LOW-MOLD DEPOSIT HALOGEN-FREE FLAME-RETARDANT THERMOPLASTIC POLYAMIDE COMPOSITION, AND PREPARATION METHOD AND USE THEREOF

Abstract

Disclosed are a low-mold deposit halogen-free flame-retardant thermoplastic polyamide composition, and a preparation method and use thereof. The composition includes the following components in parts by weight: 20 to 82 parts of a thermoplastic polyamide resin; 13 to 25 parts of a flame retardant; 1 to 5 parts of a flame-retardant synergist; 5 to 50 parts of a reinforcement material; and 0.5 to 5 parts of an adsorbent, where the flame retardant includes a phosphinate-based flame retardant and the adsorbent is an ethylene copolymer. In the present disclosure, an ethylene copolymer is added as an adsorbent and an addition amount of the ethylene copolymer is controlled, so that the prepared composition exhibits excellent flame resistance and electrical properties, and can effectively reduce the release of small molecules during the injection molding and greatly reduce an amount of the mold deposit generated during the injection molding.

Claims

1. A low-mold deposit halogen-free flame-retardant thermoplastic polyamide composition, comprising the following components in parts by weight: TABLE-US-00006 thermoplastic polyamide resin 20 to 82 parts; flame retardant 13 to 25 parts; flame-retardant synergist 1 to 5 parts; reinforcement material 5 to 50 parts; and adsorbent 0.5 to 5 parts, wherein, the flame retardant comprises a phosphinate-based flame retardant, and does not comprise red phosphorus; and the adsorbent comprises an ethylene copolymer obtained through copolymerization of the following components in parts by weight: TABLE-US-00007 ethylene 48 to 85 parts; (methyl)acrylate with 1 to 18 carbon atoms 10 to 35 parts; and functional monomer 0 to 15 parts, wherein the functional monomer is one or a combination of two or more selected from the group consisting of an epoxide, an ethylenically unsaturated monocarboxylic acid, an ethylenically unsaturated monocarboxylic anhydride, an ethylenically unsaturated dicarboxylic acid, and an ethylenically unsaturated dicarboxylic anhydride.

2. The low-mold deposit halogen-free flame-retardant thermoplastic polyamide composition according to claim 1, wherein the thermoplastic polyamide resin is one or a combination of two or more selected from the group consisting of nylon 6, nylon 66, nylon 46, nylon 6/66, nylon 610, nylon 611, nylon 612, nylon 6T, and nylon 9T.

3. The low-mold deposit halogen-free flame-retardant thermoplastic polyamide composition according to claim 1, wherein the phosphinate-based flame retardant is a phosphonate and has a structure shown as follows: ##STR00002## wherein R.sup.1 and R.sup.2 each are independently selected from the group consisting of linear or branched C.sub.1-C.sub.6 alkyl and/or aryl; M is one or a combination of two or more selected from the group consisting of an alkali metal, an alkaline-earth metal, Al, Zn, Fe, and Ti; and m is 1 to 4.

4. The low-mold deposit halogen-free flame-retardant thermoplastic polyamide composition according to claim 1, wherein the flame retardant further comprises a melamine derivative.

5. The low-mold deposit halogen-free flame-retardant thermoplastic polyamide composition according to claim 4, wherein the melamine derivative is melamine polyphosphate with a phosphorus content of 10 wt% to 15 wt%.

6. The low-mold deposit halogen-free flame-retardant thermoplastic polyamide composition according to claim 4, wherein in the flame retardant, a weight ratio of the phosphinate-based flame retardant to the melamine derivative is 1 : (0.05-20).

7. The low-mold deposit halogen-free flame-retardant thermoplastic polyamide composition according to claim 1, wherein the flame-retardant synergist is one or a combination of two or more selected from the group consisting of zinc borate, zinc stannate, zinc sulfide, and boehmite.

8. The low-mold deposit halogen-free flame-retardant thermoplastic polyamide composition according to claim 1, wherein the reinforcement material is one or a combination of two or more selected from the group consisting of an E glass fiber, a B glass fiber, a carbon fiber, a polyarylamide fiber, an asbestos fiber, a wollastonite fiber, a ceramic fiber, a potassium titanate whisker, a basic magnesium-sulfate whisker, a silicon carbide whisker, an aluminum borate whisker, silicon dioxide, aluminum silicate, silicon oxide, calcium carbonate, titanium dioxide, talc, wollastonite, diatomaceous earth, clay, kaolin, globular glass, mica, gypsum, iron oxide, magnesium oxide, and zinc oxide.

9. A preparation method of the low-mold deposit halogen-free flame-retardant thermoplastic polyamide composition according to claim 1, comprising: blending, cooling, air-drying, and granulating that are achieved through a melt blending extrusion process.

10. Use of the low-mold deposit halogen-free flame-retardant thermoplastic polyamide composition according to claim 1 in preparation of a component for an electronic device, an electrical appliance, or an electrical engineering product.

11. A preparation method of the low-mold deposit halogen-free flame-retardant thermoplastic polyamide composition according to claim 2, comprising: blending, cooling, air-drying, and granulating that are achieved through a melt blending extrusion process.

12. A preparation method of the low-mold deposit halogen-free flame-retardant thermoplastic polyamide composition according to claim 3, comprising: blending, cooling, air-drying, and granulating that are achieved through a melt blending extrusion process.

13. A preparation method of the low-mold deposit halogen-free flame-retardant thermoplastic polyamide composition according to claim 4, comprising: blending, cooling, air-drying, and granulating that are achieved through a melt blending extrusion process.

14. A preparation method of the low-mold deposit halogen-free flame-retardant thermoplastic polyamide composition according to claim 7, comprising: blending, cooling, air-drying, and granulating that are achieved through a melt blending extrusion process.

15. A preparation method of the low-mold deposit halogen-free flame-retardant thermoplastic polyamide composition according to claim 8, comprising: blending, cooling, air-drying, and granulating that are achieved through a melt blending extrusion process.

16. Use of the low-mold deposit halogen-free flame-retardant thermoplastic polyamide composition according to claim 2 in preparation of a component for an electronic device, an electrical appliance, or an electrical engineering product.

17. Use of the low-mold deposit halogen-free flame-retardant thermoplastic polyamide composition according to claim 3 in preparation of a component for an electronic device, an electrical appliance, or an electrical engineering product.

18. Use of the low-mold deposit halogen-free flame-retardant thermoplastic polyamide composition according to claim 4 in preparation of a component for an electronic device, an electrical appliance, or an electrical engineering product.

19. Use of the low-mold deposit halogen-free flame-retardant thermoplastic polyamide composition according to claim 7 in preparation of a component for an electronic device, an electrical appliance, or an electrical engineering product.

20. Use of the low-mold deposit halogen-free flame-retardant thermoplastic polyamide composition according to claim 8 in preparation of a component for an electronic device, an electrical appliance, or an electrical engineering product.

Description

DETAILED DESCRIPTION

[0041] The present disclosure will be further illustrated below with reference to specific examples, which are not intended to limit the present disclosure in any form. Unless otherwise specified, the reagents, methods, and devices used in the present disclosure are conventional reagents, methods, and devices in the prior art. Unless otherwise specified, the reagents and materials used in the present disclosure are commercially available.

[0042] The following raw materials are used in the examples of the present disclosure: [0043] PA66 resin: PA66 EPR27, Shenma Industrial Co., Ltd.; [0044] PA6 resin: PA6 M2800, Guangdong Xinhui Meida Nylon Co., Ltd.; [0045] PA9T resin: Vicnyl 400, Zhuhai Vanteque Specialty Engineering Plastic Co.,Ltd.; [0046] E glass fiber: glass fiber ECS301CL-3, Chongqing Polycomp International Co., Ltd.; [0047] kaolin: Translink 445, BASF SE; [0048] phosphinate-based flame retardant: aluminum diethylphosphinate, Exolit OP 1230, Clariant; [0049] zinc phenylphosphinate: purchased from Eastar International Trading (Shanghai) Co., Ltd.; [0050] Melamine polyphosphate: Melapur 200/70 with a phosphorus content of 12 wt% to 14 wt%, purchased from BASF SE; [0051] flame-retardant synergist: anhydrous zinc borate, ZB-500, Kaifei Company; [0052] adsorbent ethylene-methyl acrylate copolymer (with 75 wt% of ethylene and 25 wt% of methyl acrylate): Elvaloy® AC resin 1125, purchased from DuPont, USA; [0053] adsorbent ethylene-methyl acrylate-glycidyl methacrylate random tercopolymer (with about 70 wt% of ethylene, 20 wt% of methyl acrylate, and 10 wt% of glycidyl methacrylate): Elvaloy® PTW, purchased from Du Pont, USA; [0054] adsorbent ethylene-vinyl alcohol copolymer (with 75 wt% of ethylene and 25 wt% of vinyl alcohol): purchased from Shanghai Standard Biotech Co., Ltd.; [0055] POE flexibilizer: Fusabond N493, DuPont; [0056] red phosphorus: purchased from Changzhou Chuanlin Chemical Co., Ltd.; [0057] antioxidant: Irganox@ 1098, BASF SE; [0058] color additive aniline black: TN-870, Orient Chem. Limited, Japan; and [0059] lubricant: A-C540A, Honeywell.

Examples 1 to 10

[0060] In these examples, a series of low-mold deposit halogen-free flame-retardant polyamide compositions were provided.

[0061] According to the formula in Table 1, the polyamide resin, the adsorbent, and the processing aid were mixed in a mixer, and a resulting mixture was fed into an extruder through a main feed port; the reinforcement material was fed into the extruder through a first side feed port; the flame retardant and the flame-retardant synergist were mixed, and a resulting mixture was fed through a second side feed port; and the mixture was subjected to melt blending at 230° C. to 270° C., cooling, air-drying, and granulating to give the series of low-mold deposit halogen-free flame-retardant polyamide compositions.

Comparative Example 1

[0062] In this comparative example, a halogen-free flame-retardant polyamide composition was provided.

[0063] The halogen-free flame-retardant polyamide composition in this comparative example was prepared through the same method as that of Example 1, except that a POE flexibilizer was used instead of the adsorbent in Example 1.

Comparative Example 2

[0064] In this comparative example, a halogen-free flame-retardant polyamide composition was provided.

[0065] The halogen-free flame-retardant polyamide composition in this comparative example was prepared through the same method as that of Example 1, except that the adsorbent was used in an amount of 0.3 part by weight.

Comparative Example 3

[0066] In this comparative example, a halogen-free flame-retardant polyamide composition was provided.

[0067] The halogen-free flame-retardant polyamide composition in this comparative example was prepared through the same method as that of Example 1, except that the adsorbent was used in an amount of 7 parts by weight.

Comparative Example 4

[0068] In this comparative example, a halogen-free flame-retardant polyamide composition was provided.

[0069] The halogen-free flame-retardant polyamide composition in this comparative example was prepared through the same method as that of Example 1, except that a mixture of red phosphorus and a phosphinate-based flame retardant was adopted as the flame retardant.

Comparative Example 5

[0070] In this comparative example, a halogen-free flame-retardant polyamide composition was provided.

[0071] The halogen-free flame-retardant polyamide composition in this comparative example was prepared through the same method as that of Example 1, except that an ethylene-vinyl alcohol copolymer was adopted as the adsorbent.

TABLE-US-00004 Proportions (parts by weight) of components in each of the compositions of the examples and comparative examples Raw material Examples Comparative Examples 1 2 3 4 5 6 7 8 9 10 1 2 3 4 5 Polyamide PA66 55.5 - 41 70 43 43 43 - 55.5 55.5 55.5 55.5 55.5 55.5 55.5 PA6 - 52.5 20 - - - - - - - - - - - - PA9T - - - - - - - 55.5 - - - - - - - Flame retardant Aluminum diethylphosphinate 18 15 20 24 13 13 13 18 - 18 18 18 18 18 18 Zinc phenylphosphinate - - - - - - - - 13 - - - - - - melamine polyphosphate 2 3 4 1 1 1 1 2 2 2 2 2 2 - 2 Red phosphorus - - - - - - - - - - - - - 2 - Flame-retardant synergist 2 1 1 1.5 4 2 4 4 2 2 2 2 2 2 2 Reinforcement material Glass fiber 25 30 15 40 40 40 25 25 25 25 15 25 25 Kaolin - - - - - - - - 25 - - - - - - Adsorbent Elvaloy® AC resin 1125 0.5 1.5 2 5 4 - - 0.5 0.5 0.5 - 0.3 7 0.5 - Elvaloy® PTW - - - - - 4 - - - - - - - - - Ethylene-vinyl alcohol copolymer - - - - - - 4 - - - - - - - 0.5 POE flexibilizer - - - - - - - - - - 0.5 - - - - Processing aid Antioxidant 1098 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 - 0.4 0.4 0.4 0.4 0.4 Aniline black 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 - 0.2 0.2 0.2 0.2 0.2 Lubricant 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 - 0.4 0.4 0.4 0.4 0.4

[0072] The halogen-free flame-retardant polyamide compositions of examples and comparative examples each were subjected to a property test, and specific test items and test methods were as follows:

[0073] 1. Flame resistance: A 125 × 13 × 1.6 mm square board was made through injection molding, and then tested according to the ANSI/UL-94-1985 Standard.

[0074] 2. Mold deposit evaluation: An injection molding machine was used to conduct injection molding 100 times continuously at injection molding temperatures of 290° C., 285° C., 280° C., and 265° C., and small-molecule substances (namely, the mold deposit) in a mold were collected and weighed (mg).

[0075] Test results were shown in Table 2.

TABLE-US-00005 Property test results of each of the compositions of the examples and comparative examples Property Examples Comparative Examples 1 2 3 4 5 6 7 8 9 10 1 2 3 4 5 Flame resistance UL94 V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-1 V-0 V-1 V-0 V-0 Mold deposit (mg) 6.5 6.2 5.9 5.4 5.3 5.2 5.3 6.8 6.7 6.4 23 15 2.0 9.8 12

[0076] It can be seen from the data in Tables 1 and 2 that, since the adsorbent of the present disclosure is not added in Comparative Examples 1 and 5, under the same processing conditions, mold deposit contents of the two comparative examples are 3.54 and 1.85 times a mold deposit content of Example 1; since the adsorbent is added at a small amount in Comparative Example 2, the mold deposit problem is still obvious; since a content of the adsorbent is too high in Comparative Example 3, the flame resistance is decreased; a mixture of red phosphorus and a phosphinate-based flame retardant is adopted in Comparative Example 4, the mold deposit reduction is not affected, and the flame resistance is decreased; and since the ethylene copolymer of the present disclosure is not adopted in Comparative Example 5, the mold deposit is little reduced.

[0077] Therefore, it can be seen that the low-mold deposit halogen-free flame-retardant polyamide composition prepared by adding a specific content of the adsorbent to the polyamide not only exhibits excellent flame resistance, but also can significantly inhibit the release of small-molecule substances during injection molding and significantly reduce an amount of a mold deposit generated during injection molding.

[0078] The objectives, technical solutions, and beneficial effects of the present disclosure are further described in detail in the above specific implementations. It should be understood that the above are merely specific implementations of the present disclosure, and are not intended to limit the protection scope of the present disclosure. Any modification, equivalent replacement, improvement, or the like made within the spirit and principle of the present disclosure should fall within the protection scope of the present disclosure.