Reaction extruded glass fiber reinforced pa6 material and method for producing the same

Abstract

The application discloses a kind of reaction extrusion glass fiber reinforced PA6 materials, which is prepared from the following components by weight parts: caprolactam 14.8-79.1 parts, auxiliary TMI-g 0.2-2 parts, glass fiber 20-80 parts, initiator 0.3-2 parts, antioxidant 0.2-0.6 parts, light stabilizer 0.2-0.6 parts. By the method of reaction extrusion caprolactam anionic ring-opening polymerization, glass fiber reinforced PA6 material is prepared, and the self-made TMI-g material is used as catalyst and compatibilizer, so that caprolactam is closely polymerized and crystallized around glass fiber, thereby obtaining modified material with excellent performance.

Description

TECHNICAL FIELD

[0001] The application relates to the field of high polymer materials, in particular to a reaction-extruded glass fiber reinforced PA6 material and a preparation method thereof. BACKGROUND

[0002] Nylon 6 is one of the most widely used engineering plastics, PA6 has high crystallinity, high melting point, excellent mechanical properties, good impact resistance, wear resistance and self-lubricating property, and can be applied to various engineering plastic parts. The ordinary glass fiber reinforced modified PA6 is modified by blending the molten PA6 and glass fiber by means of a double screw, and the product is obtained. However, the viscosity of the molten PA6 is large, the addition ratio of the glass fiber is about 50% at most, and the process is a simple physical blending, so the bonding strength between the glass fiber and the PA6 matrix is not high, and phase separation is prone to occur. SUMMARY

[0003] Therefore, the application provides a reaction-extruded glass fiber reinforced PA6 material and a preparation method thereof to solve the problems in the background technology. The glass fiber reinforced PA6 material is prepared by a reaction-extruded lactam anion ring-opening polymerization method, and self-made TMI-g material is used as a catalyst and a compatibilizer, so that the lactam is closely polymerized and crystallized around the glass fiber, and thus a modified material with excellent performance is obtained.

[0004] To achieve the above object, the application provides the following technical scheme.

[0005] In one aspect, the application discloses a reaction-extruded glass fiber reinforced PA6 material, which is prepared from the following components by weight parts:

[0006]

[0007] As a further scheme of the application, the lactam is a crystal raw material with a purity of 99.0% or above.

[0008] As a further scheme of the application, the auxiliary agent TMI-g is prepared by the following method.

[0009] Under the condition of nitrogen protection and 78-83 DEG C, 3-isopropyl-dimethyl benzyl isocyanate and maleic anhydride are mixed in a mass ratio of 1: (1-3), heated, molten and stirred for 20-30 hours, and then cooled and crystallized to obtain the auxiliary agent TMI-g.

[0010] As a further scheme of the application, the glass fiber can be at least one of continuous glass fiber and chopped glass fiber.

[0011] As a further scheme of the application, the initiator can be at least one of sodium hydroxide, initiator C10 and initiator C1.

[0012] As a further solution of the present invention: the antioxidant is at least one of a histamine-receptive antioxidant and a phosphite.

[0013] As a further solution of the present invention: the light stabilizer is at least one of a histamine light stabilizer and a hindered phenol light stabilizer.

[0014] Another aspect of the present invention discloses a method for preparing the reaction-extruded glass fiber reinforced PA6 material as described in any one of the above, comprising the following steps:

[0015] The components were weighed according to parts by weight, and caprolactam, initiator, antioxidant and light stabilizer were fed into the twin-screw extruder through the main feeding port, the additive TMI-g was fed into the side feeding port, and the glass fiber was fed into the side feeding port. The temperature of the twin-screw extruder zone 1 was 160° C.-200° C., zone 2 was 210-230° C., zone 3 was 220-240° C., zone 4 was 220-240° C., and zone 5 was 210-230° C.

[0016] Compared with the prior art, the present invention has the following beneficial effects:

[0017] The present invention prepares a glass fiber-reinforced PA6 material through a method of reactive extrusion anionic ring-opening polymerization of caprolactam. The present invention proposes for the first time a self-made TMI-g material. TMI acts as a catalyst for the caprolactam anionic polymerization reaction and can initiate ring-opening polymerization of caprolactam in the presence of a basic anionic initiator. Maleic anhydride itself has good compatibility with glass fiber, and TMI-g can serve as both a catalyst and a compatibilizer, allowing caprolactam to polymerize and crystallize tightly around the glass fiber, thereby producing a modified material with excellent performance. Because the viscosity of melted caprolactam monomer is very low, a high proportion of glass fiber can be added to produce a glass fiber-reinforced PA6 material with a wider range of applications. The preparation method of the present invention involves adding caprolactam, glass fiber, and initiator through a main feed and adding the auxiliary agent TMI-g through a side feed. This ensures that the caprolactam contacts the catalyst after complete melting, resulting in more uniform polymerization. Premature contact between the initiator and catalyst is avoided, preventing rapid polymerization and reducing processing difficulty. Different from traditional commercial nylon, the reactive extrusion preparation process of the present invention has greater room for adjustment of polymerization degree, molecular weight and crystallinity through adjustment of the formula, and the performance of the end products that can be prepared is wider, which has broad market application prospects. DETAILED DESCRIPTION

[0018] To facilitate understanding of the present invention, the present invention will be described more fully below in conjunction with specific embodiments. However, the present invention can be implemented in many different forms and is not limited to the embodiments described herein. On the contrary, the purpose of providing these embodiments is to provide a more thorough and comprehensive understanding of the disclosure of the present invention.

[0019] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. The terminology used in the description herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the application.

[0020] The specific information of raw materials used in the following examples and comparative examples is as follows:

[0021] Caprolactam, brand Henan Shenma, purity 99.0%;

[0022] Glass fiber 1, ECS305-3-K (Chongqing International); Glass fiber 2: ECS13-03-508A (China Giant); Glass fiber 3: Continuous glass fiber-988A (China Giant);

[0023] Initiator 1: sodium hydroxide; initiator 2: initiator C10 (Bruggemann); initiator 3: initiator C1 (Bruggemann);

[0024] Antioxidant, antioxidant 1098, antioxidant 168, BASF;

[0025] Light stabilizer 1: UV-3346 (Solvay); light stabilizer 2: UV-329 (Lianlong); light stabilizer 3: UV305 (BASF); light stabilizer 4: light stabilizer 4050 (BASF);

[0026] 3-isopropyl-dimethylbenzyl isocyanate, maleic anhydride, all purchased from Aldrich Reagent;

[0027] PA6, brand 3250 (Jiangsu Hongsheng).

[0028] All materials are commercially available conventional products.

[0029] It can be understood that the above raw materials and reagents are only examples of some specific embodiments of the present application, so that the technical solutions of the present application are more clear, and do not represent that the present application can only use the above reagents, and the specific scope is subject to the scope of claims. In addition, the "parts" described in the examples and comparative examples, unless otherwise specified, all refer to parts by weight.

[0030] Any range recited herein includes the end values and any number or value between the end values, as well as any range formed by any combination of end values or any number or value between the end values.

[0031] Example 1

[0032] Take 67.2 parts of caprolactam, 1 part of auxiliary TMI-g, 30 parts of glass fiber ECS305-3-K, 1 part of initiator sodium hydroxide, 0.2 parts of antioxidant 1098, 0.2 parts of antioxidant 168, 0.4 parts of light stabilizer UV-3346 into the twin-screw extruder for melt extrusion granulation, wherein caprolactam, initiator, antioxidant 1098, antioxidant 168 and light stabilizer are fed from the main feeding port, glass fiber is fed from the glass fiber port, auxiliary TMI-g is fed from the side feeding port, the temperature of the first zone of the twin-screw extruder is 190°C, the temperature of the second zone is 220°C, the temperature of the third zone is 230°C, the temperature of the fourth zone is 230°C, and the temperature of the fifth zone is 220°C.

[0033] The preparation steps of auxiliary TMI-g are as follows:

[0034] Under the condition of nitrogen protection and 80°C, 1 part of 3-isopropyl-dimethyl benzyl isocyanate and 2 parts of maleic anhydride are heated, melted and stirred for 24 hours, and then cooled and crystallized to obtain auxiliary TMI-g.

[0035] Example 2

[0036] Take 67.2 parts of caprolactam, 1 part of auxiliary TMI-g, 30 parts of glass fiber ECS305-3-K, 1 part of initiator sodium hydroxide, 0.2 parts of antioxidant 1098, 0.2 parts of antioxidant 168, 0.4 parts of light stabilizer UV-3346 into the twin-screw extruder for melt extrusion granulation, wherein caprolactam, initiator, antioxidant, and light stabilizer are fed from the main feeding port, glass fiber is fed from the glass fiber port, auxiliary TMI-g is fed from the side feeding port, the temperature of the first zone of the twin-screw extruder is 190°C, the temperature of the second zone is 220°C, the temperature of the third zone is 230°C, the temperature of the fourth zone is 230°C, and the temperature of the fifth zone is 220°C.

[0037] The preparation steps of auxiliary TMI-g are as follows:

[0038] Under the condition of nitrogen protection and 82°C, 1 part of 3-isopropyl-dimethyl benzyl isocyanate and 1 part of maleic anhydride are heated, melted and stirred for 25 hours, and then cooled and crystallized to obtain auxiliary TMI-g.

[0039] Example 3

[0040] 27.2 parts of caprolactam, 1.2 parts of additive TMI-g, 70 parts of glass fiber ECS13-03-508A, 0.8 parts of initiator C1, 0.2 parts of antioxidant 1098, 0.2 parts of antioxidant 168, and 0.4 parts of light stabilizer UV-329 were weighed and added into a twin-screw extruder for melt extrusion and granulation, wherein caprolactam, initiator, antioxidant and light stabilizer were fed from the main feeding port, glass fiber was fed from the glass fiber port, and additive TMI-g was fed from the side feeding port. The temperature of zone 1 of the twin-screw extruder was 200°C, 220°C in zone 2, 230°C in zone 3, 220°C in zone 4, and 220°C in zone 5.

[0041] Under nitrogen protection at 80°C, 1 part of 3-isopropyl-dimethylbenzyl isocyanate and 2 parts of maleic anhydride were heated, melted, and stirred for 26 hours, and cooled to crystallize to obtain the additive TMI-g.

[0042] Example 4

[0043] 79.1 parts of caprolactam, 0.2 parts of additive TMI-g, 20 parts of continuous glass fiber 988A, 0.3 parts of initiator sodium hydroxide, 0.2 parts of antioxidant 1098, and 0.2 parts of light stabilizer UV305 were weighed and added into a twin-screw extruder for melt extrusion and granulation, wherein caprolactam, initiator, antioxidant and light stabilizer were fed from the main feeding port, continuous glass fiber was fed from the glass fiber port, and additive TMI-g was fed from the side feeding port. The temperature of zone 1 of the twin-screw extruder was 160°C, zone 2 was 210°C, zone 3 was 220°C, zone 4 was 220°C, and zone 5 was 210°C.

[0044] Under nitrogen protection at 78°C, 1 part of 3-isopropyl-dimethylbenzyl isocyanate and 1 part of maleic anhydride were heated, melted, and stirred for 20 hours, and cooled and crystallized to obtain the additive TMI-g.

[0045] Example 5

[0046] 14.8 parts of caprolactam, 2 parts of auxiliary agent TMI-g, 80 parts of glass fiber ECS13-03-508A, 2 parts of initiator C10, 0.3 parts of antioxidant 1098, 0.3 parts of antioxidant 168, and 0.6 parts of light stabilizer 4050 were weighed and added into a twin-screw extruder for melt extrusion and granulation, wherein caprolactam, initiator, antioxidant and light stabilizer were fed from the main feeding port, auxiliary agent TMI-g was fed from the side feeding port, and glass fiber was fed from the glass fiber port. The temperature of zone 1 of the twin-screw extruder was 200°C, zone 2 was 230°C, zone 3 was 240°C, zone 4 was 240°C, and zone 5 was 230°C.

[0047] Under nitrogen protection at 83°C, 1 part of 3-isopropyl-dimethylbenzyl isocyanate and 3 parts of maleic anhydride were heated, melted, and stirred for 30 hours, and cooled and crystallized to obtain the additive TMI-g.

[0048] Comparative Example 1

[0049] Take 69.2 parts of PA6 3250 (Jiangsu Hongsheng), 30 parts of glass fiber-ECS305-3-K, 0.2 parts of antioxidant 1098, 0.2 parts of antioxidant 168, 0.4 parts of light stabilizer UV-3346 into the twin-screw extruder for melt extrusion granulation, wherein PA6, glass fiber, antioxidant and light stabilizer are fed from the main feeding port, and the glass fiber is added from the side feeding glass fiber port; the temperature of the first zone of the twin-screw extruder is 190°C, the second zone is 220°C, the third zone is 230°C, the fourth zone is 230°C, and the fifth zone is 220°C.

[0050] Comparative Example 2

[0051] Take 49 parts of caprolactam PA6 3250 (Jiangsu Hongsheng), 50 parts of glass fiber ECS13-03-508A, 0.2 parts of antioxidant 1098, 0.3 parts of antioxidant 168, and 0.5 parts of light stabilizer UV-329 into the twin-screw extruder for melt extrusion granulation, wherein PA6, initiator and light stabilizer are fed from the main feeding port, and the glass fiber is added from the side feeding glass fiber port; the temperature of the first zone of the twin-screw extruder is 190°C, the second zone is 220°C, the third zone is 230°C, the fourth zone is 230°C, and the fifth zone is 220°C.

[0052] Comparative Example 3

[0053] Take 68.2 parts of PA6 3250 (Jiangsu Hongsheng), 30 parts of glass fiber-ECS305-3-K, 0.2 parts of antioxidant 1098, 0.2 parts of antioxidant 168, 0.4 parts of light stabilizer UV-3346, and 1 part of compatibilizer POE-g into the twin-screw extruder for melt extrusion granulation, wherein PA6, antioxidant, light stabilizer and compatibilizer POE-g are fed from the main feeding port, and the glass fiber is added from the side feeding glass fiber port; the temperature of the first zone of the twin-screw extruder is 190°C, the second zone is 220°C, the third zone is 230°C, the fourth zone is 230°C, and the fifth zone is 220°C.

[0054] Material performance test of Examples 1-5 and Comparative Examples 1-2: measure the flame retardancy of the material according to the UL94 standard, test the tensile strength according to ISO 527 (test temperature 23°C), test the bending strength and bending modulus according to ISO 178 (test temperature 23°C), and test the Izod notched impact strength according to ISO 180 (test temperature 23°C); the results are shown in Table 1 below:

[0055] Table 1 Performance test results of products prepared in each example and comparative example

[0056]

[0057] As can be seen from the above table, the glass fiber reinforced PA6 product prepared by the present invention has higher mechanical properties than the molten glass fiber reinforced nylon product, and the maximum glass fiber content can reach 80%, which has a broader application space.

[0058] Although this specification is described according to implementation methods, not every implementation method contains only one independent technical solution. This narrative method of the specification is only for the sake of clarity. Those skilled in the art should regard the specification as a whole. The technical solutions in each embodiment can also be appropriately combined to form other implementation methods that can be understood by those skilled in the art.

[0059] Therefore, the above description is only a preferred embodiment of the present application and is not intended to limit the scope of implementation of the present application; that is, all equivalent modifications made according to the scope of the claims of the present application are within the scope of protection of the claims of the present application.

Claims

1. A reaction extruded glass fiber reinforced PA6 material, characterized in that: It is prepared from the following components in parts by weight: 14.8-79.1 parts of caprolactam Additive TMI-g 0.2-2 parts Glass fiber 20-80 parts 0.3-2 parts initiator 0.2-0.6 parts of antioxidant Light stabilizer 0.2-0.6 parts; The preparation method of the auxiliary agent TMI-g is as follows: Under nitrogen protection, at 78°C-83°C, 3-isopropyl-dimethylbenzyl isocyanate and maleic anhydride were mixed in a mass ratio of 1:(1-3), heated to melt and stirred for 20-30 hours, and cooled to crystallize to obtain the additive TMI-g.

2. The reaction extruded glass fiber reinforced PA6 material according to claim 1, characterized in that: The caprolactam is a crystalline raw material with a purity of more than 99.0%.

3. The reaction extruded glass fiber reinforced PA6 material according to claim 1, characterized in that: The glass fiber is at least one of continuous glass fiber and chopped glass fiber.

4. The reaction extruded glass fiber reinforced PA6 material according to claim 1, characterized in that: The initiator is at least one of sodium hydroxide, initiator C10, and initiator C1.

5. The reaction extruded glass fiber reinforced PA6 material according to claim 1, characterized in that: The antioxidant is at least one of a hindered amine antioxidant and a phosphite.

6. The reaction extruded glass fiber reinforced PA6 material according to claim 1, characterized in that: The light stabilizer is at least one of a hindered amine light stabilizer and a hindered phenol light stabilizer.

7. The method for preparing the reaction-extruded glass fiber reinforced PA6 material according to any one of claims 1 to 6, characterized in that: The following steps are involved: The components were weighed according to parts by weight, and caprolactam, initiator, antioxidant and light stabilizer were fed from the main feeding port of the twin-screw extruder, the additive TMI-g was fed from the side feeding port of the twin-screw extruder, and the glass fiber was fed from the side feeding port of the twin-screw extruder; the temperature of zone 1 of the twin-screw extruder was 160°C-200°C, zone 2 was 210-230°C, zone 3 was 220-240°C, zone 4 was 220-240°C, and zone 5 was 210-230°C.

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