Biobased polyamide compositions and methods for their preparation, shaped articles made therefrom

Abstract

The present invention relates to a bio-based polyamide composition and a method for producing the same, a molded article produced from the same, wherein the bio-based polyamide composition is characterized by comprising, in 100 parts by mass of the total amount of the bio-based polyamide composition, 70 to 95 parts by mass of a bio-based polyamide, and 1 to 15 parts by mass of a naturally derived reinforcing material, and the molded article produced from the same is excellent in wear resistance, self-lubricating property, and molding processability.

Description

Technical Field

[0001] This invention relates to bio-based polyamide compositions, methods for their preparation, and molded articles made therefrom. Background Technology

[0002] Polyamide resin (commonly known as nylon) possesses excellent properties such as high mechanical strength, heat resistance, and chemical resistance, and is widely used in automobiles, industrial components, and household appliances. As a common solution for friction surfaces, polyamide composites are frequently used in combination with lubricating oils and greases in industry. However, long-term use requires external lubricating oil and grease replenishment devices, increasing production and maintenance costs.

[0003] To address this problem, researchers have developed self-lubricating polyamide composites. For example, Patent Document 1 (CN115785659A) discloses a long-fiber reinforced wear-resistant self-lubricating bio-based polyamide composite and its preparation method. This composite material uses continuous long fibers to reinforce bio-based polyamide, adds wear-resistant and self-lubricating additives, and employs a double-melt pool impregnation process, solving the problems of poor wetting effect and inability to improve mechanical properties, while simultaneously improving the wear-resistant and self-lubricating properties of the material. However, in the preparation of the aforementioned fiber-reinforced polyamide composite, the double-melt pool impregnation method requires sophisticated equipment, and the fibers need to undergo surface pretreatment with a silane coupling agent, making the preparation process cumbersome. Furthermore, although the obtained composite material has high strength, its processability is somewhat lacking. In addition, in micro-injection molding, the fiber composite material itself has defects such as easy fiber floating, and the anisotropy of the fiber material itself leads to poor uniformity.

[0004] In addition, Patent Document 2 (CN113004687A) relates to a three-dimensional carbon felt lubricating reinforcement modified MC nylon composite material. Although a certain degree of lubrication is achieved with the help of new reinforcing materials, the wear resistance is not sufficient. Furthermore, due to the use of high-priced materials such as graphene oxide, its industrial prospects are limited.

[0005] On the other hand, in addition to the various requirements for the performance of polyamide materials, with the increasing demand for carbon neutrality, traditional polyamide materials synthesized from fossil resources are gradually failing to meet the environmental protection and low-carbon requirements in terms of reducing carbon footprint. With the development of bio-based polyamides, such as the development and utilization of bio-based polyamide composite materials in Patent Document 1, it is becoming important.

[0006] Through extensive research in this field, the inventors of this invention have discovered that in numerous applications of polyamide composites with friction surfaces, materials possessing both excellent mechanical strength (such as wear resistance) and self-lubricating properties are required. Existing technologies often prioritize only one aspect, and further, the resulting composition must exhibit good processability. Furthermore, for industrial applications, the material preparation process must be simple, fully utilizing existing production equipment and enabling long-term, stable, large-scale production. Summary of the Invention

[0007] To address the technical challenges existing in the current technology, the inventors of this invention have devoted themselves to research and discovered that by including a bio-based polyamide composition containing bio-based polyamide and naturally sourced reinforcing materials in a specific ratio, a polyamide composite material with good wear resistance and self-lubrication can be provided while reducing the carbon footprint, and further, it has good molding and processability.

[0008] Specifically, the main points of this invention are as follows.

[0009] <1> A bio-based polyamide composition, characterized in that, in 100 parts by weight of the total amount of the bio-based polyamide composition, it comprises: 70 to 95 parts by weight of bio-based polyamide and 1 to 30 parts by weight of naturally derived reinforcing material.

[0010] <2> .according to <1> The bio-based polyamide composition wherein the naturally sourced reinforcing material is a plant-derived reinforcing material.

[0011] <3> .according to <2> The bio-based polyamide composition wherein the plant-derived reinforcing material is a lignocellulose material.

[0012] <4> .according to <3> The bio-based polyamide composition wherein the lignocellulosic material is alkaline lignin and / or carboxymethyl cellulose.

[0013] <6> .according to <1> The bio-based polyamide composition wherein the naturally sourced reinforcing material is a layered mineral.

[0014] <7> .according to <6> The bio-based polyamide composition wherein the layered mineral is at least one selected from nano-montmorillonite, bentonite, kaolinite, and halloysite.

[0015] <8> .according to <1> The bio-based polyamide composition wherein the bio-based polyamide is at least one selected from biologically derived PA11, PA1010, PA46, PA56, PA610, PA10T, and PA1012.

[0016] <9> .according to <1> The bio-based polyamide composition comprises: 70-95 parts by weight of bio-based polyamide and 5-10 parts by weight of a naturally derived reinforcing material, wherein the naturally derived reinforcing material is a plant-derived reinforcing material.

[0017] <10> .according to <1> The bio-based polyamide composition comprises: 70-95 parts by weight of bio-based polyamide and 1-5 parts by weight of a naturally sourced reinforcing material, wherein the naturally sourced reinforcing material is a layered mineral.

[0018] <11> .according to <1> The bio-based polyamide composition further comprises 1 to 15 parts by weight of a lubricant in 100 parts by weight of the total amount of the bio-based polyamide composition.

[0019] <12> .according to <11> The bio-based polyamide composition wherein the lubricant is a wax.

[0020] <13> .according to <12> The bio-based polyamide composition wherein the lubricant is at least one selected from paraffin wax, beeswax, and polyolefin wax.

[0021] <14> A bio-based polyamide composition, characterized in that, in 100 parts by weight of the total amount of the bio-based polyamide composition, it comprises: 70-95 parts by weight of bio-based polyamide, 3-10 parts by weight of alkaline lignin and / or carboxymethyl cellulose, and 3-10 parts by weight of paraffin and / or beeswax.

[0022] <15> A bio-based polyamide composition, characterized in that, in 100 parts by weight of the total amount of the bio-based polyamide composition, it comprises: 70-95 parts by weight of bio-based polyamide, 2-5 parts by weight of nano-montmorillonite, and 3-10 parts by weight of paraffin and / or beeswax.

[0023] <16> .according to <1> ~ <15> In any one of the bio-based polyamide compositions, the total weight of the bio-based polyamide, the naturally derived reinforcing material, and the optional lubricant is 95 parts by weight or more in 100 parts by weight of the total bio-based polyamide composition.

[0024] In another embodiment, the present invention relates to a method for preparing the above-described bio-based polyamide composition.

[0025] <17> A method for preparing a bio-based polyamide composition, which is... <1> ~ <16> The method for preparing the bio-based polyamide composition according to any one of the following is characterized by comprising mixing the bio-based polyamide, the naturally sourced reinforcing material and the optional lubricant, and melting them in a temperature range of 240 to 320°C.

[0026] The present invention further relates to injection molding materials prepared from the above-described polyamide composition and self-lubricating parts formed by injection molding.

[0027] <18> A molded article, as claimed in the claims <1> ~ <16> The bio-based polyamide composition described in any one of the above statements is made.

[0028] <19> According to the claims <18> The molded article, as claimed in the claims <1> ~ <16> The bio-based polyamide composition described in any one of the above examples is injection molded.

[0029] <20> According to the claims <18> or <19> The molded article is a self-lubricating component.

[0030] The technical effects of the bio-based polyamide composition of the present invention include at least the following:

[0031] (1) In terms of material properties, it can improve both wear resistance and self-lubrication in a balanced way, has good molding processability, and further has good compatibility between components, resulting in stable and uniform material. Using the bio-based polyamide composition of the present invention, in conventional injection molding processes, especially when there are micro-parts in the mold, it can effectively avoid appearance defects caused by the floating of fiber materials in existing polyamide composite materials, or injection molding defects such as underfilling and voids caused by unstable composition properties.

[0032] (2) Regarding environmental protection in the production environment, while possessing the aforementioned excellent properties, this invention employs bio-based polyamides and naturally sourced reinforcing materials, effectively reducing carbon emissions. Compared to existing fossil-based polyamide composites, it can reduce the carbon footprint by more than 50%. The bio-based polyamide composition of this invention avoids dust pollution and biological damage by not using reinforcing fibers such as glass fibers, thus reducing environmental pollution during production and use. Furthermore, due to the excellent degradability of bio-based polyamides, waste pollution is also reduced.

[0033] Therefore, the bio-based polyamide composition of the present invention meets the environmental protection requirements of the market from multiple perspectives, including low carbon emissions, low pollution, and biodegradability.

[0034] (3) In terms of industrial applications, the bio-based polyamide composition of the present invention not only uses industrially readily available raw materials, but also can be prepared using existing mixing, melting, and granulation equipment without modification, through conventional industrial processes such as mixing and melting. Furthermore, self-lubricating polyamide resin products with good appearance and stable performance can be obtained through conventional injection molding processes. Therefore, it is very suitable for large-scale industrial applications.

[0035] (4) In terms of actual use of the product, the components formed by the composition of the present invention do not require the installation of an external lubrication mechanism during use, and do not require maintenance personnel to perform special lubrication operations during the product's life cycle. Therefore, the corresponding manufacturing and maintenance costs are reduced, and the carbon footprint generated by the product's use and other related activities is reduced.

[0036] In summary, the bio-based polyamide composition and its preparation method of the present invention, and the molded articles made therefrom, can provide highly reliable and low-maintenance components for various friction surfaces requiring self-lubrication, including but not limited to: components such as gears, bearings, sliders, and guide rails that require low friction and high wear resistance, reducing the use of lubricating oil and lowering maintenance costs; applications in car window regulators, seat adjusters, engine components, etc., providing a long-lasting lubrication effect and improving the life and performance of parts; applications in office equipment such as printers and copiers, for gears and guide rails, ensuring smooth operation of the equipment; applications in conveying systems and packaging machinery, as they do not require external lubricants, reducing the risk of contamination and meeting hygiene standards; and applications in sliding doors and windows, furniture slides, etc., providing a quiet and smooth user experience, etc. Detailed Implementation

[0037] One embodiment of the present invention relates to a bio-based polyamide composition, comprising, in 100 parts by weight of the total amount of the bio-based polyamide composition, 70 to 95 parts by weight of bio-based polyamide and 1 to 15 parts by weight of naturally derived reinforcing material.

[0038] <Bio-based polyamide>

[0039] Bio-based polyamides refer to polyamides whose raw materials are partially or wholly derived from renewable biological resources. Typically, biomass is converted into monomers, which are then polymerized to form polyamides. Bio-based polyamides possess similar high strength and good abrasion resistance to regular polyamides, while reducing dependence on fossil fuels and contributing to lower greenhouse gas emissions and an overall carbon footprint.

[0040] The bio-based polyamide in this invention is not particularly limited, as long as at least part of the raw materials are derived from biological sources. From the perspective of reducing carbon footprint, it is preferred that more than 30% of the raw materials are derived from biological sources, or that the renewable carbon content is more than 30%. For example, monomers derived from biological sources include adipic acid, sebacic acid, and aminoundecanoic acid, as well as 1,5-pentanediamine, etc. These biological sources include vegetable oils, fibers, starch, microbial fermentation, etc.

[0041] In one embodiment, the bio-based polyamide of the present invention is at least one selected from biologically derived PA11, PA1010, PA46, PA56, PA610, PA10T, and PA1012. In one embodiment, from an industrial application perspective, at least one selected from biologically derived PA11, PA56, and PA610 is preferred.

[0042] Because bio-based polyamides use biologically derived monomers, and these monomers themselves have structures identical to their corresponding fossil-derived counterparts, it is generally believed that the physicochemical properties of bio-based polyamides are similar to those of polyamides. However, the inventors have surprisingly discovered in their research that, in the bio-based polyamide compositions of this invention, using bio-based polyamides yields better performance compared to fossil-derived polyamides. The principle behind achieving these technical effects is not yet clear, but the inventors, through long-term research, particularly through extensive trial and error with numerous reinforcing materials, have hypothesized the following possible mechanism.

[0043] In the bio-based polyamide compositions of this invention, the bio-based polyamides and fossil-derived polyamides exhibit similar tribological properties, primarily because both contain amide groups (-CONH-) in their molecular structures. These polar groups, through hydrogen bonding, dominate the surface properties and wear resistance of the materials. Furthermore, the crystallinity and amorphous region ratio of the two polyamides tend to balance their effects on hardness and toughness during friction, while differences in hygroscopicity have limited impact on short-term tribological performance. Although the long carbon chains of bio-based polyamides impart better flexibility, and the high polarity of fossil-based polyamides results in higher rigidity, these properties balance each other during friction, leading to similar overall tribological performance of the polyamide materials. However, in specific formulations of the compositions of this invention, the longer carbon chains and lower polarity of the bio-based polyamides result in better compatibility with plant-derived or natural layered mineral-derived reinforcing materials, thereby promoting uniform dispersion of the reinforcing materials. Moreover, the polar groups in the specific reinforcing materials interact with the long carbon chain molecules of the bio-based polyamides through hydrogen bonding or other physicochemical mechanisms, forming a more stable composite material and improving the coefficient of friction. In contrast, when used in the specific compositions of this invention, the shorter carbon chains and higher polarity of fossil-based polyamides result in poor compatibility with the specific reinforcing materials of this invention, leading to poor dispersibility and inferior tribological properties compared to bio-based polyamides. Furthermore, the self-lubricating properties of plant-derived or natural layered mineral-derived reinforcing materials, combined with the structural advantages of bio-based polyamides, further reduce friction and wear, improving the tribological performance of the material.

[0044] In the bio-based polyamide composition of the present invention, bio-based polyamide is the main component. In 100 parts by mass of the total bio-based polyamide composition, the content of bio-based polyamide is 50 parts by mass or more, preferably 60 to 98 parts by mass, and more preferably 70 to 95 parts by mass, which can fully obtain the combined effect of bio-based polyamide and other components.

[0045] <Naturally derived reinforcing materials: Plant-derived reinforcing materials>

[0046] In one embodiment of the present invention, the aforementioned naturally sourced reinforcing material is a plant-derived reinforcing material. By using plant-derived reinforcing materials, good mechanical properties can be provided, along with renewability and environmental friendliness. Plant-derived materials include, but are not limited to, plant fibers such as cotton and linen fibers, silicon-containing materials such as rice husk ash, starch-based reinforcing materials, and lignocellulose-based materials.

[0047] From the perspective of better achieving the technical effects of this invention, lignocellulose materials are preferred. In this invention, lignocellulose materials mainly refer to components such as cellulose, hemicellulose, and lignin, and their derivatives, which participate in the formation of plant cell walls. These components are widely available and have stable properties. From the perspective of improving the wear resistance and processability of the material, and increasing lubrication, lignocellulose materials that have been further functionalized are preferred, including basic lignin, hydroxylated cellulose, carboxylated cellulose, etc., with basic lignin and carboxymethyl cellulose being more preferred.

[0048] The reason why the above-mentioned reinforcing materials of the present invention can achieve better technical effects is speculated to be that these reinforcing materials have polar functional groups such as hydroxyl and carboxyl groups on their surface, which have good affinity with bio-based polyamides. In addition, they can form three-dimensional network structures with bio-based polyamides through hydrogen bonds, etc. These network structures provide space for good dispersion and distribution of lubricating agents, and avoid the leakage of lubricating agents.

[0049] Furthermore, compared to fiber materials such as synthetic fibers or natural fibers, the reinforcing material of the present invention avoids the anisotropy of long fibers at the microscopic level, that is, avoids the difference in mechanical strength between the fiber direction and the direction perpendicular to the fiber direction, and can provide a uniform and stable material structure at the microscopic scale, thus contributing to the overall improvement of wear resistance and lubricity.

[0050] Of 100 parts by weight of the total bio-based polyamide composition, 1 to 30 parts by weight of plant-derived reinforcing material may be included. Further, from the perspective of fully obtaining the effects of the present invention, it is preferable to include 3 to 20 parts by weight of plant-derived reinforcing material, and more preferably 3 to 10 parts by weight of plant-derived reinforcing material.

[0051] <Naturally derived reinforcing materials: layered minerals>

[0052] In one embodiment of the present invention, the aforementioned naturally sourced reinforcing material is a naturally sourced layered mineral material. In the compositions of the present invention, using layered mineral materials as reinforcing materials can achieve good mechanical properties and reduce the carbon footprint. These layered mineral materials can be common layered silicates and other inorganic minerals in the art, including but not limited to montmorillonite, bentonite, kaolinite, halloysite, mica, and layered talc.

[0053] From the perspective of better achieving the technical effects of the present invention, the layered minerals in the present invention are preferably selected from at least one of nano-montmorillonite, bentonite, kaolinite, and halloysite, and more preferably nano-montmorillonite. These reinforcing materials have good affinity with polyamides, and the mechanism by which they can obtain excellent reinforcing and lubricating effects in the present invention is speculated as follows.

[0054] Because the aforementioned reinforcing material has a nanoscale layered structure, polymer molecules, water, or other components can be inserted between the layers. In this invention, bio-based polyamide can be stably inserted between the layers, and its hydrophilicity, combined with that of layered mineral silicates, forms a stable reinforcing structure. Furthermore, after adding a lubricating agent, the lubricating agent can also be stably present in the aforementioned reinforcing structure, resulting in better technical effects.

[0055] The total amount of 100 parts by weight of the bio-based polyamide composition may include 1 to 30 parts by weight of layered minerals. Further, from the viewpoint of fully obtaining the effects of the present invention, it is preferable to include 1 to 15 parts by weight of layered minerals, and more preferably 1 to 5 parts by weight of layered minerals.

[0056] Lubricating additives

[0057] In this invention, the bio-based polyamide material itself can impart good self-lubricating properties to the composition. From the perspective of further obtaining the self-lubricating effect, it may optionally contain a lubricating agent.

[0058] The lubricating agent can be any lubricating component commonly added to polyamides in the art, including but not limited to fluoropolymers such as polytetrafluoroethylene, aromatic polyamides such as aramid, liquid lubricants such as silicone oil, inorganic lubricants such as graphite, and wax-based lubricating agents. From the perspective of better achieving the technical effects of the present invention, it is preferable to include waxes as lubricating agents, as they are widely available, have stable performance, and have good compatibility with the composition components of the present invention.

[0059] Examples of the aforementioned waxes include, but are not limited to, petroleum waxes and natural waxes. Additionally, synthetic waxes prepared by refining or chemically processing various waxes may also be used. These waxes can be used individually or in combination of two or more. Examples of petroleum waxes include paraffin wax and microcrystalline wax, petroleum-derived polyolefin waxes, etc. Any natural wax derived from resources other than petroleum can be used. Examples of natural waxes include plant waxes such as candelilla wax, carnauba wax, jasmine wax, rice wax, and jojoba wax; animal waxes such as beeswax, lanolin, and whale wax; mineral waxes such as ceresin, pure ceresin, and petrolatum; and refined products of these waxes. Preferably, at least one of paraffin wax, beeswax, and polyolefin waxes may be used, more preferably paraffin wax and / or beeswax.

[0060] When the content of lubricant is present, 1 to 15 parts by weight of lubricant may be included in 100 parts by weight of the total amount of bio-based polyamide composition, more preferably 3 to 15 parts by weight, and even more preferably 3 to 12 parts by weight.

[0061] <Other Additives>

[0062] Within the scope of not affecting the technical effect of the present invention, in addition to bio-based polyamide, naturally sourced reinforcing materials and optional lubricating agents, it may also contain other additives that may be contained in polyamide compositions, such as other reinforcing components, viscosity modifiers, molding and processing aids, colorants, antistatic agents, mildew and antifouling agents, ultraviolet absorbers, etc.

[0063] From the perspective of better achieving the effects of the invention, in 100 parts by weight of the total amount of the bio-based polyamide composition, the total amount of the above-mentioned additives is 10 parts by weight or less, more preferably 5 parts by weight or less, and even more preferably 3 parts by weight or less. That is, in 100 parts by weight of the bio-based polyamide composition, the total weight of the bio-based polyamide, the naturally derived reinforcing material, and the optional lubricant is 90 parts by weight or more, preferably 95 parts by weight or more, more preferably 97 parts by weight or more, and even more preferably 99 parts by weight or more.

[0064] In one embodiment of the present invention, the bio-based polyamide composition does not contain fiber reinforcing materials, or the content of fiber reinforcing materials is less than 0.5 parts by weight. The fiber reinforcing materials referred to here are filamentous reinforcing materials that are commonly used in the industry for polyamides, such as glass fiber, carbon fiber, basalt fiber, natural fibers like cotton and linen, and synthetic fibers like aramid.

[0065] The above describes specific embodiments of the bio-based polyamide composition of the present invention. Preferred embodiments of the present invention may include, for example:

[0066] A bio-based polyamide composition, characterized in that, in 100 parts by weight of the total bio-based polyamide composition, it comprises: 70-95 parts by weight of bio-based polyamide, 5-10 parts by weight of alkaline lignin and / or carboxymethyl cellulose, and 3-10 parts by weight of paraffin and / or beeswax.

[0067] A bio-based polyamide composition, characterized in that, in 100 parts by weight of the total amount of the bio-based polyamide composition, it comprises: 70-95 parts by weight of bio-based polyamide, 2-5 parts by weight of nano-montmorillonite, and 3-10 parts by weight of paraffin and / or beeswax.

[0068] <Preparation Method of Bio-based Polyamide Composition>

[0069] The present invention also relates to a method for preparing a bio-based polyamide composition, which is the method for preparing the above-mentioned bio-based polyamide composition, characterized in that it includes mixing bio-based polyamide, naturally sourced reinforcing materials and optional lubricants, and melting them in a temperature range of 240 to 320°C.

[0070] The above mixing process is not particularly limited as long as the raw material components of the composition are fully mixed, and there are no restrictions on the order or method of adding materials.

[0071] The melting process can utilize conventional equipment and procedures for melting polyamide compositions, such as a twin-screw extruder, with zone temperatures set to gradually increase from zone one. The melted bio-based polyamide composition can then be granulated and cooled using conventional granulation processes.

[0072] <Molded Products>

[0073] The present invention also relates to a molded article made from the above-described bio-based polyamide composition.

[0074] The molded article can be formed using methods known in the art, including but not limited to extrusion molding, calendering, blow molding, and injection molding. From the perspective of better demonstrating the technical effects of the present invention, injection molding is preferred. Using the bio-based polyamide composition of the present invention, in conventional injection molding processes, especially when there are micro-parts in the mold, it can effectively avoid appearance defects caused by the floating of fiber materials in existing polyamide composite materials, or injection molding defects such as underfilling and voids caused by the instability of the composition properties.

[0075] The molded articles of the present invention can be used for various components requiring high reliability and low maintenance, preferably self-lubricating components, such as gears, bearings, sliders, guide rails and other components requiring low friction and high wear resistance.

[0076] Example

[0077] The present invention will be further described in detail below with reference to embodiments and comparative examples, but the present invention is not limited to these embodiments.

[0078] The performance of the bio-based polyamide compositions in the examples was evaluated using the following methods:

[0079] <Coefficient of friction>

[0080] The compositions from the examples and comparative examples were injection molded into specimens measuring 30mm*7mm*6mm, and their coefficients of friction were determined according to GB / T3960-2016. The applied pressure was 0.97MPa, the friction speed was 1.75m / s, the test duration was 4 hours, and the friction pair material used was Q235B carbon steel.

[0081] <Volume Wear Rate>

[0082] While measuring the friction coefficient, the volumetric wear rate was also measured and calculated according to GB / T3960-2016.

[0083] <Friction Surface Temperature>

[0084] In the above friction and wear test, an infrared thermometer was used to measure the temperature of the friction contact surface, and the highest temperature measured during the test was selected as the friction surface temperature.

[0085] <Appearance>

[0086] Visually inspect the injection-molded samples used for friction and wear testing, and evaluate whether the sample appearance is good. If there are appearance defects such as injection defects or fiber floating, it is marked as Δ, and if there are no appearance defects, it is marked as ○.

[0087] The main raw materials involved in the examples and comparative examples are as follows.

[0088] Bio-based polyamide 56 Kaisai Biotechnology Co., Ltd.

[0089] DuPont Polyamide 66

[0090] Evonik Bio-based Polyamide 610

[0091] Arkema Bio-based Polyamide 11

[0092] Alkaline lignin Wuhan Kemike Biomedical Technology Co., Ltd.

[0093] Carboxymethyl cellulose Nanjing Songguan Biotechnology Co., Ltd.

[0094] Taishan Glass Fiber Co., Ltd.

[0095] KH550 Silane Coupling Agent, Anhui Sibao Organosilicon New Materials Co., Ltd.

[0096] Paraffin Qingdao Bonnie New Materials Co., Ltd.

[0097] Hebei Runze Wax Industry

[0098] Nano-montmorillonite Lingshou County Yuer Environmental Protection Technology Co., Ltd.

[0099] Kaolin Guangdong Yongfeng Chemical Co., Ltd.

[0100] [Example 1, Comparative Examples 1-3]

[0101] Polyamide, reinforcing material, and paraffin were added to a high-speed mixer and mixed for 4 hours according to the proportions shown in Table 1 to obtain a mixture. In the examples and comparative examples, "parts" refers to parts by weight.

[0102] The mixture was placed in a twin-screw extruder, and the screw speed was set to 400 rpm. The temperatures of the first zone of the twin-screw extruder were set to 280°C, the second zone to 285°C, the third zone to 290°C, the fourth zone to 295°C, and the fifth zone to 300°C, to obtain the self-lubricating material of this embodiment.

[0103] The obtained self-lubricating material was molded into a sample for friction and wear testing. Its appearance was observed, and its coefficient of friction, volumetric wear rate, and friction surface temperature were evaluated.

[0104] Table 1

[0105]

[0106] *The alkali-free glass fiber is treated with silane coupling agent KH550.

[0107] The above results indicate that the bio-based polyamide composition of the present invention, which simultaneously contains bio-based polyamide PA56 and plant-derived reinforcing materials, exhibits excellent overall performance.

[0108] [Examples 2-4, Comparative Examples 4-5]

[0109] Except for the proportions shown in Table 2, the method of Example 1 is implemented.

[0110] Table 2

[0111]

[0112] The above results indicate that the bio-based polyamide composition of the present invention, containing bio-based polyamide PA56 and plant-derived reinforcing materials in a specific ratio, exhibits excellent overall performance.

[0113] [Examples 5-7, Comparative Example 6]

[0114] Except for the ingredients and proportions shown in Table 3, the method of Example 1 was carried out.

[0115] Table 3

[0116]

[0117] The above results indicate that the performance of the bio-based polyamide composition of the present invention can be improved by containing a lubricant in a specific proportion, but an excessive increase in the lubricant content will not achieve the corresponding lubrication effect and will greatly affect the lubricity.

[0118] [Examples 8-11]

[0119] Except for the ingredients and proportions shown in Table 4, the method of Example 1 was carried out.

[0120] Table 4

[0121]

[0122] The above results indicate that the bio-based polyamide composition of the present invention, containing bio-based polyamide, plant-derived reinforcing materials, and lubricating agents, exhibits excellent overall performance.

[0123] [Examples 12-17]

[0124] Except for the proportions shown in Table 5, the method of Example 1 is implemented.

[0125] Table 5

[0126]

[0127] The above results indicate that the bio-based polyamide composition of the present invention, containing bio-based polyamide and reinforcing materials derived from natural minerals in a specific ratio, exhibits excellent overall performance.

[0128] The above results indicate that the bio-based polyamide composition of the present invention can improve wear resistance and self-lubrication in a balanced manner, has good injection molding processability, simplifies further manufacturing processes, and has low pollution and low carbon footprint, thus showing good prospects for industrial application.

Claims

1. A bio-based polyamide composition, characterized in that, The total amount of 100 parts by weight of the bio-based polyamide composition includes: 70 to 95 parts by weight of bio-based polyamide and 1 to 15 parts by weight of naturally derived reinforcing material.

2. The bio-based polyamide composition according to claim 1, wherein, The natural-source reinforcing material is a plant-derived reinforcing material.

3. The bio-based polyamide composition according to claim 2, wherein, The plant-derived reinforcing material is a lignocellulose material.

4. The bio-based polyamide composition according to claim 3, wherein, The lignocellulose material is alkaline lignin and / or carboxymethyl cellulose.

5. The bio-based polyamide composition according to claim 1, wherein, The naturally sourced reinforcing material is a layered mineral.

6. The bio-based polyamide composition according to claim 5, wherein, The layered mineral is selected from at least one of nano-montmorillonite, bentonite, kaolinite, and halloysite.

7. The bio-based polyamide composition according to claim 1, wherein, The bio-based polyamide is selected from at least one of the following biologically derived PA11, PA1010, PA46, PA56, PA610, PA10T, and PA1012.

8. The bio-based polyamide composition according to claim 1, wherein, Contains: 70-95 parts by weight of bio-based polyamide, and 3-10 parts by weight of plant-derived reinforcing material, or, It contains: 70 to 95 parts by weight of bio-based polyamide and 1 to 5 parts by weight of layered minerals.

9. The bio-based polyamide composition according to claim 1, wherein, The total amount of 100 parts by weight of the bio-based polyamide composition also includes 1 to 15 parts by weight of a lubricant.

10. The bio-based polyamide composition according to claim 9, wherein, The lubricant is a wax.

11. The bio-based polyamide composition according to claim 9, wherein, The lubricant is selected from at least one of paraffin wax, beeswax, and polyolefin wax.

12. A bio-based polyamide composition, characterized in that, The total amount of 100 parts by weight of the bio-based polyamide composition includes: 70-95 parts by weight of bio-based polyamide, 5-10 parts by weight of alkaline lignin and / or carboxymethyl cellulose, and 3-10 parts by weight of paraffin and / or beeswax, or... The total amount of 100 parts by weight of the bio-based polyamide composition includes: 70 to 95 parts by weight of bio-based polyamide, 2 to 5 parts by weight of nano-montmorillonite, and 3 to 10 parts by weight of paraffin and / or beeswax.

13. The bio-based polyamide composition according to any one of claims 1 to 12, wherein the total weight of the bio-based polyamide, the naturally derived reinforcing material, and the optional lubricant in 100 parts by weight of the bio-based polyamide composition is 95 parts by weight or more.

14. A method for preparing a bio-based polyamide composition, wherein the method is the same as that for preparing the bio-based polyamide composition according to any one of claims 1 to 13, characterized in that, include: Bio-based polyamide, naturally sourced reinforcing materials, and optional lubricants are mixed and melted within a temperature range of 240–320°C.

15. A molded article made from the bio-based polyamide composition according to any one of claims 1 to 13.

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