Toughening master batch for high and low temperature resistant nylon material and preparation method of toughening master batch

Abstract

The invention provides a toughening master batch for a high and low temperature resistant nylon material and a preparation method of the toughening master batch. The toughening master batch comprises the following components in percentage by mass: 40-80% of nylon 6, 20-60% of a toughening agent, 0.1-0.3% of rigid particles, 0.1-1.0% of a high temperature resistant aid and 0.4-1.0% of a lubricant, and the rigid particles are nanoparticles with the particle size of 1-100nm. The nylon carrier is nylon 6 with ultra-low viscosity, has good fluidity, can effectively solve the problem of film sticking during injection molding of the high-toughened nylon material, has excellent processing performance, and can improve the toughness of the high-toughened nylon material through the synergistic effect of the rigid particles and the toughening agent, so that the toughness of the high-toughened nylon material is improved. A hard core-soft shell coating structure with rigid particles as a hard core and a flexibilizer soft shell is formed in situ, so that the flexibilizer has a better toughening effect, has smaller influence on load thermal deformation temperature, can maintain good mechanical properties in an impact process in a low-temperature environment, and can achieve the purposes of absorbing impact energy and improving toughness.

Description

Technical Field

[0001] The invention relates to the technical field of nylon materials, and in particular to a toughening masterbatch for high and low temperature resistant nylon materials and a preparation method thereof. Background Art

[0002] Polyamide, commonly known as nylon, is a general term for thermoplastic resins containing repeated amide groups -[NHCO]- on the main chain of the molecule. As a general-purpose engineering plastic, nylon has high flexural strength, tensile strength, wear resistance, corrosion resistance, and self-lubricating properties, and is widely used in the fields of automobiles, electronic appliances, and home appliances. The best toughening effect of nylon is elastomer toughening, that is, polar monomers that can chemically react with nylon molecules are grafted onto soft polyolefin elastomers through a grafting chemical modification method, so that the polyolefin elastomer is evenly dispersed in the nylon matrix as tiny particles, and forms a firm interface layer with the nylon molecules. When subjected to interface impact, the soft polyolefin elastomer first absorbs energy, produces voids and yields, and then transmits through the interface to induce silver streaks and shear bands, consuming a lot of energy.

[0003] Currently, the most widely used nylon varieties are nylon 6 and nylon 66. However, the long-term stability of these two nylon materials in high and low temperature environments is low, especially their low-temperature impact resistance is too low. If they are to be used in environments with high toughness requirements or low temperature environments, they need to be toughened and modified. In addition, the above-mentioned nylon materials have a large friction coefficient due to their own viscosity during the preparation process, making them difficult to extrude from a twin-screw extruder, and their processing performance is poor. Summary of the invention

[0004] The present invention aims to provide a toughening masterbatch for high and low temperature resistant nylon materials and a preparation method thereof, so as to solve the problem that the existing nylon materials have insufficient stability when used under long-term low and high temperature conditions, and the problem that their processing performance is poor.

[0005] To achieve the above object, the present invention proposes the following technical solutions:

[0006] The invention provides a toughening masterbatch for high and low temperature resistant nylon material, comprising the following components in mass fraction: 40%-80% of nylon 6, 20%-60% of a toughening agent, 0.1%-0.3% of rigid particles, 0.1%-0.5% of a high temperature resistant auxiliary agent, and 0.4%-1.0% of a lubricant; wherein the rigid particles are nanoparticles with a particle size of 1-100 nm.

[0007] As a preferred technical solution of the present invention, the nylon 6 is an ultra-low viscosity nylon material with a viscosity coefficient of 2.0-2.2 cP.

[0008] As a preferred technical solution of the present invention, the rigid particles include one or a mixture of nano calcium carbonate, nano alumina and nano titanium dioxide.

[0009] As a preferred technical solution of the present invention, the toughening agent is a graft-modified polyolefin elastomer.

[0010] As a preferred technical solution of the present invention, the grafted product of the graft-modified polyolefin elastomer is at least one of maleic anhydride, acrylic acid and phthalic anhydride.

[0011] As a preferred technical solution of the present invention, the high temperature resistant auxiliary agent includes one or a mixture of several of amine antioxidants, phosphite antioxidant 168, phosphite antioxidant 9228, heat stabilizer H10, heat stabilizer H318, and heat stabilizer H3336.

[0012] As a preferred technical solution of the present invention, the lubricant is one or more of silicone lubricants, ethylene bisstearamide, and oleic acid amide.

[0013] The present invention also provides a method for preparing a toughening masterbatch for high and low temperature resistant nylon material, comprising the following steps:

[0014] Step 1: Weigh nylon 6, toughening agent, rigid particles, high temperature resistant additive and lubricant according to mass fraction, feed the above components into a high-speed mixer, and mix for 10-20 minutes to obtain a premix;

[0015] Step 2: feeding the premix into a twin-screw extruder for mixing, melt extrusion, and then drawing, cooling, and pelletizing to obtain the toughened masterbatch.

[0016] As a preferred technical solution of the present invention, the working temperature of the twin-screw extruder is 220° C.-270° C., and the screw speed of the twin-screw extruder is 200 rpm-400 rpm.

[0017] The technical solution of the present invention provides a toughening masterbatch for high and low temperature resistant nylon and a preparation method thereof. The nylon carrier of the technical solution of the present invention selects ultra-low viscosity nylon 6, which has good fluidity and can effectively solve the problem of sticking film during injection molding of highly toughened nylon materials, so that it has excellent processing performance.

[0018] The present invention also constructs a toughening masterbatch system in advance through the synergistic effect of rigid particles and toughening agents, and its role is to form a hard core-soft shell coating structure with rigid particles as hard core and toughening agents as soft shells in situ, so that the toughening effect is better, and the added rigid particles will also play a positive role in the thermal deformation temperature of the material. The toughening masterbatch can reduce the influence of the toughening agent on the tensile strength and thermal deformation temperature of the material while improving the toughness of the nylon material, thereby obtaining a high-strength and high-toughness high-temperature resistant nylon material, so that the modified nylon material can also have good mechanical properties when working for a long time in a high temperature environment, and to a certain extent solve the problem of deformation of the current toughened nylon material; in addition, the hard core-soft shell coating structure has good compatibility with the nylon system, and the structure plays an important role in triggering the shear deformation generated when the nylon matrix is ​​stressed, and can also maintain good mechanical properties during the impact process in a low temperature environment, and can achieve the purpose of absorbing impact energy and improving toughness.

[0019] It should be appreciated that all combinations of the foregoing concepts, as well as additional concepts described in greater detail below, may be considered to be part of the inventive subject matter of the present disclosure, provided such concepts are not mutually inconsistent.

[0020] Other additional aspects of the present invention, such as features and / or advantageous effects of the exemplary embodiments, will be apparent from the following description or learned through practice of specific embodiments according to the teachings of the present invention. DETAILED DESCRIPTION

[0021] In order to make the purpose, technical solution and advantages of the embodiments of the present invention clearer, the technical solution of the present invention will be clearly and completely described in combination with the embodiments of the present invention. Obviously, the described embodiments are part of the embodiments of the present invention, not all of the embodiments. Based on the described embodiments of the present invention, all other embodiments obtained by ordinary technicians in the field without creative work are within the scope of protection of the present invention. Unless otherwise defined, the technical terms or scientific terms used herein should be the common meanings understood by people with ordinary skills in the field to which the present invention belongs.

[0022] The words "first", "second" and similar words used in the patent application specification and claims of the present invention do not indicate any order, quantity or importance, but are only used to distinguish different components. Similarly, unless the context clearly indicates otherwise, the singular form of "a", "an" or "the" and similar words do not indicate a quantitative limitation, but indicate the existence of at least one. Words such as "include" or "comprise" mean that the elements or objects appearing before "include" or "comprise" include the features, wholes, steps, operations, elements and / or components listed after "include" or "comprise", and do not exclude the existence or addition of one or more other features, wholes, steps, operations, elements, components and / or their collections. "Up", "down", "left", "right" and the like are only used to indicate relative positional relationships. When the absolute position of the described object changes, the relative positional relationship may also change accordingly.

[0023] In order to solve the problem of insufficient stability of existing nylon materials when used under long-term low and high temperature conditions, as well as the problem of poor processing performance, the embodiment of the present invention provides a toughening masterbatch for high and low temperature resistant nylon materials, comprising the following components by mass fraction: 40%-80% nylon 6, 20%-60% toughening agent, 0.1%-0.3% rigid particles, 0.1%-0.5% high temperature resistant additive, and 0.4%-1.0% lubricant; wherein the rigid particles are nanoparticles with a particle size of 1-100nm.

[0024] As a preferred embodiment of the present invention, the nylon 6 is an ultra-low viscosity nylon material with a viscosity coefficient of 2.0-2.2 cP. The rigid particles include one or a mixture of nano calcium carbonate, nano alumina and nano titanium dioxide. The toughening agent is a grafted modified polyolefin elastomer, and further, the graft of the grafted modified polyolefin elastomer is at least one of maleic anhydride, acrylic acid and phthalic anhydride. The high temperature resistant additive includes one or a mixture of amine antioxidants, phosphite antioxidants 168, phosphite antioxidants 9228, heat stabilizers H10, heat stabilizers H318, and heat stabilizers H3336. The lubricant is one or more of silicone lubricants, ethylene bis stearamide, and oleic acid amide.

[0025] The embodiment of the present invention also provides a method for preparing a toughening masterbatch for high and low temperature resistant nylon material, comprising the following steps:

[0026] Step 1: Weigh nylon 6, toughening agent, rigid particles, high temperature resistant additive and lubricant according to mass fraction, feed the above components into a high-speed mixer, and mix for 10-20 minutes to obtain a premix;

[0027] Step 2: The premix is ​​sent into a twin-screw extruder for mixing, melt extrusion, and then drawing, cooling, and pelletizing to obtain the toughened masterbatch. The working temperature of the twin-screw extruder is 220°C-270°C, and the screw speed of the twin-screw extruder is 200rpm-400rpm.

[0028] Example 1

[0029] The toughening masterbatch of the embodiment of the present invention specifically includes the following components in mass fraction: 76% nylon 6, 20% toughening agent, 0.3% rigid particles, specifically nano calcium carbonate, 0.2% high temperature resistant additive, and 0.4% lubricant.

[0030] The method for preparing a toughening masterbatch for high and low temperature resistant nylon material according to an embodiment of the present invention comprises the following steps:

[0031] Step 1: Weigh nylon 6, toughening agent, rigid particles, high temperature resistant additive and lubricant according to mass fraction, feed the above components into a high-speed mixer, mix for 15 minutes, and obtain a premix;

[0032] Step 2: feeding the premix into a twin-screw extruder for mixing, melt extrusion, and then drawing, cooling, and pelletizing to obtain the toughened masterbatch, wherein the working temperature of the twin-screw extruder is 220-230°C in zone 1, 230-240°C in zone 2, 230-255°C in zone 3, and 240-260°C in zone 4, and the screw speed of the twin-screw extruder is 200rpm-400rpm.

[0033] The toughening masterbatch obtained in Example 1 was added in an amount calculated according to the POE content in the existing mature formula, and mixed evenly with ordinary nylon material to form a sample 1. Various performance tests were performed on the sample 1, and the test data results are shown in Table 1.

[0034] Example 2

[0035] The toughening masterbatch of the embodiment of the present invention specifically includes the following components in mass fraction: 56% nylon 6, 40% toughening agent, 0.2% rigid particles, specifically nano calcium carbonate, 0.4% high temperature resistant additive, and 0.8% lubricant.

[0036] The method for preparing a toughening masterbatch for high and low temperature resistant nylon material according to an embodiment of the present invention comprises the following steps:

[0037] Step 1: Weigh nylon 6, toughening agent, rigid particles, high temperature resistant additive and lubricant according to mass fraction, feed the above components into a high-speed mixer, mix for 15 minutes, and obtain a premix;

[0038] Step 2: feeding the premix into a twin-screw extruder for mixing, melt extrusion, and then drawing, cooling, and pelletizing to obtain the toughened masterbatch, wherein the working temperature of the twin-screw extruder is 220-230°C in zone 1, 230-240°C in zone 2, 230-255°C in zone 3, and 240-260°C in zone 4, and the screw speed of the twin-screw extruder is 200rpm-400rpm.

[0039] The toughening masterbatch obtained in Example 2 was added in an amount calculated according to the POE content in the existing mature formula, and mixed evenly with ordinary nylon material to form a sample 2. Various performance tests were performed on the sample 2, and the test data results are shown in Table 1.

[0040] Example 3

[0041] The toughening masterbatch of the embodiment of the present invention specifically includes the following components in mass fraction: 46% nylon 6, 50% toughening agent, 0.1% rigid particles, specifically nano calcium carbonate, 0.5% high temperature resistant additive, and 1.0% lubricant.

[0042] The method for preparing a toughening masterbatch for high and low temperature resistant nylon material according to an embodiment of the present invention comprises the following steps:

[0043] Step 1: Weigh nylon 6, toughening agent, rigid particles, high temperature resistant additive and lubricant according to mass fraction, feed the above components into a high-speed mixer, mix for 15 minutes, and obtain a premix;

[0044] Step 2: feeding the premix into a twin-screw extruder for mixing, melt extrusion, and then drawing, cooling, and pelletizing to obtain the toughened masterbatch, wherein the working temperature of the twin-screw extruder is 220-230°C in zone 1, 230-240°C in zone 2, 230-255°C in zone 3, and 240-260°C in zone 4, and the screw speed of the twin-screw extruder is 200rpm-400rpm.

[0045] The toughening masterbatch obtained in Example 3 was added in an amount calculated according to the POE content in the existing mature formula, and mixed evenly with ordinary nylon material to form a sample bar 3. Various performance tests were performed on the sample bar 3, and the test data results are shown in Table 1.

[0046] Example 4

[0047] The toughening masterbatch of the embodiment of the present invention specifically includes the following components in mass fraction: nylon 646%, toughening agent 60%, rigid particles are nano calcium carbonate (CaCO3), the content is 0.1%, high temperature resistant additive 0.5%, and lubricant 1.0%.

[0048] The method for preparing a toughening masterbatch for high and low temperature resistant nylon material according to an embodiment of the present invention comprises the following steps:

[0049] Step 1: Weigh nylon 6, toughening agent, rigid particles, high temperature resistant additive and lubricant according to mass fraction, feed the above components into a high-speed mixer, mix for 15 minutes, and obtain a premix;

[0050] Step 2: feeding the premix into a twin-screw extruder for mixing, melt extrusion, and then drawing, cooling, and pelletizing to obtain the toughened masterbatch, wherein the working temperature of the twin-screw extruder is 220-230°C in zone 1, 230-240°C in zone 2, 230-255°C in zone 3, and 240-260°C in zone 4, and the screw speed of the twin-screw extruder is 200rpm-400rpm.

[0051] The toughening masterbatch obtained in Example 4 was added in an amount calculated according to the POE content in the existing mature formula, and mixed evenly with ordinary nylon material to form a spline 4. Various performance tests were performed on the spline 4, and the test data results are shown in Table 1.

[0052] Comparative Example

[0053] The toughening masterbatch of the comparative example specifically includes the following components in mass fractions: nylon 676%, toughening agent 20%, high temperature resistant additive 0.2%, and lubricant 0.4%.

[0054] The preparation method of the comparative example is the same as that of Example 1, and the test results of various properties of the comparative example are shown in Table 1.

[0055] Table 1 Performance test results of embodiments and comparative examples

[0056]

[0057] As can be seen from Table 1 above, the density of the splines obtained in Examples 1-4 of the present invention is not much different from that of the splines of the comparative example, but the tensile strength, bending strength and simply supported beam notched impact are all better improved than those of the comparative example. Among them, the performance data of the low-temperature simply supported beam notched impact of Examples 1-3 are all higher than those of the comparative example, while the performance data of the low-temperature simply supported beam notched impact of the spline of Example 4 is slightly lower than that of the comparative example. The reason for this may be that the proportion of the toughening agent in Example 4 is relatively large, resulting in uneven dispersion of the toughening agent in the nylon resin during processing, resulting in unstable performance; at the same time, it also does not fully reflect the positive effect of the system formed by the rigid particles and the toughening agent on the material properties, so adding too high a proportion of the toughening agent may have a negative effect on the final material performance, resulting in poor performance of the material, therefore, in the formula components of the embodiments of the present invention, the amount of the toughening agent should not be too much.

[0058] Although the present invention has been disclosed as above with preferred embodiments, it is not intended to limit the present invention. A person with ordinary knowledge in the technical field to which the present invention belongs may make various changes and modifications without departing from the spirit and scope of the present invention. Therefore, the protection scope of the present invention shall be determined by the definition of the claims.

Claims

1. A toughening masterbatch for high and low temperature resistant nylon materials, characterized in that: The invention comprises the following components in mass fraction: 40%-80% nylon 6, 20%-60% toughening agent, 0.1%-0.3% rigid particles, 0.1%-1.0% high temperature resistant auxiliary agent and 0.4%-1.0% lubricant; wherein the rigid particles are nanoparticles with a particle size of 1-100nm.

2. The toughening masterbatch for high and low temperature resistant nylon material according to claim 1, characterized in that: The nylon 6 is made of ultra-low viscosity nylon material with a viscosity coefficient of 2.0-2.2 cP.

3. The toughening masterbatch for high and low temperature resistant nylon material according to claim 1, characterized in that: The rigid particles include one or a mixture of nano calcium carbonate, nano aluminum oxide and nano titanium dioxide.

4. The toughening masterbatch for high and low temperature resistant nylon material according to claim 1, characterized in that: The toughening agent is a graft-modified polyolefin elastomer.

5. The toughening masterbatch for high and low temperature resistant nylon material according to claim 4, characterized in that: The grafted product of the graft-modified polyolefin elastomer is at least one of maleic anhydride, acrylic acid and phthalic anhydride.

6. The toughening masterbatch for high and low temperature resistant nylon material according to claim 1, characterized in that: The high temperature resistant auxiliary agent includes one or a mixture of several of amine antioxidants, phosphite antioxidant 168, phosphite antioxidant 9228, heat stabilizer H10, heat stabilizer H318, and heat stabilizer H3336.

7. The toughening masterbatch for high and low temperature resistant nylon material according to claim 1, characterized in that: The lubricant is one or more of silicone lubricants, ethylene bis stearamide, and oleic acid amide.

8. A method for preparing a toughening masterbatch for high and low temperature resistant nylon material according to any one of claims 1 to 7, characterized in that: The steps include: Step 1: Weigh nylon 6, toughening agent, rigid particles, high temperature resistant additive and lubricant according to mass fraction, feed the above components into a high-speed mixer, and mix for 10-20 minutes to obtain a premix; Step 2: feeding the premix into a twin-screw extruder for mixing, melt extrusion, and then drawing, cooling, and pelletizing to obtain the toughened masterbatch.

9. The method for preparing the toughening masterbatch for high and low temperature resistant nylon material according to claim 8, characterized in that: The working temperature of the twin-screw extruder is 220° C.-270° C., and the screw speed of the twin-screw extruder is 200 rpm-400 rpm.

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