CN101370873A - Annular or tubular shaped articles of novel polymer blends - Google Patents

Annular or tubular shaped articles of novel polymer blends Download PDF

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Publication number
CN101370873A
CN101370873A CNA2006800526951A CN200680052695A CN101370873A CN 101370873 A CN101370873 A CN 101370873A CN A2006800526951 A CNA2006800526951 A CN A2006800526951A CN 200680052695 A CN200680052695 A CN 200680052695A CN 101370873 A CN101370873 A CN 101370873A
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tubular type
type goods
goods
formula
aryl
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罗伊·R·奥德尔
卡皮尔·C·谢思
迈克尔·S·多纳文
马克·A·桑纳
拉詹德拉·K·辛格
罗伯特·R·加卢奇
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SABIC Global Technologies BV
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General Electric Co
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Abstract

The present invention is directed to a tubular article of manufacture in an annular or tubular shape having an outer diameter, an inner diameter and a length comprising one or more materials selected from the group consisting of: a) an immiscible blend of polymers comprising one or more polyetherimides, having more than one glass transition temperature wherein the polyetherimide has a glass transition temperature greater than 217 DEG C; b) a miscible blend of polymers, comprising one or more polyetherimides, having a single glass transition temperature greater than 180 DEG C; or, c) a single polyetherimide having a glass transition temperature of greater than 247 DEG C.

Description

The ring-type of novel blend polymer or tubular body
Related application
The application is the continuation application of following each U.S. Patent application: with the USSN 11/228728 that the name of Gallucci etc. was submitted on September 16th, 2005, title is ＂ Flame RetardantPolysulfone Blends ＂; With the USSN11/228729 that the name of Gallucci etc. was submitted on September 16th, 2005, title is ＂ Flame Retardant Polymer Blends ＂; With the USSN 11/229455 that the name of Gallucci etc. was submitted on September 16th, 2005, title is ＂ Improved Polyaryl EtherKetone Polymer Blends ＂; And the USSN 11/314542 that submits on December 21st, 2005 with the name of Gallucci etc., title is ＂ Annular or Tubular Shaped Articles of NovelPolymer Blends ＂.
Technical field
The present invention relates to have length, the tubulose or the ring-type goods of internal diameter and external diameter, these goods comprise at least a Tg and are higher than about 180 ℃ polyetherimide polymer.
Background technology
Use in the end-use application of ring-type goods at various requirement, exist having good chemical-resistant and having the demand of permission at the material of the medium-term and long-term hot properties that uses of hot environment.
Because of the current and continuous rise of oil price, exist demand to the metal substitute parts in the vehicle, the gross weight that these metal substitute parts can alleviate vehicle also provides the life-time service performance of metal simultaneously.Fluid under the hood and gas transfer device have increased the weight of vehicle, have reduced the gasoline mileage of vehicle, have caused the proprietary unnecessary spending of vehicle.Available lighter plastic components replaces water cooler and coolant member and pipeline and the conduit made from metal, causes the minimizing of manufacturing cost and the increase of fuel efficiency.This type of plastic components needs ability to be higher than the temperature of the boiling point of water for a long time, and has the chemical-resistant to the general-utility car refrigerant.
Supply with the field at petroleum prospecting and oil, exist to can be when the high temperature work and can be exposed to the pipe of extensively multiple organic substance and the demand of tubular body.In the suction operation process of oil, usually see hot water and/or steam are poured in the oil well, thereby oil is replaced to the oil well surface.In these situations, exist the pipe or the demand of line coating, this coating has the good high-temperature characteristic and to the chemical-resistant of the organic compound of the broad range found in the oil.
In high thermopolymer field, exist lasting demand to the material that can in hot environment and application, use.Especially, in multiple technologies, exist the pipe of improvement and the height requirement of ring-type goods.
Summary of the invention
The present invention relates to have external diameter, internal diameter and length in the form of a ring or piped tubular type goods, these goods comprise one or more materials that is selected from down group: the blend polymer that a) comprises the unmixability of one or more polyetherimides, it has more than a second-order transition temperature, and the second-order transition temperature of wherein said polyetherimide is greater than 217 ℃; B) comprise the blend polymer of the compatibility of one or more polyetherimides, it has single second-order transition temperature greater than 180 ℃; Perhaps c) single polyetherimide, its second-order transition temperature is greater than 247 ℃.
The present invention also relates to tubular type goods as detailed above, wherein polyetherimide has hydrogen atom/carbon atom ratio about 0.4～0.85, and/or be substantially free of the benzylic proton.
The invention still further relates to aforesaid tubular type goods, wherein the external diameter of these goods is basic identical on whole length.
Embodiment
For the present invention, term ＂ manages (pipe) ＂, ＂ pipeline (tubing) ＂ and ＂ flexible pipe (hose) ＂ are meant the tubulose or the ring-type member of fixed length or random length, and it can make and can comprise tubulose member's wall construction (i.e. circle, side, octagon etc.) and/or fixed length tubulose member's end structure by differing materials.
The ratio ＂ of term ＂ number of hydrogen atoms/carbonatoms is that number of hydrogen atoms in polymkeric substance or the repeating unit (monomer) that constitutes polymkeric substance is to the ratio of carbonatoms.
The definition of " benzylic proton " is well known in the art, according to the present invention, " benzylic proton " comprises that at least one direct chemical is connected to the aliphatic carbon atom at least one aromatic ring (as phenyl or phenyl ring), and wherein this aliphatic carbon atom has the proton that at least one is attached thereto in addition.
In the application's context, in fact or be substantially free of the benzylic proton, meaning polymkeric substance such as polyimide sulfones product has less than about 5% mole, have in some embodiments less than about 3% mole, have in other embodiments less than about 1% mole and be derived from the structural unit that contains the benzylic proton.Do not contain benzylic proton (being also referred to as benzylic hydrogen), mean the polyetherimide goods and have 0% mole and be derived from the monomer that contains benzylic proton or benzylic hydrogen and the structural unit of end-capping reagent.The amount of benzylic proton can be measured by common chemical analysis according to chemical structure.
The present invention relates to have external diameter, internal diameter and length in the form of a ring or piped tubular type goods, it comprises one or more materials that is selected from down group: a) unmixability blend polymer, it comprises one or more polyetherimides, have more than a second-order transition temperature, wherein the second-order transition temperature of this polyetherimide is greater than 217 ℃; B) compatibility blend polymer comprises one or more polyetherimides, has single second-order transition temperature greater than 180 ℃; Perhaps c) single polyetherimide, it has the second-order transition temperature greater than 247 ℃.
The tubular type goods can also comprise polyetherimide, and the ratio of the number of hydrogen atoms/carbonatoms of this polyetherimide is about 0.4～0.85.The ratio of number of hydrogen atoms/carbonatoms can also be about 0.50～0.80,0.55～0.75 or 0.60～0.70.
The tubular type goods can also comprise the polyetherimide that is substantially free of the benzylic proton.
For physical size, ring-type goods of the present invention can have external diameter, internal diameter and length.The ring-type goods can have the external diameter of constant or approximately constant and the internal diameter of constant or approximately constant.As selection, external diameter and/or internal diameter can change simultaneously or individually in the total length of ring-type goods.The ring-type goods can have thickness, are defined as external diameter minus internal diameter, its less than, more than or equal to inside radius.
Tubular type goods of the present invention are the coating on the moulded products also, and this moulded products has the composition that is different from coating.For example, described goods can be the form of the coating on the solid wire, perhaps as the coating on the solid cable core.In an alternative embodiment, described ring-type goods can be outside surfaces complete hollow or that coat hollow piece.
Raw material
The representative example that is applicable to polymkeric substance, multipolymer and the blend of ring-type goods of the present invention is listed below:
A. Sulfone base polymer or mixture; Silicone copolymers; And come from the poly-aryl ester of Resorcinol The high-tg polymer blend
Disclosed herein is the electrical connectors (electrical connector) that comprises blend polymer, wherein the part or all of surface of this blend polymer scribbles coating material, wherein the composition of this coating material is different from described blend polymer, and wherein said blend polymer comprises: a) first resin, its be selected from polysulfones (PSu), poly-(ether sulfone) (PES) and poly-(phenylate sulfone) (PPSU), have high glass-transition temperature (Tg 〉=180 ℃); B) silicone copolymers is as siloxanes polyimide or siloxanes polycarbonate; And optional c) Resorcinol class polyarylester, wherein this blend has unexpected low heat release value (heatrelease value).
1. The polysulfones of blend, polyethersulfone and Poly-s 179 component
Can be used for the polysulfones in the goods described herein, poly-(ether sulfone) and gather (phenylate sulfone) being for example thermoplastic resin described in the United States Patent (USP) 3634355,4008203,4108837 and 4175175.
Polysulfones, poly-(ether sulfone) and poly-(phenylate sulfone) linear thermoplastic polymer have a lot of attracting characteristics, for example high thermal resistance, good electrical properties and good stability to hydrolysis.
Polysulfones comprises the repeating unit with structure shown in the following formula I:
Figure A200680052695D00171
R is an aryl in the formula, and it comprises carbon-to-carbon singly-bound, carbon-oxygen-carbon bond or carbon-to-carbon and carbon-oxygen-carbon single bond, the main polymer chain of described singly-bound component part.
Poly-(ether sulfone) comprises in main polymer chain as shown in the formula not only having ether connection base but also have the repeating unit that sulfone connects base shown in the II:
Figure A200680052695D00172
In the formula Ar and Ar ' be can be identical or different aryl.Ar and Ar ' can be identical or different.When the two was phenylene as Ar and Ar ', this polymkeric substance was commonly referred to as poly-(phenylate sulfone).When the two was arylidene as Ar and Ar ', this polymkeric substance was commonly referred to as poly-(arylene ether sulfone).The number of sulfone connection base is connected basic number with ether can be identical or different.The number of demonstration sulfone connection base is different from the exemplary configurations of the basic number of ether connection shown in following formula (III):
Figure A200680052695D00173
In the formula Ar, Ar ' and Ar ＂ be can be identical or different aryl.Ar, Ar ' and Ar ＂ can be identical or different, and for example, Ar and Ar ' can be phenylene and Ar ＂ can be two (1, the 4-phenylene) sec.-propyl.
Commercial multiple polysulfones and poly-(the ether sulfone) of obtaining comprises the polycondensation product of dihydroxy diphenylsulphone and dichloro diphenyl sulfone, reaches the polycondensation product of dihydroxyphenyl propane and/or bis-phenol and dichloro diphenyl sulfone.The example of commercial available resin comprises and derives from Solvay, the RADEL R of Inc., RADEL A and UDEL, and the ULTRASONE that derives from BASF Co..
The method for preparing polysulfones and poly-(ether sulfone) is well-known, and some suitable methods have sufficient description in the prior art.Two kinds of methods known to those skilled in the art are carbonic ether method and alkali metal hydroxide method.In the alkali metal hydroxide method, make the double alkali metal salt of dihydric phenol, under the condition of substantially anhydrous and dipolar aprotic solvent existence, contact with the dihalo benzoid compound.The carbonic ether method, wherein dihydric phenol and dihalo benzoid compound heat with for example yellow soda ash or sodium bicarbonate and second alkaline carbonate or supercarbonate, are disclosed in equally in prior art such as the United States Patent (USP) 4176222.As selection, polysulfones and poly-(ether sulfone) can be by various known any method preparations in the prior art.
The molecular weight of polysulfones or poly-(ether sulfone), with reduced viscosity (reduced viscosity) data representation in suitable solvent such as methylene dichloride, chloroform, N-Methyl pyrrolidone, can be for more than or equal to about 0.3dl/g, more specifically be more than or equal to about 0.4dl/g, and be no more than about 1.5dl/g usually.
In some situation, the weight-average molecular weight of polysulfones or poly-(ether sulfone) can be for about 10000～100000, and it utilizes ASTM method D5296 by gel permeation chromatography.Polysulfones and poly-(ether sulfone) can have about 180～250 ℃ second-order transition temperature in some situation.When polysulfones, poly-(ether sulfone) and poly-(phenylate sulfone) and resin alloy as herein described, polysulfones, poly-(ether sulfone) and poly-(phenylate) sulfone can have more than or equal to about 180 ℃ second-order transition temperature (Tg).Polysulfone resin is further described among the sulfone plastics standard specifications ASTM method D6394.
In some situation, polysulfones, poly-(ether sulfone) and gather (phenylate sulfone) and blend thereof can have and be less than or equal to hydrogen atom/carbon atom ratio (H/C) of about 0.85.Cast aside theoretical constraint, carbon content is higher than the polymkeric substance that hydrogen richness promptly has low hydrogen atom/carbon atom ratio, usually has higher FR performance.These polymkeric substance have lower fuel value, discharge less energy when burning.They can also stop burning to form the trend of adiabatic char layer between polymer fuel and ignition source.Do not rely on any concrete mechanism or the mode of action, observed and thisly have low H/C ratio of polymer and have excellent flame.In some situation, the H/C ratio can be less than or equal to 0.75, also can be less than 0.65.In other situation, preferred H/C ratio is more than or equal to about 0.4, obtaining having the polymer architecture of enough flexible linking groups, and then realizes melt processability.The H/C ratio of resulting polymers or multipolymer can be by its chemical structure, determines by calculating the carbon that is independent of in the chemical repeat unit outside any other atom and the number of hydrogen atom.
In blend polymer, the amount existence that polysulfones, poly-(ether sulfone) and poly-(phenylate sulfone) and blend thereof can about 1～99% weight is based on the gross weight of blend polymer.In this scope, the amount of polysulfones, poly-(ether sulfone) and poly-(phenylate sulfone) and composition thereof can be in particular more than or equal to about 50% weight for more than or equal to about 20% weight, more specifically is more than or equal to about 70% weight.It will be understood by those of skill in the art that polysulfones, poly-(ether sulfone) and poly-(phenylate sulfone) and composition thereof,, can about 1～99% weight, the particularly any real number between 1～70% weight exist by the weight percentage of blend polymer gross weight.
2. Mix the silicone components of thing
Silicone copolymers comprises any silicone copolymers of effective raising composition exothermicity.In some situation, can use the silicone copolymers of polyetherimide, polyetherimide sulfone, polysulfones, poly-(phenylate sulfone), poly-(ether sulfone) or poly-(phenylate).In some situation, siloxane polyetherimide multipolymer or siloxanes Copolycarbonate can reduce heat release effectively and improve the flow velocity performance.The mixture of dissimilar silicone copolymers also is fine.In one embodiment, by the gross weight of multipolymer, silicone copolymers comprises about 5～70% weight and at the siloxanes of about 20～50% weight of other situation.
The chain length of siloxanes segment can be any effective length in the multipolymer.In some instances, this chain length can be about 2～70 siloxane repeat units.In other situation, the siloxane chain segment length can be about 5～50 repeating units.In most situations, can use dimethyl siloxane.
The siloxane polyetherimide multipolymer is the specific embodiments that can be used for the silicone copolymers in the blend polymer.The example of this siloxane polyetherimide multipolymer is shown in United States Patent (USP) 4404350,4808686 and 4690997.In a kind of situation, the siloxane polyetherimide multipolymer can be similar to the mode that is used for polyetherimide and prepare, different is, with amine end groups organo-siloxane instead of part or whole organic diamine reactants, the amine end groups organo-siloxane of following formula IV for example, g is about 1～50 integer in the formula, more specifically is about 5～30 integer, and R ' is for having aryl, the alkyl or aryl alkyl of about 2～20 carbon atoms.
Figure A200680052695D00191
Formula IV
The siloxane polyetherimide multipolymer can comprise the organic diamine reaction of aromatics two (ether acid acid anhydride) with the following formula VII of following formula V by any method preparation known to those skilled in the art:
Figure A200680052695D00192
Formula V
In the formula T be-O-,-S-,-SO 2-or formula-O-Z-O-shown in group, wherein-O-or-two valence links of O-Z-O-group are 3,3 ', 3,4 ', 4,3 ' or 4,4 ' position, and wherein Z includes but not limited to replace or unsubstituted divalent organic group, for example: (a) have the aromatic hydrocarbon group and the halide derivative thereof of about 6～20 carbon atoms, (b) have the straight or branched alkylidene group of about 2～20 carbon atoms, (c) have the cycloalkylidene of about 3～20 carbon atoms, perhaps the divalent group of general formula VI below (d):
Figure A200680052695D00193
Formula (VI)
Q includes but not limited to be selected from following divalent group :-O-in the formula ,-S-, and-C (O)-,-SO 2-,-SO-,-C yH 2y-(y is 1～8 integer) and fluorinated derivatives (comprising perfluorinated alkylidene) thereof,
H 2N-R 1-NH 2Formula (VII)
R among its Chinese style VII 1Include but not limited to replace or unsubstituted divalent organic group as: (a) have the aromatic hydrocarbon group and the halide derivative thereof of about 6～24 carbon atoms, (b) has the straight or branched alkylidene group of about 2～20 carbon atoms, (c) has the cycloalkylidene of about 3～20 carbon atoms, perhaps the divalent group of (d) general formula VI.
The concrete aromatic dianhydride and the example of organic diamine for example are disclosed in the United States Patent (USP) 3972902 and 4455410.The example of the aromatic dianhydride of formula (XIV) comprising:
3,3-two [4-(3, the 4-di carboxyl phenyloxy) phenyl] propane dicarboxylic anhydride;
4,4 '-two (3, the 4-di carboxyl phenyloxy) phenyl ether dicarboxylic anhydride;
4,4 '-two (3, the 4-di carboxyl phenyloxy) diphenyl sulfide dicarboxylic anhydride;
4,4 '-two (3, the 4-di carboxyl phenyloxy) benzophenone dicarboxylic anhydride;
4,4 '-two (3, the 4-di carboxyl phenyloxy) sulfobenzide dicarboxylic anhydride;
2,2-two [4-(2, the 3-di carboxyl phenyloxy) phenyl] propane dicarboxylic anhydride;
4,4 '-two (2, the 3-di carboxyl phenyloxy) phenyl ether dicarboxylic anhydride;
4,4 '-two (2, the 3-di carboxyl phenyloxy) diphenyl sulfide dicarboxylic anhydride;
4,4 '-two (2, the 3-di carboxyl phenyloxy) benzophenone dicarboxylic anhydride;
4,4 '-two (2, the 3-di carboxyl phenyloxy) sulfobenzide dicarboxylic anhydride;
4-(2, the 3-di carboxyl phenyloxy)-4 '-(3, the 4-di carboxyl phenyloxy) phenylbenzene-2,2-propane dicarboxylic anhydride;
4-(2, the 3-di carboxyl phenyloxy)-4 '-(3, the 4-di carboxyl phenyloxy) phenyl ether dicarboxylic anhydride;
4-(2, the 3-di carboxyl phenyloxy)-4 '-(3, the 4-di carboxyl phenyloxy) diphenyl sulfide dicarboxylic anhydride;
4-(2, the 3-di carboxyl phenyloxy)-4 '-(3, the 4-di carboxyl phenyloxy) benzophenone dicarboxylic anhydride;
4-(2, the 3-di carboxyl phenyloxy)-4 '-(3, the 4-di carboxyl phenyloxy) sulfobenzide dicarboxylic anhydride,
And their mixture.
Except that above-mentioned siloxane diamine, the example of suitable diamines also comprises quadrol, propylene diamine, the trimethylene diamines, Diethylenetriamine, three second tetramines, hexanediamine, heptamethylene diamine, octamethylenediamine, nonamethylene diamine, decamethylene diamine, 1,12-dodecane diamines, 1, the 18-octadecamethylene diamine, 3-methyl heptamethylene diamine, 4,4-dimethyl-g diamines, 4-methyl nonamethylene diamine, 5-methyl nonamethylene diamine, 2,5-dimethyl hexanediamine, 2,5-dimethyl-g diamines, 2,2-dimethyl 1,3-propylene diamine, N-methyl-two (3-aminopropyl) amine, 3-methoxyl group hexanediamine, 1,2-two (the amino propoxy-of 3-) ethane, two (3-aminopropyl) thioether, 1, the 4-cyclohexane diamine, two (4-aminocyclohexyl) methane, mphenylenediamine, Ursol D, 2,4 di amino toluene, 2,6-diaminotoluene, m-xylene diamine, the p-Xylol diamines, 2-methyl-4,6-diethyl-1,3-phenylene-diamines, 5-methyl-4,6-diethyl-1,3-phenylene-diamines, p-diaminodiphenyl, 3,3 '-tolidine, 3,3 '-dimethoxy benzidine, 1,5-diaminonaphthalene, two (4-aminophenyl) methane, two (2-chloro-4-amino-3,5-diethyl phenyl) methane, two (4-aminophenyl) propane, 2,4-two (amino-tertiary butyl) toluene, two (p-amino-tert-butyl-phenyl) ether, two (p-methyl-o-aminophenyl) benzene, two (the amino amyl group of p-methyl-o-) benzene, 1,3-diamino-4-isopropyl benzene, two (4-aminophenyl) thioether, two (4-aminophenyl) sulfone, two (4-aminophenyl) ether, and comprise aforementioned two or more combination.The specific examples of siloxane diamine is 1,3-two (3-aminopropyl) tetramethyl disiloxane.In one embodiment, the diamino compounds that uses jointly with siloxane diamine is aromatic diamine, particularly between and Ursol D, alkylsulfonyl pentanoic and composition thereof.
But the organic diamine of some siloxane polyetherimide multipolymer through type VII or the amine end groups organo-siloxane of its mixture and above-mentioned formula VI react and prepare.The diamino component can with dicarboxylic anhydride reaction before physical mixed, and then form fully random multipolymer.As selection, can form block or alternating copolymer: formula VII and IV and dicarboxylic anhydride (suc as formula the dicarboxylic anhydride of V) selective reaction by such method, the polyimide segment that makes one reacts then.In another situation, the siloxanes that is used to prepare polyether imide copolymer can have acid anhydrides but not the amine end functional groups.
In a kind of situation, the siloxane polyetherimide multipolymer can be the siloxane polyetherimide multipolymer of formula VIII, in the formula T, R ' and g as mentioned above, the numerical value of b is about 5～100, Ar 1Be aryl or alkylaryl with 6～36 carbon.
Figure A200680052695D00211
Formula VIII
In some siloxane polyetherimide multipolymers, the diamine components of siloxane polyetherimide multipolymer can comprise the amine-terminated organo-siloxane of about 20～50% moles of formula IV and the organic diamine of about 50～80% moles of formula VII.In some silicone copolymers, silicone components comes from the organo-siloxane of about 25～40% moles amine or acid anhydrides end group.
The silicone copolymers component of blend polymer, by the gross weight of blend polymer, can about 0.1～40% weight or as selecting amount to exist with about 0.1～20% weight.In this scope, silicone copolymers also can about 0.1～10% even is existed with about 0.5～5.0% amount.
3. The Resorcinol of the blend arylate component of birdsing of the same feather flock together
Resorcinol class polyarylester is the polymkeric substance that comprises the arylation polyester structural units, and described arylation polyester structural units is the reaction product of dihydric phenol and aromatic dicarboxylic acid.Arylation polyester structural units to small part comprises suc as formula 1 shown in the I, and 3-dihydroxy-benzene group often is called Resorcinol or Resorcinol group in whole specification sheets.Should be appreciated that be used for Resorcinol of the present invention or Resorcinol group comprise unsubstituted 1,1 of 3-dihydroxy-benzene and replacement, the 3-dihydroxy-benzene is unless clearly state in addition.
Formula IX
In formula IX, R 2Be C when occurring independently at every turn 1-12Alkyl, C 6-C 24Aryl, C 7-C 24Alkylaryl, alkoxy or halogen; N is 0～4.
In one embodiment, Resorcinol class polyarylate resin comprises more than or equal to about 50% mole the following units, this unit comes from Resorcinol and aryl dicarboxylic acid's reaction product, perhaps Resorcinol and the reaction product that is suitable for forming aryl ester segmental aryl dicarboxylic acid's derivative such as carboxylic acid halides, carboxylicesters and carboxylate salt.
Suitable dicarboxylic acid comprises monocycle or polycyclic aromatic dicarboxylic acid.Exemplary monocycle dicarboxylic acid comprises m-phthalic acid, terephthalic acid, the perhaps mixture of m-phthalic acid and terephthalic acid.Many ring dicarboxylic acid comprise diphenyl dicarboxylic acid, phenyl ether dicarboxylic acid, and naphthalene dicarboxylic acids such as naphthalene-2,6-dicarboxylic acid.
Therefore, in one embodiment, blend polymer comprises heat stabilized polymer, and this heat stabilized polymer has the Resorcinol arylation polyester unit shown in following formula X, R in the formula 2Defined with n such as front:
Formula X
The polymkeric substance that comprises Resorcinol arylation polyester unit can prepare by interfacial polymerization.In order to prepare the polymkeric substance that comprises the Resorcinol arylation polyester unit that does not contain acid anhydrides connection base substantially, can adopt such method, wherein the first step be water and substantially not with the mixture of the miscible organic solvent of water in, mix resorcinol compound and catalyzer.Suitable resorcinol compound is suc as formula shown in the XI:
Figure A200680052695D00223
Formula XI
R in the formula 2Be C when occurring independently at every turn 1-12Alkyl, C 6-C 24Aryl, C 7-C 24Alkylaryl, alkoxy or halogen; And n is 0～4.If there is alkyl, then this alkyl is generally straight chain, side chain or cyclic alkyl, and the most often is positioned at the ortho position of two Sauerstoffatoms, although other ring position also is fine.Suitable C 1-12Alkyl includes but not limited to methyl, ethyl, n-propyl, sec.-propyl, butyl, isobutyl-, the tertiary butyl, hexyl, cyclohexyl, nonyl, decyl, and the alkyl (comprising benzyl) of aryl replacement.In specific embodiment, described alkyl is a methyl.Suitable halogen group is a bromine, chlorine, and fluorine.The numerical value of n can be 0～3 in each embodiment, can be 0～2 in some embodiments, can be 0～1 in other embodiments.In one embodiment, the Resorcinol group is the 2-methylresorcinol.In another embodiment, the Resorcinol group is 0 not replacement Resorcinol group for n wherein.This method also comprises a kind of catalyzer and reaction mixture.In each embodiment, by the integral molar quantity of acid chloride groups, the total content that described catalyzer can 0.01～10% mole exists, and exists with 0.2～6% mole total content in some embodiments.Suitable catalyzer comprises tertiary amine, quaternary ammonium salt, and quaternary alkylphosphonium salt, hexaalkylguanidium salts, and composition thereof.
Suitable dicarboxylic acid halide can comprise the aromatics dicarboxyl acyl chlorides that comes from the monocycle part, and its illustrative examples comprises m-phthaloyl chloride, p-phthaloyl chloride, the perhaps mixture of m-phthaloyl chloride and p-phthaloyl chloride.Suitable dicarboxylic acid halide can also comprise the aromatics dicarboxyl acyl chlorides that comes from many loop sections, and its illustrative examples comprises the biphenyl dimethyl chloride, phenyl ether dimethyl chloride, and naphthalene dimethyl chloride, especially naphthalene-2,6-dimethyl chloride; The mixture that also can comprise monocycle and polycyclic aromatics dicarboxyl acyl chlorides.In one embodiment, the dicarboxyl acyl chlorides comprises the mixture of m-phthaloyl chloride and/or p-phthaloyl chloride, and it is usually shown in following formula XII:
Figure A200680052695D00231
Formula XII
Can there be m-phthaloyl chloride and p-phthaloyl chloride one or both of.In some embodiments, the dicarboxyl acyl chlorides comprises that the mol ratio of isophthaloyl and p-phthaloyl chloride is the m-phthaloyl chloride of 0.25～4.0:1 and the mixture of p-phthaloyl chloride; In other embodiments, described mol ratio is about 0.4～2.5:1; In other embodiments, described mol ratio is about 0.67～1.5:1.
Dicarboxylic acid halide only provides a kind of method for preparing polymkeric substance described herein.Other method that preparation Resorcinol arylation connects base also is fine, and for example, adopts the method for dicarboxylic acid, dicarboxylic ester (particularly Acibenzolar) or dicarboxylate or the salifiable salt of part.
Also can use a kind of chain terminator (hereinafter being called end-capping reagent sometimes).The purpose of adding chain terminator is the molecular weight that restriction comprises the polymkeric substance of Resorcinol arylation polyester segment, and then the polymkeric substance with controllable molecular weight and excellent machinability is provided.Usually, chain terminator is to add under the polymkeric substance that contains the Resorcinol arylide need not to have the situation of reactive terminal group of further application.Do not having under the situation of chain terminator, the polymkeric substance that contains the Resorcinol arylide can the form in solution use, also can from solution, reclaim, be used further in the follow-up use, for example be used for existing the multipolymer of reactive terminal group (being generally hydroxyl) to form on the requirement Resorcinol arylation polyester segment.Chain terminator can be single phenolic compound, a carboxyl acyl chloride, a chloro-formic ester, perhaps two or more aforesaid combinations.Usually, the amount that chain terminator can 0.05～10% mole exists, the Resorcinol during based on single phenolic compound, and the diacid chloride during based on a carboxyl acyl chloride and/or a chloro-formic ester.
Suitable single phenolic compound comprises monocycle phenol, as phenol, and C 1-C 22The phenol that alkyl replaces, to cumyl phenol, p-tert-butylphenol, xenol; The monoether of dihydric phenol is as p methoxy phenol.The phenol that alkyl replaces comprises the substituent alkyl substituted phenol of those branched-chain alkyls with 8～9 carbon atoms, referring to United States Patent (USP) 4334053.In some embodiments, single phenols chain terminator is a phenol, to cumyl phenol, and resorcinol monobenzoate.
A suitable carboxyl acyl chloride comprises a monocyclic carboxyl acyl chloride, as Benzoyl chloride, and C 1-C 22The Benzoyl chloride that alkyl replaces, the toluene acyl chlorides, the Benzoyl chloride that halogen replaces, bromo-benzoyl chloride, cinnamyl chloride, 4-NA imide Benzoyl chloride, and composition thereof; Polycyclic one carboxyl acyl chloride, as the trimellitic acid 1,2-anhydride acyl chlorides, and naphthoyl chloride; And the mixture of monocycle and many ring one carboxyl acyl chlorides.Having at the most, the unary fatty acid muriate of 22 carbon atoms also suits.Same suitable also have functionalized unary fatty acid muriate, and for example, acrylate chloride and methacrylic chloride are suitable equally.A suitable chloro-formic ester comprises a monocyclic chloro-formic ester, and as the chloroformic acid phenylester, the phenylester that the chloroformic acid alkyl replaces, chloroformic acid be to the cumyl phenylester, chloroformic acid toluene ester, and composition thereof.
Chain terminator can mix with Resorcinol, can be included in the solution of dicarboxyl acyl chlorides, also can add in the reaction mixture after the preparation precondensate.If use a carboxyl acyl chloride and/or a chloro-formic ester as chain terminator, then they are often introduced with the dicarboxyl acyl chlorides.These chain terminators also can be added in the reaction mixture when the reaction of dicarboxyl acyl chlorides is finished or finished substantially.If use phenolic compound as chain terminator, in one embodiment, they can during reaction be added in the reaction mixture, perhaps in another embodiment, are added in the reaction mixture before Resorcinol and diacid chloride reaction beginning.If preparation contains the precondensate or the oligopolymer of hydroxy-end capped Resorcinol arylide, then can there be chain terminator, also can only there be a spot of chain terminator, to help the molecular weight of control oligopolymer.
In another embodiment, can also comprise branching agent, as trifunctional or more polyfunctional carboxyl acyl chloride and/or trifunctional or more polyfunctional phenol.If comprise this branching agent, then the amount that this branching agent usually can 0.005～1% mole is used, respectively based on employed dicarboxyl acyl chlorides or Resorcinol.Suitable branching agent comprises, for example, and trifunctional or more polyfunctional carboxyl acyl chloride, as trimesic acid three acyl chlorides, 3,3 ', 4,4 '-benzophenone tetracarboxylic acid four acyl chlorides, 1,4,5,8-naphthalenetetracarbacidic acidic four acyl chlorides or pyromellitic acid four acyl chlorides, and trifunctional or more polyfunctional phenol, as 4,6-dimethyl-2,4,6-three (4-hydroxy phenyl)-2-heptene, 4,6-dimethyl-2,4,6-three (4-hydroxy phenyl)-heptane, 1,3,5-three (4-hydroxy phenyl)-benzene, 1,1,1-three (4-hydroxy phenyl)-ethane, three (4-hydroxy phenyl)-phenylmethanes, 2,2-two [4,4-two (4-hydroxy phenyl)-cyclohexyl]-propane, 2,4-two (4-hydroxy phenyl sec.-propyl)-phenol, four (4-hydroxy phenyl)-methane, 2,6-two (2-hydroxy-5-methyl base benzyl)-4-methylphenol, 2-(4-hydroxy phenyl)-2-(2, the 4-dihydroxyphenyl)-propane, four-(4-[4-hydroxy phenyl sec.-propyl]-phenoxy group)-methane, 1,4-two [(4,4-dihydroxyl triphenyl) methyl]-benzene.The phenols branching agent can mix with resorcinol moiety earlier, and the acyl chlorides branching agent then can mix with diacid chloride.
In an one embodiment, goods comprise heat-staple Resorcinol arylation polyester, and this Resorcinol arylation polyester is by described method preparation, and are substantially free of the acid anhydrides connection base of at least two polyester chain chain links of connection.In specific embodiment, described polyester comprises the dicarboxylic acid residue of the mixture that comes from m-phthalic acid and terephthalic acid shown in the following formula XIII:
Figure A200680052695D00251
Formula XIII
R in the formula 2Be C when occurring independently at every turn 1-12Alkyl, C 6-C 24Aryl, alkylaryl, alkoxy or halogen, n are 0～4, m is more than or equal to about 5.In a lot of embodiments, n is 0, and m is about 10～300.In one embodiment, the mol ratio of isophthalic acid ester and terephthalate is about 0.25～4.0:1; In another embodiment, this mol ratio is about 0.4～2.5:1; In yet another embodiment, this mol ratio is about 0.67～1.5:1.The connection base that is substantially free of acid anhydrides means: heat described polymkeric substance in the time of 5 minutes when in about 280～290 ℃ temperature, the decrease in molecular weight amount of described polyester is in one embodiment less than 30%, in another embodiment less than 10%.
What comprise equally is the goods that contain Resorcinol arylide copolyester, and described Resorcinol arylide copolyester comprises the soft segment segment, referring to publicly-owned United States Patent (USP) 5916997.Term used herein " soft segment " is meant that some segments of polymkeric substance are to be made by the monomeric unit of non-aromatics.The monomeric unit of this non-aromatics is generally aliphatic, and known give contain this soft segment polymkeric substance with elasticity.Multipolymer comprises that those contain the multipolymer of the structural unit of following formula IX, XIV and XV:
Figure A200680052695D00261
Formula IX
Figure A200680052695D00262
Formula XIV
Figure A200680052695D00263
Formula XV
R in the formula 2Defined with n such as front; Z 1Be divalent aromatic radical; R 3C for straight chain 3-20Alkylidene group, the C of side chain 3-10Alkylidene group, perhaps C 4-10Cycloalkylidene or inferior bicyclic alkyl; And R 4And R 5Representative independently of one another:
Figure A200680052695D00264
Or-CH 2-O-
Its Chinese style XV contributes the ester of about 1～45% mole polyester to connect base.Other embodiment provides such composition, and its Chinese style XV contributes the ester of about 5～40% moles polyester to connect base in each embodiment, contributes the ester of about 5～20% moles polyester to connect base in other embodiments.Another embodiment provides such composition, wherein R 3Represent C in one embodiment 3-14Straight-chain alkyl-sub-or C 5-6Cycloalkylidene, R in another embodiment 3Represent C 3-10Straight-chain alkyl-sub-or C 6Cycloalkylidene.Formula XIV represents the aromatic dicarboxylic acid residue.Divalent aromatic radical Z among the formula XIV 1Can come from above defined suitable dicarboxylic acid residue in each embodiment, comprise 1 in some embodiments, 3-phenylene, 1,4-phenylene, 2,6-naphthylidene or aforementioned two or more combination.In each embodiment, Z 1Comprise more than or equal to about 40% mole 1 the 3-phenylene.In a lot of embodiments that contain the unitary copolyester of soft segment chain structure, the n among the formula IX is 0.
In its another embodiment, Resorcinol class polyarylester can be the block copolymerization polyestercarbonate, and it comprises the segment that contains the Resorcinol arylide with the combination of organic carbonate segment.Contain the unitary segment of Resorcinol arylide chain structure in this multipolymer and be substantially free of acid anhydrides connection base.Being substantially free of acid anhydrides connects base and mean: heating is in the time of 5 minutes during in about 280～290 ℃ temperature when described copolyester carbonic ether, and the decrease in molecular weight amount of copolyester carbonic ether is in one embodiment less than 10%, in another embodiment less than 5%.
The carbonic ether segment comprises carbonic ether and connects base, and this carbonic ether connection base forms the material of carbonic ether such as the reaction between the phosgene when coming from bis-phenol and preparation polyester carbonate copolymer.For example, Resorcinol polyarylester carbonate copolymer can comprise the reaction product of m-phthalic acid and terephthalic acid, Resorcinol and dihydroxyphenyl propane and phosgene.The Resorcinol polyester carbonate copolymer can make the minimized mode of bis-phenol dicarboxylic ester connection radix order prepare, Resorcinol and dicarboxylic acid are reacted in advance form the aryl polyester segment, make this segment and bis-phenol and carbonate reaction then, form the polycarbonate part of multipolymer.
In order to obtain best effect, the Resorcinol ester content (REC) in the Resorcinol polyestercarbonate should connect base more than or equal to about 50% mole polymkeric substance that comes from Resorcinol.In some situation, according to using, can be preferably greater than or equal about 75% mole REC, and even up to about 90 or 100% moles connection base that comes from Resorcinol.
The block copolymerization polyestercarbonate comprises that those contain alternative arylide and organic carbonate segmental block copolymerization polyestercarbonate, and is common shown in following formula XVI, R in the formula 2Defined with n such as front, R 6Be divalent organic group:
Figure A200680052695D00271
Formula XVI
The arylide segmental polymerization degree (DP) represents with m, and it is in one embodiment more than or equal to about 4, in another embodiment more than or equal to about 10, in yet another embodiment more than or equal to about 20, is about 30～150 in an embodiment again.Organic carbonate segmental DP represents with p, and it is in one embodiment more than or equal to about 2, is about 10～20 in another embodiment, is about 2～200 in yet another embodiment.Can control segmental and distribute, so that the multipolymer of the arylide segment/carbonic ether segment with any required weight ratio to be provided.Usually, arylide segmental content is about 10～95% weight in one embodiment, is about 50～95% weight in another embodiment, with respect to the gross weight of polymkeric substance.
Although the mixture of isophthalic acid ester and terephthalate is suc as formula shown in the XVI, but the dicarboxylic acid residue in the arylide segment can come from above defined any suitable dicarboxylic acid residue, perhaps the mixture of Shi Yi dicarboxylic acid residue comprises that those come from the dicarboxylic acid residue of aliphatic diacid chloride (so-called ＂ soft segment ＂ segment).In a lot of embodiments, n is 0, and the arylide segment comprises the dicarboxylic acid residue of the mixture that comes from m-phthalic acid and terephthalic acid residue, wherein the mol ratio of isophthalic acid ester and terephthalate is about 0.25～4.0:1 in one embodiment, being about 0.4～2.5:1 in another embodiment, is about 0.67～1.5:1 in yet another embodiment.
In the organic carbonate segment, each R 6Be divalent organic group when occurring independently at every turn.In a lot of embodiments, described group comprises the aromatic hydrocarbons that dihydroxyl replaces, and in the polymkeric substance more than or equal to R 6The R of group sum about 60% 6Group is the aromatics organic group, remaining R 6Group is aliphatic, alicyclic or aromatic group.Suitable R 6Group comprises metaphenylene, to phenylene, and 4,4 '-biphenylene, 4,4 '-two (3, the 5-dimethyl)-and phenylene, 2,2-two (4-phenylene) propane, 6,6 '-(3,3,3 ', 3 '-tetramethyl--1,1 '-spiral shell two [1H-indane]), and similar group, as in those and the United States Patent (USP) 4217438 with title or the disclosed dihydroxyl substituted arene corresponding base groups of chemical formula (general formula or concrete chemical formula).
In some embodiments, each R 6Be the aromatics organic group, the group shown in the formula XVII below other embodiment is:
---A 1-Y-A 2---formula XVII
Each A in the formula 1And A 2Be monocyclic divalent aryl, Y is one or two carbon atoms separate A wherein 1And A 2The bridge joint group.Free valence bond among the formula XVII is in A usually 1And A 2Go up with respect to position and contraposition between Y.R wherein 6Compound with formula XVII is a bisphenols, and for the purpose of brief introduction, term ＂ bis-phenol ＂ used herein is meant the aromatic hydrocarbons that dihydroxyl replaces sometimes.Yet, should be appreciated that and also can adopt such non-bisphenol cpd when suitable.
In formula XVII, A 1And A 2Usually represent the derivative of unsubstituted phenylene or its replacement, exemplary substituting group (one or more) is alkyl, alkenyl and halogen (particularly bromine).In one embodiment, preferred unsubstituted phenylene.A 1And A 2The two is generally phenylene, although the two also can be neighbour or metaphenylene, perhaps one for neighbour or metaphenylene another is to phenylene.
Bridge joint group Y is one or two atom separates A 1And A 2Group.In specific embodiment, an atom separates A 1And A 2The exemplary group of the type is-O--S-,-SO-,-SO 2-, methylene radical, cyclohexylmethylene, 2-[2.2.1]-two suberyl methylene radical, ethylidene, isopropylidene, new pentylidene, cyclohexylidene, cyclopentadecane fork, cyclododecane fork, Buddha's warrior attendant alkylidene, and similar group.
In some embodiments, preferably together with alkylidene group (being commonly referred to as ＂ alkylidene ＂) group.But, also comprise unsaturated group.In some embodiments, bis-phenol is 2,2-two (4-hydroxy phenyl) propane (dihydroxyphenyl propane or BPA), and wherein Y is an isopropylidene, and A 1And A 2Respectively do for oneself to phenylene.Rely on the Resorcinol that has molar excess in the reaction mixture, the R in the carbonic ether segment 6Can comprise the Resorcinol group at least in part.In other words, in some embodiments, the carbonic ether segment of formula X can comprise the Resorcinol group with at least a other dihydroxyl substituted arene combination.
Comprise diblock, three blocks and multiblock polyestercarbonate.Contain block that the Resorcinol arylide connects base and contain organic carbonic ether and be connected chemical bond between the basic block and can comprise at least a in following:
(a) between the suitable dicarboxylic acid residue of arylide and organic carbonate ester group-O-R 6Ester bond between the-O-group, for example usually shown in following formula XVIII, R in the formula 6Defined as the front:
Figure A200680052695D00291
Formula XVIII
And
(b) between the dihydric phenol residue of Resorcinol arylide group and organic carbonate ester group-(C=O)-carbonic acid ester bond between the O-group, shown in following formula XIX, R in the formula 2Defined with n such as front:
Formula XIX
In one embodiment, the copolyester carbonic ether is made up of Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock in fact, and it has carbonic ether and is connected base between Resorcinol arylide segment and organic carbonate segment.In another embodiment, the copolyester carbonic ether mainly is made up of the carbonic ether-ester-carbonate copolymer of three blocks, and it has carbonic ether and connects base between Resorcinol arylide segment and organic carbonate terminal segments.
Has copolyester carbonic ether that carbonic ether is connected base between heat-staple Resorcinol arylide segment and the organic carbonate segment normally by the oligopolymer preparation that contains the Resorcinol arylide, and described oligopolymer comprises at least one end position hydroxyl in one embodiment, comprises at least two end position hydroxyls in another embodiment.Usually, the weight-average molecular weight of this oligopolymer is about 10000～40000 in one embodiment, is about 15000～30000 in another embodiment.Heat-staple copolyester carbonic ether can be in the presence of such as catalyzer such as tertiary amines, comprises the oligopolymer of Resorcinol arylide and aromatic hydrocarbons reaction that phosgene, chain terminator and dihydroxyl replace prepares by described.
In a kind of situation, goods can comprise the blend that is selected from following resin: polysulfones, poly-(ether sulfone) and poly-(phenylate sulfone), and composition thereof; Silicone copolymers and Resorcinol class polyarylester, wherein basic for the aryl ester connection that comes from Resorcinol more than or equal to 50% mole aryl polyester connection base.
At the blend polymer that is used for preparing goods, the consumption of Resorcinol class polyarylester can change significantly according to the end-use of goods.For example, increase when being important final applications, can make the amount maximization of the polymkeric substance that contains resorcinol, with the reduction heat release and prolong the time limit of peak value heat release when goods are used for heat release or peak value heat release (peak heatrelease) time.In some situation, Resorcinol class polyarylester can be about 1～50% weight of blend polymer.Some important compositions can have the Resorcinol class polyarylester of about 10～50% weight, by the gross weight of blend polymer.
In another embodiment, the goods that comprise the following blend polymer of composition also are fine: a) polysulfones of about 1～99% weight, poly-(ether sulfone) and poly-(phenylate sulfone), perhaps its mixture;
B) silicone copolymers of about 0.1～30% weight;
C) the Resorcinol class polyarylester of about 99～1% weight, it comprises the connection base that comes from Resorcinol more than or equal to about 50% mole; And
D) metal oxide of about 0～20% weight,
Weight percentage wherein is by the gross weight of blend polymer.
On the other hand, the goods that comprise the following blend polymer of composition also are fine:
A) polysulfones of about 50～99% weight, poly-(ether sulfone), poly-(phenylate sulfone), perhaps their mixture;
B) silicone copolymers of about 0.1～10% weight;
C) the Resorcinol class polyarylate resin of about 1～50% weight, it comprises the connection base that is derived from Resorcinol more than or equal to about 50% mole;
D) metal oxide of about 0～20% weight; And
E) phosphorus-containing stabilizers of about 0～2% weight.
B. PEI, PI, PEIS and composition thereof, silicone copolymers, and Resorcinol class aryl polyester The high Tg blend of resin
Silicone copolymers (as siloxane polyetherimide multipolymer or siloxanes Copolycarbonate) and polyimide (PI), polyetherimide (PEI) or polyetherimide sulfone (PEIS) resin of high glass-transition temperature (Tg) and the combination of Resorcinol class polyarylester have the solvent resistance of unforeseeable low heat release value and raising.
The aryl polyester that comes from Resorcinol also can be to comprise the multipolymer (as Resorcinol-dihydroxyphenyl propane copolyester carbonic ether) that non-Resorcinol class connects base.In order to obtain best effect, Resorcinol ester content (REC) should be greater than about 50% mole polymkeric substance that is derived from Resorcinol and connects base.Preferred higher REC.In some situation, be preferably greater than 75% mole REC, in addition preferred up to 90% mole or 100% mole the connection base that is derived from Resorcinol.
The amount that is used for the polymkeric substance that contains resorcinol of flame retardant blends can change significantly, utilizes significant quantity to reduce heat release, increases the peak value heat release time or improves solvent resistance.In some situation, the polymkeric substance that contains resorcinol can be about 1% weight～80% weight of blend polymer.Some important composition can have 10～50% Resorcinol kind polyester.In other situation, the blend of polyetherimide or polyetherimide sulfone and high REC multipolymer can have about 150～210 ℃ single second-order transition temperature (Tg).
Resorcinol class polyarylate resin should comprise more than or equal to about 50% mole the following units, and this unit comes from Resorcinol or functionalized Resorcinol and aryl dicarboxylic acid or is suitable for forming the reaction product of aryl ester segmental dicarboxylic acid derivatives (as acid halide, carboxylicesters and carboxylate salt).
For other blend polymer, illustrate in greater detail here and can be used for Resorcinol class polyarylester of the present invention.
Between heat-staple Resorcinol arylide segment and organic carbonate segment, have at least a carbonic ether and be connected the copolyester carbonic ether of base, normally prepare by the oligopolymer that contains the Resorcinol arylide, this oligopolymer that contains the Resorcinol arylide is by each embodiment preparation of the present invention, and comprise at least one end position hydroxyl in one embodiment, comprise at least two end position hydroxyls in another embodiment.Usually, described oligopolymer has about 10000～40000 weight-average molecular weight in one embodiment, has about 15000～30000 weight-average molecular weight in another embodiment.Heat-staple copolyester carbonic ether can so prepare, even the aromatic hydrocarbons that the described oligopolymer that contains the Resorcinol arylide and phosgene, at least a chain terminator and at least a dihydroxyl replace reacts in the presence of catalyzer such as tertiary amine.
In a kind of situation, flame retardant resistance is able to improved blend polymer and comprises and be selected from following resin: polyimide, and polyetherimide, polyetherimide sulfone, and composition thereof; Silicone copolymers; And Resorcinol class aryl vibrin, wherein basic for being derived from the aryl ester connection base of Resorcinol more than or equal to 50% mole aryl polyester connection.Term ＂ polymkeric substance connects basic ＂ or ＂ polymkeric substance connects at least two kinds of monomeric reaction product that basic ＂ is defined as the formation polymkeric substance.
In some situation, it should be noted that polyimide, polyetherimide, polyetherimide sulfone and composition thereof should have and be less than or equal to hydrogen atom/carbon atom ratio (H/C) of about 0.85.Carbon content is higher than the polymkeric substance of hydrogen richness, and promptly the polymkeric substance that hydrogen atom/carbon atom ratio is low usually has improved FR performance.These polymkeric substance have lower fuel value, discharge less energy when burning.They can also stop burning to form the trend of adiabatic char layer between polymer fuel and ignition source.Do not rely on any concrete mechanism or the mode of action, observed and thisly have low H/C ratio of polymer and have excellent flame.In some situation, the H/C ratio can be less than or equal to 0.85.In other situation, preferred H/C ratio is more than or equal to about 0.4, obtaining having the polymer architecture of enough flexible linking groups, and then realizes melt processability.The H/C ratio of resulting polymers or multipolymer can be by its chemical structure, determines by calculating the carbon that is independent of in the chemical repeat unit outside any other atom and the number of hydrogen atom.
In some cases, the flame retardant polymer blend and by heat release meetings in 2 minutes of its goods of making less than about 65kW-min/m 2In other situation, peak value heat release meeting is less than about 65kW/m 2The time of peak value heat release also was that some composition reaches the favourable aspect by its goods of making greater than about 2 minutes.In other situation, can realize greater than about 4 minutes peak value heat release time.
In some compositions, polyimide, polyetherimide, polyetherimide sulfone or its mixture and silicone copolymers and the blend that comprises more than or equal to the aryl vibrin of about 50% mole chain link that comes from Resorcinol are transparent.In one embodiment, when measuring with 2 millimeters thickness according to ASTM method D1003, this blend has the percent transmittancy greater than about 50%.In other situation, when measuring according to ASTM method D1003, the percent haze of these transparent compositions is less than about 25%.In other embodiments, percent transmittancy is greater than about 60%, and percent haze is less than about 20%.In other situation, composition and have greater than about 50% transmissivity and be lower than about 25% haze value by its goods of making, the peak value heat release is for being less than or equal to 50kW/m simultaneously 2
In flame retardant blends, the amount that polyimide, polyetherimide, polyetherimide sulfone or its mixture can about 1～99% weight exists, based on the gross weight of composition.In this scope, the amount of polyimide, polyetherimide, polyetherimide sulfone or its mixture can be in particular more than or equal to about 50% weight for more than or equal to about 20% weight, even more specifically is more than or equal to about 70% weight.
In another embodiment, composition comprises the flame retardant polymer blend that composition is following:
A) polyetherimide of about 1～99% weight, polyetherimide sulfone and composition thereof,
B) the aryl vibrin of about 99～1% weight, it comprises more than or equal to about 50% mole connection base that is derived from Resorcinol,
C) silicone copolymers of about 0.1～30% weight,
D) metal oxide of about 0～20% weight,
Wherein the basis of % weight is the gross weight of composition.
On the other hand, the composition that comprises the flame retardant polymer blend that composition is following also is fine:
A) polyetherimide of about 50～99% weight or polyetherimide sulfone resins,
B) the Resorcinol class polyarylester of about 1～50% weight, it comprises more than or equal to about 50% mole connection base that is derived from Resorcinol,
C) silicone copolymers of about 0.1～10% weight,
D) metal oxide of about 0～20% weight, and
E) phosphorus-containing stabilizers of 0～2% weight.
Polyimide has following general formula (XX):
Figure A200680052695D00331
(formula XX)
A in the formula is generally about 10～1000 or bigger greater than 1, perhaps more specifically is about 10～500; V in the formula is quaternary linking group (linker), is not limited in this respect, as long as this linking group does not hinder the synthetic of polyimide and uses.Suitable linking group includes but not limited to: the replacement or unsubstituted, saturated or undersaturated aromatic monocyclic or the many cyclic groups that (a) have about 5～50 carbon atoms, (b) have the replacement or the saturated or unsaturated alkyl unsubstituted, straight or branched of 1～30 carbon atom, perhaps their combination.Preferred linking group includes but not limited to the tetravalence aromatics of formula (XXI), as
Figure A200680052695D00332
And
Figure A200680052695D00333
(formula XXI)
W is selected from following divalent group :-O-in the formula ,-S-, and-C (O)-, SO 2-,-SO-,-C yH 2y-(y is 1～8 integer) and fluorinated derivatives (comprising the perfluor alkylene) thereof, the perhaps group shown in formula-O-Z-O-, wherein-W-or-two valence links of O-Z-O-are in 3,3 '-, 3,4 '-, 4,3 '-or 4,4 '-position, and wherein Z definition as above.Z can comprise the exemplary divalent group of formula (XXII).
Figure A200680052695D00334
(formula XXII)
R in the formula (XX) 7Include but not limited to replace or unsubstituted divalent organic group as: (a) have the aromatic hydrocarbon group and the halide derivative thereof of about 6～24 carbon atoms, (b) has the alkylidene group of the straight or branched of about 2～20 carbon atoms, (c) has the cycloalkylidene of about 3～24 carbon atoms, perhaps the divalent group shown in general formula (VI) below (d)
Figure A200680052695D00341
(formula VI)
Q such as top defined in the formula.
The polyimide of some kinds comprises polyamidoimide, polyetherimide sulfone and polyetherimide, the polyetherimide of those melt processible as known in the art particularly is recorded in polyetherimide in United States Patent (USP) 3803085 and 3905942 as its preparation method and character.
Polyetherimide resin can comprise more than 1, is generally about 10～1000 or more, perhaps more specifically is the structural unit of about 10～500 following formulas (XXIII),
Figure A200680052695D00342
(formula XXIII)
T is-group shown in O-or the formula-O-Z-O-in the formula, wherein-O-or-two valence links of O-Z-O-group are positioned at 3,3 '-, 3,4 '-, 4,3 '-or 4,4 '-position, Z defines as above.In one embodiment, polyimide, polyetherimide or polyetherimide sulfone can be multipolymer.Also can adopt the mixture of polyimide, polyetherimide or polyetherimide sulfone.
Polyetherimide can comprise the aromatics two (ether acid acid anhydride) of formula (XVIII) and the organic diamine reaction of formula (VII) according to any method preparation known to those skilled in the art:
Figure A200680052695D00343
(formula V)
H 2N-R 1-NH 2(formula VII)
T and R in the formula 1As defined above.
The specific examples of aromatic dianhydride and organic diamine is referring in the United States Patent (USP) 3972902 and 4455410 for example.The illustrative examples of aromatic dianhydride comprises:
3,3-two [4-(3, the 4-di carboxyl phenyloxy) phenyl] propane dicarboxylic anhydride;
4,4 '-two (3, the 4-di carboxyl phenyloxy) phenyl ether dicarboxylic anhydride;
4,4 '-two (3, the 4-di carboxyl phenyloxy) diphenyl sulfide dicarboxylic anhydride;
4,4 '-two (3, the 4-di carboxyl phenyloxy) benzophenone dicarboxylic anhydride;
4,4 '-two (3, the 4-di carboxyl phenyloxy) sulfobenzide dicarboxylic anhydride;
2,2-two [4-(2, the 3-di carboxyl phenyloxy) phenyl] propane dicarboxylic anhydride;
4,4 '-two (2, the 3-di carboxyl phenyloxy) phenyl ether dicarboxylic anhydride;
4,4 '-two (2, the 3-di carboxyl phenyloxy) diphenyl sulfide dicarboxylic anhydride;
4,4 '-two (2, the 3-di carboxyl phenyloxy) benzophenone dicarboxylic anhydride;
4,4 '-two (2, the 3-di carboxyl phenyloxy) sulfobenzide dicarboxylic anhydride;
4-(2, the 3-di carboxyl phenyloxy)-4 '-(3, the 4-di carboxyl phenyloxy) phenylbenzene-2,2-propane dicarboxylic anhydride;
4-(2, the 3-di carboxyl phenyloxy)-4 '-(3, the 4-di carboxyl phenyloxy) phenyl ether dicarboxylic anhydride;
4-(2, the 3-di carboxyl phenyloxy)-4 '-(3, the 4-di carboxyl phenyloxy) diphenyl sulfide dicarboxylic anhydride;
4-(2, the 3-di carboxyl phenyloxy)-4 '-(3, the 4-di carboxyl phenyloxy) benzophenone dicarboxylic anhydride; And
4-(2, the 3-di carboxyl phenyloxy)-4 '-(3, the 4-di carboxyl phenyloxy) sulfobenzide dicarboxylic anhydride, and their various mixtures.
Above the included another kind of aromatics two (ether acid acid anhydride) of formula (XVIII), include but not limited to T wherein shown in following formula (XXIV) and ehter bond wherein for example be in 3,3 '-, 3,4 '-, 4,3 '-or 4,4 '-compound of position, and composition thereof
Figure A200680052695D00351
(formula XXIV)
Q such as top defined in the formula.
Can use any diamino compounds.The suitable example of this compound is a quadrol, propylene diamine, trimethylene diamines, Diethylenetriamine, three second tetramines, hexanediamine, heptamethylene diamine, octamethylenediamine, nonamethylene diamine, decamethylene diamine, 1,12-dodecane diamines, 1,18-octadecamethylene diamine, 3-methyl heptamethylene diamine, 4,4-dimethyl-g diamines, 4-methyl nonamethylene diamine, 5-methyl nonamethylene diamine, 2,5-dimethyl hexanediamine, 2,5-dimethyl-g diamines, 2,2-dimethyl 1,3-propylene diamine, N-methyl-two (3-aminopropyl) amine, 3-methoxyl group hexanediamine, 1,2-two (the amino propoxy-of 3-) ethane, two (3-aminopropyl) thioether, 1, the 4-cyclohexane diamine, two (4-aminocyclohexyl) methane, mphenylenediamine, Ursol D, 2,4 di amino toluene, 2, the 6-diaminotoluene, m-xylene diamine, p-Xylol diamines, 2-methyl-4,6-diethyl-1,3-phenylene-diamines, 5-methyl-4,6-diethyl-1,3-phenylene-diamines, p-diaminodiphenyl, 3,3 '-tolidine, 3,3 '-dimethoxy benzidine, 1, the 5-diaminonaphthalene, two (4-aminophenyl) methane, two (2-chloro-4-amino-3,5-diethyl phenyl) methane, two (4-aminophenyl) propane, 2,4-two (p-amino-tertiary butyl) toluene, two (p-amino-tert-butyl-phenyl) ether, two (p-methyl-o-aminophenyl) benzene, two (the amino amyl group of p-methyl-o-) benzene, 1,3-diamino-4-isopropyl benzene, two (4-aminophenyl) thioether, two (4-aminophenyl) sulfone, and two (4-aminophenyl) ether.Also can use the mixture of these compounds.Preferred diamino compounds is aromatic diamine, particularly mphenylenediamine and Ursol D, the alkylsulfonyl pentanoic, and composition thereof.
In one embodiment, polyetherimide resin comprises and the consistent structural unit of formula (XVII), and each R is that T is the divalent group of formula (XXV) to phenylene or metaphenylene or their mixture independently in the formula
Figure A200680052695D00361
(formula XXV)
Much preparing in the method for polyimide, particularly polyetherimide, comprising disclosed those methods in United States Patent (USP) 3847867,3852242,3803085,3905942,3983093 and 4443591.The purpose of mentioning these patents is the general and concrete grammar with way of example instruction preparation polyimide.
Polyimide, polyetherimide and polyetherimide sulfone can have the melt index of about 0.1～10 gram/minute (g/min), it is according to the D1238 of U.S. test materials association (ASTM), at 340～370 ℃, utilize 6.6 kilograms of (kg) weight measurements.In one embodiment, polyetherimide resin has the weight-average molecular weight (Mw) of about 10000～150000 gram/moles (g/mole), and it is according to gel permeation chromatography, utilizes polystyrene standards to measure.In another embodiment, polyetherimide has 20000～60000 Mw.This polyetherimide resin has usually greater than about 0.2 deciliter/gram (dl/g), more specifically is the intrinsic viscosity of about 0.35～0.7dl/g, and it is measured in meta-cresol at 25 ℃.Some examples that can be used for the polyetherimide in the blend of the present invention are set forth among the ASTM D5205 " Standard Classification System for Polyetherimide (PEI) Materials ".
The chain length of the siloxanes segment of multipolymer can be any effective length.In some instances, this length is 2～70 siloxane repeat units.In other situation, the siloxane chain segment length can be about 5～30 repeating units.As a rule, can use dimethyl siloxane.
The siloxane polyetherimide multipolymer is specializing of operable silicone copolymers.The example of this siloxane polyetherimide is shown in United States Patent (USP) 4404350,4808686 and 4690997.In a kind of situation, the polyetherimide oxyalkylene amine can be similar to the employed method preparation of polyetherimide, different is, part or all of organic diamine reactant is replaced by amine-terminated organo-siloxane, for example, the organo-siloxane of formula XXII, g is 1～50 integer in the formula, can be at some other situation g for about 5～30, R ' is for having aryl, the alkyl or aryl alkyl of about 2～20 carbon atoms.
Figure A200680052695D00371
(formula XXII)
Some polyetherimide oxyalkylene amines, but one or more dicarboxylic anhydride reactions of the amine end groups organo-siloxane of the mixture of the organic diamine of through type XIX or diamines and formula XXII and formula XVIII form.The diamino component can be before reaction and the dicarboxylic anhydride physical mixed, forms fully random multipolymer thus.As selection, can form the selective reaction of block or alternating copolymer: XIX and XXII and dicarboxylic anhydride by such method, the polyimide block that makes one reacts then.In another case, the siloxanes that is used to prepare polyether imide copolymer can have acid anhydrides rather than amine end functional groups, described in United States Patent (USP) 4404350.
In a kind of situation, the siloxane polyetherimide multipolymer can have formula XXIII, and T, R ' and g such as top defined in the formula, the numerical value of n are about 5～100, and Ar is aryl or the alkylaryl with 6～36 carbon.
Figure A200680052695D00372
(formula XXIII)
In some siloxane polyetherimides, the diamine components of siloxane polyetherimide multipolymer can comprise the amine end groups organo-siloxane of about 20% mole～50% mole of formula XXII and the organic diamine of about 50～80% moles of formula XIX.In some silicone copolymers, silicone components comprises about 25～40% moles amine or acid anhydrides end group organo-siloxane.
C. The blend polymer that high Tg is separated
This paper also discloses the blend polymer that is separated, and this blend polymer comprises the mixture of following ingredients: a) PAEK (PAEK), and it is selected from PAEK, poly-aryl ketones, polyetherketone, polyether-ether-ketone and their combination; With b) polyetherimide sulfone (PEIS), it has the connection base that comprises the aryl sulfone group more than or equal to 50% mole.
Be separated and mean PAEK and PEIS is present in the mixture with isolating chemical entity, described chemical entity can utilize standard method of analysis such as microscopy, dsc or dynamic mechanical analysis method to distinguish, demonstrate at least two different polymer phases, one comprises the PAEK resin mutually, and one comprises the PEIS resin mutually.In some situation, each comprises the corresponding resin greater than about 80% weight mutually.In other situation, blend can form isolating about 0.1～50 micron obvious zone that is of a size of, and in other situation, described zone is about 0.1～20 micron.Area size is meant the longest lineal measure that shows by microscopy.The blend that is separated is unmixing fully, also can have the partial confounding dissolubility, but its behavior must make that at least this blend has two or more different polymer phases when solid-state.
The ratio of PAEK/PEIS can have the arbitrary value of the blend that improves performance for formation, and according to end-use, described performance can be better than or too late independent arbitrary resin.By weight, this ratio can be 1:99～99:1, decides with needing improved performance according to end-use.The scope of this ratio can also be 15:85～85:15, and even 25:75～75:25.According to using, this ratio also can be 40:60～60:40.It will be understood by those of skill in the art that the variation of PAEK/PEIS ratio can be any real number ratio of described scope according to needed result.
The performance of final blend comprises heat-drawn wire and supporting capacity, and it can be adjusted by changing components in proportions.For example, in one embodiment, polyetherimide sulfone resins can exist with respect to the effective any amount that changes (promptly improving by raising) PEAK blend supporting capacity of each component itself.In some situation, the amount of about 30～70% weight that PAEK can whole mixture exists, and the amount of PEIS then can be about 70～30% weight, and wherein the basis of " % weight " is the weight sum of PAEK and PEIS.
In some embodiments, the blend polymer that is separated can have more than or equal to about 170 ℃ heat-drawn wire (HDT), and it utilizes ASTM method D5418 to measure on the 3.2mm strip at 0.46MPa (66psi).In other situation, the HDT during 0.46MPa (66psi) can be for more than or equal to 200 ℃.In other situation, the supporting capacity of the PAEK-PEIS that provides with dimension card (Vicat) temperature is for more than or equal to about 200 ℃, and it is measured in 50 newton (N) according to ASTM method D1525.
In other situation, the supporting capacity of the blend polymer that is separated that provides with modulus in flexure is for more than or equal to about 200 MPas (MPa), and it is to measure on the strip of 3.2mm at 200 ℃ according to ASTM method D5418.
The blend polymer that is separated can be by mixing a certain amount of PAEK in molten state and a certain amount of PEIS prepares.These two components can be mixed by be separated any method of blend of formation known to those skilled in the art.These class methods comprise extrude, clinkering etc.
The term " PAEK (PAEK) " that is used for this paper comprises that the polymkeric substance of several types, this polymkeric substance comprise the aromatic ring that mainly is connected with different order by ketone and ether, normally phenyl ring.The example of PAEK resin comprises polyetherketone (PEK), polyether-ether-ketone (PEEK), and polyetherketoneetherketoneketone (PEKEKK), PEKK (PEKK) contains the multipolymer of this class group and their blend.The PAEK polymkeric substance can comprise such monomeric unit, and this monomeric unit comprises aromatic ring (being generally phenyl ring), ketone group and the ether of random order.Can exist low-level for example less than 10% mole additional linking group, as long as they fundamentally do not change the performance of PAEK resin.
For example, several fusing points are the PAEK of the highly crystalline more than 300 ℃, in the blend that can be used for being separated.The example of these crystalline PAEK is shown among following structural formula XXVI, XXVII, XXVIII, XXIX and the XXX.
Figure A200680052695D00391
Formula XXVI
Formula XXVII
Figure A200680052695D00393
Formula XXVIII
Formula XXIX
Figure A200680052695D00395
Formula XXX
Other example that is applicable to crystallization PAEK of the present invention can be characterized by the repeating unit that comprises following formula (XXXI) prevailingly:
Figure A200680052695D00396
Formula XXXI
Ar in the formula 2Independently for being selected from the divalent aromatic radical of phenylene, biphenylene or naphthylidene, L is independently-O-,-C (O)-,-O-Ar-C (O)-,-S-,-SO 2-or chemical bond completely, h is 0～10 integer.
Those skilled in the art will appreciate that and exist complete and relate to patent and other document of the formation of PAEK and performance in a large number.For example, some early stage work (as United States Patent (USP) 3065205) relate to and contain close electric aromatics replacement (catalytic as the Friedel-Crafts) reaction that does not replace aromatic substance such as phenyl ether and aromatics two carboxylic acid halides.The progress of this class reaction is implemented in the United States Patent (USP) 4175175, and this patent shows, for example by the nucleophilic aromatic substitution reaction of activatory aromatics dihalide and aromatics diphenol or its salt, can form various kinds of resin.
Preparation gathers one of these class methods of aryl ketones, comprises the mixture of the halogenated phenols compound of equimolar substantially bis-phenol of heating (reacting with its bisphenolate salt usually) and dihalo benzoid compound or other situation.In other situation, can use the mixture of these compounds.For example, can make the reaction of Resorcinol and dihalo aryl ketones such as dichloro benzophenone or difluoro benzophenone, form PAEK.In other cases, dihydroxyl aryl ketones such as dihydroxy benaophenonel can with aryl dihalide such as dichlorobenzene polymerization, form the PAEK resin.In other situation, dihydroxyl aryl ethers such as dihydroxy diphenyl ether and dihalo aryl ketones such as difluoro benzophenone are reacted.In other variant, the dihydroxy compound of ether-containing key such as dihydroxybiphenyl or Resorcinol can not react as two (dichlorophenyl) benzophenone with the dihalo compound that may have ehter bond and ketonic bond.In other situation, can polymerization diaryl ether carboxylic acid or acid halide, to form PAEK.The example of this compounds is a diphenyl ether dicarboxylate, phenyl ether carboxyl acyl chloride, phenoxy group-phenoxy benzoic acid, perhaps their mixture.In other situation, can make dicarboxylic acid or dicarboxylic acid halide and diaryl ether condensation, for example, can make m-phthaloyl chloride or p-phthaloyl chloride (perhaps their mixture) and phenyl ether reaction, form the PAEK resin.
This method for example is documented in the United States Patent (USP) 4176222.This method comprises: at temperature range heating equimolar substantially (a) bis-phenol of 100～400 ℃, with (b.i) the dihalo benzoid compound and/or (b.ii) mixture of halogenated phenols, wherein in dihalo benzoid compound or halogenated phenols, utilize the mixture of yellow soda ash or sodium bicarbonate and second alkaline carbonate or supercarbonate, make halogen atom by its ortho position or contraposition-the C=O-group activates, the basic metal of described second alkaline carbonate or supercarbonate has the ordination number higher than sodium, the amount of described second alkaline carbonate or supercarbonate makes with respect to the sodium atom of every gram, the alkali metal atom that described ordination number is higher is 0.001～0.2 gram, and the total amount of alkaline carbonate or supercarbonate makes and has at least one alkali metal atom for each the phenolic group group that occurs; Reach isolating polymer from alkali metal halide thereafter.
Other PAEK also can be according to for example preparation of the method described in the United States Patent (USP) 4396755.In the method, make reactant as (a) dicarboxylic acid, (b) divalent aromatic radical and an aromatic dicarboxylic acid, and (c) i.e. (a) and combination (b) particularly react in the presence of the trifluoromethanesulfonic acid at fluoroalkane sulfonic acid.
Other PAEK can be according to for example preparation of the method described in the United States Patent (USP) 4398020, and wherein aromatics diacyl compound and aromatic substance and a carboxylic acid halides carry out polyreaction.
PAEK can have the reduced viscosity more than or equal to about 0.4～5.0dl/g, and it is measured in the vitriol oil at 25 ℃.The weight-average molecular weight of PAEK (Mw) can be about 5000～150000g/mole.In other situation, Mw can be about 10000～80000g/mole.
Second resin Composition is polyetherimide sulfone (PEIS) resin.When being used for this paper, PEIS comprises and wherein connects the have general formula structural unit of (VII) base more than or equal to about 50% mole polymkeric substance and have the aryl sulfone group
Figure A200680052695D00411
Formula (VII)
A is more than 1 in the formula, is generally about 10～1000 or bigger, more specifically is about 10～500; V is the tetravalence linking group, is not limited in this respect, as long as this linking group does not hinder the imido synthetic and use of polysulfones ether.Suitable linking group includes but not limited to: the replacement or unsubstituted saturated or undersaturated aromatic monocyclic or the many cyclic groups that (a) have about 5～50 carbon atoms; (b) have the replacement of 1～30 carbon atom or the saturated or undersaturated alkyl of unsubstituted straight or branched; Perhaps (c) their combination.Preferred linking group includes but not limited to the aromatic group of tetravalence formula (VIII),
Formula (VIII)
W is in some embodiments for being selected from following divalent group :-SO in the formula 2-,-O-,-S-,-C (O)-, C yH 2y-(y is 1～5 integer), and halide derivative comprise perfluorinated alkylidene, perhaps the group shown in formula-O-D-O-.Group D can comprise the residue of bisphenol cpd.For example, D can be any molecule shown in the formula IX,
Figure A200680052695D00421
Formula (IX)
-W-or-two valence links of O-D-O-group can be in 3,3 '-, 3,4 '-, 4,3 '-or 4,4 '-position.Also can use the mixture of aforementioned each compound.For superior melt stability, often preferably do not contain the group of benzylic proton.Wherein W is-SO 2-the group particularly important because they are aryl sulfone to be connected base be incorporated into one of method in the polysulfones ether imide resin.
The term ＂ polymkeric substance that is used for this paper connects basic ＂ or ＂ polymkeric substance and connects basic ＂ and be defined as at least two kinds of monomeric reaction product that form polymkeric substance, wherein at least a monomer is dicarboxylic anhydride or its chemical equivalence thing, and wherein second monomer is at least a diamines or its chemical equivalence thing.This polymkeric substance is made up of 100% mole this connection base.For instance, have the polymkeric substance that 50% mole of aryl sulfone connects base, its half connection base (by mole) is to comprise the connection base with at least one aryl sulfone group that comes from dicarboxylic anhydride or diamines.
Suitable dihydroxyl substituted arene as-O-D-O-group precursor also comprises the dihydroxyl substituted arene shown in the following formula (X):
Formula (X);
Each R in the formula 7Be hydrogen, chlorine, bromine, alkoxyl group, aryloxy or C independently 1-30Monovalence hydrocarbon or-oxyl, R 8And R 9Be hydrogen, aryl, fluoro-alkyl or C independently 1-30Alkyl.
Can be used as-the dihydroxyl substituted arene of the precursor of O-D-O-group comprises in United States Patent (USP) 2991273,2999835,3028365,3148172,3153008,3271367,3271368 and 4217438 with title or chemical formula those disclosed dihydroxyl substituted arene.The specific examples of spendable dihydroxyl substituted arene includes but not limited to, two (4-hydroxy phenyl) sulfone, two (4-hydroxy phenyl) thioether, two (4-hydroxy phenyl) ether, two (4-hydroxy phenyl) sulfoxide, 1, the 4-dihydroxy-benzene, 4,4 '-the oxygen biphenol, 2,2-two (4-hydroxy phenyl) HFC-236fa, 4,4 '-(3,3,5-3-methyl cyclohexanol fork) biphenol, 4,4 '-two (3, the 5-dimethyl) biphenol, 1,1-two (4-hydroxy-3-methyl phenyl) hexanaphthene, 4,4-two (4-hydroxy phenyl) heptane, 2,4 '-the dihydroxyl ditan, two (2-hydroxy phenyl) methane, two (4-hydroxy phenyl) methane, two (4-hydroxyl-5-nitrophenyl) methane, two (4-hydroxyl-2,6-dimethyl-3-p-methoxy-phenyl) methane, 1,1-two (4-hydroxy phenyl) ethane, 1,2-two (4-hydroxy phenyl) ethane, 1,1-two (4-hydroxyl-2-chloro-phenyl-) ethane, 2,2-two (3-phenyl-4-hydroxy phenyl) propane, 2,2-two (4-hydroxy-3-methyl phenyl) propane, 2,2-two (4-hydroxyl-3-ethylphenyl) propane, 2,2-two (4-hydroxyl-3-isopropyl phenyl) propane, 2,2-two (4-hydroxyl-3,5-3,5-dimethylphenyl) propane, 3,5,3 ', 5 '-tetrachloro-4,4 '-dihydroxyphenyl) propane, two (4-hydroxy phenyl) cyclohexyl-methane, 2,2-two (4-hydroxy phenyl)-1-phenyl-propane, 2,4 '-the dihydroxyphenyl sulfone, dihydroxy naphthlene, 2, the 6-dihydroxy naphthlene, Resorcinol, Resorcinol, C 1-3The Resorcinol that alkyl replaces, methylresorcinol, 1,4-dihydroxyl-3-methylbenzene, 2,2-two (4-hydroxy phenyl) butane, 2,2-two (4-hydroxy phenyl)-2-methylbutane, 1,1-two (4-hydroxy phenyl) hexanaphthene, 4,4 '-dihydroxybiphenyl, 2-(3-methyl-4-hydroxy phenyl-2-(4-hydroxy phenyl) propane, 2-(3,5-dimethyl-4-hydroxy phenyl)-and 2-(4-hydroxy phenyl) propane, 2-(3-methyl-4-hydroxy phenyl)-2-(3,5-dimethyl-4-hydroxy phenyl) propane, two (3,5-3,5-dimethylphenyl-4-hydroxy phenyl) methane, 1,1-two (3,5-3,5-dimethylphenyl-4-hydroxy phenyl) ethane, 2,2-two (3,5-3,5-dimethylphenyl-4-hydroxy phenyl) propane, 2,4-two (3,5-3,5-dimethylphenyl-4-hydroxy phenyl)-2-methylbutane, 3,3-two (3,5-3,5-dimethylphenyl-4-hydroxy phenyl) pentane, 1,1-two (3,5-3,5-dimethylphenyl-4-hydroxy phenyl) pentamethylene, 1,1-two (3,5-3,5-dimethylphenyl-4-hydroxy phenyl) hexanaphthene, two (3,5-dimethyl-4-hydroxy phenyl) sulfoxide, two (3,5-dimethyl-4-hydroxy phenyl) sulfone, and two (3,5-3,5-dimethylphenyl-4-hydroxy phenyl) thioether.Also can use the mixture of the aromatic hydrocarbons that comprises any aforementioned dihydroxyl replacement.
In specific embodiment, the dihydroxyl substituted arene that comprises the bis-phenol with sulfone key is important, because this is that aryl sulfone is connected basic another approach that is incorporated in the polysulfones ether imide resin.In other situation, can preferably not contain the bisphenol cpd of benzylic proton, have the polyetherimide sulfone of excellent melt stability with preparation.
In formula (VII), the R group is the residue of diamino compounds or its chemical equivalence thing, and it includes but not limited to replace or unsubstituted divalent organic group, as: (a) have the aromatic hydrocarbon group and the halide derivative thereof of about 6～24 carbon atoms; (b) has the alkylidene group of the straight or branched of about 2～20 carbon atoms; (c) has the cycloalkylidene of about 3～24 carbon atoms; The perhaps divalent group of (d) general formula (XI)
Figure A200680052695D00441
Q includes but not limited to be selected from following divalent group :-SO in the formula 2-,-O-,-S-,-C (O)-, C yH 2y-(y is 1～5 integer) and halide derivative (comprising perfluorinated alkylidene) thereof.In specific embodiment, R is substantially free of benzylic hydrogen.Can infer the existence of benzylic proton from chemical structural formula.
In some specific embodiments, suitable aromatic diamine comprises mphenylenediamine; Ursol D; The mixture of mphenylenediamine and Ursol D; The 2-methyl of isomery-and 5-methyl-4,6-diethyl-1,3-phenylenediamine or its mixture; Two (4-aminophenyls)-2,2-propane; Two (2-chloro-4-amino-3,5-diethyl phenyl) methane, 4,4 '-benzidine, 3,4 '-benzidine, 4 (be called sometimes 4,4 '-oxydiphenyl amine); 3,4 '-diaminodiphenyl oxide, 3,3 '-diaminodiphenyl oxide, 4,4,3,4 '-diaminodiphenylsulfone(DDS), 3,3 '-diaminodiphenylsulfone(DDS), 4,4 '-diaminodiphenyl sulfide; 3,4 '-diaminodiphenyl sulfide; 4,4 '-diaminobenzophenone, 3,4 '-diaminobenzophenone, 4,4 '-diaminodiphenyl-methane (commonly used by name 4,4 '-methylene dianiline (MDA)); 4,4 '-two (4-amino-benzene oxygen) biphenyl, 4,4 '-two (3-amino-benzene oxygen) biphenyl, 1,5-diaminonaphthalene; 3, the 3-tolidine; 3, the 3-dimethoxy benzidine; P-diaminodiphenyl; M-xylene diamine; Two (amino-benzene oxygen) fluorenes, two (amino-benzene oxygen) benzene, 1,3-two (3-amino-benzene oxygen) benzene, 1,3-two (4-amino-benzene oxygen) benzene, 1,4-two (4-amino-benzene oxygen) benzene, two (amino-benzene oxygen) phenylsulfone, two (4-(4-amino-benzene oxygen) phenyl) sulfone, two (4-(3-amino-benzene oxygen) phenyl) sulfone, diaminobenzene formylaniline, 3,3 '-diaminobenzophenone, 4,4 '-diaminobenzophenone, 2,2 '-two (4-(4-amino-benzene oxygen) phenyl) propane, 2,2-two [4-(4-amino-benzene oxygen) phenyl] HFC-236fa, 4,4 '-two (aminophenyl) HFC-236fa, 1,3-diamino-4-isopropyl benzene; 1,2-two (3-amino-benzene oxygen) ethane; 2,4-two (beta-amino-tertiary butyl) toluene; Two (p-Beta-methyl-o-aminophenyl) benzene; Two (p-beta-amino-tert-butyl-phenyl) ether; And 2, the 4-tolylene diamine.Also can use the mixture of two or more diamines.Diaminodiphenylsulfone(DDS) (DDS), two (amino-benzene oxygen phenyl) sulfone (BAPS) and composition thereof is preferred aromatic diamine.
Thermoplastic polysulfones ether imide as herein described can derive from such reactant, this reactant comprises derivative and one or more aromatic acid's ring-type dicarboxylic anhydrides (hereinafter being called aromatic dianhydride sometimes) that one or more aromatic diamines or its are chemically of equal value, the aromatic acid, perhaps it can form the derivative or the poly-different imido heat of the ready-formed/catalytically rearranging product of cyclic acid anhydride.In addition, for the reactant that comprises aromatic diamine and aromatic dianhydride, at least a portion of a kind of reactant or another reactant, perhaps at least a portion of every kind of reactant, comprise aryl sulfone linkages, make the polymkeric substance connection base of at least 50% mole of gained comprise at least one aryl sulfone group.In specific embodiment, for the reactant that comprises aromatic diamine and aromatic dianhydride, a kind of reactant or another reactant whole, perhaps every kind of reactant whole have at least one sulfone and connect base.This polymerization ofathe reactants, formation comprises cyclic imide and connects base is connected base with sulfone polymkeric substance.
The illustrative examples of aromatic dianhydride comprises:
4,4 '-two (3, the 4-di carboxyl phenyloxy) sulfobenzide dicarboxylic anhydride;
4,4 '-two (2, the 3-di carboxyl phenyloxy) sulfobenzide dicarboxylic anhydride;
4-(2, the 3-di carboxyl phenyloxy)-4 '-(3, the 4-di carboxyl phenyloxy) sulfobenzide dicarboxylic anhydride,
And composition thereof.
Other available aromatic dianhydride comprises:
2,2-two (4-(3, the 4-di carboxyl phenyloxy) phenyl) propane dicarboxylic anhydride;
4,4 '-two (3, the 4-di carboxyl phenyloxy) phenyl ether dicarboxylic anhydride;
4,4 '-two (3, the 4-di carboxyl phenyloxy) diphenyl sulfide dicarboxylic anhydride;
4,4 '-two (3, the 4-di carboxyl phenyloxy) benzophenone dicarboxylic anhydride;
2,2-two ([4-(2, the 3-di carboxyl phenyloxy) phenyl] propane dicarboxylic anhydride;
4,4 '-two (2, the 3-di carboxyl phenyloxy) phenyl ether dicarboxylic anhydride;
4,4 '-two (2, the 3-di carboxyl phenyloxy) diphenyl sulfide dicarboxylic anhydride;
4,4 '-two (2, the 3-di carboxyl phenyloxy) benzophenone dicarboxylic anhydride;
2-[4-(3, the 4-di carboxyl phenyloxy) phenyl]-2-[4-(2, the 3-di carboxyl phenyloxy) phenyl] the propane dicarboxylic anhydride;
4-(2, the 3-di carboxyl phenyloxy)-4 '-(3, the 4-di carboxyl phenyloxy) phenyl ether dicarboxylic anhydride;
4-(2, the 3-di carboxyl phenyloxy)-4 '-(3, the 4-di carboxyl phenyloxy) diphenyl sulfide dicarboxylic anhydride;
4-(2, the 3-di carboxyl phenyloxy)-4 '-(3, the 4-di carboxyl phenyloxy) benzophenone dicarboxylic anhydride;
1,4,5,8-naphthalenetetracarbacidic acidic dicarboxylic anhydride;
3,4,3 ', 4 '-benzophenone tetracarboxylic acid dicarboxylic anhydride;
2,3,3 ', 4 '-benzophenone tetracarboxylic acid dicarboxylic anhydride;
3,4,3 ', 4 '-oxygen di-Tetra hydro Phthalic anhydride; 2,3,3 ', 4 '-oxygen di-Tetra hydro Phthalic anhydride;
3,3 ', 4,4 '-the biphenyltetracarboxyacid acid dicarboxylic anhydride;
2,3,3 ', 4 '-the biphenyltetracarboxyacid acid dicarboxylic anhydride;
2,3,2 ', 3 '-the biphenyltetracarboxyacid acid dicarboxylic anhydride;
Pyromellitic acid dianhydride;
3,4,3 ', 4 '-diphenylsulfone acid's dicarboxylic anhydride;
2,3,3 ', 4 '-diphenylsulfone acid's dicarboxylic anhydride;
1,4-two (3, the 4-di carboxyl phenyloxy) phthalic acid; And
2,2-two (3,4-dicarboxyl phenyl) HFC-236fa dicarboxylic anhydride.
Polysulfones ether imide with the structural unit that comes from the mixture that comprises above-mentioned two or more dicarboxylic anhydrides also is fine.
In other situation, polysulfones ether imide has that to come from the aromatic oxide acid anhydrides more than or equal to about 50% mole be that the imide of oxygen di-Tetra hydro Phthalic anhydride connects base, in alternative embodiment, have about 60～100% moles of imides that come from oxygen di-Tetra hydro Phthalic anhydride and connect base.In alternative embodiment, about 70～99% moles imide connects base and comes from oxygen di-Tetra hydro Phthalic anhydride or chemical equivalence thing.
Term " oxygen di-Tetra hydro Phthalic anhydride " is meant the oxygen di-Tetra hydro Phthalic anhydride of formula (XII)
Formula (XII)
And derivative, as the further definition of following institute.
The oxygen di-Tetra hydro Phthalic anhydride of formula (XII) comprises 4,4 '-oxygen di-Tetra hydro Phthalic anhydride, 3,4 '-oxygen di-Tetra hydro Phthalic anhydride, 3,3 '-oxygen di-Tetra hydro Phthalic anhydride, and mixture arbitrarily.For example, comprise the polysulfones ether imide that connects base more than or equal to about 50% mole imide that comes from oxygen di-Tetra hydro Phthalic anhydride, can come from 4,4 of formula (XIII) '-oxygen di-Tetra hydro Phthalic anhydride structural unit
Figure A200680052695D00462
Formula (XIII)
As mentioned above, can adopt the derivative of oxygen di-Tetra hydro Phthalic anhydride to prepare polysulfones ether imide.Can serve as the example that imide forms the derived acids anhydride group of the chemical equivalence thing of oxygen di-Tetra hydro Phthalic anhydride in the reaction, comprise the oxygen di-Tetra hydro Phthalic anhydride derivative of formula (XIV)
Figure A200680052695D00463
Formula (XIV)
R in the formula 1And R 2Can be following any group: hydrogen, alkyl, and aryl.R 1And R 2Can be identical or different, to produce acid, the ester of oxygen di-Tetra hydro Phthalic anhydride and the acid esters of oxygen di-Tetra hydro Phthalic anhydride of oxygen di-Tetra hydro Phthalic anhydride.
The polysulfones ether imide here can comprise the imide that comes from oxygen di-Tetra hydro Phthalic anhydride derivative and connect base, and this oxygen di-Tetra hydro Phthalic anhydride derivative has two deutero-anhydride groups, for example, and the oxygen di-Tetra hydro Phthalic anhydride derivative of formula (XV)
Figure A200680052695D00471
Formula (XV)
R in the formula 1, R 2, R 3And R 4Can be following any group: hydrogen, alkyl, and aryl.R 1, R 2, R 3And R 4Can be identical or different, to produce acid, the ester of oxygen di-phthalic acid and the acid esters of oxygen di-phthalic acid of oxygen di-phthalic acid.
The imido multipolymer of polysulfones ether that comprises following structural unit also is fine, this structural unit come from have two kinds, the oxygen di-Tetra hydro Phthalic anhydride mixture of three kinds or multiple above-named different dicarboxylic anhydrides and the about imidization reaction of the organic diamine with flexible linking group of equimolar amount.In addition, following multipolymer also is fine, this multipolymer has more than or equal to about 50% mole imide that comes from above-mentioned oxygen di-Tetra hydro Phthalic anhydride (comprising its derivative) and connects base, and at the most 50% mole with the different alternative dicarboxylic anhydride of described oxygen di-Tetra hydro Phthalic anhydride.In other words, in some situation, the multipolymer that preferred preparation is such, this multipolymer is except that having more than or equal to the about 50% mole connection base that comes from oxygen di-Tetra hydro Phthalic anhydride, also comprise the imide that comes from the aromatic dianhydride different and connect base with oxygen di-Tetra hydro Phthalic anhydride, the example of this aromatic dianhydride has: dihydroxyphenyl propane dicarboxylic anhydride (BPADA), two sulfone dicarboxylic anhydrides, benzophenone dicarboxylic anhydride, two (carbonyl Phenoxyphenyl) HFC-236fa dicarboxylic anhydride, the bis-phenol dicarboxylic anhydride, pyromellitic acid dianhydride (PMDA), biphenyl acid acid anhydride, sulphur di-acid anhydrides, the sulfo group dicarboxylic anhydride, and composition thereof.
In another embodiment, above-mentioned dicarboxylic anhydride and aryl diamine reaction with sulfone key.In one embodiment, polysulfones ether imide comprises the structural unit of the aryl diamino sulfone of the formula of coming from (XVI)
H 2N-Ar-SO 2-Ar-NH 2Formula (XVI)
Ar can be for containing monocycle or polycyclic aryl in the formula.Several aryl rings can link together, and for example link together by ehter bond, sulfone key or more than one sulfone key.Aryl rings also can condense.
In alternative embodiment, the amido of aryl diamino sulfone can be in the sulfone key between the position or contraposition, for example shown in the formula (XVII)
Figure A200680052695D00481
Formula (XVII)
Aromatic diamine includes but not limited to, for example, and diaminodiphenylsulfone(DDS) (DDS) and two (amino-benzene oxygen phenyl) sulfone (BAPS).Can use above-mentioned oxygen di-Tetra hydro Phthalic anhydride, form polysulfones ether imide, and then form polyimide connection base by reacting with aryl diamino sulfone.
In some embodiments, polysulfones ether imide resin can be by aromatic diacid anhydride monomer (or aromatics two (ether acid acid anhydride) monomer) and the preparation of organic diamine monomer reaction, wherein these two kinds of monomers exist with the molar weight that equates basically, perhaps wherein a kind of monomer is to be not more than about 20% molar excess, preferably to be present in the reaction mixture less than about 10% molar excess (with respect to another monomer), perhaps wherein a kind of monomer is present in the reaction mixture to be not more than about 5% molar excess.In other situation, each monomer exists with the amount of difference less than 1% molar excess.
Can use kiber alkyl amine such as methylamine as chain terminator.For instance, also can use uncle's monoamine end-blocking or chain termination polysulfones ether imide, with the control molecular weight.In specific embodiment, uncle's monoamine comprises the aromatic primary monoamine, and its illustrative examples comprises aniline, chloroaniline, perfluoro-methyl aniline, naphthylamines etc.Can be connected with other functional group on the aromatic ring of aromatic primary monoamine, (but being not limited to) aryl for example, alkyl, aryl-alkyl, sulfuryl, ester group, amide group, halogen, haloalkyl or aryl, alkane ether, aryl ether group, perhaps arone base.The functional group that is connected should not hinder the effect of aromatic primary monoamine control polysulfones ether imide molecular weight.Suitable monoamine compound is referring to United States Patent (USP) 6919422.
Also can use aromatic dicarboxylic acid anhydride, promptly comprise the aryl of a cyclic acid anhydride group, with the molecular weight of control polyimide sulfones.Illustrative examples comprises Tetra hydro Phthalic anhydride, the Tetra hydro Phthalic anhydride of replacement such as monochloro phthalic anhydride etc.Can be connected with other functional group on the aromatic ring of described acid anhydrides, its illustrative examples comprises those functional groups of aromatic primary monoamine recited above.
In some situation, the different alkylidene that preferably can have low levels connects the polysulfones ether imide of base (isoalkylidene linkage).It is believed that in some PAEK blend the existence that different alkylidene connects base can promote compatibility, the supporting capacity when this can reduce high temperature, thereby be worthless.Compatibility PEEK blend with the polymkeric substance that comprises different alkylidene is referring to for example United States Patent (USP) 5079309 and 5171796.In some situation, the different alkylidene group of low levels is gratifying is distinguishing the flavor of and connects base less than 30% mole polysulfones ether imide and can comprise different alkylidene group; In other situation, polysulfones ether imide connects the basic different alkylidene group that can comprise less than 20% mole.In other situation, can be present in polysulfones ether imide less than 10% mole different alkylidene group and connect in the base.
Polysulfones ether imide can have the melt index of about 0.1～10 gram/minute (g/min), its according to the D1238 of U.S. test materials association (ASTM) in 340～425 ℃ of measurements.In one embodiment, polysulfones ether imide resin has the weight-average molecular weight (Mw) of about 10000～150000 gram/moles (g/mole), and it utilizes polystyrene standards to measure by gel permeation chromatography.In another embodiment, polysulfones ether imide has the Mw of 20000～60000g/mole.The example of some polyetherimides is set forth among the ASTM D5205 " Standard Classification System for Polyetherimide (PEI) Materials ".
In some situation, particularly form the situation of film and fiber at needs, composition should be substantially not fibre-bearing strengthening agent such as glass, carbon, pottery or steel fiber.In some situation, " not containing substantially " means 5% weight less than whole composition.In other cases, composition should have the fibrous reinforcement agent less than 1% weight.
In other situation, the crystallization that composition is manifested to a certain degree by cooling is useful.This can be more important for the goods with high surface area such as fiber and film, and this goods can or not develop into obtaining the needed complete crystallization of optimum performance because of the cooling rapidly of its high surface area.In some situation, crystalline forms and is reflected in the Tc (Tc), and Tc can be passed through such as dsc methods such as (DSC), and for example ASTM method D3418 measures.The temperature that can measure maximum crystallization velocity is as Tc.In some situation, for example, when 80 ℃/minute speed of cooling, can preferably have more than or equal to about 240 ℃ Tc.In other situation, for example, when slower 20 ℃/minute speed of cooling, can be preferably greater than or equal about 280 ℃ Tc.
In some situation, composition can have at least two distinct second-order transition temperatures (Tg), first Tg comes from PAEK resin or the miscible PAEK blend of part, and second Tg is relevant with polysulfones ether imide resin or the prevailing mixture of this resin.These second-order transition temperatures (Tg) can be by any ordinary method such as DSC or dynamic mechanical analysis (DMA) measurement.In some situation, first Tg can be about 120～200 ℃, and second Tg can be about 240～350 ℃.In other situation, it may be useful having about 280～350 ℃ higher the 2nd Tg.In some situation, according to the concrete resin and the molecular weight and the composition of this blend, each Tg can be completely different or each change can be partly overlapping.
In another embodiment, polysulfones ether imide PEAK blend is 380 ℃ of melt viscosities with about 200～10000 handkerchief-seconds (Pa-s), it is according to ASTM method D3835, utilizes capillary rheometer to measure when 100～10,000 1/ seconds shearing rate.Melt viscosity in the time of 380 ℃ is the resin blend of about 200～10000 handkerchief-seconds, allows the easier melt processing method that utilizes of composition to be configured as goods.In other situation, the lower melt viscosity of about 200～5000Pa-s can be useful.
Melt on the other hand, during the needed high temperature of PAEK-polysulfones ether imide composition particularly of the present invention, be the melt viscosity of composition at molding or during extruding without undergoing too much variation.One of method of measuring melt stability is, utilizes parallel-plate rheometer when processing temperature (as 380 ℃), measures viscosity over time.In some situation, when certain temperature, keep to keep initial viscosity more than or equal to about 50% more than or equal to after about 10 minutes.In other situation, changing at least about 10 minutes melt viscosities should be less than about 35% initial value.The initial melt viscosity number was measured 1～5 minute after can and reaching balance in the composition fusing.The common practice is, before measuring (record) viscosity, hotly waits for 1～5 minute after sample executing, and melts and reach balance fully to guarantee sample.Suitable measurement melt viscosity-time method is for example ASTM method D4440.Notice that melt viscosity can moor (P) or handkerchief second (Pa-s) is unit record; 1Pa-s=10P.
D. Copolyetherimides
Spendable polymkeric substance also comprises the multipolymer of second-order transition temperature more than or equal to about 218 ℃ Copolyetherimides, and this Copolyetherimides comprises the structural unit of formula (I) and formula (II):
Figure A200680052695D00501
And the structural unit of optional formula (III):
Figure A200680052695D00502
R in the formula 1Comprise unsubstituted C 6-22The C of divalent aromatic hydrocarbon or replacement 6-22Divalent aromatic hydrocarbon, the latter comprises halogen or alkyl substituent or its mixture; The perhaps divalent group of general formula (IV):
Figure A200680052695D00503
In the formula positional isomers of unspecified relevant aromatic ring or be Q between or be the contraposition of Q, Q is a covalent linkage ,-C (CH 3) 2-or be selected from the member of following formula V:
Figure A200680052695D00511
And formula C yH 2yAlkylene or alkylidene group, wherein y is 1～5 integer, R 2Be divalent aromatic radical; The unitary weight ratio of the unit of formula (I) and formula (II) is that about 99.9:0.1 is to about 25:75.Multipolymer with these integral parts is discussed in more detail, referring to the United States Patent (USP) that be entitled as " COPOLYMETHERIMIDES " 6849706 of on February 1st, 2005 with people's such as Brunelle name issue, is incorporated herein by reference this full patent texts.
D1. blend
The invention still further relates to have external diameter, the ring-type or the piped tubular type goods of internal diameter and length, these goods comprise one or more materials that is selected from down group: the blend polymer that a) comprises the unmixability of one or more polyetherimides, it has more than a second-order transition temperature, and the second-order transition temperature of wherein said polyetherimide is greater than 217 ℃; B) comprise the blend polymer of the compatibility of one or more polyetherimides, it has single second-order transition temperature greater than 180 ℃; Perhaps c) single polyetherimide and one or more following polymers blend that has greater than 247 ℃ second-order transition temperature: the homopolymer of tetrafluoroethylene; The multipolymer of tetrafluoroethylene and R 1216, vinylidene fluoride, perfluoroalkyl vinyl ether, ethylene fluoride, ethene and ter-polymers; Amorphous thermoplastic polymers comprises PPSU (PPSU), PI (polyimide), PEI (poly-(ether imide)), PSU (polysulfones), PC (polycarbonate), PPO (polyphenylene oxide), PMMA (polymethylmethacrylate), ABS (acronitrile-butadiene-styrene), PS (polystyrene) and PVC (polyvinyl chloride); Crystalline thermoplastic resin comprises PFA (perfluor alcoxyl alkane), MFA (multipolymer of TFE tetrafluoroethylene and PFVE perfluoroalkyl vinyl ether), FEP (fluorinated ethylene-propylene polymer), PPS (poly-(phenylene sulfide), PEK (poly-(ether ketone), PEEK (poly-(ether ether ketone), ECTFE (ethylene chlorotrifluoroethylene), PVDF (poly(vinylidene fluoride)), PTFE (tetrafluoroethylene), PET (polyethylene terephthalate), POM (polyacetal), PA (polymeric amide), UHMW-PE (ultrahigh molecular weight polyethylene(UHMWPE)), PP (polypropylene), PE (polyethylene), HDPE (high density polyethylene(HDPE)), and LDPE (new LDPE (film grade)); Senior engineering resin (gathers (amide-imide), PI (polyimide), PES (polyethersulfone), PAI (polyamide-imide), reaches PAS (polyaryl sulfone) as PBI (polybenzimidazole), PAI; And their blend and multipolymer.Can pass through mixed polymer, or extrude, this based composition of preparation such as coextrusion by other technology such as reactivity.For example,
＂ LCP (liquid crystalline polymers), PEN (PEN), PPL (polyphenylene) ＂
E. Other additive of blend
Except that the polymeric constituent of blend, can also add other useful composition to prepare improved goods.It will be understood by those of skill in the art that in polymkeric substance, to add a lot of batchings, to improve one or more manufacturings or use properties.
In some cases, can in polymkeric substance of the present invention, add metal oxide.In some situation, this metal oxide can improve fire-retardant (FR) performance further by the time of reducing heat release or the heat release of increase peak value.Famous is titanium dioxide.Other metal oxide comprises zinc oxide, boron oxide, weisspiessglanz, ferric oxide and transition metal oxide.In some situation, the metal oxide of preferred white.Metal oxide can use separately, also can use with other oxide-metal combinations.Metal oxide can any significant quantity, uses with 0.01～20% weight of blend polymer in some situation.
Other spendable additive comprises such as metal borate etc. and presses down fumicants, as zinc borate, basic metal or alkaline earth metal borate or other borate.In addition, can also use other boron-containing compound, as other oxygen compound of boric acid, boric acid ester, boron oxide or boron.Moreover, can adopt other flame-retardant additive, as the aromatic substance of aryl phosphate and bromination, comprise the polymkeric substance that contains the connection base of making by the bromination aryl compound.The example of halogenated aromatic compound is the bromination phenoxy resin, halogenated polystyrene, and halogenated polyimide, brominated polycarbonate, brominated epoxy resin, and composition thereof.
Also can adopt conventional flame-retardant additive, for example, phosphoric acid ester, sulfonate and halogenated aromatic compound.Can adopt the mixture of any of these fire retardant or all these fire retardants equally.The example of halogenated aromatic compound is the bromination phenoxy resin, halogenated polystyrene, and halogenated polyimide, brominated polycarbonate, brominated epoxy resin, and composition thereof.The example of sulfonate is a perfluor fourth potassium sulfonate, toluenesulfonic acid sodium salt, benzene sulfonic acid sodium salt, dichloro benzosulfonic acid sodium, potassium diphenylsulfone sulfonate, and methanesulfonic sodium.In some situation, the sulfonate of preferred as alkali or alkaline-earth metal.The example of phosphate flame retardant is a triaryl phosphate, Tritolyl Phosphate, triphenylphosphate, bisphosphate dihydroxyphenyl propane phenyl ester, bisphosphate Resorcinol phenyl ester, phenyl-two (3,5,5 '-trimethylammonium hexyl phosphoric acid ester), phosphoric acid ethyl diphenyl, di(2-ethylhexyl)phosphate (2-ethylhexyl) p-methylphenyl ester, di(2-ethylhexyl)phosphate (2-ethylhexyl) phenylester, tricresyl phosphate (nonyl phenyl) ester, phosphoric acid one hydrogen phenyl methyl ester, di(2-ethylhexyl)phosphate (dodecyl) p-methylphenyl ester, the halophosphoric acid triphenylmethyl methacrylate, di(2-ethylhexyl)phosphate butyl phenyl ester, phosphoric acid 2-chloroethyl diphenyl, phosphoric acid p-methylphenyl two (2,5,5 '-the trimethylammonium hexyl) ester, phosphoric acid 2-ethylhexyl diphenyl, phosphoric acid one diphenyl hydrogen base ester, resorcinol diphosphate etc.In some situation, can be preferably the halogen atom flame retardant composition of bromine and chlorine particularly not substantially.Substantially halogen atom does not mean composition in some embodiments and has halogen less than its weight about 3%, has the halogen less than about 1% weight of halogen atom composition weight in other embodiments.The amount of halogen atom can be passed through the general chemistry assay determination.Said composition can also be chosen wantonly and comprise the fluoropolymer that quantity is composition weight 0.01～5.0%.Fluoropolymer can be given resin combination and use with any significant quantity of antidrip performance.Some feasible examples of suitable fluoropolymer and preparation method thereof are referring to for example United States Patent (USP) 3671487,3723373 and 3383092.Suitable fluoropolymer comprises homopolymer and the multipolymer that those contain following structural unit, and this structural unit comes from one or more and fluoridizes 'alpha '-olefin monomers.Term " is fluoridized 'alpha '-olefin monomers " and is meant and comprises the substituent 'alpha '-olefin monomers of at least one fluorine atom.Some suitable 'alpha '-olefin monomers of fluoridizing comprise, for example, and vinyl fluoride such as CF 2=CF 2, CHF=CF 2, CH 2=CF 2And CH 2=CHF, and fluorine propylene such as CF 3CF=CF 2, CF 3CF=CHF, CF 3CH=CF 2, CF 3CH=CH 2, CF 3CF=CHF, CHF 2CH=CHF and CF 3CF=CH 2
Some are suitable fluoridize alpha-olefin copolymer comprise contain be derived from two or more structural units of fluoridizing 'alpha '-olefin monomers multipolymer as poly-(hexafluoropropylene (HFP)/tetrafluoroethylene (TFE)), and contain be derived from one or more fluorinated monomers and one or more can with the multipolymer of the structural unit of the nonfluorinated monoethylenically unsaturated monomer of this fluorinated monomers polymerize as (tetrafluoroethylene-ethylene-propylene) multipolymer.The example of suitable nonfluorinated monoethylenically unsaturated monomer comprises 'alpha '-olefin monomers such as ethene, propylene, butylene, acrylate monomer such as methyl methacrylate, butyl acrylate etc., preferred poly-(tetrafluoroethylene) homopolymer (PTFE).
Blend can further comprise filler and strengthening agent, for example glass fibre, glass cullet, granulated glass sphere, thin slice etc.Can add mineral, as talcum, wollastonite, mica, kaolin or illiteracy unsticking soil, silicon-dioxide, quartz and barite.Composition also can be with the mineral filler modification of significant quantity, as the carbon of carbon fiber and nanotube, steel fiber, metal-powder, conduction and comprise other additive of nanoscale strengthening agent.Also can adopt well-known other filler of those skilled in the art (can conduct electricity) so that connector assembly of the present invention provides shielding effect.
Other additive comprises oxidation inhibitor such as phosphorous acid ester, phosphinate and hindered phenol.As spendable additive, comprise that the phosphorus-containing stabilizers of triarylphosphite and aryl phosphine acid esters is famous.Also can use two functional P contained compounds.Preferred stabilizer has the molecular weight more than or equal to about 300.In other situation, can use molecular weight more than or equal to 500 phosphorus-containing stabilizers.Phosphorus-containing stabilizers is present in the composition with 0.05～0.5% weight of prescription usually.In blend, can also exist toner and photostabilizer and UV absorption agent.Flow aids and releasing agent also are fine.The example of releasing agent is the alkyl carboxylic acid ester, for example pentaerythritol tetrastearate, Tristearoylglycerol and diglycol stearate.Releasing agent is present in the composition with 0.05～0.5% weight of prescription usually.Preferred releasing agent has high molecular, is generally greater than about 300, loses from molten polymer mixture with releasing agent during preventing melt.
Can be used for additive of the present invention and comprise impact modifier, this impact modifier comprises three kinds of polymkeric substance, and wherein a kind of polymkeric substance also can have acidic component.Non-limiting instance has vinylformic acid-butadiene-styrene copolymer, carbonic acid-butadiene-styrene copolymer or contain the acidic cpd-butadiene-styrene copolymer of carbonic anhydride.Also can use impact modifier with the rubber-like composition that comprises polyolefine (as ethene or propylene).Same spendable copolymer from ethylene and propylene.Also can use the rubber-like composition, as contain the polyolefine of sour altered contents (as divinyl) or reactive epoxy functionalities.
The bat wool of length-to-diameter ratio 2～1000 can be used for giving composition with intensity.The limiting examples of this fibrid has glass fibre, hollow glass fibre, carbon fiber, hollow carbon fiber, titanium oxide whisker and wollastonite.Non-bat wool also can be used for giving pipe with intensity and spatial stability.This type of filler that can exist is the particle of plate shape, its can be crystalline form or amorphism.The limiting examples of this type of non-bat wool has talcum, clay, silica, sheet glass, granulated glass sphere and tubular fibre etc.Can use the combination of bat wool and non-bat wool equally.The consumption of impact modifier is generally about at the most 7% weight by the gross weight of composition in the pipe composition.
Except adding as the impact modifier, polyolefine also can add the chemical-resistant and the release property that are used for composition and carry out modification.Homopolymer such as polyethylene, polypropylene, polybutene etc. can be used singly or in combination.Polyethylene can high density polyethylene(HDPE) (HDPE), new LDPE (film grade) (LDPE) or branched polyethylene interpolation.Polyolefine also can use with the form of the multipolymer of following compounds: the compound of carbonic acid group-containing group, as toxilic acid or citric acid or their acid anhydrides; The acidic cpd that contains acrylic acid groups is as acrylate etc.; And comprise at least a aforesaid combination of compounds.
Also can use the alicyclic saturated hydrocarbon resin, those resins that obtain as the hydrogenation of aromatic resins, usually for example, C 9Hydrocarbon resin, C 5/ C9 hydrocarbon resin, indenes-chroman resin, vinyl aromatic resin, terpene-vinyl aromatic resin etc.As for terpenes, the terpine resin that preferably uses α-Pai Xi, beta-pinene and diterpene to form as starting material.Also can use by saturated terpene of the terpene of aromatic hydrocarbons (phenol, dihydroxyphenyl propane etc.) sex change or hydrogen etc.As for petroleum hydrocarbon, the liquid distillate of petroleum fractions is suitable for.Similarly, as for the aromatic hydrocarbons petroleum resin, the represented aromatic fraction polymkeric substance of C9 carbon class is useful.High hydrogenation ratio is preferred, preferably at least about 30%.If aromatics becomes dosis refracta higher, then the character of being wanted may incur loss.
Also can add thermo-stabilizer, it increases the thermostability of composition.This compounds comprises phosphite ester stabilizer, epoxy compounds, beta-diketon, inorganic stabilizers such as perchlorate, talcum, zeolite etc., and the combination that comprises at least a aforementioned hot stablizer.Phosphite ester stabilizer is preferably trialkyl phosphite, alkylaryl phosphorous acid ester, triaryl phosphites and the combination that comprises at least a aforementioned phosphite ester stabilizer.By the polyphenylene oxide resin and the polystyrene resin of 100 weight parts, the add-on of thermo-stabilizer can be more than or equal to about 0.01 weight part, is preferably greater than or equals about 0.1 weight part.Usually the add-on of thermo-stabilizer preferably is less than or equal to about 70 weight parts, specifically preferably is less than or equal to about 50 weight parts, by the polyphenylene oxide resin and the polystyrene resin of 100 weight parts.
Also can use such as those dripping inhibitors that prevent to drip in the combustion processes.Preferably polytetrafluoroethylene is as dripping inhibitor, and this is because it can form fibril in burning.Equally preferably can form other dripping inhibitor of fibrillar.The add-on of dripping inhibitor can be about 0.01～5 weight part, by the polyphenylene oxide resin and the polystyrene resin of 100 weight parts.In this scope, the consumption of preferred dripping inhibitor is more than or equal to about 0.05, by the polyphenylene oxide resin and the polystyrene resin of 100 weight parts.In this scope, also the add-on of preferred dripping inhibitor is less than or equal to about 3 weight parts usually, by the polyphenylene oxide resin and the polystyrene resin of 100 weight parts.
The blend polymer that is used for article according to the invention can comprise various additives such as nucleator, finings, rigidity agent and/or crystallization velocity agent equally.These additives use with convention amount in a usual manner.
Preparation is according to the method for blend of the present invention
The blend polymer that is used for article according to the invention can be by the whole bag of tricks and aforementioned composition blend, the uniform mixing of any other additive that needs in comprising material and filling a prescription.Preferable methods comprises melt blended, but solution blending also is feasible.Owing to can from commercial polymer processing facility, obtain melt blended equipment, so general preferred melt processing method.The illustrative examples that is used for the equipment of this melt processing method comprises: rotate forcing machine and reverse rotation forcing machine in the same way, single screw extrusion machine, the coextrusion machine, dish assembly type handler (disc-pack processor), and the extrusion equipment of various other types.In the method, the temperature of preferred melt minimizes, and to avoid the resin excessive degradation, in some embodiments, the composition of melt breaks away from processing units such as forcing machine by the little outlet in the mould, and the gained molten resin strip is cooled off through water-bath.The refrigerative resin streak can be lacked and cut and/or be molded as other and be suitable for packing, further process or be easy to the final suitable shape of using, and is promptly granular.
Blend as herein described can be by various melt blended method preparations.The vacuum exhaust type list screw rod or the twin screw extruder that preferably have good mixing screw.Usually, the melt temperature that can work of this forcing machine is than high about 100～150 ℃ of the Tg of thermoplastics.Each mixture of ingredients can utilize the discrete feeder or with the form of mixture all together feeds in the opening for feed of forcing machine.In some cases, for example in the blend of two or more resins, advantageously, the composition of extruding part in extruding prior to first.The remainder that in second extrudes, adds mixture then.What possibility was useful is that elder generation blendes together tinting material with enriched material in advance, then this enriched material is mixed with the remaining part of resin combination.In other cases, what possibility was useful is to add the mixture of part in the downstream of forcing machine opening for feed.After extruding, can be with polymer melt Cast Strip and cooling, the short then particle of cutting or cut into appropriate size is to be used for next manufacturing step.Preferred particle is about 1/16 to 1/8 inch long, but it will be understood by those of skill in the art that any particle size all is fine.The thermoplastic resin of dry granulated is to remove moisture and to be molded as goods of the present invention then.Preferred drying is carried out about 4～8 hours in the time of about 135～150 ℃, but can change with resinous type time of drying.Preferred injection moulding, it adopts suitable temperature, pressure and anchor clamps, and preparation has the goods of glossy surface.The melt temperature of molding is higher than about 100～200 ℃ of the Tg of resin.For the higher resin of Tg, the preferred oil heated die, and die temperature can be about 50～175 ℃, is preferably about 120～175 ℃.It will be understood by those of skill in the art that a lot of variants that can adopt these blending and condition of moulding, to prepare composition of the present invention and goods.
Also can moulding or manufacture Elastic Film, coating, sheet material, lath (strip), band (tape), rib band etc. is arranged according to blend polymer of the present invention.Can be used for preparing Elastic Film, coating and the sheet material of ring-type goods of the present invention, can be by any method preparation well known in the art, comprise inflation method (as simple inflatable and diaxial orientation method such as blow extrusion of film, two inflatable method and tentering method), cast shaping process, injection moulding, hot-forming method is extruded the applying method, profile extrusion, and sheet material extrusion molding.
Compression molding is that those skilled in the art is known, wherein blend polymer is placed die cavity or make it to contact with the metallic surface with contoured.Then under given time, pressure and temperature, apply heat and/or pressure in blend polymer by for example hydropress, condition can change according to the character of blend.Pressure from mould forces blend polymer to be full of the entire die chamber.In case the moulded product cooling can be taken out from mould by evicting mechanism from.When treating that this process is finished, blend polymer can be mold cavity or have the shape of the metallic surface of contoured.The United States Patent (USP) 4698001 of Visamara discloses the method for implementing compression molding.
Injection moulding is the method that the most general manufacturing does not have the strengthening agent plastic components, also is usually used in the plastic composite of staple fibre reinforcement.Injection moulding can be used for producing goods of the present invention.Injection moulding is such method, and wherein the blend polymer times over the article of manufacture aequum is heated into viscous fluid at heating chamber, is injected into mold cavity then under pressure.Blend polymer under high pressure is retained in the mold cavity until cooling, takes out then.The more detailed content of injection moulding and injection-moulding device is referring to the United States Patent (USP) 3915608 of Huiick, the United States Patent (USP) 3302243 of Ludwig, and the United States Patent (USP) 3224043 of Lameris.Injection moulding is usually used in using as the automobile and the consumer's goods on a large scale.Be 20～60 seconds cycling time.Injection moulding also can be produced can the approaching netted parts of height multiple.Another advantage is can center on inset, hole and core pattern material and carry out molding.Those skilled in the art can know whether injection moulding is to produce the most accurate working method of giving article made to order of the present invention.
Blowing is the method for producing hollow plastic product.Blowing comprises the extruded pipe according to thermoplastic polymer of the present invention is placed in the mould, and applies enough air pressure in pipe, so that the outside of pipe is consistent with the internal surface of die cavity.United States Patent (USP) 5551860 discloses the method by the blowing article of manufacture in more detail.Blowing is not limited to the article of production hollow.For example, can prepare " shell ", promptly, be cut into two halves then, make two shells by parts of blowing.Simple blown film processes is also disclosed, for example, referring to The Encyclopedia of Chemical Technology, Kirk-Othmer, Third Edition, John Wiley ﹠amp; Sons, New York, 1981, Vol.16, pp.416-417 and Vol.18, pp.191-192.
By blown-film extrusion, perhaps utilize conventional drawing process by stretching casting or calendered film near heat-drawn wire, can prepare the film of orientation.For example, can adopt the radial drawing pantograph to carry out multiaxis stretches simultaneously; Can utilize X-Y direction stretching pantograph on the X-Y of two dimension direction, to stretch simultaneously or one after the other.Can also adopt equipment,, as differential speed roll parts that are used for axial tension and the machine that is used for the tenter machine parts of cross directional stretch are housed with realization single shaft and biaxial stretch-formed with coaxial tensile part in succession.
The thermoplastic plastics shaping system comprises the thermoplastics extrusion dies that is used for extrusioning thermoplastic plastic's sheet material, it determines the section of sheet material by adjustable die head sluice gate spare (be dynamic die head set up), and the sheet material of extruding with change is at the thickness of the extruded material of different piece.The thermoplastics extrusion dies has cutting knife, is used to cut the thermoplastic plastic plate who extrudes from the thermoplastics extrusion dies.A plurality of can also can being installed in separately for the thermoplastics mould of pressing mold on the movable platform (as rotation platform) for vacuum mold, this platform moves a mould to certain position at every turn, to receive the thermoplastic plastic plate who cuts from the thermoplastics extruded mould.By charging from extrusion dies still heat thermoplastic material, the thermoplastic material sheet material of by this heat forms the moulded piece with variable thickness.A plurality of die heads are installed on the platform so that a die head enters the charging position of reception from the thermoplastic plastic plate of extrusion dies, and the profiled part that second mould is entered remove this mould remove the position.This platform can be the platform that comes and goes or rotate, and allows in each moulded piece of cooling, and another moulded piece is receiving the thermoplastic plastic plate.Regulation thermoplastic plastics shaping method has the following step: select the thermoplastics extrusion dies to set up according to equipment, adjust the thermoplastics extrusion dies with the thickness of change through the extruded material of the extrusion board different piece of die head.Thermoplastic material is heated to fluidised form and extrudes by selected thermoplastics die head, described die head is through adjusting the thickness with the extruded material that changes the extrusion board different piece, the thermoplastic plastic plate with variable thickness that finishing is simultaneously extruded is to predetermined size, the thermoplastic material finishing sheet material that each heat guides on the hot forming tool, and in this die for molding predetermined components, and then form moulded piece by the sheet material of extruding heating with variable thickness.About injection moulding, thermoforming, extrusion molding fit, section bar is extruded and the description of sheet material expressing technique, referring to for example " Plastics Materialsand Processes ", Seymour S.Schwartz and Sidney H.Goodman, Van NostrandReinhold CoMPany, New York, 1982, pp.527-563, pp.632-647 and pp.596-602.
Can adopt vacuum forming production according to moulded products of the present invention.According to this method, install the sheet material of fixed 1 polymeric material with chase or other, be installed on the easy-off anchor clamps, be incorporated into then in the equipment, with the ceramic heater or the wire heater that are arranged in upper-lower position it is heated there.Sheet material begins fusing during heating.In case the sagging heating that continues afterwards takes place sheet material, sheet material stretches in chase.When observing this stretching, extension, sheet material can be molded have uniform thickness and do not have wrinkle or other defective.At this moment, take out the sheet material frame in heating installation, next-door neighbour's mould is arranged, and vacuum forming when 1 atmospheric reduced pressure (reduced pressure), can obtain the goods of die needed shape thus.Thereafter, can be with goods air cooling or water spray, and from mould, take out.
According to extrusion forming, the easy to handle sheet material that will heat or become is placed on the mould, and this sheet material is exerted pressure, and makes this sheet material be the shape of mould by exerting pressure.
The goods that comprise the resin of formula (I) also can be made with the thermoprint method of forming.For example, with the formed sheet of formula (I) the polymkeric substance vertical press of in overflow mould, packing into, on required moulded products, apply 5～500kg/cm then 2(preferred 10～20kg/cm 2) pressure the time carry out thermoforming.Then make mold cools down, and from mould, take out goods by air cooling or water spray.In this moulding, the time of exerting pressure is generally at least 15 seconds, is generally 15～40 seconds.In order to improve surface property, preferably be molded under the two-stage pressure condition and carry out.In the fs, polymer materials is at 10～20kg/cm 2Pressure the time kept 15～40 seconds.Then in subordinate phase, in 40～50kg/cm 2Pressure the time kept at least 5 seconds, can make moulded product thus with excellent surface smoothness.When use contains the thermoplastic resin of formula (I) of flowability difference of mineral filler, preferred this method.
Also can use well-known injection moulding, utilize production of resins goods with formula (I).Injection moulding is a method of resin being injected mold cavity under pressure.Injection pressure is generally 40～140kg/cm 2, be preferably 70～120kg/cm 2
Pipe
Polymkeric substance of the present invention can be used for managing and the application of pipe, includes but not limited to pipe connections, adaptor (adapter) etc.The pipe that can prepare any kind of knowing altogether this area according to the present invention.This comprises the absorption that is used for heat transfer applications and/or the heat pipe of radiations heat energy, be used for liquid and/or solid being used for the fire protection pipe of aerospace application from a conduit that is transported to another place, hood down or the bend pipe of other automobile purposes or just pipe, threaded pipe, high pressure pipe and fiber reinforced pipe.
In one embodiment, polymkeric substance and blend and essential or be useful on the melt-mixing of other additive arbitrarily that improves the pipe performance can be by adding in feed throat or adding each component compounding in succession in forcing machine along the different feeds mouth at the different positions place of the machine barrel of forcing machine simultaneously.From the extrudate of forcing machine can or directly feed give mould machine, perhaps cool off and be converted into pellet, powder etc. and be used for later molded operation with the preparation duct member.As selection, can be by being molded as pipe for mould machine each component and the direct feed of additive, wherein each component can directly be mixed before molding.Polymkeric substance and/or blend also fusable links mixing also are molded as pipe then.The melt-mixing operation is carried out in forcing machine, ball formula mixing roll, roller refining machine, this kneader of cloth etc. usually.In the melt-mixing operating process, can add a small amount of solvent on demand and process with promotion in melt.In the melt-mixing process, each component can add on demand simultaneously or in succession.
Described pipe can be formed by the molded operation molding of knowing altogether as this areas such as injection moulding, extrusion moulding, blowing, vacuum formings by pellet and powder etc.Straighttube part and pipe connections can form by molding, for the usually preferred extrusion moulding of straight parts, for the then preferred injection moulding of molding web member.Can select caliber, wall thickness and shape on demand, preferred wall thickness is about 2.0～500 or 2.0～100 or 2.0～50 or 2.0～10 millimeters (mm).Tubular (pipe profile) can be cylindrical, tetragon or hexagon, pref. cylindrical usually.
Also can be built into by the pipe of polymkeric substance as herein described and blend preparation and to comprise two-layer at least multilayer or laminate form.Can use multilayer to make up multilayered tube on demand, as long as they are heat-staple and have water resistance.When pipe has two-layer or during multilayer, preferred one deck at least is constructed by the composition that comprises polyphenylene oxide resin and polystyrene resin.
Can make the pipe that is used for that water transmits and distributes, thermostability, intensity and the high-voltage resistance capability of similar and pvc pipe on its demonstration degree.In addition, do not see cracking and crack in the test of plane, this has shown the excellent compressive property of said composition.By the pipe of above-mentioned preparation of compositions component such as moisture transmissible lead not, thereby they also are favourable.Described in addition pipe does not exist usually other adverse factor relevant with steel pipe such as turbidity increase, color change, odor adsorption, loss of flavor etc.In addition, this pipe does not contain any PVC, thereby does not have chlorine from pipe water leaking-in.
In the field of method for preparing pipe and pipe prepared therefrom, provide some United States Patent (USP)s of the detailed description of state-of-the art to have: 6942016; 6920900; 6905150; 6840202.
Can use polymer materials preparation pipe as herein described.For example, have two openings pipe and
Pipeline
Polymer composition as herein described can be used for forming pipeline, the application need Nai Gaore and/or the chemical-resistant of this pipeline.For example, in oil well applications, pipeline can be used for transmitting and/or covering probe and the transmitter that gos deep into oil well.Pipeline of the present invention also can be used for transmitting the material (as liquid form) of chemistry and/or heat.For example, the method for manufacturing and use pipeline is described in United States Patent (USP) 4374530; 4345363; 4346737; 4199314; In 4109365 and 6863852.
Line coating (wire coating)
Polymer composition of the present invention also can be used as line coating or pearl coating compound.For example, it is used in the line coating in flexible pipe, band (belt) and the especially tire.Can know altogether by this area with conspicuous the whole bag of tricks construction, moulding, molding and these pneumatic tyres of conditioning.It should be understood that described tire can be manned doughnut, plane tyre or truck tire etc.Polymer composition of the present invention can be used for being coated with wiring and cable, for example the metal cable of copper cash and arbitrary form.
Can be used for the method that is coated with wiring of the present invention is that this area is in common knowledge, and it is described in for example United States Patent (USP) 4588546 of Feil etc.; The United States Patent (USP) 4038237 of Snyder etc.; The United States Patent (USP) 3986477 of Bigland etc.; And in the United States Patent (USP) 4414355 of Pokorny etc.
Line coating of the present invention is generally about 0.1～40mils, and (2.5～1000.mu.m) is thick, and (25～500.mu.m) is thick, and more preferably from about (50～250.mu.m) is thick, and most preferably from about (100～175.mu.m) is thick for 4～7mils for 2～10mils for preferred about 1～20mils.
Preferred line coating has the least possible caking and spark (spark).Line according to the coating of religious doctrine of the present invention preparation can have less than about 10 caking/135000 ft (41000m), less than about 10 sparks/135000ft (41000m); Preferably less than about 5 caking/135000 ft (41000m), less than about 5 sparks/135000ft (41000m); Be more preferably less than about 2 caking/135000 ft (41000m), be no more than about 2 sparks/135000 ft (41000m).
Embodiment
Need not further detailed description, it is believed that those skilled in the art can utilize this specification sheets to make and use the present invention.The purpose of the following example is to implement the invention provides guidance for those skilled in the art.These embodiment are representative work of the present invention and help to instruct the present invention.Therefore, the scope that do not limit the present invention in any way of these embodiment.Except as otherwise noted, all parts all by weight.
Embodiment 1
Prescription 1-9
Some performances utilize ASTM methods of test to measure.All moulded specimens were all adjusted at least 48 hours during in 50% relative humidity before test.Reverse notched izod impact value is to measure on the thick strip of 3.2mm when the room temperature according to ASTMD256.Heat-drawn wire (HDT) is to measure on the thick strip of 3.2mm when 0.46MPa (66psi) according to ASTMD648.Tensile property is to measure on the I of 3.2mm type strip according to ASTM method D638.Bending property is measured on the 3.2mm strip according to ASTM method D790.Vicat temperature is measured when the 50N according to ASTM method D1525.Differential scanning calorimeter (DSC) just adopts different heating and cooling speed according to ASTM method D3418 operation.Sample is heated to 350 ℃ and with 20 or 80 ℃/min cooling, with record peak crystallization temperature (Tc) with 20 ℃/min.Dynamic mechanical analysis (DMA) carries out on the 3.2mm strip at case of bending, and rate of heating is 3 ℃/min, and hunting frequency is 1 hertz.DMA experimental evidence ASTM method D5418 moves to 300 ℃ by about 30.Viscosity-shearing rate adopts 1 * 10mm die head to measure on capillary rheometer at 380 ℃ according to ASTM method D3835.The particle of blend, adopt parallel-plate rheometer with the melt viscosity of 10 radians/when minute measuring 380 ℃ over time before, in 150 ℃ of dryings at least 3 hours.
Second-order transition temperature (Tg) can be measured by Several Methods as known in the art, for example ASTM method D34318.In Tg measures, can adopt different rate of heating, for example per minute is 5～30 ℃, is 10～20 ℃ of per minutes in other situation perhaps.
Material
PCE is the BPA Copolycarbonate, and it comprises the 1:1 mixture and the remaining BPA carbonate group of the isophthalic acid ester of about 60% weight and terephthalic acid ester group, and Mw is about 28300, and Tg is about 175 ℃.
PSEI-1 is a polysulfones ether imide, its be by 4,4 '-4,4 (DDS) reaction of oxygen di-Tetra hydro Phthalic anhydride (ODPA) and about equimolar amount and preparing, Mw is about 33000, Tg is about 310 ℃.
PSEI-2 is a polysulfones ether imide copolymer, it is by about 80% mole 4,4 '-mixture and 4 of about equimolar amount of oxygen di-Tetra hydro Phthalic anhydride (ODPA) and about 20% mole of dihydroxyphenyl propane dicarboxylic anhydride (BPADA), 4 '-diaminodiphenylsulfone(DDS) (DDS) reaction and preparation, Mw is about 28000, and Tg is about 280 ℃.
PSEI-3 is a polysulfones ether imide, and it is that 4,4 (DDS) by dihydroxyphenyl propane dicarboxylic anhydride (BPADA) and about equimolar amount reacts and prepares, and Mw is about 34000, and Tg is about 247 ℃.
PSEI-4 is a polysulfones ether imide, and it is 1H-isoindole-1,3 (the 2H)-diketone by dihydroxyphenyl propane disodium salt and equimolar amount, 2,2 '-(alkylsulfonyl two-4,1-phenylene) two [4-chloro-(9CI) prepared in reaction, Mw is about 50000, Tg is about 265 ℃.
Prescription of the present invention 1-9 utilizes the preparation of compositions enumerated in the table 1.All with parts by weight (phr) expression with respect to per 100 parts by weight resin, wherein all resins weight comprises the stablizer when existing to the amount of all components.Polycarbonate (PCE) multipolymer is in the presence of alkali and triethylamine phase-transfer catalyst, prepares in two-phase (methylene dichloride/water) reaction of m-phthaloyl chloride and p-phthaloyl chloride and dihydroxyphenyl propane.The particular content of the type building-up reactions can be referring to for example United States Patent (USP) 5521258 (the 13rd hurdle the 15th～45 row).The gained polyester carbonate copolymer has 60% ester units (the m-phthalic acid ester units of 1:1 w/w and the mixture of terephthalate units) and 40% carbonate unit based on dihydroxyphenyl propane.The composition of enumerating in the table 1 mixes in paint mixer, and is extruding with 80～90rpm speed during in 575～640 ℉ on 2.5 inches the vacuum exhaust single screw extrusion machine.With the pelletizing of gained blend, and before being injection molded into 5 * 7 * 1/8 inch plate, drying is 4 hours when 275 ℉.Melt temperature that shaper is 675 ℉ and the die temperature of 275 ℉ are set.To each molded sample, carry out 20 ° of gloss, CIE L *The mensuration of value and outward appearance.20 degree gloss adopt black ceramic tile to measure according to ASTM D523.CIE luminance brightness (L *) value is according to R.McDonald (ed.), ＂ Colour Physics for Industry, SecondEdition ＂ The Society of Dyers and Colourists, Bradford measures described in the UK (1997).Outward appearance is meant the subjective vision inspection of moulded piece color and translucency/opaqueness.
Table 1
Prescription 1 2 3 4 5 6 7 8 9
PCE PSEI-3 PSEI-2 PSEI-1 60 40 50 50 50 50 30 70 40 60 60 40 70 30 45 55 65 35
Embodiment 2
Utilize one or more methods recited above, above-mentioned prescription 1,2,3,4 and 5 of the present invention is injection molded into duct member and pipe connections.
Embodiment 3
To be injected in the mold cavity according to the material of 6,7,8 and 9 preparations of filling a prescription in the table 1, form duct member.
Embodiment 4
Prescription 10-11
Material
Resorcinol polycarbonate (ITR) resins that are used for these prescriptions are polymkeric substance that 1:1 mixture and Resorcinol, the condensation of dihydroxyphenyl propane (BPA) photoreactive gas by m-phthaloyl chloride and p-phthaloyl chloride prepares.The ITR polymkeric substance connects the approximate molar ratio name that base/carbonic ether connects base by ester.ITR9010 has about 82% mole resorcinol and connects base, and 8% mole resorcinol carbonate connects base, and about 10% mole BPA carbonic ether connects base.Tg＝131℃。
PEI=ULTEM 1000 polyetherimides, it is by the mphenylenediamine prepared in reaction of dihydroxyphenyl propane dicarboxylic anhydride and about equimolar amount, derives from GE Plastics.
The PEI-siloxanes is the polyetherimide dimethylsiloxane copolymer, and it is by the preparation of the imidization reaction of mphenylenediamine, BPA-dicarboxylic anhydride and the functional methylsiloxane of diamino propyl group (on average containing about 10 Siliciumatoms).It has the content of siloxane of about 34% weight, and the Mn by gel permeation chromatography measurement is about 24000.
PC is the BPA polycarbonate, and LEXAN 130, derives from GE Plastics.
Blend is that the mixture of extruding Resorcinol kind polyester carbonate resin and polyetherimide and siloxanes polyimide copolymer resin prepares by in single screw rod vacuum exhaust forcing machine of 2.5 inches.Unless indicate in addition, each component is to enumerate with the % weight that accounts for whole composition.Forcing machine is arranged on about 285～340 ℃.Blend speed with about 90rpm under vacuum is carried out.With extrudate cooling, pelletizing and in 120 ℃ of dryings.Adopt 30 second cycling time, when the die temperature of 320～360 ℃ design temperatures and 120 ℃, with the test sample injection moulding.
Table 2
Figure A200680052695D00631
To be injected in the mold cavity according to the material of prescription 10 and 11 preparations, form duct member.
Embodiment 5
Utilize and prepare the identical method of the described blend of front embodiment, prepare blend 12-18.
Table 3
Prescription 12 13 14 15 16 17 18
PEI ITR9010 56.5 42.5 78.0 20.0 63.0 35.0 48.0 50.0 69.5 27.5 46.0 50.0 76.0 20.0
The PEI-siloxanes 1.0 2.0 2.0 2.0 3.0 4.0 4.0
The TiO of whole blend 3phr 2Triaryl phosphites with 0.1phr
The 12-18 that will fill a prescription extrudes separately, forms the 2mm pipeline.
Embodiment 6
Utilize and prepare the identical method of the described blend of front embodiment, prepare blend 19-25.
Table 4
Prescription 19 20 21 22 23 24 25
PEI ITR9010 PEI-siloxanes PC triaryl phosphites TiO 2 67.5 30.0 2.5 0.0 67.5 30.0 2.5 3.0 68 58 20 30 2 2 10 10 3 3 19.15 80.0 0.75 0.1 18.40 80.0 1.50 0.1 17.65 80.0 2.25 0.1
Utilize one or more aforesaid methods, with above-mentioned prescription 19-25 of the present invention on copper cash coextrusion with as the line coating.
Embodiment 7
Utilize and prepare the identical method of the described blend of front embodiment, prepare blend 26-31.
Table 5
Embodiment 26 27 28 29 30 31
PEI ITR9010 PEI-siloxanes triaryl phosphites 49.15 50.0 0.75 0.1 48.40 50.0 1.50 0.1 47.65 50.0 2.25 0.1 79.15 78.40 20.0 20.0 0.75 1.50 0.1 0.1 77.70 20.0 2.25 0.1
The 26-31 that will fill a prescription is injected into separately and is in the big cyclic mold cavity, is used for the connection of duct member.
Embodiment 8
Material
Resorcinol polycarbonate (ITR) resin that is used for these embodiment is the polymkeric substance for preparing by the 1:1 mixture of m-phthaloyl chloride and p-phthaloyl chloride and Resorcinol, the condensation of dihydroxyphenyl propane (BPA) photoreactive gas.The ITR polymkeric substance connects the approximate molar ratio name that base/carbonic ether connects base by ester.ITR9010 has about 82% mole resorcinol and connects base, and 8% mole resorcinol carbonate connects base, and about 10% mole BPA carbonic ether connects base.Tg＝131℃。The PEI-siloxanes is the polyetherimide dimethylsiloxane copolymer, and it is by the preparation of the imidization reaction of mphenylenediamine, BPA-dicarboxylic anhydride and the functional methylsiloxane of diamino propyl group (on average containing about 10 Siliciumatoms).It has the content of siloxane of about 34% weight, and the Mn by gel permeation chromatography measurement is about 24000.
PSu is the polysulfones that the reaction by dihydroxyphenyl propane and dichloro diphenyl sulfone prepares, and is sold with UDEL1700 by Solvay Co..
PES is the polyethersulfone by dihydroxy-diphenyl sulfone and dichloro diphenyl sulfone preparation, and is sold with ULTRASONE by BASF Co..
Note that the blend according to this embodiment has the titanium dioxide (TiO that 3phr adds during blending 2).This blend is that the mixture of extruding Resorcinol kind polyester carbonate resin and polysulfones or polyethersulfone and siloxanes polyimide copolymer resin prepares by on single screw rod vacuum exhaust forcing machine of 2.5 inches.Unless indicate in addition, each component is to enumerate with the % weight that accounts for whole composition.Forcing machine is set to about 285～340 ℃.Blend speed with about 90rpm under vacuum is carried out.With extrudate cooling, pelletizing and in 120 ℃ of dryings.
Table 6
Adopt 30 second cycling time, when the die temperature of 320～360 ℃ design temperatures and 120 ℃, the 32-34 injection moulding of will filling a prescription is to form duct member.
Embodiment 9
Prescription 35 and 36 in the table 7 shows the blend of the resorcinol Copolycarbonate of PSu or PES and high level (60% weight).These blends are to prepare according to the method described in the previous embodiment.
Table 7
*Blend has the TiO of 3phr 2
Adopt 30 second cycling time, when the die temperature of 320～360 ℃ design temperatures and 120 ℃, will fill a prescription 35-36 and copper cash coextrusion are to form the line of coating.
All patents that this paper is above-mentioned and patent application all integral body are incorporated herein by reference clearly, as setting forth in full.
Though described the present invention with reference to preferred implementation, it will be appreciated by those skilled in the art that and can carry out various changes and can replace its composition with Equivalent, do not deviate from scope of the present invention.In addition, can carry out multiple improvement,, and not deviate from base region of the present invention so that particular condition or material are adapted to instruction of the present invention.Therefore, this means the present invention and is not limited to implement best mode of the present invention and disclosed specific implementations as expection, but the present invention will comprise the whole embodiments that fall within the claims scope.

Claims (105)

1. ring-type or piped tubular type goods with external diameter, internal diameter and length, it comprises one or more materials that is selected from down group: a) unmixability blend polymer, it comprises one or more polyetherimides, have the second-order transition temperature more than, wherein said polyetherimide has the second-order transition temperature greater than 217 ℃; B) compatibility blend polymer, it comprises one or more polyetherimides, has single second-order transition temperature greater than 180 ℃; Perhaps c) single polyetherimide, it has the second-order transition temperature greater than 247 ℃.
2. according to the tubular type goods of claim 1, wherein said polyetherimide has hydrogen atom/carbon atom ratio of about 0.4～0.85.
3. according to the tubular type goods of claim 1, wherein said polyetherimide does not contain the benzylic proton substantially.
4. according to the tubular type goods of claim 1, the external diameter of wherein said goods is basic identical on whole length.
5. according to the tubular type goods of claim 1, the internal diameter of wherein said goods is basic identical on whole length.
6. according to the tubular type goods of claim 1, the external diameter of wherein said goods and the difference of internal diameter are basic identical on whole length.
7. according to the tubular type goods of claim 1, wherein said tubular type goods comprise the coating on the moulded products, and the composition of described moulded products is different from this coating.
8. according to the tubular type goods of claim 5, wherein said goods are the form of the coating on the solid wire.
9. according to the tubular type goods of claim 5, wherein said goods are the form of the coating on the hollow tube.
10. according to the tubular type goods of claim 5, wherein said goods are the form of the coating on the solid cable core.
11. according to the tubular type goods of claim 5, wherein said goods are the form of the lacquering on solid or the hollow core.
12. according to the tubular type goods of claim 5, wherein said goods are tubular.
13. according to the tubular type goods of claim 5, wherein said goods are the coating on the instrument of conduction current or signal.
14. according to the tubular type goods of claim 1, wherein one or more resins are form of foam.
15. according to the tubular type goods of claim 1, wherein said goods are the pipeline form.
16. according to the tubular type goods of claim 1, wherein said goods are the tubular fibre form.
17. according to the tubular type goods of claim 1, wherein said goods are the form of the insulating coating on the moulded products.
18. according to the tubular type goods of claim 1, wherein said goods are the form of the insulating coating on the moulded products, wherein this coating plays heat insulator or electrical insulator effect.
19. according to the tubular type goods of claim 1, it comprises the unmixability blend polymer that has more than a second-order transition temperature, and non-polyetherimide polymer wherein has greater than about 180 ℃ second-order transition temperature.
20. according to the tubular type goods of claim 1, it comprises the compatibility blend polymer with single glass transition temperature, described second-order transition temperature is greater than 200 ℃.
21. according to the tubular type goods of claim 1, it comprises single polyetherimide polymer, this polyetherimide polymer has the second-order transition temperature greater than 247 ℃.
22. according to the tubular type goods of claim 1, it comprises the blend of first resin, second resin and the 3rd resin, wherein said first resin is selected from: polysulfones, and polyethersulfone, Poly-s 179, and composition thereof; Described second resin comprises silicone copolymers; And described the 3rd resin comprises Resorcinol class aryl vibrin, and wherein connecting base more than or equal to 50% mole aryl polyester is that the aryl ester that is derived from Resorcinol connects basic.
23. tubular type goods according to claim 22, wherein said silicone copolymers is selected from: Polyimidesiloxane, the polyetherimide oxyalkylene amine, the polyetherimide sulfone siloxanes, polycarbonate siloxanes, polyestercarbonate siloxanes, the polysulfones siloxanes, the polyethersulfone siloxanes, the Poly-s 179 siloxanes, and composition thereof.
24. according to the tubular type goods of claim 22, the content of wherein said silicone copolymers is about 0.1～10.0% weight of blend polymer.
25. according to the tubular type goods of claim 22, wherein said silicone copolymers has the content of siloxane of about 5～70% weight.
26. according to the tubular type goods of claim 22, wherein said polysulfones, polyethersulfone, Poly-s 179 and composition thereof have and are less than or equal to hydrogen atom/carbon atom ratio of 0.85.
27. according to the tubular type goods of claim 1, it also comprises one or more metal oxides that accounts for polymer weight 0.1～20%.
28. according to the tubular type goods of claim 22, wherein said Resorcinol class aryl polyester has structure as follows:
Figure A200680052695C00041
R is at least a in following in the formula: C 1-12Alkyl, C 6-C 24Aryl, alkylaryl, alkoxy or halogen; And
N is 0～4, and m is at least about 8.
29. according to the tubular type goods of claim 22, wherein said Resorcinol kind polyester resin is to comprise the multipolymer that structure carbonic ether as follows connects base:
Figure A200680052695C00042
R is at least a in following in the formula: C 1-12Alkyl, C 6-C 24Aryl, alkylaryl, alkoxy or halogen, n are 0～4, R 5Be at least a divalent organic group, m is about 4～150, and p is about 2～200.
30. according to the tubular type goods of claim 29, wherein R 5Be derived from bisphenol cpd.
31. tubular type goods according to claim 1, wherein the blend polymer that is separated of unmixability comprises the mixture of following resin Composition: a) first resin Composition, it is for being selected from PAEK, poly-aryl ketones, one or more in polyetherketone and the polyether-ether-ketone; With b) second resin Composition, it comprises at least a polysulfones ether imide, and this polysulfones ether imide has the connection base more than or equal at least a aryl sulfone group of 50% mole contain.
32. tubular type goods according to claim 31, wherein said polysulfones ether imide comprises aryl sulfone and is connected base with aryl ethers, makes the imido at least 50% mole repeating unit of polysulfones ether comprise at least one aryl ethers and connects base, the basic base that is connected with at least two aryl imides of at least one aryl sulfone connection.
33. according to the tubular type goods of claim 31, wherein at least 50% mole polysulfones ether imide connection base comes from oxygen di-Tetra hydro Phthalic anhydride or its chemical equivalence thing.
34. according to the tubular type goods of claim 31, wherein less than basic diamines or the dicarboxylic anhydride that contains different alkylidene group that come from of 30% mole polysulfones ether imide connection.
35. according to the tubular type goods of claim 1, wherein when measuring on the 3.2mm sample when 66psi (0.46MPa) according to ASTM method D648, these goods have the heat-drawn wire (HDT) more than or equal to 170 ℃.
36. according to the tubular type goods of claim 31, wherein said polysulfones ether imide accounts for about 30～70% weight of whole goods.
37. according to the tubular type goods of claim 31, wherein when measuring on the 3.2mm sample according to ASTM D5418, the modulus of these goods in the time of 200 ℃ is greater than about 200MPa.
38. according to the tubular type goods of claim 31, wherein said polysulfones ether imide does not contain the benzylic proton substantially.
39. according to the tubular type goods of claim 31, wherein one or more in PAEK, poly-aryl ketones, polyetherketone and the polyether-ether-ketone have 300～380 ℃ crystalline melting point.
40. according to the tubular type goods of claim 38, wherein said polysulfones ether imide has 250～350 ℃ second-order transition temperature (Tg).
41. tubular type goods according to claim 1, it comprises the blend polymer with at least two different second-order transition temperatures, when measuring according to ASTM method D5418, wherein first second-order transition temperature is 120～200 ℃, and second second-order transition temperature is 250～350 ℃.
42. according to the tubular type goods of claim 1, it comprises the blend of first resin, second resin and the 3rd resin, described first resin is selected from polyimide, polyetherimide, and polyetherimide sulfone, and composition thereof; Described second resin comprises silicone copolymers; And described the 3rd resin comprises Resorcinol class aryl vibrin, and wherein connecting base more than or equal to 50% mole aryl polyester is that the aryl ester that is derived from Resorcinol connects basic.
43. tubular type goods according to claim 42, wherein said silicone copolymers is to be selected from following one or more: Polyimidesiloxane, the polyetherimide oxyalkylene amine, the polyetherimide sulfone siloxanes, the polycarbonate siloxanes, polyestercarbonate siloxanes, polysulfones siloxanes, polyethersulfone siloxanes, and Poly-s 179 siloxanes.
44. according to the tubular type goods of claim 42, the content of wherein said silicone copolymers is about 0.1～10.0% weight of blend polymer.
45. according to the tubular type goods of claim 42, wherein said silicone copolymers has the content of siloxane of 5～70% weight.
46. according to the tubular type goods of claim 42, wherein said polyimide, polyetherimide, polyetherimide sulfone and composition thereof have and are less than or equal to hydrogen atom/carbon atom ratio of 0.75.
47. according to the tubular type goods of claim 1, it further comprises one or more metal oxides, this metal oxide accounts for blend polymer 0.1～20% weight.
48. according to the tubular type goods of claim 42, wherein said Resorcinol class aryl polyester has structure as follows:
R is at least a in following in the formula: C 1-12Alkyl, C 6-C 24Aryl, alkylaryl, alkoxy or halogen,
N is 0～4, and m is at least about 8.
49. according to the tubular type goods of claim 42, wherein said Resorcinol kind polyester resin is to comprise the multipolymer that the carbonic ether with structure as follows connects base:
Figure A200680052695C00062
R is at least a in following in the formula: C 1-12Alkyl, C 6-C 24Aryl, alkylaryl, alkoxy or halogen, n are 0～4, R 5Be at least a divalent organic group, m is about 4～150, and p is about 2～200.
50. according to the tubular type goods of claim 49, wherein R 5Come from bisphenol cpd.
51. according to the tubular type goods of claim 42, wherein said polyetherimide is prepared by following material:
(a) aryl dicarboxylic anhydride, it is selected from: the dihydroxyphenyl propane dicarboxylic anhydride, oxygen di-Tetra hydro Phthalic anhydride, pyromellitic acid dianhydride, diphthalic anhydrides, the alkylsulfonyl dicarboxylic anhydride, sulphur di-acid anhydrides, the benzophenone dicarboxylic anhydride, and composition thereof; And
(b) aryl diamine, it is selected from: mphenylenediamine, Ursol D, diaminodiphenylsulfone(DDS), oxydiphenyl amine, diamino phenoxy benzene, diamino phenoxy biphenyl, diamino-phenyl benzene sulfone, diaminodiphenyl sulfide, and composition thereof.
52. according to the tubular type goods of claim 1, wherein these goods comprise the Copolyetherimides that second-order transition temperature is at least about 218 ℃, this Copolyetherimides comprises the structural unit of formula (I) and formula (II):
Figure A200680052695C00071
And the structural unit of optional formula (III):
Figure A200680052695C00072
R in the formula 1Comprise unsubstituted C 6-22The C of divalent aromatic hydrocarbon or replacement 6-22Divalent aromatic hydrocarbon, the C of described replacement 6-22Divalent aromatic hydrocarbon comprises halogen or alkyl substituent, perhaps described substituent mixture; The perhaps divalent group of general formula (IV):
Wherein the unspecified position isomerism of aromatic ring or be Q between position or be the contraposition of Q, and Q is covalent linkage or is the member who is selected from the following formula V:
(V)
-O-，-S-，
Figure A200680052695C00074
And formula C yH 2yAlkylene or alkylidene group, wherein y is 1～5 the integer that comprises end value, R 2Be divalent aromatic radical; The unitary weight ratio of the unit of formula (I) and formula (II) is that about 99.9:0.1 is to about 25:75.
53. according to the tubular type goods of claim 52, it comprises Tg greater than 225 ℃ Copolyetherimides.
54. according to the tubular type goods of claim 52, it comprises Copolyetherimides, this Copolyetherimides comprises the structural unit of formula (III).
55. according to the tubular type goods of claim 52, wherein R 1Come from least a following diamines that is selected from: mphenylenediamine, Ursol D, 2-methyl-4,6-diethyl-1, the 3-phenylenediamine, 5-methyl-4,6-diethyl-1, the 3-phenylenediamine, two (4-aminophenyls)-2,2-propane, two (2-chloro-4-amino-3,5-diethyl phenyl) methane, 4,4 '-benzidine, 3,4 '-benzidine, 4,3,4 '-diaminodiphenyl oxide, 4,4,3,4 '-diaminodiphenylsulfone(DDS), 4,4 '-diaminobenzophenone, 3,4 '-diaminobenzophenone, 2, the 4-tolylene diamine, and composition thereof.
56. according to the tubular type goods of claim 52, wherein R 2Come from the dihydroxyl substituted arene of at least a formula (VI):
HO---D---OH
D has the structure of following formula (VII) in the formula:
Figure A200680052695C00081
A in the formula 1Represent aryl;
E comprises that sulfur-bearing connects base, thioether, sulfoxide, sulfone; Phosphorous connection base, phosphinyl, phosphono; Ether connects base; Carbonyl; Uncle's nitrogen groups; Siliceous connection base; Silane; Siloxy-; Alicyclic group; Cyclopentylidene, 3,3,5-trimethylammonium cyclopentylidene, cyclohexylidene, 3,3-dimethyl cyclohexylidene, 3,3,5-3-methyl cyclohexanol fork, methyl cyclohexane fork, 2-[2.2.1]-the bicycloheptane fork, new pentylidene, cyclopentadecane fork, cyclododecane fork, Buddha's warrior attendant alkylidene; Alkylene or alkylidene group, this group is optional to be that the part of one or more condensed ring, described condensed ring are connected on one or more aryl with a hydroxyl substituent; Undersaturated alkylidene group; Perhaps two or more alkylenes or the alkylidene group that connects by the part that is different from alkylene or alkylidene, the described part that is different from alkylene or alkylidene is selected from: aromatics connects base, uncle's nitrogen connects base, ether connects base, carbonyl connects base, siliceous connection base, silane, siloxy-, sulfur-bearing connects base, thioether, sulfoxide, sulfone, phosphorous connection base, phosphinyl and phosphono;
R 3Comprise hydrogen; The monovalence alkyl, alkenyl, allyl group, alkyl, aryl, aralkyl, alkaryl, perhaps cycloalkyl;
Y 1Be independently selected from when occurring: inorganic atoms, halogen at every turn; Inorganic group, nitro; Organic group, monovalence alkyl, alkenyl, allyl group, alkyl, aryl, aralkyl, alkaryl, cycloalkyl, and alkoxyl group;
The letter " m " representative comprise 0 from 0 to A 1But go up any integer of the position of substitution number;
Letter " p " but representative comprises any integer of the position of substitution number on 0 to E of 0;
Letter " t " representative equals 1 integer at least;
Letter " s " is represented or is equaled 0 or equal 1 integer; And
" u " representative comprises 0 arbitrary integer.
57. according to the tubular type goods of claim 52, the R in each of its Chinese style (I), formula (II) and formula (III) 2Structural unit is identical.
58. according to the tubular type goods of claim 52, the R at least two of its Chinese style (I), formula (II) and formula (III) to small part 2Structural unit is not identical.
59. according to the tubular type goods of claim 52, wherein R2 is derived from least a following dihydroxyl substituted arene that is selected from: 4,4 '-(cyclopentylidene) biphenol; 4,4 '-(3,3,5-trimethylammonium cyclopentylidene) biphenol; 4,4 '-(cyclohexylidene) biphenol; 4,4 '-(3,3-dimethyl cyclohexylidene) biphenol; 4,4 '-(3,3,5-3-methyl cyclohexanol fork) biphenol; 4,4 '-(methyl cyclohexane fork) biphenol; 4,4 '-two (3, the 5-dimethyl) biphenol, 1,1-two (4-hydroxy-3-methyl phenyl) hexanaphthene; 4,4-two (4-hydroxy phenyl) heptane; 2,4 '-the dihydroxyl ditan; Two (2-hydroxy phenyl) methane; Two (4-hydroxy phenyl) methane; Two (4-hydroxyl-5-nitrophenyl) methane; Two (4-hydroxyl-2,6-dimethyl-3-p-methoxy-phenyl) methane; 1,1-two (4-hydroxy phenyl) ethane; 1,2-two (4-hydroxy phenyl) ethane; 1,1-two (4-hydroxyl-2-chloro-phenyl-) ethane; 2,2-two (4-hydroxy phenyl) propane; 2,2-two (3-phenyl-4-hydroxy phenyl) propane; 2,2-two (4-hydroxy-3-methyl phenyl) propane; 2,2-two (4-hydroxyl-3-ethylphenyl) propane; 2,2-two (4-hydroxyl-3-isopropyl phenyl) propane; 2,2-two (4-hydroxyl-3,5-3,5-dimethylphenyl) propane; 3,5,3 ', 5 '-tetrachloro-4,4 '-dihydroxyphenyl) propane; Two (4-hydroxy phenyl) cyclohexyl-methane; 2,2-two (4-hydroxy phenyl)-1-phenyl-propane; 2,4 '-the dihydroxyphenyl sulfone; Dihydroxy naphthlene, 2, the 6-dihydroxy naphthlene; Resorcinol; Resorcinol; C 1-3The Resorcinol that alkyl replaces; 2,2-two (4-hydroxy phenyl) butane; 2,2-two (4-hydroxy phenyl)-2-methylbutane; 1,1-two (4-hydroxy phenyl) hexanaphthene; Two (4-hydroxy phenyls); Two (4-hydroxy phenyl) thioether; 2-(3-methyl-4-hydroxy phenyl-2-(4-hydroxy phenyl) propane; 2-(3,5-dimethyl-4-hydroxy phenyl)-2-(4-hydroxy phenyl) propane; 2-(3-methyl-4-hydroxy phenyl)-2-(3,5-dimethyl-4-hydroxy phenyl) propane; Two (3,5-3,5-dimethylphenyl-4-hydroxy phenyl) methane; 1,1-two (3,5-3,5-dimethylphenyl-4-hydroxy phenyl) ethane; 2,2-two (3,5-3,5-dimethylphenyl-4-hydroxy phenyl) propane; 2,4-two (3,5-3,5-dimethylphenyl-4-hydroxy phenyl)-2-methylbutane; 3,3-two (3,5-3,5-dimethylphenyl-4-hydroxy phenyl) pentane; 1,1-two (3,5-3,5-dimethylphenyl-4-hydroxy phenyl) pentamethylene; 1,1-two (3,5-3,5-dimethylphenyl-4-hydroxy phenyl) hexanaphthene; Two (3,5-3,5-dimethylphenyl-4-hydroxy phenyl) thioether, 3-(4-hydroxy phenyl)-1,1,3-trimethylammonium indane-5-alcohol, 1-(4-hydroxy phenyl)-1,3,3-trimethylammonium indane-5-alcohol, 2,2,2 ', 2 '-tetrahydrochysene-3,3,3 ', 3 '-tetramethyl--1,1 '-spiral shell two [1H-indenes]-6,6 '-glycol.
60. according to the tubular type goods of claim 52, wherein R 2Come from least a dihydroxyl substituted arene that is selected from the dihydroxyl substituted arene shown in dihydroxyl substituted arene shown in the following formula (IX) and the following formula (X):
Figure A200680052695C00101
Each R in the formula 5Be hydrogen, chlorine, bromine or univalent C independently 1-30Alkyl or-oxyl, each Z 1Be hydrogen, chlorine or bromine, condition is at least one Z 1Be chlorine or bromine;
Figure A200680052695C00102
Each R in the formula 5Independently as top defined, R gAnd R hBe hydrogen or C independently 1-30Alkyl.
61. according to the tubular type goods of claim 52, wherein R 2Be derived from dihydroxyphenyl propane.
62. according to the tubular type goods of claim 52, it also comprises the structural unit that is derived from least a chain terminator.
63. according to the tubular type goods of claim 62, wherein said chain terminator is at least a following member who does not replace or replace that is selected from: alkylogen, alkyl chloride, aryl halide, aryl chloride, and the muriate of formula (XVII) and formula (XVIII):
Figure A200680052695C00103
Chlorine substituent is positioned at 3-or 4-position, Z in the formula 3And Z 4Comprise replacement or unsubstituted alkyl or aryl.
64. according to the tubular type goods of claim 62, wherein said chain terminator is to be selected from least a in following: a chlorobenzophenone, a chloro-diphenyl sulfone; One chlorophthalimide; 4-chloro-N-methyl phthalimide, 4-chloro-N-butyl phthalimide, 4-chloro-N-octadecyl phthalic imidine, 3-chloro-N-methyl phthalimide, 3-chloro-N-butyl phthalimide, 3-chloro-N-octadecyl phthalic imidine, 4-chloro-N-phenyl phthalic imidine, 3-chloro-N-phenyl phthalic imidine; Monobasic two-phthalic imidine; One chlorine, two phthaloyl imino benzene; 1-[N-(4-chlore O-phthalic acid acylimino)]-3-(N-phthaloyl imino) benzene; 1-[N-(3-chlore O-phthalic acid acylimino)]-3-(N-phthaloyl imino) benzene; One chlorine, two phthaloyl imino sulfobenzides, a chlorine two phthaloyl imino benzophenone, a chlorine two phthaloyl imino phenyl ethers; 4-[N-(4-chlore O-phthalic acid acylimino)] phenyl-4 '-(N-phthaloyl imino) phenyl ether; 4-[N-(3-chlore O-phthalic acid acylimino) phenyl]-4 '-(N-phthaloyl imino) phenyl ether, and back two kinds of compounds come from 3,4 '-the corresponding isomer of diaminodiphenyl oxide.
65. according to the tubular type goods of claim 52, the unitary weight ratio of unit of its Chinese style (I) and formula (II) is that about 99:1 is to about 25:75.
66. according to the tubular type goods of claim 52, its heat-drawn wire when 0.455MPa is at least 205 ℃.
67. according to the tubular type goods of claim 52, when measuring according to ASTM method D648, its heat-drawn wire when 0.455MPa is at least 210 ℃.
68. according to the tubular type goods of claim 52, when measuring according to ASTM method D3763, its temperature that changes between brittle state and ductility state is 30 ℃ at the most.
69. according to the tubular type goods of claim 52, wherein when measuring with respect to polystyrene standards by gel permeation chromatography, described polyetherimide has about 20000～80000 weight-average molecular weight.
70. according to the tubular type goods of claim 52, it comprises single polyetherimide, this polyetherimide has greater than 247 ℃ of second-order transition temperatures.
71. according to the tubular type goods of claim 52, it comprises blend polymer, this blend polymer comprises at least a second-order transition temperature greater than 217 ℃ polyetherimide.
72. according to the tubular type goods of claim 52, it comprises the resin blend of following resin: a) first resin, it is selected from polysulfones, polyethersulfone, Poly-s 179, and composition thereof; B) second resin, it comprises silicone copolymers; C) the 3rd resin, it comprises Resorcinol class aryl vibrin, and is wherein basic for the aryl ester connection that comes from Resorcinol more than or equal to 50% mole aryl polyester connection base; And d) the 4th resin, it comprises one or more and is selected from polyaryl ether, polycarbonate, polyestercarbonate, polyarylester, polymeric amide, and the resin of polyester.
73. according to the tubular type goods of claim 52, it comprises and is selected from following single-phase amorphous resin blend: polyetherimide, and comprise the single phase blend of polyester and polyetherimide.
74. the tubular type goods according to claim 1 also comprise the compound that contains a boron atom at least.
75. according to the tubular type goods of claim 1, when measuring according to FAR25.853, its two minute-peaks heat release is less than about 60kW-min/m 2
76. according to the tubular type goods of claim 1, when measuring according to FAR25.853, its total heat release is less than about 80kW/m 2
77. according to the tubular type goods of claim 1, wherein these goods comprise blend polymer, when measuring according to ASTM D638, the tensile fracture elongation rate of this blend polymer is more than or equal to about 50%.
78. according to the tubular type goods of claim 1, wherein when measuring according to ASTM D790, the modulus in flexure of described blend polymer is more than or equal to about 300Kpsi (2070MPa).
79. according to the tubular type goods of claim 1, wherein these goods are selected from: sheet material, film, multi-layer sheet, tubular fibre, film, multilayer film, moulded piece, extrusion profile is coated with product, and foams.
80. according to the tubular type goods of claim 1, it comprises the material with at least one Tg, this Tg is 218 ℃ or higher.
81. according to the tubular type goods of claim 1, wherein said electrical connectors comprises the material with at least one Tg, this Tg is 219 ℃ or higher.
82. according to the tubular type goods of claim 1, it comprises the material with at least one Tg, this Tg is 220 ℃ or higher.
83. according to the tubular type goods of claim 1, it comprises the material with at least one Tg, this Tg is 221 ℃ or higher.
84. according to the tubular type goods of claim 1, it comprises the material with at least one Tg, this Tg is 222 ℃ or higher.
85. according to the tubular type goods of claim 1, it comprises the material with at least one Tg, this Tg is 223 ℃ or higher.
86. according to the tubular type goods of claim 1, it comprises the material with at least one Tg, this Tg is 224 ℃ or higher.
87. according to the tubular type goods of claim 1, it comprises the material with at least one Tg, this Tg is 225 ℃ or higher.
88. according to the tubular type goods of claim 1, it comprises the material with at least one Tg, this Tg is 230 ℃ or higher.
89. according to the tubular type goods of claim 1, it comprises the material with at least one Tg, this Tg is 235 ℃ or higher.
90. according to the tubular type goods of claim 1, it comprises the material with at least one Tg, this Tg is 240 ℃ or higher.
91. according to the tubular type goods of claim 1, it comprises the material with at least one Tg, this Tg is 245 ℃ or higher.
92. according to the tubular type goods of claim 1, it comprises the material with at least one Tg, this Tg is 250 ℃ or higher.
93. according to the tubular type goods of claim 1, it comprises the material with at least one Tg, this Tg is 255 ℃ or higher.
94. according to the tubular type goods of claim 1, it comprises the material with at least one Tg, this Tg is 260 ℃ or higher.
95. according to the tubular type goods of claim 1, it comprises the material with at least one Tg, this Tg is 265 ℃ or higher.
96. according to the tubular type goods of claim 1, it comprises the material with at least one Tg, this Tg is 270 ℃ or higher.
97. according to the tubular type goods of claim 1, it comprises the material with at least one Tg, this Tg is 275 ℃ or higher.
98. according to the tubular type goods of claim 1, it comprises the material with at least one Tg, this Tg is 300 ℃ or higher.
99. according to the tubular type goods of claim 1, it comprises the material with at least one Tg, this Tg is 325 ℃ or higher.
100. according to the tubular type goods of claim 1, it comprises the material with at least one Tg, this Tg is 350 ℃ or higher.
According to the tubular type goods of claim 1, it comprises the material with at least one Tg, and this Tg is about 225～250 ℃.
According to the tubular type goods of claim 1, it comprises the material with at least one Tg, and this Tg is about 250～275 ℃.
According to the tubular type goods of claim 1, it comprises the material with at least one Tg, and this Tg is about 275～300 ℃.
According to the tubular type goods of claim 1, it comprises the material with at least one Tg, and this Tg is about 300～325 ℃.
According to the tubular type goods of claim 1, it comprises the material with at least one Tg, and this Tg is about 326～350 ℃.
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