CN104832704B - Limit element, check valve, composition, elastomeric material, grafting graphite and preparation method thereof - Google Patents

Limit element, check valve, composition, elastomeric material, grafting graphite and preparation method thereof Download PDF

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Publication number
CN104832704B
CN104832704B CN201510158765.2A CN201510158765A CN104832704B CN 104832704 B CN104832704 B CN 104832704B CN 201510158765 A CN201510158765 A CN 201510158765A CN 104832704 B CN104832704 B CN 104832704B
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CN
China
Prior art keywords
check valve
elastomeric material
elastomer layer
graphite
grafted
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CN201510158765.2A
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CN104832704A (en
Inventor
孙鑫鑫
喻学韬
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3M Innovative Properties Co
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3M Innovative Properties Co
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Priority to CN201510158765.2A priority Critical patent/CN104832704B/en
Priority to CN201610990776.1A priority patent/CN106957469B/en
Publication of CN104832704A publication Critical patent/CN104832704A/en
Priority to PCT/US2016/025500 priority patent/WO2016161252A1/en
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Publication of CN104832704B publication Critical patent/CN104832704B/en
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    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16K—VALVES; TAPS; COCKS; ACTUATING-FLOATS; DEVICES FOR VENTING OR AERATING
    • F16K25/00—Details relating to contact between valve members and seat
    • F16K25/005—Particular materials for seats or closure elements
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16K—VALVES; TAPS; COCKS; ACTUATING-FLOATS; DEVICES FOR VENTING OR AERATING
    • F16K15/00—Check valves
    • F16K15/14—Check valves with flexible valve members
    • F16K15/16—Check valves with flexible valve members with tongue-shaped laminae

Abstract

A kind of limit element of present invention offer, check valve, composition, elastomeric material, grafting graphite and preparation method thereof, belong to check valve antivibration area.The limit element for check valve of the present invention, for being arranged in motor element one end of check valve, to limit the open position of the motor element, elastomer layer is arranged in the side for being contacted with the motor element in the limit element, and the elastomer layer is made of elastomeric material.The check valve of the present invention includes above-mentioned limit element, and noise is small, long lifespan, and fluid flow rate is big.The elastomeric material of the present invention is cross-linked to form by composition, and composition includes：Nitrile rubber；It is grafted graphite comprising graphite particle and the grafted moiety being grafted in graphite particle, grafted moiety includes the copolymer group of butadiene and acrylonitrile.The elastomeric material has good dynamic anti-aging property and damping property to oily and refrigerant better resistance.

Description

Limit element, check valve, composition, elastomeric material, grafting graphite and its preparation Method
Technical field
The invention belongs to check valve antivibration areas, and in particular to a kind of limit element, check valve, composition, elasticity Body material, grafting graphite and preparation method thereof.
Background technology
Compressor is the core component of the refrigeration equipments such as air-conditioning, refrigerator, for being carried out to refrigerant (Refrigerant) gas Compression.Within the compressor, check valve is one of important component, and check valve only allows one-directional fluid flow, to realize above-mentioned compression Process.
The one-way valve structures used in a kind of compressor are as shown in Figure 1 and Figure 2 comprising valve body 1, valve block 3, limit element 2 (limiter).
Wherein, valve body 1 is equipped with valve opening 11, and 11 one end open of valve opening is on 1 surface of valve body.
Valve block 3 can be the strip thin slice made of high cycle fatigue steel (such as spring steel), and the fixed part of one end is connected to On 1 surface of valve body, the movement portion of the other end can then block the position (closed position) of the opening of valve opening 11 and leave 1 surface of valve body Position (open position) between move back and forth.When compressed fluid will be flowed up from the lower section of the valve body 1 in Fig. 2, stream Body can be open-top by valve block 3 and be flowed out；And when fluid will flow downward above valve body 1, valve block 3 can be pressed in valve by Fluid pressure The closed position on 1 surface of body, blocks valve opening 11, and fluid cannot flow through, to realize the function of " one-way flow ".
Limit element 2 includes then being located at limiting section (limit element 2 rest part of the 3 movement portion of valve block far from 1 side of valve body It is attached on 3 fixed part of valve block), on the direction from the fixed part of valve block 3 direction movement portion, limiting section and 1 surface of valve body Between distance gradually increase, i.e. the limiting section of limit element 2 is gradual " tilting ".The effect of limit element 2 is opened in valve block 3 When it " is blocked ", to limit the maximum distance that valve block 3 leaves valve body 1, that is, the open position of valve block 3 is limited, to avoid valve Piece 3 is damaged because deformation is excessive, and ensures that valve block 3 can rapidly return back to closed position, improves efficiency.
Currently, the working frequency of refrigeration equipment compressor is usually in 20Hz between 100Hz, it means that valve block therein In one second at least will switch 20 times, and each switch middle valve plate will impinge upon on limit element.And hit on the one hand meeting Cause larger noise (actually the noise is maximum noise source in compressor)；On the other hand, meeting on valve block when shock Bigger stress is generated, to reduce its service life；Meanwhile to avoid valve block from damaging, therefore limit element and valve body surface Between maximum distance cannot be too big, that is, the maximum opening degree (also referred to as " aperture " or " lift " of valve block) of valve block cannot It is excessive, to affect the flow velocity of refrigerant, reduce the efficiency of compressor.
Invention content
It is an object of the present invention to provide a kind of limit element for check valve, which can effectively buffer fortune Impact suffered by dynamic element (such as valve block) extends motor element service life, improves opening for motor element to reduce noise Degree increases the fluid flow rate of check valve, improves compressor efficiency.
This is used for the limit element of check valve for being arranged in motor element one end of check valve, to limit the fortune The open position of dynamic element, wherein
The limit element for being contacted with the motor element side be arranged elastomer layer, the elastomer layer by Elastomeric material is made.
These, it is preferred to which above-mentioned elastomeric material is preferably cross-linked to form by composition, the composition includes：Fourth Nitrile rubber (preferably hydrogenated nitrile-butadiene rubber)；It is grafted graphite comprising graphite particle and the grafting being grafted in the graphite particle Group, the grafted moiety include the copolymer group of butadiene and acrylonitrile.
These, it is preferred to which check valve is preferably used for the check valve in compressor.
Another mesh of the present invention is to provide the limit element for compressor check valve, is used to be arranged in compressor list To on valve block one end of valve, to limit the open position of the valve block, wherein
Elastomer layer is arranged in the side for being contacted with the valve block in the limit element, and the elastomer layer is by elasticity Body material is made, and the elastomeric material is cross-linked to form by composition, and the composition includes：
Nitrile rubber；
It is grafted graphite comprising graphite particle and the grafted moiety being grafted in the graphite particle, the grafted moiety Copolymer group including butadiene and acrylonitrile；
And
The weight percentage of nitrile rubber is 28% to 60% in the composition；
The weight percentage of graphite is grafted in the composition 2% to 12%；
In the grafting graphite, the weight of the relatively described graphite particle, the weight ratio of the grafted moiety 6% to 20%.
These, it is preferred to which the thickness of the elastomer layer is at 0.1 millimeter to 5 millimeters；
The valve block includes the fixed part for being connected on the valve body of check valve, and is moved for opposite valve body Movement portion；
The limit element includes the limiting section of the open position for limiting the valve block, and the limiting section is used for direction The surface of the valve block side is convex globoidal；When the limit element is set in the check valve, in consolidating from the valve block Determine portion to be directed toward on the direction in movement portion, the curvature of the convex globoidal in one to 1/172 millimeter point of 1/72 millimeter point one.
It is a further object to provide a kind of check valves using above-mentioned limit element.The check valve includes：
Valve body with valve opening；
Motor element on valve body one end is set, for closing the closed position of the valve opening and leaving the valve opening Open position between move；
The above-mentioned limit element being arranged on motor element one end, the open position for limiting the motor element, And elastomer layer is arranged in the side for being contacted with the motor element in the limit element, the elastomer layer is by elastomer Material is made.
Wherein, which is preferably used for the check valve in compressor.
Wherein, above-mentioned elastomeric material is preferably cross-linked to form by composition, and the composition includes：Nitrile rubber is (excellent Select hydrogenated nitrile-butadiene rubber)；It is grafted graphite comprising graphite particle and the grafted moiety being grafted in the graphite particle, it is described Grafted moiety includes the copolymer group of butadiene and acrylonitrile.
It is a further object to provide a kind of grafting graphite, are the originals for being used to prepare above-mentioned elastomeric material One of material.
The grafting graphite includes graphite particle and the grafted moiety that is grafted in the graphite particle, the grafted moiety packet Include the copolymer group of butadiene and acrylonitrile.
It is a further object to provide a kind of preparation methods of above-mentioned grafting graphite comprising：
Graphite particle is functionalized；
Grafted moiety is grafted in the graphite particle, obtains grafting graphite, wherein the grafted moiety includes fourth two The copolymer group of alkene and acrylonitrile.
It is a further object to provide a kind of compositions, can be used to form above-mentioned elastomeric material, including：
Nitrile rubber (preferably hydrogenated nitrile-butadiene rubber)；
Above-mentioned grafting graphite comprising graphite particle and the grafted moiety being grafted in the graphite particle, it is described to connect Branch group includes the copolymer group of butadiene and acrylonitrile.
It is a further object to provide a kind of elastomeric materials, in addition to good mechanical property, to oil Also there is good resistance (ageing resistance) with refrigerant, and there is good dynamic anti-aging property, therefore be particularly suited for use as pressing Elastomer layer in contracting machine check valve.
The elastomeric material is cross-linked to form by above-mentioned composition, and the composition includes：
Nitrile rubber (preferably hydrogenated nitrile-butadiene rubber)；
It is grafted graphite comprising graphite particle and the grafted moiety being grafted in the graphite particle, the grafted moiety Copolymer group including butadiene and acrylonitrile.
Description of the drawings
Fig. 1 is a kind of existing structural schematic diagram of compressor check valve；
Fig. 2 is a kind of existing cross-sectional view of compressor check valve；
Fig. 3 is a kind of structural schematic diagram of compressor check valve of the embodiment of the present invention；
Fig. 4 is a kind of cross-sectional view of compressor check valve of the embodiment of the present invention；
Fig. 5 is the photo of the elastomer layer in a kind of compressor check valve of the embodiment of the present invention；
Fig. 6 is the cross-sectional view of another compressor check valve of the embodiment of the present invention；
Fig. 7 is the cross-sectional view of another compressor check valve of the embodiment of the present invention；
Fig. 8 is transmission electron microscope (TEM) photo of the graphite particle in the composition of the embodiment of the present invention；
Fig. 9 is the simulation point of the maximum stress suffered by a kind of existing each position of the valve block of check valve in period of motion Butut；
Figure 10 is the maximum suffered by a kind of each position of valve block of check valve of the embodiment of the present invention in a period of motion The simulation distribution figure of stress；
Figure 11 is existing a kind of simulation drawing of the Vibration Condition of the valve block of check valve in a period of motion；
Figure 12 is a kind of simulation of the Vibration Condition of the valve block of check valve of the embodiment of the present invention in a period of motion Figure；
Figure 13 is a kind of surface topography photo of the existing nitrile rubber after anti-aging test；
Figure 14 is a kind of surface topography photo of the existing hydrogenated nitrile-butadiene rubber after anti-aging test；
Figure 15 is a kind of surface topography photo of the elastomeric material of the embodiment of the present invention after anti-aging test；
Figure 16 is a kind of size comparison photo of the existing nitrile rubber before and after anti-aging test；
Figure 17 is a kind of size comparison photo of the elastomeric material of the embodiment of the present invention before and after anti-aging test；
Wherein, reference numeral is：1, valve body；11, valve opening；2, limit element；21, matrix；22, elastomer layer；23, rigidity Layer；3, valve block；91, the first ladder；92, the second ladder；H, maximum distance；α, angle.
Specific implementation mode
To make those skilled in the art be better understood from technical scheme of the present invention, below in conjunction with the accompanying drawings and specific embodiment party Present invention is further described in detail for formula.
Term is explained
In the present invention, following term or the meaning of describing mode are as follows：
The case where description of " A and/or B " indicates any of which or two kinds simultaneously may all occur, that is, include " A and B ", " A ", " B " three kinds of situations.
The description of " A to B " includes the value of A, the value of B and any value more than A and less than B；For example, 1 to 10 include 1, 10 and it is any be more than 1 and the value less than 10, such as 2,3,4,5,6,7,8,9,2.358,3.5,5.26,7.18,9.999 etc..
The description of " about A " or " essentially A " indicate that target is A, but can have under prior art conditions between reality and A It inevitably, being capable of tolerance.
" molecular weight ", unless otherwise instructed, then so-called molecular weight is weight average molecular weight in the present invention, and is passed through Gel gas chromatography (GPC) obtains.
" substance dosage ", unless otherwise instructed, then the dosage of substance or amount ratio refer both to weight or weight ratio in the present invention.
It is the part for belonging to B that " weight percentage of A in B ", which refers to A, when the weight (including A) with B is 100% When, the percentage shared by the weight of A.
" weight of opposite B, the weight ratio of A " refers to the part that A is not B, when being 100% with the weight of B, A's The percentage of the weight relative to B of weight.
" compressor " refers to the machinery for being compressed to refrigerant in refrigeration equipment (such as refrigerator, air-conditioning).
" check valve " refers to a kind of valve, and fluid is allowed to flow into the other side from one side, reversed without permission fluid Flowing.
" elastomeric material (Elastomer) " refer to larger elastically-deformable material (be usually polymer) can occur, and " elastic deformation " refers to the deformation that can be completely disappeared or almost disappear after the stress revocation for causing strain.
" rigid material " refers to the material for having larger hardness and rigidity, to which it cannot occur elastic deformation or can only send out Raw very little elastic deformation.
" peel stress along 180 degree direction " refers to for two mutually cohesive structures, when along the adhesive surface with the two Required stress when peeling away the two at the direction at 180 degree angle, with " Newton/millimeter " for unit.
Limit element and check valve
The embodiment of the present invention provides a kind of limit element in check valve, and uses the unidirectional of the limit element Valve.
Since check valve includes limit element, therefore check valve is directly introduced herein, while also just illustrating limit therein Bit unit.
Specifically, the check valve includes：
Valve body with valve opening；
Motor element on valve body one end is set, for closing the closed position of valve opening and leaving the open position of valve opening It is moved between setting；
Limit element on motor element one end is set, the open position for limiting motor element, and limit element Elastomer layer is set in the side for being contacted with motor element, elastomer layer is made of elastomeric material.
In the check valve of the embodiment of the present invention, there is bullet in the position that motor element (such as valve block) is contacted with limit element Property body layer, to motor element hit limit element when, elastomer layer is deformable and generates cushioning effect, extend motor element The stress time, reduce the impact strength suffered by it, avoid stress concentration and vibration, thus reduce noise, extend motor element Service life, and allow motor element have bigger aperture, to improve the fluid flow rate of check valve.
Of course it is to be understood that above check valve (including limit element) can be produced and sold as product. But the limit element also can be used as independent production and sale, as long as being installed in check valve (such as compressor later Check valve) in.
Preferably, the fracture elongation of elastomeric material is at least 10%；More preferably when elongation strain is 10%, stress At least 0.5MPa.
Obviously, the elastic property of elastomeric material has a great impact to its cushioning effect, it has been investigated that, meet above The elastomeric material of condition can preferably meet buffering needs.
Preferably, Shore A hardness of the elastomeric material at 23 degrees Celsius is 30 to 80, further preferably 30 to 70.
Since elastomer layer is often subject to the shock of motor element, therefore its hardness also has certain requirement, excessively it is soft then itself It is easy to wear, it is really up to the mark, good cushioning effect cannot be played, it has been investigated that, above hardness range is proper.
Preferably, elastomeric material is damping rubber.
That is, above elastomeric material is alternatively damping material (such as damping rubber), it is slow to preferably play Punching, effectiveness in vibration suppression.Specifically, available damping rubber is preferably the damping rubber of 3M companies, such as the VC308 of 3M companies, The damping rubber of the models such as VC310.
Preferably, elastomeric material is alternatively other conventional polymer materials, specifically may include in Types Below Any one or more：Polyamide, such as nylon66 fiber, semi-aromatic nylon；Polyurethane, as polyester polyurethane, heat molten type are poly- Urethane, compound polyurethane material etc.；Polyolefin and polyolefin derivative object, such as polypropylene, polyethylene, natural rubber, butadiene rubber Glue, nitrile rubber (preferably hydrogenated nitrile-butadiene rubber) etc.；Thermoplastic vulcanizates；Fluorubber, as perfluoroelastomers, fluorine silicone rubber, Inclined fluoroether rubber etc.；Acrylic rubber, such as ethylene-acrylate rubber, epoxy acrylate rubber；Epoxy resin, such as Solid epoxy, liquid curable epoxy resin etc.；Phenolic resin.
Certainly, available elastomeric material is not limited to above citing, those skilled in the art also can be selected it is other The elastomeric material known is used as elastomer layer.
The elastomeric material of a kind of preferred embodiment as embodiment of the invention, above-mentioned elastomer layer can be by a kind of combination Object is cross-linked to form, and the composition includes：
Nitrile rubber (preferably hydrogenated nitrile-butadiene rubber)；
It is grafted graphite comprising graphite particle and the grafted moiety being grafted in graphite particle, grafted moiety includes fourth two The copolymer group of alkene and acrylonitrile.
Preferably, in composition the weight percentage of nitrile rubber 28% to 60%；Graphite is grafted in composition Weight percentage is 2% to 12%.
Preferably, in being grafted graphite, the weight of opposite graphite particle, the weight ratio of grafted moiety is 6% to 20% Between.
The check valve of the present invention is preferably the check valve in the compressor of refrigeration equipment, in the working environment of this check valve It is filled with oily (such as lubricating oil) and refrigerant, and operating temperature and pressure are higher.Therefore, the material of elastomer layer preferably cope with oil and Refrigerant has preferable resistance (ageing resistance), to ensure physical property (such as hardness, mechanics in elastomer layer in use Performance) and size constancy.Meanwhile elastomer layer can be repeatedly subjected to impact and the subtle flow of valve block, therefore its dynamic in use Ageing properties, wear-resisting property etc. are also important.
In above-mentioned elastomeric material, grafting is distributed in the base material based on nitrile rubber (preferably hydrogenated nitrile-butadiene rubber) Graphite is grafted the grafted moiety for having similar nitrile rubber molecule in the graphite particle of graphite, therefore it can be total with nitrile rubber base material The interface between graphite particle and nitrile rubber is eliminated in crosslinking, to incorporate in base material well, therefore is grafted the presence of graphite not Harmful effect can be caused to mechanical properties such as the intensity of nitrile rubber.Simultaneously as the characteristic of graphite itself, particle are necessarily Sheet, as a result, the graphite particle of sheet can stop the intrusions such as refrigerant, oil, to improve the ageing resistance of elastomeric material； And the graphite of sheet may also function as the effect for improving elastomeric material wear-resisting property and dynamic anti-aging property, improve its anti-valve The ability of piece impact.That is, above-mentioned composition, in addition to good mechanical property, anti-aging property, dynamic are anti-aging Performance, wearability etc. are also very outstanding, therefore are particularly suited for use as the elastomer layer of the check valve of compressor.The elastomeric material Concrete condition will also be discussed in detail after this patent in part, just not repeat herein.
Preferably, as shown in Fig. 3, Fig. 4, Fig. 6, Fig. 7, limit element 2 includes matrix 21；And elastomer layer 22 is at least set to The side that matrix 21 is used to contact with motor element (such as valve block 3).
That is, limit element 2 may include the conventional, matrix 21 made of hard material (such as steel), the matrix 21 Limit the basic configuration and major part of limit element 2.And it is equipped on the side that matrix 21 is used to contact with motor element Elastomer layer 22.Certainly, elastomer layer 22 can be also equipped in the other parts of matrix 21.
Specifically, a kind of preferred embodiment as embodiment of the invention, as shown in Fig. 3, Fig. 4, Fig. 6, elastomer layer 22 Positioned at the outermost of limit element 2.
That is, can be directly provided on the side surface that matrix 21 is used to contact with motor element and be provided only with one Elastomer layer 22.
Preferably, a kind of mode as embodiment of the invention, elastomer layer 22 are fastened on matrix 21, and will be elastic Body layer 22 deviates from required power from matrix 21 and is at least 30 newton.
That is, elastomer layer 22 can have energy and base as shown in figure 5, forming individual " shell-like " device The structure that body 21 connects, to which as shown in Figure 3, Figure 4, elastomer layer 22 can mechanically be clamped, be socketed on matrix 21； When in this way, to pull down elastomer layer 22 from matrix 21, then the power of 30 newton is at least needed.Such side Formula compares convenient for the replacement of elastomer layer 22.
Preferably, another way as embodiment of the invention, as shown in fig. 6, elastomer layer 22 is bonded in matrix On 21, and the peel stress between elastomer layer 22 and matrix 21 along 180 degree direction is at least 0.6 Newton/millimeter.
That is, elastomer layer 22 can be also connected on matrix 21 by bonding mode.For example, can be coated on matrix 21 Epoxies, the binders such as acrylic compounds, polyurethanes, then elastomer layer 22 is sticked to thereon；Alternatively, can also be applied on matrix 21 Cloth rubber adhesive makes elastomer layer 22 be connected to matrix with realization co-crosslinking (co-vulcanization) of matrix 21 by heating later On 21.And in this case, the 180 degree peel stress between elastomer layer 22 and matrix 21 is at least 0.6 Newton/millimeter.
Another kind preferred embodiment as embodiment of the invention, as shown in fig. 7, elastomer layer 22 is used for and motor element The side of contact is provided with rigid layer 23.
That is, can not also be provided only with elastomer layer 22 on matrix 21, but be additionally provided with outside elastomer layer 22 by Rigid layer 23 made of rigid material.
That is, outermost one layer of limit element is made of rigid material, and elastomer layer 22 is covered by rigidity In layer 23.Specifically, rigid material can be steel, cast iron, copper alloy, aluminium, aluminium alloy, titanium alloy, lead, ceramic material etc..It is this The advantages of design, is that layer on the outermost side is directly by the shock of motor element (such as valve block 3), and and external environment (such as refrigerant, oil) is in direct contact, therefore need higher wearability, corrosion resistance etc., and traditional rigid material is in this respect More preferably, its advantage can be given full play to performance by using it for outermost；Meanwhile elastomer layer 22 is additionally provided in rigid layer 23, therefore transport The impact of dynamic element can be transmitted to by rigid layer 23 on elastomer layer 22, and elastomer layer 22 still can play a buffer role in.
Preferably, rigid layer 23 is bonded on elastomer layer 22, along 180 degree direction between elastomer layer 22 and rigid layer 23 Peel stress be at least 0.6 Newton/millimeter.
Obviously, rigid layer 23 is difficult to deform, it has not been convenient to it is mechanically attached on elastomer layer 22 flexible with cutting ferrule etc., Therefore its between elastomer layer 22 preferably by the way of bonding connection.
Certainly, can be also equipped on matrix 21 by the layer of multiple and different materials form " stepped construction (wherein must include Elastomer layer 22) ".Total number of plies in the stepped construction is preferably between 2 to 20；Moreover, layer in stepped construction Specific spread pattern is various, such as, it may include multigroup rigid layer 23 being arranged alternately and elastomer layer 22, or may include more A continuous rigid layer 23 or multiple continuous elastomer layers 22 etc..
Preferably, in above-mentioned check valve, the thickness of matrix 21 can be between 0.5 millimeter to 4 millimeters；Elastomer layer 22 Thickness is at 0.1 millimeter to 5 millimeters, more preferably at 0.5 millimeter to 1.5 millimeters；And the thickness of rigid layer 23 is preferably at 0.01 millimeter To between 4 millimeters.
Clearly for above elastomer layer 22, rigid layer 23 etc., respective work cannot be played if its thickness is too thin With, it is too thick, may influence other performances (if such as rigid layer 23 it is too thick, elastomer layer 22 can be made not have cushioning effect).
Preferably, the check valve of the embodiment of the present invention is for the check valve in compressor, and above-mentioned limit element is For the limit element in compressor check valve.It is furthermore preferred that as shown in Fig. 3, Fig. 4, Fig. 6, Fig. 7, in the check valve (compressor Check valve) in：
Valve body 1 includes first surface, and valve opening 11 is open on the first surface；
Motor element be include fixed part and the valve block 3 in movement portion, fixed part connects on the first surface, and movement portion uses In movement between covering the closed position of valve opening 11 and leaving the open position of valve opening 11 (i.e. valve body 1 is moved relatively)；
Limit element 2 includes being located at limiting section of the valve block 3 far from first surface side, is directed toward from the fixed part of valve block 3 On the direction in movement portion, limiting section between first surface at a distance from gradually increase.
That is, for the check valve in compressor, motor element is preferably the form of valve block 3, and valve block 3 is strip Shape thin slice can be made of high cycle fatigue steel (such as spring steel), and one end (fixed part) is connected on valve body 1, the other end (movement Portion) flexible deformation, so as to past between the closed position and the open position for leaving 1 surface of valve body for being attached at 1 surface of valve body Multiple movement.
And one end of limit element 2 can also be fixedly connected on 1 surface of valve body, and it includes being located above 3 movement portion of valve block Limiting section, the distance (i.e. open position) on 1 surface of valve body is left to limit valve block 3.Meanwhile the limiting section of limit element 2 Be obliquely installed, it is closest with 1 surface of valve body at " root ", and " end " then with 1 most portionafrom theasurface of valve body, to limiting section It is the form that opening degree gradually increases from root to the structure of end " tilting ", thus to limit valve block 3.
Preferably, for the above-mentioned check valve in compressor, the surface of limiting section 2 towards 3 side of valve block is convex arc Face.
That is, as shown in Fig. 4, Fig. 6, Fig. 7, the face that the limiting section of limit element 2 is used to contact with valve block 3 is preferably Cambered surface and on-plane surface, and the cambered surface is the convex globoidal protruded to valve block 3, that is to say, that it is moved being directed toward from the fixed part of valve block 3 On the direction in portion, the convex globoidal is increasing with respect to the tilting degree of first surface.The design of this convex globoidal can make valve block 3 exist Stress dispersion when opening.Meanwhile as shown in figure 4, in the case where meeting conditions above, when valve block 3 is opened with limit element 2 Contact process can be divided into two stages and carry out：Valve block 3 is first bent and is attached to the table of limit element 2 when hitting limit element 2 On face (i.e. the first ladder 91), the elastomer layer 22 of part is protruded later because of stress and by compressive deformation, the table of limit element 2 Face shape generates variation, and valve block 3 also continues to move upward to the position of the second ladder 92 of dotted line in figure.That is, valve block 3 Knockout process become " staged ", to keep the stress on valve block evenly dispersed, eliminate region of stress concentration.
As shown in fig. 6, it is furthermore preferred that from the direction that the fixed part of valve block 3 is directed toward movement portion, the limit element 2 The curvature of the convex globoidal on surface is preferably the one of one to 1/172 millimeter point of 1/72 millimeter point；And/or above-mentioned convex globoidal is most At 9 degree to 40 degree, (figure middle valve plate 3 is parallel to the first table to angle α between the section and first surface of the position of first surface The one end in face, GuαJiao has been drawn in 3 surface of valve block).Preferably, the limiting section of limit element 2 is close to the side of first surface and the Maximum distance H between one surface is at 3 millimeters to 32 millimeters.
That is, the curvature of above-mentioned convex globoidal is preferably in 1/72 (mm-1) to 1/172 (mm-1) between, it in this way can be more More than good guarantee " staged " knockout process.Meanwhile the angle α between 1 surface of root and valve body of 2 limiting section of limit element is excellent It is selected in 9 degree to 40 degree.Moreover, the end of 2 limiting section of limit element between 1 surface of valve body distance H preferably 3 millimeters to 32 milli Between rice；Specifically, for the check valve in freezer compressor, distance H can be at 3 millimeters to 18 millimeters, and for air-conditioning pressure Check valve in contracting machine, distance H can be at 5 millimeters to 32 millimeters.
Obviously, above maximum distance H, curvature, angle α define the maximum opening degree (aperture) of valve block 3 jointly, The maximum opening degree of their value more big then valve block 3 is bigger, and the fluid flow rate of check valve is also bigger, and compressor efficiency is got over It is high；But it correspondingly, the deformation of valve block 3 is also bigger, is more easily damaged.Due to the limit element of the check valve of the embodiment of the present invention 2 include elastomer layer 22, can effectively reduce the stress concentration on valve block 3, therefore the value range of above-mentioned each parameter is all than existing Technology bigger, i.e. the embodiment of the present invention can increase its maximum opening degree in the case that ensureing that valve block 3 is not impaired, to Improve the efficiency of the fluid flow rate and compressor of check valve.
Described above is the structure of check valve in compressor.It will be clear that the check valve of the embodiment of the present invention does not limit the use of Within the compressor, it is alternatively the check valve of automobile air valve etc..Moreover, the structure of the check valve of the embodiment of the present invention is not yet Concrete form more than being limited to, for example, its movement portion, which is alternatively, in the position (closed position) for blocking valve opening and to leave valve opening Position (open position) between " piston " that moves.As long as in short, in check valve have valve body, motor element, limit element, and Limit element includes above-mentioned elastomer layer, that is, is belonged to the scope of protection of the present invention.
It is grafted graphite
1, it is grafted graphite
The embodiment of the present invention also provides a kind of grafting graphite, which can be used in combinations of the above object, and be somebody's turn to do Composition can be used to form the elastomeric material of the elastomer layer of the above compressor check valve.
Specifically, the grafting graphite includes graphite particle and the grafted moiety that is grafted in graphite particle, grafted moiety packet Include the copolymer group of butadiene and acrylonitrile.
Wherein, " copolymer of butadiene and acrylonitrile " is nitrile rubber, that is to say, that in the embodiment of the present invention It is grafted in graphite, the basic group of nitrile rubber molecule has been grafted in graphite particle.
Wherein, the grain size of above-mentioned graphite particle is preferably between 200 nanometers to 5000 nanometers.
Graphite particle in the particle size range may be homogenously dispersed in base material (nitrile rubber), and play improvement elastomer layer The effect of performance (such as anti-aging property).
Preferably, in being grafted graphite, the weight of opposite graphite particle, the weight ratio of grafted moiety is 6% to 20% Between；More preferably between 6% to 17%.
That is, in being grafted graphite, simple grafted moiety and the weight ratio of simple graphite particle preferably exist (0.06~0.2): 1, " grafting amount " in graphite particle is preferably between 0.06~0.2 in other words.Obviously, in graphite particle The amount of grafted moiety has the performance of elastomeric material important influence, it has been investigated that, the grafting in the above proportional region Amount can it is most effective improve elastomeric material ageing resistance, it is too small, act on unobvious, excessive, grafting process is difficult to realize.
Preferably, above-mentioned grafted moiety is the copolymer group of the butadiene and acrylonitrile of hydrogenation, and preferably block The copolymer group of (such as amino-terminated) butadiene and acrylonitrile.
That is, the nitrile rubber (copolymer of butadiene and acrylonitrile) for being grafted to graphite particle is preferred It is the nitrile rubber of hydrogenated nitrile-butadiene rubber and sealing end, can preferably improves the ageing resistance of elastomeric material in this way.
2, it is grafted the preparation method of graphite
The embodiment of the present invention also provides a kind of preparation method of above-mentioned grafting graphite comprising：
Graphite particle is functionalized；
Grafted moiety is grafted in graphite particle, obtains grafting graphite, wherein grafted moiety includes butadiene and propylene The copolymer group of nitrile.
That is, can be first functionalized to the graphite particle of sheet, make the functional group needed for its connection, Zhi Houtong It crosses these functional groups above-mentioned grafted moiety is grafted in graphite particle.
Specifically, the preparation method of grafting graphite may include following step：
S101, graphite particle is mixed with strong oxidizer.
Wherein, strong oxidizer selects benzoyl peroxide (BPO), therefore this step is specially：By raw graphite and peroxidating Benzoyl is mixed according to 100: 6 weight ratio, and 2 small by ball grinding method ground and mixed under conditions of ratio of grinding media to material is 3 to 4 When, so that the grain size of raw graphite is narrowed down to the particle size range of above-mentioned graphite particle, and be sufficiently mixed one with benzoyl peroxide It rises.
Fig. 8 is the stereoscan photograph of graphite particle, it is seen then that graphite particle is apparent laminar structured, at grain size In the range of above 200 nanometers to 5000 nanometers.
S102, it is heated, so that graphite particle is functionalized.
This step is specially that the mixture of graphite particle and strong oxidizer is heated to 110 DEG C and is kept for 10 minutes.
For the comparativity of result, in the embodiment of the present invention, above-mentioned Benzoyl Oxide is all made of as strong oxidizer, and Heating parameters more than being used uniformly.It will be clear that other substances can also be used in strong oxidizer.
Such as, it is also possible to two propyl benzene of peroxidating is strong oxidizer, at this time the weight ratio of raw graphite and two propyl benzene of peroxidating Maximum is no more than 3: 1, and heating can be in 150 DEG C of temperature holding 1 hour.
For another example, it is also possible to which potassium permanganate is that the weight ratio of strong oxidizer, at this time raw graphite and potassium permanganate most very much not surpasses 3: 1 are crossed, and heating can be in 160 DEG C of temperature holding 2 hours.
S103, graphite particle is cooled to after room temperature and is fully eluriated to neutrality, dried later, obtain the powder of brown color, As functionalized graphite particle.
At this point, being grafted a large amount of functional group in the graphite particle of sheet, wherein the graphite particle edge of sheet The functional group of part connection is based on carboxyl and hydroxyl, and the functional group of middle section connection is based on epoxy group.
S104, graphite particle is added in n,N-Dimethylformamide (DMF), and be ultrasonically treated 15 minutes, obtained uniformly Suspension.
Wherein, the weight of opposite graphite particle, the weight ratio of n,N-Dimethylformamide preferably 350% to 450%, I.e. the weight ratio of graphite particle and N,N-dimethylformamide is 1: (3.5~4.5).
S105, by the copolymer of butadiene and acrylonitrile (namely nitrile rubber, but the nitrile rubber is to prepare grafting stone It is the raw material of ink, different from the nitrile rubber in composition product), in the above-mentioned suspension of dicyclohexylcarbodiimide (DCC) addition, And stirring 30 minutes makes it be evenly distributed.
Wherein, the weight of opposite graphite particle, the weight ratio of dicyclohexylcarbodiimide is preferably in 1% to 5%, i.e. stone The weight ratio of black particle and dicyclohexylcarbodiimide is 1: (0.01~0.05).
Wherein, the weight ratio of the copolymer of the weight of opposite graphite particle, butadiene and acrylonitrile 18% to 40%, I.e. the weight ratio of the copolymer of graphite particle and butadiene and acrylonitrile is 1: (0.18~0.4).
Typically, during the reaction, the copolymer of butadiene and acrylonitrile can not possibly all be grafted on graphite particle On, therefore the dosage of the copolymer of the butadiene and acrylonitrile in reactant has to be larger than and is grafted base needed for grafting graphite products The amount of group.It has been investigated that according to above dosage, it is ensured that the grafting amount in grafting graphite products meets above 0.06~ 0.2 range.
Wherein, the copolymer of butadiene and acrylonitrile is preferably (such as amino-terminated) liquid butadiene and propylene blocked The copolymer of nitrile, and the copolymer of butadiene and acrylonitrile is preferably being total to by hydrotreated hydrogenated butadiene and acrylonitrile Polymers.For the comparativity of result, in the embodiment of the present invention, it is raw material to be all made of amino-terminated liquid nitrile rubber.
S106, heating suspension, make grafted moiety be grafted in graphite particle.
Wherein, heating preferably keeps the temperature 20 hours to 28 hours at a temperature of 80 DEG C to 100 DEG C.It is comparable for result Property in the embodiment of the present invention, heats 24 hours at a temperature of being unified in 90 DEG C.
During heating, the process of graft reaction is as follows：
Wherein, Graphite platelet indicate that the graphite particle of sheet, NBR indicate the copolymerization of butadiene and acrylonitrile Object group, NH2- NBR indicates amino-terminated nitrile rubber raw material.
S107, suspension is filtered, filtration product dries to obtain powder, as above-mentioned grafting graphite.
Composition
The embodiment of the present invention also provides a kind of composition comprising：
Nitrile rubber；
It is grafted graphite comprising graphite particle and the grafted moiety being grafted in graphite particle, grafted moiety includes fourth two The copolymer group of alkene and acrylonitrile.
The composition of the embodiment of the present invention includes that nitrile rubber (refers to individual nitrile rubber, rather than is grafted on graphite Group on grain) and above-mentioned grafting graphite, the elastomeric material of above-mentioned elastomer layer can be obtained after crosslinking.
Preferably, in the composition, the weight percentage of nitrile rubber is 28% to 60%；It is grafted the weight of graphite Percentage composition is 2% to 12%；It is further preferred that the weight percentage of nitrile rubber is 30% to 50%；It is grafted graphite Weight percentage 3.5% to 7.5%.
Nitrile rubber and above-mentioned grafting graphite are most important components in composition, their content is for being formed by The performance of elastomeric material has important influence, it has been investigated that, above content range is preferred.
Preferably, nitrile rubber herein is hydrogenated nitrile-butadiene rubber.
That is, the nitrile rubber of the main base material as composition is preferably also through over hydrogenation, further to change The anti-aging property of kind product elastomeric material.For example, nitrile rubber useful herein, which includes the trade mark 3406, (is purchased from Lang Shenggong Department), the commercially available nitrile rubber products of 4307 (are purchased from Lanxess Corporation), 4221 (being purchased from Beyer Co., Ltd) etc..
Obviously, in the composition, other conventional constituents are may further be enriched with, to improve the performance of product elastomeric material, Wherein it is possible to which the component being added includes but not limited to below one or more：
(1) crosslinking agent
Crosslinking agent is mainly for generation of free radical, to cause cross-linking reaction, between making the nitrile rubber in composition, with And it can be crosslinked together well between the same grafting graphite of nitrile rubber.
Preferably, available crosslinking agent includes peroxide crosslinking agent (such as mistake in the composition of the embodiment of the present invention Aoxidize diisopropylbenzene (DIPB)), esters crosslinking agent (such as Triallyl isocyanurate), sulfur crosslinking agent.
Preferably, in the composition, the weight percentage of crosslinking agent is 2.5% to 4%.
(2) plasticizer
It is plastic to improve its to reduce its hardness for reducing the intermolecular active force of product elastomeric material for plasticizer Property, mobility etc..Especially, in order to which the stress concentration and vibration that reduce motor element are transmitted, therefore the embodiment of the present invention The hardness of elastomer layer do not answer it is excessive, wherein should more use plasticizer.
Specifically, available plasticizer includes polyester type plasticizer, polyether-type increasing in the composition of the embodiment of the present invention Mould agent etc..Typically, in the composition, the weight percentage of plasticizer can be 4% to 10%.
Since the elastomeric material of the present invention is preferred in the check valve of compressor, therefore it can be contacted with refrigerant, oil etc., And many existing plasticizer can be dissolved among refrigerant, oil etc. and gradually fail, and lead to the productions such as hardness, the size of elastomeric material Changing, thus it is not applicable.It has been investigated that TP-759 types plasticizer is influenced minimum by refrigerant, oil, therefore especially suitable for this hair It is bright.TP-759 type plasticizer are a kind of high-compatibility polyester, polyether mixed type plasticizer, are produced by Rhom and Hass of the U.S..
(3) anti-aging agent
Anti-aging agent is mainly used for delaying the ageing process of elastomeric material, extends its service life.
Specifically, available anti-aging agent includes 2,4- trimethyl -1,2- dihydros in the composition of the embodiment of the present invention Quinoline condensate etc..
(4) accelerating agent
Accelerating agent is mainly used for increasing reaction rate.
Specifically, available accelerating agent includes in the composition of the embodiment of the present invention：Sulfo-amino class, such as dibutyl two Zinc thiocarbamate；Thiurams, such as monothio tetra methylthiuram, six thio (or four vulcanizations) double pentamethyl thiurams； Sulfenamide, such as N cyclohexyl 2 benzothiazole sulfenamide, N- dicyclohexyl -2-[4-morpholinodithio time sulphonyl.Certainly, The accelerating agent of concrete application can be the one or more combination of any of the above.
(5) filler
Filler is usually inorganic material powders, for filling in the substrate, to change mechanical property or the reduction of material entirety Cost.
Specifically, available filler includes carbon black, clay, talcum powder, calcium carbonate in the composition of the embodiment of the present invention Deng.
(6) auxiliary agent
Auxiliary agent includes a variety of different types comprising but be not limited to：Reaction promoter for promoting reaction to carry out, such as oxygen Change zinc, magnesia etc.；It is used to help molding shaping assistant, such as polyethylene glycol；It is used to help improve the processing of processing performance Auxiliary agent, such as stearic acid.
Wherein, the composition can be directly mixed to get according to a conventional method by above each component, is not described in detail herein.
Elastomeric material
The embodiment of the present invention also provides a kind of elastomeric material, is cross-linked to form by above-mentioned composition.
Specifically, the basic skills for being cross-linked to form elastomeric material by above-mentioned composition is so that each component is melted by heating And realize cross-linking reaction, heating temperature can be at 100 DEG C to 200 DEG C or so, and the time can be in dozens of minutes to a few hours；It is specific The method that technique includes the routine such as mixing, hot pressing, extrusion is made, be not described in detail herein.
It is unified to prepare elastomeric material according to technique below in various embodiments of the present invention for the comparativity of result： Composition hot pressing at 170 DEG C of temperature and the pressure of 10MPa is set to be crosslinked 10 minutes；Later in 140 DEG C of temperature in heating furnace The lower heating of degree 4 hours.
Embodiment
Different elastomeric material and check valve are prepared below according to above formula, preparation method, as the present invention's Embodiment and comparative example, illustratively to illustrate the present invention.
1, material table
The title of used substance, ingredient, parameter, source etc. are as shown in the table in embodiments：
The raw material parameter list used in table 1, the embodiment of the present invention
2, test method
To the elastomeric material and check valve of each embodiment and comparative example, some performance tests are carried out, it is specific to test Method is as follows：
(1) peel stress is tested
Elastomer layer is removed from matrix at the direction of 180 degree along with adhesive surface, it is (public purchased from Instron with puller system Department) its stress is tested as peel stress.
(2) simulation is hit
Answering for check valve operational process middle valve plate is calculated with the abaqus finite element softwares simulation of French Dassault Sys of America Power distribution, Vibration Condition, maximum stress, maximum impact pressure, aperture, fluid flow rate etc..
(3) Mechanics Performance Testing
Every mechanical property of elastomeric material is tested comprising：
Tensile strength：Elastomeric material is made to the 1st type sample in chinese national standard GB/T528, wherein sample is Dumbbell shape, thickness are 2 ± 0.2 millimeters, and total length is 115 millimeters, and intermediate narrow portion length is 33 ± 2 millimeters, and narrow portion width is 6 + 0.4 millimeter, connected by two between narrow portion and end and circular sliding slopes that direction is opposite, close to the arc transition radius of narrow portion It it is 14 ± 1 millimeters, the arc transition radius by close end is 25 ± 2 millimeters；It is (public purchased from instron with the puller system of 3365 types Department) it is stretched under the rate of 500mm/min, and the maximum stress in drawing process is tested, as tensile strength.
Fracture elongation：Elastomeric material is made to the 1st above-mentioned type sample, (is purchased from the puller system of 3365 types Instron companies) it is stretched under the rate of 500mm/min, strain when being broken using it is fracture elongation.
Hardness：Elastomeric material is made to the 1st above-mentioned type sample, (Shanghai six is purchased from the Shore A durometer of XL-A types Water chestnut instrument plant) its case hardness is tested, each sample is tested 3 times in different location and is averaged as result.
(4) anti-aging test
At a temperature of the pressure of 20 bars (Bar) and 140 DEG C, the 1st above-mentioned type sample is impregnated 40 days in simulated solution, It is observed and is tested later, judges its anti-aging property.
Wherein, simulated solution is for the environment in analog compression machine, is formed by being dissolved in oil together and refrigerant；The model of oil For 4GSI and 410W (being purchased from Japanese Sun Company, Inc.), the two weight ratio is 100: 15；The model R22 of refrigerant (is purchased from Du Pont Company), the weight ratio of refrigerant and oily (total amount) is 100: 13.
After the completion of immersion, according to the anti-aging property of following index judgement sample elastomeric material：
Whether surface has cracking, blistering, without preferably；
Size changing rate, preferably increasing degree is within 5%；
Shore hardness change rate, with reduce amplitude within 15% preferably；
Tensile strength change rate, with reduce amplitude within 20% preferably.
Wherein, each " change rate " refers to the performance of material before being impregnated when being 100%, material respective performances after immersion Variable quantity relative scale.
(5) the anti-aging test of dynamic
Elastomer layer can be repeatedly subjected to the shock of valve block in use and deform, therefore it resists the ability of repeated deformation (i.e. dynamic anti-aging property) is highly important, and the anti-aging test of dynamic includes：
25 mm wides are made in elastomeric material, 140 millimeters to 155 millimeters long, the bar-shaped sample of 6.3 millimeters thicks, on edge The side at the center of bar-shaped sample length direction processes the semi-circular recesses of 2.38 millimeters of radius through its width direction.
Bar-shaped sample both ends are clipped in two of GT7011 type moral ink West Asia flexer (being purchased from the high Inland Steel in Taiwan) On collet, above-mentioned groove is made to be in center, open testing machine, one of collet makees relatively another collet and makees " separate-close " Reciprocating motion, the stroke of the reciprocating motion is 57 millimeters, frequency 5Hz, and the maximum distance between two collets is 75 millimeters.With folder The movement of head, bar-shaped sample is also by " bend-stretch " repeatedly, after recycling certain number, observes the slight crack feelings in bar-shaped sample Condition judges its dynamic anti-aging property grade, specific as follows：
1 grade, only visually seem the slight crack of similar " acupuncture points ", and quantity is no more than 10；
2 grades, only visually seem the slight crack of similar " acupuncture points ", and quantity is more than 10；
3 grades, there is the slight crack of " crackle shape ", and maximum crack length is more than 0.5 millimeter and is no more than 1 millimeter；
4 grades, there is the slight crack of " crackle shape ", and maximum crack length is more than 1 millimeter and is no more than 1.5 millimeters；
5 grades, there is the slight crack of " crackle shape ", and maximum crack length is more than 1.5 millimeters and is no more than 3 millimeters；
6 grades, there is the slight crack of " crackle shape ", and maximum crack length is more than 3 millimeters.
3, embodiment and comparative example
According to above preparation method, selects different raw materials, formula to prepare different elastomeric material and check valve, make For specific embodiments of the present invention and comparative example, and carry out corresponding performance test.
Embodiment 1：
Coating thickness about 30um's is viscous after the matrix (being made of cold-rolled steel) of limit element butanone and isopropanol are cleaned Agent is tied, and 30 minutes dry in the environment of 60 DEG C；Then by hydrogenated nitrile-butadiene rubber with binder matrix at 160 DEG C or It is crosslinked (vulcanization) 10 minutes at a temperature of 170 DEG C, elastomer layer is formed in matrix surface；The stripping of these elastomer layers is tested later From stress, the results are shown in table below：
Table 2, the peel stress (N/mm) using elastomer layer when different binders
As it can be seen that when being bonded in elastomer layer on matrix by conventional binder, more than peel stress can all meet More than or equal to the requirement of 0.6 Newton/millimeter.
Embodiment 2：
According to above-mentioned shock analog detection method, establish the embodiment of the present invention check valve (there is elastomer layer) and The model of existing check valve (not elastomer layer), simulates their stress, Vibration Conditions etc. in use respectively.
Wherein, the structure of existing check valve model is as shown in Figure 1 and Figure 2, and specific size parameter is as follows：
Limiting section thickness：2.5mm；
Limit lower surface curvature：1/150(mm-1)；
Limiting section root and valve body angle：3.257 degree；
Throttle slice thickness：0.152 millimeter；
Valve plate movement minister's degree：14 millimeters；
Valve plate movement portion width：7.6 millimeter；
Working frequency：50Hz.
In simulation, limiting section is made of cold rolling Steel material, and valve block is made of spring steel material, the power of the two in simulations Learning parameter is respectively：
Cold-rolled steel：Young's modulus 193GPa, tensile strength 505MPa, fracture elongation 70%；
Spring steel：Young's modulus 210GPa, tensile strength 1500MPa, fracture elongation 8%.
The structure of the check valve model of the embodiment of the present invention is as shown in Figure 6, Figure 7, similar with existing check valve, and difference exists In its limiting section include above-mentioned elastomer layer.Specifically, the elastomer layer of single layer can be directly provided on the matrix of limiting section, this When elastomer layer thickness be 0.6 millimeter, and use hydrogenated nitrile-butadiene rubber or silica gel material；Alternatively, can also have stacking on matrix Structure, the stepped construction include the rigid layer for being located at the elastomer layer of inside (close to matrix) and being located at outside (separate matrix), It is 0.5 millimeter that wherein elastomer layer, which uses hydrogenated nitrile-butadiene rubber material, thickness, and rigid layer samples above-mentioned cold rolling Steel material, thickness It is 0.8 millimeter.
In simulation, the mechanics parameter of elastomer layer material is：
Hydrogenated nitrile-butadiene rubber：Young's modulus 6MPa, tensile strength 18.3MPa, fracture elongation 250%；
Silica gel：Young's modulus 3MPa, tensile strength 6.5MPa, fracture elongation 500%.
Fig. 9 and Figure 10 be respectively in a period of motion existing check valve and the embodiment of the present invention there is single layer hydrogenation The simulation distribution figure of maximum stress suffered by each position of valve block of the check valve of nitrile rubber elastomer layer.As it can be seen that increasing bullet Property body layer after, original area of stress concentration disappears in the middle part of valve block, this indicates valve block, and suffered stress is substantially during the motion Reduce, so as to extend the service life of valve block, and possibility is provided for the aperture for increasing valve block.
Figure 11 and Figure 12 be respectively in a period of motion existing check valve and the embodiment of the present invention there is single layer hydrogen Change the simulation drawing of the Vibration Condition of the valve block of the check valve of nitrile rubber elastomer layer.As it can be seen that after increasing elastomer layer, valve block The vibration of itself substantially reduces, and so as to extend valve block service life, and can reduce the disturbance of fluid, improves fluid flow rate.
Following table is the analog result of partial properties during valve plate movement.As it can be seen that the check valve phase with not elastomer layer Than, after increasing elastomer layer, maximum impact force and maximum stress suffered by valve block have respectively reduced -55.8% and -34.5%, Correspondingly, fluid (refrigerant) flow velocity of its aperture and check valve increases 7.37% and 5.9% respectively.It can be seen that elastomer The impact suffered by valve block can be greatly reduced in the presence of layer, to reduce vibration and noise, and extend the service life of valve block, simultaneously Increase the fluid flow rate of check valve, and then improves the efficiency of compressor.
The analog result of table 3, nonelastic body layer and the check valve with single layer hydrogenated nitrile-butadiene rubber elastomer layer
Project Nonelastic body layer Single layer hydrogenated nitrile-butadiene rubber elastomer layer
Maximum impact force suffered by valve block 75.6N 33.4N
Valve block maximum stress 473.213MPa 309.761MPa
Valve block aperture 3.133mm 3.364mm
Fluid flow rate 2.657kg/h 2.813kg/h
Following table be to using single layer hydrogenated nitrile-butadiene rubber and single layer silica gel as the analog result of the check valve of elastomer layer, can See, cushioning effect can also be played by using other elastomeric materials such as silica gel as elastomer layer, this shows the elastomer layer of the present invention It is not limited to hydrogenated nitrile-butadiene rubber.
The analog result of table 4, check valve with single layer hydrogenated nitrile-butadiene rubber elastomer layer or monolayer silicon glue elastomer layer
Project Monolayer silicon glue elastomer layer Single layer hydrogenated nitrile-butadiene rubber elastomer layer
Maximum impact force suffered by valve block 31.5N 33.4N
Valve block maximum stress 327.24MPa 309.761MPa
Valve block aperture 3.361mm 3.364mm
Table 5, nonelastic body layer, single layer hydrogenated nitrile-butadiene rubber elastomer layer, stepped construction check valve analog result
Project Nonelastic body layer Single layer hydrogenated nitrile-butadiene rubber elastomer layer Stepped construction
Maximum impact force suffered by valve block 75.6N 33.4N 36.4N
The time of valve plate movement in place 0.002052s 0.002069s 0.002066s
From upper table as it can be seen that valve block impact force when using single layer of elastomeric layer and stepped construction is respectively less than nonelastic body layer Situation, and (this indicates valve plate movement increased periods, suffered punching the case where the time of valve plate movement in place is all higher than nonelastic body layer Hitting power can reduce)；Therefore, both of which can play the role of buffering.In contrast, using the unidirectional of single layer of elastomeric layer The stress of valve is lower than using the check valve of stepped construction, this shows that after increasing rigid layer, the cushioning effect of valve block is dropped It is low, but the case where still better than nonelastic body layer.
Embodiment 3 to 12, comparative example 1 and 2：
As previously mentioned, the check valve of the present invention is preferably used for the check valve in compressor, and this check valve is in height Temperature, high pressure, high corrosion (refrigerant and oil) complex environment in, therefore wherein the material of elastomer layer should have resist environment above Ability.
According to the formula in above-mentioned preparation method and below table, different grafting graphite is prepared, for preparing not Same elastomeric material.
Table 6, the parameter for being grafted graphite (dosage is parts by weight)
Number It is grafted graphite 1 It is grafted graphite 2 It is grafted graphite 3 Compare graphite
F09 dosages 100 100 100 100
DMF dosages 400 400 400 400
LNBR-NH2Dosage 20 40 25 10
DCC dosages 1 1 2 1
Grafting amount 0.09 0.17 0.12 0.02
Wherein, each substance dosage refers to when preparing grafting graphite according to the method described above, the substance employed in each step Amount；And grafting amount is the weight ratio of grafted moiety and graphite particle in product grafting graphite, and graphite-phase pair is grafted according to product It is calculated in the gain in weight (because gain in weight approximation can regard the weight of grafted moiety as) of raw graphite.
Wherein, nitrile rubber amount used and final grafting amount are respectively less than the preferred model of the present invention when prepared by comparison graphite It encloses, therefore as comparative example.
By grafting graphite according to the formula in below table, it is prepared into the composition of different embodiments or comparative example, is used in combination These compositions form elastomeric material according to the method described above, and the performance of each elastomeric material is tested according still further to the above method.
Table 7, composite formula (substance dosage is its weight percent in the composition)
From upper table as it can be seen that the hardness of the elastomeric material containing grafting graphite of the embodiment of the present invention 3 to 12, stretch it is strong Performances such as degree, fracture elongation etc. all meet the requirements, can be as the material of above-mentioned elastomer layer.
From comparative example 2 as it can be seen that the comparison graphite for wherein using grafting amount smaller, the drawing of corresponding elastomeric material It stretches intensity and there was only 11.6MPa, hence it is evident that the tensile strength than the elastomeric material of the embodiment of the present invention is low.If this shows to be grafted stone The grafting amount of ink is too small (or at all non-grafted), then graphite cannot incorporate in elastomeric material well, instead can be to elasticity The performances such as the intensity of body material cause harmful effect, therefore and are not suitable for.Opposite, the grafting graphite of the embodiment of the present invention can be with Nitrile rubber realizes co-crosslinking, eliminates the interface of graphite particle and nitrile rubber, to incorporate in nitrile rubber well, therefore not Harmful effect can be caused to performances such as the intensity of elastomeric material.
The other performance of the elastomeric material of above example is described in detail below.
To existing nitrile rubber (unhydrided nitrile rubber, model 230S are purchased from JSR companies of Japan), existing hydrogenation The above-mentioned anti-aging survey of elastomeric material progress of nitrile rubber (model 4307 is purchased from Lanxess Corporation), the embodiment of the present invention 3 Examination.
Figure 13, Figure 14, Figure 15 are respectively the bullet of existing nitrile rubber, existing hydrogenated nitrile-butadiene rubber, the embodiment of the present invention 3 Surface topography photo of the elastomer material after above-mentioned anti-aging test.As it can be seen that the elastomeric material of the embodiment of the present invention 3 Surface is almost without generation cracking, blistering etc.；Opposite, there is blistering on existing nitrile rubber, hydrogenated nitrile-butadiene rubber surface, but The blistering for playing bubble ratio hydrogenated nitrile-butadiene rubber (4307) of common unhydrided nitrile rubber (230S) is more serious.
Figure 16, Figure 17 are respectively the elastomeric material of existing hydrogenated nitrile-butadiene rubber, the embodiment of the present invention 3 in anti-aging survey Size comparison's photo before and after examination, in the case where material side is aligned, the alternate position spike of the other side represents material In the size expansion after anti-aging test.As it can be seen that the elastomeric material of the embodiment of the present invention 3 is after anti-aging test The expansion very little of size, and the size expansion of existing hydrogenated nitrile-butadiene rubber is apparent.
It is above the result shows that：
The first, the elastomeric material of the embodiment of the present invention has good anti-aging property, existing nitrile rubber and hydrogen It is poor to change elastomeric material of the anti-aging property of nitrile rubber than the present invention.
The second, the anti-aging property of existing hydrogenated nitrile-butadiene rubber is again better than common unhydrided nitrile rubber.This proof, Hydrogenation is carried out to nitrile rubber and helps to improve its anti-aging property；It can be seen that in the elastomeric material of the present invention, and Grafting graphite preparation process in, using hydrogenated nitrile-butadiene rubber be raw material be preferred.
The anti-aging property of table 8, elastomeric material
Number Comparative example 1 Embodiment 3 Embodiment 4 Embodiment 5
Blistering Nothing Nothing Nothing Nothing
Cracking Nothing Nothing Nothing Nothing
Size changing rate % 12 5 8 7
Shore hardness change rate % -20 -11 -14 -13
Tensile strength change rate % -25 -6 -10 -9
Upper table is the anti-aging survey that the elastomeric material to various embodiments of the present invention and comparative example carries out according to the method described above The result of examination.As it can be seen that the elastomeric material relative to the various embodiments of the present invention containing grafting graphite, pair without grafting graphite The elastomeric material of ratio 1 is after anti-aging test, and size, hardness, the change rate of tensile strength are all significantly larger, this table If bright without grafting graphite, in the environment of refrigerant and oil, the performance of material can deteriorate rapidly.That is, the present invention The elastomeric material containing grafting graphite of embodiment has stronger resistance (to have preferably anti-aging refrigerant and oil really Performance), therefore it is preferably used as the elastomer layer in the check valve of compressor.
According to the method described above, the dynamic anti-aging property of the elastomeric material of various embodiments of the present invention and comparative example is carried out Test, the results are shown in table below.
The dynamic anti-aging property of table 9, elastomeric material
Wherein, comparative example 1 indicates the above-mentioned elastomeric material without grafting graphite, and several examples later indicate than On the basis of the elastomeric material of example 1, the bullet of gained after the grafting graphite 3 of additional 3%, 6%, 12% weight percent of difference Elastomer material (elastomeric material for being equivalent to the embodiment of the present invention).As it can be seen that with the raising of grafting content of graphite, elastomer The dynamic anti-aging property of material is also significantly improving, and it is good dynamic that this shows that the elastomeric material of the embodiment of the present invention has State anti-aging property.
In conclusion being provided with elastomer layer on the limiting section of the check valve of the embodiment of the present invention, buffering can be played Extend valve block service life to reduce stress and the vibration suffered by valve block with the effect of vibration damping, reduces noise, make valve block Aperture increases, and then improves the fluid flow rate of check valve, and improves the efficiency of compressor.
Meanwhile every mechanical property of the elastomeric material of the embodiment of the present invention meets and is wanted as elastomer layer It asks, and its anti-aging property and dynamic anti-aging property are also fine, therefore it is preferred that can be used as the elastomer of the check valve in compressor The material of layer.
It is understood that the principle that embodiment of above is intended to be merely illustrative of the present and the exemplary implementation that uses Mode, however the present invention is not limited thereto.For those skilled in the art, in the essence for not departing from the present invention In the case of refreshing and essence, various changes and modifications can be made therein, these variations and modifications are also considered as protection scope of the present invention.

Claims (19)

1. a kind of check valve, the check valve is the check valve for compressor, wherein including：
Valve body with valve opening；The valve body includes first surface, and the valve opening opening is on the first surface；
Motor element on valve body one end is set, for closing the closed position of the valve opening and leaving beating for the valve opening It is moved between open position；The motor element is the valve block for including fixed part and movement portion, and the fixed part is connected to described first On surface, the movement portion is used to moved between the closed position of the valve opening and the open position for leaving the valve opening covering；
Limit element on motor element one end is set, the open position for limiting the motor element, and the limit Elastomer layer is arranged in the side for being contacted with the motor element in element, and the elastomer layer is made of elastomeric material； The limit element includes being located at limiting section of the valve block far from first surface side, and the limiting section is towards valve block side Surface is convex globoidal, on the direction from the fixed part of valve block direction movement portion, between the limiting section and first surface Distance gradually increases, the curvature of the convex globoidal in one to 1/172 millimeter point of 1/72 millimeter point one；
Angle of the limiting section between the section near the position of the first surface and the first surface is at 9 degree to 40 Degree.
2. check valve according to claim 1, wherein
The fracture elongation of the elastomeric material is at least 10%.
3. check valve according to claim 2, wherein
Stress of the elastomeric material when elongation strain is 10% is at least 0.5MPa.
4. check valve according to claim 1, wherein
Shore A hardness of the elastomeric material at 23 degrees Celsius is 30 to 80.
5. check valve according to claim 4, wherein
Shore A hardness of the elastomeric material at 23 degrees Celsius is 30 to 70.
6. check valve according to claim 1, wherein
The elastomeric material is damping rubber.
7. check valve according to claim 1, wherein
The elastomeric material includes polyamide, polyurethane, polyolefin, polyolefin derivative object, thermoplastic vulcanizates, fluorine rubber The combination of any one or more in glue, acrylic rubber, epoxy resin, phenolic resin.
8. check valve according to claim 1, wherein the elastomeric material is cross-linked to form by composition, the combination Object includes：
Nitrile rubber；
It is grafted graphite comprising graphite particle and the grafted moiety being grafted in the graphite particle, the grafted moiety include The copolymer group of butadiene and acrylonitrile.
9. check valve according to claim 8, wherein
The weight percentage of nitrile rubber is 28% to 60% in the composition；
The weight percentage of graphite is grafted in the composition 2% to 12%.
10. check valve according to claim 8, wherein
In the grafting graphite, the weight of the relatively described graphite particle, the weight ratio of the grafted moiety 6% to 20%.
11. check valve according to claim 1, wherein
The thickness of the elastomer layer is at 0.1 millimeter to 5 millimeters.
12. check valve according to claim 11, wherein
The thickness of the elastomer layer is at 0.5 millimeter to 1.5 millimeters.
13. check valve according to claim 1, wherein
The limit element includes matrix；
The elastomer layer is at least set to the side that described matrix is used to contact with the motor element.
14. check valve according to claim 13, wherein
The elastomer layer bonds on the matrix, and along the peel stress in 180 degree direction between the elastomer layer and matrix At least 0.6 Newton/millimeter.
15. check valve according to claim 13, wherein
The elastomer layer on the matrix, and is deviate from required power at least by the elastomer layer cutting ferrule from described matrix For 30 newton.
16. check valve according to claim 13, wherein
The side that the elastomer layer is used to contact with motor element is provided with rigid layer.
17. check valve according to claim 16, wherein
The thickness of the rigid layer is at 0.01 millimeter to 4 millimeters.
18. check valve according to claim 16, wherein
The rigid layer is bonded on the elastomer layer, along the stripping in 180 degree direction between the elastomer layer and rigid layer Stress is at least 0.6 Newton/millimeter.
19. check valve according to claim 1, wherein
Maximum distance of the limiting section between the first surface side and first surface is at 3 millimeters to 32 millimeters.
CN201510158765.2A 2015-04-03 2015-04-03 Limit element, check valve, composition, elastomeric material, grafting graphite and preparation method thereof Expired - Fee Related CN104832704B (en)

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PCT/US2016/025500 WO2016161252A1 (en) 2015-04-03 2016-04-01 Position-limiting element, one-way valve, composition, elastomeric material, grafted graphite, and methods for preparing the same

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