CN108264712A - A kind of fluoropolymer composite material - Google Patents
A kind of fluoropolymer composite material Download PDFInfo
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- CN108264712A CN108264712A CN201711475818.9A CN201711475818A CN108264712A CN 108264712 A CN108264712 A CN 108264712A CN 201711475818 A CN201711475818 A CN 201711475818A CN 108264712 A CN108264712 A CN 108264712A
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- composite material
- inorganic filler
- fluoropolymer
- polyarylate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C08L27/18—Homopolymers or copolymers or tetrafluoroethene
-
- 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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
-
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
Abstract
A kind of composite material, it includes fluoropolymer, polyarylate and inorganic filler, wherein the grain size of the inorganic filler meets following at least one conditions：D90≤25 μm, D50≤10 μm and D10≤5 μm.
Description
This application claims the of entitled " a kind of fluoropolymer composite material " submitted on December 30th, 2016
201611255783.3 the priority of number Chinese patent application.Disclosure of which integrally quotes addition herein.
Technical field
The present invention relates to polymeric material fields, and high-pressure and hydraulic servo steering system (HPS) is used for more particularly to one kind
Fluoropolymer composite material and preparation method thereof.
Background technology
Fluoropolymer is the polymer material containing fluorine atom in molecular structure.Fluoropolymer has and good resistance to has
Solvent and anti acid alkali performance are widely used in fields such as machinery, electronics, space flight, chemical industry.Due to excellent resistance to of fluoropolymer
High temperature performance, self lubricity, low friction coefficient, often can be used as sealing material.But it is typically used as the known fluorine-containing of sealing material
Polymer there are abrasion resistance properties it is poor the defects of, make its application be restricted.
In recent years, in order to improve fluoropolymer-containing abrasion resistance properties, developed fluoropolymer is modified it is a variety of
Method.Inorganic filler modification is a kind of relatively convenient and widely applied processing mode.CN104817796A, which discloses to use, to be changed
Property ptfe composite of the corundum superfine powder as anti-wear agent, wherein modified corundum Ultramicro-powder is by K2O、Na2O、
Li2The corundum Ultramicro-powder that O and/or combination thereof are modified, the composite material have higher intensity and hardness.WO2006/
A kind of low abrasion polytetrafluoroethyl-ne alkenes nanocomposite, it includes nano aluminium oxide, the nanometer are disclosed in 128128A2
Aluminium oxide is irregular shape.
It is disclosed to use polymer and fluoropolymer-containing blending and modifying.It is disclosed in CN102942756A a kind of fluorine-containing poly-
Object base pressure-bearing wear-resistant material is closed, it includes polytetrafluoroethylene (PTFE), polybenzoate, bronze powder and glass fibres.CN1083464C is disclosed
Abrasion resistant fluoropolymer mixture containing fluorocarbon polymer, oxy-poly-arylene thioether and filler.
Fluoropolymer-containing performance under the conditions of specific application with added in fluoropolymer the type of material, contain
Amount and its feature are related, and there are demands to inexpensive, excellent performance the modified fluoropolymer as wear-resistant material.
Invention content
On the one hand, the present invention relates to a kind of fluoropolymer composite material, it includes fluoropolymer, polyarylate and nothings
Machine filler.In one embodiment, the grain size of the inorganic filler meets following at least one conditions：D90≤25 μm, D50≤
10 μm and D10≤5 μm.
In another embodiment, the aggregation grain size of inorganic filler meets following at least one conditions：D90≤120 μm,
D50≤70 μm and D10≤20 μm.
In one embodiment, the fluoropolymer is polytetrafluoroethylene (PTFE).In another embodiment, the polyarylate
For polybenzoate.In yet another embodiment, the inorganic filler is aluminium oxide.
In preferred embodiments, based on the fluoropolymer-containing weight, the content of the polyarylate is about 5-
40%, preferably from about 15-25%.In another preferred embodiment, based on the fluoropolymer-containing weight, the oxidation
The content of aluminium is about 1-25%, preferably from about 5-15%.
In one embodiment, the particle diameter distribution of the inorganic filler is：The μ of D90≤25 μm, D50≤10 μm and D10≤5
m；Or D90≤15 μm, D50≤6 μm and D10≤3 μm；Or D90≤10 μm, D50≤4 μm and D10≤2 μm.In another embodiment party
In case, the aggregation particle diameter distribution of the inorganic filler is：D90≤120 μm, D50≤70 μm and D10≤20 μm；Or the μ of D90≤110
M, D50≤60 μm and D10≤15 μm.In yet another embodiment, the shape of inorganic filler can be porous, sheet, spherical shape
Or irregular shape.
On the other hand, the invention further relates to a kind of sealing articles, and it includes the composite materials of the present invention.In an embodiment party
In case, sealing article is sealing ring.
Description of the drawings
Fig. 1：The scanning electron microscope diagram piece of aluminium oxide.
Fig. 2：The coefficient of friction data figure of ptfe composite.
Fig. 3：The coefficient of waste datagram of ptfe composite.
Fig. 4：The wear rate data figure of ptfe composite.
Fig. 5：The mechanical properties data figure of ptfe composite, wherein Fig. 5 A are the data of maximum tensile stress
Figure, Fig. 5 B are the datagram of maximum tension strain.
Specific embodiment
General definition and term
The present invention is described in more detail below, it should be appreciated that the term is intended to description purpose, and unrestricted is sent out
It is bright.
Unless otherwise indicated, the technical and scientific term used herein has and those skilled in the art of the invention
The identical meaning being generally understood.If there are contradiction, the definition of the application of being subject to offer.When with range, preferred scope,
Or the form of preferred numerical upper limits and preferred numerical lower limits state some amount, concentration or other values or parameter when
It waits, it should be understood that be equivalent to specific disclose by by any pair of range limit or preferred value and any range lower limit or excellent
Any range that numerical value combines is selected, without considering whether the range specifically discloses.Unless otherwise indicated, it is listed herein
Numberical range is intended to the endpoint for including range and all integers and score (decimal) in the range of this.Term " about ", " about " when
With numerical variable and used time, be often referred to the variable numerical value and the variable all numerical value in experimental error (such as flat
In the confidence interval of mean value 95%) or in ± the 10% of specified numerical value or in wider range.
It is open to state the "comprising" or similar statement " comprising " synonymous with its, " containing " and " having " etc., is not arranged
Except additional unrequited element, step or ingredient.State " Consists of " exclude unspecified any element, step or into
Point.Statement "consisting essentially of ..." how is limited in the element specified, step or ingredient, in addition what is be optionally present will not be real
Element, step or the ingredient of the basic and new feature of theme claimed are influenced in matter.It should be appreciated that statement "comprising"
Cover statement "consisting essentially of ..." and " Consists of ".
Term as used herein " optional " " optionally " refers to the event then described or situation may occur or can
It can not occur, which includes the event or situation occurs and the event or situation does not occur.
Term as used herein " at least one (a) " expression 1,2,3,4,5,6,7,8,9,10 kind (a) or more.
Term as used herein " two (kind) or more (kind) " can represent 2,3,4,5,6,7,8,9,10
(kind) or more.
Term as used herein " repetitive unit " refers to the combination of the atom connected in a certain way on polymer chain,
It is the basic unit for forming the polymer chain.For the fluoropolymer of the present invention, normally number of repeat unit can
Think about 10,000-2,000,000, about 50,000-1,000,000 or about 250,000-500,000.
Term as used herein " aggregation grain size " refers to aggregation and the aggregated form of inorganic filler.The aggregation grain of form in this way
Diameter is difficult to disperse, it is made to show porous on the whole.Aggregation and the inorganic filler of aggregated form are in use in matrix
In be generally also with it is such aggregation and aggregated form exist.
Unless otherwise indicated, the percentage of this paper, number etc. be all by weight.
Fluoropolymer
Fluoropolymer refers in repetitive unit or monomer containing fluorine atom in the fluoropolymer composite material of the present invention
Homopolymer or copolymer.The example of homopolymer includes but not limited to polyvinyl fluoride, polyvinylidene fluoride, polytetrafluoroethylene (PTFE), gathers
Chlorotrifluoroethylene etc., preferably polytetrafluoroethylene (PTFE).The example of copolymer include but not limited to tetrafluoroethene it is fluorine-containing with other/be free of
The copolymer of fluorine monomer.Wherein, the example of fluorochemical monomer includes but not limited to vinyl fluoride, vinylidene fluoride, trifluoro-ethylene, trifluoro
Vinyl chloride, hexafluoropropene etc., not fluorochemical monomer include but not limited to ethylene, propylene, n-butene, isobutene, amylene, hexene, heptan
Alkene, octene etc..Preferably, the molar ratio of tetrafluoroethene in the copolymer is about more than 60%, and preferably from about more than 70%, more preferably
About more than 80%, further preferably about more than 90%, most preferably from about more than 95%.The present invention fluoropolymer can be more than
One kind in fluoropolymer, or above two or more plants fluoropolymer-containing mixture, wherein it is preferred that tetrafluoro second
The content of alkene is about more than 70%, preferably from about more than 80%, more preferably from about more than 90%, most preferably from about more than 95%.
The fluoropolymer-containing molecular weight of the present invention is about 5,000,000-100,000,000, preferably from about 25,000,
000-50,000,000.Differential scanning calorimetry can be used by calculating crystallization heat and the equal molecule of number in fluoropolymer-containing molecular weight
The relationship of amount obtains.Number-average molecular weight can also be used standard specific gravity method and measure.
The fluoropolymer of the present invention is preferably thermoplastic polymer, is softened after the heating, and when cooling restores initial shape
State repeatedly can be heated and be cooled down repeatedly without irreversible chemical change occurs.The fluoropolymer of the present invention can be used molten
The method melted is processed.
Polyarylate
Polyarylate in the fluoropolymer composite material of the present invention is also known as aromatic polyester, refers in main polymer chain and contains
The polyester of aromatic group, wherein form the acid of polyester and at least one of alcohol should be it is aromatic.Preferably, it is of the invention
Polyarylate for it is aromatic acid with aromatic alcohol formed polyester.It can be included on the main chain of the repetitive unit of polyarylate
The mixing of benzene, biphenyl, naphthalene unit or above two or more kind.Polyarylate can be homopolymer, or two or more
The copolymer of kind monomer.The monomer of homopolymer includes but not limited to P-hydroxybenzoic acid, bisphenol-A reacts production with terephthalic acid (TPA)
Object, the reaction product of 4,4'- '-biphenyl diphenols and terephthalic acid (TPA), reaction product of terephthalyl alcohol and terephthalic acid (TPA) etc..It is excellent
The equal polycondensation monomer of choosing is P-hydroxybenzoic acid.The monomer of copolymerization includes but not limited to P-hydroxybenzoic acid, 2- hydroxyl -6- naphthalene first
Reaction product of the reaction product of sour, bisphenol-A and terephthalic acid (TPA), 4,4'- '-biphenyl diphenols and terephthalic acid (TPA) etc..Para hydroxybenzene
The ratio of formic acid in the copolymer is about more than 70%, preferably from about more than 80%, more preferably from about more than 90%, further preferably about
More than 95%, most preferably from about more than 98%.The polyarylate of the present invention can be one kind in more than polyarylate, or a variety of
The mixture of polyarylate, mixed proportion are not particularly limited.Preferred polyarylate is polybenzoate, such as BASF Aktiengesellschaft
Or the product of the husky basic company of uncle, such as k-090,505R.
Preferred polyarylate has following structure：
Wherein, n, x, y are respectively each number of repeat unit purpose average on polymer macromolecule chain.Normally, n is about
16-10,000, for example, about 18-5,000, about 20-2,800 etc..X, y is each independently about 0-10,000, for example, about 18-5,
000, about 20-2,800 etc..
Polyarylate should have good thermal stability, be not easy to thermally decompose.The molecular weight of polyarylate is typically about 2,000-1,
000,000, preferably from about 4,000-500,000, even more preferably about 8,000-250,000.
Inorganic filler
The present invention fluoropolymer composite material in inorganic filler, for high rigidity, can provide well it is wear-resistant
Performance is damaged, and is not susceptible to the filler of deformation under loads.Inorganic filler can be oxide, nitride, carbide or it is mixed
Close object.The example of wherein oxide includes but not limited to aluminium oxide, zinc oxide, silica, titanium oxide, zirconium oxide etc.；Nitridation
The example of object includes but not limited to boron nitride, aluminium nitride, silicon nitride etc.；The example of carbide includes but not limited to silicon carbide, carbon
Change boron etc..Inorganic filler can be salt such as carbonate, silicates, Sulfates etc., and the example includes but not limited to carbon
Sour calcium, calcium sulfate, barium sulfate etc..Inorganic filler can also be natural mineral fillers.The example of natural mineral fillers is included but not
It is limited to talcum powder, diatomite, kaolin, marble, lime stone, mica, bentonite etc..The fluoropolymer composite wood of the present invention
A kind of inorganic filler can be used in material, above two or more can also be used to plant the mixture of inorganic filler.The present invention's
Inorganic filler is preferably aluminium oxide, zinc oxide, silicon carbide, boron carbide and its mixing of two or more, is more preferably aoxidized
Aluminium.
The shape of inorganic filler can be spherical shape, irregular shape, rodlike, plate, sheet, needle-shaped, hexagonal plate, fiber
The combination of shape, porous etc. or above two or more kind shape.The inorganic filler of the present invention is preferably spherical, no
The combination of regular shape, sheet, porous, sheet and irregular shape.Such shape is conducive to improve the resistance to of composite material
Mill property.The shape of inorganic filler is often referred to the shape of individually primary inorganic filler, but may be the inorganic filler of aggregation
Shape.Such as in one embodiment, the aggregation of inorganic filler makes it show porous.The shape of inorganic filler can lead to
The many indexs such as circularity, draw ratio, porosity are crossed to weigh.
The grain size of inorganic filler may be used different methods and measure.The example of measuring method includes but not limited to settle
Method, micro-image method, sieve method, laser method, light blockage method, electric-resistivity method, specific surface area method etc..For different measuring methods, institute
Particle size can difference.Normally, the shape of particle is more complicated, and the result error measured using distinct methods is got over
Greatly.Since the grain size of inorganic filler is often not regular spherical shape, equivalent grain size can also be used instead of grain size, i.e., in candidate particles
With the spheric granules of homogeneity in a certain physical characteristic it is close or identical in the case of, replace practical with the diameter of spheric granules
The diameter of grain.The particle size distribution of inorganic filler may be used the methods of graphic-arts technique, schedule method, function method and represent.Particle ruler
D50, D10, D90, D5 etc. may be used to represent in very little and its distribution.D50 is also known as median particle diameter, refers to the accumulative particle size of sample
Percentile reaches grain size corresponding when 50%, and size is more than and respectively accounts for 50% less than the particle of the value in sample.It is similar
Ground, the grain diameter that the corresponding particle size values of D90 refer in sample 90% are below the particle size values.D10, D5 also have to be contained accordingly
Justice.For example, the D90=25 μm of grain diameter for representing in particle 90% is less than 25 μm.Correspondingly, D90≤25 μm can represent
The grain size of at least 90% particle is less than 25 μm.Similarly, D5 >=0.5 μm represents that the grain size of at most 5% particle is 0.5 μm
Below.
In various embodiments, the grain size of inorganic filler is the rank of micron.Herein, the rank of micron refers to inorganic
The grain size of filler is in such as 0.1 μm or more, preferably 0.2 μm or more, more preferable 0.5 μm or more, such as D5 >=0.2 μm, as D5 >=
0.5μm.In one embodiment, the grain size of inorganic filler is D90≤25 μm, preferred D90≤15 μm, more preferable D90≤10 μm,
Such as D90 is 24,11,8,7 μm.In one embodiment, the grain size of inorganic filler is D50≤10 μm, preferred D50≤6 μm, more
It is preferred that D50≤4 μm, such as D50 are 6,4,3.8,3.5 μm.In one embodiment, the grain size of inorganic filler is D10≤5 μm,
It is preferred that D10≤3 μm, more preferable D10≤2 μm, such as D10 are 1.8,1.6,1.4,0.8 μm.
In an exemplary embodiment, the particle diameter distribution of inorganic filler is D90≤25 μm, D50≤10 μm and D10≤5 μm.
In another embodiment, the particle diameter distribution of inorganic filler is D90≤15 μm, D50≤6 μm and D10≤3 μm.In another implementation
In scheme, the particle diameter distribution of inorganic filler is D90≤10 μm, D50≤4 μm and D10≤2 μm.
In order to obtain the grain size of suitable size, inorganic filler can be obtained by grinding, crushing the modes such as bulky grain filler,
It can also prepare the modes such as inorganic filler by vapor deposition, sol-gel and obtain.In application process, inorganic filler may
Reunite so that its primary grain size assembles grain size much smaller than grain size is measured.In one embodiment, inorganic filler is poly-
Collection grain size meets following at least one conditions：D90≤120 μm, D50≤70 μm and D10≤20 μm.In another embodiment,
The aggregation grain size of inorganic filler is distributed as D90≤120 μm, D50≤70 μm, D10≤20 μm.In preferred embodiments,
The aggregation grain size of inorganic filler is distributed as D90≤110 μm, D50≤60 μm, D10≤15 μm, such as D90=105 μm, D50=
52 μm and at least one of D10=12 μm, such as D90=105 μm, D50=52 μm and D10=12 μm.
Inorganic filler can carry out surface modification to prevent particle agglomeration by surface treatment mode physically or chemically.This hair
Bright inorganic filler does not preferably have additional surface treatment mode.
Composite material
In the composite material of the present invention, based on weight fluoropolymer-containing in composite material, the content of the polyarylate
It is about 5-40%, preferably from about 15-25%.Too low polyarylate content is unfavorable for so that composite material has preferable mechanicalness
Can, excessively high polyarylate content can cause the structural behaviour of fluoropolymer composite material significantly to change.
In the composite material of the present invention, based on weight fluoropolymer-containing in composite material, the content of inorganic filler is
About 1-25%, preferably from about 5-15%.Excessively high filer content can lead to destruction and the friction coefficient of composite material toughness
Increase, and too low filer content will then cause due to loading deficiency so that fluoropolymer wearability enough cannot change
It is kind.It is preferred that appropriate inorganic filler is added so that it has in fluoropolymer composite material disperses well, and fluorine-containing poly-
The wearability of compound composite material reaches mechanical performance of the optimal level without damaging composite material.
Also add in the composite material of the present invention optionally including what is usually included in such composite material preparation process
Add agent, such as antioxidant, anti-aging agent, coupling agent, coloring agent.
Preparation method
The invention further relates to a kind of methods for preparing fluoropolymer composite material, and the method includes will be in composite material
Each component is uniformly mixed, is compacted and is sintered.
The fluoropolymer-containing average diameter of the present invention is about 15-35 μm, preferably from about 20-30 μm.The poly- virtue of the present invention
The average diameter of ester is about 10-30 μm, preferably from about 12-20 μm.People in the art may be used in fluoropolymer, polyarylate
Method known to member, which is granulated, to be obtained, such as non-slurry pelletizing, wet granulation etc..
In one embodiment, fluoropolymer composite material of the invention is mixed using the method for high speed shear, preferably
High-speed shearing equipment have excellent dispersion effect, highly viscous material quickly can be smashed and be disperseed.Preferred
In embodiment, suitable high-speed shearing equipment is high speed shear dispersion machine.
In one embodiment, the feed postition of each component can use gravity to feed or force charging in composite material,
Preferably gravity feeds.
Each component in composite material can be that primary add in adds in multiple.In one embodiment, by fluoropolymer
Composition granule, polyarylate particle and inorganic filler are disposably sequentially added in mixing apparatus.In another embodiment, it is fluorine-containing poly-
Polymer beads first add in mixing apparatus, and polyarylate and inorganic filler are then gradually gradually mixed into.In yet another embodiment, in order to
Inorganic filler is made to be better mixed with fluoropolymer particles, the two is pre-mixed before mixing apparatus is mixed into.It is described pre-
The mode of mixing can be that inorganic filler is scattered in solvent, add in fluoropolymer particles, uniformly after mixing, remove solvent
To obtain fluoropolymer particles-inorganic filler complex.Wherein, the example of the solvent includes but not limited to water, methanol, second
Alcohol, isopropanol, normal propyl alcohol, acetone, butanone etc..
The temperature range of high speed shear is not particularly limited, as long as will not cause each component physically and/or chemically property
Variation.Preferred high speed shear temperature is room temperature.
Well-mixed composite material can be prepared by hot pressed sintering or cold-rolled sintered mode, it is preferable to use being cold-pressed burning
Knot.Specifically, the composite material being uniformly mixed uniformly being put into corresponding mold is cold-pressed.The pressure of cold pressing should make
The each component for obtaining composite material is able to be compacted and does not damage the original physically and/or chemically performance of each component, while to equipment not
It can damage.The pressure of application can be more than 600PSI, more preferable 1, more than 000PSI, and be 25, below 000PSI.Pressure
After the preform demoulding of system, it is sintered in sintering furnace.The temperature of sintering is it is required that the fluoropolymer in composite material obtains
With melting, and composite material each component will not decompose.Preferably, the temperature of sintering be 270 DEG C or more, more preferably 300
DEG C or more, and be less than 500 DEG C.The time of sintering is not particularly limited, and composite material each component will not decompose.It is logical
Often preferred sintering time is 1 hour or more, more preferable 1.5 hours or more, and less than 48 hours.Sinter is cooled down to obtain
To the product of required size.
The wear-resisting property of the fluoropolymer composite material of the present invention can be characterized by following test.
The coefficient of waste
The coefficient of waste can be described as K factor again.The coefficient of waste is the important indicator of judgement material wearability.The present invention's is fluorine-containing
Polymer composites have about 40 × 10-6mm3/ Nm is hereinafter, preferably from about 36 × 10-6mm3The coefficient of waste of/below Nm.Abrasion
Coefficient can for example be measured using LRI thrust bearing test machines according to ASTMD3702.
Wear rate
Wear rate is the intuitive index of judgement material wearability.Height change after being worn by material directly obtains
Wear rate score.Abrasion rate score also can be used to intuitively predict the service life of material wear-resistant.The addition of inorganic filler can
The tensile strength and elongation at break of material can be reduced to a certain extent, but are advantageous for reducing wear rate.Usually need
Obtain the balance between preferable tensile strength and relatively low wear rate.The fluoropolymer composite material of the present invention has about
8.0 μm/hr is hereinafter, the preferably from about wear rate of 7.0 μm/below hr.Wear rate can for example use LRI thrust bearing test machine roots
It is measured according to ASTMD3702.
Friction coefficient
For wear-resistant material, it is usually desirable to which it is with smaller friction coefficient.But after the wear-resisting inorganic filler of addition, usually
Friction coefficient can be caused slightly to increase.Friction coefficient can for example be carried out using LRI thrust bearings test machine according to ASTMD3702
It measures.The fluoropolymer composite material of the present invention is with about 0.2 hereinafter, preferably from about less than 0.15 friction coefficient.
Advantageous effect
The fluoropolymer composite material of the present invention has the mechanicalnesses such as good maximum tensile stress, maximum tension strain
Can and the relatively low coefficient of waste, relatively low wear rate, higher service life, and with lubricating oil good compatibility.Using the present invention
Fluoropolymer composite material have excellent leakproofness.Prepared sealing article such as sealing ring turns available for hydraulic booster
To system.
Embodiment
The preparation of fluoropolymer composite material
1. the composition according to each fluoropolymer composite material in table 1 is by 100 parts of polytetrafluoroethylene (PTFE), 20 parts of polybenzoate, 10
Part aluminium oxide (if present) is added in high speed shear dispersion machine (SHR high-speed mixers), is uniformly mixed.
2. the mixture in step (1) is added in mold, apply the pressure of 1,000PSI at normal temperatures.
3. preform is demoulded, it is put into sintering furnace, is sintered 1.5 hours at a temperature of 300 DEG C.
4. cooling down preform, required product is obtained.
Material
Polytetrafluoroethylene (PTFE)：M-18F, Daikin company
Polybenzoate：CGZ-351, Sichuan morning twilight research institute
Aluminium oxide：CAP02, Nanjing Tian Hang new materials Co., Ltd
SHA03, Guangzhou Xin Xi chemical metallurgies Co., Ltd
325th, 295,250, Nabaltec AG
The composition of 1 fluoropolymer composite material of table
Test method
The mechanical performance of composite material is tested using the method for ASTM D638.Ptfe composite according to
Prepared by the method for ASTM D4745, by molding, sinter embryo into, then cut and become band, dumbbell shape sample is made with pressing.Sample
The treatment conditions of product are 23 DEG C, 40h under 50%RH, and test condition is 23 DEG C, 50%RH, clamp distance 22mm, tensile speed
For 50mm/min.It is tested using Instron universal testing machines.
According to the polishing machine of the method test compound material of ASTM D3702.The preparation process of sample is by polytetrafluoroethyl-ne
Alkene composite material sinters embryo into, then be machined to standard size by molding.The treatment conditions of sample are 23 DEG C, under 50%RH
40h.The test condition of sample to be lubricated in steering hydraulic oil DEXRON II, 120 DEG C, load 2.5MPa, rotary speed be
Under conditions of 0.021m/s, testing time 45h.Test equipment is LRI thrust bearing test machines.
As a result
As shown in Fig. 2 and table 2, the friction coefficient of the composite material of embodiment 1-5 is only slightly higher than comparative example.
The friction coefficient of 2 embodiment 1-5 of table and the composite material of comparative example
As shown in Fig. 3-4 and table 3, the coefficient of waste, the wear rate of the composite material of embodiment 1-4 are substantially less than comparative example.
That is compared to comparative example, under conditions of friction coefficient is basically unchanged, the coefficient of waste of composite material of the invention and
Wear rate is substantially reduced.The composite material of the present invention has excellent wear-resisting property.
The coefficient of waste and wear rate of 3 embodiment 1-4 of table and the composite material of comparative example
The measuring mechanical property result of embodiment 1 and embodiment 5 is as shown in Figure 5.The maximum tension of the material of embodiment 1 should
Become the material for being slightly below embodiment 5.Specifically, the maximum tensile stress of the material of embodiment 1 is 11.49MPa, and maximum tension should
Become 118.41%.The maximum tensile stress of the material of embodiment 5 is 11.52MPa, and maximum tension strain is 135.48%.This
The composite material of invention has excellent mechanical performance.
It will be clear for a person skilled in the art that many modifications and variations of the present invention can be carried out without departing from its spirit and model
It encloses.Specific embodiment as described herein is only provided by way of example, is not meant to limit in any way.The present invention
True scope and spirit show that description and embodiments are only exemplary by the appended claims.
Claims (12)
1. a kind of composite material, it includes
Fluoropolymer, polyarylate and inorganic filler,
The grain size of wherein described inorganic filler meets following at least one conditions：
D90≤25 μm,
D50≤10 μm and
D10≤5μm。
2. a kind of composite material, it includes
Fluoropolymer, polyarylate and inorganic filler,
The aggregation grain size of wherein described inorganic filler meets following at least one conditions：
D90≤120 μm,
D50≤70 μm and
D10≤20μm。
3. the composite material described in claims 1 or 2, wherein the fluoropolymer is polytetrafluoroethylene (PTFE).
4. the composite material described in one of claim 1-3, wherein the polyarylate is at least one of following polymer：
Wherein, n, x, y are respectively each number of repeat unit purpose average on polymer macromolecule chain；
Preferably polybenzoate.
5. the composite material described in one of claim 1-4, wherein based on the fluoropolymer-containing weight, the polyarylate
Content is 5-40%, preferably 15-25%.
6. the composite material described in one of claim 1-5, wherein based on the fluoropolymer-containing weight, the inorganic filler
Content be 1-25%, preferably 5-15%.
7. the composite material described in one of claim 1-6, wherein the particle diameter distribution of the inorganic filler is：D90≤25 μm,
D50≤10 μm and D10≤5 μm,
D90≤15 μm, D50≤6 μm and D10≤3 μm or
D90≤10 μm, D50≤4 μm and D10≤2 μm.
8. the composite material described in one of claim 1-6, wherein the aggregation particle diameter distribution of the inorganic filler is：D90≤120
μm, D50≤70 μm and D10≤20 μm or
D90≤110 μm, D50≤60 μm and D10≤15 μm.
9. the composite material described in one of claim 1-8, wherein the shape of the inorganic filler is porous, sheet, spherical shape
Or irregular shape.
10. the composite material described in one of claim 1-9, wherein the inorganic filler is aluminium oxide.
11. a kind of sealing article, it includes the composite materials described in one of claim 1-10.
12. the sealing article of claim 11 is the form of sealing ring.
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| CN201611255783 | 2016-12-30 | ||
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2024070415A1 (en) * | 2022-09-29 | 2024-04-04 | 日鉄ケミカル＆マテリアル株式会社 | Dispersion composition, fluororesin film, metal-clad laminated board, and method for producing same |
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| CN103703065A (en) * | 2011-05-13 | 2014-04-02 | 纳幕尔杜邦公司 | Low-wear fluoropolymer composites |
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| CN1379798A (en) * | 1999-10-21 | 2002-11-13 | 大金工业株式会社 | Resin articles for molding and process for producing same |
| CN1425715A (en) * | 2002-12-31 | 2003-06-25 | 四川大学 | Self lubricating wear resistant polyaryl thioether composite material and its preparing method |
| CN102352095A (en) * | 2003-12-30 | 2012-02-15 | 沙伯基础创新塑料知识产权有限公司 | Polymer compositions, method of manufacture, and articles formed therefrom |
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| WO2024070415A1 (en) * | 2022-09-29 | 2024-04-04 | 日鉄ケミカル＆マテリアル株式会社 | Dispersion composition, fluororesin film, metal-clad laminated board, and method for producing same |
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Application publication date: 20180710 |