second component specific refractory power satisfy following formula:
0.006 〉=RI (second component)-RI (first component) 〉=-0.0006
Perhaps
The (ii) even adulterant of the commentaries on classics amide groupization of first and second polymeric amide, at least a in this polymeric amide have aromatic moieties, and wherein the weight percent of first and second polymeric amide is chosen as and makes the specific refractory power of second component satisfy following formula:
0.006 〉=RI (second component)-RI (first component) 〉=-0.0006
Wherein RI is a specific refractory power; And
(D), has at least 75% transmittance percentage and 10% or non-miscible adulterant of lower turbidity with generation with the described first and second component melts fusion.
Of the present invention aspect another, first component comprises and contains terephthalic acid, 2,2,4,4-tetramethyl--1, the polyester of the residue of 3-cyclobutanediol and 1,4 cyclohexane dimethanol.Therefore, the present invention also provides a kind of method for preparing transparent polymer blend, and this method comprises:
(A) selection contains first component of at least a polyester, and this polyester contains:
(a) diacid residues, based on all diacid residues, it comprises at least a modified aliphatic dicarboxylic acid residue of 16 carbon atoms at the most that has of about terephthalic acid residue of 70 to about 100mol%, 0 to about 30mol% at least a modified aromatic family's dicarboxylic acid residue with 20 carbon atoms at the most and 0 to about 10mol%; And
(b) diol residue, based on all diol residue, it comprises that about 1 arrives 2,2,4 of about 99mol%, 4-tetramethyl--1,3-cyclobutanediol residue and about 1 arrives the 1,4 cyclohexane dimethanol residue of about 99mol%; And
(B) measure the specific refractory power (RI) of this first component;
(C) provide second component that comprises following substances
(i) have the copolyamide of the aliphatics and the aromatic moieties of certain mol proportion, wherein the mol ratio of aliphatics and aromatic moieties is chosen as and makes the second component specific refractory power satisfy following formula:
0.006 〉=RI (second component)-RI (first component) 〉=-0.0006
Perhaps
The (ii) even adulterant of the commentaries on classics amide groupization of first and second polymeric amide, at least a in this polymeric amide have aromatic moieties, and wherein the weight percent of first and second polymeric amide is chosen as and makes the specific refractory power of second component satisfy following formula:
0.006 〉=RI (second component)-RI (first component) 〉=-0.0006
Wherein RI represents the specific refractory power of first and second components; And
(D), has at least 75% transmittance percentage and 10% or non-miscible adulterant of lower turbidity with generation with the first and second component melts fusion.
Method of the present invention comprises the various embodiments of above-mentioned polyester, polycarbonate, polyarylester, its even adulterant, copolyamide and polymeric amide and any combination thereof.
Method of the present invention comprises selects first component, and it can be polyester, polycarbonate, polyarylester or its even adulterant.The specific refractory power of first component can use the method that well known to a person skilled in the art to measure.Second component that can comprise the even adulterant of single copolyamide or at least two kinds of polymeric amide is adjusted into the specific refractory power of first component by following manner closely mates: the suitable mixture of selecting aromatics and aliphatic monomer under the situation of copolyamide, if perhaps use the even adulterant of polymeric amide, then selection contains the polyamide compound of the desired mixt of aromatics and aliphatic residue.The selection of the suitable proportion of monomer or polymeric amide can be determined by trial and error method, perhaps in another example, measure aromatic moieties and the polymeric amide of aliphatic residue or the index of refraction diagram of copolyamide by drawing the various differences that contain, and selection will provide the aromatics of the polymeric amide of targeted refractive index: the mol ratio of aliphatic residue or weight percent.First and second components can the fusion fusion.When second component comprises the even adulterant of commentaries on classics amide groupization of at least two kinds of polymeric amide, need under the temperature that can carry out transmidation effectively, carry out fusion fusion step.Typical transmidation temperature range as previously mentioned.
Thermoplastic polymer also can be chosen as the refractive index match with second component.Therefore, another aspect of the present invention is a kind of method for preparing transparent polymer blend, and this method comprises:
(A) selection comprises second component of following substances
(i) has the copolyamide of the aliphatics and the aromatic moieties of certain mol proportion; Or
The (ii) even adulterant of the commentaries on classics amide groupization of first and second polymeric amide, at least a polymeric amide has aromatic moieties;
(B) measure the specific refractory power of this second component;
(C) provide and comprise at least a polyester, polycarbonate, polyarylester and even first component of the thermoplastic polymer of adulterant thereof of being selected from, wherein polyester, polycarbonate, polyarylester or its even adulterant are chosen as and make the specific refractory power of first component satisfy following formula:
0.006 〉=RI (second component)-RI (first component) 〉=-0.0006
Wherein RI is a specific refractory power; And
(D), produce and to have at least 75% transmittance percentage and 10% or non-miscible adulterant of lower turbidity with the first and second component melts fusion.As mentioned above, first component comprises and contains terephthalic acid, 2,2,4,4-tetramethyl--1, the polyester of the residue of 3-cyclobutanediol and 1,4 cyclohexane dimethanol.Therefore, the present invention has also comprised a kind of method for preparing transparent polymer blend, and this method comprises:
(A) selection comprises second component of following substances
(i) has the copolyamide of the aliphatics and the aromatic moieties of certain mol proportion; Or
The (ii) even adulterant of the commentaries on classics amide groupization of first and second polymeric amide, at least a polymeric amide has aromatic moieties;
(B) measure the specific refractory power of this second component;
(C) selection contains first component of at least a polyester, and this polyester contains:
(a) diacid residues, based on all diacid residues, it comprises at least a modified aliphatic dicarboxylic acid residue of 16 carbon atoms at the most that has of about terephthalic acid residue of 70 to about 100mol%, 0 to about 30mol% at least a modified aromatic family's dicarboxylic acid residue with 20 carbon atoms at the most and 0 to about 10mol%; And
(b) diol residue, based on all diol residue, it comprises that about 1 arrives 2,2,4 of about 99mol%, 4-tetramethyl--1,3-cyclobutanediol residue and about 1 arrives the 1,4 cyclohexane dimethanol residue of about 99mol%; And
Wherein this polyester is chosen as and makes the specific refractory power of first component satisfy following formula:
0.006 〉=RI (second component)-RI (first component) 〉=-0.0006
Wherein RI is a specific refractory power; And
(D), produce and to have at least 75% transmittance percentage and 10% or non-miscible adulterant of lower turbidity with the first and second component melts fusion.
It is also understood that aforesaid method also comprises any combination of the numerous embodiments of above-mentioned polyester, polycarbonate, polyarylester, its even adulterant, copolyamide and polymeric amide.
In an example, the fusion thermoplastic polymer can specifically illustrate with reference to the polycarbonate/polyester adulterant to obtain to have about 0.006 second component and first component to the refringence of pact-0.0006.For example, the complete miscibility of the polycarbonate of dihydroxyphenyl propane and PCTG allows to adjust by the ratio of regulating polycarbonate/PCTG the specific refractory power (RI) of polycarbonate/PCTG adulterant.By regulating the ratio of polycarbonate, the specific refractory power of first component of the present invention can be complementary with the specific refractory power of second component of the even adulterant of the commentaries on classics amide groupization that contains copolyamide or polymeric amide, its difference about 0.006 to approximately between-0.0006.For example, if form transparent blends: 1) with polymer-modified and the adulterant that has the in advance fusion mutually that contains polycarbonate and polyester portion by following manner, perhaps 2) will polymer-modified and polycarbonate part fusion before introducing polyester portion, perhaps 3) will polymer-modified and polyester portion fusion before introducing the polycarbonate part, perhaps 4) before fusion, polymer-modified, polycarbonate part and polyester portion are mixed, can determine that then polymkeric substance is the suitable polymer-modified of the even adulterant of polyester/polycarbonate mentioned above.
Transparent blends of the present invention still can pass through to add polymer-modified modification, thus the performance adulterant (performance blends) that generation may be not necessarily transparent.For example, the nylon 6 of polymeric amide as deriving from Du Pont, 6, poly-(ether imide) ULTEM poly-(ether imide) as deriving from General Electric, polyphenylene oxide is as poly-(2,6-dimethyl phenylate) or gather (phenylate)/polystyrene adulterant as deriving from the NORYL resin of General Electric, polyester, polyphenylene sulfide, polyphenylene sulfide/sulfone, poly-(ester-carbonic ether) is as LEXAN 3250 poly-(ester-carbonic ether) (General Electric), the polycarbonate that is different from the LEXAN polycarbonate that derives from General Electric, polyarylester such as ARDELD100 polyarylester (Amoco), polysulfones, polysulfones ether, poly-(ether-ketone) or aromatic dihydroxy compound can be as changing character or reducing flammable adulterant properties-correcting agent.Some aromatic dihydroxy compounds that are used to prepare these polymkeric substance are at United States Patent (USP) 3,030,335 and United States Patent (USP) 3,317,466 in open.
The even adulterant of the copolyamide of composition of the present invention or polymeric amide can play barrier polymer, thereby has improved the barrier property of integrally combined thing.Here employed term " barrier polymer " is meant the polymkeric substance with one or more following character: (1) water-permeable is 2gm-mil/100 square inch/24 hour or lower, and it is measured down at 38 ℃ by ASTM method F1249; (2) oxygen-permeable is 5cc (STP)-mil/100 square inch/24 hour-atm or lower, and it is measured down at 23 ℃ by ASTM method D3985; Perhaps (3) carbon dioxide permeability is 25cc (STP)-mil/100 square inch/24 hour-atm or lower, and it is measured down at 23 ℃ by ASTM method D1434.
Barrier property can improve by the deoxidizing compositions of adding metal catalyst with the reaction of one or more polymeric amide in generation Catalytic Oxygen and the said composition.Therefore, the present invention further provides a kind of deoxidizing compositions that contains following substances:
(A) comprise non-miscible adulterant of following substances:
(i) comprise at least a first component that is selected from the thermoplastic polymer of polyester, polycarbonate, polyarylester and even adulterant thereof; And
Second component of even adulterant that (ii) comprises the commentaries on classics amide groupization of at least two kinds of polymeric amide;
Wherein second component (ii) with the refringence of first component (i), RI (second component)-RI (first component) is about 0.006 to approximately-0.0006, and the transmittance percentage of this non-miscible adulterant is at least 75%, and turbidity is 10% or lower; And
(B) at least a periodic table of elements 3-12 family, the metal that 4-6 is capable of being selected from.
First component of this non-miscible adulterant can comprise and contains terephthalic acid, 2,2,4,4-tetramethyl--1, the polyester of the residue of 3-cyclobutanediol and 1,4 cyclohexane dimethanol.Therefore, another embodiment of the invention is a kind of deoxidizing compositions that contains following substances:
(A) comprise non-miscible adulterant of following substances:
(i) contain first component of at least a polyester, this polyester contains:
(a) diacid residues, based on all diacid residues, it comprises at least a modified aliphatic dicarboxylic acid residue of 16 carbon atoms at the most that has of about terephthalic acid residue of 70 to about 100mol%, 0 to about 30mol% at least a modified aromatic family's dicarboxylic acid residue with 20 carbon atoms at the most and 0 to about 10mol%; And
(b) diol residue, based on all diol residue, it comprises that about 1 arrives 2,2,4 of about 99mol%, 4-tetramethyl--1,3-cyclobutanediol residue and about 1 arrives the 1,4 cyclohexane dimethanol residue of about 99mol%; And
Second component of even adulterant that (ii) comprises the commentaries on classics amide groupization of at least two kinds of polymeric amide;
Wherein second component (ii) with the refringence of first component (i), RI (second component)-RI (first component) is about 0.006 to approximately-0.0006, and the transmittance percentage of this non-miscible adulterant is at least 75%, and turbidity is 10% or lower.
(B) at least a periodic table of elements 3-12 family, the metal that 4-6 is capable of being selected from.
Except that the even adulterant of one or more polymeric amide, deoxidizing compositions of the present invention can also comprise the single copolyamide that is used for other embodiment of the present invention mentioned above.Therefore, the present invention also provides a kind of deoxidizing compositions that contains following substances:
(A) comprise non-miscible adulterant of following substances:
(i) comprise at least a first component that is selected from the thermoplastic polymer of polyester, polycarbonate, polyarylester and even adulterant thereof; And
Second component that (ii) comprises copolyamide;
Wherein second component (ii) with the refringence of first component (i), RI (second component)-RI (first component) is about 0.006 to approximately-0.0006, and the transmittance percentage of this non-miscible adulterant is at least 75%, and turbidity is 10% or lower; With
(B) at least a periodic table of elements 3-12 family, the metal that 4-6 is capable of being selected from.
As mentioned above, first component of non-miscible adulterant can comprise and contains terephthalic acid, 2,2,4,4-tetramethyl--1, the polyester of the residue of 3-cyclobutanediol and 1,4 cyclohexane dimethanol.Therefore, another embodiment of the invention is a kind of deoxidizing compositions that contains following substances:
(A) comprise non-miscible adulterant of following substances:
(i) contain first component of at least a polyester, this polyester contains:
(a) diacid residues, based on all diacid residues, it comprises at least a modified aliphatic dicarboxylic acid residue of 16 carbon atoms at the most that has of about terephthalic acid residue of 70 to about 100mol%, 0 to about 30mol% at least a modified aromatic family's dicarboxylic acid residue with 20 carbon atoms at the most and 0 to about 10mol%; And
(b) diol residue, based on all diol residue, it comprises that about 1 arrives 2,2,4 of about 99mol%, 4-tetramethyl--1,3-cyclobutanediol residue and about 1 arrives the 1,4 cyclohexane dimethanol residue of about 99mol%; And
Second component that (ii) comprises copolyamide;
Wherein second component (ii) with the refringence of first component (i), RI (second component)-RI (first component) is about 0.006 to approximately-0.0006, and the transmittance percentage of this non-miscible adulterant is at least 75%, and turbidity is 10% or lower; With
(B) at least a periodic table of elements 3-12 family, the metal that 4-6 is capable of being selected from.
It is also understood that deoxidizing compositions comprises any combination of the numerous embodiments of above-mentioned first and second components, polyester, polycarbonate, polyarylester, its even adulterant, copolyamide and polymeric amide.
Similarly, another embodiment of the invention is a kind of deoxidizing compositions of being made up of following substances basically:
(A) non-miscible adulterant of forming by following substances basically:
(i) first component of forming by at least a thermoplastic polymer that is selected from polyester, polycarbonate, polyarylester and even adulterant thereof basically;
(ii) second component of forming by the even adulterant of the commentaries on classics amide groupization of copolyamide or at least two kinds of polymeric amide basically;
Wherein second component (ii) with the refringence of first component (i), RI (second component)-RI (first component) is about 0.006 to approximately-0.0006, and the transmittance percentage of this non-miscible adulterant is at least 75%, and turbidity is 10% or lower; With
(B) at least a periodic table of elements 3-12 family, the metal that 4-6 is capable of being selected from.
Wherein the difference of the specific refractory power absolute value of first component and second component is 0.008 or lower, and molded article has at least 75% transmissivity and 10% or lower turbidity.In another example, the invention provides a kind of deoxidizing compositions of forming by following substances basically:
(A) comprise non-miscible adulterant of following substances:
(i) first component of forming by at least a polyester that comprises following substances basically:
(a) diacid residues, based on all diacid residues, it comprises at least a modified aliphatic dicarboxylic acid residue of 16 carbon atoms at the most that has of about terephthalic acid residue of 70 to about 100mol%, 0 to about 30mol% at least a modified aromatic family's dicarboxylic acid residue with 20 carbon atoms at the most and 0 to about 10mol%; And
(b) diol residue, based on all diol residue, its basically by about 1 to about 99mol% 2,2,4,4-tetramethyl--1,3-cyclobutanediol residue and about 1 is to the 1,4 cyclohexane dimethanol residue of about 99mol% composition; And
(ii) second component of forming by the even adulterant of the commentaries on classics amide groupization of at least two kinds of polymeric amide basically;
Wherein second component (ii) with the refringence of first component (i), RI (second component)-RI (first component) is about 0.006 to approximately-0.0006, and the transmittance percentage of this non-miscible adulterant is at least 75%, and turbidity is 10% or lower; With
(B) at least a periodic table of elements 3-12 family, the metal that 4-6 is capable of being selected from.
In these embodiments, composition is understood that not comprise any % turbidity, % transmissivity, the miscibility of first and second components or composition that composition removes oxygen characteristic that will change the essential property of this phrase indication composition such as the specific refractory power of component, non-miscible adulterant in fact.For example, other deoxygenation component such as diene, polyethers or any adding that is different from the oxidable organic compound of the listed component of claim of adulterant that is different from the commentaries on classics amide groupization of copolyamide or polymeric amide is excluded.
Deoxidizing compositions of the present invention can comprise a kind of periodic table of elements 3-12 family, metal that 4-6 is capable of being selected from, and this periodic table of elements is 1984 revised editions of the periodictable of Internation Union of Pure and AppliedChemistry.Typical oxide catalyst comprises transition-metal catalyst, and it can change between at least two kinds of oxidation state easily.The example of operable metal comprises copper, nickel, cobalt, iron, manganese and combination thereof.Effective any catalytic amount all can use in catalytic deoxidation, but usually this metal with about 5ppm to about 1, the amount of 000ppm is used.Other scope of metal concentration comprises that based on the gross weight of deoxidizing compositions, about 50ppm is to about 750ppm, and about 5 to about 600ppm, about 10 arrive about 500ppm, and about 50ppm arrives about 500ppm, and 50 to about 300ppm.Metal can use with this metallic element itself usually, uses as the metal complexes that contains organic aglucon, uses as oxide compound, perhaps uses as metal-salt.The example of the counterion of metal-salt includes but not limited to hydrochloride, acetate, acetylacetonate, stearate, palmitate, 2-ethylhexoate, neodecanoate, octylate or naphthenate and adulterant thereof.Metal-salt can also be an ionic polymer, uses the polymeric counterion in this case.Such ionic polymer is being known in the art.
In an example, metal catalyst is cobalt or compound that contains cobalt such as cobalt salt.Cobalt can be+2 or+3 oxidation state.Other example of metal catalyst is+rhodium of 2 oxidation state and the copper of+2 oxidation state.Metal can be easily as carboxylate salt such as cobalt octoate, Cobaltous diacetate or new cobalt decanoate and add with salt form.The amount of being reported is based on the weight of polymer blend, and is based on this metal but not joins that the weight of its compound in the said composition measures.Under the situation of cobalt as metal, typical amount is 50ppm at least, or 60ppm at least, or 75ppm at least, or 100ppm at least, or 125ppm at least.Catalyzer can join with pure substance or in carrier (as liquid or wax) in extrusion machine or other device with the preparation goods, perhaps its can with the concentrated solution of polyamide polymer, with the concentrated solution of polyesters copolymer or with the concentrated solution of non-miscible adulterant in add.Carrier can and first and second components between responding property or anergy, and can use volatility or nonvolatile carrier liq.In the preparation process of deoxidizing compositions, metal catalyst can be at multiple spot, by multiple fusion approach adding.A kind of useful especially method is in the latter stage of the final adulterant composition of preparation even the latter stage of the final fusion step before forming goods, polymeric amide and transition metal is put together, so that the removing oxygen activity and can not start prematurely of polymeric amide.In some cases, for example when cobalt is provided as transition metal, can preferably in the process of fusion first and second components rather than for example, in the process of preparation thermoplastic polymer, add cobalt.
In one embodiment, for example, first component of deoxidizing compositions can comprise the polyester with above-mentioned any monomer residue combination.For example, polyester can comprise (a) diacid residues, based on all diacid residues, it comprises that 80mol%'s at least is selected from terephthalic acid, m-phthalic acid, naphthalic acid and 1, the residue of at least a dicarboxylic acid of 4-cyclohexane dicarboxylic acid, and the residue of 0 to about 20mol% at least a modification dicarboxylic acid with 2 to 20 carbon atoms; And (b) diol residue, integral molar quantity based on diol residue, it comprises that 80mol%'s at least is selected from ethylene glycol, 1,4 cyclohexane dimethanol, neopentyl glycol, glycol ether, 1, ammediol, 1,4-butyleneglycol and 2,2,4,4-tetramethyl--1, the residue of at least a glycol of 3-cyclobutanediol, and the residue of 0 to about 20mol% at least a modification glycol with 3 to 16 carbon.In another example, diacid residues can comprise that about 60 arrive the terephthalic acid residue of 100mol% and 0 to about 40mol% isophthalic acid residues, and diol residue can comprise the 1,4 cyclohexane dimethanol residue of about 100mol%.In another example, diacid residues can comprise the terephthalic acid residue based on about 100mol% of diacid residues integral molar quantity.Other object lesson that can be used as the polyester of first component comprises the polyester that contains following substances: (i) about 80 to about 100mol% terephthalic acid residues and about 50 arrive 1, the 4 cyclohexanedimethanol residue of about 90mol% and about 10 to about 50mol% neopentyl glycol residue; (ii) the terephthalic acid residue of about 100mol% and about 10 arrives the 1,4 cyclohexane dimethanol of about 40mol% and 60 to about 90mol% glycol residue; And (iii) the terephthalic acid residue and about 10 of about 100mol% arrives the glycol ether residue of about 25mol% to the 1,4 cyclohexane dimethanol residue of about 99mol%, 0 to about 90mol% glycol residue and about 1.To be those based on all diacid residues contain other example of polyester has an appointment 70 to about 100mol% terephthalic acid residue and contain any one polyester of following diol residue in forming based on all diol residue: (i) about 5 to about 60mol% 2,2,4,4-tetramethyl--1,3-cyclobutanediol residue and about 40 arrives the 1,4 cyclohexane dimethanol residue of about 95mol%; (ii) about 15 arrive 2,2,4 of about 40mol%, 4-tetramethyl--1, and 3-cyclobutanediol residue and about 60 arrives the 1,4 cyclohexane dimethanol residue of about 85mol%; (iii) about 20 arrive 2,2,4 of about 30mol%, 4-tetramethyl--1, and 3-cyclobutanediol residue and about 70 arrives the 1,4 cyclohexane dimethanol residue of about 80mol%; And (iv) about 20 to about 25mol% 2,2,4,4-tetramethyl--1,3-cyclobutanediol residue and about 75 arrives the 1,4 cyclohexane dimethanol residue of about 80mol%.This polyester can also further comprise about 0.1 to about 1mol% at least a trimellitic acid as indicated above, trimellitic acid 1,2-anhydride and pyromellitic dianhydride, glycerine, the Sorbitol Powder, 1 of being selected from based on all diacid residues, 2, the cladodification agent of 6-hexanetriol, tetramethylolmethane, tartrate, citric acid, trimethylolethane and trimesic acid.
Other example of polyester is that those contain any one polyester in forming based on the terephthalic acid residue of about 100mol% of all diacid residues and based on the following diol residue of all diol residue: (i) about 1 to about 5mol% 1,4 cyclohexane dimethanol residue and about 99 arrives the glycol residue of about 95mol%; (ii) about 29 to about 33mol% 1,4 cyclohexane dimethanol and about 71 arrives the glycol residue of about 67mol%; (iii) about 45 to about 55mol% 1,4 cyclohexane dimethanol residue and about 55 arrives the glycol residue of about 45mol%; (iv) about 60 to about 65mol% 1,4 cyclohexane dimethanol residue and about 40 arrives the glycol residue of about 35mol%; (v) about 79 to about 83mol% 1,4 cyclohexane dimethanol residue residue and about 21 arrives the glycol residue of about 17mol%; (the vi) 1,4 cyclohexane dimethanol residue of about 100mol%; (vii) about 5 arrive 2,2,4 of about 60mol%, 4-tetramethyl--1, and 3-cyclobutanediol residue and about 40 arrives the 1,4 cyclohexane dimethanol residue of about 95mol%; (viii) about 15 arrive 2,2,4 of about 40mol%, 4-tetramethyl--1, and 3-cyclobutanediol residue and about 60 arrives the 1,4 cyclohexane dimethanol residue of about 85mol%; (ix) about 20 to about 30mol% 2,2,4,4-tetramethyl--1,3-cyclobutanediol residue and about 70 arrives the 1,4 cyclohexane dimethanol residue of about 80mol%; (x) about 20 to about 25mol% 2,2,4,4-tetramethyl--1,3-cyclobutanediol residue and about 75 arrives the 1,4 cyclohexane dimethanol residue of about 80mol%.
First component can also comprise the even adulterant of at least a polyester and at least a polycarbonate.The polycarbonate that can be used for these even adulterants as previously mentioned.
The even adulterant or the copolyamide that change amide groupization can comprise for example various nylon of aforesaid any polymeric amide.Yet advantageously, the even adulterant of the copolyamide of deoxidizing compositions or polymeric amide comprises the residue of m-xylene diamine, p dimethylamine or its combination.For example, second component can comprise first polymeric amide that contains m-xylene diamine and hexanodioic acid residue and the even adulterant that contains second polymeric amide of nylon 6, nylon 6,6 or its adulterant.As another example, this even adulterant can combine with even adulterant that contains polyester and first component that comprises the polycarbonate of dihydroxyphenyl propane residue in non-miscible adulterant.For optimum deoxygenation character, the even adulterant that it is desirable to copolyamide or polymeric amide contains 20mmol/kg or free amino group still less.The concentration of free amino group can use the technology of well known to a person skilled in the art such as titration to determine.
In another example, deoxidizing compositions comprises the copolyamide of m-xylene diamine adipic acid ester.Use the m-xylene diamine adipic acid ester (m-xylylenediamine adipate) of modification can provide a kind of deoxidizing compositions of comparing the deoxygenation character with improvement with the composition that only contains m-xylene diamine adipic acid ester homopolymer, wherein some hexanodioic acid residues and/or some the m-xylene diamine residues in the m-xylene diamine adipic acid ester of this modification is replaced by other residue.Other polymeric amide barrier polymer as herein described also can be as the component of deoxidizing compositions.
Above described composition of the present invention can be used to make molded article such as sheet material, film, pipeline, preformed member, bottle or profile.Such goods can form by well known to a person skilled in the art any way, for example by extruding, calendering, thermoforming, blowing, extrusion blow, injection moulding, compression moulding, curtain coating, drawing-off, tentering or blowing.
For example, composition of the present invention can be made molded article such as film by any technology well known in the art.The formation of film can melt extrude or realizes by for example United States Patent (USP) 4,427,614 described compression moulding or by any other suitable method by United States Patent (USP) for example 4,880,592 is described.For example, film can be produced by known cast film, blown film and extrusion coating technology, and the latter comprises and being expressed on the substrate.Such substrate also can comprise articulamentum (tie-layer).The film of producing by fusion curtain coating or blowing can use tackiness agent in conjunction with or be sealed on the substrate.Composition can be made the film of single or multiple lift by any technology well known in the art.For example, the film of single or multiple lift can be produced by known cast film, blown film and extrusion coating technology, and the latter comprises and being expressed on the substrate.Representational substrate comprises film, sheet material and woven fabric and non-woven fabrics.The film of the single or multiple lift of producing by fusion curtain coating or blowing can use tackiness agent in conjunction with or be sealed on the substrate.
For example, composition can use conventional blown film equipment to form film.Film-forming apparatus can be to be called as the equipment of " blown film " equipment in this field, and comprises the circular die that is used for the bubble blown film, the oppressed and formation film " bubble " by its composition." bubble " finally collapses and forms film.
Composition can also be used for forming molded article by extrusion blow and injection stretch-blowing.Injection moulding is with copolyamide or polyamide compounds is softening in the heating cylinder uniformly, when its fusion under high pressure it is expelled in the closed die, and cooling die solidifies with initiation, and the preformed member of molding is released from mould.Moulding compound is suitable for producing preformed member most, and then these preformed member reheat being stretched-are blow molded into has the final bottle shape of required character.The preformed member of injection moulding is heated to suitable orientation temperature (100 ℃ to 150 ℃), stretching-blowing then.Back one method is by forming down: for example by with the promotion of plug inset and axially hot preformed member being carried out first stretching, be blown into high-pressure air (500psi at the most) then to stretch in hoop (hoop) direction by mechanical process.Like this, the blown bottle that has prepared two-way stretch.Typical blow-up ratio is 5/1 to 15/1.
The outstanding transparency of composition of the present invention and low turbidity make it possible to the transparent molded article that significant quantity waste of polymeric or " regrowth " are introduced in preparation.Here employed term " regrowth " is understood that to have its implication commonly used in the art,, reclaims and be ground into more short grained waste of polymeric from product forming process that is.Usually, regrowth is sold as waste material, and is used for adding the wherein transparency molded article unessential to its application of these goods.For bottle and the film of some molded article as being used for package application, low turbidity and high-clarity are the features that needs.Make these goods, particularly multi-layer product, produce a large amount of waste of polymeric inherently, these waste material polymkeric substance usually can not be got back in the product forming process, because it has formed unacceptable turbidity level.Because the specific refractory power of first and second components is mated very much, can be by the transparent formed articles of the low turbidity of the composition production of the present invention that comprises regrowth.
Therefore, another aspect of the present invention is a kind of method that forms molded article, and this method comprises:
(A) with following substances fusion fusion:
(i) comprise at least a first component that is selected from the thermoplastic polymer of polyester, polycarbonate, polyarylester and even adulterant thereof; And
Second component of even adulterant that (ii) comprises the commentaries on classics amide groupization of copolyamide or at least two kinds of polymeric amide;
Wherein first component (i) and second component (ii) form non-miscible adulterant, the refringence of second component and first component, RI (second component)-RI (second component), be about 0.006 to about-0.0006, and the transmittance percentage of this non-miscible adulterant is at least 75%, and turbidity is 10% or lower;
(B) form molded article;
(C) recovery comprises first and second components (i) of fusion and waste of polymeric composition (ii);
(D) this waste of polymeric composition is ground to produce polymer recycled thing;
(E) randomly, dry this waste of polymeric composition; With
(F) will this polymer recycled thing and first and second components (i) of step (A) and (ii) merging.
In another example, first component can comprise and contains terephthalic acid, 2,2,4,4-tetramethyl--1, the polyester of the residue of 3-cyclobutanediol and 1,4 cyclohexane dimethanol.Therefore, the present invention also comprises a kind of method that forms molded article, and this method comprises:
(A) with following substances fusion fusion:
(i) contain first component of at least a polyester, this polyester contains:
(a) diacid residues, based on all diacid residues, it comprises at least a modified aliphatic dicarboxylic acid residue of 16 carbon atoms at the most that has of about terephthalic acid residue of 70 to about 100mol%, 0 to about 30mol% at least a modified aromatic family's dicarboxylic acid residue with 20 carbon atoms at the most and 0 to about 10mol%; And
(b) diol residue, based on all diol residue, it comprises that about 1 arrives 2,2,4 of about 99mol%, 4-tetramethyl--1,3-cyclobutanediol residue and about 1 arrives the 1,4 cyclohexane dimethanol residue of about 99mol%; And
Second component of even adulterant that (ii) comprises the commentaries on classics amide groupization of copolyamide or at least two kinds of polymeric amide;
Wherein first component (i) and second component (ii) form non-miscible adulterant, the refringence of second component and first component, RI (second component)-RI (second component), be about 0.006 to about-0.0006, and the transmittance percentage of this non-miscible adulterant is at least 75%, and turbidity is 10% or lower;
(B) form molded article;
(C) recovery comprises first and second components (i) of fusion and waste of polymeric composition (ii);
(D) this waste of polymeric composition is ground to produce polymer recycled thing;
(E) randomly, dry this waste of polymeric composition; With
(F) will this polymer recycled thing and first and second components (i) of step (A) and (ii) merging.
Therefore, method of the present invention allows to add the waste of polymeric regrowth and keeps low turbidity and high-clarity in molded article.It is also understood that aforesaid method comprises the numerous embodiments of above-mentioned first and second components, polyester, polycarbonate, polyarylester, its even adulterant, copolyamide, polymeric amide, deoxidizing compositions and any combination thereof.
For example, as mentioned above, the non-miscible adulterant that is formed by first and second components may further include at least a periodic table of elements 3-12 family, the metal that 4-6 is capable of being selected from.The example of metal includes but not limited to copper, nickel, cobalt, iron, manganese and combination thereof.Usually, based on the gross weight of molded article, the amount of this metal is about 5 to about 600ppm weight metal.Preferred metal is a cobalt.
The molded article of the inventive method can form by any method well known in the art and mentioned above.For example, molded article can form by extruding, calendering, thermoforming, blowing, extrusion blow, injection moulding, compression moulding, curtain coating, drawing-off, tentering or blowing.
Although method of the present invention can be used to prepare any molded article, the representative article that can produce is sheet material, film, preformed member, pipeline and bottle.These goods can have individual layer or contain 2 to about 7 layers.Regrowth can join in these layers one or more layers, and based on one or more layers weight, these layers can comprise about 50 to 100wt% regrowth usually.Other example that may reside in the regrowth level in the molded article is, based on one or more layers gross weight 5 to about 95wt%, about 10 to about 60wt%, about 15 arrive about 50wt%, and about 20 arrive about 30wt%.
Molded article can comprise multilayer, and wherein one or more layers comprises first and second components as non-miscible adulterant, and perhaps wherein first component and second component are present in the independent layer.Therefore, another aspect of the present invention is a kind of multilevel shaping goods, and these goods comprise:
(i) comprise at least a the first layer that is selected from the thermoplastic polymer of polyester, polycarbonate, polyarylester and even adulterant thereof; And
The second layer of even adulterant that (ii) comprises the commentaries on classics amide groupization of at least two kinds of polymeric amide;
Wherein the second layer (ii) and the refringence of the first layer (i), RI (second layer)-RI (the first layer) is about 0.006 to approximately-0.0006, and the transmittance percentage of this molded article is at least 75%, turbidity is 10% or lower.
In one aspect of the method, the first layer can comprise and contains terephthalic acid, 2,2,4,4-tetramethyl--1, the polyester of the residue of 3-cyclobutanediol and 1,4 cyclohexane dimethanol.Therefore, another embodiment of the invention is a kind of multilevel shaping goods, and these goods comprise:
(i) contain the first layer of at least a polyester, this polyester contains:
(a) diacid residues, based on all diacid residues, it comprises at least a modified aliphatic dicarboxylic acid residue of 16 carbon atoms at the most that has of about terephthalic acid residue of 70 to about 100mol%, 0 to about 30mol% at least a modified aromatic family's dicarboxylic acid residue with 20 carbon atoms at the most and 0 to about 10mol%; And
(b) diol residue, based on all diol residue, it comprises that about 1 arrives 2,2,4 of about 99mol%, 4-tetramethyl--1,3-cyclobutanediol residue and about 1 arrives the 1,4 cyclohexane dimethanol residue of about 99mol%; And
The second layer of even adulterant that (ii) comprises the commentaries on classics amide groupization of at least two kinds of polymeric amide;
Wherein the second layer (ii) and the refringence of the first layer (i), RI (second layer)-RI (the first layer) is about 0.006 to approximately-0.0006, and the transmittance percentage of this molded article is at least 75%, turbidity is 10% or lower.Molded article can comprise the numerous embodiments of above-mentioned first and second components, polyester, polycarbonate, polyarylester, its even adulterant, copolyamide, polymeric amide, deoxidizing compositions, molded article and any combination thereof.
These multilevel shaping goods can be produced by extruding, calendering, thermoforming, blowing, extrusion blow, injection moulding, compression moulding, curtain coating, drawing-off, tentering or blowing.Because unusual coupling between first and second layers the specific refractory power, this multi-layer product may further include the regrowth of the mixture that contains first and second layers, and this regrowth can join in the combination of the first layer, the second layer or first and second layers.Usually, based on the gross weight of described goods, the amount of this regrowth is that about 5wt% of multi-layer product arrives about 60wt%.Other example of the weight percent of regrowth is that about 10wt% of this goods gross weight arrives about 30wt% to about 40wt% and about 20wt% in the molded article.
Use according to its expection, multi-layer product can have 2 to about 7 layers.For example, as mentioned above, molded article can be sheet material, film, pipeline, bottle or preformed member.It also can be lamination layer structure.For example, molded article can have the laminate structure by ABA, ABABA, ABCBA or ACBCA representative, its middle level A wraps the first layer (i), layer B comprises the second layer (ii), and layer C comprise contain first and second layers useless (i) and (ii), from the regrowth of the mixture of the polyester that consumes the acquisition of circulation back or polycarbonate or its combination.According to the composition of regrowth, maybe advantageously difference RI (layer B)-RI of the specific refractory power of layer B and layer C (layer C) be about 0.006 to approximately-0.0006, to keep the ability of goods transparency and adding regrowth.
In another embodiment, a layer A can comprise the second layer (ii), and a layer B comprises the first layer (i), and layer C comprise first and second layers useless (i) and (ii), from the regrowth of the mixture of the polyester that consumes the acquisition of circulation back or polycarbonate or its combination.
In addition, the second layer of novel multi-layer goods of the present invention (ii) may further include at least a periodic table of elements 3-12 family, the metal that 4-6 is capable of being selected from.The example of metal comprises copper, nickel, cobalt, iron, manganese and combination thereof.Usually, based on the gross weight of molded article, the amount of this metal is about 10 to about 500ppm weight metal.About 5ppm that other example of metal concentration is based on the gross weight of molded article arrives about 600ppm, and 10ppm is to about 750ppm.Preferred metal is a cobalt.
In another embodiment, molded article of the present invention may further include one deck extra play at least, and this extra play comprises the regrowth that arrives about 100wt% based on about 50 of layer gross weight.The extra play that contains regrowth may further include at least a periodic table of elements 3-12 family, the metal that 4-6 is capable of being selected from.The example of metal comprises copper, nickel, cobalt, iron, manganese and combination thereof.Usually, based on the gross weight of molded article, the amount of this metal is about 10 to about 500ppm weight metal.About 5ppm that other example of metal concentration is based on the gross weight of molded article arrives about 600ppm, and 10ppm is to about 750ppm.Preferred metal is a cobalt.
As mentioned above, the multilevel shaping goods can comprise the various embodiments of aforesaid molded article, thermoplastic polymer, polymeric amide, non-miscible adulterant, even adulterant and deoxidizing compositions.For example, at least a thermoplastic polymer can comprise polyester and one or more barrier polymer of straight or branched, this polyester comprises that based on all diacid residues 80mol%'s at least is selected from terephthalic acid, m-phthalic acid, naphthalic acid and 1, the residue of at least a dicarboxylic acid of 4-cyclohexane dicarboxylic acid, and the residue of 0 to about 20mol% at least a modification dicarboxylic acid with 2 to 20 carbon atoms; (b) diol residue, integral molar quantity based on diol residue, it comprises the ethylene glycol that is selected from of 80mol% at least, 1, the 4-cyclohexanedimethanol, neopentyl glycol, glycol ether, 1, ammediol, 1,4-butyleneglycol and 2,2,4,4-tetramethyl--1, the residue of at least a glycol of 3-cyclobutanediol, and the residue of 0 to about 20mol% at least a modification glycol with 3 to 16 carbon, these one or more barrier polymer comprise first polymeric amide that contains m-xylene diamine and hexanodioic acid residue and comprise nylon 6, the even adulterant of second polymeric amide of nylon 6,6 or its adulterant.Other example of polyester be those contain about terephthalic acid residue of 70 to about 100mol% based on all diacid residues, 0 to about 30mol% at least a modified aromatic family dicarboxylic acid residue with 20 carbon atoms at the most, 0 to about 10mol% have an at least a modified aliphatic dicarboxylic acid residue of 16 carbon atoms at the most; And based on 2,2,4 of any one polyester (i) about 5 to about 60mol% in the following diol residue composition of all diol residue, 4-tetramethyl--1,3-cyclobutanediol residue and about 40 arrives the 1,4 cyclohexane dimethanol residue of about 95mol%; (ii) about 15 arrive 2,2,4 of about 40mol%, 4-tetramethyl--1, and 3-cyclobutanediol residue and about 60 arrives the 1,4 cyclohexane dimethanol residue of about 85mol%; (iii) about 20 arrive 2,2,4 of about 30mol%, 4-tetramethyl--1, and 3-cyclobutanediol residue and about 70 arrives the 1,4 cyclohexane dimethanol residue of about 80mol%; And (iv) about 20 to about 25mol% 2,2,4,4-tetramethyl--1,3-cyclobutanediol residue and about 75 arrives the 1,4 cyclohexane dimethanol residue of about 80mol%.This polyester can also further comprise about 0.1 to about 1mol% at least a trimellitic acid as indicated above, trimellitic acid 1,2-anhydride and pyromellitic dianhydride, glycerine, the Sorbitol Powder, 1 of being selected from based on all diacid residues, 2, the cladodification agent of 6-hexanetriol, tetramethylolmethane, tartrate, citric acid, trimethylolethane and trimesic acid.
For example, thermoplastic polymer can comprise branched polyesters.In another example, thermoplastic polymer further comprises polyester and contains the even adulterant of the polycarbonate of dihydroxyphenyl propane residue.
Multilevel shaping goods of the present invention can prepare by any method known to those skilled in the art.For example, this molded article can form by any ordinary method that is used to form film, comprise lamination, extrude lamination, be total to injection, stretching-blowing and coextrusion blowing, and can specifically describe with reference to typical method by coextrusion manufacturing multilayer film.For example, first and second components and any optional layer are fed in the same number of extrusion machine loading hopper, and each extrusion machine is handled the material that is used for one or more layers.Usually, for composition of the present invention, before extruding and in the extrusion process, first and second components all are heated to about Tg+100 ℃ to about Tg+300 ℃ temperature, and wherein Tg is the second-order transition temperature by first or second component of dsc measurement.Melt-flow from each extrusion machine is fed in the coextrusion die head of independent manifold.In this die head, a plurality of layers are connected and combination, and the single multilayer film as polymeric material are discharged from die head then.After leaving die head, on the temperature control casting roller, by this first roller, curtain coating is to the cold second temperature control roller of common ratio first roller then by curtain coating for film.Temperature control roller major control film leaves the rate of cooling behind the die head.In another approach, film-forming apparatus can be to be called as the equipment of blown film equipment in this field, and comprises the branch manifold circular die that is used for the bubble blown film, by the oppressed formation of its this film composite film forming film bubble that finally can break.The coextrusion method that forms film and sheet material layered product is known.Perhaps each individual course can at first form sheet material then the heating with pressure under having or do not having the situation laminated of intermediate adhesive layer to be in the same place.
The transparency of the present composition and low turbidity make the multiwalled of the waste of polymeric introduced significant quantity or " regrowth ", the preparation of transparent molded article to carry out.Therefore, the present invention also provides a kind of method that forms the multilevel shaping goods, and this method comprises:
(i) will contain about Tg+100 ℃ to about Tg+300 ℃ the temperature that at least a first component that is selected from the thermoplastic polymer of polyester, polycarbonate, polyarylester and even adulterant thereof is heated to this first component;
Second component of even adulterant that (ii) will contain the commentaries on classics amide groupization of copolyamide or at least two kinds of polymeric amide is heated to about Tg+100 ℃ to about Tg+300 ℃ temperature of this second component;
(iii) form the molded article of first and second components in independent layer;
(iv) reclaim useless first and second components;
(first and second components of v) should giving up are ground to produce regrowth;
(vi) randomly, dry this regrowth; And
(vii) regrowth and step (i) and first component (ii), second component or its combination are merged;
Wherein step second component (ii) and the refringence of first component of step (i), RI (second component)-RI (first component) is about 0.006 to approximately-0.0006, and the transmittance percentage of this molded article is at least 75%, turbidity is 10% or lower.In another example, first component can comprise and contains terephthalic acid, 2,2,4,4-tetramethyl--1, the polyester of the residue of 3-cyclobutanediol and 1,4 cyclohexane dimethanol.Therefore, another aspect of the present invention is a kind of method that forms the multilevel shaping goods, and this method comprises:
(i) first component is heated to about Tg+100 ℃ to about Tg+300 ℃ temperature of this first component, this first component contains polyester, and this polyester contains:
(a) diacid residues, based on all diacid residues, it comprises at least a modified aliphatic dicarboxylic acid residue of 16 carbon atoms at the most that has of about terephthalic acid residue of 70 to about 100mol%, 0 to about 30mol% at least a modified aromatic family's dicarboxylic acid residue with 20 carbon atoms at the most and 0 to about 10mol%; And
(b) diol residue, based on all diol residue, it comprises that about 1 arrives 2,2,4 of about 99mol%, 4-tetramethyl--1,3-cyclobutanediol residue and about 1 arrives the 1,4 cyclohexane dimethanol residue of about 99mol%;
Second component of even adulterant that (ii) will contain the commentaries on classics amide groupization of copolyamide or at least two kinds of polymeric amide is heated to about Tg+100 ℃ to about Tg+300 ℃ temperature of this second component;
(iii) form the molded article of first and second components in independent layer;
(iv) reclaim the first and second useless components;
(first and second components of v) should giving up are ground to produce regrowth;
(vi) randomly, dry this regrowth; And
(vii) regrowth and step (i) and first component (ii), second component or its combination are merged;
Wherein step second component (ii) and the refringence of first component of step (i), RI (second component)-RI (first component) is about 0.006 to approximately-0.0006, and the transmittance percentage of this molded article is at least 75%, turbidity is 10% or lower.Aforesaid method can comprise the numerous embodiments of above-mentioned first and second components, polyester, polycarbonate, polyarylester, its even adulterant, copolyamide, polymeric amide, deoxidizing compositions, molded article, goods manufacturing process and any combination thereof.
Therefore, method of the present invention allows to add the regrowth of significant quantity and keeps low turbidity and high-clarity in molded article.Regrowth generally includes the mixture of step (i) and first and second components (ii), it produces as waste material in the forming process of goods, but can use any polymer materials, as long as its specific refractory power and second component differ about 0.006 to about-0.0006.The regrowth material of this method can with first component of step (i), step (ii) second component or the combination of first and second components merge.Regrowth can join first or the second layer in, and based on the gross weight of this molded article, the 5wt% that can be this molded article is to about 60wt%.Other representative example of the regrowth content of the molded article of the inventive method is that about 10wt% of this molded article arrives about 20wt% of about 40wt% and this molded article to about 30wt%.
Use according to its expection, the multi-layer product of method of the present invention can have 2 to about 7 layers.For example, as mentioned above, the multilevel shaping goods can be sheet material, film, pipeline, bottle or preformed member.It also can be lamination layer structure.For example, molded article can have the laminate structure by ABA, ABABA, ABCBA or ACBCA representative, its middle level A comprises first component of step (i), layer B comprises step second component (ii), and layer C comprises the regrowth that contains from the mixture of step (i) and useless first and second components (ii), the polyester that obtains from consumption circulation back or polycarbonate or its combination.According to the composition of regrowth, maybe advantageously difference RI (layer B)-RI of the specific refractory power of layer B and layer C (layer C) be about 0.006 to approximately-0.0006, to keep the ability of goods transparency and adding regrowth.
In another embodiment, group A can comprise step second component (ii), layer B comprises first component of step (i), and layer C comprises the regrowth of the mixture that contains in steps (i) and useless first and second components (ii), the polyester that obtains from consumption circulation back or polycarbonate or its combination.
In addition, the step of novel multi-layer goods of the present invention second component (ii) may further include at least a periodic table of elements 3-12 family, the metal that 4-6 is capable of being selected from.The example of operable metal comprises copper, nickel, cobalt, iron, manganese and combination thereof.Usually, based on the gross weight of molded article, the amount of this metal is about 10 to about 500ppm weight metal.About 5ppm that other example of metal concentration is based on the gross weight of molded article arrives about 600ppm, and 10ppm is to about 750ppm.Preferred metal is a cobalt.When having metal, advantageously regulate the ratio of diacid-diamines so that the concentration of the terminal amine group that is produced is 20mmol/kg or lower.
In another embodiment, the step of the inventive method (iii) may further include and forms one deck extra play at least, and this extra play comprises the regrowth that arrives about 100wt% based on about 50 of this layer gross weight.The extra play that contains regrowth may further include at least a periodic table of elements 3-12 family, the metal that 4-6 is capable of being selected from.The example of metal comprises copper, nickel, cobalt, iron, manganese and combination thereof.Usually, based on the gross weight of molded article, the amount of this metal is about 10 to about 500ppm weight metal.About 5ppm that other example of metal concentration is based on the gross weight of molded article arrives about 600ppm, and 10ppm is to about 750ppm.Preferred metal is a cobalt.
As mentioned above, the multilevel shaping goods can comprise the various embodiments of aforesaid molded article, thermoplastic polymer, polymeric amide, non-miscible adulterant, even adulterant and deoxidizing compositions.For example, at least a thermoplastic polymer can polyester, this polyester comprises that based on all diacid residues 80mol%'s at least is selected from terephthalic acid, m-phthalic acid, naphthalic acid and 1, the residue of at least a dicarboxylic acid of 4-cyclohexane dicarboxylic acid, and the residue of 0 to about 20mol% at least a modification dicarboxylic acid with 2 to 20 carbon atoms; (b) diol residue, based on the integral molar quantity of diol residue, it comprises that 80mol%'s at least is selected from ethylene glycol, 1,4 cyclohexane dimethanol, neopentyl glycol, glycol ether, 1, ammediol, 1,4-butyleneglycol and 2,2,4,4-tetramethyl--1, the residue of at least a glycol of 3-cyclobutanediol; And the residue of 0 to about 20mol% at least a modification glycol with 3 to 16 carbon; These one or more barrier polymer comprise first polymeric amide that contains m-xylene diamine and hexanodioic acid residue and the even adulterant that comprises second polymeric amide of nylon 6, nylon 6,6 or its adulterant.Other example of polyester is that those comprise about 70 terephthalic acid residues that arrive about 100mol% based on all diacid residues, at least a modified aromatic family's dicarboxylic acid residue of 0 to about 30mol% with 20 carbon atoms at the most and 0 to about 10mol% have an at least a modified aliphatic dicarboxylic acid residue of 16 carbon atoms at the most, and any one polyester in forming based on the following diol residue of all diol residue: (i) about 5 to about 60mol% 2,2,4,4-tetramethyl--1,3-cyclobutanediol residue and about 40 arrives the 1,4 cyclohexane dimethanol residue of about 95mol%; (ii) about 15 arrive 2,2,4 of about 40mol%, 4-tetramethyl--1, and 3-cyclobutanediol residue and about 60 arrives the 1,4 cyclohexane dimethanol residue of about 85mol%; (iii) about 20 arrive 2,2,4 of about 30mol%, 4-tetramethyl--1, and 3-cyclobutanediol residue and about 70 arrives the 1,4 cyclohexane dimethanol residue of about 80mol%; And (iv) about 20 to about 25mol% 2,2,4,4-tetramethyl--1,3-cyclobutanediol residue and about 75 arrives the 1,4 cyclohexane dimethanol residue of about 80mol%.This polyester can also further comprise about 0.1 to 1mol% at least a trimellitic acid as indicated above, trimellitic acid 1,2-anhydride and pyromellitic dianhydride, glycerine, the Sorbitol Powder, 1 of being selected from based on all diacid residues, 2, the cladodification agent of 6-hexanetriol, tetramethylolmethane, tartrate, citric acid, trimethylolethane and trimesic acid.
For example, thermoplastic polymer can comprise branched polyesters.In another example, thermoplastic polymer further comprises polyester and contains the even adulterant of the polycarbonate of dihydroxyphenyl propane residue.
Therefore, another embodiment of the invention further is a kind of method that forms the multilevel shaping goods, and this method comprises:
(A) will comprise that first component of following material is heated to about Tg+100 ℃ to about Tg+300 ℃ temperature of this first component: at least a polyester that (i) comprises following part: (a) diacid residues, based on all diacid residues, it comprises the terephthalic acid residue at least about 95mol%, (b) diol residue, integral molar quantity based on diol residue, it comprises the residue of at least a glycol that is selected from ethylene glycol and 1,4 cyclohexane dimethanol of 95mol% at least; At least a polycarbonate that (ii) comprises the dihydroxyphenyl propane residue; Or (iii) its even adulterant;
(B) second component that will comprise following material is heated to about 290 ℃ temperature: this second component comprises polymeric amide and at least a nylon 6 and the nylon 6 of being selected from that contains diamines and diacid residues, the even adulterant of the commentaries on classics amide groupization of 6 polymeric amide, this polymeric amide that contains diamines and diacid residues comprise based on the m-xylene diamine residue of about 100mol% of all diamines residues with based on the hexanodioic acid residue of about 100mol% of all diacid residues;
(C) form the molded article of first and second polymer compositions in independent layer;
(D) reclaim the first and second useless components;
(E) should give up the grinding of first and second components to produce regrowth;
(F) randomly, dry this regrowth; And
(G) regrowth and step (A) and first component (B), second component or its combination are merged;
The refringence of first component of second component of step (B) and step (B) wherein, RI (second component)-RI (first component) is about 0.006 to approximately-0.0006, and the transmittance percentage of this molded article is at least 75%, turbidity is 10% or lower.In another example, first component can comprise and contains terephthalic acid, 2,2,4,4-tetramethyl--1, the polyester of the residue of 3-cyclobutanediol and 1,4 cyclohexane dimethanol.Therefore, another embodiment of the invention is a kind of method that forms the multilevel shaping goods, and this method comprises:
(A) first component is heated to about Tg+100 ℃ to about Tg+300 ℃ temperature of this first component, this first component contains at least a polyester, and this polyester contains:
(a) diacid residues, based on all diacid residues, it contains 95 terephthalic acid residues that arrive about 100mol% that have an appointment; With
(b) diol residue, based on all diol residue, it comprises that about 15 arrive 2,2,4 of about 40mol%, 4-tetramethyl--1,3-cyclobutanediol residue and about 60 arrives the 1,4 cyclohexane dimethanol residue of about 85mol%;
Wherein the logarithmic viscosity number of this polyester is about 0.55 to about 0.75dL/g;
(B) second component is heated to about 290 ℃ and arrives about 310 ℃ temperature, this second component comprises the even adulterant of the commentaries on classics amide groupization of following substances: (a) contain the polymeric amide of diamines and diacid residues, it comprises based on the residue of the m-xylene diamine of about 100mol% of all diamines residues and based on the hexanodioic acid residue of about 100mol% of all diacid residues; (b) at least a polymeric amide that is selected from nylon 6 and nylon 6,6;
(C) form the molded article of first and second polymer compositions in independent layer;
(D) reclaim the first and second useless components;
(E) should give up the grinding of first and second components to produce regrowth;
(F) randomly, dry this regrowth; And
(G) regrowth and step (A) and first component (B), second component or its combination are merged;
The refringence of first component of second component of step (B) and step (B) wherein, RI (second component)-RI (first component) is about 0.006 to approximately-0.0006, and the transmittance percentage of this molded article is at least 75%, turbidity is 10% or lower.
Aforesaid method can comprise the numerous embodiments of above-mentioned first and second components, polyester, polycarbonate, polyarylester, its even adulterant, copolyamide, polymeric amide, deoxidizing compositions, molded article, goods manufacturing process and any combination thereof.
As mentioned above, regrowth can comprise first and second components (i) and mixture (ii), and can with first component (i), second component (ii) or its combination merge.Based on the gross weight of molded article, the amount of regrowth can arrive about 60wt% for about 5wt% of this molded article.Other representative example of the regrowth content of the molded article of the inventive method is that about 10wt% of this molded article arrives about 20wt% of about 40wt% and this molded article to about 30wt%.The polyester of this method can comprise the diacid residues that contains at least about the terephthalic acid residue of 95mol%, and can have large-scale diol component.For example, this polyester can comprise that containing has an appointment and 1 arrives the glycol residue of about 95mol% to the 1,4 cyclohexane dimethanol residue of about 5mol% and about 99.Other example that the glycol of the polyester of the inventive method is formed includes but not limited to: comprise that (i) the about 29 1,4 cyclohexane dimethanol residues and about 71 that arrive about 33mol% arrive the diol residue of the glycol residue of about 67mol%; Comprise that (ii) the about 45 1,4 cyclohexane dimethanol residues and about 55 that arrive about 55mol% arrive the diol residue of the glycol residue of about 45mol%; Comprise that (iii) the about 60 1,4 cyclohexane dimethanol residues and about 40 that arrive about 65mol% arrive the diol residue of the glycol residue of about 35mol%; Comprise that (iv) the about 79 1,4 cyclohexane dimethanol residues and about 21 that arrive about 83mol% arrive the diol residue of the glycol residue of about 17mol%; And (the diol residue that v) comprises the 1,4 cyclohexane dimethanol residue of about 100mol%.Other example of polyester is that those comprise any one polyester in forming based on the terephthalic acid residue of about 95 about 100mol% of all diacid residues and based on the following diol residue of all diol residue: (i) about 5 to about 60mol% 2,2,4,4-tetramethyl--1,3-cyclobutanediol residue and about 40 arrives the 1,4 cyclohexane dimethanol residue of about 95mol%; (ii) about 15 arrive 2,2,4 of about 40mol%, 4-tetramethyl--1, and 3-cyclobutanediol residue and about 60 arrives the 1,4 cyclohexane dimethanol residue of about 85mol%; (iii) about 20 arrive 2,2,4 of about 30mol%, 4-tetramethyl--1, and 3-cyclobutanediol residue and about 70 arrives the 1,4 cyclohexane dimethanol residue of about 80mol%; And (iv) about 20 to about 25mol% 2,2,4,4-tetramethyl--1,3-cyclobutanediol residue and about 75 arrives the 1,4 cyclohexane dimethanol residue of about 80mol%.This polyester can also further comprise about 0.01 to 1mol% at least a trimellitic acid as indicated above, trimellitic acid 1,2-anhydride and pyromellitic dianhydride, glycerine, the Sorbitol Powder, 1 of being selected from based on all diacid residues, 2, the cladodification agent of 6-hexanetriol, tetramethylolmethane, tartrate, citric acid, trimethylolethane and trimesic acid.
In another example, thermoplastic polymer may further include polyester and contains the even adulterant of the polycarbonate of dihydroxyphenyl propane residue.Each polyester and polycarbonate can be straight or brancheds.
In addition, the step of novel method of the present invention second component (ii) may further include at least a periodic table of elements 3-12 family, the metal that 4-6 is capable of being selected from.The example of operable metal comprises copper, nickel, cobalt, iron, manganese and combination thereof.Usually, based on the gross weight of molded article, the amount of this metal is about 10 to about 500ppm weight metal.About 5ppm that other example of metal concentration is based on the gross weight of molded article arrives about 600ppm, and 10ppm is to about 750ppm.Preferred metal is a cobalt.When having metal, advantageously regulate the ratio of diacid-diamines so that the concentration of the terminal amine group that is produced is 20mmol/kg or lower.
In another embodiment, the step of the inventive method (C) may further include and forms one deck extra play at least, and this extra play comprises the regrowth that arrives about 100wt% based on about 50 of this layer gross weight.The extra play that contains regrowth may further include at least a periodic table of elements 3-12 family, the metal that 4-6 is capable of being selected from.The example of metal comprises copper, nickel, cobalt, iron, manganese and combination thereof.Usually, based on the gross weight of molded article, the amount of this metal is about 10 to about 500ppm weight metal.About 5ppm that other example of metal concentration is based on the gross weight of molded article arrives about 600ppm, and 10ppm is to about 750ppm.Preferred metal is a cobalt.
Molded article of the present invention can be further directed by stretching, and this can improve the barrier property of these goods.As mentioned above, it is desirable to other conventional additives or polymer-modifiedly add with polymeric composition of the present invention.What for example, can add has antioxidant, light and heat stablizer, dyestuff, static inhibitor, lubricant, sanitas, processing aid, surface slip agent, anti, pigment, fire retardant, a whipping agent etc.Can use more than a kind of additive.Additive can exist with the amount of any needs, but about 20wt% of common no more than this molded article gross weight of its amount, preferred no more than 10wt%.
Zhi Bei polymer composition, deoxidizing compositions and molded article can also comprise about at the most 30wt%, preferably be lower than some plate-like particles from least a layered silicate material (platelet particle) of about 20wt%, to improve its barrier property thus.Plate-like particles can be come modification with at least a ammonium compound.The amount of plate-like particles can be measured by following manner: when handling according to ASTM D5630-94, measure the residual ash of polymkeric substance-plate-like particles composition.When the plate-like particles concentration in the raising mixture, can increase improvement usually to gas-barrier.Though about 0.01% the plate-like particles amount of being low to moderate provides the obstruct that improves (particularly when good distribution and arrangement), preferably has the composition at least about the 0.5wt% plate-like particles, because they have shown desirable having improved breathability.
Usually the layered silicate material is a kind of intensive caking of plate-like particles of the card sample that closely is stacked.Plate-like particles of the present invention has thickness and about 10 diameters to about 5000 nanometers that are lower than about 2 nanometers usually.For the purposes of the present invention, measurement only relates to plate-like particles, and does not relate to ammonium compound or operable any other dispersing auxiliary and handle compound.Suitable plate-like particles is from the layered silicate material, and it is common free-pouring powder, has about 0.3 to about 3 meq/g cation exchange capacity, and preferred about 0.8 to about 1.5meq/g.Suitable layered silicate examples of substances comprises mica type stratiform leaf silicate (phyllosilicate), comprises clay, montmorillonitic clay, sodium montmorillonite, sodium hectorite, wilkinite, nontronite, beidelite, volonsloite, saponite, sauconite, magadite, fibrous morphology crystals, synthetic sodium hectorite etc.The clay of this characteristic can derive from a plurality of companies, comprises Southern Clay Products andNanocor, Inc..Most preferred plate-like particles derives from sodium bentonite or sodium montmorillonite.Such clay can easily obtain in the U.S.'s (it is called as Wyoming type polynite) and the other parts in the world, comprises deriving from Kunimine Industries the Kunipia clay of Inc.
The layered silicate material is handled usually to improve the dispersion in polymer composition.Many useful clay treatments are well known in the art, these are handled also can be before joining mixture of the present invention with layered silicate material, afterwards or among use, can not deviate from scope of the present invention like this.The example of useful processing includes but not limited to handle with silane compound, swelling agent, polymkeric substance and oligopolymer, dispersing auxiliary, organic cation salt and combination thereof.
The example of the useful processing of carrying out with silane compound comprises that those disclosed is handled among the open WO93/11190 of international patent application.The example of useful silane compound comprises (3-glycidoxy propyl group) Trimethoxy silane, 2-methoxyl group (polyethyleneoxy) propyl group seven methyl trisiloxanes, octadecyl dimethyl (3-trimethoxy-silylpropyl) ammonium chloride etc.
The example of the useful processing of carrying out with swelling agent comprises oligopolymer well known in the art.The representative polymer and the oligopolymer that are used to handle clay comprise United States Patent (USP) 5,552, those disclosed in 469 and 5,578,672.Many dispersing auxiliaries are known, comprise multiple material, comprise water, alcohol, ketone, aldehyde, chlorinated solvent, varsol, aromatic solvent etc. or its combination.
Embodiment
Summary: invention is illustrated further by the following examples.The second-order transition temperature of polyester, polymeric amide and adulterant (Tg) is to use TAInstruments 2920 differential scanning calorimeters (DSC) to measure under the scanning speed of 20 ℃/min by ASTM method D3418.Heat deflection temperature (HDT) is measured by ASTM method D648, and the Izod notched Izod impact strength is measured according to ASTM Method D256.Flexural property is measured according to ASTM method D790.The tensile property of adulterant is measured down at 23 ℃ according to ASTM method D638.The logarithmic viscosity number of polyester is in the phenol/tetrachloroethane of 60/40 (wt/wt), measures under 25 ℃ under the concentration of 0.5g/100ml.The glycol content of the polyester portion of these adulterants be by proton magnetic resonance (PMR) spectrum ( 1H NMR) measures.The miscibility of adulterant is that the dsc of passing through the object of the film suppressed and institute's molding is measured.
Turbidity value is to use HunterLab UltraScan Sphere 8000 colourimeters by ASTM method D1003 (% turbidity=100 * diffuse transmission/total transmission), use Hunter ' s common software (3.8 editions) to measure, this colourimeter is by Hunter Associates Laboratory, Inc., VA makes.The calibration of this instrument is carried out according to the HunterLab users' guidebook with operation.Diffuse transmission (% transmission) thus be by eliminating straight-through light path and obtain placing ligh trap from the integrating sphere opposite of sample port.Only measure the light that scattering is higher than 2.5 degree.Total transmission comprises measures directly by the light of sample and the outer light of axle that is arrived transmitter by sample scattering.Sample is placed on the outlet opening place of ball, so that make the outer light of axle from whole ball all can be used for scattering.Transparency is measured by vision and turbidimetry.For adulterant of the present invention and various composition, turbidity is measured by following method: it is 1/8 inch or lower sheet material, film or thin plate that above-mentioned composition is formed into thickness, and measures turbidity and transmittance percentage according to aforesaid method.For molded article, comprise the multilevel shaping goods, turbidity and transmittance percentage are measured by following manner: downcutting thickness from this goods is 1/8 inch or lower sub-fraction (that is, 1 * 1cm), and measure turbidity and transmittance percentage according to aforesaid method.
Specific refractory power is at 633 nanometers Metricon Prism Coupler TMModel 2010 refractometers (deriving from Metricon company) are measured, and it is reported as the mean value of going up the specific refractory power of measuring at 3 orthogonal directionss (extruding or draw direction, horizontal direction and thickness direction).Alignment films is to go up at the long film drawer of TM (name of manufacturers) to produce, and this machine carries out single shaft or biaxial stretch-formed to the sample of compacting, blowing or extrusion film.The operation of film drawer is based on two pull bars that are perpendicular to one another moving on the hydraulic drive rod.With each move towbar relative a fixed towbar all arranged.These to opposition move and fixed traction bars (the four edges edge of film sample is attached to it) form the twin shafts that are perpendicular to one another, along this twin shaft, sample stretches with any stretch ratio of four or seven times of original sizes (according to employed machine) at the most.Sample is placed in the anchor clamps on the machine, and then is heated before stretching if desired.From the output of this device is that stress under experimental temperature and the Elastic Film condition is to the data (if desired) of extensibility.
The oxygen-permeable of film is to use MOCON, Inc Minneapolis, and the Ox-Tran oxygen flow instrument that MN makes is measured.Oxygen-permeable is to be calculated by known testing film area, film thickness, the poor and measured stable state transmissivity of oxygen partial pressure of crossing over this film.Transmissivity shows that at sample measured flux is not really to be in stable state under the active situation of deoxygenation, because when the efficient of deoxygenation reaction changed in time, can change at leisure.Yet in this case, at the duration that infiltration is measured, oxygen-permeable can be considered to be in pseudostable state usually.In the active deoxygenation sample that embodiment comprised subsequently, elimination efficiency does not obviously almost change to and changes during measuring, and perviousness is to be calculated by measured pseudostable state transmission rates.
Comparative example 1-12: the copolyesters of listing in the table 1 is prepared by terephthalic acid, ethylene glycol and 1,4 cyclohexane dimethanol (CHDM) except that polyester G.The amount of CHDM is as shown in table 1 in the polyester.Embodiment F contains 100% CHDM (0% ethylene glycol), but the acid moieties of 26mol% is m-phthalic acid rather than terephthalic acid.Polyester G is prepared as follows: 21.24 pounds of (49.71 Gram-mole) dimethyl terephthalate (DMT), 12.61 pounds of (39.77 Gram-moles) 1,4-cyclohexanedimethanol and 6.30 pounds of (19.88 Gram-moles) 2,2,4,4-tetramethyl--1, next reacts the 3-cyclobutanediol in the existence of catalyzer three (2 ethyl hexanoic acid) butyl tin of 200ppm.2,2,4,4-tetramethyl--1, the cis/trans ratio of 3-cyclobutanediol is about 50/50.The cis/trans ratio of 1,4 cyclohexane dimethanol is about 30/70.Reaction is to be furnished with in 18 gallons of stainless steel pressure containers of condensation tower, vacuum system and HELICONE type agitator to carry out under nitrogen purging.Agitator moves with 25rpm, and the temperature of reaction mixture is elevated to 250 ℃, and pressure is elevated to 20psig.Reaction mixture kept 2 hours under 250 ℃ and 20psig pressure.Then pressure is reduced to 0psig with the speed of 3psig/min.Then the temperature of reaction mixture is elevated to 270 ℃ and pressure is reduced to 90mmHg.After 270 ℃ and 90mmHg keep 1 hour, agitator speed is reduced to 15rpm, the temperature of reaction mixture is elevated to 290 ℃, and pressure is reduced to＜1mmHg.Reaction mixture 290 ℃ and＜maintenance 12 minutes down of the pressure of 1mmHg.Use nitrogen that the pressure of pressurized vessel is increased to 1 normal atmosphere then.Then molten polymer is extruded from pressurized vessel.The refrigerative extruded polymer is ground to sieve by 6mm.The logarithmic viscosity number of polymkeric substance is 0.590dL/g, and Tg is 106 ℃.NMR analyze to show that this polymkeric substance comprises 2,2,4 of the 1,4 cyclohexane dimethanol residue of 77.1mol% and 22.9mol%, 4-tetramethyl--1,3-cyclobutanediol residue.The colour of polymkeric substance is: L *=83.27, a *=-1.34, b *=5.08.
Table 1
Polyester CHDM in the polyester (mol%) Tg The specific refractory power of polyester
A 1.5 81 1.5708
B 31 83 1.5644
C 50 84 1.5593
D 62 86 1.5573
E 81 91 1.5547
F 100 88 1.5519
G 77 106 1.5470
Copolyesters and MXD6 6121 polymeric amide (contain the m-xylene diamine of 100mol% and the hexanodioic acid of 100mol%, derive from Mitsubishi Corporation) are 70 ℃ of dried overnight.In these copolyesters each all with 1,3 and the MXD6 of 5wt% carry out bag and mix (bag blended), and be fed in following temperature and set (degree centigrade) down in 1.5 inches single-screw extrusion machines of Sterling of 90rpm, form adulterant:
1 district 2 districts 3 districts 4 districts 5 districts
240 250 260 260 260
Adulterant is 70 ℃ of dried overnight, is being injection molded into 1/8 inch thick 4 under 270 ℃ then on Toyo 90 injection moulding machines " square sheets.The measuring result of the specific refractory power of MXD6 is 1.5824.The result that turbidity value that obtains and nylon specific refractory power deduct the polyester specific refractory power is displayed in Table 2:
Table 2
Embodiment Polyester type Polyester (wt%) MXD6 (wt％) The % turbidity Total transmission (%) RI (nylon)-RI (polyester)
C-1 A 99 1 5.2 82.8 0.0116
C-2 A 97 3 14.3 81.6 0.0116
C-3 A 95 5 29.8 82.0 0.0116
C-4 B 99 1 5.1 79.5 0.0180
C-5 B 97 3 22.4 70.7 0.0180
C-6 B 95 5 42.9 62.4 0.0180
C-7 C 99 1 8.5 80.7 0.0231
C-8 C 97 3 31.0 70.4 0.0231
C-9 C 95 5 50.7 62.6 0.0231
C-10 D 99 1 11.5 77.6 0.0251
C-11 D 97 3 59.0 63.3 0.0231
C-12 D 95 5 81.6 53.5 0.0231
Embodiment 13-24,27-29,31-32,34-36,38 and comparative example 25-26,30,33,36-37 and 39: nylon 6 (derives from the Zytel of DuPont 7335F) and MXD6 (6121 grades) 120 ℃ of dryings 48 hours, and carry out bag with various ratios and mix.Then polymeric amide bag blending compound is delivered to following condition (℃) under 1.5 inches single-screw extrusion machines of Sterling of 90rpm in, form the even adulterant that has the commentaries on classics amide groupization that the single Tg value relevant with composition show by each adulterant.The Tg value is displayed in Table 3.
1 district 2 districts 3 districts 4 districts 5 districts
250 270 300 300 300
Part is changeed the nylon adulterant of amide groupization or MXD6 120 ℃ of dried overnight, is injection molded into 1/8 inch thick sample or is squeezed into the thick film of 15mil at 240 ℃ on Toyo 90 injection moulding machines at 240 ℃ then.Film prepares by following extrusion process: employed extrusion machine is the Killian extrusion machine of conventional 2.54 cm diameters, its have 24: 1 L: D (length: ratio diameter), be furnished with the spiral charging and the twisting maddock mixing section of 3: 1 compression ratios.Conventional feed mechanism is used for melt Conveying to 15.24 centimetres conventional rack-style (coathanger) die head.Pile structure is used for melt quenching under the dual roll type cast film.Then, these films are stretching in all directions on TM-Long 4x under 95 ℃.Characteristic before the stretching of these films is displayed in Table 3, and the characteristic after the stretching shows in table 3A.Should be noted that the oxygen-permeable of table among the 3A is with 100% O under 30 ℃ and 50% relative humidity 2Measure as test gas.
Film characteristics before table 3-stretches
Embodiment MXD6 (wt％) Nylon 6 (wt%) Tg (℃) Oxygen-permeable (cc *mil/100in 2*day *atm) Thickness (mil) Specific refractory power
13 100 0 88 0.533 15.003 1.5824
14 95 5 87 0.440 15.000 1.5772
15 90 10 83 0.100 14.465 1.5739
16 87 13 83 0.063 14.498 1.5724
17 85 15 81 0.413 14.065 1.5717
18 75 25 77 1.266 15.260 1.5655
19 73 27 76 1.060 14.065 1.5641
20 70 30 75 1.317 14.535 1.5617
21 65 35 72 1.334 14.755 1.5599
22 62 38 72 0.740 16.385 1.5575
23 60 40 70 0.709 14.630 1.5536
Embodiment MXD6 (wt％) Nylon 6 (wt%) Tg (℃) Oxygen-permeable (cc *mil/100in 2*day *atm) Thickness (mil) Specific refractory power
24 0 100 44 1.5318
Film characteristics after table 3A-stretches
Embodiment MXD6(wt％) Nylon 6 (wt%) Oxygen-permeable (cc *mil/(100in 2*day *atm) Thickness (mil)
13 100 0 0.230 0.900
14 95 5 0.238 0.930
15 90 10 0.263 0.850
16 87 13 0.340 0.860
17 85 15 0.325 0.820
18 75 25 0.499 0.900
19 73 27 1.402 0.885
20 70 30 0.622 0.880
21 65 35 0.215 0.970
22 62 38 0.847 1.095
23 60 40 0.982 0.995
24 0 100
For producing embodiment and the comparative example that shows in the table, part is changeed adulterant or MXD6 dried overnight between 70 ℃ to 120 ℃ of amide groupization, and the polyester with table 1 is mixed then.Polyester is dried overnight between 70 to 120 ℃.The adulterant of the commentaries on classics amide groupization in the selected table 3 of these polyester in the table 1 each and 10wt% or MXD6 carry out bag to be mixed, and be fed in following temperature and set (℃) down in 1.5 inches single-screw extrusion machines of Sterling of 90rpm, form non-miscible adulterant:
1 district 2 districts 3 districts 4 districts 5 districts
240 260 280 280 280
Adulterant is injection molded into 1/8 inch 4 thick " square sheets at 270 ℃ then 70 ℃ of dried overnight on Toyo 90 injection moulding machines.The result that turbidity value that obtains and nylon specific refractory power deduct the polyester specific refractory power is displayed in Table 4.
Be to produce embodiment 38 and comparative example C-39,70 ℃ of dried overnight, to carry out bag mixed with the polyester A of table 1 or C then from the adulterant of the commentaries on classics amide groupization of the embodiment in the table 3 20.This polyester is dried overnight between 70 to 120 ℃ also.Then, bag blending compound is injection molded into 1/8 inch 4 thick " square sheets at 270 ℃ on the Toyo90 injection moulding machine.The result that the specific refractory power of turbidity value that obtains and MXD6 or nylon adulterant deducts the polyester specific refractory power is displayed in Table 4.
Table 4-polyester blend and uniform MXD6/ nylon 6 adulterants
Embodiment Polyester type The adulterant embodiment of table 3 CHDM in the polyester (mol%) Adulterant MXD6 (wt%) Adulterant nylon 6 (wt%) Turbidity % Total transmission % RI (nylon)-RI (polyester)
C-25 A 13 1.5 100 0 28.1 71.1 0.0116
C-26 A 14 1.5 95 5 13.5 76.0 0.0064
27 A 15 1.5 90 10 6.3 77.8 0.0031
28 A 16 1.5 87 13 6.9 78.1 0.0016
29 A 17 1.5 85 15 7.7 77.9 0.0009
C-30 B 17 31 85 15 21.3 81.8 0.0073
31 B 18 31 75 25 5.0 86.5 0.0011
32 B 19 31 73 27 8.5 85.4 -0.0003
C-33 B 20 31 70 30 16.2 84.1 -0.0027
34 C 20 50 70 30 4.1 86.8 0.0024
36 C 21 50 65 35 8.3 84.5 0.0006
C-36 C 22 50 62 38 13.6 82.8 -0.0018
C-37 C 23 50 60 40 19.3 80.2 -0.0057
38 C 20 50 70 30 3.7 86.3 0.0024
C-39 A 20 3.5 70 30 33.0 69.9 -0.0091
Embodiment 40: in this pre-example, and two kinds of polymeric amide of fusion using the synthetic route of polymeric amide rather than resembling among the foregoing description 13-24 with appropriate index.Any method well known in the art can be used for producing these direct synthetic polymeric amide.Usually by the melt phase polymerization preparation of diacid-two amine compound, this diacid-two amine compound can prepare or prepare in independent step polymeric amide on the spot.In any method, diacid and diamines are as initial substance.Perhaps, can use the ester-formin of diacid, preferred dimethyl ester.If the use ester, then reaction must be generally 80 to 120 ℃ carrying out under the low temperature relatively, is converted into acid amides up to ester.Then, mixture is heated to polymerization temperature.For this pre-example, institute's synthetic polymeric amide is poly-(an xylylene pimeloyl amine), and it is by diamines m-xylene diamine and diacid pimelic acid synthetic.Then, the copolyesters A in the table 1 of this polymeric amide and 90wt% carries out fusion according to disclosed method among the embodiment 25-39.Predict that the refringence between these copolyesters A and poly-(the xylylene pimeloyl amine) is 0.0034, and predict that it is transparent.The adulterant that prediction obtains has turbidity value that is lower than 10% and the transmissivity that is higher than 75%.
Embodiment 42,47-49 and 56 and comparative example 41,43-46 and 50-55.The single thin film of adulterant and deoxidizing compositions: the adulterant that some MXD6/N6 change amide groupization with discuss among the foregoing description 13-24 with table 5 in the mode that provides prepare.The refractive index value of listing in the table 5 is to measure on the film of the adulterant of these commentaries on classics amide groupization of 15mil in the mode of discussing among the foregoing description 13-24.According to table 6, these of 3wt% or 5wt% change the pre-adulterant of MXD6/N6 of amide groupization or MXD6 and some copolyesters from table 1, and to carry out bag mixed.Then with these pill adulterants 60 ℃ of-70 ℃ of dried overnight, deliver to then in the 1.0 inches single-screw extrusion machines of Killian of the 95rpm under temperature shown in the table 6, form by non-miscible adulterant and be nominally the thick film of 30mil.All films that contain pure MXD6 have and are higher than 10% turbidity value.Wherein the difference of the specific refractory power of the specific refractory power of nylon adulterant and corresponding polyester is that 0.006 to-0.0006 film is transparent (turbidity≤10%).
Uniform MXD6/ nylon 6 adulterants of table 5-
Nylon Form Specific refractory power Tg (℃)
W- Change the nylon 6 pre-adulterants of the MXD6/23wt% of amide groupization 1.5650 78
X- Change the nylon 6 pre-adulterants of the MXD6/30wt% of amide groupization 1.5617 75
Y- Change the nylon 6 pre-adulterants of the MXD6/41wt% of amide groupization 1.5528 70
Z- Change the nylon 6 pre-adulterants of the MXD6/50wt% of amide groupization 1.5472 66
MXD6 MXD6 1.5824 88
For producing deoxidizing compositions, in two kinds of films, add the enriched material that contains new cobalt decanoate.This enriched material is prepared as follows.(it is the form of lozenge, as Cobalt Ten-Cem with reinforced respectively polyester type C and new cobalt decanoate TM22.5% supply derives from OMG Corp.) be fed in the 57mm twin-screw extruder, and in about 235 ℃ cylinder (barrel) setting point fusion fusion.The fused polymkeric substance is so that " the pencil form of diameter is left extrusion machine, and it uses water quenching, and cuts near 0.125 " the pill of length near 0.08.Polyester is 93: 5 to 5 to 1.5 with the condensation of polymeric amide than (calculating by weight), and the cobalt metal concentration in the condenses makes this ratio cobalt of 140 to 150ppm that causes having an appointment in the final adulterant film.The sample that contains cobalt shows the outstanding oxygen capacity of removing.These samples (it is being placed in 1 week on the Ox-Tran permeability testing machine after extruding) have the 0.15cc of being lower than (STP) above in 6 months time under these conditions *The mil/100 inch 2The average apparent perviousness of/sky/atm.
The single thin film result of table 6-30mil
Embodiment Polyester Nylon Melt temperature The % turbidity Total transmission (%) RI (nylon)-RI (polyester) Oxygen-permeable *
C-41 B 3％MXD6 250℃ 22.72 88.1 0.0180
42 B 3％W 250℃ 1.13 90.5 0.0006
C-43 C 250℃ 0.47 90.8 n/a 25.06
C-44 C 3％MXD6 250℃ 35.90 87.8 0.0231
C-45 C 5％MXD6 280℃ 53.57 87.7 0.0231 13.62
C-46 C 5％MXD6+Co 280℃ 34.12 86.2 0.0231 0.20
47 C 3％X 250℃ 1.00 90.7 0.0024
48 C 5％X 280℃ 0.98 90.6 0.0024 20.70
49 C 5％X+Co 280℃ 1.10 90.4 0.0024 0.09
C-50 E 3％MXD6 290℃ 27.12 85.6 0.0277
C-51 E 3％Y 290℃ 2.99 90.8 -0.0019
C-52 F 3％MXD6 250℃ 64.06 87.9 0.0305
C-53 F 3％Z 250℃ 2.28 92.3 -0.0047
C-54 G 280℃ 0.74 90.9 n/a
C-55 G 3％MXD6 280℃ 82.57 81.0 0.0354
56 G 3％Z 280℃ 2.09 90.8 0.0002
*Under 23 ℃ and about relative humidity of 60 to 80%, use air as the upstream test gas measure be placed on the instrument after 15 days apparent perviousness (2 films of each composition and the mean value of 3 perviousness measurements)
Embodiment 59 and 62 and the regrowth of comparative example 57-58 and 60-61-multilayer film: multilayer film are by the polyester C of 2 layers of 15mil is carried out coextrusion the preparation around thick MXD6 of one deck 4mil or the MXD6/30wt%N6 adulterant " X " that changes amide groupization.This is called as " ABA " structure, and wherein " A " layer is outer, and " B " layer is an internal layer.Killian 1 " ectrusion press is in extrude this skin from polyester C under 265 ℃ temperature.0.75 " the Killian ectrusion press is in extruding this internal layer, for MXD6, temperature is 285 ℃, and for MXD6/30wt% nylon 6 adulterants " X ", temperature is 275 ℃.For simulate these multilayer film at single layer structure as the re-using of regrowth, these multilayer film pulverized and do fusion with 50/50 ratio with other polyester C pill.Then, should do adulterant, and " under 240 ℃ temperature, be squeezed into the film of 20mil on the extrusion machine at Killian 1 70 ℃ of dryings.Turbidity value is displayed in Table 7.These co-extrusion films all have and are lower than 2% turbidity value.Yet, be re-ground when these films and during with clean polyester " C " fusion, contain this value in the film of C/MXD6 regrowth fusion and increase to and be higher than 10%.The film that contains " C/X " regrowth keeps transparent.
Multilayer film can center on the thick MXD6 of one deck 5mil by the polyester G with two-layer 15mil in a similar manner or change coextrusion preparation of MXD6/50wt%N6 adulterant " Z " of amide groupization.This is called as " ABA " structure, and wherein " A " layer is outer, and " B " layer is an internal layer.Killian 1 " ectrusion press is in extrude this skin from polyester G under 285 ℃ temperature.0.75 " the Killian ectrusion press is in extruding MXD6 or change the internal layer of MXD6/50wt% nylon 6 adulterants " Z " of amide groupization under 285 ℃ temperature.For simulate these multilayer film in single layer structure as the re-using of regrowth, these multilayer film pulverized and do fusion with 50/50 ratio with other polyester G pill.Then, should do adulterant, and " under 280 ℃ temperature, be squeezed into the film of 20mil on the extrusion machine at Killian 1 100 ℃ of dryings.Turbidity value is displayed in Table 7.These co-extrusion films all have and are lower than 2.5% turbidity value.Yet, when these films are re-ground and during with clean polyester " G " fusion, contain this value in the film of G/MXD6 regrowth adulterant and increase to and be higher than 10%.The film that contains " G/Z " regrowth keeps transparent.Table 7
30mil ABA co-extrusion film (the B layer of 4mil) The 20mil single thin film of producing by the adulterant of 50% " C " or " G " pill and 50% ground co-extrusion film
Embodiment Material Turbidity (%) Total transmittance (%) Turbidity (%) Total transmittance (%) RI (nylon)-RI (polyester)
C-57 C 0.12 91.5 0.09 91.5 n/a
C-58 C/MXD6/C 1.49 91.1 16.44 87.3 0.0231
59 C/X/C 0.62 91.2 0.37 91.5 0.0022
C-60 G 0.74 90.9 0.24 91.1 n/a
C-61 G/MXD6/G 2.15 91.1 87.34 82.5 0.0354
62 G/Z/G 0.74 90.9 1.88 90.6 0.0002
Embodiment 64 and comparative example 63-multilayer film bonding: the ABA film is by the polyester C of 2 layers of 15mil is carried out coextrusion the preparation around thick MXD6 of one deck 4mil or the MXD6/30wt%N6 adulterant " X " that changes amide groupization.The nylon 6 of adulterant that is used for the commentaries on classics amide groupization of this embodiment is Zytel 7301.Killian 1 " the polyester C layer of ectrusion press outside under 265 ℃ temperature, extruding.0.75 " the Killian ectrusion press is in extrude internal layer under the temperature shown in the table 8.The MXD6/30wt%N6 adulterant " X " that changes amide groupization has shown MXD6 excellent bonding to polyester C.And, when the internal layer melt temperature when 280 ℃ are brought up to 285 ℃, obtained to change improved bonding to polyester C of amide group MXD6/30wt%N6 adulterant.MXD6 is bonding can not to be shown any and dependency temperature.
Table 8
Embodiment Material The average stripping strength of " B " layer melt temperature
g/mm
C-63 C/MXD6/C 270℃ 280℃ 285℃ 1.74 1.7 1.88
64 C/X/C 270℃ 280℃ 285℃ 4.33 4.42 7.14

Claims (69)

1. deoxidizing compositions, it comprises:
(A) comprise non-miscible adulterant of following substances:
(i) contain first component of at least a polyester, this polyester contains:
(a) diacid residues, based on all diacid residues, it comprises at least a modified aliphatic dicarboxylic acid residue of 16 carbon atoms at the most that has of about terephthalic acid residue of 70 to about 100mol%, 0 to about 30mol% at least a modified aromatic family's dicarboxylic acid residue with 20 carbon atoms at the most and 0 to about 10mol%; And
(b) diol residue, based on all diol residue, it comprises that about 1 arrives 2,2,4 of about 99mol%, 4-tetramethyl--1,3-cyclobutanediol residue and about 1 arrives the 1,4 cyclohexane dimethanol residue of about 99mol%; And
Second component of even adulterant that (ii) comprises the commentaries on classics amide groupization of at least two kinds of polymeric amide;
Wherein said second component (ii) with the refringence of described first component (i), RI (second component)-RI (first component) is about 0.006 to approximately-0.0006, and the transmittance percentage of described non-miscible adulterant is at least 75%, turbidity is 10% or lower; With
(B) at least a periodic table of elements 3-12 family, the metal that 4-6 is capable of being selected from.
2. deoxidizing compositions according to claim 1, the even adulterant of wherein said commentaries on classics amide groupization are to form by making described at least two kinds of polymeric amide arrive to contact under about 340 ℃ temperature at about 290 ℃.
3. deoxidizing compositions according to claim 2, wherein said contact is undertaken by fusion fusion or extruding.
4. deoxidizing compositions according to claim 1, it comprises based on about 5 described second components that arrive about 1wt% to described first component (i) of about 99wt% and about 95 of described deoxidizing compositions gross weight (ii).
5. deoxidizing compositions according to claim 4, it comprises based on about 50 described second components that arrive about 1wt% to described first component (i) of about 99wt% and about 50 of described deoxidizing compositions gross weight (ii).
6. deoxidizing compositions according to claim 5, it comprises based on about 70 described second components that arrive about 1wt% to described first component (i) of about 99wt% and about 30 of described deoxidizing compositions gross weight (ii).
7. deoxidizing compositions according to claim 1, wherein said second component (ii) with the refringence of described first component (i), RI (second component)-RI (first component) is about 0.005 to approximately-0.0006.
8. deoxidizing compositions according to claim 1, wherein said modified aromatic family dicarboxylic acid is selected from 4,4 '-biphenyl dicarboxylic acid, m-phthalic acid, 1,4-naphthalic acid, 1,5-naphthalic acid, 2,6-naphthalic acid, 2,7-naphthalic acid, 4,4 '-oxybenzene formic acid and trans-4,4 '-the Stilbene dicarboxylic acid; And described modified aliphatic dicarboxylic acid is selected from propanedioic acid, succsinic acid, pentanedioic acid, hexanodioic acid, pimelic acid, suberic acid, nonane diacid and dodecanedioic acid.
9. deoxidizing compositions according to claim 1, wherein said diol residue further comprises based on about 25mol% of all diol residue or at least a modification diol residue still less, described at least a modification glycol is selected from ethylene glycol, 1,2-propylene glycol, 1, ammediol, 1,4-butyleneglycol, 1,5-pentanediol, 1,6-hexylene glycol, terephthalyl alcohol, neopentyl glycol, polyoxyethylene glycol, glycol ether and polytetramethylene glycol.
10. deoxidizing compositions according to claim 1, wherein said polyester further comprises at least a cladodification agent residue that arrives 1mol% based on about 0.01 of all diacid or diol residue, described at least a cladodification agent is selected from trimellitic acid, trimellitic acid 1,2-anhydride and pyromellitic dianhydride, glycerine, Sorbitol Powder, 1,2,6-hexanetriol, tetramethylolmethane, tartrate, citric acid, trimethylolethane and trimesic acid.
11. deoxidizing compositions according to claim 1, wherein said diol residue comprise that about 5 arrive 2,2,4 of about 60mol%, 4-tetramethyl--l, and 3-cyclobutanediol residue and about 40 arrives the 1,4 cyclohexane dimethanol residue of about 95mol%.
12. deoxidizing compositions according to claim 11, wherein said diol residue comprise that about 15 arrive 2,2,4 of about 40mol%, 4-tetramethyl--1, and 3-cyclobutanediol residue and about 60 arrives the 1,4 cyclohexane dimethanol residue of about 85mol%.
13. deoxidizing compositions according to claim 12, wherein said diol residue comprise that about 20 arrive 2,2,4 of about 30mol%, 4-tetramethyl--1, and 3-cyclobutanediol residue and about 70 arrives the l of about 80mol%, 4-cyclohexanedimethanol residue.
14. according to the described deoxidizing compositions of claim l, wherein said diacid residues comprises the terephthalic acid of about 100mol%.
15. deoxidizing compositions according to claim 14, wherein said diol residue comprise that about 5 arrive 2,2,4 of about 60mol%, 4-tetramethyl--1, and 3-cyclobutanediol residue and about 40 arrives the 1,4 cyclohexane dimethanol residue of about 95mol%.
16. according to the described deoxidizing compositions of claim l5, wherein said diol residue comprises that about 15 arrive 2,2,4 of about 40mol%, 4-tetramethyl--1, and 3-cyclobutanediol residue and about 60 arrives the 1,4 cyclohexane dimethanol residue of about 85mol%.
17. deoxidizing compositions according to claim 16, wherein said diol residue comprise that about 20 arrive 2,2,4 of about 30mol%, 4-tetramethyl--1, and 3-cyclobutanediol residue and about 70 arrives the 1,4 cyclohexane dimethanol residue of about 80mol%.
18. deoxidizing compositions according to claim 1, wherein said first component further comprise described polyester and contain the even adulterant of the polycarbonate of dihydroxyphenyl propane residue.
19. deoxidizing compositions according to claim 18, wherein said polyester and described polycarbonate are side chains.
20. a deoxidizing compositions, it comprises:
(A) comprise non-miscible adulterant of following substances:
(i) contain first component of at least a polyester, this polyester contains:
(a) diacid residues, based on all diacid residues, it comprises at least a modified aliphatic dicarboxylic acid residue of 16 carbon atoms at the most that has of about terephthalic acid residue of 70 to about 100mol%, 0 to about 30mol% at least a modified aromatic family's dicarboxylic acid residue with 20 carbon atoms at the most and 0 to about 10mol%; And
(b) diol residue, based on all diol residue, it comprises that about 1 arrives 2,2,4 of about 99mol%, 4-tetramethyl--1,3-cyclobutanediol residue and about 1 arrives the 1,4 cyclohexane dimethanol residue of about 99mol%; And
Second component that (ii) comprises copolyamide;
Wherein said second component (ii) with the refringence of described first component (i), RI (second component)-RI (first component) is about 0.006 to approximately-0.0006, and the transmittance percentage of described non-miscible adulterant is at least 75%, turbidity is 10% or lower; With
(B) at least a periodic table of elements 3-12 family, the metal that 4-6 is capable of being selected from.
21. deoxidizing compositions according to claim 20, wherein said copolyamide comprises the residue of m-xylene diamine, p dimethylamine or its combination; And at least a terephthalic acid, m-phthalic acid, hexanodioic acid, pimelic acid, suberic acid, nonane diacid, sebacic acid, 11 carbon diacid, dodecanedioic acid, hexanolactam, butyrolactam, the amino 11 carbon diacid and 1 of 11-, the residues of monomers of 6-hexanediamine of being selected from.
22. deoxidizing compositions according to claim 21, wherein said copolyamide comprise based on total amount be 100mol% the diamines residue about 15 to about 100mol% m-xylene diamine residue; With based on total amount be 100mol% diacid residues about 15 arrive one or more aliphatics of about 15mol% or alicyclic dicarboxylic acid's residue to about 85mol% hexanodioic acid residue and about 85, wherein this aliphatics or alicyclic dicarboxylic acid are selected from pimelic acid, suberic acid, nonane diacid, sebacic acid, 11 carbon diacid, dodecanedioic acid and 1,4-cyclohexane dicarboxylic acid.
23. deoxidizing compositions according to claim 22, wherein said copolyamide comprise 20mmol/Kg or terminal amine group still less.
24. deoxidizing compositions according to claim 20, wherein said modified aromatic family dicarboxylic acid is selected from 4,4 '-biphenyl dicarboxylic acid, m-phthalic acid, 1,4-naphthalic acid, 1,5-naphthalic acid, 2,6-naphthalic acid, 2,7-naphthalic acid, 4,4 '-oxybenzene formic acid and trans-4,4 '-the Stilbene dicarboxylic acid; And described modified aliphatic dicarboxylic acid is selected from propanedioic acid, succsinic acid, pentanedioic acid, hexanodioic acid, pimelic acid, suberic acid, nonane diacid and dodecanedioic acid.
25. deoxidizing compositions according to claim 20, wherein said diol residue further comprises based on about 25mol% of all diol residue or at least a modification diol residue still less, described modification glycol is selected from ethylene glycol, 1,2-propylene glycol, 1, ammediol, 1,4-butyleneglycol, 1,5-pentanediol, 1,6-hexylene glycol, terephthalyl alcohol, neopentyl glycol, polyoxyethylene glycol, glycol ether and polytetramethylene glycol.
26. deoxidizing compositions according to claim 20, it further comprises at least a cladodification agent residue that arrives 1mol% based on about 0.01 of all diacid or diol residue, described cladodification agent is selected from trimellitic acid, trimellitic acid 1,2-anhydride and pyromellitic dianhydride, glycerine, Sorbitol Powder, 1,2,6-hexanetriol, tetramethylolmethane, tartrate, citric acid, trimethylolethane and trimesic acid.
27. deoxidizing compositions according to claim 20, wherein said diol residue comprise that about 5 arrive 2,2,4 of about 60mol%, 4-tetramethyl--20, and 3-cyclobutanediol residue and about 40 arrives 20 of about 95mol%, 4-cyclohexanedimethanol residue.
28. deoxidizing compositions according to claim 27, wherein said diol residue comprise that about 15 arrive 2,2,4 of about 40mol%, 4-tetramethyl--1, and 3-cyclobutanediol residue and about 60 arrives the 1,4 cyclohexane dimethanol residue of about 85mol%.
29. deoxidizing compositions according to claim 28, wherein said diol residue comprise that about 20 arrive 2,2,4 of about 30mol%, 4-tetramethyl--1, and 3-cyclobutanediol residue and about 70 arrives the 1,4 cyclohexane dimethanol residue of about 80mol%.
30. deoxidizing compositions according to claim 21, wherein said diacid residues comprises the terephthalic acid of about 100mol%.
31. deoxidizing compositions according to claim 30, wherein said diol residue comprise that about 5 arrive 2,2,4 of about 60mol%, 4-tetramethyl--1, and 3-cyclobutanediol residue and about 40 arrives the 1,4 cyclohexane dimethanol residue of about 95mol%.
32. deoxidizing compositions according to claim 31, wherein said diol residue comprise that about 15 arrive 2,2,4 of about 40mol%, 4-tetramethyl--1, and 3-cyclobutanediol residue and about 60 arrives the 1,4 cyclohexane dimethanol residue of about 85mol%.
33. deoxidizing compositions according to claim 32, wherein said diol residue comprise that about 20 arrive 2,2,4 of about 30mol%, 4-tetramethyl--1, and 3-cyclobutanediol residue and about 70 arrives the 1,4 cyclohexane dimethanol residue of about 80mol%.
34. deoxidizing compositions according to claim 20, wherein said first component further comprise described polyester and contain the even adulterant of the polycarbonate of dihydroxyphenyl propane residue.
35. deoxidizing compositions according to claim 34, wherein said polyester and described polycarbonate are side chains.
36. deoxidizing compositions according to claim 1, wherein said second component (ii) comprises a kind of even adulterant, and this even adulterant comprises first polymeric amide that contains aromatic moieties and second polymeric amide that contains aliphatic residue.
37. deoxidizing compositions according to claim 36, wherein said even adulterant comprises first polymeric amide of the residue that contains m-xylene diamine and hexanodioic acid, and described second polymeric amide contains at least one diacid of selecting oneself, pimelic acid, suberic acid, nonane diacid, sebacic acid, 11 carbon diacid, dodecanedioic acid, hexanolactam, butyrolactam, the amino 11 carbon diacid of 11-and the aliphatics of hexanediamine or the residue of alicyclic monomer.
38. according to the described deoxidizing compositions of claim 37, wherein said second polymeric amide comprises that at least one is selected from nylon 4, nylon 6, nylon 9, Ni Long11, nylon 12, nylon 6,6, nylon 5,10, nylon 6,12, the polymeric amide of nylon 6,11, nylon 10,12 and combination thereof.
39. according to the described deoxidizing compositions of claim 38, wherein said second polymeric amide comprises nylon 6, nylon 6,6 or its adulterant.
40. according to the described deoxidizing compositions of claim 38, wherein said even adulterant comprises 20mmol/Kg or terminal amine group still less.
41. according to the described deoxidizing compositions of claim 39, wherein said diol residue comprises that about 5 arrive 2,2,4 of about 60mol%, 4-tetramethyl--1, and 3-cyclobutanediol residue and about 40 arrives the 1,4 cyclohexane dimethanol residue of about 95mol%.
42. according to the described deoxidizing compositions of claim 41, wherein said diol residue comprises that about 15 arrive 2,2,4 of about 40mol%, 4-tetramethyl--1, and 3-cyclobutanediol residue and about 60 arrives the 1,4 cyclohexane dimethanol residue of about 85mol%.
43. according to the described deoxidizing compositions of claim 42, wherein said diol residue comprises that about 20 arrive 2,2,4 of about 30mol%, 4-tetramethyl--1, and 3-cyclobutanediol residue and about 70 arrives the 1,4 cyclohexane dimethanol residue of about 80mol%.
44. according to the described deoxidizing compositions of claim 39, wherein said diacid residues comprises the terephthalic acid of about 100mol%.
45. according to the described deoxidizing compositions of claim 44, wherein said diol residue comprises that about 5 arrive 2,2,4 of about 60mol%, 4-tetramethyl--1, and 3-cyclobutanediol residue and about 40 arrives the 1,4 cyclohexane dimethanol residue of about 95mol%.
46. according to the described deoxidizing compositions of claim 45, wherein said diol residue comprises that about 15 arrive 2,2,4 of about 40mol%, 4-tetramethyl--1, and 3-cyclobutanediol residue and about 60 arrives the 1,4 cyclohexane dimethanol residue of about 85mol%.
47. according to the described deoxidizing compositions of claim 46, wherein said diol residue comprises that about 20 arrive 2,2,4 of about 30mol%, 4-tetramethyl--1, and 3-cyclobutanediol residue and about 70 arrives the 1,4 cyclohexane dimethanol residue of about 80mol%.
48. according to the described deoxidizing compositions of claim 39, wherein said first component further comprises described polyester and contains the even adulterant of the polycarbonate of dihydroxyphenyl propane residue.
49. according to the described deoxidizing compositions of claim 48, wherein said polyester and described polycarbonate are side chains.
50. according to the described deoxidizing compositions of claim 49, wherein said polyester further comprises at least a cladodification agent residue that arrives 1mol% based on about 0.01 of all diacid or diol residue, described cladodification agent is selected from trimellitic acid, trimellitic acid 1,2-anhydride and pyromellitic dianhydride, glycerine, Sorbitol Powder, 1,2,6-hexanetriol, tetramethylolmethane, tartrate, citric acid, trimethylolethane and trimesic acid.
51. according to the described deoxidizing compositions of claim 48, wherein said diol residue comprises that about 5 arrive 2,2,4 of about 60mol%, 4-tetramethyl--1, and 3-cyclobutanediol residue and about 40 arrives the 1,4 cyclohexane dimethanol residue of about 95mol%.
52. according to the described deoxidizing compositions of claim 51, wherein said diol residue comprises that about 15 arrive 2,2,4 of about 40mol%, 4-tetramethyl--1, and 3-cyclobutanediol residue and about 60 arrives the 1,4 cyclohexane dimethanol residue of about 85mol%.
53. according to the described deoxidizing compositions of claim 52, wherein said diol residue comprises that about 20 arrive 2,2,4 of about 30mol%, 4-tetramethyl--1, and 3-cyclobutanediol residue and about 70 arrives the 1,4 cyclohexane dimethanol residue of about 80mol%.
54. according to the described deoxidizing compositions of claim 48, wherein said diacid residues comprises the terephthalic acid of about 100mol%.
55. according to the described deoxidizing compositions of claim 54, wherein said diol residue comprises that about 5 arrive 2,2,4 of about 60mol%, 4-tetramethyl--1, and 3-cyclobutanediol residue and about 40 arrives the 1,4 cyclohexane dimethanol residue of about 95mol%.
56. according to the described deoxidizing compositions of claim 55, wherein said diol residue comprises that about 15 arrive 2,2,4 of about 40mol%, 4-tetramethyl--1, and 3-cyclobutanediol residue and about 60 arrives the 1,4 cyclohexane dimethanol residue of about 85mol%.
57. according to the described deoxidizing compositions of claim 56, wherein said diol residue comprises that about 20 arrive 2,2,4 of about 30mol%, 4-tetramethyl--1, and 3-cyclobutanediol residue and about 70 arrives the 1,4 cyclohexane dimethanol residue of about 80mol%.
58. deoxidizing compositions according to claim 1, wherein said metal is selected from copper, nickel, cobalt, iron, manganese and combination thereof.
59. according to the described deoxidizing compositions of claim 58, based on the gross weight of described composition, said composition contains the 10 described metals to about 500ppm weight of having an appointment.
60. according to the described deoxidizing compositions of claim 59, it comprises about 50 to about 300ppm described metal.
61. a molded article, it comprises any one the described deoxidizing compositions in the claim 1,12,16,18,20,32,38,46 or 52.
62. according to the described molded article of claim 61, it forms by extruding, calendering, thermoforming, blowing, extrusion blow, injection moulding, compression moulding, curtain coating, drawing-off, tentering or blowing.
63. according to the described molded article of claim 62, it is sheet material, film, pipeline, preformed member or bottle.
64. according to the described molded article of claim 63, it is a bottle.
65. according to the described molded article of claim 63, it has 2 to 7 layers.
66. according to any one the described deoxidizing compositions in the claim 1,12,16,18,20,32,38,46 or 52, the logarithmic viscosity number of wherein said polyester is 0.5 to 0.75dL/g.
67. according to the described deoxidizing compositions of claim 66, wherein said logarithmic viscosity number is 0.6 to 0.72dL/g.
68. according to any one the described deoxidizing compositions in the claim 1,12,16,18,20,32,38,46 or 52, the second-order transition temperature of wherein said polyester is about 110 ℃ to about 150 ℃.
69. according to the described deoxidizing compositions of claim 68, wherein said second-order transition temperature is about 120 ℃ to 135 ℃.
CNA2006800205700A 2005-06-17 2006-03-30 Transparent deoxidizing compositions comprising polymer containing a cyclobutanediol and articles prepared therefrom Pending CN101193979A (en)

Applications Claiming Priority (15)

Application Number Priority Date Filing Date Title
US69156705P 2005-06-17 2005-06-17
US60/691,567 2005-06-17
US60/731,389 2005-10-28
US60/731,454 2005-10-28
US60/738,869 2005-11-22
US60/739,058 2005-11-22
US60/750,692 2005-12-15
US60/750,547 2005-12-15
US60/750,682 2005-12-15
US60/750,693 2005-12-15
US11/363,417 2006-02-27
US11/363,481 2006-02-27
US11/363,418 2006-02-27
US11/363,374 2006-02-27
US11/363,375 2006-02-27

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CN2006800206544A Active CN101203543B (en) 2005-06-17 2006-03-30 Polyester compositions which comprise cyclobutanediol having certain cis/trans ratios
CNA2006800205452A Pending CN101193938A (en) 2005-06-17 2006-03-30 Polyester compositions containing high amounts of cyclobutanediol and articles made therefrom
CNA200680020572XA Pending CN101193721A (en) 2005-06-17 2006-03-30 Preparation of transparent, shaped articles containing polyesters comprising a cyclobutanediol
CNA2006800207458A Pending CN101193946A (en) 2005-06-17 2006-03-30 Film(s) and/or sheet(s) comprising polyester compositions which comprise cyclobutanediol
CNA2006800205518A Pending CN101193941A (en) 2005-06-17 2006-03-30 Glass laminates comprising polyester compositions formed from 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1,4-cyclohexanedimethanol
CNA2006800205838A Pending CN101193945A (en) 2005-06-17 2006-03-30 LCD films or sheets comprising polyester compositions formed from 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1,4-cyclohexanedimethanol
CNA2006800206489A Pending CN101213239A (en) 2005-06-17 2006-03-30 Thermoformed sheet(s) comprising polyester compositions which comprise cyclobutanediol
CNA2006800205397A Pending CN101193934A (en) 2005-06-17 2006-03-30 Container comprising polyester compositions which comprise cyclobutanediol
CNA2006800205255A Pending CN101203540A (en) 2005-06-17 2006-03-30 Eye device comprising polyester compositions formed from 2,2,4,4-tetramethyl-1,3- cyclobutanediol and 1,4-cyclohexanedimethanol
CN2006800205378A Active CN101193933B (en) 2005-06-17 2006-03-30 Film(s) and/or sheet(s) comprising polyester compositions which comprise cyclobutanediol and have a certain combination of inherent viscosity and moderate glass transition temperature
CNA2006800205236A Pending CN101193977A (en) 2005-06-17 2006-03-30 Intravenous components comprising polyester compositions formed from 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1,4-cyclohexanedimethanol
CN2006800205607A Active CN101193942B (en) 2005-06-17 2006-03-30 Film(s) and/or sheet(s) comprising polyester compositions which comprise cyclobutanediol and articles made therefrom
CNA2006800205448A Pending CN101203542A (en) 2005-06-17 2006-03-30 Optical mediam comprising polyester compositions formed from 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1,4-cyclohexanedimethanol
CN2006800205058A Active CN101203541B (en) 2005-06-17 2006-03-30 Polyester compositions which comprise cyclobutanediol and have a certain combination of inherent viscosity and high glass transition temperature and product made therefrom
CN2006800205626A Active CN101193943B (en) 2005-06-17 2006-03-30 Film(s) and/or sheet(s) comprising polyester compositions which comprise cyclobutanediol and have a certain combination of inherent viscosity and moderate glass transition temperature
CN2006800207443A Active CN101203544B (en) 2005-06-17 2006-03-30 Thermoplastic articles comprising cyclobutanediol having a decorative material embedded therein
CN200680020542.9A Active CN101193936B (en) 2005-06-17 2006-03-30 Polyester compositions comprising a cyclobutanediol and articles prepared therefrom
CN200680020540XA Active CN101193935B (en) 2005-06-17 2006-03-30 Feeder comprising polyester compositions which comprise cyclobutanediol
CNA2006800205823A Pending CN101193733A (en) 2005-06-17 2006-03-30 Transparent, multilayered article containing polyesters comprising a cyclobutanediol and its preparing method
CNA2006800205490A Pending CN101193940A (en) 2005-06-17 2006-03-30 Outdoor signs comprising polyester compositions formed from 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1,4-cyclohexanedimethanol
CNA2006800205895A Pending CN101193980A (en) 2005-06-17 2006-03-30 Methods for preparing transparent formed articles comprising polymer containing a cyclobutanediol
CNA2006800205467A Pending CN101193939A (en) 2005-06-17 2006-03-30 Polyester compositions containing cyclobutanediol and articles made therefrom
CNA2006800205700A Pending CN101193979A (en) 2005-06-17 2006-03-30 Transparent deoxidizing compositions comprising polymer containing a cyclobutanediol and articles prepared therefrom
CN2006800205433A Active CN101193937B (en) 2005-06-17 2006-03-30 Bottle comprising polyester compositions which comprise cyclobutanediol
CNA2006800205594A Pending CN101193978A (en) 2005-06-17 2006-03-30 Transparent polymer blends containing polyesters comprising a cyclobutanediol and articles prepared therefrom
CNA2006800205819A Pending CN101193944A (en) 2005-06-17 2006-03-30 Anti-protein articles comprising cyclobutanediol
CN2006800205611A Active CN101193932B (en) 2005-06-17 2006-03-30 Polyester compositions which comprise cyclobutanediol and have a certain combination of inherent viscosity and moderate glass transition temperature and articles made therefrom
CNA2006800205804A Pending CN101193668A (en) 2005-06-17 2006-03-30 Dialysis filter shell comprising polyester compositions formed from 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1,4-cyclohexanedimethanol

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CN2006800206544A Active CN101203543B (en) 2005-06-17 2006-03-30 Polyester compositions which comprise cyclobutanediol having certain cis/trans ratios
CNA2006800205452A Pending CN101193938A (en) 2005-06-17 2006-03-30 Polyester compositions containing high amounts of cyclobutanediol and articles made therefrom
CNA200680020572XA Pending CN101193721A (en) 2005-06-17 2006-03-30 Preparation of transparent, shaped articles containing polyesters comprising a cyclobutanediol
CNA2006800207458A Pending CN101193946A (en) 2005-06-17 2006-03-30 Film(s) and/or sheet(s) comprising polyester compositions which comprise cyclobutanediol
CNA2006800205518A Pending CN101193941A (en) 2005-06-17 2006-03-30 Glass laminates comprising polyester compositions formed from 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1,4-cyclohexanedimethanol
CNA2006800205838A Pending CN101193945A (en) 2005-06-17 2006-03-30 LCD films or sheets comprising polyester compositions formed from 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1,4-cyclohexanedimethanol
CNA2006800206489A Pending CN101213239A (en) 2005-06-17 2006-03-30 Thermoformed sheet(s) comprising polyester compositions which comprise cyclobutanediol
CNA2006800205397A Pending CN101193934A (en) 2005-06-17 2006-03-30 Container comprising polyester compositions which comprise cyclobutanediol
CNA2006800205255A Pending CN101203540A (en) 2005-06-17 2006-03-30 Eye device comprising polyester compositions formed from 2,2,4,4-tetramethyl-1,3- cyclobutanediol and 1,4-cyclohexanedimethanol
CN2006800205378A Active CN101193933B (en) 2005-06-17 2006-03-30 Film(s) and/or sheet(s) comprising polyester compositions which comprise cyclobutanediol and have a certain combination of inherent viscosity and moderate glass transition temperature
CNA2006800205236A Pending CN101193977A (en) 2005-06-17 2006-03-30 Intravenous components comprising polyester compositions formed from 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1,4-cyclohexanedimethanol
CN2006800205607A Active CN101193942B (en) 2005-06-17 2006-03-30 Film(s) and/or sheet(s) comprising polyester compositions which comprise cyclobutanediol and articles made therefrom
CNA2006800205448A Pending CN101203542A (en) 2005-06-17 2006-03-30 Optical mediam comprising polyester compositions formed from 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1,4-cyclohexanedimethanol
CN2006800205058A Active CN101203541B (en) 2005-06-17 2006-03-30 Polyester compositions which comprise cyclobutanediol and have a certain combination of inherent viscosity and high glass transition temperature and product made therefrom
CN2006800205626A Active CN101193943B (en) 2005-06-17 2006-03-30 Film(s) and/or sheet(s) comprising polyester compositions which comprise cyclobutanediol and have a certain combination of inherent viscosity and moderate glass transition temperature
CN2006800207443A Active CN101203544B (en) 2005-06-17 2006-03-30 Thermoplastic articles comprising cyclobutanediol having a decorative material embedded therein
CN200680020542.9A Active CN101193936B (en) 2005-06-17 2006-03-30 Polyester compositions comprising a cyclobutanediol and articles prepared therefrom
CN200680020540XA Active CN101193935B (en) 2005-06-17 2006-03-30 Feeder comprising polyester compositions which comprise cyclobutanediol
CNA2006800205823A Pending CN101193733A (en) 2005-06-17 2006-03-30 Transparent, multilayered article containing polyesters comprising a cyclobutanediol and its preparing method
CNA2006800205490A Pending CN101193940A (en) 2005-06-17 2006-03-30 Outdoor signs comprising polyester compositions formed from 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1,4-cyclohexanedimethanol
CNA2006800205895A Pending CN101193980A (en) 2005-06-17 2006-03-30 Methods for preparing transparent formed articles comprising polymer containing a cyclobutanediol
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CNA2006800205819A Pending CN101193944A (en) 2005-06-17 2006-03-30 Anti-protein articles comprising cyclobutanediol
CN2006800205611A Active CN101193932B (en) 2005-06-17 2006-03-30 Polyester compositions which comprise cyclobutanediol and have a certain combination of inherent viscosity and moderate glass transition temperature and articles made therefrom
CNA2006800205804A Pending CN101193668A (en) 2005-06-17 2006-03-30 Dialysis filter shell comprising polyester compositions formed from 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1,4-cyclohexanedimethanol

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CN101193935B (en) 2013-01-02
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CN101203540A (en) 2008-06-18
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