CN112322031A - High-impact-strength PA6 composite material and preparation method thereof - Google Patents
High-impact-strength PA6 composite material and preparation method thereof Download PDFInfo
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/06—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials
- C08J5/08—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials glass fibres
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- C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
- C08J2377/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
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- C08J2451/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J2451/04—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to rubbers
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- C08J2477/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
- C08J2477/06—Polyamides derived from polyamines and polycarboxylic acids
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- C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
- C08J2483/04—Polysiloxanes
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
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- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
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- C08K7/14—Glass
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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Abstract
The invention discloses a high-impact reinforced polyamide PA6 composite material, which comprises the following components in parts by weight: the composite material is prepared by adding a maleic anhydride grafted EPDM toughening agent into a glass fiber reinforced polyamide PA6 material, so that the composite material has high impact property, and simultaneously adding semi-aromatic nylon PA6I/6T to play a role in reinforcing the glass fibers, wherein the prepared composite material has the characteristics of high impact property, high rigidity, high tensile strength, excellent weather resistance and low diffusion property, and is particularly suitable for automobile interior parts, such as door and window frame decorative strips, inner door buckle shells and other parts. The invention also discloses a preparation method of the high-impact reinforced polyamide PA6 composite material.
Description
Technical Field
The invention relates to the technical field of high polymer materials, and particularly relates to a high-impact reinforced polyamide PA6 composite material and a preparation method thereof.
Background
The polyamide is generally called nylon, is a general term for polymers containing amide group repeating units in a polymer macromolecular chain, is mainly obtained by polycondensation or self-polymerization of dibasic acid and diamine or amino acid lactam, and is the earliest developed and most used thermoplastic engineering plastic. Polyamide 6 has the advantages of high mechanical strength, high melting point, wear resistance, oil resistance and the like, and is widely used in the fields of automobiles, electromechanics, electronics, textiles, household appliances and the like.
The PA6 is easy to absorb water due to containing a large amount of polar groups, and has large shrinkage after molding, so that the impact resistance and the tensile property are required to be improved.
Disclosure of Invention
A first object of the present invention is to provide a high impact reinforced PA6 composite material that has the advantages of high impact resistance and high tensile strength.
The technical purpose of the invention is realized by the following technical scheme:
a high-impact reinforced polyamide PA6 composite material comprises the following components in parts by weight:
further setting: the toughening agent adopts one or more of maleic anhydride grafted EPDM, SEBS-g-MAH and POE-g-MAH.
Further setting: the antioxidant is one or more of antioxidant 1010, antioxidant 168, antioxidant 1076 and antioxidant 1098, and the ultraviolet absorber is one of UV-234 and UV-531.
Further setting: the lubricant is powdered silicone.
Further setting: the coupling agent is one or more of epoxy silane coupling agent, fluorine-containing silane coupling agent and diamino silane coupling agent.
Further setting: comprises the following components in parts by weight:
further setting: comprises the following components in parts by weight:
the glass fibers are added into the composite material and randomly exist in the form of fiber monofilaments, and each glass fiber plays a certain tensile and deformation resistant role when PA6 is stressed. The more the glass fiber content, the more uniform the dispersion of the filaments in the composite material, the greater the load, when the composite material is subjected to an external force, the force is transmitted to the glass fibers through the interface, and the glass fibers bear a part of the force, so that the glass fibers are broken or pulled out no matter whether the glass fibers are stretched or broken, and the better the glass fibers are bonded with the PA6, the greater the stress is required.
The silane coupling agent is a monomer silicon compound, wherein an ethoxy group (also called an inorganic end) at one end is firstly hydrolyzed to form silanol, and nascent silanol hydroxyl is very active and is easy to react with hydroxyl on the surface of the glass fiber to form firm chemical combination with the surface of the glass fiber; the amino group at the other end (also called organic end) can react with the carboxyl group on the PA6 molecule, thereby tightly combining the inorganic glass fiber and the organic resin. Meanwhile, the surface of the glass fiber is roughened after being treated by the silane coupling agent, and the glass fiber is firmly combined in the composite material.
The semi-aromatic nylon PA6I/6T contains a PA6T molecular chain segment component in a molecular chain, so that the material has the characteristics of high rigidity and high tensile strength and has a synergistic effect with glass fiber reinforcement; the semi-aromatic nylon PA6I/6T belongs to amorphous non-crystalline polyamide nylon materials, so that the composite material has good processability.
Two amino groups of the diamino silane coupling agent can be simultaneously combined with PA6 and PA6T, the semi-aromatic nylon PA6I/6T is better combined with PA6, and the diamino silane coupling agent contains free amino groups, so that the diamino silane coupling agent has high alkalinity and high reaction activity. And as the amino group increases, the bending strength of the composite material also increases correspondingly. Especially in the wet state, the increase is more pronounced. The epoxy silane coupling agent has a long alkylene chain and does not contain an ether-oxygen bond, so that the epoxy silane coupling agent has good water resistance and heat resistance. After the two silane coupling agents are mixed according to the proportion of 1:1, the amino group content is large, the reaction between the silane coupling agents and a PA6 matrix is quicker, and meanwhile, after an alkylene chain is mixed, the water resistance and the heat resistance are increased, so that a finished product is not easily influenced by the external environment, good adhesion between glass fiber and PA6 can be kept in different environments, the mechanical property is improved, and the service life is prolonged.
The silicone oil is used as a lubricant, so that the PA6 has better fluidity, but the problem of precipitation on the surface of PA6 can be caused, the precipitation on the surface of PA6 can be reduced after the solid silicone powder is adopted, and the fluidity of PA6 can be improved.
The ultraviolet absorbent UV-234 has low emittance, strong light absorption, good compatibility with PA6 and low volatility; and the thermal stability is good, and the thermal decomposition is avoided.
The maleic anhydride grafted EPDM has normal-temperature and low-temperature toughening effects on the glass fiber reinforced PA6 composite material, so that the material has the characteristics of normal-temperature and low-temperature high impact toughness;
the high-impact reinforced polyamide PA6 composite material has excellent weather resistance and low diffusion property, and has a long service life when being applied to automobile interior parts such as automobile door and window plate and window frame decorative strips, inner door buckle shells and the like.
The invention also aims to provide a preparation method of the high-impact reinforced polyamide PA6 composite material, which has the advantages of simple operation and high yield.
The technical purpose of the invention is realized by the following technical scheme:
a preparation method of a high-impact reinforced polyamide PA6 composite material comprises the following steps:
step 1: weighing the components of the composite material according to the proportion, and blending at a high speed of 250r/min for 5-10min at 100-;
step 2: and then melt-extruding through an extruder, pelletizing and cooling to obtain the high impact reinforced polyamide PA6 composite material.
Further setting: the double-screw extruder used in the second step is divided into 9 sections, the set temperatures are respectively 180-.
Detailed Description
Example 1: a high impact reinforced polyamide PA6 composite material comprises the following components by weight, unit (g)
The preparation method comprises the following steps:
step 1: weighing the components of the composite material according to the proportion, and blending at a high speed of 250r/min for 8min at 100-;
step 2: and then melt-extruding through an extruder, pelletizing and cooling to obtain the high impact reinforced polyamide PA6 composite material.
The double-screw extruder is divided into 9 sections, the set temperatures are respectively 180 DEG, 230 DEG, 250 DEG, and the screw rotation speed is 300 r/min.
Example 2: a high impact reinforced polyamide PA6 composite material comprises the following components by weight, unit (g)
The preparation method comprises the following steps:
step 1: weighing the components of the composite material according to the proportion, and blending at a high speed of 175r/min for 5 min;
step 2: and then melt-extruding through an extruder, pelletizing and cooling to obtain the high impact reinforced polyamide PA6 composite material.
The double-screw extruder is divided into 9 sections, the set temperature is respectively 180 DEG plus 230 ℃, 230 DEG plus 250 ℃, 250 DEG plus 270 ℃ and the screw rotating speed is 450 r/min.
Example 3: a high impact reinforced polyamide PA6 composite material comprises the following components by weight, unit (g)
The preparation method comprises the following steps:
step 1: weighing the components of the composite material according to the proportion, and blending at a high speed of 100r/min for 10 min;
step 2: and then melt-extruding through an extruder, pelletizing and cooling to obtain the high impact reinforced polyamide PA6 composite material.
The double-screw extruder is divided into 9 sections, the set temperatures are respectively 180 DEG, 230 DEG, 250 DEG, and the screw rotation speed is 400 r/min.
Example 4: a high impact reinforced polyamide PA6 composite material comprises the following components by weight, unit (g)
The preparation method comprises the following steps:
step 1: weighing the components of the composite material according to the proportion, and blending at a high speed of 225r/min for 10 min;
step 2: and then melt-extruding through an extruder, pelletizing and cooling to obtain the high impact reinforced polyamide PA6 composite material.
The double-screw extruder is divided into 9 sections, the set temperature is respectively 180 DEG plus 230 ℃, 230 DEG plus 250 ℃, 250 DEG plus 270 ℃ and the screw rotating speed is 500 r/min.
Example 5: a high impact reinforced polyamide PA6 composite material comprises the following components by weight, unit (g)
The preparation method comprises the following steps:
step 1: weighing the components of the composite material according to the proportion, and blending at a high speed of 125r/min for 8 min;
step 2: and then melt-extruding through an extruder, pelletizing and cooling to obtain the high impact reinforced polyamide PA6 composite material.
The double-screw extruder is divided into 9 sections, the set temperatures are respectively 180 DEG, 230 DEG, 250 DEG, and the screw rotation speed is 600 r/min.
Example 6: a high impact reinforced polyamide PA6 composite material comprises the following components by weight, unit (g)
The preparation method comprises the following steps:
step 1: weighing the components of the composite material according to the proportion, and blending at a high speed of 200r/min for 8 min;
step 2: and then melt-extruding through an extruder, pelletizing and cooling to obtain the high impact reinforced polyamide PA6 composite material.
The double-screw extruder is divided into 9 sections, the set temperatures are respectively 180 DEG, 230 DEG, 250 DEG, and the screw rotation speed is 550 r/min.
Example 7: a high impact reinforced polyamide PA6 composite material comprises the following components by weight, unit (g)
The preparation method comprises the following steps:
step 1: weighing the components of the composite material according to the proportion, and blending at a high speed of 200r/min for 8 min;
step 2: and then melt-extruding through an extruder, pelletizing and cooling to obtain the high impact reinforced polyamide PA6 composite material.
The double-screw extruder is divided into 9 sections, the set temperatures are respectively 180 DEG, 230 DEG, 250 DEG, and the screw rotation speed is 550 r/min.
Example 8: a high impact reinforced polyamide PA6 composite material comprises the following components by weight, unit (g)
The preparation method comprises the following steps:
step 1: weighing the components of the composite material according to the proportion, and blending at a high speed of 200r/min for 8 min;
step 2: and then melt-extruding through an extruder, pelletizing and cooling to obtain the high impact reinforced polyamide PA6 composite material.
The double-screw extruder is divided into 9 sections, the set temperatures are respectively 180 DEG, 230 DEG, 250 DEG, and the screw rotation speed is 550 r/min.
Comparative example 1: a high impact reinforced polyamide PA6 composite material comprises the following components by weight, unit (g)
The preparation method comprises the following steps:
step 1: weighing the components of the composite material according to the proportion, and blending at a high speed of 200r/min for 8 min;
step 2: and then melt-extruding through an extruder, pelletizing and cooling to obtain the high impact reinforced polyamide PA6 composite material.
The double-screw extruder is divided into 9 sections, the set temperatures are respectively 180 DEG, 230 DEG, 250 DEG, and the screw rotation speed is 550 r/min.
Comparative example 2: a high impact reinforced polyamide PA6 composite material comprises the following components by weight, unit (g)
The preparation method comprises the following steps:
step 1: weighing the components of the composite material according to the proportion, and blending at a high speed of 200r/min for 8 min;
step 2: and then melt-extruding through an extruder, pelletizing and cooling to obtain the high impact reinforced polyamide PA6 composite material.
The double-screw extruder is divided into 9 sections, the set temperatures are respectively 180 DEG, 230 DEG, 250 DEG, and the screw rotation speed is 550 r/min.
And (3) performance detection:
the granular materials obtained in examples 1 to 8 and comparative examples 1 to 2 were sampled and the melt index was determined according to the standard ISO 1133-1991; detecting the tensile strength and the bending strength on a universal mechanical testing machine; notched impact strength was measured according to standard GB/T1843-2008 and the results reported in Table 1 below.
Table 1 table of performance test results
As can be seen from the table above, the addition of PA6I/6T and maleic anhydride grafted EPDM better increases the mechanical properties of the material, so that the modified PA6 can meet the requirements of high impact occasions; meanwhile, the mixed bis-silane coupling agent is adopted, so that the PA6I/6T and the glass fiber are combined with the PA6 more firmly, and the mechanical property is better.
The above-described embodiments do not limit the scope of the present invention. Any modification, equivalent replacement, and improvement made within the spirit and principle of the above-described embodiments should be included in the protection scope of the technical solution.
Claims (9)
1. The high-impact reinforced polyamide PA6 composite material is characterized by comprising the following components in parts by weight:
2. the high impact reinforced polyamide PA6 composite material according to claim 1, wherein the toughening agent employs one or more of maleic anhydride grafted EPDM, SEBS-g-MAH, and POE-g-MAH.
3. The high impact reinforced polyamide PA6 composite material according to claim 2, wherein the antioxidant is one or more of an antioxidant 1010, an antioxidant 168, an antioxidant 1076 and an antioxidant 1098, and the ultraviolet absorber is one of UV-234 and UV-531.
4. The high impact reinforced polyamide PA6 composite material according to claim 3, wherein the lubricant is powdered silicone.
5. The high impact reinforced polyamide PA6 composite material according to claim 4, wherein the coupling agent is one or more of an epoxy type silane coupling agent, a fluorine-containing silane coupling agent and a diamino type silane coupling agent.
6. The high impact reinforced polyamide PA6 composite material according to claim 5, comprising the following components in parts by weight:
7. the high impact reinforced polyamide PA6 composite material according to claim 6, comprising the following components in parts by weight:
8. a preparation method of a high-impact reinforced polyamide PA6 composite material is characterized by comprising the following steps: the method comprises the following steps:
step 1: weighing the components of the composite material according to the proportion, and blending at a high speed of 250r/min for 5-10min at 100-;
step 2: and then melt-extruding through an extruder, pelletizing and cooling to obtain the high impact reinforced polyamide PA6 composite material.
9. The method for preparing the high impact reinforced polyamide PA6 composite material as claimed in claim 8, wherein the twin-screw extruder used in the second step is divided into 9 sections, and the set temperatures are respectively 180-.
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| CN202011109199.3A CN112322031A (en) | 2020-10-16 | 2020-10-16 | High-impact-strength PA6 composite material and preparation method thereof |
| CN202110087214.7A CN112662169A (en) | 2020-10-16 | 2021-01-22 | High-impact-strength PA6 composite material and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP7276731B1 (en) * | 2022-01-18 | 2023-05-18 | 東レ株式会社 | POLYAMIDE RESIN COMPOSITION, MOLDED PRODUCTS MOLDED THEREOF, AND PRODUCTION METHOD THEREOF |
| WO2023140043A1 (en) * | 2022-01-18 | 2023-07-27 | 東レ株式会社 | Polyamide resin composition, molded article obtained by molding same, and methods for producing those |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE112013003661T5 (en) * | 2012-07-26 | 2015-06-25 | Invista Technologies S.A.R.L. | Thermoplastic composition for use in high impact applications |
| CN104804416A (en) * | 2015-03-17 | 2015-07-29 | 南京利华工程塑料有限公司 | Colorful photoaging-resistant glass fiber reinforced polyamide and preparation method thereof |
| CN106883598A (en) * | 2015-12-15 | 2017-06-23 | 上海杰事杰新材料(集团)股份有限公司 | Semi-aromatic nylon fiber reinforced nylon composite material and its preparation method and application |
| CN106700535B (en) * | 2017-02-13 | 2019-02-15 | 上海跃贝新材料科技股份有限公司 | A kind of automobile-used structural member fiber glass reinforced polyamide 66 and semi-aromatic nylon composite and preparation method |
| CN111320866A (en) * | 2018-12-14 | 2020-06-23 | 株式会社日立制作所 | Polyamide composition and method for improving wear resistance of polyamide composition |
| CN109722014A (en) * | 2018-12-17 | 2019-05-07 | 会通新材料股份有限公司 | A kind of ultra-toughness low-temperature impact-resistant polyamide material and preparation method thereof |
| CN111748201A (en) * | 2020-07-28 | 2020-10-09 | 横店集团得邦工程塑料有限公司 | High-strength glass fiber reinforced PA6 composite material and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP7276731B1 (en) * | 2022-01-18 | 2023-05-18 | 東レ株式会社 | POLYAMIDE RESIN COMPOSITION, MOLDED PRODUCTS MOLDED THEREOF, AND PRODUCTION METHOD THEREOF |
| WO2023140043A1 (en) * | 2022-01-18 | 2023-07-27 | 東レ株式会社 | Polyamide resin composition, molded article obtained by molding same, and methods for producing those |
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