CN101410455A - Molding compositions containing modified polybutylene terephthalate (PBT) random copolymers derived from polyetheylene terephthalate (PET) - Google Patents

Molding compositions containing modified polybutylene terephthalate (PBT) random copolymers derived from polyetheylene terephthalate (PET) Download PDF

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CN101410455A
CN101410455A CNA2007800112560A CN200780011256A CN101410455A CN 101410455 A CN101410455 A CN 101410455A CN A2007800112560 A CNA2007800112560 A CN A2007800112560A CN 200780011256 A CN200780011256 A CN 200780011256A CN 101410455 A CN101410455 A CN 101410455A
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polyethylene terephthalate
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derived
group
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克里斯滕·科霍恩
谢利·V·加萨韦
加尼什·坎南
肯尼思·F·米勒
远田加代子
达瓦尔·沙
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SABIC Global Technologies BV
General Electric Co
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SABIC Innovative Plastics IP BV
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    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02WCLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
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Abstract

A molding composition comprises: (a) from 40 to 99.99 wt% of a modified polybutylene terephthalate random copolymer that (1) is derived from polyethylene terephthalate component selected from the group consisting of polyethylene terephthalate and polyethylene terephthalate copolymers and (2) has at least one residue derived from the polyethylene terephthalate component, and (b) from 0.01 to 20 wt. % of a carboxy reactive component, wherein the modified polybutylene terephthalate random copolymer, the carboxy reactive component, and optionally at least one additive, are present in a total amount of 100 w t%.

Description

Contain moulding compound derived from polybutylene terephthalate (PBT) random copolymers of the modification of polyethylene terephthalate (PET)
The cross reference of related application
The application requires the right of priority of U.S. Provisional Patent Application sequence number of submitting on January 27th, 2,006 60/763109 and the U.S. Provisional Patent Application sequence number of submitting on July 26th, 2,006 60/820465, incorporates the full content of described patent application into the application by reference.
Background technology
Polyethylene terephthalate (being also referred to as " PET ") is the polyester of terephthalic acid and ethylene glycol, can be by the polycondensation of dimethyl terephthalate (DMT) and ethylene glycol, and the polycondensation of terephthalic acid and ethylene glycol or oxyethane and obtaining.PET exists with amorphous (transparent) and hypocrystalline (opaque and white) thermoplastic material.Generally speaking, it has useful chemical resistance to mineral oil, solvent and acid, but not to the chemical resistance of alkali.Hypocrystalline PET has good intensity, ductility, rigidity and hardness.Amorphous PET has better ductility, but rigidity and hardness are relatively poor.PET is used to prepare Sofe drink bottle and other family expenses and consuming product.Regrettably, although carried out the effort of reclaiming, the whole world still has tens pounds PET to be introduced in the refuse landfill every year.Other PET that utilizes is not again burned.The PET of landfill disposal produces huge waste.Burn PET and wasted a large amount of resources that originally can be effectively utilized more.
Thermoplastic composition based on polybutylene terephthalate (being also referred to as " PBT ") and epoxide is used for various application.Though traditional PBT-epoxy molding composition all is that useful, traditional PBT-epoxy molding composition can not be made by the PBT that reclaims the source usually for many human consumers, this is because lack PBT.Different with PBT, the preparation amount of PET is significantly bigger, and part reclaims from human consumer's waste product.If PET (depleted) material can be changed into PBT and changes into useful moulding compound, so just can there be valuable mode, satisfies the needs to the waste PET that use is underused in the PBT thermoplastic composition effectively of failing to satisfy.
Summary of the invention
The present invention relates to moulding compound, it comprises:
(a) the polybutylene terephthalate random copolymers of the modification of 40~99.99wt%, its (1) is derived from the polyethylene terephthalate component that is selected from polyethylene terephthalate and pet copolymer, and (2) have at least a derived from described polyethylene terephthalate component residue and
(b) the carboxyl-reactive component of 0.01~20wt%;
(c) impact modifier of 0~25wt%;
(d) ultra-violet stabilizer of 0~1wt%;
(e) flame retardance element of 0~30wt%; With
(f) releasing agent of 0~1wt%,
The total amount that the polybutylene terephthalate random copolymers of wherein said modification, carboxyl-reactive component, ultra-violet stabilizer, flame retardance element, releasing agent and optional at least a additive exist is 100wt%.
In another embodiment, the present invention relates to moulding compound, it comprises:
(a) the polybutylene terephthalate random copolymers of the modification of 70~99.99wt%, its (1) is derived from the polyethylene terephthalate component that is selected from polyethylene terephthalate and pet copolymer, and (2) have at least a derived from described polyethylene terephthalate component residue and
(b) the carboxyl-reactive component of 0.01~20wt%;
(c) impact modifier of 0~25wt%;
(d) ultra-violet stabilizer of 0~1wt%;
(e) flame retardance element of 0~30wt%; With
(f) releasing agent of 0~1wt%,
The total amount that the polybutylene terephthalate random copolymers of wherein said modification, carboxyl-reactive component, ultra-violet stabilizer, flame retardance element, releasing agent and optional at least a additive exist is 100wt%.
In another embodiment, the present invention relates to moulding compound, it comprises:
(a) first polyester components, its limiting viscosity is 0.5~1.0dL/g, and comprise: the polybutylene terephthalate random copolymers of the modification of 20~49.9wt%, described random copolymers (1) is derived from the polyethylene terephthalate component that is selected from polyethylene terephthalate and pet copolymer, and (2) have at least a derived from described polyethylene terephthalate component residue and
(b) second polyester components, its limiting viscosity is 1.1~1.4dL/g, and comprise: the polybutylene terephthalate random copolymers of the modification of 20~49.9wt%, described random copolymers (1) is derived from the polyethylene terephthalate component that is selected from polyethylene terephthalate and pet copolymer, and (2) have at least a derived from described polyethylene terephthalate component residue and
(c) the carboxyl-reactive component of 0.01~20wt%;
Wherein said first polyester components, the total amount that second polyester components and optional at least a additive exist is 100wt%.
In another embodiment, the present invention relates to composition, it comprises:
(a) first polyester components, its limiting viscosity is 0.5~1.0dL/g, and comprise: the polybutylene terephthalate random copolymers of the modification of 20~49.9wt%, described random copolymers (1) is derived from the polyethylene terephthalate component that is selected from polyethylene terephthalate and pet copolymer, and (2) have at least a derived from described polyethylene terephthalate component residue and
(b) second polyester components, its limiting viscosity is 1.1~1.4dL/g, and comprise: the polybutylene terephthalate random copolymers of the modification of 20~49.9wt%, described random copolymers (1) is derived from the polyethylene terephthalate component that is selected from polyethylene terephthalate and pet copolymer, and (2) have at least a derived from described polyethylene terephthalate component residue and
(c) the carboxyl-reactive component of 0.01~20wt%;
(d) the carboxyl-reactive component of 0.01~20wt%;
(e) impact modifier of 0~25wt%;
(f) ultra-violet stabilizer of 0~1wt%;
(g) flame retardance element of 0~30wt%; With
(h) releasing agent of 0~1wt%,
The total amount that wherein said first polyester components, second polyester components, carboxyl-reactive component, impact modifier, ultra-violet stabilizer, flame retardance element, releasing agent and optional at least a additive exist is 100wt%;
Wherein said composition is compared with the composition of making based on monomeric polybutylene terephthalate homopolymer, melt volume speed height at least 10%, described melt volume speed record with 240 seconds the residence time and 2.1mm aperture with 5kgf at 250 ℃ according to the ISO1133 method on pellet;
Wherein said composition is greater than 180 ℃ in the heat-drawn wire of 0.455MPa; With
The monomer total content that is selected from ethylene glycol, m-phthalic acid group and diethylene glycol group of wherein said composition is for greater than 0 and be less than or equal to 17 normal residues, described residue is selected from m-phthalic acid group, ethylene glycol group and diethylene glycol group, and combination, based on the total amount of 100 normal two pure and mild 100 normal diacid groups in the polybutylene terephthalate random copolymers of modification.
In another embodiment, the present invention relates to form method for compositions, it comprises the component melts blend with any composition of the present invention.
In another embodiment, the present invention relates to by the method for preparation of compositions goods of the present invention with by the goods of preparation of compositions of the present invention.
Embodiment
The present invention is based on such discovery, can prepare moulding compound now, described moulding compound contain or based on derived from the modification of refuse poly-(ethylene glycol terephthalate)-the PBT component.Different with the conventional composition that uses " pure " PBT (derived from monomeric PBT), be used for moulding compound described modification-the PBT component also contains ethylene glycol and m-phthalic acid group (be not present in " pure " based on the component among the monomeric PBT).Although on the utilization structure with known moulding compound in the different material of PBT that uses, the performance that moulding compound of the present invention demonstrates is with equally matched with the moulding compound of making of pure PBT.
Different among the embodiment with operation, perhaps unless otherwise noted, mention that all numerals of amount of composition, reaction conditions etc. or statement all are construed as by term " about " in all cases to modify.Various numerical ranges are disclosed in the present patent application.Because these scopes are successive, so they are included in each value between minimum and the maximum value.Unless spell out in addition, each numerical range among the application all is proximate.
What unless otherwise noted, all ASTM test and data all came from 2003 editions ASTM standard rolls up (Annual Book) in year.
All molecular weight all are meant the number-average molecular weight of using polystyrene standards to obtain among the application.Ins and outs comprise following: (i) equipment: Waters 2695 separation modules (separation module); (ii) detector: the Waters 2487 Dual Absorbance UltravioletDetector and Water 410 refractometers (refractomer) of 273 and 295 nanometers; (iii) moving phase: 5%HFIP 95% chloroform; (iv) GPC post: Polymer Labs PL HFIPgel 250x4.6mm, (V) flow rate: 0.3ml/min; (vi) volume injected 10 μ l; (vii) polystyrene standards: Polymer Lab ' s Easical PS-1,580-7,500,000Da.
For the reason that clearly illustrates, term terephthalic acid group, m-phthalic acid group, butyleneglycol group, ethylene glycol group have following implication in formula.Term " terephthalic acid group " (R ') in composition, be meant remove terephthalic acid-carboxyl after remaining divalence 1, the 4-phenyl (1,4-(C 6H 4)-).Term " m-phthalic acid group " (R ") be meant remove m-phthalic acid-carboxyl after remaining divalence 1, the 3-phenyl ((1,3-C 6H 4)-)." butyleneglycol group " (D) is meant remaining divalence butylidene ((C after the hydroxyl of removing butyleneglycol 4H 8)-).Term " ethylene glycol group " (D ') is meant remaining divalence ethylidene ((C after the hydroxyl of removing ethylene glycol 2H 4)-).About use term " m-phthalic acid group ", " the ethylene glycol group " and " diethylene glycol group " of (for example representing the wt% of this group in composition) in other context, term " m-phthalic acid group " is meant formula (O (CO) C 6H 4(CO)-) group, term " terephthalic acid group " is meant formula (O (CO) C 6H 4(CO)-) group, term " diethylene glycol group " is meant formula (O (C 2H 4) O (C 2H 4The group of)-), term " butyleneglycol group " is meant formula (O (C 4H 8The group of)-), and term " ethylene glycol group " is meant formula (O (C 2H 4The group of)-).
Embodiments of the present invention relate to moulding compound, and it comprises:
(a) the polybutylene terephthalate random copolymers of the modification of 40~99.99wt%, described random copolymers (1) is derived from the polyethylene terephthalate component that is selected from polyethylene terephthalate and pet copolymer, and (2) have at least a derived from described polyethylene terephthalate component residue and
(b) the carboxyl-reactive component of 0.01~20wt%;
(c) impact modifier of 0~25wt%;
(d) ultra-violet stabilizer of 0~1wt%;
(e) flame retardance element of 0~30wt%; With
(f) releasing agent of 0~1wt%,
The total amount that the polybutylene terephthalate random copolymers of wherein said modification, carboxyl-reactive component, ultra-violet stabilizer, flame retardance element, releasing agent and optional at least a additive exist is 100wt%.
Derived from the polyethylene terephthalate component that is selected from polyethylene terephthalate and pet copolymer, and (2) have at least a residue derived from described polyethylene terephthalate component derived from the polybutylene terephthalate component (the PBT component of PET-deutero-modification) (1) of the modification of ethylene glycol terephthalate.In one embodiment, the polybutylene terephthalate component of described modification also can be derived from biomass-deutero-1,4-butyleneglycol, such as grain deutero-1,4-butyleneglycol or derived from 1 of cellulosic material, 4-butyleneglycol.
The residue derived from the polyethylene terephthalate component that exists in the polybutylene terephthalate component of modification can be selected from ethylene glycol group, diethylene glycol group, the m-phthalic acid group, antimony containing compounds, germanium-containing compound, titanium-containing compound, cobalt compound, sn-containing compound, aluminium, aluminium salt, 1,3-cyclohexanedimethanol isomer, 1,4-cyclohexanedimethanol isomer, 1, the cis-isomeride of 3-cyclohexanedimethanol, 1, the cis-isomeride of 4-cyclohexanedimethanol, 1 of cyclohexanedimethanol, the 3-trans-isomer(ide), 1,1 of 4-cyclohexanedimethanol, the 4-trans-isomer(ide), an alkali metal salt, alkaline earth salt, calcium for example, magnesium, sodium and sylvite, P contained compound and negatively charged ion, sulfocompound and negatively charged ion, naphthalene dicarboxylic acids, 1, ammediol group, and combination.
According to factor for example polyethylene terephthalate and pet copolymer, described residue can comprise various combinations.For example in one embodiment, residue comprises the mixture of ethylene glycol and glycol ether.In another embodiment, residue comprises the mixture of ethylene glycol, glycol ether and m-phthalic acid.In another embodiment, residue derived from polyethylene terephthalate also comprises 1, the cis-isomeride of 3-cyclohexanedimethanol, 1, the cis-isomeride of 4-cyclohexanedimethanol, 1, the trans-isomer(ide) of 3-cyclohexanedimethanol, 1, the trans-isomer(ide) of 4-cyclohexanedimethanol, and combination.In another embodiment, residue comprises 1, the cis-isomeride of 3-cyclohexanedimethanol, the cis-isomeride of 1,4 cyclohexane dimethanol, 1, the trans-isomer(ide) of 3-cyclohexanedimethanol, the trans-isomer(ide) of 1,4 cyclohexane dimethanol, and combination.In another embodiment, residue can be the cis-isomeride of ethylene glycol, glycol ether, m-phthalic acid group, cyclohexanedimethanol, the trans-isomer(ide) of cyclohexanedimethanol and the mixture of combination thereof.In one embodiment, the mixture that comprises ethylene glycol, glycol ether and cobalt compound derived from the residue of polyethylene terephthalate.The mixture of this cobalt compound also can contain the m-phthalic acid group.
For example, in one embodiment, by the polybutylene terephthalate component derived from the modification of polyethylene terephthalate of method of the present invention preparation (the PBT component of PET-deutero-modification, or contain polybutylene terephthalate multipolymer derived from the modification of the residue of polyethylene terephthalate) is to contain the random copolymers that is selected from following group:
Figure A20078001125600131
Wherein R ' be the terephthalic acid group (1,4-(C 6H 4)-group),
R " be the m-phthalic acid group (1,3-(C 6H 4)-),
D is butyleneglycol group ((C 4H 8)-),
D ' is ethylene glycol group ((C 2H 4)-).
The polybutylene terephthalate multipolymer that contains derived from the modification of the residue of polyethylene terephthalate also can contain diethylene glycol group.
Ethylene glycol group, diethylene glycol group and the amount of m-phthalic acid group in the main polymer chain of the PBT of modification component can change.The PBT component of PET-deutero-modification contains the m-phthalic acid group usually, and its amount is 0.1mol% at least, and can be 0 or 0.1~10mol% (0 or 0.07~7wt%).The PBT component of PET-deutero-modification contains ethylene glycol usually, and its amount is 0.1mol% at least, and its amount can be 0.1~10mol% (0.02~2wt%).In one embodiment, the ethylene glycol content of the PBT component of PET-deutero-modification is greater than 0.85wt%.The PBT component of modification also can contain glycol ether, and its amount is 0.1~10mol% (0.04~4wt%).The amount of butyleneglycol group is generally 98mol%, and can be changed to 99.8mol% from 95mol% in some embodiments.The amount of terephthalic acid group is generally about 98mol%, and can be changed to 99.9mol% from 90mol% in some embodiments.
Unless otherwise noted, all molar weights of m-phthalic acid group and/or terephthalic acid group all are based on the total mole number of diacid/diester in the composition.Unless otherwise noted, all molar weights of butyleneglycol, ethylene glycol and diethylene glycol group all are based on the total mole number of glycol in the composition.Above-mentioned weight percentage measurement is based on the mode that defines terephthalic acid group, m-phthalic acid group, ethylene glycol group and diethylene glycol group in this application.
The total amount of the material of polyethylene terephthalate component residue in the polybutylene terephthalate random copolymers of modification can change.For example, the amount of mixture can be 1.8~2.5wt%, perhaps 0.5~2wt%, perhaps 1~4wt%.Ethylene glycol, glycol ether and cyclohexanedimethanol group can be separately or in the mode of combination, exist with the amount of 0.1~10mol%, based on the glycol of 100mol% moulding compound.The amount that the m-phthalic acid group exists can be 0.1~10mol%, based on the 100mol% diacid/diester in the moulding compound.
Have been found that the melt temperature Tm that makes the polybutylene terephthalate multipolymer when expectation during at least 200 ℃, the total amount of glycol ether, ethylene glycol and m-phthalic acid group should be in certain scope.Equally, in one embodiment, glycol ether, ethylene glycol and the m-phthalic acid group total amount in the polybutylene terephthalate component of modification is greater than 0 and is less than or equal to 23 equivalents, based on the total amount of 100 equivalents, two pure and mild 100 equivalent diacid groups in the polybutylene terephthalate random copolymers of modification.In another suitable embodiment, the total amount of m-phthalic acid group, ethylene glycol group and diethylene glycol group is 3 to being less than or equal to 23 equivalents, based on the total amount of 100 equivalents, two pure and mild 100 equivalent diacid groups in the polybutylene terephthalate random copolymers of modification.In another suitable embodiment, the total amount of m-phthalic acid group, ethylene glycol group and diethylene glycol group is 3 to being less than or equal to 10 equivalents, based on the total amount of 100 equivalents, two pure and mild 100 equivalent diacid groups in the polybutylene terephthalate random copolymers of modification.In another suitable embodiment, the total amount of m-phthalic acid group, ethylene glycol group and diethylene glycol group is 10 to being less than or equal to 23 equivalents, based on the total amount of 100 equivalents, two pure and mild 100 equivalent diacid groups in the polybutylene terephthalate random copolymers of modification.In one embodiment, can in technological process, add glycol ether, ethylene glycol and/or m-phthalic acid.
According to application and user's needs, the total amount of ethylene glycol group, m-phthalic acid group and diethylene glycol group can change.In one embodiment, the amount of the total monomer content that is selected from ethylene glycol, m-phthalic acid group and diethylene glycol group of composition can be greater than 0 and is less than or equal to 17 equivalents, based on the total amount of 100 equivalents, two pure and mild 100 equivalent diacid groups in the polybutylene terephthalate random copolymers of modification.Advantageously, this composition can keep useful properties, for example greater than 180 ℃ heat-drawn wire.
Have been found that total amount derived from the inorganic residue of polyethylene terephthalate can be greater than 0ppm and 1000ppm at the most.The example of this inorganic residue is optional from antimony containing compounds, germanium-containing compound, titanium-containing compound, cobalt compound, sn-containing compound, aluminium, aluminium salt, alkaline earth salt, an alkali metal salt, comprise calcium salt, magnesium salts, sodium salt and sylvite, P contained compound and negatively charged ion, sulfocompound and negatively charged ion, and combination.In another embodiment, the amount of inorganic residue can be 250~1000ppm.In another embodiment, the amount of inorganic residue can be 500~1000ppm.
By PET component of polybutylene terephthalate random copolymers of its preparation modification can be can be used according to the invention any form.Usually, the PET component comprises recirculation (waste material) PET of thin slice, powder/fragment, film or pellet form.Before using, process PET usually to remove for example paper of impurity, tackiness agent, polyolefine be polypropylene, polyvinyl chloride (PVC), nylon, poly(lactic acid) and other pollutent for example.Equally, the PET component can comprise such PET, and it is not the waste of thin slice, fragment or pellet form.Equally, but high yield and (productively and effectively) use efficiently now can be placed in the PET in the refuse landfill usually.In one embodiment, the PET component also can comprise other polyester.The PET component also can comprise polyester copolymer.The example of this material comprises polyalkylene terephthalates, it is optional from polyethylene terephthalate, the poly terephthalic acid cyclohexyl, terephthalate and the copolyesters that contains the comonomer of cyclohexyl dimethanol and ethylene glycol, terephthalic acid and the copolyesters that contains the comonomer of cyclohexyl dimethanol and ethylene glycol, polybutylene terephthalate, poly terephthalic acid benzene dimethyl ester, poly terephthalic acid straight-chain paraffin diol ester (polydianolterephthalates), polybutylene terephthalate, poly terephthalic acid 1, the ammediol ester, polyester naphthalene two acid esters (polyester naphthalate), and combination.
Polybutylene terephthalate random copolymers derived from the modification of polyethylene terephthalate component can be by any method derived from the polyethylene terephthalate component, described any method comprises the polyethylene terephthalate component and 1 that makes the depolymerization of polyethylene terephthalate component and make depolymerization, and the 4-butyleneglycol aggregates into the polybutylene terephthalate random copolymers of modification.For example, polybutylene terephthalate component derived from the modification of polyethylene terephthalate component can be by such method preparation, described method is included in 180 ℃~230 ℃ temperature, under agitation, at least equaling under the 1 atmospheric pressure, in the presence of catalyst component, at elevated temperatures, under inert atmosphere, use 1,4-butyleneglycol component makes the polyethylene terephthalate component depolymerization that is selected from polyethylene terephthalate and pet copolymer, thereby generation molten mixture, it contains and is selected from following component: the oligopolymer that contains the ethylene glycol terephthalate part, the oligopolymer that contains the ethylene isophthalate part, the oligopolymer that contains terephthalic acid glycol ether ester moiety, the oligopolymer that contains m-phthalic acid glycol ether ester moiety, the oligopolymer that contains mutual-phenenyl two acid bromide two alcohol ester's part, the oligopolymer that contains m-phthalic acid butanediol ester part, the oligopolymer part that contains the covalent bonding of at least two kinds of aforementioned parts, 1, the 4-butyleneglycol, ethylene glycol, and combination; With under the condition of the polybutylene terephthalate random copolymers that is enough to form modification, be lower than this molten mixture of stirring under 1 normal atmosphere, and the temperature of molten mixture is increased to high temperature, described random copolymers contains at least a residue derived from described polyethylene terephthalate component.
Under agitation with polyester portion and 1, the 4-butyleneglycol merges in the liquid phase, can be with 1, and 4-butyleneglycol continuous backflow is returned in the reactor in step (a) process.Can remove THF and the water that forms in this stage by distillation or partial condensation.
Usually with polyethylene terephthalate component and 1,4-butyleneglycol component under atmospheric pressure merges.But, in another embodiment of the present invention, can use to be higher than atmospheric pressure.For example, in one embodiment, polyethylene terephthalate component and 1, the pressure that the 4-butyleneglycol is stood is 2 normal atmosphere, and is perhaps higher.For higher pressure, can be with reaction mixture in the temperature depolymerization that is higher than 230 ℃.
Make polyethylene terephthalate component and 1,4-butyleneglycol component merges and the temperature of reaction is enough to impel the polyethylene terephthalate component to depolymerize to the mixture of following material: the oligopolymer that contains the ethylene glycol terephthalate part, the oligopolymer that contains the ethylene isophthalate part, the oligopolymer that contains terephthalic acid glycol ether ester moiety, the oligopolymer that contains m-phthalic acid glycol ether ester moiety, the oligopolymer that contains mutual-phenenyl two acid bromide two alcohol ester's part, the oligopolymer that contains m-phthalic acid butanediol ester part, the oligopolymer part that contains the covalent bonding of at least two kinds of aforementioned parts, 1, the 4-butyleneglycol, ethylene glycol, and combination.With polyethylene terephthalate component and 1, the temperature that 4-butyleneglycol component merges is generally 180 ℃~230 ℃.1, the 4-butyleneglycol uses with the amount excessive with respect to the polyethylene terephthalate component usually.In one embodiment, used 1, the amount of the molar excess of 4-butyleneglycol is 2~20.
During the initial period of technology, when making polyethylene terephthalate component and 1, the 4-butyleneglycol merges and during reaction (" step (a) "), under atmospheric at least pressure and conditions suitable, polyethylene terephthalate component and 1, the 4-butyleneglycol depolymerizes to molten mixture.Usually recirculation 1,4-butyleneglycol, ethylene glycol, and in the process of " step (a) " of technology, distill out tetrahydrofuran (THF).Molten mixture contains: contain ethylene glycol terephthalate part oligopolymer, contain the ethylene isophthalate part oligopolymer, contain terephthalic acid glycol ether ester moiety oligopolymer, contain m-phthalic acid glycol ether ester moiety oligopolymer, contain mutual-phenenyl two acid bromide two alcohol ester's part oligopolymer, contain m-phthalic acid butanediol ester part oligopolymer, contain the oligopolymer part, 1 of the covalent bonding of at least two kinds of aforementioned parts, 4-butyleneglycol, ethylene glycol, and combination.
According to each factor for example available equipment, produce the final character of needs, expectation etc., polyethylene terephthalate component and 1, the time of the step that the 4-butyleneglycol reacts can change.In one embodiment, this step was carried out 2 hours at least.In another embodiment, this step was carried out 2~5 hours.
This method is further comprising the steps of: molten mixture is in is lower than under 1 normal atmosphere, and the temperature of molten mixture is increased to 240 ℃~260 ℃ temperature, and form polybutylene terephthalate component thus derived from the modification of polyethylene terephthalate component.
Preferably remove excessive butyleneglycol, ethylene glycol and tetrahydrofuran (THF) (THF), and under agitation carry out step (b).Molten mixture when placing when being lower than under 1 atmospheric pressure in sufficiently long time of suitable temperature regulation, aggregates into the polybutylene terephthalate random copolymers derived from the modification of polyethylene terephthalate component.
Usually, make this molten mixture stand to be pressed onto pressure less than 1Torr from being lower than 1 atmosphere.In one embodiment, pressure is dropped in a continuous manner the pressure of 100~0.05Torr.In another embodiment, pressure is dropped in a continuous manner the pressure of 10~0.1Torr.
Advantageously, molten mixture can be placed to be lower than under 1 atmospheric pressure, and from molten mixture, not separate and any material of stripping (dissolution).Avoid carrying out the practicality that this step has improved this technology greatly.
In this step, be lower than under 1 atmospheric pressure and during elevated temperature, excessive butyleneglycol, ethylene glycol and THF removed from reactor, and the molecular weight of oligopolymer is increased when molten mixture is placed.But continuously stirring is so that remove low boiling component, and allows that the molecular weight of polymkeric substance increases.After obtaining enough molecular weight, the fusion PBT polymkeric substance that obtains is cast (cast) from reactor by die head, use water cooling, form the line material and be cut into pellet.
According to each factor for example available equipment, produce the final character of needs, expectation etc., molten mixture is from polyethylene terephthalate and poly-(mutual-phenenyl two acid bromide two alcohol ester) oligopolymer, 1, and the time of 4-butyleneglycol and ethylene glycol step of polymerization (above-mentioned step (b)) can change.In one embodiment, this step was carried out 2 hours at least.In another embodiment, this step was carried out 2~5 hours.
Molten mixture places the temperature that is lower than under 1 atmospheric pressure enough high, to promote polyethylene terephthalate and poly-(mutual-phenenyl two acid bromide two alcohol ester) oligopolymer, 1,4-butyleneglycol and ethylene glycol aggregate into the polybutylene terephthalate component derived from the modification of polyethylene terephthalate component.Usually, temperature is at least 230 ℃.In one embodiment, temperature is 250 ℃~275 ℃.
Two steps of this technology all can be carried out in identical reactor.But in one embodiment, this technology is carried out in two reactors that separate, and wherein step (a) is carried out in first reactor, when forming molten mixture, just molten mixture is placed second reactor and carries out step (b).In another embodiment, can in more than two reactor, carry out this technology.In another embodiment, this technology can be carried out in the reactor of contact continuously (continuous serie).
Be used to promote that the catalyst for reaction component of this technology generally includes this catalyst for reaction of promotion.Catalyzer can be selected from antimony compounds, tin compound, titanium compound, many other metal catalysts that disclose in its combination and the document and the combination of metal catalyst.The amount of catalyzer will change according to concrete needs.The appropriate catalyst amount is 1~5000ppm, or more.
Usually initial in the polyethylene terephthalate component with 1, in the step process when the 4-butyleneglycol merges, add catalyst component.But, in another embodiment, catalyst component can be added to polyethylene terephthalate component and 1, in the molten mixture that forms after 4-butyleneglycol component merges.
Preparation is preferably carried out under agitation condition derived from the method for the polybutylene terephthalate component of the modification of polyethylene terephthalate component.Term " agitation condition " or " stirring " are to instigate polyethylene terephthalate component and 1,4-butyleneglycol or molten mixture stand such condition, comprise when agitation condition is applied to polyethylene terephthalate component, 1,4-butyleneglycol " step (a) ", or by polyethylene terephthalate oligopolymer, 1, during the PBT that 4-butyleneglycol and ethylene glycol aggregate into " step (b) ", physical mixed polyethylene terephthalate component, 1 under the condition that promotes the PET depolymerization, 4-butyleneglycol or molten mixture.Can finish physical mixed by any suitable manner.In one embodiment, can use contain rotating shaft and with the mixing tank of the vertical blade of rotating shaft.
Preparation can comprise derived from the method for the polybutylene terephthalate component of the modification of polyethylene terephthalate component: contain alkali-metal basic cpd reduces the amount of the THF that produces and reduces the formation of THF thus in technological process step by adding in the reactor of step (a).
Basic cpd contains basic metal, and can be selected from one or more of following compound: sodium alkoxide, sodium hydroxide, sodium acetate, yellow soda ash, sodium bicarbonate, potassium alcoholate, potassium hydroxide, potassium acetate, salt of wormwood, saleratus, lithium alkoxide, lithium hydroxide, lithium acetate, Quilonum Retard, lithium bicarbonate, pure calcium, calcium hydroxide, lime acetate, lime carbonate, Calcium hydrogen carbonate, magnesium alkoxide, magnesium hydroxide, magnesium acetate, magnesiumcarbonate, Magnesium hydrogen carbonate, aluminium alcoholates, aluminium hydroxide, aluminum acetate, aluminium carbonate, hydrogen-carbonate aluminium, and combination.
The amount that is added to the basic cpd in the mixture is generally 0.1ppm at least.In one embodiment, the amount of basic cpd is 0.1~50ppm.In another embodiment, the amount of basic cpd is 1~10ppm.
With do not exist the technology under the basic cpd to compare, add and to contain alkali-metal basic cpd and can reduce the amount that total THF produces.In one embodiment, compare with the technology of not using basic cpd, the total THF that produces in technological process has reduced at least 10%.In another embodiment, the total THF that produces in technological process has reduced at least 10%~50%, and is perhaps more.
In another embodiment, can add two functional epoxy compoundss, thereby reduce the formation of THF.Epoxy compounds can be selected from two sense epoxide.The example of two suitable sense epoxy compoundss includes but not limited to 3,4-epoxycyclohexyl-3,4-epoxycyclohexyl carboxylicesters, two (3,4-epoxycyclohexyl methyl) adipic acid ester, the vinyl cyclohexene diepoxide, bisphenol diglycidyl is bisphenol A diglycidyl ether for example, the tetrabromo-bisphenol diglycidylether, Racemic glycidol, the diglycidyl adducts of amine and acid amides, the diglycidyl adducts of carboxylic acid is the diglycidyl ester of phthalic acid for example, the diglycidyl ester of hexahydrophthalic acid and two (3,4-epoxy-6-methyl cyclohexane ylmethyl) adipic acid ester, the divinyl diepoxide, the vinyl cyclohexene diepoxide, Dicyclopentadiene (DCPD) diepoxide etc.Especially preferred is 3,4-epoxycyclohexyl-3,4-epoxycyclohexyl carboxylicesters.The amount that can join the epoxy in the mixture is generally 0.05wt% at least.In one embodiment, the amount of epoxy compounds is 0.1~1wt%.In another embodiment, the amount of epoxy compounds is 0.2~0.5wt%.In one embodiment, the invention provides other embodiment, wherein a kind of like this method reduces the generation of THF, and this method may further comprise the steps:
(a) in the reactor under being in atmospheric at least pressure, in the presence of catalyst component, temperature at 190 ℃~250 ℃, under inert atmosphere, be enough to that the polyethylene terephthalate component is depolymerized under the condition of first molten mixture, make polyethylene terephthalate component that (i) be selected from polyethylene terephthalate and pet copolymer and be selected from ethylene glycol, propylene glycol, and the diol component of combination reaction, described first molten mixture contains and is selected from following component: the oligopolymer that contains the ethylene glycol terephthalate part, the oligopolymer that contains the ethylene isophthalate part, the oligopolymer that contains terephthalic acid glycol ether ester moiety, the oligopolymer that contains m-phthalic acid glycol ether ester moiety, contain terephthalic acid 1, the oligopolymer of-3 propylene glycol esters part, contain m-phthalic acid 1, the oligopolymer of ammediol ester moiety, the oligopolymer part that contains the covalent bonding of at least two kinds of aforementioned parts, ethylene glycol, propylene glycol and combination thereof; Wherein under agitation polyethylene terephthalate component and diol component are merged;
(b) in the presence of catalyst component, temperature at 190 ℃~240 ℃, be enough to form under the condition of second molten mixture, with 1, the 4-butyleneglycol is added in first molten mixture in the reactor, described second molten mixture contains and is selected from following component: the oligopolymer that contains the ethylene glycol terephthalate part, the oligopolymer that contains the ethylene isophthalate part, the oligopolymer that contains terephthalic acid glycol ether ester moiety, the oligopolymer that contains m-phthalic acid glycol ether ester moiety, contain terephthalic acid 1, the oligopolymer of ammediol ester moiety, contain m-phthalic acid 1, the oligopolymer of ammediol ester moiety, the oligopolymer that contains mutual-phenenyl two acid bromide two alcohol ester's part, the oligopolymer that contains m-phthalic acid butanediol ester part, the oligopolymer part that contains the covalent bonding of at least two kinds of aforementioned parts, 1, the 4-butyleneglycol, propylene glycol, ethylene glycol, and combination; With
(c) be lower than 1 atmospheric pressure and stir under the temperature of second molten mixture is increased to 240 ℃~260 ℃ temperature, form the polybutylene terephthalate random copolymers of modification thus, it contains at least a residue derived from described polyethylene terephthalate component.
This three steps embodiment is provided for being prepared by PET the other favourable mode of the PBT random copolymers of modification.Used diol component can be selected from ethylene glycol, propylene glycol in the step (a) of three step embodiments, and combination.The molar weight that this diol component exists in step (a) can be the amount of half at least of the ethylene glycol part that exists in the polyethylene terephthalate component.The time that the depolymerization of polyethylene terephthalate component is carried out can change.In one embodiment, depolymerization was carried out 25 minutes at least.
Used 1 in the step (b) of three step embodiments, the adding molar weight of 4-butyleneglycol can be excessive with respect to the molar weight that is attached to the butyleneglycol part in the modification polybutylene terephthalate random copolymer component that obtains in the step (c).
In technological process, used compound is reusable and/or it can be collected in this method.In one embodiment, in step (b), remove and be selected from ethylene glycol, propylene glycol, and the diol component of combination and (2) 1,4-butyleneglycols, and it is collected in the container.In another embodiment, in step (b), with 1, the 4-butyleneglycol refluxes back in the reactor, and removes following component: excessive butyleneglycol, ethylene glycol, propylene glycol, tetrahydrofuran (THF), and combination.(b) carries out the sufficiently long time with step, thereby is reduced by at least 65% ethylene glycol from second molten mixture.The time length of step (b) also can change.In one embodiment, step (b) continues at least 45 minutes.Carry out the changeable pressureization of step (b).In one embodiment, step (b) is carried out under atmospheric condition.In another embodiment, step (b) is carried out being lower than under 1 atmospheric pressure.Also can use different combinations.In one embodiment, step (b) is carried out under the absolute pressure of 4-butyleneglycol and 300~1500mbar excessive 1.In another embodiment, used 1, the amount of the molar excess of 4-butyleneglycol is 1.1~5.
According to the difference of using, also can make a change when carrying out the step (c) of three step embodiments.For example, in one embodiment, in step (c), remove and be selected from excessive butyleneglycol, ethylene glycol, propylene glycol, tetrahydrofuran (THF), and the component of combination.The pressure that carries out step (c) also can change.In one embodiment, step (c) is carried out being lower than under the pressure of 10mbar.Can in same reactor, carry out described three one step process.Perhaps, can at least two reactors, carry out described three one step process.
In another embodiment, described three one step process can be included in step (a), step (b), step (c), and add basic cpd in the process of combination, and further reduce the step that THF produces thus.With identical in the two step embodiments, basic cpd can contain above-described those compounds.Perhaps, can in the process of step (b), add two sense epoxy compoundss with above-described amount.
Advantageously, with with 1, the diol component that the 4-butyleneglycol replaces being selected from ethylene glycol, propylene glycol and combination thereof is compared the amount of the tetrahydrofuran (THF) that the method for polyethylene terephthalate component depolymerization produces, and the diminishbb tetrahydrofuran (THF) amount of three one step process is at least 30%.
Preparation can contain additional step derived from the method for the polybutylene terephthalate component of the modification of polyethylene terephthalate component, in this step, makes the PBT that is formed by molten mixture stand solid-state polymerization.Solid-state polymerization generally includes and makes the PBT that is formed by molten mixture be in inert atmosphere or be lower than under 1 normal atmosphere and be heated to certain temperature and keep the sufficiently long time so that the molecular weight of PBT increases.Usually, the temperature that PBT is heated to is the fusing point that is lower than PBT, for example, is lower than 5 ℃~60 ℃ of the fusing points of PBT.In one embodiment, this temperature can be 150 ℃~210 ℃.According to condition and device, solid-state polymerization carries out can be 2~20 hours during suitable.Solid-state polymerization carries out being enough to impel PBT further to aggregate under the chaotic condition (tumultuouscondition) of suitable molecular weight usually.This chaotic condition can produce by the following method: make PBT stand to roll, promote for example fluidisation of pellet, fragment, flocculus, powder etc. of polymer particle thereby rare gas element pumped in this system.Solid-state polymerization can be under normal atmosphere and/or decompression (1 normal atmosphere~1mbar) carry out for example.
The present invention includes a kind of embodiment, wherein 1, the 4-butyleneglycol can be derived from biomass.Term " biomass " is meant and can be directly or subsequently converted into living or dead biological substance of useful chemical substance that described chemical substance is usually derived from non-renewable hydrocarbon source.Biomass can comprise cellulosic material, cereal, the starch derived from cereal, lipid acid, vegetables oil, and the derivative of these biomass examples.The example of useful chemical substance includes but not limited to glycol; Diacid; Be used to prepare for example monomer of Succinic Acid of glycol or acid; Be used to prepare the monomer of polymkeric substance; Deng.Butyleneglycol based on biomass can derive from several sources.For example, can use following method to obtain based on 1 of biomass the 4-butyleneglycol.Can will change into Succinic Acid based on the biomass such as grain of agricultural by the fermentation process that also consumes carbonic acid gas.This Succinic Acid is commercially available from several sources, for example with trade name " BioAmber TM" derive from Diversified Natural Products Inc..Can be by several pieces of disclosed documents United States Patent (USP) 4,096 for example, the method described in 156 easily changes into 1 with this Succinic Acid, and the 4-butyleneglycol is incorporated into the full content of described patent among the application.Also can be with-1 of biomass derived, the 4-butyleneglycol changes into tetrahydrofuran (THF), and further converts it into polytetrahydrofuran, is also referred to as polybutylene oxide glycol (polybutylene oxide glycol).Description changes into 1 with Succinic Acid, and the other method of 4-butyleneglycol is described among the Life Cycles Engineering Guidelines of Smith etc., described in EPA publication EP A/600/R-1/101 (2001).
The amount of the polybutylene terephthalate random copolymers of modification (the PBT component of PET-deutero-modification) in moulding compound changes with concrete application.Usually, the amount of PBT component in moulding compound of the present invention of PET-deutero-modification is 5~90wt%.In another embodiment, the amount of the PBT component of PET-deutero-modification existence is 10~50wt%.In one embodiment, this amount can be 40~99.99wt%.In another embodiment, this amount can be 80~99.99wt%.When the PBT component comprised at least two kinds of polyester components with different qualities viscosity, the amount of every kind of polyester components can change.
Described carboxyl-reactive material is polymeric or non-polymeric simple function or multifunctional carboxyl-reactive material, or its combination.The example of carboxyl-reactive group comprises epoxide, carbodiimide, ortho ester, oxazoline, oxyethane, aziridine and acid anhydride.The carboxyl-reactive material also can be included in to have reactive or not to have reactive other functional group under the described processing conditions.The limiting examples of reactive part comprises reactive silicon-containing material, for example epoxide modified organosilicon and silane monomer and polymkeric substance.If desired, can use catalyzer or cocatalyst system to quicken reaction between carboxyl-reactive material and the polyester.
There are at least two carboxyl-reactive group in each molecule that is meant this material with term " multifunctional (polyfunctional) " or " multifunctional (multifunctional) " of carboxyl-reactive material coupling.Useful especially multifunctional carboxyl-reactive material comprises the material with at least two reactive epoxy groups.Multi-functional epoxy's material can contain aromatics and/or aliphatic residue.Example comprises epoxy-Novolak resin, epoxidised vegetables oil (for example, soybean oil, Toenol 1140), tetraphenyl ethylene epoxidizing thing contains the styrene-propene acid copolymer of side group glycidyl, contain glycidyl methacrylate-polymkeric substance and multipolymer, with two sense epoxy compoundss for example 3,4-epoxycyclohexyl methyl-3,4-epoxycyclohexane carboxylate.
In one embodiment, described multifunctional carboxyl-reactive material is epoxy functionalized polymkeric substance, and it comprises oligopolymer when being used for the application.Illustrative polymers with a plurality of epoxide groups is drawn together one or more ethylenically unsaturated compounds (for example, vinylbenzene, ethene etc.) and ethylenically unsaturated monomers (for example, the C that contains epoxy 1-4(alkyl) glycidyl acrylate, ethylacrylic acid allyl glycidyl (allyl glycidyl ethacrylate), and glycidyl itoconate) reaction product.
For example, in one embodiment, described multifunctional carboxyl-reactive material is the styrene-propene acid copolymer (comprising oligopolymer) that contains as side chain bonded glycidyl.Several useful examples are described in and transfer Johnson Polymer, among International Patent Application WO 03/066704 A1 of LLC, incorporate the full content of this patent application into the application by reference.These materials are formed the multipolymer of block based on having vinylbenzene and acrylate, and it has as side chain bonded glycidyl.Expecting has a large amount of epoxide groups in each polymer chain, at least about 10, for example, perhaps greater than about 15, perhaps greater than about 20.The common molecular weight of these polymeric materials is greater than about 3000, be preferably greater than about 4000, more preferably greater than about 6000.They can with
Figure A20078001125600231
Trade name, preferred
Figure A20078001125600232
ADR 4368 materials are available from Johnson Polymer, LLC.
Another example of carboxyl-reactive multipolymer is epoxy functionalized C 1-4(alkyl) acrylic monomer and non-functionalized styrene system and/or C 1-4The reaction product of (alkyl) acrylate and/or olefinic monomer.In one embodiment, epoxy polymer is the reaction product of epoxy functionalized (methyl) acrylic monomer and non-functionalized styrene system and/or (methyl) acrylate monomer.These carboxyl-reactive materials are characterised in that molecular weight is lower.In another embodiment, the carboxyl-reactive material is epoxy functionalized vinylbenzene (methyl) acrylic copolymer, and it is made by epoxy functionalized (methyl) acrylic monomer and vinylbenzene.The used term " (methyl) acrylic acid or the like " of the application comprises acrylic acid or the like and methacrylic monomer, and " (methyl) acrylate comprises acrylate and methacrylate monomer to term.The example of concrete epoxy functionalized (methyl) acrylic monomer includes but not limited to contain 1, those of 2-epoxide group, for example glycidyl acrylate and glycidyl methacrylate.
Appropriate C 1-4(alkyl) acrylate co-monomers includes but not limited to for example methyl acrylate of acrylate and methacrylate monomer, ethyl propenoate, the vinylformic acid n-propyl, isopropyl acrylate, n-butyl acrylate, vinylformic acid sec-butyl ester, isobutyl acrylate, tert-butyl acrylate, the vinylformic acid n-pentyl ester, the vinylformic acid isopentyl ester, isobornyl acrylate, the just own ester of vinylformic acid, vinylformic acid 2-ethyl-butyl ester, 2-EHA, the vinylformic acid n-octyl, vinylformic acid ester in the positive last of the ten Heavenly stems, vinylformic acid methylcyclohexyl ester, vinylformic acid ring pentyl ester, the vinylformic acid cyclohexyl ester, methyl methacrylate, Jia Jibingxisuanyizhi, n propyl methacrylate, n-BMA, isopropyl methacrylate, Propenoic acid, 2-methyl, isobutyl ester, the methacrylic acid n-pentyl ester, the just own ester of methacrylic acid, the methacrylic isoamyl valerate, methacrylic acid sec-butyl ester, the methacrylic tert-butyl acrylate, methacrylic acid 2-ethyl butyl ester, methyl methacrylate basic ring polyhexamethylene, methacrylic acid cassia bark ester, the methacrylic acid butene esters, cyclohexyl methacrylate, methacrylic acid ring pentyl ester, methacrylic acid 2-ethoxy ethyl ester, and isobornyl methacrylate.Can use the combination that comprises at least a aforementioned comonomer.
Suitable styrenic monomers includes but not limited to vinylbenzene, alpha-methyl styrene, Vinyl toluene, p-methylstyrene, t-butyl styrene, chloro styrene, and the mixture that comprises at least a aforementioned substances.In some embodiments, described styrene monomer is polystyrene and/or alpha-methyl styrene.
In another embodiment, the carboxyl-reactive material is the epoxy compounds with two terminal epoxy-functionals and optional other epoxy (or other) functional group.This compound also can only contain carbon, hydrogen and oxygen.Two sense epoxy compoundss especially only contain carbon, and those of hydrogen and oxygen can have and are lower than about 1000g/mol molecular weight, thereby are convenient to and the vibrin blend.In one embodiment, two sense epoxy compoundss have at least one epoxide group on cyclohexane ring.Two exemplary sense epoxy compoundss include but not limited to 3,4-epoxycyclohexyl-3,4-epoxycyclohexyl carboxylicesters, two (3,4-epoxycyclohexyl methyl) adipic acid ester, the vinyl cyclohexene diepoxide, bisphenol diglycidyl is bisphenol A diglycidyl ether for example, the tetrabromo-bisphenol diglycidylether, Racemic glycidol, the diglycidyl adducts of amine and acid amides, the diglycidyl adducts of carboxylic acid is the diglycidyl ester of phthalic acid for example, the diglycidyl ester of hexahydrophthalic acid and two (3,4-epoxy-6-methyl cyclohexane ylmethyl) adipic acid ester, the divinyl diepoxide, vinyl cyclohexene diepoxide, Dicyclopentadiene (DCPD) diepoxide etc.Especially preferred is 3,4-epoxycyclohexyl-3,4-epoxycyclohexyl carboxylicesters.
Can prepare two sense epoxy compoundss by well known to a person skilled in the art technology.For example, can make corresponding α-or beta-dihydroxyl compound dehydration, obtain epoxide group, maybe can be by to make corresponding unsaturated compound epoxidation with peracid such as peracetic acid treatment in the technique known.This compound also can be buied.
Other preferred substance with a plurality of epoxide groups is acrylic acid or the like and/or polyolefinic multipolymer and the oligopolymer that contains as side chain bonded glycidyl.Suitable epoxy functionalized material can trade name D.E.R.332, D.E.R.661 and D.E.R.667 derive from Dow Chemical Company; Derive from ResolutionPerformance Products with trade name EPON Resin 1001F, 1004F, 1005F, 1007F and 1009F; Derive from Shell OilCorporation with trade name Epon 826,828 and 871; Derive from Ciba-Giegy Corporation with trade name CY-182 and CY-183; With derive from Dow Chemical Co. with trade name ERL-4221 and ERL-4299.Shown in embodiment, Johnson Polymer Co is the supplier of material who is called the epoxy-functional of ADR4368 and 4300.Another example of multifunctional carboxyl-reactive material is to comprise ethene and unitary multipolymer of glycidyl methacrylate (GMA) or terpolymer, its by Arkema with trade name
Figure A20078001125600251
Sell.
In another embodiment, the carboxyl-reactive material is the multifunctional material with two or more reactive groups, and wherein at least one group is that epoxide group and at least one group are can be with the group of pet reaction but be not epoxide group.Second reactive group can be hydroxyl, isocyanic ester, silane etc.
The example of this multifunctional carboxyl-reactive material comprises having epoxy and silane functional, the material of the combination of preferred terminal epoxy and silane group.Epoxy silane normally wherein this epoxy be in an end of molecule and be attached to alicyclic group, and silane is in the epoxy silane of any kind of the other end of molecule.The epoxy silane of the expectation in this generality is described has following formula:
Figure A20078001125600252
Wherein m is an integer 1,2 or 3, n is integer 1~6 (comprising end points), X, Y are identical with Z or different, preferably identical, and be the alkyl of 1 to 20 (comprising end points) carbon atom, the cycloalkyl of 4 to 10 (comprising end points) carbon atoms, alkylidene group phenyl (wherein alkylidene group has 1~10 (comprising end points) carbon atom) and phenylene alkyl (wherein alkyl has 1~6 (comprising end points) carbon atom).The epoxy silane of expecting in this scope is that wherein m is 2, and n is 1 or 2, and is preferred 2, identical with Z with X, Y and be the compound of the alkyl of 1,2 or 3 carbon atom.Especially spendable epoxy silane is that wherein m is 2 in this scope, and n is 2, and is identical with Z with X, Y and be those compounds of methyl or ethyl.
This material for example comprises that β-(3, the 4-epoxycyclohexyl) ethyl triethoxysilane can derive from GE with trade name CoatOSil 1770.Other example is to derive from β-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane of GE and can derive from the 3-glycidoxypropyl triethoxyl silane of GE with trade name SilquestY-15589 with trade name SilquestA-186.
The carboxyl-reactive material is added in the polymer blend, and add-on is improved the physical properties of visual property and/or measurement effectively.In one embodiment, the carboxyl-reactive material is added in the polymer blend, add-on is improved the solvent resistance of composition effectively, especially the character of the anti-fuel of composition.The guidance that those skilled in the art use the application to provide does not need too much experiment just can determine the optimum type and the amount of any given carboxyl-reactive material.
The type of carboxyl-reactive material and amount will depend on the desired characteristic of composition, and the type of used polyester is present in the type and the amount of other additive in the composition, and similar Consideration, be generally the 0.01wt% at least of composition total weight.In one embodiment, the carboxyl-reactive amount of substance is 0.01~20wt%.In one embodiment, the carboxyl-reactive amount of substance is 0.01~30wt%., or more.
Moulding compound of the present invention also can contain ultra-violet stabilizer.Suitable ultra-violet stabilizer generally includes wide in range various UV light absorber.The example of UV light absorber includes but not limited to Whitfield's ointment UV light absorber, benzophenone UV-absorber, benzotriazole UV absorbers, cyanoacrylate UV light absorber and composition thereof.
The amount that can be used for the ultra-violet stabilizer in the moulding compound is generally 0.01wt% at least.In one embodiment, the amount of ultra-violet stabilizer is 0.01~0.5wt%.In another embodiment, the amount of ultra-violet stabilizer is 0.5~1wt%.
In another embodiment, moulding compound also can comprise impact modifier.The impact modifier component is generally rubber-like substance, when using it with appropriate vol, gives to the endergonic character of composition.Suitable rubber-like impact modifier comprises (a) methacrylic ester-Afpol, (b) acrylic elastomer, (c) acrylonitrile-styrene-acrylic ester rubber, (d) high grafting rubbers acrylonitrile-butadiene-styrene (ABS), (e) acrylate-olefin copolymer, (f) polyolefin modifiers, or (g) organosilicon-acrylic acid or the like properties-correcting agent (for example, METABLEN of making of Mitsubishi Rayon TMS).
More specifically, impact modifier can comprise acrylonitrile-butadiene-styrene (ABS) (ABS) polymkeric substance as high grafting rubbers impact modifier.Comprise the monovinylidene aromatic graft copolymer of (a) modified rubber and (b) the monovinylidene aromatic resin of the modified rubber of grafted rigid copolymer not, usually by the graft copolymerization and preparing in the presence of one or more rubbery polymer matrix of the mixture of monovinylidene aromatic monomer and one or more comonomers.According to the amount of the rubber that exists, can obtain not the independent matrix of grafted rigid polymer (multipolymer) or the monovinylidene aromatic graft copolymer of successive rigidity phase and modified rubber simultaneously.Described resin also can make by the monovinylidene aromatic graft copolymer blend with rigidity monovinylidene aromatic copolymer and one or more modified rubbers.
Usually, the resin of modified rubber comprises that content is total resin weight 5~100wt%, more preferably 10~95wt%, more preferably 20~90wt% and the most preferably graft copolymer of the modified rubber of 15~85wt%; Comprise that with the resin of modified rubber content is total resin weight 0~95wt%, more preferably 5~90wt%, more preferably 10~80wt%, the most preferably not grafted rigid polymer of 15~85wt%.The rubber of high level is preferred.
Especially preferred is to have greater than 30wt% rubbery polymer matrix, is preferably greater than the acrylonitrile-butadiene-styrene copolymer of about 45wt% rubbery polymer matrix.Most preferred rubber-like matrix comprises polyhutadiene or styrene-butadiene copolymer.The also acrylonitrile-butadiene-styrene copolymer of high grafting rubbers preferably.Term " high grafting rubbers " typically refers to graft copolymer resin, wherein at least about 30wt%, preferably at least about the rigid polymer phase chemistry bonding of 45wt% or be grafted to rubbery polymer and go up mutually.The high rubber graft copolymer of suitable ABS-type can be for example with trade mark
Figure A20078001125600271
Resin grades 336 or 338 is buied.A kind of preferred high rubber graft is General Electric Company, Advanced Materials's
Figure A20078001125600272
The C874202 resin.The title that the method for preparing graft copolymer resin is described in Lowry is Semi-batch Emulsion Process for Making DieneRubber Latex, Rubber Latex Made Thereby, the United States Patent (USP) 6 of and Graft Copolymer MadeTherefrom, in 384,129.
Other typical impact modifier is following material, or the blend of two or more these materials: (1) Paraloid EXL3300, and it is butyl acrylate-methacrylic ester core-shell rubber; (2) ASA-HRG, it is acrylonitrile-styrene-butyl acrylate copolymer; (3) AES, it is acrylonitrile-styrene-EPDM multipolymer, wherein EPDM is an ethylene-propylene non-conjugated diene elastomerics; (4) Lotader AX8900, it is ethylene-methyl acrylate-glycidyl methacrylate copolymer, wherein methacrylate content is about 8wt%.The content of impact modifier is more preferably less than 30wt% preferably less than 40wt%, most preferably less than 20wt%.
Core-shell multipolymer prepares the method for core-shell multipolymer and core-shell multipolymer and is described in United States Patent (USP) 3,864 as the purposes of impact modifier and polycarbonate combination, in 428 and 4,264,487.Suitable core-shell multipolymer is to comprise that second-order transition temperature (" Tg ") is lower than about 10 ℃ rubber-like " core " and Tg more than or equal to those of about 10 ℃ rigidity " shell ", and described " core " comprises that described " shell " has the repeating unit derived from single ethylenically unsaturated monomers derived from one or more single ethylenically unsaturated monomers repeating unit of acrylate monomer such as butyl acrylate and conjugate diene monomer such as divinyl for example.
The amount of impact modifier is generally 1wt% at least.In one embodiment, the amount of impact modifier is 1wt%~50wt%.In another embodiment, the amount of impact modifier is 1 or 5~25wt%.
Moulding compound of the present invention also can contain thermo-stabilizer.Suitable thermo-stabilizer includes but not limited to phenol stablizer, organic thioether stablizer, organic phosphorous acid ester stabilizer, hindered amine stabilizer, epoxy stabilizer and composition thereof.Can add heat-stable stablizer with the form of solid or liquid.
The amount that can be present in the thermo-stabilizer in the moulding compound is generally 0.01wt.% at least.In one embodiment, the amount of thermo-stabilizer is 0.01~0.5wt.%.In another embodiment, the amount of thermo-stabilizer is 0.05~1wt.%.In another embodiment, the amount of thermo-stabilizer is 0.05~3wt%.
In another embodiment, except the PBT component that contains the modification of PET-deutero-, moulding compound also can comprise releasing agent.The example of releasing agent includes but not limited to natural and synthetic paraffin, polyethylene wax (polyethylene waxe), fluorocarbon and other hydro carbons releasing agent; Stearic acid, oxystearic acid and other higher fatty acid, hydroxy fatty acid, and other lipid acid releasing agent; Stearylamide, ethylenebisstearamide, and other fatty amide, the two fatty amides of alkylidene group and other fatty amide releasing agent; Stearyl alcohol, hexadecanol and other Fatty Alcohol(C12-C14 and C12-C18), polyvalent alcohol, polyoxyethylene glycol, Polyglycerine and other alcohols releasing agent; Butyl stearate, the low-carbon-ester of pentaerythritol tetrastearate and other lipid acid, the polyol ester of lipid acid, the macrogol ester of lipid acid and other fatty acid ester releasing agent; Silicone oil and other silicone release, the functional equivalent of aforementioned substances (functionally equivalent) material, and the mixture of any aforementioned substances.For example poly-(tetrafluoroethylene) styrene-acrylonitrile of releasing agent and other additive can be used in combination.
The amount of releasing agent in moulding compound can be 0.1wt.% at least usually.In one embodiment, the amount of releasing agent is 0.1~2wt.%.In another embodiment, the amount of releasing agent is 0.05 or 0.5~1wt.%.
In another embodiment, the amount of releasing agent is 0.5~1wt%.
In one embodiment, composition contains flame retardance element.Flame retardance element can be added in the composition, thereby suppress, reduce, postpone or change flame by composition or based on the propagation of the goods of said composition.Flame retardance element can be the halon compound and the reactive flame retardant of bromine (chloride and), inorganic combustion inhibitor (boron compound, weisspiessglanz, aluminium hydroxide, molybdenum compound, zinc and magnesium oxide), P contained compound (organophosphate, phosphinate [salt] (phosphinate), phosphorous acid ester (phosphite), phosphonic acid ester, phosphurane, halogenated phosphorus compound and contain the salt of inorganic phosphorus) and nitrogenous compound such as melamine cyanurate (melamine cyanurate) and Tripyrophosphoric acid trimeric cyanamide.
Inorganic combustion inhibitor can comprise metal hydroxides, antimony compounds, boron compound, other metallic compound, phosphorus compound, other inorganic fire-retarded compound.The example of suitable metal hydroxides comprises the oxyhydroxide of magnesium hydroxide, aluminium hydroxide and other metal.The example of suitable fire retardant based on antimony comprises antimonous oxide, sodium antimonate, antimony peroxide and other mineral compound based on antimony.The example of suitable boron compound comprises zinc borate, boric acid, borax, and other is based on the mineral compound of boron.The example of other metallic compound comprises molybdenum compound, molybdic oxide, ammonium octamolybdate (AOM), zirconium compounds, titanium compound, zn cpds for example zinc, alkali formula zinc (zinchydroxy-stannate), or the like.
Flame retardance element can comprise halogen-containing compound.The example of suitable halogenated organic fire-retardant can comprise fire retardant, the chlorating fire retardant of bromination.The example of this fire retardant comprises tetrabromo-bisphenol, octabromodiphenyl ether, decabromodiphynly oxide, two (tribromophenoxy) ethane, tetrabromodiphenyl ether, hexabromocyclododecane, tribromophenol, two (tribromophenoxy) ethane tetrabromobisphenol a polycarbonate oligopolymer, tetrabromo-bisphenol epoxy oligomer.Typical halogenated aromatics fire retardant comprises tetrabromobisphenol a polycarbonate oligopolymer, many bromobenzenes ether (polybromophenyl ether), brominated Polystyrene, bromination BPA polyepoxide, bromination imide, brominated polycarbonate, poly-(vinylformic acid halogenated aryl ester), poly-(methacrylic acid halogenated aryl ester), or its mixture.
The example of the fire retardant that other is suitable is for example poly-Dowspray 9 of brominated Polystyrene and poly-tribromo-benzene ethene, decabrominated dipheny base ethane, tetrabromo biphenyl, the α of bromination, ω-alkylidene group-two-phthalimide, N for example, N '-ethylidene-two-tetrabromo phthalimide, oligomeric bromination carbonic ether, especially derived from the carbonic ether of tetrabromo-bisphenol, if necessary, it can be used the phenoxy group end-blocking, perhaps use bromination phenoxy group end-blocking, or brominated epoxy resin.
The chlorating fire retardant comprises chlorating paraffin, two (hexachlorocyclopentadiene base) cyclooctane, and other this functionalized Equivalent.
Flame retardance element can comprise P contained compound.The example of suitable phosphorus fire retardant comprises red phosphorus, ammonium polyphosphate.Organophosphorous fire retardant can comprise Firemaster 836, non-halogenated compound.The example of this material comprises tricresyl phosphate (1-chloro-2-propyl group) ester, tricresyl phosphate (2-chloroethyl) ester, tricresyl phosphate (2, the 3-dibromopropyl) ester, phosphoric acid ester, trialkylphosphate, triaryl phosphate, aryl phosphate-alkyl ester, and combination.Other fire retardant can comprise polyvalent alcohol, Phosphonium derivative, phosphonic acid ester, phosphine (phosphane), phosphine.
The concrete structure of P contained compound is as described below:
Figure A20078001125600301
Phosphoric acid ester, wherein R can be selected from alkyl, aryl, aralkyl, cyclohexyl, sec.-propyl, isobutyl-etc.
Figure A20078001125600302
Phosphonic acid ester, wherein X is H, and R, wherein R can be selected from alkyl, aryl, aralkyl, cyclohexyl, sec.-propyl, isobutyl-etc.
Figure A20078001125600303
Phosphinate [salt], wherein X and Y=H and R, wherein R can be selected from the compound of alkyl, aryl, aralkyl, cyclohexyl, sec.-propyl, isobutyl-etc., OH, aminofunctional.
Figure A20078001125600304
Phosphine oxide, wherein X, Y, Z=H and R, wherein R can be selected from alkyl, aryl, aralkyl, cyclohexyl, sec.-propyl, isobutyl-etc.
Figure A20078001125600305
Phosphine, wherein x, y and z can be selected from H, alkyl, aryl, aralkyl etc.
Figure A20078001125600306
Phosphorous acid ester, wherein R can be selected from alkyl, aryl, aralkyl, cyclohexyl, sec.-propyl, isobutyl-etc., and H.
Equally, addible suitable fire retardant can be the organic compound of phosphorous, bromine and/or chlorine.Since on the rules, in some applications can preferred non-bromination and non-chlorating phosphonium flame retardant, for example organophosphate and the organic compound that contains phosphorus-to-nitrogen bonds.
The exemplary organophosphate of one class is formula (GO) 3The aromatic phosphate acid ester of P=O, wherein each G is alkyl, cycloalkyl, aryl, alkaryl or aralkyl independently, condition is that at least one G is an aromatic group.Two G groups can combine and obtain cyclic group, for example, the bisphosphate diphenyl pentaerythritol, as Axelrod at United States Patent (USP) 4,154, described in 775.Other suitable aromatic phosphate acid ester can for, for example, phosphoric acid phenyl two (dodecyl) ester, phosphoric acid phenyl two (neo-pentyl) ester, phosphoric acid phenyl two (3,5,5 '-the trimethylammonium hexyl) ester, phosphoric acid ethyl diphenyl, phosphoric acid 2-ethylhexyl two (right-tolyl) ester, di(2-ethylhexyl)phosphate (2-ethylhexyl) is right-the tolyl ester, lindol, di(2-ethylhexyl)phosphate (2-ethylhexyl) phenylester, tricresyl phosphate (nonyl phenyl) ester, di(2-ethylhexyl)phosphate (dodecyl) is right-the tolyl ester, di(2-ethylhexyl)phosphate butyl phenyl ester, phosphoric acid 2-chloroethyl diphenyl, phosphoric acid is right-tolyl two (2,5,5 '-the trimethylammonium hexyl) ester, phosphoric acid 2-ethylhexyl diphenyl, or the like.Concrete aromatic phosphate acid ester is the phosphoric acid ester that each G is aromatics, for example, and triphenylphosphate, Tritolyl Phosphate, the triphenylphosphate of isopropylation etc.Also can use two-or many-functional aromatics P contained compound, for example, the compound shown in the following formula:
Each G wherein 1Independently for having the alkyl of 1~30 carbon atom; Each G 2Independently for having the alkyl or the-oxyl of 1~30 carbon atom; Each X mBe bromine or chlorine independently; M is 0~4; And n is 1~about 30.Suitable two-or the example of many-functional aromatics P contained compound comprise bisphosphate Resorcinol four phenyl esters (RDP), two (phenylbenzene) phosphoric acid ester of two (phenylbenzene) phosphoric acid ester of quinhydrones and dihydroxyphenyl propane, and their oligomeric and polymeric counterpart (counterpart) etc.
The example of the suitable flame-retardant compound that contains phosphorus-to-nitrogen bonds comprises the phosphonium chloride nitrile, phosphide acid amides, phosphoamide, phosphonic acid amide, phosphinic acid amide, three (ethylenimine base) phosphine oxide.When existing, phosphonium flame retardant can exist with the amount of 1~about 20 weight parts, based on the total composition of 100 weight parts.
In one embodiment, flame retardant polyester composition comprises that a kind of of fire-retardant amount contains nitrogen combustion inhibitor for example triazine, guanidine, cyanurate and isocyanurate, or contains the mixture of nitrogen combustion inhibitor.Suitable triazine has following formula:
Figure A20078001125600321
R wherein 1, R 2And R 3Be C independently 1-C 12Alkyl, C 1-C 12Alkoxyl group, C 6-C 12Aryl, amino, C 1-C 12The amino that alkyl replaces, or hydrogen.Highly suitable triazine comprises 2,4,6-triamine-1; 3,5-triazine (trimeric cyanamide, CAS Reg.No.108-78-1); melamine derivative, melam, melem; melon; cyanurodiamide (CAS Reg.No.645-92-1), melon (CAS Reg.No.645-93-2), 2-urea groups trimeric cyanamide; acetoguanamine (CAS Reg.No.542-02-9), benzoguanamine (benzoguanamine) (CAS Reg.No.91-76-9) etc.Salt/the adducts of these compounds and boric acid or phosphoric acid can be used for composition.Example comprises melamine pyrophosphate and polyphosphoric acid trimeric cyanamide.Suitable cyanurate/tricarbimide salt compound comprises the salt/adducts of triaizine compounds and cyanuric acid, for example any mixture and the melamine cyanurate of melamine salt.
Suitable guanidine compound comprises guanidine; Aminoguanidine; Deng; And the salt and the adducts of they and boric acid, carbonic acid, phosphoric acid, nitric acid, sulfuric acid etc.; And the mixture that comprises at least a aforementioned guanidine compound.
Contain nitrogen combustion inhibitor and one or more compounds based on phosphorus are used in combination.Phosphinates and diphosphinic acid salt comprise listed those in the United States Patent (USP) 6,255,371 of Schosser etc.Described concrete phosphinates comprises diethyl phospho acid aluminium (DEPAL) and diethyl phospho acid zinc (DEPZN).Phosphinates has formula (I)
Figure A20078001125600322
And/or formula II,
Figure A20078001125600323
And/or comprise the polymkeric substance of this formula I or II,
R wherein 1And R 2Be identical or different, and be H, the C of straight chain or branching 1-C 6-alkyl and/or aryl; R 3Be the C of straight chain or branching 1-C 10Alkylidene group, C 6-C 10-arylidene ,-alkyl arylene or-aryl alkylene; M is any metal, and still suitable is magnesium, calcium, aluminium or zinc, and m is 1,2 or 3; N is 1,2 or 3; X is 1 or 2.
In one embodiment, except quoting the substituting group of listing, R 1And R 2Also can be H.This causes hypophosphite, the part of phosphinates, for example calcium propionate, hypo-aluminum orthophosphate etc.
Usually with fire retardant and synergistic agent (synergist), especially inorganic antimony compounds is used together.These compounds can extensively obtain, and perhaps can prepare by known methods.Usually, inorganic synergist compound comprises Sb 2O 5, SbS 3, sodium antimonate etc.That especially suitable is antimonous oxide (Sb 2O 3).The synergistic agent for example common consumption of weisspiessglanz is about 0.5~15wt% of the resin in the final composition.
Equally, final composition can contain polytetrafluoroethylene (PTFE) type resin or multipolymer, is used for reducing the drippage of flame-proofed thermoplastic plastics.Perhaps, in one embodiment, composition can contain polyetherimide.
The amount that the expectation flame retardant additives exists is enough to reduce the combustibility of vibrin at least, preferably combustibility is reduced to the UL94V-0 grade.The amount of flame retardant additives will be along with the effect of the character of resin and additive and is changed.The amount of flame retardance element is generally 1wt.% at least.In one embodiment, the amount of flame retardance element is 5wt.%~30wt.%.In another embodiment, the amount of flame retardance element is 10~20wt.%.
Description above is illustrative, should be clear, and moulding compound can comprise such embodiment, wherein has one or more optional components in composition.Equally, in one embodiment, moulding compound is contained in the present invention, and it comprises:
(a) the PBT component of the PET-deutero-modification of 70~99.99wt%, its main polymer chain comprises following group:
Figure A20078001125600331
Wherein R ' is the terephthalic acid group ,-1, and 4-(C6H4)-
R " be the m-phthalic acid group ,-1,3-(C6H4)-
D be the butanediol group and-C4H8-
D ' is the ethylene glycol group;-C2H4-
(b) the multifunctional carboxyl-reactive component of 0.01~20wt%; With
(c) be selected from the component of impact modifier, ultra-violet stabilizer, thermo-stabilizer, releasing agent and combination thereof.
Moulding compound of the present invention is given the physical properties that can be used in the various application.For example, the moulding compound of the present invention shock resistance of giving is generally at least 30 joules/m (recording in room temperature according to notched izod) in room temperature.In one embodiment, the moulding compound shock resistance of giving is 30~200 joules/m.In another embodiment, the moulding compound shock resistance of giving is 50~100 joules/m.In another embodiment, the moulding compound shock resistance of giving is 200~1000 joules/m.
The tensile fracture elongation rate (%) that moulding compound is given is generally at least 5%.In another embodiment, tensile fracture elongation rate (%) is 30%~300%.In one embodiment, tensile fracture elongation rate (%) is 40%~75%.
The tensile stress at yield that moulding compound is given (MPa) is generally 20MPa at least.In another embodiment, tensile stress at yield (MPa) is 20MPa~200Mpa.In one embodiment, tensile stress at yield (MPa) is 40~75MPa.
The modulus in flexure that moulding compound is given (MPa) is generally 1500MPa at least.In one embodiment, modulus in flexure (MPa) is 1500~10,000MPa.In another embodiment, modulus in flexure (MPa) is 2000~3000MPa.
The faulted flexure stress (MPa) that moulding compound is given is generally 50MPa at least.In another embodiment, faulted flexure stress (MPa) is 50~300MPa.In one embodiment, faulted flexure stress (MPa) is 75~100MPa.
Moulding compound is generally at least 40 ℃ to the 3.2mm strip in the heat-drawn wire that 1.82MPa gave.In another embodiment, heat-drawn wire is 40 ℃~220 ℃.In one embodiment, heat-drawn wire is 40~60 ℃.Composition can comprise the material that influences composition character.For example, composition also can comprise the material of at least 1~10 ℃ of the heat-drawn wire increases that can make composition.This material can be selected from talcum, nanoparticle, tetrafluoroethylene, clay, the mica with minuteness particle, and combination.
Composition of the present invention can demonstrate melt volume speed (MVR) and be higher than the MVR of use based on the same combination of monomeric polybutylene terephthalate homopolymer preparation.For example, the comparable combination object height at least 10% based on monomeric polybutylene terephthalate homopolymer preparation of the melt volume speed of composition, described melt volume speed records with 240 seconds the residence time and 2.1mm aperture with 5kgf at 250 ℃ according to ISO 1133 methods on pellet.In one embodiment, compare with the composition of making by the PBT rather than the PBT random copolymers of monomer derived, the melt volume speed of composition of the present invention is high by 10%~80%, or higher, described melt volume speed records with 240 seconds the residence time and 2.1mm aperture with 5kgf at 250 ℃ according to the ISO1133 method on pellet.In another embodiment, the heat-drawn wire of composition can be at least 80 ℃, and described heat-drawn wire records at 0.455MPa by ASTM D648 standard.
The molding shrinkage that moulding compound is given (mold shrinkage) is usually less than 5%.In one embodiment, molding shrinkage is 0~5%.In another embodiment, molding shrinkage is 2~2.5%.
Moulding compound of the present invention is usually by under appropriate condition, in forcing machine (equipment that is mixed that perhaps function is identical) the carboxyl-reactive material of merging appropriate amount, PET-deutero-PBT component and any other additive and prepare.Can with carboxyl-reactive material, PET-deutero-PBT component and any annexing ingredient can be simultaneously, be mixed separately or in the mode of the combination that contains two or three component.Extrusion can comprise through the forcing machine one or many.
The present invention includes preparation method for compositions and goods.For example, the present invention includes the method that makes composition molding, it comprises any component melts blend with the present composition.Method can comprise that the composition with melt blending carries out moulding, extrudes or molding.Method can comprise makes suitable goods with the composite mold of melt blending.And composition of the present invention comprises the goods derived from any composition of the present invention.
The advantage that can not obtain before the invention provides.For example, the invention provides moulding compound, although it contains different m-phthalic acid group and ethylene glycol groups derived from the PET that is used to prepare PBT on the structure, function is with equally matched based on those of pure PBT.Because moulding compound does not need the PBT of conventional preparation,, and the needs of in refuse landfill, handling PET or handling it by burning have been reduced thus so the present invention has increased and uses the demand of PET refuse by producing value-added PBT composition.Said composition also demonstrates the character of improvement because having used multifunctional carboxyl-reactive material.
In addition, the preparation method of PBT random copolymers that is used for the PET-deutero-modification of the present composition can advantageously significantly reduce the release and the solid waste of carbonic acid gas.Owing to the PBT random copolymers of the PET-deutero-polyester modification for preparing by method of the present invention is made by refuse PET rather than monomer, so this method has significantly reduced amount and solid waste that carbonic acid gas discharges.Cause the minimizing (or saving of crude oil) of carbon refuse, this is because not using to constitute prepares the dimethyl terephthalate (DMT) of polyester or the carbon of terephthalic acid usually, the substitute is the PET component, for example polyester waste.The method that is prepared DMT or TPA by crude oil is the height energy-intensive, therefore can discharge CO in a large number when the burning Nonrenewable energy resources 2In atmosphere.By not using DMT or TPA to prepare PET deutero-PBT, the release of carbonic acid gas has obtained saving.In one embodiment, compare with the method that is prepared pure PBT homopolymer by monomer, for the PBT of the every kilogram of PET-deutero-modification for preparing with present method, the method for the PBT of preparation PET-deutero-modification can be eliminated 1kgCO at least 2Discharge.In another embodiment, compare with the method that is prepared pure PBT homopolymer by monomer, for the PBT of the every kilogram of PET-deutero-modification for preparing with present method, the method for the PBT of preparation PET-deutero-modification can be eliminated 1kg~1.5kg, perhaps more CO 2Discharge.In addition, when reclaiming the ethylene glycol by product and being used for replacing common ethylene glycol in the mill, but the release of conserve energy/minimizing carbonic acid gas.
In addition, the raw material that derives from biomass derived when the BDO source is for example during Succinic Acid, because the former thereby further saving that increases carbonic acid gas of two aspects.Biologically-derived Succinic Acid is by sugar or derived from other biologically-derived hydrocarbon preparation of big gas carbon rather than fossil oil carbon source, reduce thus based on the BDO derived polymers of Succinic Acid in authigenic material source to the influence of environment.In addition, fermentation produces Succinic Acid needs carbonic acid gas as input, further causes carbonic acid gas to reduce thus.
Advantageously, the moulding compound that contains the polybutylene terephthalate random copolymers of modification can have the CO of reduction 2Discharge index (emissions index).The CO of Ding Yi reduction in this application 2The release index is meant, and uses the CO in kg that produces when preparing composition derived from monomeric polybutylene terephthalate 2Amount compare the CO that when preparation 1kg contains the composition of polybutylene terephthalate random copolymers of modification, is saved in kg 2Amount.In general, the CO of the common reduction of composition of the present invention 2Discharge index greater than about 0.06kg, and can be 0.06kg~2.25kg.
The basis of this feature is discussed below.Prepare in the usual way process of PBT of pure monomer derived and the CO that produces in the procedure of the polybutylene terephthalate random copolymers of preparation 1kg modification 2The difference of amount can be 1.3kg~2.5kg, be 1.7kg~2.2kg perhaps preferablyly.Should be noted that this difference is based on beginning whole process to monomer to PBT from crude oil with respect to beginning from refuse PET to oligopolymer calculating to the PBT of modification again.In other words, compare with the method for preparing the pure PBT of 1kg from crude oil, the method for the polybutylene terephthalate random copolymers of preparation 1kg modification produces 1.3~2.5 kilograms of CO less 2(it has the PBT random copolymers of modification, and the amount of existence is the CO of 5~90wt.%) reduction in order to determine composition of the present invention 2Discharge the exponential scope, CO 2Reducing index can followingly calculate: the upper limit amount that the lower limit amount in per-cent that is present in the polybutylene terephthalate in the composition multiply by 1.3 (0.05x1.3=0.065) and polybutylene terephthalate multiply by 2.5 (0.90x 2.5=2.25).
Can be by using matter and energy EQUILIBRIUM CALCULATION FOR PROCESS (the known calculating of field of chemical engineering), and will prepare the amount of the used energy of the PBT random copolymers of modification from PET and make comparisons with the amount for preparing the used energy of PBT from terephthalic acid, derive and confirm these results.
Further describe the present invention in following illustrative embodiment, wherein unless otherwise indicated, all umbers and percentage ratio all are based on weight.
Embodiment
Material
Provide the tabulation of the composition that uses in the embodiments of the invention below.
Figure A20078001125600371
Figure A20078001125600381
Method 1:
At 240~265 ℃ machine barrels and die head temperature, with the screw speed of 150~300rpm, each composition of embodiment that will be as shown in following table is extruded on the 40mm Werner Pfleiderer twin screw extruder with vacuum exhaust mixing screw (vacuum ventedmixing screw).Forcing machine has 8 feeders that independently are used for different material, and forcing machine can be with the maximum rate operation of 300lbs/hr (136kg/ hour).Extrudate is cooled off granulation then by water-bath.At design temperature is injection moulding test parts on about 240~265 ℃ van Dorn mould machine.Before injection moulding, with pellet in the circulation baking oven of forced ventilation at 120 ℃ of dry 3-4 hours.
Method 2:
At 240~265 ℃ machine barrels and die head temperature, with the screw speed of 150~300rpm, the composition of embodiment that will be as shown in following table is extruded having on the 37mm ToshibaTEM-37BS twin screw extruder of vacuum exhaust mixing screw.Forcing machine has 8 feeders that independently are used for different material, and forcing machine can be with the maximum rate operation of 200lbs/hr.Extrudate is cooled off granulation then by water-bath.At design temperature is injection moulding test parts on about 240~265 ℃ NISSEI ES3000 (for the ASTM strip) or FANUC S-2000i (for the ISO strip) moulding machine.Before injection moulding, with pellet in the circulation baking oven of forced ventilation at 120 ℃ of dry 3-4 hours.
Method 3
At 240~265 ℃ machine barrels and die head temperature, with the screw speed of 400~500rpm, the composition of embodiment that will be as shown in following table is extruded on the 27mm Werner Pfleiderer twin screw extruder with vacuum exhaust mixing screw (vacuum vented mixingscrew).Forcing machine has 4 feeders that independently are used for different material, and forcing machine can be with the maximum rate operation of 75lbs/hr (34kg/hr).Extrudate is cooled off granulation then by water-bath.At design temperature is injection moulding test parts on about 240~265 ℃ van Dorn mould machine.Before injection moulding, with pellet in the circulation baking oven of forced ventilation at 120 ℃ of dry 3-4 hours.
Method 4
The composition that is shown in the embodiment in following each table is extruded on s-generation 30mm co-rotating twin screw extruder.This forcing machine is equipped with 9 barrel section (L/D=29) and 2 and is used for raw material is fed to the feeder of feed throat.Usually with 30lbs (13.6kgs)~60lbs (27.3kgs) speed hourly material is fed in the forcing machine.Usually screw speed is adjusted to 300 and 500RPM between value.For the residence time that makes specific energy and material minimizes, thereby select the precise combination of input speed and screw speed to produce high input speed and high moment of torsion.With the pellet that is mixed in air circulating oven 250 °F (121 ℃) dry 3-4 hour, molded then.Use van Dorn injection moulding machine, it has following temperature distribution (from back to front): 554 (290 ℃), 570 (299 ℃), 570 (299 ℃), 590 (310 ℃).Typically be provided with as follows: the 100rpm screw speed, 600psi (421,800kg/m 2) pressurize, and 75psi (52,725kg/m 2) back-pressure and 30sec cycling time.The temperature and the pressurize/back-pressure of machine barrel front are adjusted to the difference that adapts to processibility between the formulation.All standardized units all are 0.125 " (3.12mm) thick.
Test method
The melt volume speed (MVR) of pellet (before measuring 120 ℃ of dryings 2 hours) is measured with 240 seconds the residence time and the aperture of 0.0825 inch (2.1mm) according to the ISO1133 method.
Capillary viscosity (it is another index of fluidity of molten) is according to ASTM D3835 standard or ISO D11433 canonical measure.The exsiccant pellet is extruded by capillary rheometer, determined the power under various shearing rates, thereby estimate shear viscosity.
Tensile property at 23 ℃ according to the pinblock velocity determination with 5mm/min on the injection moulding strip of 150x10x 4mm (length x width x thickness) of ISO 527 standards.Unnotched Izod impact strength uses 5.5 joules pendulum to measure according to ISO 180 methods on 80x 10x 4mm (length x width x thickness) impact strip at 23 ℃.Flexural property or three-point bending performance are impacted the pinblock speed of use 2mm/min on the strip according to ISO 178 canonical measures at 23 ℃ at 80x 10x4mm (length x width x thickness).
In other cases, articles injection-mouldedly test according to the ASTM standard.The notched izod test is at 3x 1/ 2Use ASTM method D256 to finish on the strip of x 1/8 inch (76.2x 12.7x 3.2mm).Before oven ageing, make strip is formed breach, sample is tested in room temperature.The tensile fracture elongation rate uses the pinblock speed of 2in./min (50.8mm/min) (for the filling glass sample) and 0.2in/min (5.08mm/min) (for unfilled sample) to test by using ASTM D648 method in room temperature on the injection moulding strip of 7x1/8 inch (177.8x 3.3mm).Flexural property uses ASTM 790 or ISO 178 methods to measure.The twin shaft shock test is sometimes referred to as apparatus shock test (instrumented impact testing), uses the moulded disks of 4x 1/8 inch (101.6x 3.2mm) to finish according to ASTM D3763 standard.The total energy of absorption of sample is recorded as ft-lbs or J.In room temperature molded or stove aged sample are tested.Heat-drawn wire uses ASTM method D648 to test on 5 strips that are of a size of 0.125 inch of 5x 0.5x (127x 12.7x 3.2mm).
The summary such as the table 1 of all correlation tests and test method are listed.
Table 1: test method and description
Touchstone The sample type of acquiescence Unit
The ASTM flexure test ASTM D790 Strip-127x 12.7x 3.2mm Mpa
The ISO flexure test ISO 178 Multi-usage ISO 3167A type Mpa
ASTM HDT test ASTM D648 Strip-127x 12.7x 3.2mm
ISO HDT test ISO 75 Strip-80x 10x 4mm
ASTM HDT test ASTM D648 Strip-127x 12.7x 3.2mm
ISO HDT test ISO 75 Multi-usage ISO 3167A type
The tension test that ASTM fills ASTM D638 ASTM I type tensile bar Mpa
The tension test that ISO fills ISO 527 Multi-usage ISO 3167A type Mpa
The ISO izod of room temperature ISO 180 Multi-usage ISO 3167A type kJ/m 2
The ASTM izod of room temperature Breach ASTMD256 Strip-63.5x 12.7x 3.2mm J/m
The ASTM multiaxis impacts ASTM D3763 Disk-101.6mm diameter x 3.2mm thickness J
ISO Sha Erpi impacts ISO 179 Strip-80x 10x 4mm kJ/m 2
ISO density ISO 1183 Strip-80x 10x 4mm g/cm 3
Shrinking percentage The GEP method Disk-101.6mm diameter x 3.2mm thickness
The speed trial of ISO melt volume ISO 1133 Pellet cm 3/10min
The ASTM melt flow rate (MFR) ASTM D1238 Pellet g/10min
The ISO vicat softening temperature ISO 306 Strip-80x 10x 4mm
The ISO thermal expansivity ISO 11359-2 Multi-usage ISO 3167A type um/(m-℃)
Embodiment 1 and 2 aging testing method
To place container by the molded tensile bar of the moulding compound shown in the table 3 (comprising embodiment 1 and 2), this container is loaded in the autoclave chamber that is arranged on 110 ℃ and 100% relative humidity.From chamber, take out 5 strips of each embodiment during each time period of 1,3 and 7 day from exposing beginning.Make strip carry out tension test then, calculate the per-cent retention value, provide with the per-cent of Comparative Examples 2 with respect to the property retention value of embodiment 1.
Following examples explanation the present invention, but be not intended to limit the scope of the invention.Embodiment to following table extrudes and molding according to the method shown in the table 2.
Table 2: the extrusion method of different samples
Embodiment Method
1-2 1
3-4 2
5-6 7-8 3 3
9-13 4
All components are all listed with weight %.
Embodiment 1 and Comparative Examples 2
The purpose of purpose-these embodiment has 5.At first, these embodiment show and can prepare useful moulding compound by PET deutero-PBT.The character of these compositions is suitable with character derived from the pure PBT of dimethyl terephthalate (DMT).The second, these embodiment also prove, comprise Resins, epoxy and PET deutero-PBT formulation character with comprise Resins, epoxy and suitable derived from the character of the formulation of the pure PBT of dimethyl terephthalate (DMT).The 3rd, these embodiment also will confirm, when hydrolysising aging during each time period, contain Resins, epoxy and PET deutero-PBT composition character with comprise Resins, epoxy and suitable derived from those formulations of the pure PBT of dimethyl terephthalate (DMT).The 4th, compare with PBT based on DMT, consume more a spot of energy when producing these embodiment.The energy here is meant employed non-renewable energy when the preparation moulding compound.It comprises that all components to system carries out (cradle to grave) energy spectrometer from start to finish, and calculates their needed total energies of preparation.Shown in all embodiment in, this energy difference only is owing to using PET deutero-PBT or using the PBT based on DMT to cause.Other all compositions remain unchanged, so their contribute energy in whole composition can be ignored.The 5th, these embodiment will confirm, when hydrolysising aging, contain Resins, epoxy and PET deutero-PBT composition character with comprise that those formulations of Resins, epoxy and pure PBT are suitable.
Embodiment 1 and 2 composition are as shown in table 3.
Table 3: ' PET deutero-PBT ' composition and Comparative Examples with various additives
Figure A20078001125600411
The character of the moulding compound shown in the table 3 is shown in Table 4.
The physical property data of table 4: embodiment 1 and Comparative Examples 2
Test Unit 1 2 (Comparative Examples)
Modulus in flexure; 1.27mm/min; (ASTM) MPa 2060 2210
Modulus in flexure; ISO MPa 1965 2116.4
Texturing temperature, 1.82Mpa; ASTM 45 47
Texturing temperature, flat board, 1.8Mpa; ISO 45 47
Tensile modulus; 50mm/min; ASTM MPa 2120 2220
Tensile stress at yield; ASTM MPa 48 50
Tensile stress at break; ASTM MPa 22 25
The surrender tensile elongation; ASTM 3.7 3.7
The tensile fracture elongation rate; ASTM 66 125
Tensile modulus; ISO MPa 2036 1539
Tensile stress at yield; ISO MPa 48 48
Tensile stress at break; ISO MPa 33 25
Tensile strain at yield; ISO 3.3 3.4
The fracture tension strain; ISO 36 69
Notched izod impact strength; ISO; 25 ℃ kJ/m 2 8 11
Notched izod impact strength; ASTM; 25 ℃ J/m 70 92
Multiaxis impacts total energy, 2.3m/s, 25 ℃; ASTM J 46 54
Charpy impact strength, 25 ℃ kJ/m 2 10 12
Density-ISO g/cm 3 1.28 1.28
Parallel molding shrinkage rate (Mold ShrinkageParallel); The GE method 2.3 2.3
The molding shrinkage rate; Vertically; The GE method 2.2 2.3
MVR,250℃,2.16Kg,240s cm 3/10min 47.8 22.2
MFR,250℃,2.16Kg,360s g/10min 54.9 24.6
Vicat softening temperature, 50N, 120 ℃/hr; ISO 206 215
The line style thermal expansivity, flow direction; ISO um/(m-℃) 91 88
The line style thermal expansivity, crossing flow direction; ISO um/(m-℃) 92 91
Melt viscosity speed (Melt Viscosity Rate), 250 ℃, 2.16Kg, 240s; ISO cm 3/10min 48 22
Melt flow rate (MFR), 250 ℃, 2.16Kg, 360S; ASTM g/10min 55 25
Character and the per-cent of moulding compound shown in the table 3 behind hydrolysising aging (hydro aging) keeps being calculated as follows in the table 5 listed.
Table 5: before the hydrolysising aging of various time periods and afterwards embodiment 1 and 2 hydrolysising aging data
Figure A20078001125600431
Relatively demonstration between embodiment 1 and the embodiment 2 can obtain the suitable moulding compound of character with PET deutero-PBT.Can think that the notched izod under these situations equates in the experimental error limit of this test.The value of tensile fracture elongation rate also is such.Have that ' heat-drawn wire (HDT) of the composition of PET deutero-PBT ' is than having derived from low 2 ℃ of the heat-drawn wire of the composition of the pure PBT of DMT.But the MVR of compositions for use is significantly higher than compositions for use in the Comparative Examples 2 among the embodiment 1.
Embodiment 1 and the embodiment 2 relatively demonstration aspect the hydrolysising aging of all temps can use PET deutero-PBT to obtain to have the suitable moulding compound of character when aging.About tensile modulus and yielding stress, the per-cent reduction of maximum is 13% when adding PET deutero-PBT.For this data set, this reduction is not significant, and does not react the statistical discrepancy (statistical difference) between embodiment 1 and the Comparative Examples 2.Therefore, when hydrolysising aging under the described conditions, can think that the surrender tensile modulus of embodiment 1 and Comparative Examples 2 and tensile stress at yield value are the data sets that equates.When using PET deutero-PBT, the increase of the per-cent reduction value of tensile fracture elongation rate observed value is to cause owing to numerical value related in the experimental error of this test and this percentage calculation is low.Can think that the tensile fracture elongation rate equates in the experimental error limit.But about MVR, the composition of embodiment 1 significantly is better than compositions for use in the Comparative Examples 2.
Embodiment 1 lacks the energy that consumes about 27MJ/kg moulding compound than Comparative Examples.Therefore, embodiment 1 is than embodiment 2 moulding compound of Energy Efficient more.
Embodiment 3 and Comparative Examples 4
The purpose of purpose-these embodiment has three.At first, these embodiment show and can prepare useful moulding compound by PET deutero-PBT.The character of these compositions is suitable with character derived from the pure PBT of dimethyl terephthalate (DMT).The second, these embodiment also confirm, comprise Resins, epoxy and PET deutero-PBT formulation character with comprise Resins, epoxy and suitable derived from the character of the formulation of the pure PBT of DMT.The 3rd, compare with PBT based on DMT, consume more a spot of energy when producing these embodiment.The energy here is meant employed non-renewable energy when the preparation moulding compound.It comprises that all components to system carries out energy spectrometer from start to finish, and calculates their needed total energies of preparation.Shown in all embodiment in, this energy difference only is owing to using PET deutero-PBT or using the PBT based on DMT to cause.Other all compositions remain unchanged, so their contribute energy in whole composition can be ignored.
Embodiment 3 and 4 composition are as shown in table 6.
Table 6: ' PET deutero-PBT ' composition and Comparative Examples with various additives
Component Unit 3 4 (Comparative Examples)
GE PBT 315(1.2iv) 21.87
PET deutero-PBT (1.2iv) 21.87
GE PBT 195(0.65iv) 21.82
PET deutero-PBT (0.65iv) 21.82
NaSt 0.1 0.1
PETS 0.1 0.1
Brominated epoxy resin 15 15
Glass fibre 30 30
Sb 2O 3/PE 80/20 5 5
Irgaphos 168 0.05 0.05
Lotader AX8900 3 3
Antioxidant 60 0.06 0.06
Hytrel 4056 3 3
The character of the moulding compound shown in the table 6 is shown in Table 7.
The physical property data of table 7: embodiment 3 and Comparative Examples 4
Figure A20078001125600441
Figure A20078001125600451
Comparison shows that between the embodiment 3 and 4 can obtain the suitable moulding compound of character with PET deutero-PBT.Can think that the tensile modulus under these situations equates in the experimental error limit of this test.Have that ' heat-drawn wire (HDT) of the composition of PET deutero-PBT ' is than low 4 ℃ of the heat-drawn wire of the composition with pure PBT.
Compare embodiment 3 few energy that consume about 13.3MJ/kg moulding compound with Comparative Examples.Therefore, embodiment 3 is than embodiment 4 moulding compound of Energy Efficient more.
Embodiment 5 and Comparative Examples 6
The purpose of purpose-these embodiment has three.At first, these embodiment show and can prepare useful moulding compound by PET deutero-PBT.The character of these compositions is suitable with character derived from the pure PBT of dimethyl terephthalate (DMT).The second, these embodiment also confirm, comprise Resins, epoxy and PET deutero-PBT formulation character with comprise Resins, epoxy and suitable derived from the character of the formulation of the pure PBT of DMT.The 3rd, compare with PBT based on DMT, consume more a spot of energy when producing these embodiment.The energy here is meant employed non-renewable energy when the preparation moulding compound.It comprises that all components to system carries out (cradle to grave) energy spectrometer from start to finish, and calculates their needed total energies of preparation.Shown in all embodiment in, this energy difference only is owing to using PET deutero-PBT or using the PBT based on DMT to cause.Other all compositions remain unchanged, so their contribute energy in whole composition can be ignored.
Embodiment 5 and 6 composition are as shown in table 8.
Table 8: ' PET deutero-PBT ' composition and Comparative Examples with various additives
Component Unit 5 6 (Comparative Examples)
GE PBT 315(1.2iv) 54.27
PET deutero-PBT (1.2iv) 54.27
GEPBT 195(0.65iv) 44.4
PET deutero-PBT (0.65iv) 44.4
NaSt 0.07 0.07
Hindered phenol stabilizer 0.06 0.06
ERL4221 1.1 1.1
PETS 0.1 0.1
The character of the moulding compound shown in the table 8 is shown in Table 9.
The physical property data of table 9: embodiment 5 and Comparative Examples 6
5 6 (Comparative Examples)
HDT-ASTM-GLB-MTV Texturing temperature, 1.82MPa (ASTM) 47.9 50.9
HDT-ISO-GLB-MTV Texturing temperature, flat board, 1.8MPa (ISO) 46 48.15
HDT-ISO-GLB-MTV Texturing temperature, 0.456MPa (ISO) 128.95 133.05
TENS-ASTM-GLB-FI-MTV Tensile modulus (ASTM) MPa 2830 2920
TENS-ASTM-GLB-FI-MTV Tensile stress at yield (ASTM) MPa 58 59.1
TENS-ASTM-GLB-FI-MTV Tensile stress at break (ASTM) MPa 37.7 23.2
TENS-ASTM-GLB-FI-MTV Surrender tensile elongation (ASTM) 3.4 3.3
TENS-ASTM-GLB-FI-MTV Tensile fracture elongation rate (ASTM) 212.8 101.5
TENS-ISO-GLB-FIL-MTV Tensile modulus (ISO) MPa 2507.6 2827.6
TENS-ISO-GLB-FIL-MTV Tensile stress at yield (ISO) MPa 55.96 56.54
TENS-ISO-GLB-FIL-MTV Tensile stress at break (ISO) MPa 55.6 53.46
TENS-ISO-GLB-FIL-MTV Tensile strain at yield (ISO) 3.1 2.94
TENS-ISO-GLB-FIL-MTV Fracture tension strain (ISO) 3.63 13.96
IZOD-ASTM-GLB-MTV Notched izod impact strength (ASTM) ,-40 ℃, 2LBF/FT J/m 30.1 36.8
IZOD-ASTM-GLB-MTV Notched izod impact strength (ASTM) ,-30 ℃, 2LBF/FT J/m 30.1 38.9
MVR-ISO-GLB-MTV MVR,250℃,5Kg,240s(ISO) cm 3/10 min 127.5 52
MVR-ASTM-GLB-MTV MVR,250℃,5Kg,360s (ASTM) cm 3/10 min 137 54.8
MV M-ISO-GLB-MTV Apparent viscosity (App.Viscosity) @ 644.50 apparent shear rates (App shear rate) @1/s; 250 ℃ Pa-s 145.1 300
Comparison shows that between the embodiment 5 and 6 can use PET deutero-PBT to obtain the character of suitable moulding compound.Can think that the tensile modulus under these situations equates in the experimental error limit of this test.The value of tensile fracture elongation rate also is such.Have that ' heat-drawn wire (HDT) of the composition of PET deutero-PBT ' is than low 2-4 ℃ of the heat-drawn wire of the composition with pure PBT.
Compare embodiment 5 few energy that consume about 30MJ/kg moulding compound with Comparative Examples.Therefore, embodiment 5 is than embodiment 6 moulding compound of Energy Efficient more.
Embodiment 7 and Comparative Examples 8
The purpose of these embodiment has three.At first, these embodiment show and can prepare useful moulding compound by PET deutero-PBT.The character of these compositions is suitable with character derived from the pure PBT of dimethyl terephthalate (DMT).The second, these embodiment also confirm, comprise Resins, epoxy and PET deutero-PBT formulation character with comprise Resins, epoxy and suitable derived from the character of the formulation of the pure PBT of DMT.The 3rd, compare with PBT based on DMT, consume more a spot of energy when producing these embodiment.The energy here is meant employed non-renewable energy when the preparation moulding compound.It comprises that all components to system carries out (cradle to grave) energy spectrometer from start to finish, and calculates their needed total energies of preparation.Shown in all embodiment in, this energy difference only is owing to using PET deutero-PBT or using the PBT based on DMT to cause.Other all compositions remain unchanged, so their contribute energy in whole composition can be ignored.
Embodiment 7 and 8 composition are as shown in table 10.
Table 10: ' PET deutero-PBT ' composition and Comparative Examples with various additives
Component Unit 7 8 (Comparative Examples)
GE PBT 315(1.2iv) 28.6579
PET deutero-PBT (1.2iv) 28.6579
Hindered phenol stabilizer 0.08 0.08
ERL4221 0.05 0.05
SEENOX 412S 0.4 0.4
Irgaphos 168 0.3 0.3
Lexan 4701R 14 14
PC100 6.29 6.29
Lexan ML8199-111N 34.6321 34.6321
Phosphorous acid 45% 0.05 0.05
UV A 234 0.54 0.54
PC 80%/EMA-GMA 20 % enriched materials 15 15
The character of the moulding compound shown in the table 10 is shown in the following table 11.
The physical property data of table 11: embodiment 7 and Comparative Examples 8
Test Unit 7 8 (Comparative Examples)
HDT-ASTM-GLB-MTV Heat-drawn wire, 1.82 MPa (ASTM) 82 86.5
HDT-ISO-GLB-MTV Heat-drawn wire, flat board, 1.8MPa (ISO) 79.15 82
HDT-ASTM-GLB-MTV Heat-drawn wire, 0.455 MPa (ASTM) 95.9 104
HDT-ISO-GLB-MTV Heat-drawn wire, 0.456 MPa (ISO) 92.55 102.1
TENS-ASTM-GLB-FI-MTV Tensile modulus (ASTM) MPa 2420 2400
TENS-ASTM-GLB-FI-MTV Tensile stress at yield (ASTM) MPa 62.1 59.1
TENS-ASTM-GLB-FI-MTV Tensile stress at break (ASTM) MPa 43.6 58.9
TENS-ASTM-GLB-FI-MTV Surrender tensile elongation (ASTM) 4.4 4.5
TENS-ISO-GLB-FIL-MTV Tensile modulus (ISO) MPa 2465.8 2556.2
TENS-ISO-GLB-FIL-MTV Tensile stress at yield (ISO) MPa 59.72 59.92
TENS-ISO-GLB-FIL-MTV Tensile stress at break (ISO) MPa 52.6 57.84
TENS-ISO-GLB-FIL-MTV Tensile strain at yield (ISO) 3.96 4.18
TENS-ISO-GLB-FIL-MTV Fracture tension strain (ISO) 122.42 128.52
ZOD-ASTM-GLB-MTV Notched izod impact strength (ASTM) ,-40 ℃, 2LBF/FT J/m 94.5 97.5
IZOD-ASTM-GLB-MTV Notched izod impact strength (ASTM) ,-30 ℃, 2LBF/FT J/m 89.5 98.7
IZOD-ISO-GLB-MTV Notched izod impact strength (ISO) ,-40 ℃, 5.5J kJ/m 2 5.27 9.05
IZOD-ISO-GLB-MTV Notched izod impact strength (ISO) ,-30 ℃, 5.5J kJ/m 2 7.26 10.07
MVR-ISO-GLB-MTV MVR,250℃,5Kg, 240s(ISO) cm 3/10 min 13 12.5
MVR-ASTM-GLB-MTV MVR,250℃,5Kg, 360s(ASTM) cm 3/10 min 13.8 12.2
MV M-ISO-GLB-MTV Biao Guanniandu @644.50 apparent shear rate @ 1/s; 250 ℃ Pa-s 755.3 787.9
Comparison shows that between the embodiment 7 and 8 can obtain the suitable moulding compound of character with PET deutero-PBT.Have that ' heat-drawn wire (HDT) of the composition of PET deutero-PBT ' is than low 3-9 ℃ of the heat-drawn wire of the composition with pure PBT.Compare with Comparative Examples, embodiment 7 few energy that consume are about 8.7MJ/kg moulding compound.Therefore, the composition of embodiment 7 is than the moulding compound of Energy Efficient more of compositions for use among the embodiment 8.
Embodiment 9-13
The purpose of these embodiment is to produce the PET deutero-PBT multipolymer with different copolymer monomer content.Known, that fusing point shows one's usefulness greater than 200 ℃ material engineering thermoplastics type's character.Therefore, below all embodiment all show, can synthesize useful PET deutero-PBT multipolymer (fusing point is greater than 200 ℃).The method of producing these materials is as follows.Embodiment 9-13 has shown different PET-deutero-PBT resin used in the composition of embodiment 14-18.Table 12 has been listed the raw material that is used for synthetic PET-deutero-PBT.
Table 12: the details that are used for the material quantity of embodiment 9-13 (PET deutero-PBT)
Figure A20078001125600491
Be used to make the preparation method of PET-deutero-PBT
Pilot plant method (BDO: PET=2.9: 1)
The polybutylene terephthalate random copolymers of modification in helical reactors (heliconereactor) on a large scale by polyethylene terephthalate component goods.Helical reactors be 40 liters, and the paired screw-blade that is oppositely arranged of particular design is installed, this blade has the distortions of 270 degree; Constitute by 316SS with 16g polishing finish paint.Blade speed can be 1~65rpm.Agitator is connected to operates in 230/460VAC, on the 7.5HP Constant TorqueInverter Duty Motor of 3PH and 60Hz.These agitators increase to the molecular weight of polymer melt good surface-area are provided.Also this helical reactors can be designed to have the overhead product condenser, with the vapour condensation in glycolysis, transesterification reaction (if any) and the polymerization stage.
25lbs (11.4kgs) recovery PET pellet and 35lbs (15.9kgs) butyleneglycol (mol ratio 2.9: 1) are charged in the helical reactors.Also the TPT catalyzer with 4.6ml (100ppm is in Ti) is added in the reaction mixture.The temperature of heated oil (for helical reactors) is set to 250 ℃.Agitator speed is set to peaked 67%.Butyleneglycol was refluxed in reactor 2 hours.Should be appreciated that the design of overhead product condenser system can not make the butyleneglycol total reflux.As a result, about 5lbs (2.3kgs)~10lbs (4.5kgs) butyleneglycol of initial period generation can not reflux.After this butyleneglycol of Chan Shenging can return in the reactor by total reflux.
For polymerization stage (being also referred to as ' polymerization stage ' in this application), vacuum is applied in the helical reactors, stop butyleneglycol being back in the reactor.It is peaked 60% that the speed of agitator is set to, and the target current of motor is 3.5 amperes.Agitator speed is as shown in table 3 with the relation that the growth of polymericular weight changes.Make system pressure be reduced to 0.5Torr (0.066kPa) by vacuum blower (vacuum blower).React till polymkeric substance reaches its 3rd growth.Enter the 3rd growth reaction is stopped, polymkeric substance is prolonged (cast in blobs) with the glue drip.Make the product drying then, and be ground into pellet.
Analyze and the result
Carry out following test: iv and measure on polymer samples, NMR analyzes and dsc analysis.
Table 13: poor formula scanning calorimetric (DSC), limiting viscosity (IV) and the composition data that obtain through the NMR analysis of embodiment 9-13
Figure A20078001125600501
*With respect to the total amount of 100 equivalents, two pure and mild 100 normal diacid groups, the equivalents of residue ((m-phthalic acid group+DEG group+EG group) x2)
Embodiment 14-18
As follows, in these embodiments, preparation contains the composition of the PET-deutero-PBT of embodiment 9-13, and it is estimated.
Use composition respectively from the synthetic embodiment 14-18 of resin of embodiment 9-13.The formulation of embodiment 14-18 is as shown in table 14 below.
Table 14: the composition of embodiment 14-18
Component Unit Embodiment 14 Embodiment 15 Embodiment 16 Embodiment 17 Embodiment 18
PET deutero-PBT (content) with different comonomers 43.69 43.69 43.69 43.69 43.69
New LDPE (film grade) 1.0 1.0 1.0 1.0 1.0
Glass fibre 30.0 30.0 30.0 30.0 30.0
Brominated epoxy resin 16.0 16.0 16.0 16.0 16.0
IRGAPHOS 168 0.05 0.05 0.05 0.05 0.05
PETS 0.10 0.10 0.10 0.10 0.10
NaST 0.10 0.10 0.10 0.10 0.10
Lotader AX8900 3.0 3.0 3.0 3.0 3.0
Antioxidant 60 0.06 0.06 0.06 0.06 0.06
Hytrel 4056as F121 3.0 3.0 3.0 3.0 3.0
The character of the moulding compound shown in the table 14 is listed in the table below in 15.
Table 15: the physical property data of embodiment 14-18
Figure A20078001125600511
Figure A20078001125600521
*With respect to the total amount of 100 equivalents, two pure and mild 100 normal diacid groups, the equivalents of residue ((m-phthalic acid group+DEG group+EG group) x2)
Known, because business reason, HDT (at 0.455MPa) is useful greater than 180 ℃ moulding compound.Moulding compound shown in the embodiment 18 uses PET deutero-PBT preparation, its total copolymerization monomer content is the 17.2 normal m-phthalic acid groups that are selected from, ethylene glycol group and diethylene glycol group, and the residue of combination, based on the total amount of 100 equivalents, two pure and mild 100 equivalent diacid groups in the polybutylene terephthalate random copolymers of modification.HDT (at the 0.455MPa) value of observing said composition is 183.4 ℃.Notice that also interestingly the tensile modulus of all embodiment shown in the table 15 all has approximately uniform value.This proof, it is very little to the tensile modulus influence of moulding compound to have higher co-monomer content at PET deutero-PBT.Equally, these results show, and are as implied above, even total have up to 17.2 normal copolymerization monomers, also can make the moulding compound that contains PET-deutero-PBT with useful quality.
Though describe the present invention in detail, also have other variant with reference to some preferred scheme.Therefore, the explanation of the spirit and scope of the claims scheme that should be not limited to comprise in this application and put down in writing.

Claims (38)

1. moulding compound, it comprises:
(a) the polybutylene terephthalate random copolymers of the modification of 40~99.99wt%, its (1) derived from the polyethylene terephthalate component that is selected from polyethylene terephthalate and pet copolymer and (2) have at least a derived from described polyethylene terephthalate component residue and
(b) the carboxyl-reactive component of 0.01~20wt%;
(c) impact modifier of 0~25wt%;
(d) ultra-violet stabilizer of 0~1wt%;
(e) flame retardance element of 0~30wt%; With
(f) releasing agent of 0~1wt%,
The total amount that the polybutylene terephthalate random copolymers of wherein said modification, carboxyl-reactive component, ultra-violet stabilizer, flame retardance element, releasing agent and optional at least a additive exist is 100wt%.
2. the composition of the material of claim 1, wherein said residue derived from the polyethylene terephthalate component is selected from ethylene glycol group, diethylene glycol group, m-phthalic acid group, antimony containing compounds, germanium-containing compound, titanium-containing compound, cobalt compound, sn-containing compound, aluminium, aluminium salt, 1,3-cyclohexanedimethanol isomer, 1,4-cyclohexanedimethanol isomer, an alkali metal salt, alkaline earth salt, P contained compound and negatively charged ion, sulfocompound and negatively charged ion, naphthalene dicarboxylic acids, 1, ammediol group, and combination.
3. the composition of the material of claim 1, wherein said at least a residue derived from the polyethylene terephthalate component comprises the mixture of ethylene glycol and diethylene glycol group.
4. the composition of the material of claim 3, wherein said residue derived from the polyethylene terephthalate component also comprises the m-phthalic acid group.
5. the composition of the material of claim 3, wherein said residue derived from the polyethylene terephthalate component also comprises and is selected from following group: 1, the cis-isomeride of 3-cyclohexanedimethanol, 1, the cis-isomeride of 4-cyclohexanedimethanol, 1, the trans-isomer(ide) of 3-cyclohexanedimethanol, 1, the trans-isomer(ide) of 4-cyclohexanedimethanol, and combination.
6. the composition of the material of claim 1, wherein said residue derived from the polyethylene terephthalate component also comprises and is selected from following group: 1, the cis-isomeride of 3-cyclohexanedimethanol, 1, the cis-isomeride of 4-cyclohexanedimethanol, 1, the trans-isomer(ide) of 3-cyclohexanedimethanol, 1, the trans-isomer(ide) of 4-cyclohexanedimethanol, and combination.
7. the composition of the material of claim 1, wherein said residue derived from the polyethylene terephthalate component is selected from the cis-isomeride of ethylene glycol group, diethylene glycol group, m-phthalic acid group, cyclohexanedimethanol, the trans-isomer(ide) of cyclohexanedimethanol, and combination.
8. the composition of the material of claim 1, wherein said at least a residue derived from the polyethylene terephthalate component comprises the mixture of ethylene glycol group, diethylene glycol group and cobalt compound.
9. the composition of the material of claim 8, wherein said at least a residue derived from the polyethylene terephthalate component also comprises the m-phthalic acid group.
10. the composition of the material of claim 1, wherein said residue derived from the polyethylene terephthalate component is selected from ethylene glycol group, diethylene glycol group and cyclohexanedimethanol group, the amount of this residue is 0.1~10mol%, based on the 100mol% glycol in the moulding compound.
11. the composition of the material of claim 10, wherein said residue derived from the polyethylene terephthalate component comprises that also its amount is the m-phthalic acid group of 0~10mol%, based on the 100mol% acid in the polybutylene terephthalate random copolymers of modification.
12. the composition of claim 1, wherein said carboxyl-reactive component are selected from polymeric carboxyl-reactive material, non-polymeric carboxyl-reactive material, and combination.
13. the composition of claim 1, wherein said composition comprise that also its amount is the ultra-violet stabilizer of 0.05~1wt%.
14. the composition of claim 1, wherein said composition also comprises ultra-violet stabilizer, described ultra-violet stabilizer is selected from Whitfield's ointment UV light absorber, benzophenone UV-absorber, benzotriazole UV absorbers, cyanoacrylate UV light absorber, and composition thereof.
15. the composition of claim 1, wherein said composition comprise that also its amount is the thermo-stabilizer of 0.05~3wt%.
16. the composition of claim 1, wherein said thermo-stabilizer are selected from phenol stabilizer, organic thioether stablizer, organic phosphorous acid ester stabilizer, hindered amine stabilizer, epoxy stabilizer and composition thereof.
17. the composition of claim 1, wherein said composition also comprises the releasing agent of 0.05~1wt%.
18. the composition of claim 1, wherein said composition also comprises releasing agent, and described releasing agent is selected from natural and synthetic paraffin, polyethylene wax, fluorocarbon, stearic acid, oxystearic acid, hydroxy fatty acid, stearylamide, ethylenebisstearamide, alkylene bis-fatty acid amides, stearyl alcohol, hexadecanol, polyvalent alcohol, polyoxyethylene glycol, Polyglycerine; Butyl stearate, pentaerythritol tetrastearate, the polyol ester of lipid acid, the macrogol ester of lipid acid, silicone oil, the functional equivalent material of aforementioned substances, and the mixture of any aforementioned substances.
19. the composition of claim 1, wherein said composition also comprises impact modifier, and described impact modifier is selected from methacrylic ester-Afpol, acrylic elastomer, acrylonitrile-styrene-acrylic ester rubber, high grafting rubbers acrylonitrile-butadiene-styrene (ABS), acrylate-olefin copolymer and combination thereof.
20. the composition of claim 19, the amount that wherein said impact modifier exists is 1wt% at least.
21. the composition of the material of claim 1, the polybutylene terephthalate random copolymers of wherein said modification be derived from 1 of biomass derived, the 4-butyleneglycol.
22. the composition of the material of claim 1 is wherein made the CO of the composition of goods by it 2Reduce index and be 0.06kg at least.
23. the composition of claim 1, wherein said composition also comprise can be with the material of at least 1~10 ℃ of the heat-drawn wire increases of described composition.
24. the composition of claim 23, wherein said material are selected from talcum, nanoparticle, poly-(tetrafluoroethylene), clay, the mica with particulate, and combination.
25. the composition of claim 1, wherein said composition is compared with the composition made from PBT, melt volume speed height at least 10%, described melt volume speed record with 240 seconds the residence time and 2.1mm aperture with 5kgf at 250 ℃ according to ISO 1133 methods on pellet.
26. the composition of claim 1, wherein said composition is compared with the composition of being made by the PBT rather than the PBT random copolymers of monomer derived, melt volume speed is high by 10%~80%, and described melt volume speed records with 240 seconds the residence time and 2.1mm aperture with 5kgf at 250 ℃ according to ISO 1133 methods on pellet.
27. the composition of claim 1, the heat-drawn wire of wherein said composition is at least 180 ℃, and described heat-drawn wire records at 0.455MPa according to ASTM D648 standard.
28. the composition of claim 1, the monomer total content that is selected from ethylene glycol, m-phthalic acid group and diethylene glycol group of wherein said composition is for greater than 0 and be less than or equal to 17 normal residues, described residue is selected from m-phthalic acid group, ethylene glycol group and diethylene glycol group, and combination, based on the total amount of 100 normal two pure and mild 100 normal diacid groups in the polybutylene terephthalate random copolymers of modification.
29. the composition of claim 1, the monomer total content that is selected from ethylene glycol, m-phthalic acid group and diethylene glycol group of the polybutylene terephthalate multipolymer of wherein said modification is for greater than 0 and be less than or equal to 23 normal residues, described residue is selected from m-phthalic acid group, ethylene glycol group and diethylene glycol group, and combination, based on the total amount of 100 normal two pure and mild 100 normal diacid groups in the polybutylene terephthalate random copolymers of modification.
30. moulding compound, it comprises:
(a) the polybutylene terephthalate random copolymers of the modification of 70~99.99wt%, its (1) is derived from the polyethylene terephthalate component that is selected from polyethylene terephthalate and pet copolymer, and (2) have at least a derived from described polyethylene terephthalate component residue and
(b) the carboxyl-reactive component of 0.01~20wt%;
(c) impact modifier of 0~25wt%;
(d) ultra-violet stabilizer of 0~1wt%;
(e) flame retardance element of 0~30wt%; With
(f) releasing agent of 0~1wt%,
The total amount that the polybutylene terephthalate random copolymers of wherein said modification, carboxyl-reactive component, ultra-violet stabilizer, flame retardance element, releasing agent and optional at least a additive exist is 100wt%.
31. moulding compound, it comprises:
(a) first polyester components, its limiting viscosity is 0.5~1.0, and comprise: the polybutylene terephthalate random copolymers of the modification of 20~49.9wt%, described random copolymers (1) is derived from the polyethylene terephthalate component that is selected from polyethylene terephthalate and pet copolymer, and (2) have at least a derived from described polyethylene terephthalate component residue and
(b) second polyester components, its limiting viscosity is 1.1~1.4, and comprise: the polybutylene terephthalate random copolymers of the modification of 20~49.9wt%, described random copolymers (1) is derived from the polyethylene terephthalate component that is selected from polyethylene terephthalate and pet copolymer, and (2) have at least a derived from described polyethylene terephthalate component residue and
(b) the carboxyl-reactive component of 0.01~20wt%;
The total amount that wherein said first polyester components, second polyester components and optional at least a additive exist is 100wt%.
32. the formation method for compositions, it comprises the component melts blend with the composition of claim 1.
33. the method for claim 32 comprises that also the composition to described melt blending carries out moulding, extrudes or molding.
34. the method for claim 32 comprises that also the composition to described melt blending carries out molding.
35. comprise the goods of the composition of claim 1.
36. comprise the moulded product of the composition of claim 30.
37. the formation method for compositions, it comprises the component melts blend with the composition of claim 31.
38. comprise the moulded product of the composition of claim 31.
Composition, it comprises:
(a) first polyester components, its limiting viscosity is 0.5~1.0, and comprise: the polybutylene terephthalate random copolymers of the modification of 20~49.9wt%, described random copolymers (1) is derived from the polyethylene terephthalate component that is selected from polyethylene terephthalate and pet copolymer, and (2) have at least a derived from described polyethylene terephthalate component residue and
(b) second polyester components, its limiting viscosity is 1.1~1.4, and comprise: the polybutylene terephthalate random copolymers of the modification of 20~49.9wt%, described random copolymers (1) is derived from the polyethylene terephthalate component that is selected from polyethylene terephthalate and pet copolymer, and (2) have at least a derived from described polyethylene terephthalate component residue and
(c) the carboxyl-reactive component of 0.01~20wt%;
(d) the carboxyl-reactive component of 0.01~20wt%;
(e) impact modifier of 0~25wt%;
(f) ultra-violet stabilizer of 0~1wt%;
(g) flame retardance element of 0~30wt%; With
(h) releasing agent of 0~1wt%,
The total amount that wherein said first polyester components, second polyester components, carboxyl-reactive component, impact modifier, ultra-violet stabilizer, flame retardance element, releasing agent and optional at least a additive exist is 100wt%;
Wherein said composition is compared with the composition of making based on monomeric polybutylene terephthalate homopolymer, melt volume speed height at least 10%, described melt volume speed record with 240 seconds the residence time and 2.1mm aperture with 5kgf at 250 ℃ according to the ISO1133 method on pellet;
Wherein said composition is greater than 180 ℃ in the heat-drawn wire of 0.455MPa; With
The monomer total content that is selected from ethylene glycol, m-phthalic acid group and diethylene glycol group of wherein said composition is for greater than 0 and be less than or equal to 17 normal residues, described residue is selected from m-phthalic acid group, ethylene glycol group and diethylene glycol group, and combination, based on the total amount of 100 normal two pure and mild 100 normal diacid groups in the polybutylene terephthalate random copolymers of modification.
CNA2007800112560A 2006-01-27 2007-01-25 Molding compositions containing modified polybutylene terephthalate (PBT) random copolymers derived from polyetheylene terephthalate (PET) Pending CN101410455A (en)

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US76310906P 2006-01-27 2006-01-27
US60/763,109 2006-01-27
US60/820,465 2006-07-26
US11/626,105 2007-01-23

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104497253A (en) * 2014-12-14 2015-04-08 天津利安隆新材料股份有限公司 Polyalcohol composition
CN105014837A (en) * 2015-08-19 2015-11-04 胡承华 Release agent special for meltable fluororesin molding processing
CN105175701A (en) * 2015-09-09 2015-12-23 济南大学 Preparation method and application of PET-based multi-component synergetic polyol
CN113966358A (en) * 2020-05-20 2022-01-21 Sabic环球技术有限责任公司 Shaped object comprising polyester and aluminium

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104497253A (en) * 2014-12-14 2015-04-08 天津利安隆新材料股份有限公司 Polyalcohol composition
CN104497253B (en) * 2014-12-14 2017-08-11 天津利安隆新材料股份有限公司 A kind of glycol composition
CN105014837A (en) * 2015-08-19 2015-11-04 胡承华 Release agent special for meltable fluororesin molding processing
CN105175701A (en) * 2015-09-09 2015-12-23 济南大学 Preparation method and application of PET-based multi-component synergetic polyol
CN113966358B (en) * 2019-05-21 2023-12-05 Sabic环球技术有限责任公司 Shaped object comprising polyester and aluminium
CN113966358A (en) * 2020-05-20 2022-01-21 Sabic环球技术有限责任公司 Shaped object comprising polyester and aluminium

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