CN105385053B - A kind of R1234yf air-conditioner pipes internal layer glue composition, preparation method and air conditioning hose - Google Patents
A kind of R1234yf air-conditioner pipes internal layer glue composition, preparation method and air conditioning hose Download PDFInfo
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- CN105385053B CN105385053B CN201510976748.XA CN201510976748A CN105385053B CN 105385053 B CN105385053 B CN 105385053B CN 201510976748 A CN201510976748 A CN 201510976748A CN 105385053 B CN105385053 B CN 105385053B
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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
- C08L23/26—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment
- C08L23/28—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment by reaction with halogens or compounds containing halogen
- C08L23/283—Halogenated homo- or copolymers of iso-olefins
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
- B29B7/02—Mixing; Kneading non-continuous, with mechanical mixing or kneading devices, i.e. batch type
- B29B7/06—Mixing; Kneading non-continuous, with mechanical mixing or kneading devices, i.e. batch type with movable mixing or kneading devices
- B29B7/10—Mixing; Kneading non-continuous, with mechanical mixing or kneading devices, i.e. batch type with movable mixing or kneading devices rotary
-
- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
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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
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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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
- C08L2203/00—Applications
- C08L2203/18—Applications used for pipes
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- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- General Engineering & Computer Science (AREA)
- General 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)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The present invention provides a kind of R1234yf air-conditioner pipes internal layer glue compositions.The beautiful powder of silicon is added in the composition as filler, resistance to tearing, pressure-resistant denaturation and the high temperature resistance of obtained rubber material can be improved.So as to solve the low tear-resistant intensity of air conditioning hose inner layer material in the prior art, pressure-resistant denaturation difference and high temperature resistance poor, the technical issues of new R1234yf working medium use needs can not be met.Meanwhile the present invention also provides a kind of preparation method of R1234yf air conditioning hoses hose lining, the beautiful powder of filler silicon is added in the method mixing step, thus the resistance to tearing of obtained rubber material and pressure-resistant denaturation can be improved.Further, the present invention also provides a kind of R1234yf air-conditionings glue hose, rubber material obtained in the process of the present invention is as inner glue layer material in the sebific duct, thus can improve the resistance to tearing of sebific duct and pressure-resistant denaturation.
Description
Technical field
The present invention relates to a kind of air conditioner rubber pipe fields, are combined in particular to a kind of R1234yf air-conditioner pipes hose lining
Object, preparation method and empty soft pipe.
Background technology
Refrigerant be in process of refrigerastion complete refrigeration cycle working media, the refrigerant used in early stage air-conditioning and refrigerator etc.
It is halogenated hydrocarbons.However, the discharge of this halogenated hydrocarbon coolant can destroy atmospheric ozone layer, refrigerant is to the destruction journey of ozone layer
Degree with destruction ozone layer dive value (Ozone depletion potential abbreviation ODP) represent.Meanwhile these halogenated hydrocarbons are also
One of inducement of global warming is caused, because the discharge of halogenated hydrocarbon coolant can trigger greenhouse effects, and then causes the whole world
It warms, influence degree is represented with global warming potential (Global warming potential, abbreviation GWP).
Before Montreal Agreement bookmark is ordered, automotive air-conditioning system is mainly using CFC12 as refrigerant, but this system
The ODP values of cryogen are higher, thus, according to Montreal Agreement book, CFC12 is level-one by limitation refrigerant.
In order to find new refrigerant instead of CFC12, air conditioner industry is made that extensive research, it is desirable to which developing ODP values is
Zero Biological process.In these researchs, the refrigerant HFC134a of E.I.Du Pont Company's exploitation is successfully applied in refrigeration industry.
Since HFC134a is without chlorine atom, and with good security performance, meanwhile, the physical property of this refrigerant also with tradition
CFC12 refrigerants be closer to, thus the remodeling of refrigeration system is also easier.Further, HFC134a heat transfer characters
It is more excellent than CFC12, thus, in use, the dosage of HFC134a is also less, more suitable to be used as air conditioner refrigerating medium.
However, according to European Union by fluorine-containing greenhouse-gas control regulation requirement, from 11 days January in 2011,
The air conditioning for automobiles for forbidding new production is more than 150 refrigerant by European Union using GWP value, due to what is largely used now
The GWP value of HFC134a refrigerants is 1300, so will be prohibited from using.Further, European Union provided, from January 1st, 2017
It rises, all air conditioning for automobiles will be forbidden to use refrigerant of the GWP value more than 150.Thus, refrigeration is made using low GWP in air conditioning for automobiles
Agent will become trend and certainty.
U.S. Honeywell (Honeywell) company and E.I.Du Pont Company have developed jointly novel environment-friendly refrigerant R1234yf,
Its chemical name is tetrafluoropropene, and molecular formula is CF3CF=CH2, the GWP value of HFO-1234yf is 4, empty far below European Union's automobile
Adjust the regulation of instruction.Thus R1234yf is more suitable as automobile air-conditioning refrigeration medium, and as refrigerant performance also by
Step is approved.
Since novel environment-friendly refrigerant R1234yf is more and more introduced into automotive air-conditioning system, thus it is matching
The exploitation of the material of air conditioner rubber pipe is imperative.
However, the tear-resistant intensity of existing air conditioner rubber pipe inner glue layer material and pressure-resistant denaturation index be not high, though
It so disclosure satisfy that the requirement of existing R134a, but can not simultaneously meet the work requirements of the Novel condensations medium such as R1234yf.
In view of this, it is special to propose the present invention.
The content of the invention
The first object of the present invention is to provide a kind of R1234yf air-conditioner pipes internal layer glue composition.Add in the composition
The beautiful powder of silicon is entered as filler, resistance to tearing, pressure-resistant denaturation and the high temperature resistance of obtained rubber material can be improved.
So as to solve, the tear-resistant intensity of air conditioning hose inner layer material in the prior art is low, pressure-resistant denaturation is poor and high temperature resistance
Difference, the technical issues of new R1234yf working medium use needs can not be met.
Second object of the present invention is to provide a kind of preparation method of R1234yf air conditioning hoses hose lining, the side
The beautiful powder of filler silicon is added in method mixing step, thus the resistance to tearing of obtained rubber material and resistance to buckling can be improved
Property.
Third object of the present invention is to provide a kind of R1234yf air-conditioner pipes, in the air-conditioner pipe in the process of the present invention
Obtained rubber material can improve the resistance to tearing of sebific duct and pressure-resistant denaturation as inner glue layer material.
In order to realize the above-mentioned purpose of the present invention, spy uses following technical scheme：
R1234yf air conditioning hoses internal layer glue composition of the present invention, is mainly made of following components：Butyl rubber bromide
Glue, reinforcing agent, plasticizer, filler, activating agent, vulcanizing agent, vulcanization accelerator.Wherein, the filler is the beautiful powder of silicon.Into one
Step, according to parts by weight, in the composition, brombutyl, reinforcing agent, plasticizer, filler, activating agent, vulcanization
The ratio of agent and vulcanization accelerator is：(60-100)：(30-90)：(5-20)：(10-40)：(1-5)：(1-9)：(1-5).
In the present composition, due to adding the beautiful powder of silicon as filler, it is thus possible to rubber material obtained by raising
Resistance to tearing, it is pressure-resistant denaturation and the adhesiveness of high temperature resistance and each layer of sebific duct.
Optionally, in the present invention, the brombutyl is EXXON brombutyls, LANXESS butyl rubber bromides
Glue, one kind in BBK brombutyls or its combination.Preferably, in the present invention, the brombutyl is EXXON bromines
Change butyl rubber or LANXESS brombutyls.It is furthermore preferred that in the present invention, the brombutyl is
One or more of EXXON2211, EXXON2222, EXXON2235, EXXON2244, EXXON2255, EXXON3343's is mixed
Close object.
In the present invention, by the adjustment and optimization to raw material brombutyl, obtained rubber can be further improved
The resistance to tearing of material and pressure-resistant denaturation, and the resistance to low temperature of rubber material can be improved.
Optionally, the present invention in, the beautiful powder of silicon for SILLITIN N85, SILLITIN Z86, SILLITIN V88,
The mixture of one or more of SILLITIN V8；Preferably, in the present invention, the beautiful powder of silicon for SILLITIN Z86 or
The mixture of one or both in person SILLITIN V88.
In the present invention, by the further selection and adjustment to the beautiful powder of silicon, obtained rubber material can be further improved
Performance.
Optionally, in the present invention, the reinforcing agent is carbon black N330 and carbon black N774.
In the present invention, by the selection and adjustment to reinforcing agent, the intensity of obtained rubber material can be improved.
Optionally, in the present invention, the mass ratio of the carbon black N330 and carbon black N744 is 1:5-5:1；Preferably, this hair
In bright, the mass ratio of the carbon black N330 and carbon black N744 is 1:1-1:3.
Optionally, the present invention in, the vulcanization accelerator be N, N'- meta-phenylene bismaleimides.
Optionally, in the present invention, the activating agent is stearic acid.
Optionally, in the present invention, the plasticizer is paraffin oil.
Optionally, in the present invention, the vulcanizing agent is zinc oxide.
It is double using zinc oxide-stearic acid-N, N'- metaphenylene by the selection and adjustment to vulcanizing system in the present invention
The vulcanizing system of maleimide can further improve the tearing-resistant performance and bond properties of obtained rubber material.
Meanwhile the present invention also provides a kind of preparation method of R1234yf air conditioning hoses inner glue layer rubber material, including
Following steps：Composition of the present invention is kneaded back glue, cooling park after to get to rubber material.
In the method for the present invention, by adding the beautiful powder of filler silicon in the standby mixing step of its rubber system, thus can be with
The resistance to tearing of rubber material obtained by raising and pressure-resistant denaturation.
Optionally, in the method for the present invention, the temperature of the dumping is 90-120 DEG C；Preferably, it is described in the method for the present invention
Dump temperature is 100-110 DEG C.
In the present invention, by the adjustment and optimization to dump temperature, so as to further improve to obtained rubber material
The pressure-resistant denaturation of material.
And the adhesiveness with other rubber materials.
Optionally, in the method for the present invention, the storage period is 8-320h.
Optionally, in the method for the present invention, the mixing step can further include following steps：(1) by raw material bromination
Butyl rubber is kneaded after being mixed with activating agent；(2) reinforcing agent and plasticizer and filler are added in into system after mixing,
Continue to be kneaded a period of time；(3) to continuing to add in vulcanizing agent and vulcanization accelerator in system after being kneaded, continue to be kneaded,
It carries bolt and terminates to be kneaded, treat dumping.
In the method for the present invention, the method due to further using one section of mixing, thus for being kneaded compared to two sections, it can be with
Save mixing time.
Optionally, in the method for the present invention, the mixing carries out in mixer.
Optionally, in the method for the present invention, the temperature that the step (1) is kneaded is 60-100 DEG C；Preferably, it is described to be kneaded temperature
It spends for 70-80 DEG C.
Optionally, in the method for the present invention, the mixing of the step (1) carries out in mixer, wherein, the mixing
Machine is cooled down by water flowing.
Optionally, the mixing time of step described in the method for the present invention (1) is 5s-60s；Preferably, the mixing time
For 10-30s.
Optionally, in the method for the present invention, in the mixing process of the step (1), the rotating speed of mixer is 15-25rmp；It is excellent
Choosing, in the method for the present invention, the rotating speed of the mixer is 16-20rmp.
Optionally, in the method for the present invention, in the mixing process of step (2), the rotating speed of mixer is 10-20rmp；It is preferred that
, in the method for the present invention, the rotating speed of the mixer is 12-15rmp.
Optionally, in the method for the present invention, the melting temperature of step (3) is 60-90 DEG C；Preferably, the melting temperature is
75-80℃。
Optionally, in the method for the present invention, step (3) puies forward bolt temperature as 80-110 DEG C；Preferably, the bolt temperature that carries is
90-100℃。
Optionally, in the method for the present invention, banbury rotating speed is 10-17rmp when step (3) carries bolt；Optionally, the rotating speed
For 12-15rmp.
Further, the present invention also provides a kind of R1234yf air conditioner rubber pipes, the air conditioning hose is respectively from inside to outside
Interior permeable formation, inner glue layer, polyester fiber enhancement layer and outer glue-line；Wherein, the inner glue layer material is by side of the present invention
Method is prepared.
In the present invention, rubber material obtained in the process of the present invention, thus can as inner glue layer material in the sebific duct
To improve the resistance to tearing of sebific duct and pressure-resistant denaturation.
Compared with prior art, beneficial effects of the present invention are：
(1) in the present composition, the beautiful powder of silicon is added as filler, and further by butyl rubber bromide collagen
The adjustment of material and vulcanizing system can improve resistance to tearing, pressure-resistant denaturation and the high temperature resistance of obtained rubber material.
So as to solve the tear-resistant intensity of air conditioning hose inner layer material in the prior art it is low, it is pressure-resistant denaturation and high temperature resistance it is poor,
The technical issues of new R1234yf working medium use needs thus can not be met.
(2) in the method for the present invention, it is used as filler and using the method for one section of mixing by adding in the beautiful powder of silicon, thus can be with
While rubber material resistance to tearing, pressure-resistant denaturation and high temperature resistance obtained by raising, mixing action can also be simplified
Step saves mixing time, improves efficiency.
(3) in sebific duct of the present invention, by using the rubber material obtained by the method for the present invention as inner glue layer material, thus
Resistance to tearing, pressure-resistant denaturation and the high temperature resistance of rubber material can be improved；Simultaneously as rubber made from the method for the present invention
Glue material has very high adhesiveness with other rubber materials in sebific duct, can also further improve the whole knot of obtained sebific duct
The stability of structure.
Specific embodiment
Embodiment of the present invention is described in detail below in conjunction with embodiment, but those skilled in the art will
Understand, the following example is merely to illustrate the present invention, and is not construed as limiting the scope of the invention.It is not specified in embodiment specific
Condition person, the condition suggested according to normal condition or manufacturer carry out.Reagents or instruments used without specified manufacturer is
The conventional products that can be obtained by commercially available purchase.
Embodiment 1-3
Using EXXON2244 as raw material brombutyl, and original is carried out according to key component weight grams as shown in table 1 below
Material weighs, and obtains the R1234yf air conditioning hose inner glue layer rubber composition rubber compoundings of embodiment 1-3.
1 embodiment 1-3 building rubber compounds composition formula (unit g) of table
It is heated after mixer water flowing is cooled down, when mixer temperature reaches 70 DEG C, by raw material brombutyl
It is kneaded in EXXON2244 and activating agent stearic acid input mixer, wherein, banbury rotating speed 20rmp.It is kneaded 10s
Afterwards, reinforcing agent carbon black N330, carbon black N744, the beautiful powder SILLITIN Z86 of filler silicon and plasticizer paraffin oil are added in and are kneaded
In system, continue to be kneaded, and banbury rotating speed is adjusted to 16rpm, continue to be kneaded.Then, mixer is warming up to 75 DEG C, adds in
Vulcanizing agent zinc oxide and vulcanization accelerator N, N'- meta-phenylene bismaleimide, and banbury rotating speed is adjusted to
12rmp continues to be kneaded.Next, mixer is warming up to 90 DEG C, bolt is carried, and banbury rotating speed is adjusted to 12rmp.Finally, it is close
Mill is warming up to 100 DEG C, and is 20rmp by its adjustment of rotational speed, then dumping, and obtained sizing material is cooled down, and stops
After putting 10h, the rubber material of embodiment 1-3 is obtained, and it is tested for the property.
The performance test results of rubber material are as shown in table 2 below obtained by embodiment 1-3：
2 embodiment 1-3 rubber material the performance test results of table
Embodiment 4-8
Respectively with brombutyl EXXON2244, EXXON2255, EXXON3343, LANXESS2030 and BBK232
For raw material brombutyl, and according to material rate shown in embodiment 2 weigh in composition in addition to brombutyl
Other raw materials, to obtain the rubber composition of embodiment 4-8.
According to method shown in a 1-3 is performed as described above, composition described in embodiment 4-8 is kneaded, is squeezed out, and cooled down and stop
It puts, obtains the rubber material of embodiment 4-8, then it is tested for the property, it is as a result as shown in table 3 below：
3 embodiment 4-8 rubber material performance tests of table
Comparative example 1-3
Using EXXON2255 as raw material brombutyl, and each component raw material is weighed according to the material rate of such as the following table 4,
To obtain the rubber composition of comparative example 1-3.
4 comparative example 1-3 building rubber compounds composition formula (unit g) of table
According to method shown in a 1-3 is performed as described above, composition described in comparative example 1-3 is kneaded, is squeezed out, and cooled down and stop
It puts, obtains the rubber material of comparative example 1-3, then it is tested for the property, it is as a result as shown in table 5 below：
5 comparative example 1-3 rubber material the performance test results of table
Further, rubber material obtained in the application method is also used as inner glue layer material preparation as having
Interior permeable formation, inner glue layer, the R1234yf air conditioner rubber pipes of polyester fiber enhancement layer and outer glue-line structure, its step are as follows：
First, interior infiltration layer material is introduced into extruder, obtains interior permeable formation sebific duct；Then, by interior permeable formation sebific duct
It is introduced into extruder, so as to add inner glue layer on interior permeable formation sebific duct surface, wherein, the inner glue layer material is the application method
Obtained rubber material；Next, the sebific duct obtained in step before is further introduced into braider, so as to permeate inside
Layer-inner glue layer structure glue pipe surface Woven polyester fiber-reinforced layer.Finally, there is permeable formation-inner glue layer-polyester by obtained
The sebific duct of fiber reinforcement layer structure is introduced into extruder, obtains being respectively interior permeable formation, inner glue layer, polyester fiber increasing from the inside to the outside
The R1234yf air conditioner rubber pipes of strong layer and outer glue-line structure.
Although illustrate and describing the present invention with specific embodiment, it will be appreciated that without departing substantially from the present invention's
Many other change and modification can be made in the case of spirit and scope.It is, therefore, intended that in the following claims
Including belonging to all such changes and modifications in the scope of the invention.
Claims (3)
1. a kind of preparation method of R1234yf air-conditioner pipes hose lining, which is characterized in that it includes the following steps：R1234yf is empty
Inner tube layer glue composition is adjusted to be kneaded back glue, cooling park after to get to rubber material；
In parts by weight, the composition is mainly made of following components：60-100 parts of brombutyl, reinforcing agent
30-90 parts, 5-20 parts of plasticizer, 10-40 parts of filler, 1-5 parts of activating agent, 1-9 parts of vulcanizing agent, 1-5 parts of vulcanization accelerator；
Wherein, the filler is the beautiful powder of silicon；
The reinforcing agent is that the mass ratio of carbon black N330 and carbon black N744, carbon black N330 and carbon black N744 are 1:5-5:1；
The vulcanization accelerator be N, N'- meta-phenylene bismaleimides；
The mixing includes the following steps：
(1) it is kneaded after raw material brombutyl is mixed with activating agent；
(2) reinforcing agent, plasticizer and filler are added in into system after mixing, continues to be kneaded a period of time；
(3) to continuing to add in vulcanizing agent and vulcanization accelerator in system after being kneaded, continue to be kneaded, and carry bolt, treat dumping；
The dump temperature is 90-110 DEG C.
2. preparation method according to claim 1, which is characterized in that the brombutyl is EXXON brominated butyls
Rubber, LANXESS brombutyls, one kind in BBK brombutyls or its combination.
3. preparation method according to claim 1, which is characterized in that the beautiful powder of silicon for SILLITINN85,
The mixture of one or more of SILLITINZ86, SILLITINV88, SILLITINV8.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510976748.XA CN105385053B (en) | 2015-12-21 | 2015-12-21 | A kind of R1234yf air-conditioner pipes internal layer glue composition, preparation method and air conditioning hose |
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| CN201510976748.XA CN105385053B (en) | 2015-12-21 | 2015-12-21 | A kind of R1234yf air-conditioner pipes internal layer glue composition, preparation method and air conditioning hose |
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| CN105385053B true CN105385053B (en) | 2018-06-01 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106633448A (en) * | 2016-12-28 | 2017-05-10 | 太仓冠联高分子材料有限公司 | Environment-friendly butyl capsule adhesive capable of making direct contact with drinking water and preparation method thereof |
| CN114891305A (en) * | 2022-06-24 | 2022-08-12 | 青岛三祥科技股份有限公司 | Rubber composition and automobile air conditioner hose |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010110419A1 (en) * | 2009-03-27 | 2010-09-30 | 株式会社ブリヂストン | Refrigerant transport hose, and polyamide resin composition for forming gas barrier layer for the hose |
| CN102010551A (en) * | 2010-11-30 | 2011-04-13 | 天津鹏翎胶管股份有限公司 | EPDM (ethylene-propylene-diene monomer) composition and hose |
| CN102417667A (en) * | 2011-11-02 | 2012-04-18 | 天津鹏翎胶管股份有限公司 | Brominated butyl rubber composition for air conditioner hose of automobile |
-
2015
- 2015-12-21 CN CN201510976748.XA patent/CN105385053B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010110419A1 (en) * | 2009-03-27 | 2010-09-30 | 株式会社ブリヂストン | Refrigerant transport hose, and polyamide resin composition for forming gas barrier layer for the hose |
| CN102010551A (en) * | 2010-11-30 | 2011-04-13 | 天津鹏翎胶管股份有限公司 | EPDM (ethylene-propylene-diene monomer) composition and hose |
| CN102417667A (en) * | 2011-11-02 | 2012-04-18 | 天津鹏翎胶管股份有限公司 | Brominated butyl rubber composition for air conditioner hose of automobile |
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