CN111849153A - Modified nylon material for automobile brake hose and preparation method thereof - Google Patents
Modified nylon material for automobile brake hose and preparation method thereof Download PDFInfo
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- CN111849153A CN111849153A CN202010684165.0A CN202010684165A CN111849153A CN 111849153 A CN111849153 A CN 111849153A CN 202010684165 A CN202010684165 A CN 202010684165A CN 111849153 A CN111849153 A CN 111849153A
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- automobile brake
- nylon material
- brake hose
- modified nylon
- elastomer
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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
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
-
- 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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- 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
- 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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- 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
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/08—Polymer mixtures characterised by other features containing additives to improve the compatibility between two polymers
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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
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/04—Thermoplastic elastomer
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Extrusion Moulding Of Plastics Or The Like (AREA)
Abstract
The invention discloses a modified nylon material for an automobile brake hose and a preparation method thereof, wherein the modified nylon material comprises a polyamide matrix, an elastomer, a toughening agent, a plasticizer, a compatilizer, an antioxidant and other auxiliaries; the preparation method comprises the steps of adding the polyamide matrix, the elastomer, the toughening agent, the plasticizer, the compatilizer, the antioxidant and other auxiliaries into a double-screw extruder according to a preset proportion, melting, extruding, granulating and drying to obtain the polyamide composite material. According to the invention, pure PA6 slices are modified by using a proper amount of elastomer and plasticizer, so that the obtained modified nylon material can meet the index requirements of automobile brake hose materials, namely excellent physical and mechanical properties, good hardness and resilience and large bursting strength, and can replace PA6 and PA11 alloy toughening, PA6 and PA12 alloy toughening and PA11 and PA12 products in application of automobile brake hoses.
Description
Technical Field
The invention belongs to the field of modified engineering plastics, and particularly relates to a modified nylon material for an automobile brake hose and a preparation method thereof.
Background
The automobile brake hose, commonly called brake pipe, is a part used in an automobile brake system, and mainly has the main function of transmitting brake media in automobile braking, ensuring that the brake force is transmitted to an automobile brake shoe or a brake caliper to generate brake force, so that the braking is effective at any time.
The nylon modified material applied to manufacturing the automobile brake hose needs to have excellent physical and mechanical properties, good hardness and resilience and high bursting strength. At present, the nylon modified material applied to manufacturing the automobile brake hose takes PA6 and PA11 alloy toughening, PA6 and PA12 alloy toughening, PA11 and PA12 as main materials, the pure PA6 toughening modified material is less applied to the automobile brake hose, the pure PA6 toughening modified material technology has no complete breakthrough so far, the product performance is still insufficient, and the market needs cannot be met, so the nylon modified material applied to the brake hose has excellent modification research and development performance and stable indexes by utilizing the pure PA6, and becomes another trend in the domestic nylon modification industry.
Disclosure of Invention
The invention is provided for overcoming the defects of complex production process and relatively high production cost of materials for automobile brake hoses in the prior art, and aims to provide a modified nylon material for the automobile brake hoses and a preparation method thereof.
The invention is realized by the following technical scheme:
a modified nylon material for an automobile brake hose comprises the following components in percentage by weight:
45% -65% of a polyamide matrix;
8% -20% of an elastomer;
3% -18% of a toughening agent;
1% -6% of a plasticizer;
2% -8% of a compatilizer;
0.8% -2% of an auxiliary agent.
In the above technical solution, the polyamide matrix is polyamide 6 chips with a viscosity of 3.8.
In the above technical solution, the elastomer is a thermoplastic elastomer.
In the above technical solution, the thermoplastic elastomer is any one or a combination of more of a polyurethane elastomer TPU containing aromatic hard segments and polyether soft segments, a thermoplastic polyamide elastomer TPA containing polyether soft segments, and an ethylene-vinyl acetate copolymer EVA with a Vinyl Acetate (VA) content of more than 30%.
In the technical scheme, the toughening agent is a low-temperature nylon toughening agent maleic anhydride grafted ethylene-octene copolymer POE-g-MAH.
In the technical scheme, the plasticizer is N-butyl benzene sulfonamide; the compatilizer is MAH-g-EVA.
In the technical scheme, the auxiliary agent is one or a combination of two of an antioxidant and a heat stabilizer.
In the above technical scheme, the antioxidant is a phosphite antioxidant: 3, 5-di-tert-butyl-4-hydroxyphenylpropionyl-hexamethylenediamine, tris 2, 4-di-tert-butylphenol phosphite; the stabilizer is a copper salt heat stabilizer: organic copper carboxylate, copper thiophosphate, copper thiocarbamate, sulfurized copper borate, cuprous iodide, etc.
A preparation method of a modified nylon material for an automobile brake hose comprises the following specific steps: adding the polyamide matrix, the elastomer, the toughening agent, the plasticizer, the compatilizer and the auxiliary agent into a double-screw extruder according to the proportion, melting, extruding, granulating and drying to obtain the polyamide composite material.
In the technical scheme, the melting temperature is 235-270 ℃.
The invention has the beneficial effects that:
the invention provides a modified nylon material for automobile brake hoses and a preparation method thereof, wherein a proper amount of elastomer is added into a pure polyamide 6 slice to adjust the hardness of the product to be close to the hardness and resilience of PA12, and a part of compatilizer is added to ensure the processability of the product and the compatibility of the elastomer and polyamide 6.
Detailed Description
In order to make those skilled in the art better understand the technical solution of the present invention, the technical solution of the modified nylon material for automobile brake hose and the preparation method thereof of the present invention will be further described below by specific embodiments.
Example 1
Weighing 55kg of polyamide 6 slices, 22 kg of ethylene-vinyl acetate copolymer EVA with an elastomer vinyl acetate content higher than 30%, 15.4kg of low-temperature nylon toughening agent POE-g-MAH, 6.6kg of plasticizer N-butylbenzene sulfonamide, 8.8kg of compatilizer MAH-g-EVA, 2.2kg of auxiliary agent phosphite antioxidant 3, 5-di-tert-butyl-4-hydroxybenzoyl-hexamethylene diamine, adding into a double-screw extruder, controlling the temperature of the double-screw extruder at 245 ℃, and properly adjusting the feeding speed and the screw rotating speed to finally obtain the modified nylon material for the automobile brake hose.
And (3) taking 20kg of nylon modified material for injection molding, fully washing a vehicle before injection molding to ensure the cleanliness of the screw, and respectively injecting and molding a tensile sample strip, a bent sample strip and a standard color plate by using four groups of molds. Tests show that the tensile strength of the product reaches more than 35MPa at the Susan normal temperature (23 ℃); the impact of the simple beam gap at normal temperature (23 ℃) reaches 84.16Kj/m2Above, simply supported beam The non-notch impact normal temperature (23 ℃) reaches 84.55Kj/m2. The Shore hardness D15 reaches 55, and the sample plate is placed in an oven and baked for 72 hours at 100 ℃ without cracks, carbonization and thermal degradation.
Example 2
Weighing 66kg of polyamide 6 slices, 18.7 kg of ethylene-vinyl acetate copolymer EVA with an elastomer vinyl acetate content higher than 30%, 12.1kg of low-temperature nylon toughening agent POE-g-MAH, 4.4kg of plasticizer N-butylbenzene sulfonamide, 6.6kg of compatilizer MAH-g-EVA and 2.2kg of assistant copper salt heat stabilizer cuprous iodide, adding the mixture into a double-screw extruder, controlling the temperature of the double-screw extruder at 260 ℃, and properly adjusting the feeding speed and the screw rotating speed to finally obtain the modified nylon material for the automobile brake hose.
And (3) taking 20kg of nylon modified material for injection molding, fully washing a vehicle before injection molding to ensure the cleanliness of the screw, and respectively injecting and molding a tensile sample strip, a bent sample strip and a standard color plate by using four groups of molds. Tests show that the tensile strength of the product reaches more than 35MPa at the Susan normal temperature (23 ℃); the impact of the simple beam notch at normal temperature (23 ℃) reaches 80.52Kj/m2Above, the non-notch impact normal temperature (23 ℃) of the simply supported beam reaches 81.64Kj/m2. The Shore hardness D15 reaches 56, and the sample plate is placed in an oven and baked for 72 hours at 100 ℃ without cracks, carbonization and thermal degradation.
Example 3
69.3kg of polyamide 6 chips, 16.5 kg of ethylene-vinyl acetate copolymer EVA with an elastomer vinyl acetate content higher than 30%, 11kg of low-temperature nylon toughening agent POE-g-MAH, 6.6kg of plasticizer N-butylbenzene sulfonamide, 5.5kg of compatilizer MAH-g-EVA and 1.1kg of auxiliary phosphite antioxidant tris (2, 4-di-tert-butylphenol) phosphite are added into a double-screw extruder, the temperature of the double-screw extruder is controlled at 245 ℃, the feeding speed and the screw rotating speed are properly adjusted, and finally the modified nylon material for the automobile brake hose is obtained.
And (3) taking 20kg of nylon modified material for injection molding, fully washing a vehicle before injection molding to ensure the cleanliness of the screw, and respectively injecting and molding a tensile sample strip, a bent sample strip and a standard color plate by using four groups of molds. Tests show that the tensile strength of the product reaches more than 35MPa at the Susan normal temperature (23 ℃); simple and convenientThe normal temperature (23 ℃) of the notch impact of the supporting beam reaches 78.64Kj/m2Above, the non-notch impact normal temperature (23 ℃) of the simply supported beam reaches 80.31Kj/m2. The Shore hardness D15 reaches 58, and the sample plate is placed in an oven to be baked for 72 hours at 100 ℃ without cracks, carbonization and thermal degradation.
Example 4
Weighing 71.5kg of polyamide 6 slices, 16.5 kg of ethylene-vinyl acetate copolymer EVA with an elastomer vinyl acetate content higher than 30%, 11kg of low-temperature nylon toughening agent POE-g-MAH, 4.4kg of plasticizer N-butylbenzene sulfonamide, 5.5kg of compatilizer MAH-g-EVA and 1.1kg of assistant copper salt heat stabilizer cuprous iodide, adding the mixture into a double-screw extruder, controlling the temperature of the double-screw extruder at 260 ℃, and properly adjusting the feeding speed and the screw rotating speed to finally obtain the modified nylon material for the automobile brake hose.
And (3) taking 20kg of nylon modified material for injection molding, fully washing a vehicle before injection molding to ensure the cleanliness of the screw, and respectively injecting and molding a tensile sample strip, a bent sample strip and a standard color plate by using four groups of molds. Tests show that the tensile strength of the product reaches more than 35MPa at the Susan normal temperature (23 ℃); the impact of the simple beam notch at normal temperature (23 ℃) reaches 75.87Kj/m2Above, the non-notch impact normal temperature (23 ℃) of the simply supported beam reaches 79.33Kj/m2. The Shore hardness D15 reaches 61, and the sample plate is placed in an oven to be baked for 72 hours at 100 ℃ without cracks, carbonization and thermal degradation.
The project takes PA6 slices with 3.8 viscosity produced by a company as a base material, the softness and resilience of the product are adjusted to be close to those of PA12 by adding the elastomer, and meanwhile, a part of compatilizer is added to ensure the processability of the product and the compatibility of the elastomer and the PA. The modified nylon product produced by the process method has good flexibility and impact resistance, has hardness closer to PA12, and is suitable for being applied to automobile brake hoses.
It should be noted that the embodiments and features of the embodiments may be combined with each other without conflict.
The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the scope and disclosure of the present invention.
Claims (10)
1. The modified nylon material for the automobile brake hose is characterized in that: the modified nylon material comprises the following components in percentage by weight:
45% -65% of a polyamide matrix;
8% -20% of an elastomer;
3% -18% of a toughening agent;
1% -6% of a plasticizer;
2% -8% of a compatilizer;
0.8% -2% of an auxiliary agent.
2. The modified nylon material for an automobile brake hose according to claim 1, wherein: the polyamide matrix was polyamide 6 chips with a viscosity of 3.8.
3. The modified nylon material for an automobile brake hose according to claim 1, wherein: the elastomer is a thermoplastic elastomer.
4. The modified nylon material for an automobile brake hose according to claim 3, wherein: the thermoplastic elastomer is any one or combination of more of polyurethane elastomer containing aromatic hard segment and polyether soft segment, thermoplastic polyamide elastomer containing polyether soft segment, and ethylene-vinyl acetate copolymer with the vinyl acetate content higher than 30%.
5. The modified nylon material for an automobile brake hose according to claim 1, wherein: the toughening agent is a low-temperature nylon toughening agent; the auxiliary agent is one or a combination of two of an antioxidant and a heat stabilizer.
6. The modified nylon material for an automobile brake hose according to claim 1, wherein: the plasticizer is N-butyl benzene sulfonamide; the compatilizer is MAH-g-EVA.
7. The modified nylon material for an automobile brake hose according to claim 5, wherein: the antioxidant is phosphite ester antioxidant; the heat stabilizer is a copper salt heat stabilizer.
8. The modified nylon material for an automobile brake hose according to claim 5, wherein: the low-temperature nylon toughening agent is maleic anhydride grafted ethylene-octene copolymer POE-g-MAH.
9. The modified nylon material for an automobile brake hose according to claim 7, wherein: the phosphite antioxidant is any one of 3, 5-di-tert-butyl-4-hydroxy-phenylpropionyl-hexamethylene diamine or tri-2, 4-di-tert-butylphenol phosphite; the copper salt heat stabilizer is any one of organic copper carboxylate, copper thiophosphate, copper thiocarbamate, copper sulfide-hydrocarbon borate or cuprous iodide.
10. The preparation method of the modified nylon material for the automobile brake hose according to any one of claims 1 to 9, which is characterized by comprising the following steps: adding the polyamide matrix, the elastomer, the toughening agent, the plasticizer, the compatilizer and the auxiliary agent into a double-screw extruder according to the proportion, melting, extruding, granulating and drying to obtain the polyamide composite material; the melting temperature is 235-270 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010684165.0A CN111849153A (en) | 2020-07-16 | 2020-07-16 | Modified nylon material for automobile brake hose and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010684165.0A CN111849153A (en) | 2020-07-16 | 2020-07-16 | Modified nylon material for automobile brake hose and preparation method thereof |
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| Publication Number | Publication Date |
|---|---|
| CN111849153A true CN111849153A (en) | 2020-10-30 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN202010684165.0A Pending CN111849153A (en) | 2020-07-16 | 2020-07-16 | Modified nylon material for automobile brake hose and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112430391A (en) * | 2020-11-23 | 2021-03-02 | 山东星达新材料有限公司 | Super-tough super-low temperature-resistant super-wear-resistant flexible nylon alloy material and preparation method thereof |
| CN114836026A (en) * | 2022-06-14 | 2022-08-02 | 安徽农业大学 | High-impact-toughness bio-based polyamide composite material, and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1106652A1 (en) * | 1999-12-06 | 2001-06-13 | Hyundai Motor Company | Polyamide resin composition |
| CN102766330A (en) * | 2012-07-12 | 2012-11-07 | 漯河科莱堡洁具配件有限公司 | Low-temperature-resistant ultra-toughness modified nylon alloy material and preparation method thereof |
| CN111004503A (en) * | 2019-12-29 | 2020-04-14 | 无锡殷达尼龙有限公司 | Formula of nylon hose material |
-
2020
- 2020-07-16 CN CN202010684165.0A patent/CN111849153A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1106652A1 (en) * | 1999-12-06 | 2001-06-13 | Hyundai Motor Company | Polyamide resin composition |
| CN102766330A (en) * | 2012-07-12 | 2012-11-07 | 漯河科莱堡洁具配件有限公司 | Low-temperature-resistant ultra-toughness modified nylon alloy material and preparation method thereof |
| CN111004503A (en) * | 2019-12-29 | 2020-04-14 | 无锡殷达尼龙有限公司 | Formula of nylon hose material |
Non-Patent Citations (1)
| Title |
|---|
| 周敏: "改性尼龙软管", 《黑龙江科技信息》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112430391A (en) * | 2020-11-23 | 2021-03-02 | 山东星达新材料有限公司 | Super-tough super-low temperature-resistant super-wear-resistant flexible nylon alloy material and preparation method thereof |
| CN114836026A (en) * | 2022-06-14 | 2022-08-02 | 安徽农业大学 | High-impact-toughness bio-based polyamide composite material, and preparation method and application thereof |
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