CN112321921A - Rubber composition for automobile air conditioning pipe and preparation method thereof - Google Patents
Rubber composition for automobile air conditioning pipe and preparation method thereof Download PDFInfo
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L15/00—Compositions of rubber derivatives
- C08L15/005—Hydrogenated nitrile rubber
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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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/221—Oxides; Hydroxides of metals of rare earth metal
- C08K2003/2213—Oxides; Hydroxides of metals of rare earth metal of cerium
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/262—Alkali metal carbonates
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
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- C08L2201/00—Properties
- C08L2201/14—Gas barrier composition
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- C—CHEMISTRY; METALLURGY
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- C08L2203/18—Applications used for pipes
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- C—CHEMISTRY; METALLURGY
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- 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
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- 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
Abstract
The invention provides a rubber composition for an automobile air-conditioning pipe and a preparation method thereof, wherein the rubber composition comprises the following raw material components in parts by weight: 80-90 parts of hydrogenated nitrile rubber, 10-20 parts of poly (nonane terephthalamide), 2-4 parts of an anti-aging agent, 7-12 parts of a heat-resistant agent, 20-40 parts of carbon black, 102-202 parts of a permeation blocking agent, 10-30 parts of a damping agent, 10-15 parts of a peroxide crosslinking agent and 3-6 parts of an auxiliary crosslinking agent; the permeation barrier agent includes graphene and DK2 polymer grade organoclay. The rubber composition has the advantages of heat resistance, up-line temperature of 180 ℃, better heat-resistant service life and better carbon dioxide permeability resistance, and the rubber hose made of the rubber composition can meet the use requirement of the air conditioning pipe for carbon dioxide refrigerant.
Description
Technical Field
The invention belongs to the technical field of automobile part production, and particularly relates to a rubber composition for an automobile air conditioner pipe and a preparation method thereof.
Background
According to the requirements of fluorine-containing greenhouse gas control regulations which have been passed by the european union, since 2011, the european union prohibits the use of refrigerants having a GWP value of more than 150 for newly produced automobile air conditioners, and since the GWP value (global warming potential) of R134a refrigerant which has been used in large quantities at present is 1300, the use of refrigerants will be prohibited. With CO2The GWP of the raw material refrigerant R744 (carbon dioxide refrigerant) is 1, and because of its environmental protection, wide source, low cost, safety and non-toxicity characteristics, it has been gradually popularized and used in air-conditioning refrigeration systems.
Compared with the conventional refrigerant, due to CO2The higher critical temperature point, the higher pressure, the higher temperature, and the larger suction/exhaust pressure difference, the high temperature of 180 ℃ are generated by the compressor work using the R774 refrigerant, which provides a new challenge for the design and manufacture of the pipeline of the automobile air conditioning system.
At present, air conditioning pipes using carbon dioxide refrigerant are generally used in the industrial refrigeration industry, and all air conditioning pipelines of the air conditioning pipes are made of metal hard pipes. However, due to the low noise requirement of the passenger car on the automobile air-conditioning system, the automobile air-conditioning pipeline system cannot use a metal hard pipe, and the rubber materials of the air-conditioning hose commonly used for the automobile, such as HNBR, EPDM, IIR, BIIR and CR rubber, have the maximum working temperature not exceeding 150 ℃, and cannot meet the requirements of high temperature resistance, refrigerant permeation resistance and NVH shock absorption and noise reduction of the carbon dioxide refrigerant. At present, no automobile air conditioner hose capable of meeting the use requirement of a carbon dioxide refrigerant exists in the market, and the application of the carbon dioxide refrigerant in the field of automobile air conditioners is limited.
Disclosure of Invention
The rubber composition has the heat resistance up to 180 ℃, has good heat resistance life and good carbon dioxide permeability resistance, and the rubber hose made of the rubber composition can meet the use requirement of the air conditioning pipe for carbon dioxide refrigerant.
In order to achieve the above object, one aspect of the present invention provides a rubber composition for an automotive air conditioning pipe, comprising the following raw material components in parts by weight: 80-90 parts of hydrogenated nitrile rubber, 10-20 parts of poly (nonane terephthalamide), 2-4 parts of an anti-aging agent, 7-12 parts of a heat-resistant agent, 20-40 parts of carbon black, 102-202 parts of a permeation blocking agent, 10-30 parts of a damping agent, 10-15 parts of a peroxide crosslinking agent and 3-6 parts of an auxiliary crosslinking agent; the permeation barrier agent includes graphene and DK2 polymer grade organoclay.
Preferably, the content of acrylonitrile in the hydrogenated nitrile-butadiene rubber is 42-49%, and the saturation degree is 99%.
Preferably, the poly (nonane terephthalamide) is poly (1, 9-nonyleneterephthalamide).
Preferably, the antioxidant is antioxidant MC.
Preferably, the heat-resistant agent includes cerium oxide and lithium carbonate.
Preferably, the mass ratio of the cerium oxide to the lithium carbonate is 2: 5-2: 10.
Preferably, the mass ratio of the graphene to the DK2 polymer-grade organoclay in the permeation barrier agent is 1: 50-1: 100.
Preferably, the carbon black is carbon black N115 and/or carbon black N234.
Preferably, the damping agent is KY-1330.
Preferably, the auxiliary crosslinking agent is ethylene glycol dimethacrylate.
Preferably, the peroxide crosslinking agent is TMCH.
10. In another aspect of the present invention, there is provided a method for preparing the rubber composition for an automotive air conditioning tube, comprising the steps of:
(1) the hydrogenated nitrile rubber, the poly-para-nonane terephthalamide, the damping agent and the graphene are soaked in a mixed solution of dimethyl formamide and xylene according to a proportion, and are subjected to high-speed shearing stirring in a closed container, and then the mixture of the hydrogenated nitrile rubber and the poly-para-nonane terephthalamide is obtained through the processes of condensation, solvent separation and drying.
(2) And (2) putting the blend obtained in the step (1), the heat-resistant agent, the anti-aging agent, the carbon black and the DK2 polymer-grade organoclay into an internal mixer for pressurization and mixing, discharging the mixed rubber material to an upper sheet and a lower sheet of an open mill, and standing for later use.
(3) And (3) putting the product obtained in the step (2), the auxiliary crosslinking agent and the peroxide crosslinking agent into an internal mixer for mixing, discharging the mixed rubber material to an open mill for back mixing, and pressing the rubber material into rubber strips suitable for processing on a tablet press to obtain the rubber composition for the automobile air conditioner pipe.
Preferably, in the step (1), the volume ratio of the dimethylformamide to the xylene in the mixed solution is 30:70, the temperature in the high-speed shearing and stirring process is 120-130 ℃, the rotating speed of the stirrer is 3000r/min, and the stirring time is 4-6 h.
Preferably, in the step (2), when the temperature is 180-190 ℃, the mixed rubber materials are discharged to an open mill for loading and unloading, and are parked for 16-24 hours for later use.
Preferably, in the step (3), when the temperature reaches 100-105 ℃, the mixed rubber material is discharged to an open mill to be returned for mixing for 2-3 min, and then the rubber material is pressed into rubber strips suitable for processing on a tablet press, so that the rubber composition for the automobile air-conditioning tube is obtained.
Compared with the prior art, the invention has the advantages that: the invention provides a rubber composition for an automobile air-conditioning pipe and a preparation method thereof, the rubber composition has the advantages of heat resistance up to the upper line of 180 ℃, better heat-resistant service life and better carbon dioxide permeability resistance, and a rubber hose made of the rubber composition can meet the use requirement of the air-conditioning pipe for a carbon dioxide refrigerant. Specifically, the method comprises the following steps:
1. the invention adopts hydrogenated nitrile rubber as a main material, uses poly (nonane terephthalamide), and increases the upper limit of heat resistance of HNBR from 160 ℃ to 180 ℃ through a heat-resistant agent and a reactive anti-aging agent which are reasonably compatible.
2. The permeation blocking agent provided by the invention adopts graphene and DK2 polymer-grade organoclay, and the graphene and the DK2 polymer-grade organoclay are matched to play a good blocking effect, so that the impermeability of the product to carbon dioxide refrigerant R774 is remarkably improved.
3. Compared with the existing air-conditioning pipe made of EPDM and IIR rubber materials, the rubber composition for the automobile air-conditioning pipe has the advantages that the impermeability of the product to carbon dioxide refrigerant R774 is remarkably improved, and compared with a hard air-conditioning pipe, the NVH performance of an air-conditioning hose made of the material is remarkably improved.
Detailed Description
In order to make the objects, technical solutions and advantages of the present application more apparent, the present application is described and illustrated below with reference to the embodiments. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.
It should be understood that the specific embodiments described herein are merely illustrative of the present application and are not intended to limit the present application. All other embodiments obtained by a person of ordinary skill in the art based on the embodiments provided in the present application without any inventive step are within the scope of protection of the present application.
It is obvious that the following description is only some examples or embodiments of the present application, and it will be obvious to those skilled in the art that the present application can be applied to other similar scenarios without inventive effort. Moreover, it should be appreciated that in the development of any such actual implementation, as in any engineering or design project, numerous implementation-specific decisions must be made to achieve the developers' specific goals, such as compliance with system-related and business-related constraints, which may vary from one implementation to another.
Reference in the specification to "an embodiment" means that a particular feature, structure, or characteristic described in connection with the embodiment can be included in at least one embodiment of the specification. The appearances of the phrase in various places in the specification are not necessarily all referring to the same embodiment, nor are separate or alternative embodiments mutually exclusive of other embodiments. Those of ordinary skill in the art will explicitly and implicitly appreciate that the embodiments described herein may be combined with other embodiments without conflict.
Unless defined otherwise, technical or scientific terms referred to herein shall have the ordinary meaning as understood by those of ordinary skill in the art to which this application belongs. Reference to "a," "an," "the," and similar words throughout this application are not to be construed as limiting in number, and may refer to the singular or the plural. The present application is directed to the use of the terms "including," "comprising," "having," and any variations thereof, which are intended to cover non-exclusive inclusions; the term "plurality" as referred to herein means two or more. "and/or" describes an association relationship of associated objects, meaning that three relationships may exist, for example, "A and/or B" may mean: a exists alone, A and B exist simultaneously, and B exists alone. The character "/" generally indicates that the former and latter associated objects are in an "or" relationship. Reference herein to the terms "first," "second," "third," and the like, are merely to distinguish similar objects and do not denote a particular ordering for the objects.
The embodiment of the invention provides a rubber composition for an automobile air-conditioning pipe, which comprises the following raw material components in parts by weight: 80-90 parts of hydrogenated nitrile rubber, 10-20 parts of poly (nonane terephthalamide), 2-4 parts of an anti-aging agent, 7-12 parts of a heat-resistant agent, 20-40 parts of carbon black, 102-202 parts of a permeation blocking agent, 10-30 parts of a damping agent, 10-15 parts of a peroxide crosslinking agent and 3-6 parts of an auxiliary crosslinking agent; the permeation barrier agent includes graphene and DK2 polymer grade organoclay.
The preparation method of the rubber composition for the automobile air conditioning pipe comprises the following steps:
(1) the hydrogenated nitrile rubber, the poly-para-nonane terephthalamide, the damping agent and the graphene are soaked in a mixed solution of dimethyl formamide and xylene according to a proportion, and are subjected to high-speed shearing stirring in a closed container, and then the mixture of the hydrogenated nitrile rubber and the poly-para-nonane terephthalamide is obtained through the processes of condensation, solvent separation and drying.
(2) And (2) putting the blend obtained in the step (1), the heat-resistant agent, the anti-aging agent, the carbon black and the DK2 polymer-grade organoclay into an internal mixer for pressurization and mixing, discharging the mixed rubber material to an upper sheet and a lower sheet of an open mill, and standing for later use.
(3) And (3) putting the product obtained in the step (2), the auxiliary crosslinking agent and the peroxide crosslinking agent into an internal mixer for mixing, discharging the mixed rubber material to an open mill for back mixing, and pressing the rubber material into rubber strips suitable for processing on a tablet press to obtain the rubber composition for the automobile air conditioner pipe.
The inventor finds out through a large number of experiments that the temperature resistance of the hydrogenated nitrile rubber (HNBR) can be obviously improved by using the hydrogenated nitrile rubber and the poly (nonane terephthalamide), and the upper limit of the temperature resistance is increased from 150 ℃ to 180 ℃. In order to improve the comprehensive performance of rubber and rubber tubes, the rubber composition provided by the invention is added with an anti-aging agent, a heat-resistant agent and a permeation blocking agent, so that the heat-resistant life and the gas permeability of the rubber composition are further improved. The permeation blocking agent adopts graphene and DK2 polymer-grade organic clay, the DK2 polymer-grade organic clay is hydroxyl-containing organic amine modified nano montmorillonite, the graphene and the nano montmorillonite are fillers with lamellar structures, a lamellar structure gas blocking layer can be formed in HNBR rubber, the inventor finds that the gas blocking effect cannot be achieved when the HNBR rubber is used singly, and the two are matched to be used to achieve a better blocking effect. The inventors analyzed that the reason for this should be: because the molecular weight of carbon dioxide is too small, the different particle size structures of graphene and nano montmorillonite oil, if the graphene is used singly, the dosage is too small, the gas barrier effect cannot be achieved, if the dosage is too large, the aggregation is easy to occur in the mixing process to form aggregated graphite, the dispersion is poor, and the gas barrier effect is poor on the contrary. In the embodiment, a small amount of graphene and a large amount of nano montmorillonite are used simultaneously, and can be combined with carbon black to achieve a synergistic effect, so that the HNBR rubber has a remarkable effect on improving the air tightness.
In the preparation method provided by the invention, the poly (nonane terephthalamide) and the damping agent have high softening points and the graphene is difficult to disperse, and as the most key raw materials in the formula, a special wet high-speed shearing mixing process is required to be adopted to form a premix with HNBR, and then the premix and the rest materials are mechanically sheared and mixed to form a uniform mixture. In order to reduce the influence of structural fatigue accumulated by the action of mechanical force on the rubber performance in the mixing process of rubber macromolecules, the step (2) designs a parking process, so that the rubber macromolecules are loosened in the parking process to ensure the rubber performance. Meanwhile, the placing can further disperse the anti-aging agent, the heat-resistant agent and the vulcanizing agent in the placing process through retraction of rubber macromolecules. In addition, the wet high-speed shearing mixing and mechanical mixing processes adopted in the step (1) are combined, so that the materials are uniformly dispersed in the rubber phase, and the effect of air tightness can be achieved.
In a preferred embodiment, the mass ratio of the graphene to the DK2 polymer-grade organoclay in the permeation blocking agent is 1: 50-1: 100. Specifically, the permeation blocking agent is industrial grade graphene TNIRGO produced by Chinese academy of sciences organic chemistry GmbH and DK2 polymer grade organic clay produced by Zhejiang Fenghong new material GmbH.
In a preferred embodiment, the hydrogenated nitrile rubber contains 42-49% of acrylonitrile and has a saturation degree of 99%, and specifically, ZN43053 and/or ZN50050 which contains 42-49% of acrylonitrile and has a saturation degree of 90% and is produced by adopting the Zainan technology is adopted. The inventor finds that the acrylonitrile content has obvious influence on the permeation of the hydrogenated nitrile rubber composition, the higher the acrylonitrile content is, the better the R774 refrigerant permeation resistance of the hydrogenated nitrile rubber is, the hydrogenated nitrile rubber with the acrylonitrile content of below 40% has poor permeation resistance, the hydrogenated nitrile rubber with the acrylonitrile content of 42-49% has high polarity and strong steric hindrance, and the compatible rubber composition has the optimal R774 refrigerant permeation resistance.
In a preferred embodiment, the poly (nonane terephthalamide) is poly (1, 9-nonylene terephthalamide), specifically, PA9T from Colorado, PA9T is poly (1, 9-nonylene terephthalamide), and has many unique properties different from general PA, PA9T is a homopolymer, a semi-aromatic main chain, and a long carbon chain structure of 9 carbons, and the heat resistance temperature is 200-250 ℃. PA9T has good compatibility with hydrogenated nitrile rubber, and the upper limit of heat resistance of the hydrogenated nitrile rubber can be effectively improved by rubber-plastic blending.
In a preferred embodiment, the anti-aging agent is an anti-aging agent MC (N-4 (anilinophenyl) maleimide), and specifically adopts a SANYANGSHI technology anti-aging agent MC (CAS No:32099-65-3, N-4 (anilinophenyl) maleimide). MC is a reactive non-extraction anti-aging agent, and can receive free radicals to open double bonds in the vulcanization process of a maleimide system to form transverse bonds to generate crosslinking with rubber, so that the anti-aging non-extraction effect is achieved, and the transverse bonds have high stability for thermal oxidation. In addition, the N-substituted derivative of maleimide can be used as vulcanizing agent, for example, peroxide is added during vulcanization to initiate generation of free radicals, then graft polymerization is caused to generate crosslinking, so that the formed macromolecules are not easy to extract, a longer-lasting anti-aging effect can be maintained, and the heat-resistant grade of the polymer can be improved. The common anti-aging agents 445, MBZ and RD in the hydrogenated nitrile rubber are easy to dissolve and extract in compressor lubricating oil during use, so that the anti-aging effect of the rubber is obviously reduced in the later use period. In the embodiment, based on the hydrogenated nitrile-butadiene rubber composition, the reactive antioxidant is reasonably matched, and the antioxidant and the hydrogenated nitrile-butadiene rubber main chain generate crosslinking, so that the antioxidant can be prevented from being dissolved and extracted by lubricating oil.
In a preferred embodiment, the heat-resistant agent comprises cerium oxide and lithium carbonate, and specifically, the heat-resistant agent adopts cerium oxide (CAS: 1306-38-3) produced by Hangzhou Wanjing New Material Co., Ltd and industrial grade lithium carbonate produced by Sichuan Tianqi lithium industry Co., Ltd. In the use process of the rubber, the cerium oxide can capture free radicals, and prevent oxygen radicals outside the rubber from attacking rubber macromolecules to cause rubber molecule breakage. The lithium carbonate can absorb acidic substances generated in the rubber aging process, the aging speed caused by rubber acidification is slowed down, and the lithium carbonate and the rubber can synergistically improve the heat resistance of the rubber.
In a preferred embodiment, the mass ratio of the cerium oxide to the lithium carbonate is 2:5 to 2: 10.
In a preferred embodiment, the carbon black is carbon black N115 and/or carbon black N234. Specifically, the carbon black is high-structure-degree N115 and N234 carbon black produced by Cabot corporation. The carbon black adopts carbon black N115 and/or carbon black N234 with fine particle size and high structure degree, and the carbon black with fine particle size and high structure degree has good reinforcing effect on HNBR. The superfine high-structure-degree carbon black and the HNBR rubber form carbon black combined glue, so that the refrigerant permeability resistance of the HNBR rubber can be effectively improved while the HNBR rubber is reinforced.
In a preferred embodiment, the damping agent is KY-1330(CAS:1709-70-2, name: 1,3, 5-trimethyl-2, 4,6- (3, 5-di-tert-butyl-4-hydroxybenzyl) benzene). Specifically, KY-1330 is an amorphous polymorphic substance, the molecular structure of the polymorphic substance contains hydrogen bonds with strong polarity, the polymorphic substance is added into hydrogenated nitrile rubber with polar groups, the damping performance of the hydrogenated nitrile rubber can be obviously improved through the hydrogen bond interaction between a polymer and organic small molecules and the hydrogen bond interaction of the organic small molecules, and KY1300 has the super-damping performance and is a damping endowing agent with excellent performance.
In a preferred embodiment, the co-crosslinking agent is ethylene glycol dimethacrylate. Specifically, the auxiliary crosslinking agent is a rubber complexing agent produced by Langshan chemistry
EDMA/S (CAS: 97-90-5, Chinese name: ethylene glycol dimethacrylate). EDMA/S is a high-efficiency assistant crosslinking agent, and has faster vulcanization speed compared with common assistant crosslinking agents TAIC and TAC when being applied to the system.
In a preferred embodiment, the peroxide crosslinking agent is a vulcanizing agent TMCH. Specifically, the peroxide crosslinking agent is ketal organic peroxide TMCH (CAS: 6731-36-8, Chinese name: 1, 1-bis (t-butylperoxy) -3, 3, 5-trimethylcyclohexane) produced by Jiangsu Qiangsheng functional chemical Co., Ltd. The rubber hose is usually vulcanized by low-pressure steam, rubber expands in volume when heated before reaching a positive vulcanization temperature in the initial vulcanization stage, and fine clearance channels are formed inside the expanded rubber, so that the air tightness of the rubber is reduced. TMCH is an odorless environment-friendly vulcanizing agent, the half-life period of 1 minute is 153 ℃, compared with the common crosslinking agents DCP and BIBP, the TMCH has lower crosslinking temperature, and the auxiliary crosslinking agent is ethylene glycol dimethacrylate, so that the TMCH and the auxiliary crosslinking agent are reasonably compatible, and can be quickly vulcanized at low temperature during vulcanization, and the air-tight seal reduction caused by the heated expansion of rubber can be effectively prevented.
In a preferred embodiment, in the step (1), the volume ratio of the dimethylformamide to the xylene in the mixed solution is 30:70, the temperature in the high-speed shearing and stirring process is 120-130 ℃, the rotating speed of the stirrer is 3000r/min, and the stirring time is 4-6 h.
In a preferred embodiment, in the step (2), when the temperature is 180-190 ℃, the mixed rubber material is discharged to an open mill for upper and lower pieces, and is placed for 16-24 hours for later use.
In a preferred embodiment, in the step (3), when the temperature reaches 100 ℃ to 105 ℃, the mixed rubber material is discharged to an open mill to be returned for rubber mixing for 2 min to 3min, and then the rubber material is pressed into rubber strips suitable for processing on a tablet press, so that the rubber composition for the automobile air conditioner pipe is obtained.
In order to more clearly and specifically describe a rubber composition for an air conditioning pipe for an automobile and a method for preparing the same according to embodiments of the present invention, the following description will be given with reference to specific examples.
Example 1
A rubber composition for an automobile air conditioning pipe comprises the following raw material components in parts by weight: ZN 4305380 parts, PA9T 20 parts, antioxidant MC 4 parts, lithium carbonate 5 parts, cerium oxide 2 parts, KY-133010 parts, carbon black N11520 parts, industrial-grade graphene 2 parts, DK2 polymer-grade organoclay 200 parts, vulcanizing agent TMCH 10 parts, and crosslinking assistant EDMA/S4 parts.
The preparation method of the rubber composition for the automobile air conditioning pipe comprises the following steps:
(1) ZN43053, PA9T, KY-1330 and graphene are soaked in a mixed solution of dimethylformamide and xylene 30/70 (volume ratio) according to a certain proportion, and in a closed container at 120 ℃, the mixture is subjected to high-speed shearing stirring at 3000r/min for 4 hours, and then the mixture is subjected to processes of coagulation, solvent separation, drying and the like to form a hydrogenated nitrile rubber/poly (nonane terephthalamide) blend;
(2) putting the blend obtained in the step (1), carbon black N115, an anti-aging agent MC, lithium carbonate, cerium oxide and DK2 polymer-grade organoclay into an internal mixer for pressurizing and mixing, discharging the mixed rubber material to an upper sheet and a lower sheet of an open mill when the temperature reaches 180 ℃, and standing for 16 hours for later use;
(3) and (3) putting the product obtained in the step (2), EDMA/S and TMCH into an internal mixer, mixing until the temperature reaches 100 ℃, discharging the mixed rubber material onto an open mill, returning the rubber material for mixing for 2 minutes, and pressing into rubber strips suitable for processing on a tablet press to obtain the rubber composition for the automobile air conditioner pipe.
Example 2
A rubber composition for an automobile air conditioning pipe comprises the following raw material components in parts by weight: ZN 4305350 parts, ZN 5005035 parts, PA9T 15 parts, antioxidant MC 3 parts, lithium carbonate 6 parts, cerium oxide 2 parts, KY-133015 parts, carbon black N11510 parts, carbon black N23420 parts, industrial-grade graphene 2 parts, DK2 polymer-grade organoclay 180 parts, vulcanizing agent TMCH 12 parts and auxiliary crosslinking agent EDMA/S3 parts.
The preparation method of the rubber composition for the automobile air conditioning pipe comprises the following steps:
(1) ZN43053, ZN50050, PA9T, KY-1330 and graphene are soaked in a mixed solution of dimethylformamide and xylene 30/70 (volume ratio) according to a certain proportion, and the mixture is subjected to high-speed shearing stirring at 3000r/min for 6 hours at 130 ℃ in a closed container, and then subjected to processes of coagulation, solvent separation, drying and the like to form the hydrogenated nitrile rubber/poly (phencyno-yl) diamine blend.
(2) And (2) putting the blend obtained in the step (1), carbon black N115, carbon black N234, an anti-aging agent MC, lithium carbonate, cerium oxide and DK2 polymer-grade organoclay into an internal mixer for pressurizing and mixing, discharging the mixed rubber material to an upper sheet and a lower sheet of an open mill when the temperature reaches 190 ℃, and standing for 24 hours for later use.
(3) And (3) putting the product obtained in the step (2), EDMA/S and TMCH into an internal mixer, mixing until the temperature reaches 105 ℃, discharging the mixed rubber material to an open mill, returning the rubber material for mixing for 3 minutes, and pressing the rubber material into rubber strips suitable for processing on a tablet press to obtain the rubber composition for the automobile air conditioner pipe.
Example 3
A rubber composition for an automobile air conditioning pipe comprises the following raw material components in parts by weight: ZN 4305340 parts, ZN 5005050 parts, PA9T 10 parts, antioxidant MC 2 parts, lithium carbonate 8 parts, cerium oxide 2 parts, KY-133020 parts, carbon black N23430 parts, industrial-grade graphene 2 parts, DK2 polymer-grade organoclay 150 parts, vulcanizing agent TMCH 14 parts and auxiliary crosslinking agent EDMA/S2 parts.
The preparation method of the rubber composition for the automobile air conditioning pipe comprises the following steps:
(1) ZN43053, ZN50050, PA9T, KY-1330 and graphene are soaked in a mixed solution of dimethylformamide and xylene 30/70 (volume ratio) according to a certain proportion, and the mixture is subjected to high-speed shearing stirring at 3000r/min for 5 hours at 125 ℃ in a closed container, and then subjected to processes of coagulation, solvent separation, drying and the like to form the hydrogenated nitrile rubber/poly (phencyno-yl) diamine blend.
(2) And (2) putting the blend obtained in the step (1), carbon black N234, an anti-aging agent MC, lithium carbonate, cerium oxide and DK2 polymer-grade organoclay into an internal mixer for pressurization and mixing, discharging the mixed rubber material to an upper sheet and a lower sheet of an open mill when the temperature reaches 185 ℃, and standing for 20 hours for later use.
(3) And (3) putting the product obtained in the step (2), EDMA/S and TMCH into an internal mixer, mixing until the temperature reaches 102 ℃, discharging the mixed rubber material onto an open mill, returning the rubber material for mixing for 2.5 minutes, and pressing into rubber strips suitable for processing on a tablet press to obtain the rubber composition for the automobile air-conditioning pipe.
Example 4
A rubber composition for an automobile air conditioning pipe comprises the following raw material components in parts by weight: ZN 5005090 parts, PA9T 10 parts, anti-aging agent MC 2 parts, lithium carbonate 10 parts, cerium oxide 2 parts, KY-133030 parts, carbon black N23440 parts, industrial grade graphene 2 parts, DK2 polymer grade organic clay 100 parts, vulcanizing agent TMCH 15 parts and crosslinking assistant agent EDMA/S2 parts.
The preparation method of the rubber composition for the automobile air conditioning pipe comprises the following steps:
(1) ZN50050, PA9T, KY-1330 and graphene are soaked in a mixed solution of dimethylformamide and xylene 30/70 (volume ratio) according to a certain proportion, and the mixture is subjected to coagulation, solvent separation, drying and other processes after being sheared and stirred at a high speed of 3000r/min for 5 hours in a closed container at the temperature of 120 ℃ to form a hydrogenated nitrile rubber/poly (nonane terephthalamide) blend.
(2) And (2) putting the blend obtained in the step (1), carbon black N234, an anti-aging agent MC, lithium carbonate, cerium oxide and DK2 polymer-grade organoclay into an internal mixer for pressurization and mixing, discharging the mixed rubber material to an upper sheet and a lower sheet of an open mill when the temperature reaches 180 ℃, and standing for 20 hours for later use.
(3) And (3) putting the product obtained in the step (2), EDMA/S and TMCH into an internal mixer, mixing until the temperature reaches 100 ℃, discharging the mixed rubber material onto an open mill, returning the rubber material for mixing for 3 minutes, and pressing into rubber strips suitable for processing on a tablet press to obtain the rubber composition for the automobile air conditioner pipe.
Example 5 performance testing test 1:
the performance detection test is carried out on the rubber of the embodiment 1-4, two groups of traditional air conditioner pipe rubbers are set as a control group, and the specific raw material components of the control group are as follows:
comparative example 1:
the common butyl rubber composition for the air-conditioning pipe comprises the following raw material components in parts by weight: 100 parts of butyl rubber, 5 parts of chloroprene rubber, 5 parts of zinc oxide, 1 part of stearic acid, 2 parts of an antioxidant RD, 1 part of an antioxidant MB, 50 parts of carbon black N550, 5 parts of paraffin oil, 10 parts of vulcanized resin and 40 parts of talcum powder.
The preparation method of the butyl rubber composition commonly used for the air conditioner pipe comprises the following steps:
(1) the butyl rubber, the chloroprene rubber, the zinc oxide, the stearic acid, the antioxidant RD, the antioxidant MB, the carbon black N550, the paraffin oil and the talcum powder are put into an internal mixer for pressurized mixing, and when the temperature reaches 140 ℃, the mixed rubber material is discharged to an open mill for upper and lower sheet cooling for standby.
(2) And (2) putting the product obtained in the step (1) and vulcanized resin into an internal mixer, mixing until the temperature reaches 110 ℃, discharging the mixed rubber material onto an open mill, returning the rubber material to the mixer for mixing for 3 minutes, and pressing into rubber strips suitable for processing on a tablet press to obtain the butyl rubber composition for the automobile air conditioner pipe.
Comparative example 2:
the hydrogenated nitrile rubber composition commonly used for the air conditioner pipe comprises the following raw material components in parts by weight: 100 parts of hydrogenated nitrile rubber, 5 parts of zinc oxide, 1 part of stearic acid, 4452 parts of an anti-aging agent, 55070 parts of carbon black N, 40 parts of talcum powder, 10 parts of TOTM, 407 parts of BIBP-407 and 703 parts of TAIC-703.
The preparation method of the hydrogenated nitrile rubber composition commonly used for the air conditioner pipe comprises the following steps:
(1) hydrogenated nitrile rubber, zinc oxide, stearic acid, an anti-aging agent 445, carbon black N550, talcum powder and TOTM are put into an internal mixer for pressure mixing, and when the temperature reaches 150 ℃, the mixed rubber material is discharged to an open mill for cooling of an upper sheet and a lower sheet for standby.
(2) And (2) putting the product obtained in the step (1), BIBP-40 and TAIC-70 into an internal mixer, mixing until the temperature reaches 105 ℃, discharging the mixed rubber material onto an open mill, returning the rubber material, mixing for 3 minutes, and pressing into rubber strips suitable for processing on a tablet press to obtain the hydrogenated nitrile rubber composition.
The test method comprises the following steps:
1. the examples and comparative examples were each tested using a Mooney tester to test the Mooney viscosity of the samples at 100 ℃;
2. the rubber compositions of examples and comparative examples were respectively tested for their properties after vulcanization according to the national standard GB/T528 after vulcanization in a press vulcanizer at 165 ℃ for 30min and after secondary vulcanization in an oven at 170 ℃ for 2h, and the test results are shown in Table 1.
TABLE 1 comparison of the Properties of the rubber compositions of the invention with those of the comparative butyl and hydrogenated nitrile rubbers
As is apparent from the data results in Table 1, the rubber compositions of examples 1 to 4 exhibited aging property changes at 180 ℃ which were much better than those of conventional HNBR and conventional IIR, heat-resistant formulations of conventional HNBR having a heat-resistant upper limit of 150 ℃ and air-conditioning hoses produced using the rubber compositions of examples 1 to 4, than those of conventional butyl rubber (conventional IIR) and hydrogenated nitrile rubber (conventional HNBR), and all of the aging properties of the rubber compositions of examples 1 to 4 satisfied the aging requirements at 180 ℃.
The inventor believes that the reason is that the HNBR rubber and proper amount of poly-para-nonane terephthalamide are blended, the poly-para-nonane terephthalamide improves the mechanical strength of the HNBR rubber at high temperature, and the addition of the heat-resistant agent and the reactive anti-aging agent improves the deficiency of the heat aging resistance of the HNBR rubber, so that the heat-resistant upper limit of the HNBR rubber blend is raised to 180 ℃. The 1,3, 5-trimethyl-2, 4,6- (3, 5-di-tert-butyl-4-hydroxybenzyl) benzene) molecular structure contains hydrogen bonds with strong polarity, and the hydrogen bonds are added into hydrogenated nitrile rubber with high-polarity groups, so that the damping performance of the hydrogenated nitrile rubber can be obviously improved to exceed that of butyl rubber with the best damping performance in the conventional rubber through the hydrogen bond interaction between a polymer and an organic micromolecule and the hydrogen bond interaction of the organic micromolecule. Meanwhile, the graphene and the montmorillonite with different particle size gradients are filled, the synergistic effect is formed by the graphene and the montmorillonite and the superfine high-structure-degree carbon black combined glue, the shielding layer is uniformly dispersed in the rubber, and the air seal same as that of the butyl rubber can be achieved. The rubber composition of the embodiment has the advantages that the components are compatible with each other, the heat resistance, air tightness and damping performance are good, the heat resistance upper limit of the rubber composition is increased to 180 ℃, and the performance of the rubber composition can meet the use requirement of a carbon dioxide air conditioning pipe of a passenger vehicle.
Example 6 performance testing experiment 2:
this example is to verify the compatibility of the invention and the patent examples of the invention prove that the rubber collection and the types of the auxiliary materials of the invention have good synergistic effect.
The formulation of each sample in this example is shown in table 2, the numerical values in the table represent the parts by mass of the raw materials, and each sample in this example was prepared by the same preparation method as in example 1.
Table 2 sample recipe list
The results of the performance testing of each sample are shown in table 3:
table 3 sample performance test results tabulation
As can be seen from the comparison of the performances in Table 3, the performance retention rate of sample 2, sample 1 and sample 2 after aging at 180 ℃ for 70h is improved by 1 time by using poly (nonane terephthalamide) (PA9T) and compatible with a heat-resistant agent; compared with the sample 2, the DK2 polymer-grade organic clay (modified nano montmorillonite) is added in the sample 3, although the permeability of carbon dioxide resistance is improved, the reason is not obvious, and the inventor analyzes that the reason is that the particle size of montmorillonite is too large, and the montmorillonite is agglomerated in the mixing process, so that molecules of the vulcanized rubber still have partial larger gaps, and the permeation improvement is not obvious; sample 4 is compared with sample 3, the carbon dioxide permeability resistance can be obviously improved by adding graphene into sample 4, and the superfine carbon black and the nano-scale lamellar graphene in sample 4 can form a synergistic effect with the nano-montmorillonite, so that the molecular gap of the sizing material can be effectively supplemented, and the permeability of the carbon dioxide refrigerant can be improved by about 50%; and in the sample 5, a macromolecular damping agent KY-1330 is added on the basis of the sample 4, and because KY-1330 increases the hydrogen bond acting force in the sizing material, the damping performance of the sample at high temperature is obviously improved.
The content in table 3 is only a part of compatibility screening, the auxiliary material components provided by the invention are compatible with each other, and the inventor proves that the heat resistance of the hydrogenated nitrile rubber is remarkably improved compared with the traditional hydrogenated nitrile rubber formula by matching poly (nonane terephthalamide) and a heat-resistant agent through a large amount of experiments in the process of researching the formula of the invention, and the carbon dioxide resistant refrigerant permeation of the hydrogenated nitrile rubber is remarkably improved by matching superfine carbon black, graphene and modified montmorillonite due to the system effect of the three.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein. In addition, the technical solutions between the various embodiments can be combined with each other, but must be based on the realization of those skilled in the art; where combinations of features are mutually inconsistent or impractical, such combinations should not be considered as being absent and not within the scope of the claimed invention.
Claims (10)
1. The rubber composition for the automobile air conditioner pipe is characterized by comprising the following raw material components in parts by weight: 80-90 parts of hydrogenated nitrile rubber, 10-20 parts of poly (nonane terephthalamide), 2-4 parts of an anti-aging agent, 7-12 parts of a heat-resistant agent, 20-40 parts of carbon black, 102-202 parts of a permeation blocking agent, 10-30 parts of a damping agent, 10-15 parts of a peroxide crosslinking agent and 3-6 parts of an auxiliary crosslinking agent; the permeation barrier agent includes graphene and DK2 polymer grade organoclay.
2. A rubber composition for an automotive air-conditioning duct according to claim 1, characterized in that the hydrogenated nitrile rubber has an acrylonitrile content of 42 to 49% and a saturation of 99%.
3. A rubber composition for a tube for an automobile air conditioner according to claim 1, wherein the poly (nonane terephthalamide) is poly (1, 9-nonyleneterephthalamide).
4. A rubber composition for an automotive air-conditioning duct according to claim 1, characterized in that the antioxidant is antioxidant MC.
5. A rubber composition for an automotive air-conditioning pipe according to claim 1, characterized in that the heat-resistant agent comprises cerium oxide and lithium carbonate.
6. A rubber composition for an automotive air conditioning pipe according to claim 5, characterized in that the mass ratio of cerium oxide to lithium carbonate is 2:5 to 2: 10.
7. The rubber composition for an automobile air-conditioning pipe as claimed in claim 1, wherein the mass ratio of the graphene to the DK2 polymer-grade organoclay in the permeation barrier agent is 1: 50-1: 100.
8. A rubber composition for an automotive air conditioning pipe according to claim 1, characterized in that the carbon black is carbon black N115 and/or carbon black N234; the damping agent is KY-1330; the auxiliary crosslinking agent is ethylene glycol dimethacrylate; the peroxide crosslinking agent is TMCH.
9. A method for preparing a rubber composition for a tube for an automobile air conditioner according to any one of claims 1 to 8, comprising the steps of:
(1) the hydrogenated nitrile rubber, the poly-para-nonane terephthalamide, the damping agent and the graphene are soaked in a mixed solution of dimethyl formamide and xylene according to a proportion, and are subjected to high-speed shearing stirring in a closed container, and then the mixture of the hydrogenated nitrile rubber and the poly-para-nonane terephthalamide is obtained through the processes of condensation, solvent separation and drying.
(2) And (2) putting the blend obtained in the step (1), the heat-resistant agent, the anti-aging agent, the carbon black and the DK2 polymer-grade organoclay into an internal mixer for pressurization and mixing, discharging the mixed rubber material to an upper sheet and a lower sheet of an open mill, and standing for later use.
(3) And (3) putting the product obtained in the step (2), the auxiliary crosslinking agent and the peroxide crosslinking agent into an internal mixer for mixing, discharging the mixed rubber material to an open mill for back mixing, and pressing the rubber material into rubber strips suitable for processing on a tablet press to obtain the rubber composition for the automobile air conditioner pipe.
10. A method for preparing a rubber composition for an air-conditioning tube of an automobile according to claim 9, wherein in the step (1), the volume ratio of dimethylformamide to xylene in the mixed solution is 30:70, the temperature during the high-speed shearing and stirring process is 120 ℃ to 130 ℃, the rotating speed of a stirrer is 3000rad/min, and the stirring time is 4 to 6 hours; in the step (2), when the temperature is up to 180-190 ℃, the mixed rubber materials are discharged to an open mill for loading and unloading, and are placed for 16-24 hours for later use; and (3) when the mixing temperature reaches 100-105 ℃, discharging the mixed rubber material to an open mill, returning the rubber material for mixing for 2-3 min, and pressing the rubber material into rubber strips suitable for processing on a tablet press to obtain the rubber composition for the automobile air conditioner pipe.
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