Antibacterial, antistatic, halogen-free and flame-retardant reinforced polyamide composition and preparation method thereof

Abstract

The invention relates to an antibacterial, antistatic, halogen-free and flame-retardant reinforced polyamide composition and a preparation method thereof. The present application first relates to a modified glass fiber, the surface of which is loaded with silver-containing particles, the silver-containing particles comprising silver and a polyphenol compound. The invention also relates to a method for preparing the modified glass fiber. Further, the present application relates to a polyamide composition comprising a) a polyamide resin; b) modified glass fibers; c) silver-containing particles; optionally d) a halogen-free flame retardant; optionally e) an antioxidant; optionally f) a processing aid; and optionally g) a color master batch.

Description

Technical Field

[0001] The present application relates to the field of polymer materials, and particularly to an antibacterial, antistatic, halogen-free flame-retardant reinforced polyamide composition and a preparation method thereof. Background Art

[0002] As an important lightweight thermoplastic, polyamide (nylon) is widely used in fields such as aerospace, automotive, instrumentation, household appliances, electronic communication, and new energy due to its excellent mechanical properties, wear resistance, and chemical corrosion resistance. In the field of civil aviation, polyamide is mainly used in parts such as radomes, landing gears, inner and outer flap bays, cabin doors, and cabin interiors, with a very wide range of applications.

[0003] However, unmodified polyamide materials have disadvantages such as flammability, weak bonding between glass fibers and the matrix, and easy generation of electrostatic discharge, which cannot meet the usage requirements of the above industries. Therefore, polyamide needs to be modified. Currently used modifiers have negative impacts. For example, traditional glass fiber surface modifiers (mainly silane coupling agents) and halogenated flame retardants are prone to generate volatile organic compounds, which is not conducive to environmental protection; traditional antistatic modifiers are low-molecular antistatic agents, and there are disadvantages such as the modification effect being prone to deteriorate over time. With the improvement of people's living standards, the development of antibacterial products is of great significance to people's living health.

[0004] Therefore, there is an urgent need for a flame-retardant polyamide composition that can have antistatic and antibacterial properties in addition to good mechanical properties. Summary of the Invention

[0005] The purpose of the present application is to solve the above technical problems. Specifically, the purpose of the present application is to provide a polyamide composition that has antibacterial and antistatic properties without sacrificing mechanical properties and a manufacturing method thereof.

[0006] The purpose of the present application is also to provide a modified glass fiber and a method for preparing the modified glass fiber.

[0007] The first aspect of the present application relates to a modified glass fiber, on the surface of which silver-containing particles are loaded, and the silver-containing particles contain silver and polyphenol compounds.

[0008] The second aspect of the present application relates to a method for preparing a modified glass fiber, and the method includes the following steps:

[0009] 1) Prepare a first solution and a second solution, where the first solution is a salt solution containing complexed silver ions and counter ions, and the second solution is a solution of polyphenol compounds;

[0010] 2) Mix the first solution and the second solution to obtain a first mixture containing silver-containing particles;

[0011] 3) Add glass fibers to the first mixture to obtain the modified glass fibers and a second mixture.

[0012] The third aspect of the present application relates to glass fibers prepared by the method of the second aspect of the present application.

[0013] The fourth aspect of the present application relates to a polyamide composition, which comprises:

[0014] a) A polyamide resin, which is selected from aliphatic polyamide resins and semi-aromatic polyamide resins, or a blend or copolymer thereof;

[0015] b) The modified glass fibers as described in the first aspect or the modified glass fibers prepared by the method described in the second aspect of the present application;

[0016] c) Silver-containing particles, wherein the silver-containing particles comprise silver and polyphenolic compounds.

[0017] The fifth aspect of the present application relates to the use of the modified glass fibers of the first aspect of the present application or the modified glass fibers prepared by the method described in the second aspect of the present application in the preparation of a polyamide composition having both antibacterial and antistatic properties.

[0018] The applicant has unexpectedly found that by incorporating both the modified glass fibers defined in the first aspect of the present application and the silver-containing particles, or by incorporating both the modified glass fibers defined in the method described in the second aspect of the present application and the silver-containing particles into the polyamide composition, a polyamide composition having both antistatic and antibacterial properties on the basis of desired mechanical properties can be obtained. Brief Description of the Drawings

[0019] The present application will now be described in conjunction with the following drawings. Those skilled in the art will understand that the provision of the following drawings and specific embodiments is for illustrative purposes only and in no way limits the present application.

[0020] Figure 1 is a scanning electron microscope (SEM) image of silver-containing particles according to an embodiment of the present application.

[0021] Figure 2A is a transmission electron microscope (TEM) image of silver-containing particles according to an embodiment of the present application.

[0022] Figure 2B is Figure 2A the Ag element mapping of the silver-containing particles in

[0023] Figure 3 is the modified glass fibers according to an embodiment of the present application. Detailed Description of the Embodiments

[0024] The "ranges" disclosed herein are defined in terms of a lower limit and an upper limit. A given range is defined by selecting a lower limit and an upper limit, and the selected lower limit and upper limit define the boundaries of a particular range. The ranges defined in this way can include or exclude the end values and can be combined arbitrarily, i.e., any lower limit can be combined with any upper limit to form a range. For example, if ranges of 60 to 120 and 80 to 110 are listed for a particular parameter, ranges of 60 to 110 and 80 to 120 are also contemplated. In addition, if the minimum range values 1 and 2 are listed, and if the maximum range values 3, 4, and 5 are listed, then the following ranges are all contemplated: 1 to 3, 1 to 4, 1 to 5, 2 to 3, 2 to 4, and 2 to 5. In this application, unless otherwise specified, the numerical range "a to b" represents an abbreviated representation of any combination of real numbers between a and b, where a and b are both real numbers. For example, the numerical range "0 to 5" means that all real numbers between "0 to 5" are fully listed herein, and "0 to 5" is only an abbreviated representation of these numerical combinations. Additionally, when stating that a certain parameter is an integer ≥2, it is equivalent to disclosing that the parameter is, for example, the integers 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, etc.

[0025] In this application, if not otherwise specified, all the embodiments and preferred embodiments mentioned herein can be combined with each other to form new technical solutions.

[0026] In this application, if not otherwise specified, all the technical features and preferred features mentioned herein can be combined with each other to form new technical solutions.

[0027] In this application, if not otherwise specified, all the steps mentioned herein can be carried out sequentially or randomly, but preferably sequentially. For example, the method includes steps (a) and (b), which means that the method can include steps (a) and (b) carried out sequentially, or can also include steps (b) and (a) carried out sequentially. For example, it is mentioned that the method may further include step (c), which means that step (c) can be added to the method in any order. For example, the method can include steps (a), (b), and (c), or can also include steps (a), (c), and (b), or can also include steps (c), (a), and (b), etc.

[0028] In this application, if not otherwise specified, the "including" and "comprising" mentioned herein mean open-ended or can also be closed-ended. For example, the "including" and "comprising" can mean that other components not listed can also be included or comprised, or can also mean that only the listed components are included or comprised.

[0029] In the description of this text, it should be noted that unless otherwise specified, "above" and "below" include the number itself, and in "one or several", "several" means two or more.

[0030] In the description of this text, unless otherwise specified, the term "or" is inclusive. For example, the phrase "A or B" means "A, B, or both A and B". More specifically, any of the following conditions satisfies the condition "A or B": A is true (or exists) and B is false (or does not exist); A is false (or does not exist) and B is true (or exists); or both A and B are true (or exist).

[0031] In this text, unless otherwise specified, percentages (%) or parts refer to weight percentages or weight parts relative to the composition.

[0032] In this text, unless otherwise stated, the sum of the contents of the components in the composition is 100%.

[0033] In this text, unless otherwise stated, the sum of the parts of the components in the composition can be 100 weight parts.

[0034] In this text, unless otherwise specified, "its combination" refers to a multi-component mixture of the described components, such as a two-component, three-component, four-component, and up to the maximum possible multi-component mixture.

[0035] If not specifically indicated, the term "one" used in this specification means "at least one".

[0036] In this text, unless otherwise specified, each reaction is carried out at normal temperature and pressure.

[0037] In the context of this application, the term "polyamide" can be used interchangeably with "polyamide resin", "PA", or "PA resin". For example, the term "aliphatic / semi-aromatic / aromatic polyamide resin" can be used interchangeably with the terms "aliphatic / semi-aromatic / aromatic polyamide", "aliphatic / semi-aromatic / aromatic PA", and "aliphatic / semi-aromatic / aromatic PA resin".

[0038] This application achieves beneficial technical effects in at least one of the following aspects:

[0039] - Tensile strength, which can be tested, for example, according to the ISO 527 standard;

[0040] - Tensile strength retention rate, which can be tested, for example, according to the ISO 527 standard;

[0041] - Flexural strength, which can be tested, for example, according to the ISO 178 standard;

[0042] - Flexural strength retention rate, which can be tested, for example, according to ISO 178 standard

[0043] - Compressive strength, which can be tested, for example, according to ASTM D695-10 standard;

[0044] - Compressive strength retention rate, which can be tested, for example, according to ASTM D695-10 standard;

[0045] - Notched impact strength, which can be tested, for example, according to ISO 179 standard;

[0046] - Warpage height, which can be measured with a scale;

[0047] - Softening point, which can be tested, for example, according to GB1633-79 standard;

[0048] - Flame retardant performance, which can be tested, for example, according to UL94 standard;

[0049] - Coefficient of sliding friction, which can be tested, for example, according to GB 5763 standard;

[0050] - Aging performance, which can be tested, for example, according to GB / T7141-2008 standard;

[0051] - Mechanical properties of the material in the case of recycling and reuse.

[0052] The first aspect of the present application relates to modified glass fibers, on the surface of which silver-containing particles are loaded, and the silver-containing particles contain silver and polyphenol compounds.

[0053] According to an embodiment, the silver-containing particles have a core-shell structure, wherein the core contains Ag and the shell contains the polyphenol compound.

[0054] According to an embodiment, the polyphenol compound is selected from catechol, tannic acid, dopamine, catechin, gallic acid and green tea extract. According to a preferred embodiment, the polyphenol compound is dopamine.

[0055] According to a preferred embodiment, the silver-containing particles further contain metal M and / or its ions, where M is selected from transition metals and is different from Ag. As non-limiting examples of metal M, mention may be made of lithium, sodium, potassium, magnesium, calcium, scandium, titanium, zirconium, vanadium, niobium, chromium, molybdenum, manganese, iron, cobalt, nickel, copper, zinc. According to a preferred embodiment, M is zinc.

[0056] According to a preferred embodiment, the silver-containing particles further contain carbon nanotubes. As non-limiting examples of carbon nanotubes, one or several combinations selected from multi-walled carbon nanotubes (MWCNT), double-walled carbon nanotubes (DWCNT) and single-walled carbon nanotubes (SWCNT) are used.

[0057] The size of the silver-containing particles can be selected according to the properties of the ultimately desired polyamide composition. According to one embodiment, the size of the silver-containing particles is 20 to 400 nm, or 30 to 350 nm, or 40 to 300 nm. For example, the size of the silver-containing particles can be 20 nm, or 30 nm, or 40 nm, or 50 nm, or 60 nm, or 70 nm, or 80 nm, or 90 nm, or 100 nm, or 110 nm, or 120 nm, or 130 nm, or 140 nm, or 150 nm, or 160 nm, or 170 nm, or 180 nm, or 190 nm, or 200 nm, or 210 nm, or 220 nm, or 230 nm, or 240 nm, or 250 nm, or 260 nm, or 270 nm, or 280 nm, or 290 nm, or 300 nm, or 310 nm, or 320 nm, or 330 nm, or 340 nm, or 350 nm, or 360 nm, or 370 nm, or 380 nm, or 390 nm, or 400 nm.

[0058] According to one embodiment, in the silver-containing particles of the present application, Ag has a higher concentration near the core. According to one embodiment, in the silver-containing particles of the present application, the polyphenol compound has a higher concentration away from the core.

[0059] In the modified glass fiber of the first aspect of the present application, the diameter of the glass fiber can be selected according to the properties of the desired polyamide composition. According to one embodiment, the diameter of the glass fiber in the modified glass fiber of the first aspect of the present application is 5 to 30 μm, or 10 to 20 μm. For example, the diameter of the glass fiber in the modified glass fiber of the first aspect of the present application is 5 μm, or 6 μm, or 7 μm, or 8 μm, or 9 μm, or 10 μm, or 11 μm, or 12 μm, or 13 μm, or 14 μm, or 15 μm, or 16 μm, or 17 μm, or 18 μm, or 19 μm, or 20 μm, or 21 μm, or 22 μm, or 23 μm, or 24 μm, or 25 μm, or 26 μm, or 27 μm, or 28 μm, or 29 μm, or 30 μm.

[0060] In the modified glass fiber of the first aspect of the present application, the length of the glass fiber can be adjusted according to the properties of the desired polyamide composition. According to one embodiment, the length of the glass fiber is 0.5 to 10 mm, or 1 to 8 mm, or 2 to 6 mm. For example, the length of the glass fiber can be 0.5 mm, or 1 mm, or 1.5 mm, or 2 mm, or 2.5 mm, or 3 mm, or 3.5 mm, or 4 mm, or 4.5 mm, or 5 mm, or 5.5 mm, or 6 mm, or 6.5 mm, or 7 mm, or 7.5 mm, or 8 mm, or 8.5 mm, or 9 mm, or 9.5 mm, or 10 mm.

[0061] The second aspect of the present application relates to a method for preparing modified glass fibers, the method comprising the following steps:

[0062] 1) Prepare a first solution and a second solution, wherein the first solution is a salt solution complexing silver ions and the second solution is a solution of a polyphenol compound

[0063] 2) Mix the first solution and the second solution to obtain a first mixture;

[0064] 3) Add the glass fibers to the first mixture and treat for a time t 1 under T 1 to obtain a second mixture;

[0065] 4) Filter the product in step 3) or step 4) to obtain modified glass fibers and a first filtrate;

[0066] Optionally 5) Separate the silver-containing particles from the first filtrate.

[0067] First solution

[0068] In the method of the second aspect of the present application, the first solution is a salt solution comprising complexed silver ions and counter ions.

[0069] Those skilled in the art know that any suitable ligand can be selected to complex Ag ions. Non-limiting examples of such ligands are ammonia, hydroxyl, oxalate, carbonyl, EDTA, cyano, etc. According to a preferred embodiment, the first solution is a silver ammonia solution.

[0070] The concentration of Ag ions in the first solution can be adjusted according to actual needs. According to one embodiment, the concentration of Ag ions in the first solution is 1 to 15 mmol / L, or 3 to 13 mmol / L, or 5 to 11 mmol / L. For example, the concentration of Ag ions in the first solution can be 1 mmol / L, or 1.5 mmol / L, or 2 mmol / L, or 2.5 mmol / L, or 3 mmol / L, or 3.5 mmol / L, or 4 mmol / L, or 4.5 mmol / L, or 5 mmol / L, or 5.5 mmol / L, or 6 mmol / L, or 6.5 mmol / L, or 7 mmol / L, or 7.5 mmol / L, or 8 mmol / L, or 8.5 mmol / L, or 9 mmol / L, or 9.5 mmol / L, or 10 mmol / L, or 10.5 mmol / L, or 11 mmol / L, or 11.5 mmol / L, or 12 mmol / L, or 12.5 mmol / L, or 13 mmol / L, or 13.5 mmol / L, or 14 mmol / L, or 14.5 mmol / L, or 15 mmol / L.

[0071] Those skilled in the art know that the counterions in the first solution are not particularly limited. As non-limiting examples of counterions, hydroxide ions, nitrate ions, chloride ions, bromide ions, and fluoride ions can be mentioned. According to a preferred embodiment, the counterion is nitrate ion.

[0072] Those skilled in the art know that the solvent of the first solution is not particularly limited. According to an exemplary embodiment, the solvent in the first solution is selected from one or more of water, ethanol, and acetone, preferably water.

[0073] Second solution

[0074] In the method of the second aspect of the present application, the second solution is a solution of a polyphenol compound.

[0075] According to one embodiment, the polyphenol compound is selected from catechol, tannic acid, dopamine, catechin, gallic acid, and green tea extract. According to a preferred embodiment, the polyphenol compound in the second solution is dopamine.

[0076] The concentration of the second solution can be adjusted according to actual needs. According to one embodiment, the concentration of the polyphenol compound in the second solution is 1 to 30 mmol / L, or 5 to 25 mmol / L, or 10 to 20 mmol / L. For example, the concentration of the polyphenol compound in the second solution can be 1 mmol / L, or 2 mmol / L, or 3 mmol / L, or 4 mmol / L, or 5 mmol / L, or 6 mmol / L, or 7 mmol / L, or 8 mmol / L, or 9 mmol / L, or 10 mmol / L, or 11 mmol / L, or 12 mmol / L, or 13 mmol / L, or 14 mmol / L, or 15 mmol / L, or 16 mmol / L, or 17 mmol / L, or 18 mmol / L, or 19 mmol / L, or 20 mmol / L, or 21 mmol / L, or 22 mmol / L, or 23 mmol / L, or 24 mmol / L, or 25 mmol / L, or 26 mmol / L, or 27 mmol / L, or 28 mmol / L, or 29 mmol / L, or 30 mmol / L.

[0077] Step 3)

[0078] The method of the second aspect of the present application includes step 3) adding glass fibers to the first mixture to obtain the modified glass fibers and a second mixture.

[0079] Step 3) of the second aspect of the present application can be carried out at a temperature considered suitable by those skilled in the art. According to one embodiment, in the method of the second aspect of the present application, step 3) is carried out at 10 to 40 °C, or 15 to 35 °C 1 under.

[0080] In a non-limiting example, this 1 can be 10 °C, or 11 °C, or 12 °C, or 13 °C, or 14 °C, or 15 °C, or 16 °C, or 17 °C, or 18 °C, or 19 °C, or 20 °C, or 21 °C, or 22 °C, or 23 °C, or 24 °C, or 25 °C, or 26 °C, or 27 °C, or 28 °C, or 29 °C, or 30 °C, or 31 °C, or 32 °C, or 33 °C, or 34 °C, or 35 °C, or 36 °C, or 37 °C, or 38 °C, or 39 °C, or 40 °C.

[0081] In the method of the second aspect of the present application, the duration of step 3) can be adjusted by those skilled in the art according to actual needs.

[0082] According to one embodiment, in the method of the second aspect of the present application, the duration t 1 of step 3) is 1 to 8 h, or 1 to 6 h, or 1 to 4 h, or 1 to 2 h.

[0083] According to a non-limiting example, in the method of the second aspect of the present application, the duration t of step 3) 1 is 1 h, or 1.5 h, or 2 h, or 2.5 h, or 3 h, or 3.5 h, or 4 h, or 4.5 h, or 5 h, or 5.5 h, or 6 h, or 6.5 h, or 7 h, or 7.5 h, or 8 h.

[0084] According to a preferred embodiment, in step 3) of the method of the second aspect of the present application, carbon nanotubes are further added to the first mixture.

[0085] The addition amount or addition ratio of the carbon nanotubes can be adjusted according to the desired properties of the polyamide composition.

[0086] According to one embodiment, the carbon nanotubes are added to the first mixture in an amount of 0.01 to 1 g / L, or 0.01 to 0.8 g / L, or 0.01 to 0.6 g / L, or 0.01 to 0.4 g / L, or 0.01 to 0.2 g / L.

[0087] For example, the carbon nanotubes can be added to the first mixture in an amount of 0.01 g / L, or 0.02 g / L, or 0.03 g / L, or 0.04 g / L, or 0.05 g / L, or 0.06 g / L, or 0.07 g / L, or 0.08 g / L, or 0.09 g / L, or 0.10 g / L, or 0.15 g / L, or 0.20 g / L, or 0.25 g / L, or 0.30 g / L, or 0.35 g / L, or 0.40 g / L, or 0.45 g / L, or 0.50 g / L, or 0.55 g / L, or 0.60 g / L, or 0.65 g / L, or 0.70 g / L, or 0.75 g / L, or 0.80 g / L, or 0.85 g / L, or 0.90 g / L, or 0.95 g / L, or 1.00 g / L.

[0088] The carbon nanotubes described in the method of the second aspect of the present application can be as described in the first aspect of the present application.

[0089] Salt solution of M

[0090] The second aspect of the present application may further include the following step: adding a salt solution of metal M to the above first mixture or second mixture to obtain a third mixture.

[0091] The order of this step is not particularly limited. For example, this step can be carried out simultaneously with step 2), between step 2) and step 3), simultaneously with step 3), or after step 3) is completed.

[0092] The metal M is as described in the first aspect of the present application.

[0093] According to one embodiment, the salt solution of M is added at a concentration such that the concentration of M ions is 1 to 15 mmol / L, or 3 to 12 mmol / L, or 3 to 10 mmol / L, or 3 to 8 mmol / L. For example, the M salt solution can be added such that the concentration of M ions is 1 mmol / L, or 1.5 mmol / L, or 2 mmol / L, or 2.5 mmol / L, or 3 mmol / L, or 3.5 mmol / L, or 4 mmol / L, or 4.5 mmol / L, or 5 mmol / L, or 5.5 mmol / L, or 6 mmol / L, or 6.5 mmol / L, or 7 mmol / L, or 7.5 mmol / L, or 8 mmol / L, or 8.5 mmol / L, or 9 mmol / L, or 9.5 mmol / L, or 10 mmol / L, or 10.5 mmol / L, or 11 mmol / L, or 11.5 mmol / L, or 12 mmol / L, or 12.5 mmol / L, or 13 mmol / L, or 13.5 mmol / L, or 14 mmol / L, or 14.5 mmol / L, or 15 mmol / L.

[0094] Separate silver-containing particles

[0095] According to a preferred embodiment, the method of the second aspect of the present application may include separating the silver-containing particles from the first mixture or the second mixture.

[0096] The step of separating the silver-containing particles can be carried out by methods well known to those skilled in the art. For example, the silver-containing particles can be separated by centrifugation. However, those skilled in the art know that this step can be completed in a similar manner.

[0097] As a non-limiting example, the method of the second aspect of the present application may include the following steps:

[0098] 1) Prepare an aqueous solution of AgNO 3 and then slowly dropwise add ammonia water thereto. Immediately, a precipitate is formed. Continue to add ammonia water and shake until the precipitate just disappears to obtain a first solution, which is a colorless silver ammonia solution; prepare an aqueous solution of L-dopamine as a second solution;

[0099] 2) Slowly add the first solution to the second solution drop by drop with a dropper under rapid stirring to obtain a first mixture, which is a silver ammonia-L-dopamine reaction solution;

[0100] 3) Add a certain amount of carbon nanotubes and chopped glass fibers to the first mixture, and react at a magnetic stirring speed of 100 rpm to 350 rpm and a reaction temperature T of 10 °C to 40 °C 1 for a time t of 1.5 h to 2 h1 , a modified glass fiber and a second mixed solution are obtained;

[0101] 3') Add a certain amount of zinc nitrate solution to the second mixed solution, and continue to react for 2 h to 8 h;

[0102] 4) After the reaction is completed, separate the system in step 3'), and obtain a first solid. The first solid is washed and dried to obtain a modified glass fiber;

[0103] 5) Centrifuge, wash, and perform low-temperature freeze-drying on the filtered second mixed solution to obtain silver-containing particles.

[0104] As a non-limiting alternative example, the method of the second aspect of the present application may further include the following steps:

[0105] 1) Prepare an aqueous solution of AgNO 3 , and then slowly dropwise add ammonia water thereto. Immediately, a precipitate is generated. Continue to add ammonia water and shake until the precipitate just disappears to obtain a first solution as a colorless silver ammonia solution; Prepare an aqueous solution of L-dopamine as a second solution;

[0106] 2) Slowly add the first solution to the second solution drop by drop with a dropper under rapid stirring conditions to obtain a first mixed solution as a silver ammonia-L-dopamine reaction solution;

[0107] 2') Add a certain amount of zinc nitrate solution to the second mixed solution, and continue to react for 2 h to 8 h;

[0108] 3) Add a certain amount of carbon nanotubes and chopped glass fibers to the first mixed solution, and react at a magnetic stirring speed of 100 rpm to 350 rpm and a reaction temperature T of 10 °C to 40 °C 1 for a time t of 1.5 h to 2 h 1 to obtain a second mixed solution;

[0109] 4) After the reaction is completed, separate the system in step 3), and obtain a first solid. The first solid is washed and dried to obtain a modified glass fiber;

[0110] 5) Centrifuge, wash, and perform low-temperature freeze-drying on the second mixed solution to obtain silver-containing particles.

[0111] However, the above examples are only provided for illustrative purposes. The above examples do not limit the present application in any way, nor should the above examples be construed as limiting the present application. The spirit and scope of protection of the present application are only limited by the appended claims.

[0112] The third aspect of the present application relates to a glass fiber prepared by the method of the second aspect of the present application.

[0113] The fourth aspect of the present application relates to a polyamide composition, which comprises:

[0114] a) a polyamide resin selected from aliphatic polyamide resins and semi-aromatic polyamide resins, or a blend or copolymer thereof;

[0115] b) the modified glass fiber as described in the first aspect or the modified glass fiber prepared by the method described in the second aspect of the present application;

[0116] c) silver-containing particles, wherein the silver-containing particles comprise silver and polyphenol compounds.

[0117] Component a) Polyamide resin

[0118] The polyamide composition described in the third aspect of the present application comprises a polyamide resin, wherein the polyamide resin is selected from aliphatic polyamide resins and semi-aromatic polyamide resins.

[0119] The nomenclature used to define polyamides is described in ISO standard 1874-1:2011 Plastics - Polyamide (PA) Moulding And Extrusion Materials - Part 1: Designation and is well-known to those skilled in the art.

[0120] Aliphatic polyamide resin

[0121] According to one embodiment, the aliphatic polyamide resin of the polyamide composition applicable to the third aspect of the present application is obtained by the condensation of:

[0122] -C x aliphatic lactams;

[0123] -C y aliphatic amino acids; or

[0124] -C a aliphatic diacids and C b aliphatic diamines.

[0125] According to one embodiment, the C x aliphatic lactams are selected from C 4 to C 12 aliphatic lactams, or C 4 to C 10 aliphatic lactams, or C 4 to C 8 aliphatic lactams.

[0126] According to one embodiment, the C x aliphatic lactams are selected from: C 4 aliphatic lactams, or C5 aliphatic lactam, or C 6 aliphatic lactam, or C 7 aliphatic lactam, or C 8 aliphatic lactam, or C 9 aliphatic lactam, or C 10 aliphatic lactam, or C 11 aliphatic lactam, or C 12 aliphatic lactam.

[0127] As non-limiting examples of C x aliphatic lactams that can be used in the present application, mention may be made of: butyrolactam, valerolactam, caprolactam, enantholactam, caprylolactam, pelargonolactam, capric lactam, undecanolactam, laurolactam.

[0128] According to one embodiment, the C y aliphatic amino acids are selected from C 4 to C 12 aliphatic amino acids, or C 4 to C 10 aliphatic amino acids, or C 4 to C 8 aliphatic amino acids.

[0129] According to one embodiment, the C y aliphatic amino acids are selected from: C 4 aliphatic amino acids, or C 5 aliphatic amino acids, or C 6 aliphatic amino acids, or C 7 aliphatic amino acids, or C 8 aliphatic amino acids, or C 9 aliphatic amino acids, or C 10 aliphatic amino acids, or C 11 aliphatic amino acids, or C 12 aliphatic amino acids.

[0130] As non-limiting examples of C y aliphatic amino acids that can be used in the present application, mention may be made of: 4-aminobutyric acid, 5-aminovaleric acid, 4-aminopentanoic acid, 6-aminohexanoic acid, 5-aminohexanoic acid, 7-aminoheptanoic acid, 6-aminoheptanoic acid, 8-aminooctanoic acid, 7-aminooctanoic acid, 9-aminononanoic acid, 8-aminononanoic acid, 10-aminodecanoic acid, 9-aminodecanoic acid, 11-aminoundecanoic acid, 10-aminoundecanoic acid, 12-aminododecanoic acid, 11-aminododecanoic acid.

[0131] According to one embodiment, the C a aliphatic diacids are selected from: C 4 to C 12 aliphatic diacids, or C 4 to C10 aliphatic diacid, or C 4 to C 8 aliphatic diacid.

[0132] According to one embodiment, the C a aliphatic diacid is selected from: C 4 aliphatic diacid, or C 5 aliphatic diacid, or C 6 aliphatic diacid, or C 7 aliphatic diacid, or C 8 aliphatic diacid, or C 9 aliphatic diacid, or C 10 aliphatic diacid, or C 11 aliphatic diacid, or C 12 aliphatic diacid.

[0133] As non-limiting examples of the C a aliphatic diacid that can be used in the present application, mention may be made of: succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid.

[0134] According to one embodiment, the C b aliphatic diamine is selected from: C 4 to C 12 aliphatic diamine, or C 4 to C 10 aliphatic diamine, or C 4 to C 8 aliphatic diamine.

[0135] According to one embodiment, the C b aliphatic diamine is selected from: C 4 aliphatic diamine, or C 5 aliphatic diamine, or C 6 aliphatic diamine, or C 7 aliphatic diamine, or C 8 aliphatic diamine, or C 9 aliphatic diamine, or C 10 aliphatic diamine, or C 11 aliphatic diamine, or C 12 aliphatic diamine.

[0136] As non-limiting examples of the C b aliphatic diamine that can be used in the present application, mention may be made of: 1,4-tetramethylenediamine, 1,5-pentamethylenediamine, 1,6-hexamethylenediamine, 1,7-heptamethylenediamine, 1,8-octamethylenediamine, 1,9-nonamethylenediamine, 1,10-decamethylenediamine, 1,11-undecamethylenediamine, 1,12-dodecamethylenediamine.

[0137] Semi-aromatic polyamide

[0138] According to one embodiment, the semi-aromatic polyamide resin that can be used in the polyamide composition described in the third aspect of the present application is obtained by the following condensation:

[0139] C c aliphatic diacid and C d aromatic diamine, or C e aromatic diacid and C f aliphatic diamine.

[0140] According to one embodiment, the C c aliphatic diacid is selected from C 4 to C 12 aliphatic diacid, or C 4 to C 10 aliphatic diacid, or C 4 to C 8 aliphatic diacid.

[0141] According to one embodiment, the C c aliphatic diacid is selected from: C 4 aliphatic diacid, or C 5 aliphatic diacid, or C 6 aliphatic diacid, or C 7 aliphatic diacid, or C 8 aliphatic diacid, or C 9 aliphatic diacid, or C 10 aliphatic diacid, or C 11 aliphatic diacid, or C 12 aliphatic diacid.

[0142] As non-limiting examples of the C c aliphatic diacid that can be used in the present application, mention may be made of: succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid.

[0143] According to one embodiment, the C d aromatic diamine is selected from C 6 to C 18 aromatic diamine, or C 6 to C 16 aromatic diamine, or C 6 to C 14 aromatic diamine, or C 6 to C 12 aromatic diamine, or C 6 to C 10 aromatic diamine.

[0144] According to one embodiment, the C d aromatic diamine is selected from C 6 aromatic diamine, or C 7 aromatic diamine, or C8 Aromatic diamine, or C 9 Aromatic diamine, or C 10 Aromatic diamine, or C 11 Aromatic diamine, or C 12 Aromatic diamine, or C 13 Aromatic diamine, or C 14 Aromatic diamine, or C 15 Aromatic diamine, or C 16 Aromatic diamine, or C 17 Aromatic diamine, or C 18 Aromatic diamine.

[0145] As non-limiting examples of C that can be used in the present application d For aromatic diamines, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, o-phthalyl diamine, m-phthalyl diamine, p-phthalyl diamine, naphthalene diamine can be mentioned.

[0146] According to one embodiment, the C e Aromatic diacids are selected from C 6 to C 18 Aromatic diacids, or C 6 to C 16 Aromatic diacids, or C 6 to C 14 Aromatic diacids, or C 6 to C 12 Aromatic diacids, or C 6 to C 10 Aromatic diacids.

[0147] According to one embodiment, the C e Aromatic diacids are selected from C 6 Aromatic diacids, or C 7 Aromatic diacids, or C 8 Aromatic diacids, or C 9 Aromatic diacids, or C 10 Aromatic diacids, or C 11 Aromatic diacids, or C 12 Aromatic diacids, or C 13 Aromatic diacids, or C 14 Aromatic diacids, or C 15 Aromatic diacids, or C 16 Aromatic diacids, or C 17 Aromatic diacids, or C 18 Aromatic diacids.

[0148] As non-limiting examples of C that can be used in the present application e For aromatic diacids, furan dicarboxylic acid, thiophene dicarboxylic acid, phthalic acid, isophthalic acid, terephthalic acid, naphthalene dicarboxylic acid can be mentioned.

[0149] According to one embodiment, the Cf The aliphatic diamine is selected from C 4 to C 12 aliphatic diamine, or C 4 to C 10 aliphatic diamine, or C 4 to C 8 aliphatic diamine.

[0150] According to one embodiment, the C f aliphatic diamine is selected from: C 4 aliphatic diamine, or C 5 aliphatic diamine, or C 6 aliphatic diamine, or C 7 aliphatic diamine, or C 8 aliphatic diamine, or C 9 aliphatic diamine, or C 10 aliphatic diamine, or C 11 aliphatic diamine, or C 12 aliphatic diamine.

[0151] As non-limiting examples of the C f aliphatic diamine that can be used in the present application, mention may be made of: 1,4-tetramethylenediamine, 1,5-pentamethylenediamine, 1,6-hexamethylenediamine, 1,7-heptamethylenediamine, 1,8-octamethylenediamine, 1,9-nonamethylenediamine, 1,10-decamethylenediamine, 1,11-undecamethylenediamine, 1,12-dodecamethylenediamine.

[0152] According to one embodiment, the polyamide resin of the polyamide composition for the third aspect of the present application is selected from one or more of: PA46, PA56, PA6, PA66, PA12, PA4T, PA5T, PA6T / 6, PA6T / 66, PA6T / 66 / 6, PA9T, PA10T, PA10T / 66.

[0153] In the polyamide composition for the third aspect of the present application, the content of component a) the polyamide resin can be adjusted according to the desired properties of the polyamide composition.

[0154] According to one embodiment, in the polyamide composition for the third aspect of the present application, the content of component a) the polyamide resin is 30 to 90% by weight, or 30 to 80% by weight, or 30 to 70% by weight, or 30 to 60% by weight, based on the total weight of the polyamide composition.

[0155] According to a non-limiting embodiment, in the polyamide composition of the third aspect of the present application, the content of component a) polyamide resin can be 30% by weight, or 31% by weight, or 32% by weight, or 33% by weight, or 34% by weight, or 35% by weight, or 36% by weight, or 37% by weight, or 38% by weight, or 39% by weight, or 40% by weight, or 41% by weight, or 42% by weight, or 43% by weight, or 44% by weight, or 45% by weight, or 46% by weight, or 47% by weight, or 48% by weight, or 49% by weight, or 50% by weight, or 51% by weight, or 52% by weight, or 53% by weight, or 54% by weight, or 55% by weight, or 56% by weight, or 57% by weight, or 58% by weight, or 59% by weight, or 60% by weight, or 61% by weight, or 62% by weight, or 63% by weight, or 64% by weight, or 65% by weight, or 66% by weight, or 67% by weight, or 68% by weight, or 69% by weight, or 70% by weight, or 71% by weight, or 72% by weight, or 73% by weight, or 74% by weight, or 75% by weight, or 76% by weight, or 77% by weight, or 78% by weight, or 79% by weight, or 80% by weight, or 81% by weight, or 82% by weight, or 83% by weight, or 84% by weight, or 85% by weight, or 86% by weight, or 87% by weight, or 88% by weight, or 89% by weight, or 90% by weight, based on the total weight of the polyamide composition.

[0156] b) Modified glass fiber

[0157] The polyamide composition according to the third aspect of the present application comprises component b) modified glass fiber.

[0158] The modified glass fiber that can be used in the polyamide composition according to the third aspect of the present application can be as described in the first aspect of the present application, or prepared by the method described in the second aspect of the present application.

[0159] In the polyamide composition according to the third aspect of the present application, the content of component b) can be adjusted according to the desired properties of the polyamide composition.

[0160] According to one embodiment, in the polyamide composition according to the third aspect of the present application, the content of component b) modified glass fiber is 10 to 40% by weight, or 10 to 35% by weight, or 10 to 30% by weight, or 10 to 25% by weight, based on the total weight of the polyamide composition.

[0161] According to a non-limiting embodiment, in the polyamide composition described in the third aspect of the present application, the content of component b) the modified glass fiber may be: 10% by weight, or 11% by weight, or 12% by weight, or 13% by weight, or 14% by weight, or 15% by weight, or 16% by weight, or 17% by weight, or 18% by weight, or 19% by weight, or 20% by weight, or 21% by weight, or 22% by weight, or 23% by weight, or 24% by weight, or 25% by weight, or 26% by weight, or 27% by weight, or 28% by weight, or 29% by weight, or 30% by weight, or 31% by weight, or 32% by weight, or 33% by weight, or 34% by weight, or 35% by weight, or 36% by weight, or 37% by weight, or 38% by weight, or 39% by weight, or 40% by weight, based on the total weight of the polyamide composition.

[0162] c) Silver-containing particles

[0163] The polyamide composition described in the third aspect of the present application comprises component c) silver-containing particles, wherein the silver-containing particles comprise silver and polyphenol compounds.

[0164] The silver-containing particles are as described in the first aspect of the present application.

[0165] In the polyamide composition described in the third aspect of the present application, the content of component c) can be adjusted according to the desired properties of the polyamide composition.

[0166] According to one embodiment, in the polyamide composition described in the third aspect of the present application, the content of component c) is 2 to 5% by weight, or 2.5 to 4.5% by weight, based on the total weight of the polyamide composition

[0167] According to a non-limiting embodiment, in the polyamide composition described in the third aspect of the present application, the content of component c) may be 2% by weight, or 2.1% by weight, or 2.2% by weight, or 2.3% by weight, or 2.4% by weight, or 2.5% by weight, or 2.6% by weight, or 2.7% by weight, or 2.8% by weight, or 2.9% by weight, or 3.0% by weight, or 3.1% by weight, or 3.2% by weight, or 3.3% by weight, or 3.4% by weight, or 3.5% by weight, or 3.6% by weight, or 3.7% by weight, or 3.8% by weight, or 3.9% by weight, or 4.0% by weight, or 4.1% by weight, or 4.2% by weight, or 4.3% by weight, or 4.4% by weight, or 4.5% by weight, or 4.6% by weight, or 4.7% by weight, or 4.8% by weight, or 4.9% by weight, or 5.0% by weight.

[0168] d) Halogen-free flame retardant

[0169] According to a preferred embodiment, the polyamide composition according to the third aspect of the present application comprises component d) a halogen-free flame retardant, wherein the halogen-free flame retardant is added to the polyamide composition in the form of a composite masterbatch, and the composite masterbatch comprises a halogen-free flame retardant and a part of component a) polyamide resin.

[0170] Those skilled in the art will understand that the content of component d) in the polyamide composition according to the third aspect of the present application can be adjusted according to the desired final properties of the polyamide composition and is not particularly limited.

[0171] According to one embodiment, in the polyamide composition according to the third aspect of the present application, the mass fraction of the composite masterbatch of the halogen-free flame retardant is 20 to 30% by weight, based on the total weight of the polyamide composition.

[0172] According to a non-limiting embodiment, in the polyamide composition according to the third aspect of the present application, the mass fraction of the composite masterbatch of the halogen-free flame retardant is 20% by weight, or 21% by weight, or 22% by weight, or 23% by weight, or 24% by weight, or 25% by weight, or 26% by weight, or 27% by weight, or 28% by weight, or 29% by weight, or 30% by weight.

[0173] Those skilled in the art know that the selected halogen-free flame retardant is not particularly limited. According to a preferred embodiment, component d) the halogen-free flame retardant is selected from one or more of hypophosphites, polyphosphates, and borates. According to a preferred embodiment, the halogen-free flame retardant is a blend of aluminum organic hypophosphite, melamine polyphosphate, and zinc borate. According to a more preferred embodiment, in the blend, the weight ratio of aluminum organic hypophosphite, melamine polyphosphate, and zinc borate is 50:15:2 to 20:15:2.

[0174] According to non-limiting examples, in the blend, the weight ratio of aluminum organic hypophosphite, melamine polyphosphate, and zinc borate is 20:15:2, or 21:15:2, or 22:15:2, or 23:15:2, or 24:15:2, or 25:15:2, or 26:15:2, or 27:15:2, or 28:15:2, or 29:15:2, or 30:15:2, or 31:15:2, or 32:15:2, or 33:15:2, or 34:15:2, or 35:15:2, or 36:15:2, or 37:15:2, or 38:15:2, or 39:15:2, or 40:15:2, or 41:15:2, or 42:15:2, or 43:15:2, or 44:15:2, or 45:15:2, or 46:15:2, or 47:15:2, or 48:15:2, or 49:15:2, or 50:15:2.

[0175] e) Antioxidant

[0176] According to a preferred embodiment, the polyamide composition according to the third aspect of the present application comprises component e) an antioxidant.

[0177] According to one embodiment, the antioxidant is selected from one or more of copper salts, hindered phenols, or phosphites. As non-limiting examples of copper salts, mention may be made of those antioxidants that can be obtained under the trade names BTN, H318, H3386.

[0178] The content of the antioxidant in the polyamide composition according to the third aspect of the present application can be selected according to the properties of the desired final polyamide composition, which is readily understood by those skilled in the art.

[0179] According to one embodiment, in the composition according to the third aspect of the present application, the content of component e) the antioxidant is 0.001 to 1% by weight, or 0.001 to 0.8% by weight, or % by weight, or 0.001 to 0.6% by weight, or 0.001 to 0.4% by weight, or 0.001 to 0.3% by weight, based on the total weight of the polyamide composition.

[0180] According to a non-limiting embodiment, in the composition according to the third aspect of the present application, the content of component e) the antioxidant can be 0.001% by weight, or 0.01% by weight, or 0.02% by weight, or 0.05% by weight, or 0.1% by weight, or 0.2% by weight, or 0.3% by weight, or 0.4% by weight, or 0.5% by weight, or 0.6% by weight, or 0.7% by weight, or 0.8% by weight, or 0.9% by weight, or 1.0% by weight, based on the total weight of the polyamide composition.

[0181] f) Processing aid

[0182] According to a preferred embodiment, the polyamide composition according to the third aspect of the present application may further comprise a processing aid.

[0183] In the context of the present application, the term "processing aid" means a component that can impart beneficial properties to the final product or make processing easier, in addition to the above components a) to e) and component g).

[0184] As non-limiting examples of processing aids that can be used in the present application, mention may be made of OP wax, rice bran wax, CAV102, 816A, pentaerythritol stearate, ethylene bisoleamide, aluminum stearate, calcium montanate, sodium montanate, or combinations thereof. However, those skilled in the art know that the processing aids that can be used in the present application are by no means limited to this.

[0185] In the polyamide composition according to the first aspect of the present application, the content of the processing aid can be adjusted according to the desired properties of the final product.

[0186] According to one embodiment, in the polyamide composition according to the third aspect of the present application, the content of component f) the processing aid is 0.001 to 2% by weight, or 0.001 to 1.5% by weight, or 0.001 to 1.0% by weight, or 0.001 to 1.8% by weight, based on the total weight of the polymer composition.

[0187] According to a non-limiting embodiment, in the polyamide composition according to the third aspect of the present application, the content of component f) the processing aid can be 0.001% by weight, or 0.01% by weight, or 0.02% by weight, or 0.05% by weight, or 0.1% by weight, or 0.2% by weight, or 0.3% by weight, or 0.4% by weight, or 0.5% by weight, or 0.6% by weight, or 0.7% by weight, or 0.8% by weight, or 0.9% by weight, or 1.0% by weight, or 1.1% by weight, or 1.2% by weight, or 1.3% by weight, or 1.4% by weight, or 1.5% by weight, or 1.6% by weight, or 1.7% by weight, or 1.8% by weight, or 1.9% by weight, or 2.0% by weight, based on the total weight of the polymer composition.

[0188] g) Color masterbatch

[0189] According to one embodiment, the polyamide composition according to the third aspect of the present application further comprises component g) a masterbatch.

[0190] In the context of the present application, the term "masterbatch" means a component capable of providing the desired aesthetic appearance to the polyamide composition.

[0191] According to one embodiment, the masterbatch may comprise one or more of pigments, colorants, dyes. According to one embodiment, the masterbatch may comprise at least a part of component a).

[0192] In the polyamide composition according to the third aspect of the present application, the content of component g) the masterbatch can be adjusted according to the desired properties of the polyamide composition, which is readily understood by those skilled in the art.

[0193] According to one embodiment, in the polyamide composition according to the third aspect of the present application, the content of component g) is 0.001 to 1% by weight, based on the total weight of the polyamide composition.

[0194] According to a non-limiting embodiment, in the polyamide composition described in the third aspect of the present application, the content of component g) can be 0.001% by weight, or 0.01% by weight, or 0.02% by weight, or 0.05% by weight, or 0.1% by weight, or 0.2% by weight, or 0.3% by weight, or 0.4% by weight, or 0.5% by weight, or 0.6% by weight, or 0.7% by weight, or 0.8% by weight, or 0.9% by weight, or 1.0% by weight.

[0195] According to a non-limiting specific example, the polyamide composition described in the third aspect of the present application can be prepared by a method comprising the following steps:

[0196] I) Weigh polyamide resin, halogen-free flame retardant composite masterbatch, silver-containing particles, antioxidant, processing aid, and color masterbatch by weight parts, and stir and mix them evenly through a high-speed mixer to obtain a first premix;

[0197] II) Add the first premix through the main feeding port of a twin-screw extruder, add modified glass fiber through the side feeding port of the twin-screw extruder, and obtain the antibacterial, antistatic, halogen-free flame retardant reinforced polyamide composition of the present invention after processes such as melt extrusion, pelletizing, and drying;

[0198] Wherein the silver-containing particles and the modified glass fiber are prepared by the method described in the second aspect of the present application, or as described in the first aspect of the present application.

[0199] The fifth aspect of the present application relates to the use of the modified glass fiber of the first aspect of the present application or the modified glass fiber prepared by the method described in the second aspect of the present application in the preparation of a polyamide composition having both antibacterial and antistatic properties.

[0200] Example

[0201] The following further elaborates and illustrates the present application in conjunction with examples. However, the following examples are merely illustrative and in no way limit the present application. The examples and comparative examples of the present application use the materials described in Table 1 below, but are not limited to the materials described in Table 1.

[0202] Nylon 66 resin, trade name EP1106, Huafeng Group Co., Ltd.;

[0203] Flame retardant, NFP71TT - halogen-free flame retardant masterbatch;

[0204] Processing aid, trade name BRO-R05, Chongqing Hecai Chemical Technology Co., Ltd.;

[0205] L-DOPA, J&K Scientific Ltd., Shanghai;

[0206] Zinc nitrate, J&K Scientific Ltd. (Shanghai);

[0207] Silver nitrate, Lingfeng Chemical Reagent Co., Ltd. (Shanghai);

[0208] Ammonia water (28%), Lingfeng Chemical Reagent Co., Ltd. (Shanghai);

[0209] Glass fiber, Chongqing International Composite Materials Co., Ltd.;

[0210] Antioxidant 1010, Double Bond Chemical Industry Co., Ltd.;

[0211] Antioxidant 9228, Dover Chemical Corporation;

[0212] Black masterbatch, PA6 - 2015, Shanghai Xukun Plastic Raw Materials Co., Ltd.;

[0213] Carbon nanotubes, LG Chem;

[0214] Inorganic silver - based antibacterial masterbatch, Jinda Nano Technology (Xiamen) Co., Ltd.

[0215] The performance test standards and / or methods in the examples and comparative examples of this application are as follows:

[0216] (1) Tensile strength: According to ISO 527 method, the specimen size is 170 * 10 * 4 mm, and the test speed is 5 mm / min;

[0217] (2) Notched impact strength: According to ISO 179 / 1eA method, the specimen size is 80 * 10 * 4 mm;

[0218] (3) Flame retardant performance: According to UL94 method, the specimen size is 125 * 10 * 1.6 mm;

[0219] (4) Antibacterial property: Scored on a scale of 0 - 10, the higher the score, the better the antibacterial property. Specific scoring method: Add 3% of the inorganic silver - based antibacterial masterbatch to the polyamide raw material, extrude and injection - mold it, cut it into sheets with a size of 5 cm * 5 cm * 0.5 cm, and refer to ISO 22196 standard for antibacterial effect test to observe the ability of the antibacterial modified plastic surface to inhibit bacterial growth.

[0220] The polyamide compositions in the examples and comparative examples of this application are prepared by the following method:

[0221] 1) Prepare a solution with a concentration of 1 mg / mL of AgNO in reactor 1 3An aqueous solution, and then ammonia water was slowly added dropwise thereto. Immediately, a precipitate was formed. Ammonia water was continuously added dropwise and shaken until the precipitate just disappeared, obtaining a colorless silver ammonia solution 1 (the first solution); An aqueous solution of L-dopamine 2 (the second solution) with a concentration of 2.5 mg / mL was prepared in a reaction kettle 2; The volume ratio of the first solution to the second solution was 1:4;

[0222] 2) The first solution was slowly added dropwise to the second solution with a dropper under the condition of rapid stirring, obtaining a silver ammonia-L-dopamine reaction solution 3 (the first mixture);

[0223] 3) Carbon nanotubes and chopped glass fibers that had been ultrasonically separated in advance were added to the first mixture. The addition ratios of carbon nanotubes and chopped glass fibers were 0.1 g / L and 50 g / L respectively. Under magnetic stirring, at a rotation speed of 220 rpm, and at a reaction temperature T of 30 °C 1 for a reaction time t of 1.5 h 1 ;

[0224] 5) Zinc nitrate was added to the above silver ammonia-L-dopamine reaction solution 3, and the addition ratio was 1 mg / mL, and then the reaction continued for 5 h;

[0225] 6) After step 5) was completed, the glass fibers and the L-dopamine suspension were separated, and after washing and drying, modified glass fibers and a third mixture were obtained;

[0226] 7) The third mixture was centrifuged, washed, and freeze-dried at low temperature to obtain silver particles;

[0227] 8) Finally, polyamide resin, a halogen-free flame retardant composite masterbatch, silver particles, an antioxidant, a processing aid, and a color masterbatch were weighed according to the formulation ratios in Table 1, and were stirred and mixed evenly by a high-speed mixer to obtain a first premix;

[0228] 9) The first premix was added from the main feeding port of a twin-screw extruder, and the modified glass fibers were added from the side feeding port of the twin-screw extruder. After processes such as melt extrusion, pelletizing, and drying, the antibacterial, antistatic, halogen-free flame retardant reinforced polyamide composition of the present invention was obtained.

[0229] Table 1 shows the test results of the examples and comparative examples with different formulations of the present invention:

[0230] Table 1

[0231]

[0232] As can be seen from the results in Table 1, by incorporating both the modified glass fiber and the silver-containing particles defined in the first aspect of the present application, or by incorporating both the modified glass fiber and the silver-containing particles defined in the method described in the second aspect of the present application, a polyamide composition having antistatic and antibacterial properties in addition to the desired mechanical properties can be obtained.

[0233] Specifically, the difference between Comparative Example 3 and Example 1 is only that Comparative Example 3 uses glass fiber not modified with silver-containing particles, while Example 1 uses the modified glass fiber described in the present application. The results in Table 1 show that the unmodified glass fiber can neither provide the desired tensile strength and notched impact strength, nor the desired antistatic and antibacterial properties. The antibacterial property of the polyamide composition in Comparative Example 3 is significantly lower than that in Example 1, and it does not have antistatic property like the polyamide composition in Example 1.

[0234] The difference between Comparative Example 4 and Comparative Example 3 is that Comparative Example 4 uses an inorganic silver-based antibacterial masterbatch instead of the silver-containing particles described in the present application. The results show that using the inorganic silver-based antibacterial masterbatch endows the polyamide composition with antibacterial property, but does not endow the polyamide composition with antistatic property. This is unexpected.

[0235] Without wishing to be bound by theory, from the results of Comparative Examples 3 to 4, it can be seen that the combined action of the silver-containing particles and the modified glass fiber of the present application not only endows the polyamide composition with the desired mechanical properties (such as tensile strength and notched impact strength), but also makes the polyamide composition have both antistatic and antibacterial properties.

[0236] The above are only the preferred embodiments of the present application and are not intended to limit the present application. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principle of the present application shall be included in the protection scope of the present application.

Claims

1. A modified glass fiber, wherein the surface of the modified glass fiber is loaded with silver-containing particles, wherein the silver-containing particles contain silver and a polyphenol compound; Preferably, the modified glass fiber has one or more of the following characteristics: (1) the silver-containing particles have a core-shell structure, wherein the core comprises Ag and the shell comprises the polyphenol compound; (2) the polyphenol compound is selected from catechol, tannic acid, dopamine, catechin, gallic acid and green tea extract, preferably dopamine; (3) The silver-containing particles further contain a metal M and / or its ions, wherein M is selected from transition metals and is different from Ag; preferably, M is selected from one or more of the following: lithium, sodium, potassium, magnesium, calcium, scandium, titanium, zirconium, vanadium, niobium, chromium, molybdenum, manganese, iron, cobalt, nickel, copper, zinc; preferably, M is Zn; (4) the silver-containing particles further comprise carbon nanotubes; (5) The diameter of the silver-containing particles ranges from 20 to 400 nm, or from 30 to 350 nm, or from 40 to 300 nm; (6) The diameter of the glass fiber is 5 to 30 μm, or 10 to 20 μm; (7) The length of the glass fiber is 0.5 to 10 mm, or 1 to 8 mm, or 2 to 6 mm.

2. A method for preparing a modified glass fiber, the method comprising the following steps: 1) preparing a first solution and a second solution, wherein the first solution is a salt solution containing complexed silver ions and counter ions, and the second solution is a solution of a polyphenol compound; 2) mixing the first solution and the second solution to obtain a first mixed solution containing silver particles; 3) adding glass fiber to the first mixed solution for treatment to obtain the modified glass fiber and a second mixed solution; Preferably, the method has one or more of the following features: (1) In the first solution, the complexed silver ions are complexed by one or more ligands selected from ammonia, hydroxyl, oxalate, carbonyl, EDTA, and cyano; preferably, the first solution is a silver ammonia solution; (2) the counter ion is selected from one or more of hydroxide ion, nitrate ion, chloride ion, bromide ion and fluoride ion, preferably nitrate ion; (3) In the first solution, the solvent is selected from one or more of water, ethanol, and acetone, preferably water; (4) the concentration of silver ions in the first solution is 1 to 15 mmol / L, or 3 to 13 mmol / L, or 5 to 11 mmol / L; (5) In the second solution, the polyphenol compound is selected from catechol, tannic acid, dopamine, catechin, gallic acid and green tea extract, preferably dopamine; (6) In the second solution, the concentration of the polyphenol compound is 1 to 30 mmol / L, or 5 to 25 mmol / L, or 10 to 20 mmol / L; (7) Step 3) is carried out at a temperature T1 of 10 to 40° C., or 15 to 35° C.; (8) step 3) lasts for a time t1 of 1 to 8 hours, or 1 to 6 hours, or 1 to 4 hours, or 1 to 2 hours; (9) adding glass fiber to the first mixed solution in an amount of 1 to 150 g / L, or 1 to 120 g / L, or 1 to 90 g / L; (10) In step 3), carbon nanotubes are further added to the first mixed solution; preferably, the carbon nanotubes are added to the first mixed solution in an amount of 0.01 to 1 g / L, or 0.01 to 0.8 g / L, or 0.01 to 0.6 g / L, or 0.01 to 0.4 g / L, or 0.01 to 0.2 g / L.

3. The method as claimed in claim 2, wherein the method further comprises the following steps: adding a salt solution of metal M to the first mixed solution or the second mixed solution; Preferably, the method has one or more of the following features: (1) adding an M salt solution at a concentration such that the M ion concentration is 1 to 15 mmol / L, or 3 to 12 mmol / L, or 3 to 10 mmol / L, or 3 to 8 mmol / L; (2) The metal M is selected from one or more of the following: lithium, sodium, potassium, magnesium, calcium, scandium, titanium, zirconium, vanadium, niobium, chromium, molybdenum, manganese, iron, cobalt, nickel, copper, and zinc; preferably, M is zinc.

4. A polyamide composition comprising: a) a polyamide resin, wherein the polyamide resin is selected from an aliphatic polyamide resin and a semi-aromatic polyamide resin, or a blend or a copolymer thereof; b) the modified glass fiber according to claim 1 or the modified glass fiber prepared by the method according to any one of claims 2 to 3; c) silver-containing particles, wherein the silver-containing particles comprise silver and a polyphenol compound; Preferably, the polyamide composition has one or more of the following properties: (1) The aliphatic polyamide resin is obtained by the condensation of: -C x Aliphatic lactams; -C y aliphatic amino acids; or -C a Aliphatic diacids and C b Aliphatic diamines; (2) The semi-aromatic polyamide resin is obtained by the condensation of: C c Aliphatic diacids and C d Aromatic diamine, or C e Aromatic diacids and C f Aliphatic diamines; (3) The polyamide resin is selected from one or more of PA46, PA56, PA6, PA66, PA12, PA4T, PA5T, PA6T / 6, PA6T / 66, PA6T / 66 / 6, PA9T, PA10T, and PA10T / 66; (4) the content of the polyamide resin of component a) is 30 to 90 wt %, or 30 to 80 wt %, or 30 to 70 wt %, or 30 to 60 wt %, relative to the total weight of the polyamide composition; (5) the content of the modified glass fiber of component b) is 10 to 40 wt%, or 10 to 35 wt%, or 10 to 30 wt%, or 10 to 25 wt%, relative to the total weight of the polyamide composition; (6) the silver-containing particles have a core-shell structure, wherein the core comprises Ag and the shell comprises the polyphenol compound; (7) component c) contains silver particles in an amount of 2 to 5% by weight, or 2.5 to 4.5% by weight, relative to the total weight of the polyamide composition; (8) The polyamide composition comprises component d) a halogen-free flame retardant, wherein the halogen-free flame retardant is added to the polyamide composition in the form of a composite masterbatch comprising the halogen-free flame retardant and a portion of component a) the polyamide resin.

5. The polyamide composition of claim 4, wherein the polyamide composition has one or more of the following characteristics: (1) C x The aliphatic lactam is selected from C4 to C 12 Aliphatic lactam, or C4 to C 10 Aliphatic lactam, or C4 to C8 aliphatic lactam; (2) C y The aliphatic amino acids are selected from C4 to C 12 Aliphatic amino acids, or C4 to C 10 Aliphatic amino acids, or C4 to C8 aliphatic amino acids; (3) C a The aliphatic diacid is selected from C4 to C 12 Aliphatic diacids, or C4 to C 10 an aliphatic diacid, or a C4 to C8 aliphatic diacid; (4) C b The aliphatic diamine is selected from C4 to C 12 Aliphatic diamine, or C4 to C 10 Aliphatic diamine, or C4 to C8 aliphatic diamine.

6. The polyamide composition of claim 4, wherein the polyamide composition has one or more of the following characteristics: (1) C c The aliphatic diacid is selected from C4 to C 12 Aliphatic diacids, or C4 to C 10 an aliphatic diacid, or a C4 to C8 aliphatic diacid; (2) C d Aromatic diamines are selected from C6 to C 18 Aromatic diamine, or C6 to C 16 Aromatic diamine, or C6 to C 14 Aromatic diamine, or C6 to C 12 Aromatic diamine, or C6 to C 10 Aromatic diamines; (3) C e Aromatic diacids are selected from C6 to C 18 Aromatic diacids, or C6 to C 16 Aromatic diacids, or C6 to C 14 Aromatic diacids, or C6 to C 12 Aromatic diacids, or C6 to C 10 Aromatic diacids; (4) C f The aliphatic diamine is selected from C4 to C 12 Aliphatic diamine, or C4 to C 10 Aliphatic diamine, or C4 to C8 aliphatic diamine.

7. The polyamide composition of claim 4, wherein the polyamide composition further comprises component d) a halogen-free flame retardant. Preferably, the polyamide composition has one or more of the following characteristics: (1) the mass fraction of the composite masterbatch of the halogen-free flame retardant is 20 to 30 weight %, relative to the total weight of the polyamide composition; (2) The halogen-free flame retardant is selected from one or more of hypophosphites, polyphosphates, and borates; preferably, the halogen-free flame retardant is a mixture of organic aluminum hypophosphite, melamine polyphosphate, and zinc borate; preferably, in the mixture, the weight ratio of organic aluminum hypophosphite, melamine polyphosphate, and zinc borate is 50:15:2 to 20:15:

2.

8. The polyamide composition of claim 4, wherein the polyamide composition comprises component e) an antioxidant; Preferably, the polyamide composition has one or more of the following characteristics: (1) The antioxidant is selected from one or more of copper salts, hindered phenols, or phosphites; (2) The content of the antioxidant is 0.001 to 1 wt %, or 0.001 to 0.8 wt %, or 0.001 to 0.6 wt %, or 0.001 to 0.4 wt %, or 0.001 to 0.3 wt %, relative to the total weight of the polyamide composition.

9. The polyamide composition of claim 4, wherein the polyamide composition comprises component f) a processing aid; Preferably, the polyamide composition has one or more of the following characteristics: (1) the content of the processing aid is 0.001 to 2 wt %, or 0.001 to 1.5 wt %, or 0.001 to 1.0 wt %, or 0.001 to 1.8 wt %, relative to the total weight of the polyamide composition; (2) The processing aid is selected from one or more of the following: OP wax, rice bran wax, CAV102, 816A, pentaerythritol stearate, ethylene bisoleamide, aluminum stearate, calcium montanate, sodium montanate.

10. The polyamide composition of claim 4, wherein the polyamide composition comprises g) a masterbatch; Preferably, the mass fraction of the masterbatch is 0.001 to 1 wt %, relative to the total weight of the polyamide composition.

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