CN102356115A - Co-polymer based polyimide articles and their uses in high temperature applications - Google Patents

Co-polymer based polyimide articles and their uses in high temperature applications Download PDF

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CN102356115A
CN102356115A CN201080012382XA CN201080012382A CN102356115A CN 102356115 A CN102356115 A CN 102356115A CN 201080012382X A CN201080012382X A CN 201080012382XA CN 201080012382 A CN201080012382 A CN 201080012382A CN 102356115 A CN102356115 A CN 102356115A
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goods
moles
filler
polyimide
000psi
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J·P·坎宁安
J·L·卢丁
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EIDP Inc
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EI Du Pont de Nemours and Co
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
    • B29C43/003—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor characterised by the choice of material
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
    • F02M—SUPPLYING COMBUSTION ENGINES IN GENERAL WITH COMBUSTIBLE MIXTURES OR CONSTITUENTS THEREOF
    • F02M26/00—Engine-pertinent apparatus for adding exhaust gases to combustion-air, main fuel or fuel-air mixture, e.g. by exhaust gas recirculation [EGR] systems
    • F02M26/11—Manufacture or assembly of EGR systems; Materials or coatings specially adapted for EGR systems
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2079/00—Use of polymers having nitrogen, with or without oxygen or carbon only, in the main chain, not provided for in groups B29K2061/00 - B29K2077/00, as moulding material
    • B29K2079/08—PI, i.e. polyimides or derivatives thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/04—Condition, form or state of moulded material or of the material to be shaped cellular or porous
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2503/00—Use of resin-bonded materials as filler
    • B29K2503/04—Inorganic materials
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N13/00—Exhaust or silencing apparatus characterised by constructional features ; Exhaust or silencing apparatus, or parts thereof, having pertinent characteristics not provided for in, or of interest apart from, groups F01N1/00 - F01N5/00, F01N9/00, F01N11/00
    • F01N13/16—Selection of particular materials
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
    • F02B—INTERNAL-COMBUSTION PISTON ENGINES; COMBUSTION ENGINES IN GENERAL
    • F02B39/00—Component parts, details, or accessories relating to, driven charging or scavenging pumps, not provided for in groups F02B33/00 - F02B37/00

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Medicinal Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Mechanical Engineering (AREA)
  • Combustion & Propulsion (AREA)
  • General Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)

Abstract

Disclosed herein is a method for making polyimide articles that are suitable for high temperature applications. The articles disclosed herein are rigid, oxidatively stable, wear-resistant, and permeable to heated moisture and gases, and comprise co-polymer based polyimide, and at least one additive or filler, and are made using 20,000 to 50,000 psi of compression pressure.

Description

Polyimide goods and their purposes in high temperature is used based on multipolymer
Invention field
Plastic material has wide industrial to be used, and comprises some high temperature application.Polyimide can be used for some high temperature to be used, but possibly still need have some other physical property.The polyimide goods that are based on multipolymer disclosed herein, said goods are applicable to that high temperature uses, and the anti-defective when still having enhanced permeability, weather resistance, oxidative stability, suitable wear life and heat and exposing.
Background of invention
The high-temperature operation condition needs to use the material that tolerates said condition with the industry manufacturing.As before, current metal, pottery, graphite, asbestos and other material of having used is used for the high temperature application.The part that plastics can be used for substituting in these materials is used to be used for high temperature.Yet some uses the material also need have bells and whistles, for example wear resistance, chemical-resistant, low frictional properties, reduction abradability and other characteristic of its application being provided consistency.
Some application needs can be good at tolerating the appropriate materials that is higher than 400 degree celsius temperature.For example, implement the glass production operation down at about 1400 ℃ to 1600 ℃.Other system such as oil engine need use and can stand high temperature and do not lose efficacy fast because of these high temperature or the material of loss.
Can make and be applicable to that pyritous is used to make the material of goods or mechanical part.Yet along with the xsect of mechanical part increases, captive heated moisture and gas are difficult for arriving the surf zone of said parts, thereby have limited their release.In the case, because the heat of rapid thermal cycles exposes, mechanical part is easy to produce defective as bubbling.The circulation that the moisture exposure and the heat of carrying out repeatedly exposes, the also reduction gradually of possibility generation part mechanical characteristics is by reduction (also being called " hygrometric state Tg reduction " sometimes) confirmation of measured resin glass transition temperature (tg).
Graphite has been used to during high temperature uses, but frangible, therefore lacks weather resistance, can not stand the load that some is applied in using, and not reach the desired wear life of many application.
Used other material that makes by plastic material, like thermosetting material.Yet many these materials are not suitable for high temperature to be used, and lacks intensity, weather resistance and required mechanical characteristics, causes than the faster loss of graphite.
Some polyimide materials have also been used; But many materials are because of the concrete TR of using; Or because of polyimide parts can't have the parts surface zone that discharges heated moisture and gas when exposing with heat is compared significantly or bigger xsect has restriction, make it not be suitable in the high temperature application.
The purpose of this invention is to provide the method for preparing goods; Said goods are made by polyimide compositions; Wherein said goods are applicable to that high temperature uses, and have rigidity, oxidative stability, to the perviousness of heated moisture and gas, to avoid exposing the defective that causes because of rapid thermal cycles or heat.
In addition, the polyimide parts that is made by the inventive method is not easy to accumulate the oil residue of degraded, and the material based on graphite that is used for identical or similar application is like this.
The accompanying drawing summary
Fig. 1 be according to the disclosure comprising of making based on the tensile strength of the goods of the polyimide of multipolymer diagram to compaction pressure.
Fig. 2 be according to the disclosure comprising of making based on the elongation of the goods of the polyimide of multipolymer diagram to compaction pressure.
Summary of the invention
Herein disclosed is the method that preparation is applicable to the goods of high-temperature systems, said system is made up of instrument and equipment, and said goods comprise the polyimide compositions based on multipolymer, and wherein said compsn comprises:
A) aromatics tetracarboxylic acid dianhydride component; With
B) diamine components, said diamine components also comprises:
(i) greater than 60 moles of % to the Ursol D of about 85 moles of % and
(ii) 15 moles of % are to the mphenylenediamine less than 40 moles of %;
Wherein a) and b) exist with 1: 1 ratio; And
Said method comprises:
Adopt compression to form the parts of predetermined shape; The force value that wherein is used to compress is about 20, and 000psi is to about 50, and 000psi is to obtain porous article, and said goods have the moisture permeability, and have resistance to exposing the defective that causes by heat.
This paper also discloses the goods that are applicable to high-temperature systems, and said system is made up of instrument and equipment, and said goods comprise the polyimide compositions based on multipolymer, and wherein said compsn comprises:
A) aromatics tetracarboxylic acid dianhydride component; With
B) diamine components, said diamine components also comprises:
I) greater than 60 moles of % to the Ursol D of about 85 moles of % and
Ii) 15 moles of % are to the mphenylenediamine less than 40 moles of %;
Wherein a) and b) exist with 1: 1 ratio; And
Said goods are porous, and have the moisture permeability, and have resistance to exposing the defective that causes by heat.
Detailed Description Of The Invention
Polyimide material is easy to absorb the moisture in the atmosphere.According to environment, trim point can be greater than 1 weight %.When polyimide material is heated, this moisture will discharge.Yet, if material with than the heating of this moisture effusion speed faster rate the time, possibly bubble.
The invention provides the method that preparation is applicable to the goods of high-temperature systems, said system is made up of instrument and equipment.The goods that make according to the inventive method are such goods, and wherein said goods are durable, and in time passing is attrition resistant in high temperature is used, and is inflexible, is oxidation-stabilized, and the defective that is caused by rapid thermal cycles is had resistance.
In the methods of the invention, said goods comprise the polyimide compositions based on multipolymer, and wherein said compsn comprises:
A) aromatics tetracarboxylic acid dianhydride component; With
B) diamine components, said diamine components also comprises:
I) greater than 60 moles of % to the Ursol D of about 85 moles of % and
Ii) 15 moles of % are to the mphenylenediamine less than 40 moles of %;
Wherein a) and b) exist with 1: 1 ratio; And
Said method comprises:
Adopt compression to form the parts of predetermined shape; The force value that wherein is used to compress is about 20, and 000psi is to about 50, and 000psi is to obtain porous article, and said goods have the moisture permeability, and have resistance to exposing the defective that causes by heat.
In one embodiment of the invention, compression pressure can be scheduled to, to make the goods with certain desired density.
In an embodiment of the inventive method, said goods can have with the product surface zone compares bigger transverse cross-sectional area, and said goods can discharge moisture and the gas that is present in the article cross sections zone through the product surface zone.
In another embodiment of method disclosed herein, polyimide compositions can comprise at least a filler.The filler that is used for the present invention is a carbonaceous filler, and said carbonaceous filler is selected from natural graphite, synthetic graphite and thomel; Fluoropolymer includes but not limited to tetrafluoroethylene; And mineral filler, said mineral filler is selected from kaolinite, sepiolite; And their mixture.
The present invention can be used for multiple high-temperature systems, and said system is made up of instrument and equipment.The goods that openly make according to this paper can be used for the alternative pyritous conventional material that is used for.For example, the goods that openly make according to this paper can be used for substituting mechanical organ, the parts that mainly are made up of graphite, metal, pottery or asbestos.
Use goods of the present invention, isolate the diffraction chamber as being used to, be used for automotive system, comprise as blowdown system parts, internal combustion engine component, sleeve pipe, bearing, packing ring, wear ring, pad abrasive disc and slide block as the parts in convection oven, the scientific instrument.Other application of the open parts of this paper is selected from recirculation system; Clutch system; Pump; Turbo-supercharger; Thrust reverser; Cabin, the system of flaps; Injection moulding machine; Transport unit; With the tentering machine frame.
The invention provides the method that is prepared profiled part by polyimide compositions, wherein said parts have the oxidative stability and the superior tensile of improvement.This type of profiled part can be used in the high temperature application, or is used for 400 ℃ or the higher temperature application of operation down.Other application of the goods that made by the inventive method comprises scientific instrument, convection oven, the transport unit that is heated, road vehicle application and aerospace mover.Adopt parts that the inventive method makes and other goods also can be used for following in: motor car engine; Other vehicle subsystem such as tail gas recirculation system and clutch system; Pump; Non-aircraft is used reaction propulsion engine; Turbo-supercharger; Material processing plant such as injection moulding machine; Materials handling equipment such as transport unit, belt press and tentering machine frame; And other application of film, sealing member, packing ring, bearing, sleeve pipe, pad, pad abrasive disc, wear ring, slide block and push-piece and the low wearing and tearing of its desired.In some applications, when wherein there are the equipment of the parts that make according to the open method of this paper or other goods in assembling and normal use, make the parts that make according to the open method of this paper or other goods and metallic contact for some time at least.
Term " rigidity polyimide " is meant and does not have flexible linking group in the polyimide unit.
The aromatics tetracarboxylic acid dianhydride component that is used to prepare multipolymer polyimide of the present invention comprises pyromellitic acid anhydride (PMDA), 3,3 ' 4, and 4 '-bibenzene tetracarboxylic dianhydride (BPDA) and any other rigidity aromatic dianhydride.When using BPDA, obtain optimum as the dicarboxylic anhydride component.With regard to the preferred embodiment of the invention, adopt solution imidization method that the compsn of the rigidity aromatic polyimide with following repeating unit is provided
Figure BPA00001437728400051
Wherein R is that PPD unit and 15 greater than 60 to 85 moles of % is to the MPD unit less than 40 moles of %.The polyimide compositions that preferably has 70%PPD and 30%MPD.
In the preparation of polyimide compositions of the present invention, use solution imidization method as follows.Generally at first diamines (PPD and MPD) is dissolved in the solvent, forms diamine components.In general, in the solvent that diamine components is dissolved in desired concn after, dicarboxylic anhydride is joined in the reaction soln with equimolar amount basically, form polyamic acid (PAA) polymers soln.The mole number of dicarboxylic anhydride or diamine components is excessive slightly to be feasible.Find that the diamine components mole number is excessive 0.5 to 1.0%, optimal results is provided.Known like those of ordinary skills, as routine, the more approaching mole stoichiometry that waits obtains good more tensile properties, but this must the high more viscosity of appearance balance each other when mole point such as reaching.
In for some time, gained PAA polymers soln is transferred in the hot soln of solvent.The PAA polymers soln that shifts is continued heating and stirring, to accomplish the reaction of solubility PAA to insoluble polyimide slurries.
With solvent wash gained polyimide slurries, and at 100 to 230 ℃, preferred 140 to 190 ℃, more preferably 180 ℃ are descended drying, the polyimide slurries are transformed into the polyimide resin of the powder type with high surface area.180 ℃ optimum temps obtains higher working (machining) efficiency and better physical property.According to the granularity that obtains by the polyamic acid of reaction soln deposition, can be through for example suitable grinding technology with the further modification of polyimide particles, so that the expectation granularity that is suitable for handling with follow-up moulding to be provided.
Can be used for the organic solvent that any significance degree reaction does not take place with any reactant (BPDA or diamines) for its functional group for solvent in the solution polymerization process of synthetic PAA polymers soln.Said solvent shows about pH of 8 to 10, and this can use pH test paper or probe measurement to measure through with said solvent and mixes with small amount of water then.This type of solvent comprises for example pyridine and beta-picoline.Gall with authorize in the United States Patent(USP) No. 3,179,614 of Edwards in the disclosed solvent, (KB=1.4 * 10-9) is the preferred solvent of these reactants in the polyreaction to pyridine, and as catalyzer.With regard to dicarboxylic anhydride and diamine reactant formation PAA polymers soln, need basic catalyst.Because pyridine is a basic cpd, so it is in this article as catalyzer and solvent.
The amount of solvent is important for the product that acquisition has high surface area.Specifically, should there be certain amount of solvent, makes that the concentration of PAA polymers soln is about 1 to 15 weight % solid, preferred about 8 to 12 weight % solids.
The surface-area of the polyimide resin that is obtained by polyimide compositions of the present invention should be 20m2/g at least.Said surface-area is preferably 75m2/g at least, to obtain acceptable physical property and to be easy to processibility.
In PAA preparation, necessary is, molecular weight makes the limiting viscosity (IV) of PAA polymers soln be 0.2dl/g at least, and preferred 0.5 to 2.0dl/g.The method of measuring and calculate IV is described in hereinafter.
Polyimide compositions comprises at least a filler or one type of filler usually.Filler in the polyimide compositions of the present invention can comprise clay such as kaolinite or sepiolite; Fluoropolymer or multipolymer such as tetrafluoroethylene; Molybdenumdisulphide; And/or carbonaceous filler such as graphite, thomel.Said filler can be used for improving polyimide compositions and by the wearing and tearing and the friction characteristic of its parts that make, keeps excellent stretchiness and oxidative stability simultaneously.
The graphite that is applicable to this paper can be naturally occurring graphite or synthetic graphite.Natural graphite generally has concentration range impurity widely, and the synthetic commercially available acquisition of graphite that makes has the reactive impurities of lower concentration.The graphite that comprises unacceptable high concentration impurities can be comprised and for example used the mineral acid chemical treatment by any purifying in the multiple known treatment.Under for example high temperature or reflux temperature,, can be used for impurity is reduced to desired degree with sulfuric acid, nitric acid or the impure graphite of salt s.t..
Sepiolite filler, kaolin filler or their mixture also are applicable among this paper.The sepiolite filler that is applicable to this paper comprises sepiolite self [Mg 4Si 6O 15(OH) 26 (H 2O)], it is for showing the hydrated magnesium silicate filler of high aspect ratio because of its fibrous texture.Sepiolite is made up of the strip crystallite, and this is only in silicate, and wherein the silicon-dioxide chain is parallel to the fibre axis extension.Show that said material comprises two kinds of forms, α and beta form.Known alpha-form is long bundle fiber, and said form is rendered as amorphous aggregate.
The sepiolite filler that is applicable to this paper also comprises attapulgite (also being called magnalium skin stone), and it is structurally almost identical with sepiolite with chemically, and different is that attapulgite has slightly little structure cell.
The sepiolite filler that is applicable to this paper also comprises clay; It is the stratification filamentary material, and wherein each layer is made up of [referring to people's such as for example L.Bokobza " Polymer International " two tetrahedron silicon-dioxide unit with the octahedra dice bonding in the center that comprises mg ion 53, the Fig. 1 and 2 among the 1060-1065 (2004)].The said fiber formation fibrous bundle that sticks together, it can form agglomerate then.Can these agglomerates be broken up (referring to the European patent of for example authorizing Tolsa S.A. 170,299) by commercial run such as micronization or chemical modification.
In one embodiment; The sepiolite filler that is applicable to this paper comprises rheology level sepiolite clay; Like EP-A-454,222 and/or EP-A-170, those described in 299; And (Madrid Spain) sells by Tolsa S.A. with trade mark Pangel
Figure BPA00001437728400071
.In this context, term " rheology level " is meant that sepiolite clay has greater than 120m usually 2The average surface area of/g is [according to the Brunauer/Emmett/Teller method, at N 2In record (like " Adsorption of Gases in Multimolecular Layers " (Journal of the American Chemical Society of people such as Brunauer; 60:309-19; 1938) described in], and have the average fiber size about 200 to 2000nm long, that 10-30nm is wide and 5-10nm is thick usually.Rheology level sepiolite derives from natural sepiolite via method of micronization, and said method of micronization has prevented that basically sepiolite fibre is damaged, makes sepiolite be easy to be scattered in water and other polar liquid, and has highly irregular outside surface, greater than 300m 2The high-ratio surface of/g and the highdensity active site that is used to adsorb, this makes in the time can forming hydrogen bridge with the active site with comparalive ease, to it very high water retention capacity is provided.The fento characteristic of rheology level sepiolite particle makes sepiolite become to have the material of high porosity and low bulk density.
In addition; Rheology level sepiolite has low-down cation exchange capacity (10-20meq/100g); And with electrolytical interaction very a little less than, the influence that this causes rheology level sepiolite existed by salt in its existing medium then, so it is keeping stable in the pH scope widely.The rheology level sepiolite of above-mentioned quality also can be present in the rheology level attapulgite; It has the granularity less than 40 microns usually, like ATTAGEL
Figure BPA00001437728400081
the clay series (for example ATTAGEL 40 and ATTAGEL 50) by Engelhard Corporation (United States) produce and market; With the MIN-U-GEL product line that derives from Floridin Company.
The kaolin filler that is applicable to this paper comprises kaolinite self, and it is a sheet silicate, and its molecule is arranged with two lamellas or the two flaggy forms of a lamella silicon-dioxide and a lamella aluminum oxide.Kaolinite is to have Al 2Si 2O 5(OH) 4The clay mineral of chemical constitution.It is the stratification silicate mineral, has a tetrahedron lamella that is connected with the octahedra lamella of an alumina octahedra through Sauerstoffatom.Be rich in kaolinic sillar and be called as potter's clay or kaolin.By contrast, terre verte if you would take off the stone clay mineral with two silicon-dioxide lamellas and an aluminum oxide lamella form arrangement.Those of kaolinite classification are compared, and what the terre verte molecule was looser links together, so spacing is bigger.Keep the phase stability of sheet silicate crystal structure to suit, with in higher temperature as being up to about 450 ℃ of thermostabilitys the same [shown in for example thermogravimetric analysis (TGA)] that keep sheet silicate sturcture water down.During polyimide compositions is handled, lose water of constitution, possibly damage the polyimide integrity, and possibly change the crystalline structure of sheet silicate, obtain harder compound more easy to wear.Enough stable and instance that be not included in the sheet silicate in the compsn described herein is smectite, vermiculite and pyrophyllite.Be applicable to that the kaolin filler of this paper is discussed further in " the Applied Clay Science " 17 (2000) of Murray, among the 207-221.
Be applicable to the sepiolite filler of this paper and " the Applied Clay Science " 17 (2000) that the kaolin filler is discussed further in Murray, among the 207-221.
In embodiment of the present invention; Shifting PAA polymers soln (or other solution of other type monomers) before; Usually will be incorporated in the hot solvent as graphite, sepiolite and/or the kaolin of filler; Make the gained polyimide come out, thereby be incorporated in the said compsn in component (b) and the settle that exists (c).
Choose wantonly and be applicable to that the additional additives in this paper compsn can unrestrictedly comprise one or more following materials: pigment; Inhibitor; Give the material of low thermal coefficient of expansion, for example thomel; Give the material of high-strength characteristic, for example spun glass, ceramic fiber, boron fibre, glass bead, whisker, graphite whisker or diamond powder; Give the material of heat dissipation or heat-resistant quality, for example Kevlar, steel fiber, ceramic fiber, whisker, silicon-dioxide, silit, silicon oxide, aluminum oxide, magnesium powder or titanium valve; Give the material of corona resistance, for example natural mica, synthetic mica or aluminum oxide; Give the material of electroconductibility, for example carbon black, silver powder, copper powder, aluminium powder or nickel powder; Further reduce the material of wearing and tearing or frictional coefficient, for example SP 1 or gather (tetrafluoroethylene) homopolymer and multipolymer.Can before the parts manufacturing, filler be joined in the final resin with dry powder form.
The content any or combination of additive and/or filler can be in 0.1 to 80 weight % scope.Certainly, it will be apparent for a person skilled in the art that selected one or more concrete fillers and consumption will depend on effect desired in the final composition.
These additives or filler usually but always were not incorporated in the hot solvent before the PAA polymers soln shifts, and made polyimide come out in the settle that exists of filler, thereby mixed said filler.In some cases, with one or more fillers or additive or the two and polyimide particles blend.Form of bio-carrier will depend on the purposes of filler in the finished product.For example, filler can be particle or fibers form.
As previously mentioned, polyimide compositions of the present invention is oxidation-stabilized.For the test oxidative stability, be described below and process tensile bar, then experience fixed for some time under extreme temperature.Testing before and the said tensile bar of weighing afterwards, and the calculated weight percent loss.If weight loss per-cent is less than 5%; Preferably less than 3%; Think that then rigidity aromatic polyimide compsn of the present invention is oxidation-stabilized; Because this weight loss can not damaged the integrity of tensile bar, or more particularly, can not damage the integrity of the parts that make by the inventive method disclosed herein.
The characteristic of polyimide goods of the present invention not only is independent excellent heat oxidative stability; Or any independent specific character; And be that superior tensile and high temperature not are inapparent other characteristic in using, the anti-defective when exposing like the permeability of weather resistance, wear resistance and wear life, rigidity, heated moisture and gas and heat.With regard to using as stated, tensile strength and elongation are the characteristics that is even more important.Known usually like those of ordinary skills, the product with low elongation is tending towards fracture, this cause during machining or load-bearing use in cracking
Can under high pressure be molded as multiple configuration according to the polyimide compositions that makes disclosed herein.For many application, about 50,000 to 100, the pressure of 000psi (345 to 690MPa) and envrionment temperature molded polyimide compositions.
The method that preparation is used for the goods that high temperature uses comprises that (comprising heated moisture and gas permeability) is the straight forming method, and through polyimide compositions is joined in the mould, at about 300 ℃ of sintering polyimide compositions under about 450 ℃ high temperature extremely; Use approximately 20 simultaneously, 000psi is to about 50,000psi; Preferred about 35,000psi is to about 45,000psi; And most preferably from about 40, the pressure of 000psi is suppressed said parts and is implemented, and forms goods or parts.
Through about 20,000psi is to about 50, and goods that 000psi pressed polyimide compositions makes or parts can be used for during high temperature uses.More particularly, the parts goods that made by the inventive method can be used in the glass manufacturing, and more particularly, can be used in the Glass Containers manufacturing.This based article or parts include but not limited to glass treatment subassembly and assembly thereof.These comprise sample-pickup tongs subassembly and assembly (comprising sample-pickup tongs double wedge piece) thereof, dead plate zhao, clearing apparatus, loading stage, loading stage pad, loading stage bearing and any assembly in these.
Polyimide material is easy to absorb the moisture in the atmosphere.According to environment, trim point can be greater than 1 weight %.When polyimide material is heated, this moisture will discharge.Yet, if material with than the heating of this moisture effusion speed faster rate the time, possibly bubble.This phenomenon can limit polyimide material and be used for many application.In order to overcome this restriction, we after deliberation the infiltrative method of raising polyimide material.We are verified, at lower pressure lower compression or compacting polyimide material, can obtain porous structure more, have significantly better resistance to blistering between hot exposure period or during being exposed to rapid thermal cycles simultaneously.We confirm that also this can realize under the situation of not remarkably influenced material mechanical characteristic that said mechanical characteristics is the key of its high temperature wear resistance and weather resistance.
In some high temperature is used like hot glass treatment application, aircraft engine and parts or scientific analysis instrument; Compare with carbonaceous graphite material (material that does not for example contain polyimide) with using the conventional polyimide material, the used polyimide based on multipolymer has been given favorable factor in one or more methods of the present invention and one or more goods.
Method disclosed herein and purposes provide lower thermal conductivity, show that Heat transfer coefficient is than low about 50 to 100 times of the goods that use conventional carbonaceous graphite to make.Than the relevant use of the goods of the present invention and the goods of the present invention of lower thermal conductivity, make and farthest reduce or eliminated bubble and crack splitting, thereby reduced rate off quality and improved output.
Find that also the inventive method goods provide high 70 to 100% the high impact properties of carbonaceous graphite member commonly used in the specific heat glass manufacturing application.Goods manufacturing, processing and breakage rate reduction between the usage period have prolonged product life, and this has improved reliability of technology then and has reduced running cost.
In the inventive method and goods, also observing oil absorbs.The few 30 times of extremely zero oil suction degree of the oil ratio carbonaceous graphite member that the assembly that the present invention makes absorbs.Reducing or eliminating the oil absorption provides the advantage of minimizing inspection with the container of said goods operation, thereby has improved container output, and has reduced running cost.
Another advantage of the inventive method and goods is low wearing and tearing.Test result shows that under 600 Fahrenheit degrees (315 degrees centigrade) oscillating condition, wear intensity is lower three times than carbonaceous graphite, and display life is than 2 to 11 times of glass treatment carbonaceous graphite sampling double wedge block lengths.This advantage is converted into the significantly long running stores life-span, has improved production efficiency.
Embodiment
Figure BPA00001437728400111
With regard to the test data described in the last table; According to ASTM E8-" Standard Tension Test Specimen for Powdered Metal Products-Flat Un-machined Tensile Test Bar "; In room temperature and 20; 000 to 100, under the pressure in the 000psi scope, will be processed into tensile bar like polyimide compositions sample disclosed herein.Use nitrogen purging, with tensile bar sintering 3 hours under 405C.Measure tensile strength and elongation according to ASTM D638.
Adopting Archimedes' principle to measure proportion (promptly through measuring the weight of sample in water, deducts dry weight with said weight, confirms volume.Then with said dry weight divided by this volume, confirm proportion).
The following thermo-oxidative stability (TOS) of measuring: at first a tensile bar or a tensile bar part were soaked in alcohol 15 minutes, and under 300F drying 1 hour.After the cooling, the weighing sample, under air atmosphere, experience is 100 hours under 700F temperature and 70psia pressure then.Carry out final weight and measure, and according to computes tensile bar weight loss per-cent:
Weight loss %=(initial weight-final weight/initial weight) * 100
Resistance to blistering during exposure of following mensuration heat or the rapid thermal cycles a: at first tensile bar or a tensile bar part were soaked 12 days in 95 ℃ of water.Then, sample is put in the baking oven of preheating under the assigned temperature.There are not visible cracking or bubble in the sample of back if this heat exposes, then obtain qualified result.20,000 and 40, the sample of 000psi pressed is at the most and after comprising 400 ℃ exposure, showing does not have visible defects.60,000-100, the sample of 000psi pressed demonstrate defective after under 325 ℃ and higher temperature, exposing.
It should be noted that; 40; The sample of 000psi pressed keeps 100; The tensile strength of 000psi pressed sample 88% and 94% elongation, under 400 ℃, demonstrate simultaneously positive resistance to blistering can, and only demonstrate positive resistance to blistering ability at 325 ℃ at the sample of high pressure pressed more.
Should be pointed out that and to use other method to obtain the parts that low density or hole density improve, as be added in degraded behind heat, chemistry or the mechanical process or peel off or the protectiveness filler of disintegration, obtain the vestibule or the channel network that supply water and separate.Yet methods described herein are economical, because do not need additional filler and operation, the parts that acquisition simultaneously has the suitable mechanical integrity are used to be used for high temperature.
Embodiment 2: comparative analysis
Tradition polyimide and graphite and based on the performance comparison of the polyimide of multipolymer
Figure BPA00001437728400121
In " embodiment 2: comparative analysis ", use sample to obtain to be denoted as the result in " traditional polyimide " hurdle with the conventional polyimide of 60 weight % and 40 weight % graphite.Use the graphite that does not contain polyimide to obtain the result of " traditional carbonaceous graphite ".Use has the result of the sample acquisition " the present invention is based on the polyimide of multipolymer " of 50 weight % polyimide compositions disclosed herein and 50 weight % graphite.

Claims (15)

1. preparation is applicable to the method for the goods of high-temperature systems, and said system is made up of instrument and equipment, and said goods comprise the polyimide compositions based on multipolymer, and wherein said compsn comprises:
A) aromatics tetracarboxylic acid dianhydride component; With
B) diamine components, said diamine components also comprises:
(i) greater than 60 moles of % to the Ursol D of about 85 moles of % and
(ii) 15 moles of % are to the mphenylenediamine less than 40 moles of %;
Wherein a) and b) exist with 1: 1 ratio; And said method comprises:
Adopt compression to form the parts of predetermined shape; The force value that wherein is used to compress is about 20, and 000psi is to about 50, and 000psi is to obtain porous article, and said goods have the moisture permeability, and have resistance to exposing the defective that causes by heat.
2. the process of claim 1 wherein that said compression pressure is about 35,000psi is to about 45,000psi.
3. the process of claim 1 wherein that said compression pressure is about 40,000psi.
4. the process of claim 1 wherein that said goods have with said product surface zone compares bigger transverse cross-sectional area, and said goods can discharge moisture and the gas that is present in the said article cross sections zone through said product surface zone.
5. the process of claim 1 wherein that said polyimide compositions comprises at least a filler or additive.
6. the method for claim 5, wherein said filler is a carbonaceous filler, said carbonaceous filler is selected from natural graphite, synthetic graphite and thomel.
7. the method for claim 6, wherein said filler is a fluoropolymer, and said fluoropolymer is selected from tetrafluoroethylene.
8. the method for claim 5, wherein said filler is selected from kaolinite, sepiolite and their mixture.
9. the goods that make by the method for claim 1.
10. according to the goods of claim 9, wherein said goods are applicable to that the scientific analysis instrument is to isolate the diffraction chamber.
11. according to the goods of claim 9, wherein said goods are applicable to the transport unit of convection oven or heating.
12. according to the goods of claim 9, wherein said goods are applicable to motor car engine or motor vehicle subsystem.
13. according to the goods of claim 12, wherein said motor vehicle subsystem is selected from tail gas recirculation system, clutch system, pump and turbo-supercharger.
14. according to the goods of claim 12, wherein said goods are sealing member, packing ring, bearing, sleeve pipe, pad and wear ring.
15. be applicable to the manufacturing goods of high-temperature systems, said system is made up of instrument and equipment, said goods comprise the polyimide compositions based on multipolymer,
Wherein said compsn comprises:
A) aromatics tetracarboxylic acid dianhydride component; With
B) diamine components, said diamine components also comprises:
I) greater than 60 moles of % to the Ursol D of about 85 moles of % and
Ii) 15 moles of % are to the mphenylenediamine less than 40 moles of %;
Wherein a) and b) exist with 1: 1 ratio; And
Said goods are porous, and have the moisture permeability, and have resistance to exposing the defective that causes by heat.
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