CN110564140A - High-performance antistatic filling reinforced polyamide composite material and preparation method thereof - Google Patents
High-performance antistatic filling reinforced polyamide composite material and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a high-performance antistatic filling reinforced polyamide composite material and a preparation method thereof, and the high-performance antistatic filling reinforced polyamide composite material is specifically composed of the following raw materials in parts by weight: 50-80 parts of polyamide resin, 5-30 parts of antistatic agent, 2-8 parts of compatilizer and 5-15 parts of surface-treated basalt fiber, wherein the surface-treated basalt fiber is a basalt fiber subjected to plasma surface activation treatment; compared with the prior art, the invention has the advantages that: the composite filling and reinforcing mode of fibers and fillers is adopted to realize a small amount of efficient antistatic effect. On one hand, the activated basalt fiber with high surface energy can effectively adsorb antistatic agent powder particles and promote the more uniform distribution of the antistatic agent powder particles in matrix resin; on the other hand, the fibers with one-dimensional orientation characteristics can effectively construct three-dimensional net-shaped paths for charge conduction, so that the effective using amount of the antistatic agent is greatly reduced to about 60 percent, and the surface resistivity and the volume resistivity of the material are still kept to be less than or equal to 108Level of. omega. cm.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a high-performance and antistatic filling reinforced polyamide composite material and a preparation method thereof.
Background
Polyamide (PA, also called nylon) is the largest polymer used in high-performance engineering plastics and has the widest application field. The polyamide material is generally known by the characteristics of high rigidity, high impact resistance, low creep, high heat resistance, chemical resistance and the like, and the excellent comprehensive performance advantage of the polyamide material enables the polyamide material to be used in key fields of automobiles and industrial electronic and electrical appliances, such as engine compartments, fuel systems, high and low voltage electric appliance shells, brackets and the like.
The functional improvement of polyamide is always the focus field of modification research, and the reason is that polar amide groups on a molecular chain can form good interaction with some polar functional fillers, and the filler molecules have strong adsorption force with matrix resin and are not easy to migrate, so that the polyamide composite material is endowed with a very stable modification effect. In recent years, with the gradual popularization of new energy regeneration process of automobiles, automobile power systems face a great challenge of converting traditional fuel oil power into electric power drive, and complicated electric power management determines that used materials have different conductive or insulating properties, so that the improvement of antistatic performance becomes a hot spot direction of current polyamide functional research.
the conventional antistatic improvement of polyamide is realized by adding a large amount of antistatic agent, for example, the antistatic polyamide resin described in CN107778478 is realized by adding a certain amount of dibasic acid containing sulfonate groups in the amide polymerization process, so that the particles of the antistatic agent can be ensured to have ideal distribution effect, and the material can be ensured to have ideal antistatic effect, but the modification process is complex and the influence of the antistatic agent on the polymerization reaction is difficult to control; CN106479166 adopts a relatively simple blending modification mode, and obtains a relatively good antistatic effect by adding functionalized graphene and auxiliary dispersing master batch, however, the use amount of graphene is very high (more than 16-24 parts), which results in greatly increased modification cost and brings a certain reduction on the rigidity and impact resistance of polyamide. From the above, as an outstanding representative of high-performance engineering plastics, an ideal antistatic polyamide material should combine two aspects of stable and efficient antistatic performance and excellent mechanical properties, which is a technical means lacking in the current technical scheme.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, provides a high-performance and antistatic filling reinforced polyamide composite material, and aims to solve the problems of difficult dispersion, large using amount, high cost, mechanical property loss and the like caused by singly adding antistatic agent powder particles in the conventional means.
The purpose of the invention is realized by the following technical scheme:
A high-performance, antistatic, filled reinforced polyamide composite characterized by: the feed comprises the following raw materials in parts by weight:
Wherein the basalt fiber subjected to surface treatment is a basalt fiber subjected to plasma surface activation treatment.
the preparation method of the basalt fiber subjected to surface treatment comprises the following steps: the preparation method of the basalt fiber subjected to surface treatment comprises the following steps: soaking the basalt fiber in a 30% dilute hydrochloric acid solution for 30-60 minutes to remove metal oxides and other inorganic impurities on the surface of the fiber, cleaning, filtering, transferring the fiber to a plasma gas generating device, activating the surface of the fiber by using plasma gas under the conditions of 65 ℃ and high sealing for 3-5 hours, placing the basalt fiber in a vacuum drying oven at 95 ℃ after the activation, vacuumizing and drying to 0.05-0.01MPa, and removing water contained on the surface of the fiber to obtain the basalt fiber subjected to surface activation.
Further, the polyamide resin is one or a mixture of more of PA6, PA66, PA46, PA610, PA1010, PA612 and PA 1212.
Furthermore, the antistatic agent is one or more of inorganic or organic compounds such as carbon black, metal oxide, quaternary ammonium salt, polyol fatty acid ester, borate, polyether block copolymer and the like.
Further, the compatilizer is one or more of maleic anhydride grafted polyolefin elastomer POE-MAH, glycidyl methacrylate grafted polyolefin elastomer POE-GMA, glycidyl methacrylate grafted ethylene-ethyl acetate copolymer EVA-GMA and the like. Further, the basalt fiber is a chopped strand mat of the basalt fiber, the fiber diameter is 10-13um, and the chopped length is 4.5 mm.
The second purpose of the invention is to provide a preparation method of the high-performance antistatic filling reinforced polyamide composite material, which comprises the following steps:
(1) weighing polyamide resin, an antistatic agent and a compatilizer according to the weight parts, and uniformly mixing to obtain a mixed raw material:
(2) Placing the dried mixed raw materials into a main feeding bin of a double-screw extruder which is tightly meshed and rotates in the same direction, and adding the dried mixed raw materials into a machine barrel of the extruder through a feeding screw; and placing the basalt fiber subjected to surface treatment in a side feeding bin of a screw rod of the extruder, and adding the basalt fiber into a machine barrel of the extruder through a feeding screw rod. The diameter of the screw extruder used was 36mm, the length-diameter ratio L/D was 44, and the temperatures of the zones from the feed port to the head outlet of the main barrel were set as follows: the high-performance antistatic filling reinforced polyamide composite material is obtained by the working procedures of melt extrusion, granulation, drying and the like at the temperature of 150 ℃, 210 ℃, 220 ℃, 235 ℃, 240 ℃, 230 ℃ and the rotating speed of a main engine of 250 revolutions per minute.
Compared with the prior art, the invention has the following beneficial effects:
1. Firstly, a conventional modification mode of melt blending extrusion is adopted, the selectivity of the components of the material formula is strong, a plurality of antistatic agents with different characteristics can be added to carry out a contrast test, and the modification process is mature, stable, efficient and low in cost.
2. More importantly, aiming at the key factor that the antistatic effect of the polymer material directly depends on the dispersion distribution effect of antistatic agent molecules, a composite filling and reinforcing mode of a fiber reinforcement body with high length-diameter ratio and antistatic agent powder particles is adopted, wherein, after the high-performance basalt chopped fiber is subjected to plasma surface activation treatment, the surface energy of the basalt chopped fiber is greatly enhanced, can form good intermolecular force with polar antistatic agent molecules and polyamide molecular chains, thus ensuring the uniform dispersion effect of the antistatic agent molecules, and the basalt fiber can form a three-dimensional space network structure with a certain structure in the matrix resin after melting and mixing, thereby establishing an effective path for charge conduction within the polyamide composite material, which is an excellent factor contributing to the improvement of its antistatic properties, the reduction of surface area and volume resistivity.
3. The high-performance antistatic polyamide composite material obtained by the technical scheme of the invention realizes a good antistatic effect (the surface and volume resistivity is less than or equal to 10) on the premise of 10-15% of the dosage of the antistatic agent8Ω ∑ cm), which is only about 50-60% of the amount of antistatic agent used in conventional solutions; more importantly, the negative effects of antistatic agent powder on the low strength and impact resistance of the material are effectively compensated by the compound use of the fiber reinforcement, the tensile strength of the material is reduced by 10-15% from the previous point to be improved by 20-30%, the maximum tensile strength is more than 100MPa, the bending modulus is greatly improved from 2500MPa to more than 5000MPa, the impact resistance strength is also improved to a certain degree in the same way, and the high-performance polyimide is stable in antistatic property and outstanding in mechanical propertyThe amine composite material is particularly suitable for the fields of three-way electric systems of new energy automobiles and parts of industrial high-voltage and low-voltage electronic appliances with special requirements.
Detailed Description
the invention is further illustrated by the following specific examples, which are intended to be illustrative only and not limiting.
The raw materials used in the embodiment of the invention are as follows:
Polyamide: PA6-2000, Henan Shenma Nylon chemical Co., Ltd., Ubbelohde viscometer test relative viscosity 2.0.
Antistatic agent-1: carbon black F300A, average particle diameter of 20-40nm, specific surface area of 700-900m2Kg, Tianjin Yibo Rui chemical Co., Ltd.
Antistatic agent-2: ethoxylated boric acid ester B-902, milk white particles, pH value of 5 +/-2.0, ash content of less than or equal to 10 percent, Qingdao four-dimensional chemical company Limited.
Antistatic agent-3: polyether Block Polyamide elastomer PEBAX MV2030, density 1.14g/cm3Melting point 200 ℃ from Arkema, France.
Compatibilizer-1: the grafting rate of the maleic anhydride grafted polyolefin elastomer POE-MAH, Jiangsu good easy compatilizer company Limited is 0.7 percent by chemical titration.
Compatibilizer-2: the POE-GMA is prepared by self-making glycidyl methacrylate grafted polyolefin elastomer POE-GMA, testing the grafting rate to be 0.85% by a chemical titration method, and grafting the POE elastomer in a molten state by initiating a GMA/styrene St mixture by a peroxide initiator through a double-screw extruder.
basalt fiber: BCS13-132, the fiber diameter is 13um, Jiangsu Tianlong continuous basalt fiber GmbH, and the chopped length is 4.5 mm.
And (3) product performance testing:
Tensile property: the test was carried out at a test rate of 5mm/min at normal temperature (23 ℃) after injection molding of a standard specimen in accordance with the specimen size specified in ISO 527-2.
bending property: according to the sample strip size specified in ISO178, a standard sample strip is injection-molded and then tested, the test span is 64mm, the test speed is 2mm/min, and the test is carried out at normal temperature (23 ℃).
Impact properties: according to the sample strip size specified by ISO179-1 standard, the test is carried out after the injection molding of a standard sample strip on a simply supported beam impact tester, the sample strip is unnotched, and the test is carried out at normal temperature (23 ℃).
Surface resistivity and volume resistivity test: a sample plate with the size of 355 multiplied by 100 multiplied by 3.2mm is injected according to the standard method of ISO3915 and is tested on an ST2255 high-resistance volume resistivity and surface resistivity tester, the loading voltage is 5000V, the loading time is 60s, and the surface resistivity and the volume resistivity of the sample plate are respectively tested.
Example 1
The polyamide resin, the antistatic agent and the compatilizer are weighed according to the data of example 1 shown in the table 1 and are uniformly mixed to obtain the mixed raw materials:
Placing the dried mixed raw materials into a main feeding bin of a double-screw extruder which is tightly meshed and rotates in the same direction, and adding the dried mixed raw materials into a machine barrel of the extruder through a feeding screw; and placing the basalt fiber subjected to surface treatment in a side feeding bin of a screw rod of the extruder, and adding the basalt fiber into a machine barrel of the extruder through a feeding screw rod. The diameter of the screw extruder used was 36mm, the length-diameter ratio L/D was 44, and the temperatures of the zones from the feed port to the head outlet of the main barrel were set as follows: the high-performance antistatic filling reinforced polyamide composite material is obtained by the working procedures of melt extrusion, granulation, drying and the like at the temperature of 150 ℃, 210 ℃, 220 ℃, 235 ℃, 240 ℃, 230 ℃ and the rotating speed of a main engine of 250 revolutions per minute.
TABLE 1 formulation Table (Unit: g) of high-performance, antistatic, filled, reinforced polyamide materials
Example 2
The polyamide resin, the antistatic agent and the compatilizer are weighed according to the data of example 2 shown in the table 1 and are uniformly mixed to obtain the mixed raw materials:
placing the dried mixed raw materials into a main feeding bin of a double-screw extruder which is tightly meshed and rotates in the same direction, and adding the dried mixed raw materials into a machine barrel of the extruder through a feeding screw; and placing the basalt fiber subjected to surface treatment in a side feeding bin of a screw rod of the extruder, and adding the basalt fiber into a machine barrel of the extruder through a feeding screw rod. The diameter of the screw extruder used was 36mm, the length-diameter ratio L/D was 44, and the temperatures of the zones from the feed port to the head outlet of the main barrel were set as follows: the high-performance antistatic filling reinforced polyamide composite material is obtained by the working procedures of melt extrusion, granulation, drying and the like at the temperature of 150 ℃, 210 ℃, 220 ℃, 235 ℃, 240 ℃, 230 ℃ and the rotating speed of a main engine of 250 revolutions per minute.
Example 3
the polyamide resin, the antistatic agent and the compatilizer are weighed according to the data of example 3 shown in the table 1 and are uniformly mixed to obtain the mixed raw materials:
placing the dried mixed raw materials into a main feeding bin of a double-screw extruder which is tightly meshed and rotates in the same direction, and adding the dried mixed raw materials into a machine barrel of the extruder through a feeding screw; and placing the basalt fiber subjected to surface treatment in a side feeding bin of a screw rod of the extruder, and adding the basalt fiber into a machine barrel of the extruder through a feeding screw rod. The diameter of the screw extruder used was 36mm, the length-diameter ratio L/D was 44, and the temperatures of the zones from the feed port to the head outlet of the main barrel were set as follows: the high-performance antistatic filling reinforced polyamide composite material is obtained by the working procedures of melt extrusion, granulation, drying and the like at the temperature of 150 ℃, 210 ℃, 220 ℃, 235 ℃, 240 ℃, 230 ℃ and the rotating speed of a main engine of 250 revolutions per minute.
example 4
the polyamide resin, the antistatic agent and the compatilizer are weighed according to the data of example 4 shown in the table 1 and are uniformly mixed to obtain the mixed raw materials:
Placing the dried mixed raw materials into a main feeding bin of a double-screw extruder which is tightly meshed and rotates in the same direction, and adding the dried mixed raw materials into a machine barrel of the extruder through a feeding screw; and placing the basalt fiber subjected to surface treatment in a side feeding bin of a screw rod of the extruder, and adding the basalt fiber into a machine barrel of the extruder through a feeding screw rod. The diameter of the screw extruder used was 36mm, the length-diameter ratio L/D was 44, and the temperatures of the zones from the feed port to the head outlet of the main barrel were set as follows: the high-performance antistatic filling reinforced polyamide composite material is obtained by the working procedures of melt extrusion, granulation, drying and the like at the temperature of 150 ℃, 210 ℃, 220 ℃, 235 ℃, 240 ℃, 230 ℃ and the rotating speed of a main engine of 250 revolutions per minute.
Example 5
The polyamide resin, the antistatic agent and the compatilizer are weighed according to the data of example 5 shown in the table 1 and are uniformly mixed to obtain the mixed raw materials:
Placing the dried mixed raw materials into a main feeding bin of a double-screw extruder which is tightly meshed and rotates in the same direction, and adding the dried mixed raw materials into a machine barrel of the extruder through a feeding screw; and placing the basalt fiber subjected to surface treatment in a side feeding bin of a screw rod of the extruder, and adding the basalt fiber into a machine barrel of the extruder through a feeding screw rod. The diameter of the screw extruder used was 36mm, the length-diameter ratio L/D was 44, and the temperatures of the zones from the feed port to the head outlet of the main barrel were set as follows: the high-performance antistatic filling reinforced polyamide composite material is obtained by the working procedures of melt extrusion, granulation, drying and the like at the temperature of 150 ℃, 210 ℃, 220 ℃, 235 ℃, 240 ℃, 230 ℃ and the rotating speed of a main engine of 250 revolutions per minute.
Comparative example 1
Weighing polyamide resin, antistatic agent and compatilizer according to the data of comparative example 1 shown in the table 1, and uniformly mixing to obtain mixed raw materials:
placing the dried mixed raw materials into a main feeding bin of a double-screw extruder which is tightly meshed and rotates in the same direction, adding the dried mixed raw materials into a machine barrel of the extruder through a feeding screw, wherein the diameter of the used screw extruder is 36mm, the length-diameter ratio L/D is 44, and the temperature of each subarea of the main machine barrel from a feeding port to a machine head outlet is set as follows: the high-performance antistatic filling reinforced polyamide composite material is obtained by the working procedures of melt extrusion, granulation, drying and the like at the temperature of 150 ℃, 210 ℃, 220 ℃, 235 ℃, 240 ℃, 230 ℃ and the rotating speed of a main engine of 250 revolutions per minute.
Comparative example 2
Weighing polyamide resin, antistatic agent and compatilizer according to the data of comparative example 2 shown in the table 1, and uniformly mixing to obtain mixed raw materials:
Placing the dried mixed raw materials into a main feeding bin of a double-screw extruder which is tightly meshed and rotates in the same direction, adding the dried mixed raw materials into a machine barrel of the extruder through a feeding screw, wherein the diameter of the used screw extruder is 36mm, the length-diameter ratio L/D is 44, and the temperature of each subarea of the main machine barrel from a feeding port to a machine head outlet is set as follows: the high-performance antistatic filling reinforced polyamide composite material is obtained by the working procedures of melt extrusion, granulation, drying and the like at the temperature of 150 ℃, 210 ℃, 220 ℃, 235 ℃, 240 ℃, 230 ℃ and the rotating speed of a main engine of 250 revolutions per minute.
TABLE 2 test results for high-performance, antistatic, filled, reinforced polyamide materials
As can be seen from the material test data of each example and comparative example in Table 2, the mechanical property and antistatic property of the polyamide composite material can be comprehensively improved by adding the basalt fiber reinforcement subjected to the surface activation treatment; comparing the data of examples 3 and 4 with those of comparative examples 1 and 2, it can be seen that the surface resistivity and volume resistivity of comparative examples 1 and 2 were only 10 even when the antistatic agent was added in a relatively high amount (18%)8-109Ω ≥ cm, which indicates that the dispersion profile of antistatic molecules in the material is not ideal, leading to the bottleneck for improved antistatic properties; the poor dispersion condition is obviously improved after the functional basalt fiber is added, the volume resistivity of the material is reduced by one order of magnitude under the same dosage (embodiment 3), and in the most ideal embodiment 4, the surface resistivity and the volume resistivity of the material reach 10 percent under the premise of 12 percent dosage of the antistatic agent by matching 10 percent of basalt fiber and the high-efficiency compatilizer with a specific structure7More importantly, the mechanical property data of comparative example 4 and comparative example 1 show that the composite material has rigidity indexes such as tensile strength, bending strength and modulus which are all improved by at least 40%, the tensile strength is improved from 64MPa to 104MPa, and the bending modulus is greatly improved from 2890 MPa to more than 5000MPa, which is the largest improvement range in the mechanical property indexes of the composite material. In addition, as can be seen from comparison with other examples (1, 2, 3), if the amount of the fiber and the antistatic agent is further increased on the basis of example 4 (example 5), although the antistatic property is more excellent, the loss of the mechanical property index is unavoidable, and if the amount of the fiber and the antistatic agent is decreased (examples 1, 2), the antistatic property and the mechanical property are also decreased, so that it is suggested that the proper amount of the basalt fiber and the antistatic agent is a necessary condition for establishing the internal charge conduction path of the polyamide composite material.
the high-performance antistatic filling reinforced polyamide composite material and the preparation method thereof effectively overcome the defects that only improvement of antistatic performance is focused in the traditional technical method, and loss of mechanical properties of the material cannot be avoided, the obtained material has outstanding comprehensive performance and good antistatic effect, can completely meet the design requirements of a novel polymer-based composite material with high rigidity, high impact resistance and good antistatic effect in a three-way system of a current new energy automobile, and must play a good role in promoting the innovation of a power system of the automobile industry.
Claims (7)
1. A high-performance, antistatic, filled reinforced polyamide composite characterized by: the feed comprises the following raw materials in parts by weight:
Wherein the basalt fiber subjected to surface treatment is a basalt fiber subjected to plasma surface activation treatment.
2. a high performance, antistatic filled reinforced polyamide composite as claimed in claim 1 wherein: the polyamide resin is one or a mixture of more of PA6, PA66, PA46, PA610, PA1010, PA612 and PA 1212.
3. A high performance, antistatic filled reinforced polyamide composite as claimed in claim 1 wherein: the antistatic agent is one or more of carbon black, metal oxide, quaternary ammonium salt, polyol fatty acid ester, boric acid ester and inorganic or organic compounds of polyether block copolymer.
4. A high performance, antistatic filled reinforced polyamide composite as claimed in claim 1 wherein: the compatilizer is one or more of maleic anhydride grafted polyolefin elastomer POE-MAH, glycidyl methacrylate grafted polyolefin elastomer POE-GMA and glycidyl methacrylate grafted ethylene-ethyl acetate copolymer EVA-GMA.
5. a high performance, antistatic filled reinforced polyamide composite as claimed in claim 1 wherein: the preparation method of the basalt fiber subjected to surface treatment comprises the following steps: soaking the basalt fiber in a 30% dilute hydrochloric acid solution for 30-60 minutes to remove metal oxides and other inorganic impurities on the surface of the fiber, cleaning, filtering, transferring the fiber to a plasma gas generating device, activating the surface of the fiber by using plasma gas under the conditions of 65 ℃ and high sealing for 3-5 hours, placing the basalt fiber in a vacuum drying oven at 95 ℃ after the activation, vacuumizing and drying to 0.05-0.01MPa, and removing water contained on the surface of the fiber to obtain the basalt fiber subjected to surface activation.
6. a high performance, antistatic filled reinforced polyamide composite as claimed in claim 5 wherein: the basalt fiber is a chopped strand mat of the basalt fiber, the fiber diameter is 10-13um, and the chopped length is 4.5 mm.
7. A process for the preparation of a high performance, antistatic filled reinforced polyamide composite as claimed in any one of claims 1 to 6, characterized in that it comprises the following steps:
(1) weighing polyamide resin, an antistatic agent and a compatilizer according to the weight parts, and uniformly mixing to obtain a mixed raw material:
(2) Placing the dried mixed raw materials into a main feeding bin of a double-screw extruder which is tightly meshed and rotates in the same direction, and adding the dried mixed raw materials into a machine barrel of the extruder through a feeding screw; and placing the basalt fiber subjected to surface treatment in a side feeding bin of a screw rod of the extruder, and adding the basalt fiber into a machine barrel of the extruder through a feeding screw rod. The diameter of the screw extruder used was 36mm, the length-diameter ratio L/D was 44, and the temperatures of the zones from the feed port to the head outlet of the main barrel were set as follows: the high-performance antistatic filling reinforced polyamide composite material is obtained by the working procedures of melt extrusion, granulation, drying and the like at the temperature of 150 ℃, 210 ℃, 220 ℃, 235 ℃, 240 ℃, 230 ℃ and the rotating speed of a main engine of 250 revolutions per minute.
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| CN111117220A (en) * | 2019-12-31 | 2020-05-08 | 会通新材料(上海)有限公司 | Polyamide composition with permanent static dissipation function and application thereof |
| CN111472067A (en) * | 2020-06-16 | 2020-07-31 | 广州红象科技有限公司 | Antistatic polymer composite fiber |
| CN112521747A (en) * | 2020-12-08 | 2021-03-19 | 安徽江淮汽车集团股份有限公司 | PA66 composite material and preparation method and application thereof |
| CN115612290A (en) * | 2022-11-01 | 2023-01-17 | 东北林业大学 | Low-temperature wear-resistant antistatic polyamide composite material and preparation method and application thereof |
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