CN105778305A - Rubber tube middle rubber layer composition, preparation method, air-conditioner rubber tube and preparation method - Google Patents

Rubber tube middle rubber layer composition, preparation method, air-conditioner rubber tube and preparation method Download PDF

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Publication number
CN105778305A
CN105778305A CN201610242316.0A CN201610242316A CN105778305A CN 105778305 A CN105778305 A CN 105778305A CN 201610242316 A CN201610242316 A CN 201610242316A CN 105778305 A CN105778305 A CN 105778305A
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Prior art keywords
mesoglea
rubber
air conditioner
rubber pipe
resin
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CN105778305B (en
Inventor
张洪起
张志朝
薛俊芳
王学荣
高贤华
张宝新
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Tianjin Peng Ling group Limited by Share Ltd
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Tianjin Pengling Rubber Hose Co Ltd
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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
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/15—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor incorporating preformed parts or layers, e.g. extrusion moulding around inserts
    • B29C48/151—Coating hollow articles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/16—Articles comprising two or more components, e.g. co-extruded layers
    • B29C48/18—Articles comprising two or more components, e.g. co-extruded layers the components being layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B1/00—Layered products having a non-planar shape
    • B32B1/08—Tubular products
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B25/00—Layered products comprising a layer of natural or synthetic rubber
    • B32B25/02—Layered products comprising a layer of natural or synthetic rubber with fibres or particles being present as additives in the layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B25/00—Layered products comprising a layer of natural or synthetic rubber
    • B32B25/04—Layered products comprising a layer of natural or synthetic rubber comprising rubber as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B25/08—Layered products comprising a layer of natural or synthetic rubber comprising rubber as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B25/00—Layered products comprising a layer of natural or synthetic rubber
    • B32B25/10—Layered products comprising a layer of natural or synthetic rubber next to a fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B25/00—Layered products comprising a layer of natural or synthetic rubber
    • B32B25/14—Layered products comprising a layer of natural or synthetic rubber comprising synthetic rubber copolymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/02—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by a sequence of laminating steps, e.g. by adding new layers at consecutive laminating stations
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
    • B32B37/15—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer being manufactured and immediately laminated before reaching its stable state, e.g. in which a layer is extruded and laminated while in semi-molten state
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
    • B32B5/028—Net structure, e.g. spaced apart filaments bonded at the crossing points
    • 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
    • F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
    • F16L11/00—Hoses, i.e. flexible pipes
    • F16L11/04—Hoses, i.e. flexible pipes made of rubber or flexible plastics
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2023/00—Tubular articles
    • B29L2023/005—Hoses, i.e. flexible
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/02—Synthetic macromolecular fibres
    • B32B2262/0276—Polyester fibres
    • B32B2262/0284—Polyethylene terephthalate [PET] or polybutylene terephthalate [PBT]
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
    • B32B2264/10—Inorganic particles
    • B32B2264/107—Ceramic
    • B32B2264/108—Carbon, e.g. graphite particles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/552—Fatigue strength
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2597/00—Tubular articles, e.g. hoses, pipes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/18—Applications used for pipes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Rigid Pipes And Flexible Pipes (AREA)

Abstract

The invention provides a rubber tube middle rubber layer composition. According to the middle rubber layer composition, ethylene propylene terpolymer is adopted as a main sizing material, white carbon black and other auxiliary materials are added, and therefore the obtained middle rubber layer material can have the good adhesiveness with a blocked layer PPA; accordingly, the structural integrity of the rubber tube is improved. The invention further provides a preparation method of the middle rubber layer. According to the method, the rubber tube middle rubber layer composition is adopted as a raw material, mixing and rubber discharging are performed to obtain a rubber material, and the method has the advantages that operation is easy and the obtained middle rubber layer material has the good adhesiveness with a PPA material. The invention further provides a preparation method of a rubber tube. According to the method, the rubber tube is prepared through a method for sequentially extruding a rubber material and/or weaving on a core rod, and the method has the advantages that operation is easy and convenient, the obtained rubber tube is good in integrity, and the requirement for R1234yf medium working is met.

Description

Sebific duct mesoglea compositions, preparation method and air conditioner rubber pipe and preparation method
Technical field
The present invention relates to sebific duct field, in particular to a kind of sebific duct mesoglea compositions, preparation method and air conditioner rubber pipe and preparation method.
Background technology
Cold-producing medium is the working media completing kind of refrigeration cycle in process of refrigerastion, and the cold-producing medium used by early stage air-conditioning and refrigerator etc. is halogenated hydrocarbons.But, the discharge of this halogenated hydrocarbons cold-producing medium can destroy atmospheric ozone layer, and the destructiveness of ozone layer is represented by cold-producing medium by the latent value (Ozonedepletionpotential is called for short ODP) that damages the ozone layer.Simultaneously, these halogenated hydrocarbons are also one of inducements causing global warming, because the discharge of halogenated hydrocarbons cold-producing medium can cause greenhouse effect, and then cause global warming, its influence degree global warming potential (Globalwarmingpotential is called for short GWP) represents.
Before Montreal Agreement bookmark is ordered, automotive air-conditioning system is mainly using CFC12 as cold-producing medium, but the ODP value of this cold-producing medium is higher, thus, according to Montreal Agreement book, CFC12 is that one-level is limited cold-producing medium.
Replacing CFC12 to find new coolant, air conditioner industry is made that and studies widely, it is desirable to develop the Biological process that ODP value is zero.In these researchs, the cold-producing medium HFC134a of E.I.Du Pont Company's exploitation is successfully applied in refrigeration industry.Due to the not chloride atom of HFC134a, and having good security performance, meanwhile, the physical property of this cold-producing medium is also closer to traditional CFC12 cold-producing medium, thus the remodeling of refrigeration system is also easier.Further, HFC134a heat transfer character is also more excellent than CFC12, thus, in use the consumption of HFC134a is also less, also suitableeer as air conditioner refrigerating medium.
But, according to European Union already by the requirement of fluorine-containing greenhouse-gas control regulation, from 11 days January in 2011, the air conditioning for automobiles forbidding new production is used the GWP value cold-producing medium more than 150 by European Union, the GWP value of the HFC134a cold-producing medium owing to having used in a large number now is 1300, so will be prohibited from using.Further, European Union specifies, from 1 day January in 2017, will forbid that all air conditioning for automobiles use the GWP value cold-producing medium more than 150.Thus, air conditioning for automobiles uses low GWP to prepare cold-producing medium will become trend and certainty.
U.S. Honeywell (Honeywell) company and E.I.Du Pont Company have developed jointly novel environment-friendly refrigerant R1234yf, and its chemical name is tetrafluoropropene, and molecular formula is CF3CF=CH2, the GWP value of HFO-1234yf is 4, far below the regulation of European Union's air conditioning for automobiles instruction.Thus R1234yf is more suitable as automobile air-conditioning refrigeration medium, and the performance of cold-producing medium is it can be used as also progressively to obtain accreditation.
Owing to novel environment-friendly refrigerant R1234yf is more and more introduced into automotive air-conditioning system, thus the exploitation of the material of the air conditioner rubber pipe matched is imperative.
PPA (polyphthalamide) is a kind of novel nylon material, and under humid tropical condition, the tensile strength of PPA is higher than nylon 6 by 20%, also exceeds much than nylon66 fiber；Meanwhile, the bending modulus of PPA material is higher by 20% than nylon, and hardness is bigger, is resistant to long tensile creep, and the ability of the resistance to gasoline of PPA, grease resistance and coolant is also strong than PA.Further, PPA material can the continuous high temperature of resistance to 200 DEG C, and good dimensional stability can also be kept, thus be more suitable for the barrier material of air conditioner rubber pipe, also be more suitable for the demand of novel R1234yf cold-producing medium simultaneously.
But, in existing air-conditioner pipe, wherein glue line material is typically all employing butyl rubber, and this butyl rubber can not carry out bonds well with PPA barrier layer, and this result also in the PPA barrier layer of prepared air conditioner rubber pipe and can be easily separated with butyl rubber mesoglea, the globality of sebific duct is poor, it is impossible to practical application.
In view of this, the special proposition present invention.
Summary of the invention
The first object of the present invention is in that to provide a kind of sebific duct mesoglea compositions, with ethylene propylene diene rubber for main sizing material in described mesoglea compositions, and with the addition of the adjuvants such as white carbon, thus obtained mesoglea material can have good cohesive with barrier layer PPA, thus improving the globality of sebific duct, so can solve existing butyl rubber mesoglea cannot with PPA material carry out good bonding caused obtained sebific duct globality poor, cannot the technical problem of practical application.
The second object of the present invention is in that the preparation method providing a kind of described mesoglea, in the inventive method, with the present composition for raw material, and by mixing binder removal to obtain elastomeric material, there is method simple to operate, the advantages such as obtained mesoglea material is good with PPA adhesion.
3rd purpose of the present invention is in that to provide a kind of air conditioner rubber pipe, air conditioner rubber pipe of the present invention prepares the mixing thing of EPT rubber composition as mesoglea material using the method for the invention, obtained mesoglea material can realize good cohesive with PPA barrier layer, such that it is able to improve the structural integrity of air conditioner rubber pipe of the present invention.Simultaneously, sebific duct of the present invention is with PPA material for barrier layer, thus has good ageing-resistant performance, and can under the maximum conditions of long high temperature, high pressure and high-moisture percentage, it still is able to keep good physical property, and meets the work requirements of R1234yf cooling medium.
4th purpose of the present invention is in that the preparation method providing a kind of sebific duct, in the inventive method, prepare sebific duct by being sequentially extruded the method for sizing material and/or braiding on plug, there is method simplicity, obtained sebific duct good integrity, is suitable to the advantages such as R1234yf media operation demand.
In order to realize the above-mentioned purpose of the present invention, spy by the following technical solutions:
A kind of air conditioner rubber pipe mesoglea compositions, according to parts by weight meter, described mesoglea is mainly made up of following components: ethylene propylene diene rubber 100-300 part, binding agent 5-30 part, polyisobutylene 5-20 part, binder resin 1-15 part, white carbon 10-50 part.
In the present invention, by with ethylene propylene diene rubber for main sizing material, and with the addition of the adjuvant such as white carbon, binding agent, such that it is able to improve the bond properties of obtained mesoglea elastomeric material and PPA material, and then improve the structural integrity of prepared air conditioner rubber pipe further.
Optionally, in the present invention, in described air conditioner rubber pipe mesoglea compositions, according to parts by weight meter, described mesoglea is mainly made up of following components: ethylene propylene diene rubber 100-150 part, binding agent 10-20 part, polyisobutylene 10-15 part, binder resin 5-10 part, white carbon 20-40 part.
In the present invention, by adjusting further and optimizing each raw material components consumption, thus further increasing the cohesive of obtained elastomeric material and PPA material, and then also further increase the globality of obtained air conditioner rubber pipe.
Optionally, in the present invention, described ethylene propylene diene rubber is the mixing ethylene propylene diene rubber of one or more in Mitsui EPDM, Korea S SKEPDM, Du Pont DuPontEPDM；Preferably, in the present invention, described mesoglea ethylene propylene diene rubber is the mixture of one or more in Mitsui EPDM3045, EPDM3062E, EPDM3070, EPDM3072E, EPDM3090E, EPDM3091, EPDM3095 or Korea S SKEPDMS501, EPDMS505, EPDMS512, EPDMS600.
In the present invention, by adjusting further and optimizing raw material ethylene propylene diene rubber, select to have the ethylene propylene diene rubber of better physical property, ozone resistance, resistance to low temperature and heat aging property as raw material sizing material, thus improve the physicochemical property such as resistance to ag(e)ing of obtained sebific duct.
Optionally, in the present invention, described binding agent is the mixed adhesive of one or more in adhesive A, adhesive A B-30, adhesive RS, binding agent RL, binding agent RE, binding agent RH.
In the present invention, by adjusting further and optimizing binding agent, thus further increasing the bond properties of obtained mesoglea material and PPA barrier material, and then improve the structural integrity of obtained sebific duct.
Optionally, in the present invention, described polyisobutylene is the mixture of one or more in BASFOppanol polyisobutylene, Ineos polyisobutylene.
In the present invention, adjust further by what polyisobutylene used was made and optimize, such that it is able to improve the bond properties of obtained mesoglea material and PPA material, and then the structural integrity of obtained sebific duct further can also be improved.
Optionally, in the present invention, described polyisobutylene is the mixture of one or more in BASF OppanolB10, B12, B15, B30, B50, B80, B100, B150, B200, B10N, B12N, B15N polyisobutylene or Ineos H-100, H-300.
Optionally, in the present invention, described binder resin is the hybrid bonding resin of one or more in binder resin PN, coumarone indene resin, rosin resin, phenolic resin, carbon nine resin, epoxy resin, terpene resin.
In the present invention, by adjusting further and optimizing binder resin, and use the better binder resin of bond properties as raw material, thus further increasing the bond properties of obtained mesoglea material and PPA barrier material, and then improve the structural integrity of obtained sebific duct.
Optionally, in the present invention, described white carbon is that TOKUSIL white carbon, the sub-white carbon in sieve ground and Degussa win the mixing white carbon of one or more in wound white carbon.
Meanwhile, the preparation method that present invention also offers a kind of described air conditioner rubber pipe mesoglea, by the heretofore described mixing rear binder removal of air conditioner rubber pipe mesoglea compositions, obtain described mesoglea material.
In mesoglea preparation method of the present invention, with the present composition for raw material, and by mixing binder removal to obtain elastomeric material, there is method simple to operate, the advantages such as obtained mesoglea material is good with PPA adhesion.
Further, the present invention additionally provides a kind of air conditioner rubber pipe simultaneously, and described sebific duct includes barrier layer, mesoglea, braid and outer glue-line；Wherein, described mesoglea material is prepared by air conditioner rubber pipe mesoglea preparation method of the present invention.
In air conditioner rubber pipe of the present invention, prepare the mixing thing of EPT rubber composition as mesoglea using the method for the invention, such that it is able to realize good cohesive with PPA barrier layer, and then the globality of air conditioner rubber pipe of the present invention can be improved.Meanwhile, sebific duct PPA material of the present invention has the physicochemical properties such as good resistance to ag(e)ing and resistance to pressure, it is possible to be suitable to the work requirements of R1234yf medium.
Optionally, in the present invention, the barrier material of described air conditioner rubber pipe is PPA；Further, in the present invention, described PPA is the mixing PPA of one or more in the blue strange PPA of the base of a fruit of Italy, France A Kema PPA, U.S. AmodelPPA, Du Pont DuPontPPA；Further, in the present invention, described barrier layer is A Kema PPAGF30, AmodelA1000 Series P PA, AmodelA4000 Series P PA, AmodelA6000 Series P PA, the mixing PPA material of one or more in DuPontZytelHTN51G Series P PA, DuPontZytelHTN52G Series P PA.
Optionally, in the present invention, the braid of described air conditioner rubber pipe is braided polyester layer (having network structure).
Optionally, in the present invention, the outer glue line material of described air conditioner rubber pipe is ethylene propylene diene rubber；Further, described ethylene propylene diene rubber is the composite material of one or more in Mitsui EPDM, Korea S SKEPDM, Du Pont DuPontEPDM；Further, described mesoglea ethylene propylene diene rubber is the mixing ethylene propylene diene rubber of one or more in Mitsui EPDM3045, EPDM3062E, EPDM3070, EPDM3072E, EPDM3090E, EPDM3091, EPDM3095 or Korea S SKEPDMS501, EPDMS505, EPDMS512, EPDMS600.
Same, the preparation method that present invention also offers a kind of air conditioner rubber pipe, described method comprises the steps: extrusion PPA raw material on sebific duct die mandrel, and makes PPA be coated on plug to form barrier layer, then on the plug with barrier layer, extrude mesoglea, and weave at mesoglea outer surface, it is braid, on braid, then extrudes outer glue-line, it is semi-finished product air conditioner rubber pipe, after semi-finished product rubber pipe is vulcanized, and plug is taken out, namely obtain final finished sebific duct；Wherein, described mesoglea is prepared by compositions of the present invention.
In the present invention, prepare sebific duct by being sequentially extruded the method for sizing material and/or braiding on plug, there is method simplicity, obtained sebific duct good integrity, be suitable to the advantages such as R1234yf media operation demand.
Optionally, the present invention can also provide a kind of air conditioner rubber pipe prepared by the method for the invention.
Compared with prior art, the invention have the benefit that
(1) in the present invention, by with ethylene propylene diene rubber for main sizing material, and add the adjuvants such as white carbon, so that obtained mesoglea material can have good cohesive with barrier layer PPA, and improve the structural integrity of sebific duct.
(2) in the present invention, by adjusting further and optimizing adjuvants such as ethylene propylene diene rubber sizing material and binding agents, thus further increasing the cohesive of obtained mesoglea material and barrier layer PPA material, and then improve the structural integrity preparing sebific duct further.
(3) air conditioner rubber pipe of the present invention is with PPA material for barrier material, thus obtained air conditioner rubber pipe has the physicochemical properties such as good resistance to ag(e)ing and resistance to pressure, it is possible to be suitable to the work requirements of R1234yf medium.
Detailed description of the invention
Below in conjunction with embodiment, embodiment of the present invention are described in detail, it will be appreciated by those skilled in the art that the following example is merely to illustrate the present invention, and are not construed as restriction the scope of the present invention.Unreceipted actual conditions person in embodiment, conventionally the condition of condition or manufacturer's suggestion carries out.Agents useful for same or the unreceipted production firm person of instrument, be and can pass through the commercially available conventional products bought and obtain.
Embodiment 1-5
With EPDM3045 for mesoglea raw material ethylene propylene diene rubber, and carry out raw material according to key component weight grams as shown in table 1 below and weigh, obtain the mesoglea composite formula of embodiment 1-5.
Table 1 embodiment 1-5 building rubber compound composition formula (unit g)
Then, air conditioner rubber pipe is prepared in accordance with the following steps:
1) by sebific duct die mandrel by PPA extruder, and on plug, extrude PPA raw material, and make PPA be coated on plug formation barrier layer；
2) after respectively mixing for raw material described in embodiment 1-5, the mesoglea sizing material of embodiment 1-5 will be obtained, then will be coated with the plug of PPA barrier layer by extruder, and respectively at the mesoglea sizing material described in its Surface coating embodiment 1-5；
3) plug being coated with barrier layer and mesoglea is introduced in braider, and at mesoglea outer surface Woven polyester braid；
4) plug after cladding-braiding is introduced in extruder, and outside braid, extrude the outer glue-line of EPDM3091, namely obtain semi-finished product rubber pipe；
5) semi-finished product rubber pipe is put into vulcanization plant adds heat cure, after sulfuration cooling, by hydraulic pressure, plug is got, namely obtain the air conditioner rubber pipe of embodiment 1-5.
Then, the air conditioner rubber pipe obtained by embodiment 1-5 carrying out mesoglea and barrier layer bond strength test, result is as shown in table 2 below:
Table 2 embodiment 1-5 air conditioner rubber pipe mesoglea and barrier layer bonding strength
Embodiment 6-10
Respectively with EPDM3062E, EPDM3070, EPDM3091, the mixture of EPDMS505 and EPDMS512 and EPDM3062E (weight ratio is 1:1) is mesoglea raw material ethylene propylene diene rubber rubber, and formula described in embodiment 4 weighs all the other each raw materials, and obtain the mesoglea compositions of embodiment 6-10.
Then, method described in embodiment 1 prepares the air conditioner rubber pipe of embodiment 6-10, and to its mesoglea and barrier layer bond strength test, result is as shown in table 3 below:
Table 3 embodiment 6-10 air conditioner rubber pipe mesoglea and barrier layer bonding strength
Comparative example 1-4
With EPDM3045 for mesoglea raw material ethylene propylene diene rubber rubber, and carry out raw material according to key component weight grams as shown in table 4 below and weigh, obtain the R1234yf air conditioning hose inner glue layer rubber composition rubber compounding of comparative example 1-4.
Table 4 comparative example 1-4 building rubber compound composition formula (unit g)
Then, method described in embodiment 1-5 prepares the air conditioner rubber pipe described in comparative example 1-4.
Comparative example 5
With butyl rubber for mesoglea crude rubber, then, the air conditioner rubber pipe of comparative example 5 is prepared in accordance with the following steps.Specifically comprise the following steps that
By sebific duct die mandrel by PPA extruder, and on plug, extrude PPA raw material, and make PPA be coated on plug formation barrier layer；The plug being coated with PPA barrier layer is passed through extruder, and respectively at its Surface coating butyl rubber mesoglea；The plug being coated with barrier layer and mesoglea is introduced in braider, and at mesoglea outer surface Woven polyester braid；Plug after cladding-braiding is introduced in extruder, and outside braid, extrudes the outer glue-line of EPDM3091, namely obtain semi-finished product rubber pipe.Semi-finished product rubber pipe is put in vulcanization plant and add heat cure, after sulfuration cooling, by hydraulic pressure, plug is got, namely obtain the air conditioner rubber pipe of comparative example 5.
Experimental example 1
Air conditioner rubber pipe obtained by comparative example 1-5 carries out mesoglea and barrier layer bond strength test, and result is as shown in table 5 below:
Table 5 comparative example 1-5 air conditioner rubber pipe mesoglea and barrier layer bonding strength
Experimental example 2
The limit test to embodiment 4, the sebific duct of 6-10 respectively when high temperature, high pressure and high-moisture percentage, result is as shown in table 6 below:
Table 6 embodiment 4,6-10 sebific duct the performance test results
Mesoglea material prepared by mesoglea compositions of the present invention and PPA barrier material have good cohesive, so that obtained air conditioner rubber pipe has good structural integrity further；Meanwhile, air conditioner rubber pipe of the present invention has the physicochemical properties such as good resistance to ag(e)ing and resistance to pressure, it is possible to be suitable to the work requirements of R1234yf medium.
Although illustrate and describing the present invention with specific embodiment, however it will be appreciated that may be made that when without departing substantially from the spirit and scope of the present invention many other change and amendment.It is, therefore, intended that include all such changes and modifications belonging in the scope of the invention in the following claims.

Claims (10)

1. an air conditioner rubber pipe mesoglea compositions, it is characterized in that, according to parts by weight meter, described mesoglea is mainly made up of following components: ethylene propylene diene rubber 100-300 part, binding agent 5-30 part, polyisobutylene 5-20 part, binder resin 1-15 part, white carbon 10-50 part.
2. compositions according to claim 1, it is characterized in that, according to parts by weight meter, described mesoglea is mainly made up of following components: ethylene propylene diene rubber 100-150 part, binding agent 10-20 part, polyisobutylene 10-15 part, binder resin 5-10 part, white carbon 20-40 part.
3. the compositions according to claim 1 or 2, it is characterised in that described ethylene propylene diene rubber is the mixing ethylene propylene diene rubber of one or more in Mitsui EPDM, Korea S SKEPDM, Du Pont DuPontEPDM.
4. the compositions according to claim 1 or 2, it is characterised in that described binding agent is the mixed adhesive of one or more in adhesive A, adhesive A B-30, adhesive RS, binding agent RL, binding agent RE, binding agent RH.
5. the compositions according to claim 1 or 2, it is characterised in that so polyisobutylene is the mixture of one or more in BASFOppanol polyisobutylene, Ineos polyisobutylene.
6. the compositions according to claim 1 or 2, it is characterised in that described binder resin is the hybrid bonding resin of one or more in binder resin PN, coumarone indene resin, rosin resin, phenolic resin, carbon nine resin, epoxy resin, terpene resin.
7. compositions according to claim 1 and 2, it is characterised in that described white carbon is that TOKUSIL white carbon, the sub-white carbon in sieve ground and Degussa win the mixing white carbon of one or more in wound white carbon.
8. the preparation method of air conditioner rubber pipe mesoglea according to any one of claim 1-7, it is characterised in that by the mixing rear binder removal of compositions according to any one of claim 1-7, obtain described mesoglea material.
9. an air conditioner rubber pipe, it is characterised in that described sebific duct includes barrier layer, mesoglea, braid and outer glue-line from inside to outside successively；
Wherein, the material of described mesoglea method described in claim 8 prepares.
10. the preparation method of an air conditioner rubber pipe, it is characterized in that, described method comprises the steps: extrusion PPA raw material on sebific duct die mandrel, and makes PPA be coated on plug to form barrier layer, then on the plug with barrier layer, extrude mesoglea, and weave at mesoglea outer surface, it is braid, on braid, then extrudes outer glue-line, it is semi-finished product air conditioner rubber pipe, after semi-finished product rubber pipe is vulcanized, and plug is taken out, namely obtain finished product sebific duct；
Wherein, described mesoglea compositions described in any one of claim 1-7 is made.
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Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101948588A (en) * 2010-10-25 2011-01-19 天津鹏翎胶管股份有限公司 Outer layer glue of carbon dioxide refrigerant air conditioner rubber hose

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101948588A (en) * 2010-10-25 2011-01-19 天津鹏翎胶管股份有限公司 Outer layer glue of carbon dioxide refrigerant air conditioner rubber hose

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