Polyamide / polyketone alloy material as well as preparation method and application thereof

Abstract

The invention discloses a polyamide / polyketone alloy material as well as a preparation method and application thereof. The polyamide / polyketone alloy material is prepared from the following raw materials in parts by weight: 10-84.95% of polyamide resin; 5 to 25% of polyketone resin; 0.01%-5% of a compatilizer 1; 0.01 to 5% of a compatilizer 2; 10 to 50% of glass fiber; 0.01%-1% of a nucleating agent A; 0.01%-1% of a nucleating agent B; 0.01 to 1% of an antioxidant; and 0-2% of other additives. The problem of compatibility of polyamide and polyketone is solved through the synergistic effect of the multi-component compatilizers in formula design, the improvement of the compatibility is beneficial to improving the mechanical property of the alloy material, and meanwhile, the difference of the cooling crystallization temperature and rate of polyamide and polyketone is improved through the compounded nucleating agent; the compatibility of the polyamide and the polyketone in the cooling crystallization process is further improved, and the improvement of the compatibility of the polyamide and the polyketone is beneficial to the improvement of the mechanical property of the alloy material. The mechanical property of the prepared polyamide / polyketone alloy material is greatly improved, and the preparation method is simple and suitable for industrial production and application.

Description

Technical Field

[0001] The invention relates to the field of polymer materials, and in particular to a polyamide / polyketone alloy material and a preparation method and application thereof. Background Art

[0002] Polyamide, commonly known as nylon, has good comprehensive properties, including mechanical properties, chemical resistance, heat resistance, wear resistance, self-lubrication, low friction coefficient, certain flame retardancy, easy processing, and suitable for filling and reinforcing modification with glass fiber and other fillers, which further improves the performance of polyamide and expands its application range. Polyamide can include PA6, PA66, PA46, PA6T / X, PA12, etc. according to the difference in chemical structure. These characteristics make polyamide a leader in engineering plastics and are widely used in various fields, from wear-resistant parts to automobile manufacturing parts, from household appliance parts to chemical machinery parts, polyamide plays an indispensable role.

[0003] POK, the full name of which is Polyketone, belongs to the polyketone class of materials and is a new type of green polymer material made by the polymerization of carbon monoxide, ethylene and propylene. POK has excellent wear resistance, chemical resistance, high impact resistance and barrier properties. A large amount of carbon monoxide is consumed during the synthesis process. For every 50,000 tons of POK produced, the mass of carbon monoxide consumed is 25,000 tons, which is equivalent to the purification effect of 3.8 million pine trees for 5 years. Therefore, vigorously developing the production and application of POK is in line with the green and sustainable development strategy.

[0004] Polyamide and polyketone as alloys combine the performance advantages of both and have important research value. Chinese patent CN107189425A discloses a highly wear-resistant polyamide / polyketone alloy, the raw materials include polyamide, polyketone, compatibilizer and other additives, and also include needle coke, and the compatibilizer is an ethylene maleic anhydride alternating copolymer. The prepared material has excellent wear resistance and good dimensional stability, low water absorption, and can be used to manufacture transmission parts for automobiles, electronic appliances and various machinery, as well as parts requiring high strength, high wear resistance and dimensional stability. Chinese patent CN110951159A provides a polypropylene / polyamide / polyketone composition and a preparation method thereof, wherein the polypropylene / polyamide / polyketone composition is prepared from the following raw materials: polypropylene resin, polyamide resin, polyketone resin, compatibilizer, scratch resistant agent, antioxidant and lubricant; the compatibilizer is at least one of maleic anhydride grafted polypropylene and maleic anhydride grafted polyethylene; the scratch resistant agent is composed of cubic boron nitride and hexagonal boron nitride. The polypropylene / polyamide / polyketone composition has high hardness and excellent scratch resistance, and also has good mechanical properties. Chinese patent CN113480807A relates to a polyamide, polyketone and polyolefin alloy material and a preparation method thereof. The polyamide, polyketone and polyolefin alloy material described in the present invention has extremely low water absorption, dimensional stability, wear resistance, high toughness, chemical resistance, hydrolysis resistance, relatively high heat deformation temperature, good strain capacity and resilience, and has a relatively wide processing window, excellent melt strength and easy extrusion processing advantages, and has broad application prospects. The currently disclosed patents have made certain studies on the performance of polyamide / polyketone alloy materials, but the research content is limited to the types of alloy resins, and compatibility is a key factor affecting the performance of alloys. The disclosed inventions lack research on the influence of polyamide / polyketone formula composition and processing technology on the compatibility of alloy materials. Increasing the compatibility of polyamide and polyketone by formula design of compound compatibilizers and nucleating agents and studying the influence of preparation process on compatibility are of great significance for improving the comprehensive performance of polyamide / polyketone alloy materials and expanding their application fields. Summary of the invention

[0005] In order to fill the gap in the prior art, the present invention provides a polyamide / polyketone alloy material and a preparation method and application thereof, which improves the compatibility of polyamide and polyester in multiple dimensions by formula design, compatibilizer compounding and nucleating agent compounding, and improves the mechanical properties of the polyamide / polyketone alloy material. The preparation method of the present invention is simple and suitable for industrial production and application.

[0006] The present invention is achieved through the following technical solutions:

[0007] A polyamide / polyketone alloy material, comprising the following raw materials in percentage by weight:

[0008]

[0009]

[0010] The polyamide resin is a PA66 slice having reactive amino groups at the ends thereof, the polyamide resin has a melting point of 255-265° C., a relative viscosity of 2.6±0.6, and a terminal amino content of ≥80 mmol / kg.

[0011] The polyketone resin is a ternary copolymer of carbon monoxide, ethylene and propylene (POK-ep), with a melt index of 10-50 g / 10 min (test conditions 230° C., 2.16 kg), a number average molecular weight Mn ≥ 60,000, a melting point of 210-220° C., and a structural formula as follows:

[0012]

[0013] Where n and m represent the number of repeating units.

[0014] The compatibilizer 1 is a block copolymer of polyamide, polyester and polyether, with a number average molecular weight Mn≥10000 and a general structural formula:

[0015] -[BD-BM]n-

[0016] Wherein, BD comprises polyamide blocks, BM comprises polyether and polyester block polymerization sequences, n represents the number of copolymer repeating units, and the weight percentage of polyamide blocks is 60-80%.

[0017] The compatibilizer 2 is a polyvinyl pyrrole derivative containing a pyrrole structure, which is prepared from polyketone by amidation reaction, and has the following general structural formula:

[0018]

[0019] Wherein n and m represent the number of repeating units, n:m>5:1, n+m>500.

[0020] The glass fiber has an alkali content of less than 0.8% and a volume density of 0.6-0.8 g / cm 3 , single fiber diameter: 7-13μm, short cut length: 2-5mm, moisture content ≤0.05%.

[0021] The nucleating agent A is CuCl2-PA-66, and the ion content is 2-7 mol%.

[0022] The nucleating agent B is a rare earth metal complex, and the general structural formula is as follows:

[0023] (Cp)nM-[RC(NR')2]-

[0024] Wherein M is a lanthanide metal, preferably La, and [RC(NR')2] represents an amidine ligand, and the structural formula is as follows:

[0025]

[0026] Cp represents a cyclopentadienyl ligand, and the structural formula is as follows:

[0027]

[0028] Where 1≤n≤5.

[0029] The antioxidant is a mixture of a phosphite antioxidant and a hindered phenol antioxidant in a ratio of 1:1 (by weight), wherein the phosphite antioxidant may be tetrakis(2,4-di-tert-butylphenol)-4,4'-biphenyl diphosphite, CAS: 119345-01-6; tris[2.4-di-tert-butylphenyl]phosphite, CAS No. 31570-04-4; 3,9-bis(2,4-dicumylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, CAS No. 154862-43-8; and the hindered phenol antioxidant may be N,N'-bis-(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl)hexanediamine, CAS No.23128-74-7; triethylene glycol ether-di(3-tert-butyl-4-hydroxy-5-methylphenyl) propionate, CAS No.36443-68-2; pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate, CAS No.6683-19-8, etc.

[0030] The hindered phenol antioxidant of the present invention is preferably pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, and the phosphite antioxidant is preferably 3,9-bis(2,4-dicumylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane.

[0031] The other auxiliary agents may be one or more of lubricants and colorants.

[0032] The polyamide / polyketone alloy material and its preparation method and application are characterized by comprising the following steps:

[0033] (1) Weigh various dried raw materials according to the formula ratio; mix the polyamide resin, compatibilizer 1, nucleating agent A, antioxidant and other additives uniformly by high-speed stirring (mixture A) and set aside. Mix the polyketone resin, compatibilizer 2 and nucleating agent B uniformly by high-speed stirring (mixture B) and set aside; weigh glass fiber according to the ratio and set aside;

[0034] (2) The mixture A is added through the main feed port of a twin-screw extruder, the mixture B is added through the first side feed port (close to the main feed port) of the twin-screw extruder, and the glass fiber is added from the second side feed port (close to the die head) of the twin-screw extruder. After melt extrusion, granulation, drying and other processes, the polyamide / polyketone alloy material is obtained.

[0035] The preparation method of the polyamide / polyketone alloy material is simple and suitable for industrial production and application.

[0036] The advantage of the present invention is that according to the characteristics of the molecular structures of polyamide and polyketone, the compatibility problem of polyamide and polyketone is effectively solved by formula design and compounding compatibility. The improvement of compatibility helps to improve the mechanical properties of the alloy material. At the same time, the difference in cooling crystallization temperature and rate between polyamide and polyketone is improved by the compounded nucleating agent, which further increases the compatibility of the cooling crystallization process of polyamide and polyketone, and improves the mechanical properties of the alloy material.

[0037] The beneficial effects of the present invention are:

[0038] 1) The present invention selects polyamide, polyester and polyether block copolymers and polyvinyl pyrrole derivatives containing pyrrole structure as compatibilizers. Polyamide, polyester and polyether block copolymers contain the same segments of polyamide and polyketone, which can improve the compatibility of polyamide and polyketone, and achieve the desired effect by limiting the ratio of polyamide and polyketone in the formula and the ratio of each structural unit of polyamide, polyester and polyether block copolymers. The polyvinyl pyrrole derivative containing pyrrole structure contains the structure and amino group of polyketone, which can effectively increase the compatibility of polyamide, polyketone and glass fiber. The compatibilizer compounded in the present invention increases the compatibility of polyamide, polyketone and glass fiber through the combined action of "similar compatibility" and "chemical compatibilization", and improves the mechanical properties of nylon polyketone alloy materials.

[0039] 2) The present invention selects ionic polymer nucleating agent CuCl2-PA-66 and rare earth metal complex as compound nucleating agent. The introduction of ionic groups produces strong ion-dipole interaction on the interface layer of polyamide and polyketone, which enhances the interfacial compatibility of the two phases. The interfacial compatibilization makes the crystal nucleus size of the dispersed phase of the nucleating agent smaller and the crystal nucleus number density higher, thereby significantly improving the nucleation efficiency of the nucleating agent. 2+ It has excellent coordination effect, and a small amount of addition can achieve excellent effect. Rare earth metal compounds can accelerate and refine the grain structure. Organic complexation can increase the compatibility of nucleating agents with resins and increase the dispersibility of nucleating agents in resins. The synergistic effect of compound nucleating agents improves the difference in cooling crystallization temperature and rate between polyamide and polyketone, and further increases the compatibility of polyamide and polyketone in cooling crystallization process.

[0040] 3) The present invention uses specific formula components and a two-step preparation process, which, compared with the disclosed one-step processing process, enables a polyamide / polyketone composition with excellent mechanical properties to be obtained.

[0041] 4) The present invention limits the structure of polyamide and polyketone resins. The limit of the number of amino groups in polyamide resin can achieve a better chemical compatibilization effect of polyamide resin, glass fiber and polyvinyl pyrrole derivatives containing pyrrole structure as a compatibilizer. The polyketone material prepared by ternary copolymerization of carbon monoxide, ethylene and propylene has a low melting point, which can achieve better dispersion in polyamide resin.

[0042] 5) The present invention is based on the structural characteristics of polyamide and polyketone, and is designed to increase the compatibility between the components of the alloy material from the perspective of formula design and processing technology, thereby improving the mechanical properties of the alloy material. The preparation method is simple and suitable for industrial production and application.

[0043] The above beneficial effects achieve excellent mechanical properties of the polyamide / polyketone alloy material. DETAILED DESCRIPTION

[0044] In order to make the technical problems, technical solutions and intentions to be solved by the present invention clearer, the present invention will be further described in detail below in conjunction with embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not used to limit the present invention.

[0045] The embodiments and comparative examples of the present invention use the following materials, but are not limited to the following materials:

[0046] Polyamide resin PA66, commercially available;

[0047] Polyketone resin POK-ep, commercially available;

[0048] Glass fiber, trade name ECS301HP-3, produced by Chongqing International Composite Materials Co., Ltd.;

[0049] Compatibilizer 1, polyamide, polyester and polyether block copolymer, commercially available;

[0050] Compatibilizer 2, polyvinylpyrrole derivative, commercially available;

[0051] Nucleating agent A, CuCl2-PA-66, commercially available;

[0052] Nucleating agent B, rare earth metal complex, commercially available;

[0053] Processing aid, trade name LYSI-100E silicone powder, commercially available;

[0054] Antioxidant 1010, hindered phenol antioxidant, commercially available;

[0055] Antioxidant 9228, phosphite antioxidant, commercially available;

[0056] Black masterbatch, PA6-2015, commercially available;

[0057] Preparation methods of Examples 1-7 and Comparative Examples 1-6:

[0058] Two-step preparation method of polyamide / polyketone alloy material

[0059] (1) Weighing various dried raw materials according to the formula ratio; mixing polyamide resin, compatibilizer 1, nucleating agent A, antioxidant and other additives uniformly by high-speed stirring (mixture A), and setting aside; mixing polyketone resin, compatibilizer 2, nucleating agent B uniformly by high-speed stirring (mixture B), and setting aside; weighing glass fiber according to the ratio, and setting aside;

[0060] (2) The mixture A is added through the main feed port of a twin-screw extruder, the mixture B is added through the first side feed port (close to the main feed port) of the twin-screw extruder, and the glass fiber is added from the second side feed port (close to the die head) of the twin-screw extruder. After melt extrusion, granulation, drying and other processes, the polyamide / polyketone alloy material is obtained.

[0061] One-step preparation method of polyamide / polyketone alloy material

[0062] (1) Weighing various dried raw materials according to the formula ratio; mixing polyamide resin, polyketone resin, compatibilizer 1, compatibilizer 2, nucleating agent A, nucleating agent B, antioxidant and other additives uniformly by high-speed stirring, and setting aside; weighing glass fiber according to the ratio, and setting aside;

[0063] (2) The above mixture is added through the main feeding port of a twin-screw extruder, and glass fiber is added from the side feeding port of the twin-screw extruder. After melt extrusion, granulation, drying and other processes, the polyamide / polyketone alloy material is obtained.

[0064] Preparation of polyamide / polyketone alloy material test specimens:

[0065] The above materials were dried in a forced air drying oven at 120° C. for 4 hours and then injection molded into standard specimens at an injection molding temperature of 280-310° C. The prepared mechanical properties specimens were conditioned in a standard laboratory environment (23° C., 50% RH) for 24 hours before testing.

[0066] Test methods for each performance index:

[0067] Tensile properties: According to ISO 527 method, sample size: 170*10*4mm, test speed 5mm / min.

[0068] Bending strength: According to ISO 178 method, sample size: 80*10*4mm, test speed 2mm / min.

[0069] Bending properties: According to ISO 178 method, sample size: 80*10*4mm, test speed 2mm / min.

[0070] Notched impact performance: According to ISO 179 method, sample size: 80*10*4mm.

[0071] Table 1: Composition and properties of polyamide / polyketone alloy materials of Examples 1-7 and Comparative Examples 1-6

[0072]

[0073]

[0074] It can be seen from the results of the embodiments and comparative examples in Table 1 that the embodiments of the present invention are greatly improved in mechanical properties such as tensile strength, flexural strength, flexural modulus and notched impact. It can be seen from Example 1, Examples 4-5 and Comparative Examples 1-2 that the compounding of compatibilizers can effectively improve the mechanical properties of polyamide / polyketone alloy materials, and its effect is better than the performance improvement brought by changing the addition amount of a single compatibilizer. This is because the compounding of compatibilizers takes into account the joint effects of "similar compatibility" and "chemical compatibilization", and the two can be effectively coordinated in increasing the compatibility of polyamide and polyketone. It can be seen from Example 1, Examples 6-7 and Comparative Examples 3-4 that compared with a single nucleating agent, the compounding of nucleating agents can increase the mechanical properties of nylon polyketone alloy materials to obtain a more ideal effect. The nucleating agent can reduce the size of the crystal nucleus, increase the crystal nucleus, improve the nucleation efficiency, thereby reducing the difference in the cooling crystallization temperature and rate between polyamide and polyketone, and improving the compatibility of the two in the cooling crystallization process. It can be seen from Example 1 and Comparative Example 6 that the specific formula components and the two-step preparation process can obtain a polyamide / polyketone composition with excellent mechanical properties compared to the disclosed one-step processing process. It can be seen from Examples 1-3 and Comparative Example 5 that the present invention can increase the compatibility of different proportions of polyketone, polyamide, and glass fiber, and the preparation method of the present invention is simple and suitable for industrial production and application.

Claims

1. A polyamide / polyketone alloy material, characterized in that: The raw material composition is as follows by weight percentage:

2. The polyamide / polyketone alloy material according to claim 1, characterized in that: The polyamide resin is a PA66 slice having reactive amino groups at the ends thereof, the polyamide resin has a melting point of 255-265° C., a relative viscosity of 2.6±0.6, and a terminal amino content of ≥80 mmol / kg.

3. The polyamide / polyketone alloy material according to claim 1, characterized in that: The polyketone resin is a ternary copolymer of carbon monoxide, ethylene and propylene (POK-ep), with a melt index of 10-50 g / 10 min (test conditions 230° C., 2.16 kg), a number average molecular weight Mn ≥ 60,000, a melting point of 210-220° C., and a structural formula as follows: Where n and m represent the number of repeating units.

4. The polyamide / polyketone alloy material according to claim 1, characterized in that: The compatibilizer 1 is a block copolymer of polyamide, polyester and polyether, with a number average molecular weight Mn≥10000 and a general structural formula: -[BD-BM]n- Wherein, BD comprises polyamide blocks, BM comprises polyether and polyester block polymerization sequences, n represents the number of copolymer repeating units, and the weight percentage of polyamide blocks is 60-80%.

5. A polyamide / polyketone alloy material according to claim 1, wherein: the compatibilizer 2 is a polyvinyl pyrrole derivative containing a pyrrole structure, which is prepared from polyketone by amidation reaction, and has the following general structural formula: Wherein n and m represent the number of repeating units, n:m>5:1, n+m>500.

6. The polyamide / polyketone alloy material according to claim 1, wherein the glass fiber has an alkali content of less than 0.8% and a bulk density of 0.6-0.8 g / cm 3 , single fiber diameter: 7-13μm, short cut length: 2-5mm, moisture content ≤0.05%.

7. The polyamide / polyketone alloy material according to claim 1, wherein the nucleating agent A is CuCl2-PA-66, and the ion content is 2-7 mol%.

8. According to the polyamide / polyketone alloy material of claim 1, the nucleating agent B is a rare earth metal complex with the following general structural formula: (Cp) n -M-[RC(NR')2]- Wherein M is a lanthanide metal, preferably La, and [RC(NR')2] represents an amidine ligand, and the structural formula is as follows: Cp represents a cyclopentadienyl ligand, and the structural formula is as follows: Where 1≤n≤5.

9. The polyamide / polyketone alloy material according to claim 1, characterized in that: The antioxidant is a mixture of a phosphite antioxidant and a hindered phenol antioxidant in a weight ratio of 1:1, wherein the phosphite antioxidant can be tetrakis(2,4-di-tert-butylphenol)-4,4'-biphenyl diphosphite, CAS: 119345-01-6; tris[2.4-di-tert-butylphenyl]phosphite, CAS No. 31570-04-4; 3,9-bis(2,4-dicumylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, CAS No. 154862-43-8; the hindered phenol antioxidant can be: N,N'-bis-(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl)hexanediamine, CAS No.23128-74-7; triethylene glycol ether-di(3-tert-butyl-4-hydroxy-5-methylphenyl) propionate, CAS No.36443-68-2; pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate, CAS No.6683-19-8.

10. The polyamide / polyketone alloy material according to claim 9, characterized in that: The hindered phenol antioxidant is selected from pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, and the phosphite antioxidant is preferably 3,9-bis(2,4-dicumylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane.

11. The polyamide / polyketone alloy material according to claim 1, characterized in that: The other auxiliary agents may be one or more of lubricants and colorants.

12. A method for preparing a polyamide / polyketone alloy material according to any one of claims 1 to 11, characterized in that: The following steps are involved: (1) Weigh various dried raw materials according to the formula ratio; mix the polyamide resin, compatibilizer 1, nucleating agent A, antioxidant and other additives by high-speed stirring to obtain a mixture A, which is set aside. Mix the polyketone resin, compatibilizer 2 and nucleating agent B by high-speed stirring to obtain a mixture B, which is set aside, and weigh glass fiber according to the ratio, which is set aside; (2) The mixture A is added through the main feed port of a twin-screw extruder, the mixture B is added through the first side feed port of the twin-screw extruder close to the main feed port, and the glass fiber is added from the second side feed port of the twin-screw extruder close to the die head. After melt extrusion, granulation, drying and other processes, the polyamide / polyketone alloy material is obtained.

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