Polyamide composite material, method for producing same, and use thereof

Abstract

The application provides a polyamide composite material and a preparation method and application thereof, and the polyamide composite material comprises, in parts by weight, 20-60 parts of a polyamide resin, 8-25 parts of polyvinylpyrrolidone, 0.5-3 parts of polyethylene glycol, 15-40 parts of glass fiber and 17-40 parts of a flame retardant. In the application, the polyamide composite material is prepared by adding polyvinylpyrrolidone and polyethylene glycol, and the two are compounded in specific contents, which is beneficial to improving the surface energy of the polyamide material, thereby improving the silk printing capacity of the polyamide composite material.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of engineering plastics, and particularly relates to a polyamide composite material and a preparation method and application thereof. BACKGROUND

[0002] Polyamide, commonly known as nylon, is a general term for thermoplastic resins containing repeating amide groups in the molecular backbone. It can be used as fiber and engineering plastic, and nylon is the earliest synthetic fiber developed, which has good comprehensive performance, such as high strength, good rigidity, impact resistance, oil and chemical resistance, wear resistance and good self-lubricating property, and the raw material is easy to obtain and the cost is low, so it is widely used in industrial, clothing, automobile, electronic and electrical, rail transportation and other fields. After glass fiber reinforcement and flame retardant modification, the mechanical strength of the nylon material is higher, the flame retardancy is better, and the application is wider, especially in the field of electronic and electrical appliances, which can replace some metals and other thermoplastic engineering plastics.

[0003] Generally, in order to meet specific needs, it is necessary to silk screen the nylon material, for example, to mark the material. However, the traditional nylon material has poor silk screening effect.

[0004] Therefore, it is an urgent problem in the field to develop a polyamide composite material with good silk screening effect. SUMMARY

[0005] In view of the deficiencies in the prior art, the purpose of the present application is to provide a polyamide composite material and a preparation method and application thereof. The polyamide composite material has high surface energy, which solves the problem of poor silk screening of traditional polyamide materials.

[0006] To achieve this purpose, the technical scheme adopted by the present application is as follows:

[0007] In the first aspect, the present application provides a polyamide composite material, which comprises, by weight, 20-60 parts of polyamide resin, 8-25 parts of polyvinylpyrrolidone, 0.5-3 parts of polyethylene glycol, 15-40 parts of glass fiber and 17-40 parts of flame retardant.

[0008] In the present application, the polyamide composite material, by adding polyvinylpyrrolidone and polyethylene glycol, and compounding them in a specific content, is beneficial to improve the surface energy of the polyamide material, thereby improving the silk screening capacity of the polyamide composite material.

[0009] In the present invention, the polyamide resin is 20-60 parts, for example, it can be 20 parts, 22 parts, 24 parts, 26 parts, 28 parts, 30 parts, 32 parts, 34 parts, 36 parts, 38 parts, 40 parts, 42 parts, 44 parts, 46 parts, 48 parts, 50 parts, 52 parts, 54 parts, 56 parts, 58 parts, 60 parts, and the range between any of the above values, preferably 25-58 parts, more preferably 30-55 parts.

[0010] In the present invention, the polyvinylpyrrolidone is 8-25 parts, for example, it can be 8 parts, 8.5 parts, 9 parts, 9.5 parts, 10 parts, 10.5 parts, 11 parts, 11.5 parts, 12 parts, 12.5 parts, 13 parts, 13.5 parts, 14 parts, 14.5 parts, 15 parts, 15.5 parts, 16 parts, 16.5 parts, 17 parts, 17.5 parts, 18 parts, 18.5 parts, 19 parts, 19.5 parts, 20 parts, 20.5 parts, 21 parts, 21.5 parts, 22 parts, 23 parts, 24 parts, 25 parts, or the range between any of the above values, preferably 12-21 parts, more preferably 18.5-20.5 parts.

[0011] In the present invention, the polyethylene glycol is 0.5-3 parts, for example, it can be 0.5 parts, 0.52 parts, 0.54 parts, 0.56 parts, 0.58 parts, 0.6 parts, 0.62 parts, 0.65 parts, 0.68 parts, 0.7 parts, 0.72 parts, 0.75 parts, 0.78 parts, 0.8 parts, 0.82 parts, 0.85 parts, 0.88 parts, 0.9 parts, 0.92 parts, 0.95 parts, 0.98 parts, 1 parts, 1.1 parts, 1.2 parts, 1.3 parts, 1.4 parts, 1.5 parts, 1.6 parts, 1.7 parts, 1.8 parts, 1.9 parts, 2 parts, 2.1 parts, 2.2 parts, 2.3 parts, 2.4 parts, 2.5 parts, 2.6 parts, 2.7 parts, 2.8 parts, 2.9 parts, 3 parts, or the range between any of the above values; preferably 0.8-2.5 parts, more preferably 1-2 parts.

[0012] In the present invention, the glass fiber is 15-40 parts, for example, it can be 15 parts, 16 parts, 18 parts, 20 parts, 22 parts, 24 parts, 25 parts, 26 parts, 28 parts, 30 parts, 32 parts, 34 parts, 35 parts, 36 parts, 38 parts, 40 parts, or the range between any of the above values; preferably 20-30 parts.

[0013] In the present invention, the flame retardant is 17-40 parts, for example, it can be 17 parts, 18 parts, 20 parts, 22 parts, 24 parts, 25 parts, 26 parts, 28 parts, 30 parts, 32 parts, 34 parts, 35 parts, 36 parts, 38 parts, 40 parts, or the range between any of the above values; preferably 20-30 parts.

[0014] Preferably, the polyamide resin comprises at least one of a condensation product of a diacid with a diamine, a condensation product of an aminocarboxylic acid, or a ring-opening polymerization product of an internal lactam.

[0015] Preferably, the polyamide resin comprises polyhexamethylene adipamide and / or polycaprolactam, more preferably polyhexamethylene adipamide.

[0016] Preferably, the polyamide resin has a relative viscosity of 2.0 to 3.4, for example 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3, 3.1, 3.2, 3.3, 3.4, or a range between any of the aforementioned values.

[0017] In the present application, the relative viscosity of the polyamide resin is the relative viscosity of the polyamide resin at a concentration of 1 g / mL in 96% concentrated sulfuric acid at 25°C, and the specific test method comprises: weighing 0.5 g of polyamide resin, transferring it into a 50 mL volumetric flask, adding about 40 mL of 96% mass fraction of concentrated sulfuric acid, ultrasonic oscillation until the polyamide resin is completely dissolved, cooling the solution to 25°C, diluting to the mark with concentrated sulfuric acid, and mixing uniformly, testing the flow time of 0.01 g / mL of the polyamide resin solution through the Ubbelohde viscometer at 25°C, recorded as t1, testing the flow time of the solvent concentrated sulfuric acid with the same viscometer, recorded as t2, and t1 / t2 is the relative viscosity.

[0018] Preferably, the polyvinylpyrrolidone has a melting point of 110 to 180°C, for example 110°C, 120°C, 130°C, 140°C, 150°C, 160°C, 170°C, 180°C, or a range between any of the aforementioned values.

[0019] In the present application, the polyvinylpyrrolidone has a K value of 75 to 115, for example 75, 76, 78, 80, 82, 84, 86, 88, 90, 92, 94, 96, 98, 100, 102, 104, 106, 108, 110, 112, 114, 115, or a range between any of the aforementioned values; more preferably 85 to 105.

[0020] Preferably, the polyethylene glycol has a number average molecular weight of 3500 to 12000, for example, 3500, 3600, 3800, 4000, 4200, 4500, 4800, 5000, 5200, 5500, 5800, 6000, 6200, 6500, 6800, 7000, 7200, 7500, 7800, 8000, 8200, 8500, 8800, 9000, 9200, 9500, 9800, 10000, 10200, 10500, 10800, 11000, 11200, 11500, 11800, 12000, or a range between any of the aforementioned values; further preferably, 7500 to 11000, more preferably, 8500 to 10500.

[0021] Preferably, the glass fiber comprises at least one of an E-glass fiber, an A-glass fiber, an S-glass fiber, a D-glass fiber, a C-glass fiber, or a quartz glass fiber; preferably, an E-glass fiber.

[0022] Preferably, the flame retardant comprises 13 to 30 parts by weight of an organic phosphinate salt flame retardant (for example, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, or a range between any of the aforementioned values, more preferably, 15 to 25 parts) and 4 to 10 parts by weight of a synergistic flame retardant (for example, 4, 4.5, 5, 5.5, 6, 6.5, 7, 7.5, 8, 8.5, 9, 9.5, 10, or a range between any of the aforementioned values, more preferably, 4.5 to 8.5 parts).

[0023] Preferably, the organic phosphinate salt flame retardant comprises aluminum diethylphosphinate.

[0024] Preferably, the synergistic flame retardant comprises a melamine-based flame retardant and / or zinc borate.

[0025] Preferably, the melamine-based flame retardant comprises at least one of melamine polyphosphate, melamine aluminum polyphosphate, melamine magnesium polyphosphate, or melamine zinc polyphosphate, more preferably, melamine polyphosphate.

[0026] Preferably, the polyamide composite further comprises 0.1 to 10 parts by weight of other auxiliary agents, for example, 0.1, 0.2, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, or a range between any of the aforementioned values.

[0027] Preferably, the other additives include at least one of an antioxidant, a lubricant, or a heat stabilizer.

[0028] In the present application, the antioxidant includes at least one of a hindered phenol antioxidant, an amine antioxidant, a cuprous halide complex antioxidant, or a benzophenone antioxidant.

[0029] In the present application, the lubricant includes at least one of a hydrocarbon lubricant, an ester lubricant, an alcohol lubricant, a fatty acid lubricant, a fatty acid amide lubricant, or a metal soap lubricant; preferably an ester lubricant, such as a fatty acid ester, a polyol ester, a polyethylene glycol ester, etc.

[0030] In the present application, the heat stabilizer includes a phosphite heat stabilizer; the phosphite heat stabilizer has a structural formula of P(OR)3, wherein R is the same or different, each independently selected from any one of C1-C20 alkyl, C3-C22 alkenyl, C6-C40 cycloalkyl, C7-C40 cycloalkylene, a substituted or unsubstituted aryl; the substituent of the substituted substituent includes an alkyl group containing at least one carbon atom.

[0031] In the present application, the other additives include 0.1-1 parts of an antioxidant and 0.2-1.2 parts of a lubricant by weight.

[0032] In a second aspect, the present application provides a method for preparing the polyamide composite material of the first aspect, the method comprising the following steps:

[0033] The components are mixed and extruded to obtain the polyamide composite material.

[0034] Preferably, the mixed material further includes other additives.

[0035] In the present application, the mixing includes: mixing the polyamide resin, the polyvinylpyrrolidone, the polyethylene glycol, the flame retardant, and the optional other additives in a high-speed mixer for 3-10 min, and then adding to the main feeding hopper of a twin-screw extruder; adding the glass fiber to the side feeding hopper of the twin-screw extruder for mixing.

[0036] Preferably, the extrusion temperature is 160-260°C, for example, it can be 160°C, 165°C, 170°C, 175°C, 180°C, 185°C, 190°C, 195°C, 200°C, 205°C, 210°C, 215°C, 220°C, 225°C, 230°C, 235°C, 240°C, 245°C, 250°C, 255°C, 260°C, or a range between any of the above values.

[0037] In the present application, the screw rotation speed of the double screw extruder is 300-800 rpm, the length-diameter ratio is 36:1-48:1, the barrel temperature of each section of the double screw extruder is 160-250 DEG C, and the head temperature is 230-260 DEG C.

[0038] In a third aspect, the present application provides a silk printing material, which comprises the polyamide composite material according to the first aspect.

[0039] In the present application, the polyamide composite material has excellent silk printing performance and high impact strength, and can meet the requirements of the automobile, electronic and electrical, connector, energy storage and other industries on material performance.

[0040] The numerical range in the present application not only includes the point values listed above, but also includes any point values between the above numerical ranges that are not listed, and the specific point values included in the range are not listed due to the length and for the sake of simplicity.

[0041] Compared with the prior art, the present application has the following beneficial effects:

[0042] The polyamide composite material provided by the present application is prepared by adding polyvinylpyrrolidone and polyethylene glycol in a specific content, and compounding with polyamide resin, glass fiber and flame retardant, so that the glass fiber reinforced and flame retardant modified polyamide composite material has high surface energy and good silk printing capacity, and can meet the requirements of the automobile, electronic and electrical, connector, energy storage and other industries on material performance. DETAILED DESCRIPTION

[0043] The technical solutions of the present application will be further described below through specific embodiments. Those skilled in the art should understand that the embodiments are only to help understand the present application, and should not be regarded as a specific limitation on the present application.

[0044] The materials used in the present application can be obtained by market or conventional methods, and if not specifically stated, the materials used in the present application are as follows:

[0045] Polyhexamethylene adipamide: Nylon 66 (PA66), Sima Group EPR24, relative viscosity 2.4;

[0046] Polycaprolactam: Nylon 6 (PA6), Jiangsu Haiyang Chemical Fiber HY-2800A, relative viscosity 2.75;

[0047] Aluminum diethyl phosphinate: Clariant Exolit OP 1230;

[0048] Synergistic flame retardant: polyphosphoric acid melamine, Budit 3141 of Baud;

[0049] Glass fiber: ECS10-03-568H of China Jushi Co., Ltd.

[0050] Polyvinylpyrrolidone (PVP)

[0051] PVP-1: PVP K90 from Beijing Solabio Technology Co., Ltd.

[0052] PVP-2: PVP K85 from Gobekie;

[0053] PVP-3: PVP K100 from Gobekie;

[0054] PVP-4: PVP K80 from Gobekie;

[0055] PVP-5: PVP K110 from Gobekie;

[0056] Polyethylene glycol (PEG)

[0057] PEG-1: PEG-4000 with a number average molecular weight of 4000 from Guangzhou Jinchangsheng Technology Co., Ltd.

[0058] PEG-2: PEG-8000 with a number average molecular weight of 8000 from Guangzhou Fentian Chemical Co., Ltd.

[0059] PEG-3: PEG-10000 with a number average molecular weight of 10000 from Guangzhou Rongda Chemical Co., Ltd.

[0060] PEG-4: PEG-12000 with a number average molecular weight of 12000 from Zeye Bioengineering Co., Ltd.

[0061] Antioxidant: Hindered phenolic antioxidant, IRGANOX 1098 from BASF;

[0062] Lubricant: Ester lubricant, TR044W from Struktol;

[0063] Glycerol: Molecular weight 92.09, Jiangsu Lunfeng Synthetic Technology Co., Ltd.

[0064] Examples 1-20, Comparative Examples 1-8

[0065] Examples 1-20 and Comparative Examples 1-8 each provide a polyamide composite material, the formulation of which is shown in Tables 1-4, in parts by weight, wherein " / " indicates that the component is not present in the formulation; the polyamide composite material is prepared by mixing the components except for the glass fiber in a high-speed mixer for 6 minutes, and then adding to the main feeding hopper of a twin-screw extruder; the glass fiber is added to the side feeding hopper of the sixth section of the barrel of the twin-screw extruder, and after being sufficiently plasticized and melted in the twin-screw extruder, it is extruded, drawn, cooled, and pelletized to obtain the polyamide composite material. The screw rotation speed of the twin-screw extruder is 500 rpm, the length-diameter ratio is 44:1, the barrel temperature of each section of the extruder is 180°C, and the die temperature is 240°C.

[0066] Table 1

[0067]

[0068] Table 2

[0069]

[0070]

[0071] Table 3

[0072]

[0073] Table 4

[0074]

[0075]

[0076] Performance Test

[0077] (1) Surface energy: the contact angle of the polyamide composite material provided in Examples 1-20 and Comparative Examples 1-8 is tested using a contact angle tester, and the surface energy of the polyamide composite material is calculated with the aid of the Fowkes model; the liquid used for testing is water; the greater the surface energy, the better the silk printing ability.

[0078] (2) Silk printing ability: the polyamide composite material provided in Examples 1-20 and Comparative Examples 1-8 is silk printed using ink (FBS series-PAHS ink, JinSi plastic new materials), the silk printing effect of the material is observed by visual observation, and the silk printing effect is divided into three levels, in order: A, B, and C; wherein A indicates that it is excellent, the gloss after silk printing is good, the surface is smooth, and there are no defects; B indicates that it is good, the surface after silk printing is defect-free and smooth, but the gloss is poor; C indicates that it is unqualified, the surface after silk printing has defects (such as the presence of fine pores, cracking, etc.), and the gloss is poor, and the surface is rough.

[0079] The specific test results are shown in Table 5.

[0080] Table 5

[0081]

[0082]

[0083] It can be seen from Table 5 that the polyamide composite provided by the application has high surface energy and good silk printing capacity by adding polyvinylpyrrolidone and polyethylene glycol of specific content to polyamide resin, glass fiber and flame retardant, and the glass fiber reinforced and flame retardant modified polyamide composite has surface energy ≥ 27.5 mN / m and good silk printing effect.

[0084] It can be seen from the comparative example that the polyamide composite is not compounded by adding polyvinylpyrrolidone of specific content and polyethylene glycol of specific content, the surface energy is reduced, and the silk printing effect is poor.

[0085] The above specific embodiments further illustrate the purpose, technical solutions and beneficial effects of the application, and it should be understood that the above description is only a specific embodiment of the application and is not used to limit the application, and any modification, equivalent replacement, improvement, etc. within the spirit and principle of the application should be included in the protection scope of the application.

Claims

1. A polyamide composite, characterized in that, The polyamide composite comprises 20-60 parts by weight of a polyamide resin, 8-25 parts by weight of polyvinylpyrrolidone, 0.6-3 parts by weight of polyethylene glycol, 15-40 parts by weight of glass fiber, and 17-40 parts by weight of a flame retardant. The flame retardant comprises 13-30 parts by weight of an organic phosphinate salt flame retardant and 4-10 parts by weight of a synergistic flame retardant.

2. The polyamide composite according to claim 1, characterized in that, The polyamide resin comprises at least one of a condensation product of a diamine and a diacid, a condensation product of an aminocarboxylic acid, or a ring-opening polymerization product of a cyclic lactam.

3. The polyamide composite according to claim 2, characterized in that, The polyamide resin comprises polyhexamethylene adipamide and / or polycaprolactam.

4. The polyamide composite according to claim 3, characterized in that, The polyamide resin is polyhexamethylene adipamide.

5. The polyamide composite of claim 1, wherein, The polyamide resin has a relative viscosity of 2.0-3.

4. The relative viscosity of the polyamide resin is the relative viscosity of a polyamide resin having a concentration of 1 g / mL in 96% concentrated sulfuric acid at 25°C, and the specific test method comprises: weighing 0.5 g of the polyamide resin, transferring it into a 50 mL volumetric flask, adding 40 mL of 96% mass fraction concentrated sulfuric acid, ultrasonic oscillation until the polyamide resin is completely dissolved, cooling the solution to 25°C, diluting to the mark with concentrated sulfuric acid, and mixing uniformly, testing the flow time of a 0.01 g / mL polyamide resin solution through an Ubbelohde viscometer at 25°C, and recording it as t1, testing the flow time of the solvent concentrated sulfuric acid through the same viscometer, and recording it as t2, t1 / t2 is the relative viscosity.

6. The polyamide composite of claim 1, wherein, The polyvinylpyrrolidone has a K value of 75-115.

7. The polyamide composite according to claim 6, characterized in that, The polyvinylpyrrolidone has a K value of 85-105.

8. The polyamide composite of claim 1, wherein, The polyethylene glycol has a number average molecular weight of 3500-12500.

9. The polyamide composite according to claim 8, characterized in that, The polyethylene glycol has a number average molecular weight of 7500-11000.

10. The polyamide composite of claim 1, wherein, The glass fiber comprises at least one of an alkali-free glass fiber, a high-alkali glass fiber, a D glass fiber, a medium-alkali glass fiber, or a quartz glass fiber.

11. The polyamide composite according to claim 10, characterized in that, The glass fiber comprises an alkali-free glass fiber.

12. The polyamide composite of claim 1, wherein, The organic phosphinate salt flame retardant comprises aluminum diethylphosphinate.

13. The polyamide composite of claim 1, wherein, The synergistic flame retardant comprises a melamine-based flame retardant and / or zinc borate.

14. The polyamide composite according to claim 13, characterized in that The melamine-based flame retardant comprises at least one of melamine polyphosphate, melamine aluminum polyphosphate, melamine magnesium polyphosphate, or melamine zinc polyphosphate.

15. The polyamide composite according to claim 14, characterized in that The melamine-based flame retardant is melamine polyphosphate.

16. The polyamide composite of claim 1, wherein, The polyamide composite further comprises 0.1-10 parts by weight of other auxiliary agents.

17. The polyamide composite of claim 16, wherein, The other auxiliary agents comprise at least one of an antioxidant, a lubricant, or a heat stabilizer.

18. A process for the production of a polyamide composite according to any one of claims 1 to 15, characterized in that The preparation method comprises the following steps: mixing the components, and extruding to obtain the polyamide composite.

19. The method of claim 18, wherein, The mixed material further comprises other auxiliary agents.

20. The method of claim 18, wherein, The extrusion temperature is 160-260°C.

21. A screen printing material, characterized by, The silk printing material comprises the polyamide composite according to any one of claims 1-17.

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