Highly transparent flame-retardant bio-based polyamide materials, methods of making and applications thereof

Abstract

The application discloses a kind of high transparency flame-retardant bio-based polyamide materials, its preparation method and application.The high transparency flame-retardant bio-based polyamide material is prepared from the following raw materials: bio-based transparent polyamide, fluorophlogopite, bis (4-carboxyl phenyl) phenyl phosphine oxide, polytin glycol dilaurate and antioxidant.The high transparency flame-retardant bio-based polyamide material is prepared by double screw extruder.The polyamide material of the application adds transparent fluorophlogopite as reinforcing agent and flame retardant, composite polytin glycol dilaurate, while introducing bis (4-carboxyl phenyl) phenyl phosphine oxide, utilize fluorine, tin, silicon, phosphorus synergistic effect, so as to meet excellent flame retardant performance under lower flame retardant addition amount while ensuring that polyamide has excellent transparency, material has excellent optical performance, flame retardant performance and processability simultaneously, can be realized in the preparation of electronic and electrical, new energy automobile shell shield and other fields of application.

Description

TECHNICAL FIELD

[0001] The present application relates to a kind of polyamide materials, specifically relates to a kind of high transparency flame-retardant bio-based polyamide material and its preparation method and application, belong to high polymer material technical field. BACKGROUND

[0002] Transparent polyamide is a kind of high polymer material with excellent comprehensive performance, it not only has excellent mechanical properties, good corrosion resistance and other advantages, also has excellent processing performance, non-toxic, odorless and other characteristics, and is widely concerned by domestic and foreign researchers.Compared with traditional PC, PMMA and other transparent materials, transparent polyamide not only has excellent transparency, but also has the advantages of environmental stress cracking resistance, oil solvent resistance, scratch resistance, wear resistance and the like.

[0003] For transparent polyamide, the optical properties are generally regulated by structure at present, side groups, heterocyclic structures or other structures are introduced into the polyamide molecular chain, or copolymerization means is used to destroy the ordered arrangement of molecular chain and reduce the crystallinity of polyamide.For example, a high transparent copolymerized polyamide with microcrystalline structure is prepared by introducing multi-component polymerization monomers into the molecular chain structure through copolymerization means in Chinese invention patent CN110172147A.A transparent polyamide is prepared by polymerizing hexanediamine and isophthalic acid in Chinese invention patent CN106589351A.Due to the asymmetric structure of isophthalic acid, the hydrogen bond density between molecular chains is reduced, and a highly transparent PA6I resin is obtained.However, current transparent polyamide resins are mainly petroleum-based polymers, and there is little research on bio-based transparent polyamide PA5T / 5I, so further research and development are needed.

[0004] Although the above-mentioned transparent polyamide materials have excellent transparency and mechanical properties, they still cannot meet the performance requirements in some fields, so it is necessary to modify the transparent polyamide resin to give it special properties to meet the use requirements.In the fields of electronics, electrical appliances and household appliances, there are countless fires caused by poor flame retardant performance of polyamide, causing great losses.Therefore, the flame retardant modification of polyamide has become a common concern and research topic in the academic and industrial circles.

[0005] In the prior art, the skilled person usually adds halogen or halogen-free flame retardants to polyamide to achieve flame retardation.However, the required amount of flame retardant is high, which can easily reduce the optical and mechanical properties of the material, limiting its application in fields with high optical requirements.Therefore, it is of practical significance to prepare a high transparency flame-retardant polyamide to expand the application of polyamide materials and promote the development of the electronics and electrical industry. SUMMARY

[0006] The main purpose of the present application is to solve the above-mentioned technical defects, provide a high-transparency flame-retardant bio-based polyamide material and a preparation method thereof, which has excellent optical performance, flame-retardant performance and processability.

[0007] Another purpose of the present application is to provide the application of the high-transparency flame-retardant bio-based polyamide material.

[0008] To achieve the above-mentioned purposes, the technical solutions adopted by the present application include:

[0009] The present application provides a high-transparency flame-retardant bio-based polyamide material, which is prepared from the following raw materials: bio-based transparent polyamide, fluorophlogopite, bis(4-carboxyphenyl)phenyl phosphine oxide, polytin glycol dilaurate and antioxidant.

[0010] In some embodiments, the high-transparency flame-retardant bio-based polyamide material is prepared from the following raw materials in terms of weight parts: bio-based transparent polyamide 86.5-96.6 parts, fluorophlogopite 2.0-8.0 parts, bis(4-carboxyphenyl)phenyl phosphine oxide 1.0-3.0 parts, polytin glycol dilaurate 0.3-2.0 parts and antioxidant 0.1-0.5 parts.

[0011] The present application also provides a preparation method of the high-transparency flame-retardant bio-based polyamide material, which includes: fully melting and plasticizing the mixture of bio-based transparent polyamide, fluorophlogopite, bis(4-carboxyphenyl)phenyl phosphine oxide, polytin glycol dilaurate and antioxidant as the base material, then drawing, cooling and granulating to obtain the high-transparency flame-retardant bio-based polyamide material.

[0012] The present application also provides the application of the high-transparency flame-retardant bio-based polyamide material in the field of preparing electronic and electrical or automobile shell shields.

[0013] Compared with the prior art, the present application has the following advantages:

[0014] The present application uses bis(4-carboxyphenyl)phenyl phosphine oxide as a chain extender and flame-retardant reinforcing agent, which on the one hand reacts with the terminal amino group of polyamide to improve the material performance, and on the other hand introduces phosphorus element to improve the carbonization performance of the material; at the same time, transparent fluorophlogopite is added as a reinforcing agent and flame retardant, which uses inorganic components to block heat and oxygen, and polytin glycol dilaurate is compounded, which uses fluorine, tin and silicon elements to synergize, effectively improves the flame-retardant performance of the material, and polytin glycol dilaurate has excellent lubricity, effectively improves the processability of the material, so as to meet the excellent flame-retardant performance at a low flame-retardant additive amount while ensuring the excellent transparency of the polyamide. DETAILED DESCRIPTION

[0015] In order to overcome the defects of the prior art, the present inventors have made long-term research and a large number of practices, and finally proposed the technical scheme of the present application, which mainly provides a high-transparency flame-retardant bio-based polyamide material and a preparation method thereof. The material has excellent optical performance, flame-retardant performance and processability. The technical scheme of the present application will be described clearly and completely below. Obviously, the described embodiments are part of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor fall within the scope of protection of the present application.

[0016] One aspect of the embodiments of the present application provides a high-transparency flame-retardant bio-based polyamide material, which is prepared from the following raw materials in parts by weight: bio-based transparent polyamide 86.5-96.6 parts, fluorophlogopite 2.0-8.0 parts, bis(4-carboxyphenyl)phenyl phosphine oxide 1.0-3.0 parts, polytin glycol dilaurate 0.3-2.0 parts and antioxidant 0.1-0.5 parts.

[0017] In some embodiments, the material of the bio-based transparent polyamide includes a combination of PA5T and PA5I (PA5T / 5I), wherein the molar ratio of PA5T and PA5I is 3:7, the glass transition temperature Tg is 130-135℃, the relative viscosity is 1.8-2.2, and the end amino group content is 90-150 mol / t.

[0018] In some embodiments, the fluorophlogopite has a flaky structure, a thickness of 0.02-0.05 mm, a mesh number of 20-2000, and a whiteness of more than 95%.

[0019] In some embodiments, the mass ratio of the fluorophlogopite to the polytin glycol dilaurate is 3:1-8:1.

[0020] Further, the antioxidant includes antioxidant 1098, but is not limited thereto.

[0021] Another aspect of the embodiments of the present application provides a preparation method of a high-transparency flame-retardant bio-based polyamide material, which includes: fully melting and plasticizing a mixture of bio-based transparent polyamide, fluorophlogopite, bis(4-carboxyphenyl)phenyl phosphine oxide, polytin glycol dilaurate and antioxidant as a base material, and then drawing, cooling and granulating to obtain the high-transparency flame-retardant bio-based polyamide material.

[0022] In the preparation process of the present application, the types of the bio-based transparent polyamide and the antioxidant are as described above, and will not be repeated here.

[0023] In some more specific embodiments, the high transparency flame-retardant bio-based polyamide material is prepared by a twin-screw extruder, and the preparation method can specifically include:

[0024] The bio-based transparent polyamide, fluorphlogopite, bis(4-carboxyphenyl)phenyl phosphine oxide, polytin glycol dilaurate and antioxidant are fed from the main feeding port of the twin-screw extruder, and the mixture is fully melted and plasticized under the action of twin-screw conveying and shearing, and then the strand is drawn, cooled and cut into particles to obtain the high transparency flame-retardant bio-based polyamide material.

[0025] Further, the rotation speed of the twin-screw extruder is 300-500 rpm, and the processing temperature is 250-290℃.

[0026] Another aspect of the embodiment of the present application also provides a high transparency flame-retardant bio-based polyamide material prepared by any one of the aforementioned preparation methods.

[0027] In summary, in the preparation of the high transparency flame-retardant bio-based polyamide material, the mechanism of each component is as follows: bis(4-carboxyphenyl)phenyl phosphine oxide is used as a chain extender and a flame-retardant reinforcing agent, which on the one hand reacts with the terminal amino group of the polyamide to improve the material performance, and on the other hand introduces phosphorus elements to improve the carbonization performance of the material; transparent fluorphlogopite is added as a reinforcing agent and a flame retardant, which uses inorganic components to block heat and oxygen, and polytin glycol dilaurate is added to use the synergistic effect of fluorine, tin and silicon elements to effectively improve the flame-retardant performance of the material, and polytin glycol dilaurate has excellent lubricating performance, which effectively improves the processing performance of the material, so as to achieve excellent flame-retardant performance at a low flame-retardant additive amount while ensuring excellent transparency of the polyamide.

[0028] Further, the high transparency flame-retardant bio-based polyamide material of the embodiment of the present application has excellent optical performance, flame-retardant performance and processability, and can be applied in the preparation of electronic and electrical products, new energy automobile shell covers and the like.

[0029] The technical solutions of the present application will be further described in detail below in combination with several preferred embodiments. Obviously, the described embodiments are only a part of the embodiments of the present application, rather than all the embodiments. It should be noted that the following described embodiments are intended to facilitate the understanding of the present application, and do not have any limiting effect on it. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor belong to the scope of protection of the present application. The experimental methods not specified in the following examples are usually carried out under conventional conditions or under the conditions recommended by the manufacturer. The raw materials used in the following examples are:

[0030] PA5T / 5T (Zhejiang Xinli New Material, mass ratio of 5T and 5I is 3:7, glass transition temperature is 130-135℃, relative viscosity is 1.8-2.2, end amino group content is 90-150 mol / t), bis(4-carboxyphenyl) phenyl phosphine oxide (Wuhan Kamik Technology Co., Ltd.), polytin glycol dilaurate (Japan phosphorus chemical industry Co., Ltd.), fluorophlogopite (Shijiazhuang Oukai mineral products Co., Ltd., flaky structure, thickness is 0.02-0.05mm, mesh is 20-2000, whiteness is more than 95%).

[0031] Examples 1-8 and Comparative Examples 1-5

[0032] The bio-based transparent polyamide base material, fluorophlogopite, bis(4-carboxyphenyl) phenyl phosphine oxide, polytin glycol dilaurate and antioxidant 1098 are fed from the main feeding port of the twin-screw extruder, and after the materials are fully melted and plasticized under the action of twin-screw conveying and shearing, the strands are drawn, cooled and pelletized to obtain the bio-based transparent polyamide. The rotation speed of the twin-screw extruder is 300-500 rpm, and the processing temperature is 250-290℃.

[0033] The specific proportions of each raw material in Examples 1-8 and Comparative Examples 1-5 are shown in Table 1.

[0034] Table 1 Proportions of each raw material in Examples 1-8 and Comparative Examples 1-5

[0035]

[0036]

[0037] The obtained pellets are injection molded into corresponding samples, and then tested after being placed in an environment of 23±2℃ and 50±5% relative humidity for 24h; the haze / transmittance is tested according to GB / T 2410-2008, with a thickness of 2mm; the flame retardant performance is tested according to GB / T 2408-2008, with a thickness of 1.5mm; the processing performance is determined by observing whether the sample is stuck to the mold by continuously injection molding a notched impact sample.

[0038] The test results are shown in Table 2.

[0039] Table 2 Test results of Examples 1-8 and Comparative Examples 1-5

[0040] Test item Transmittance / % Vertical burning rating Processability (whether sticking to mold) Example 1 86.2 V0 No Example 2 86.5 V0 No Example 3 86.5 V0 No Example 4 86.8 V0 No Example 5 87.0 V0 No Example 6 87.9 V0 No Example 7 88.7 V0 No Example 8 88.9 V0 No Comparative Example 1 91.2 V2 Yes Comparative Example 2 90.3 V2 Yes Comparative Example 3 89.7 V2 Yes Comparative Example 4 89.8 V2 No Comparative Example 5 87.6 V1 No

[0041] The embodiments 1-8 of the present application add fluorophlogopite, bis(4-carboxylphenyl) phenyl phosphine oxide, polytin glycol dilaurate synergistic flame retardant system in PA5T / 5I, which can realize that the polyamide has higher light transmittance while meeting V0, and has less effect on the optical performance of the material. The difference between the embodiments 1-8 and the comparative examples 1-5 is that: the comparative example 1 does not add flame retardant, and the flame retardant grade is V2, the flame retardant grade of the comparative examples 2-4 which separately add fluorophlogopite, bis(4-carboxylphenyl) phenyl phosphine oxide and polytin glycol dilaurate is still V2, but the addition of polytin glycol dilaurate makes the material have better processing performance, the comparative example 5 adds synergistic flame retardant system in order to obtain better flame retardant grade, but because the ratio of fluorophlogopite and polytin glycol dilaurate exceeds the range 3:1-8:1, the flame retardant effect can only reach V1.

[0042] As can be seen from the above, the polyamide composite material obtained by the embodiments 1-8 has high flame retardant performance and processing performance while having little effect on the transparency of the material, and can be applied to the preparation of electronic and electrical products, new energy automobile shell shields and the like.

[0043] In addition, the present inventors have also carried out tests with reference to the foregoing embodiments, using other raw materials, process operations and process conditions described in the present specification, and have obtained relatively ideal results.

[0044] The above is only a few embodiments of the present application, and does not limit the present application in any form. Although the present application is disclosed with the preferred embodiments as above, it is not intended to limit the present application, and any skilled person in the art can make some changes or modifications to the above disclosed technical content without departing from the scope of the technical solution of the present application, which are equivalent to equivalent embodiments, and belong to the scope of the technical solution.

Claims

1. A high-transparency, flame-retardant, bio-based polyamide material, characterized in that, The high-transparency flame-retardant bio-based polyamide material is prepared from the following raw materials in parts by weight: 86.5-96.6 parts of bio-based transparent polyamide, 2.0-8.0 parts of fluorophlogopite, 1.0-3.0 parts of bis(4-carboxyphenyl)phenylphosphine oxide, 0.3-2.0 parts of polytin glycol dilaurate, and 0.1-0.5 parts of antioxidant, wherein the mass ratio of fluorophlogopite to polytin glycol dilaurate is 3:1-8:

1.

2. The high-transparency flame-retardant bio-based polyamide material according to claim 1, characterized in that, The bio-based transparent polyamide is a combination of PA5T and PA5I, with a molar ratio of PA5T to PA5I of 3:7, a glass transition temperature of 130℃~135℃, a relative viscosity of 1.8~2.2, and a terminal amino content of 90~150 mol / t.

3. The high-transparency flame-retardant bio-based polyamide material according to claim 1, characterized in that: The fluorophlogopite has a sheet-like structure with a thickness of 0.02mm to 0.05mm, a mesh size of 20 to 2000 mesh, and a whiteness of over 95%.

4. The high-transparency flame-retardant bio-based polyamide material according to claim 1, characterized in that: The antioxidant is antioxidant 1098.

5. The method for preparing the high-transparency flame-retardant bio-based polyamide material according to any one of claims 1-4, characterized in that, include: A mixture of bio-based transparent polyamide, fluorophlogopite, bis(4-carboxyphenyl)phenylphosphine oxide, polytin glycol dilaurate, and antioxidants is fully melted and plasticized, then stretched, cooled, and pelletized to obtain a high-transparency flame-retardant bio-based polyamide material.

6. The preparation method according to claim 5, characterized in that, Specifically, it includes: Bio-based transparent polyamide, fluorophlogopite, bis(4-carboxyphenyl)phenylphosphine oxide, polytin glycol dilaurate, and antioxidants are fed into the main feed port of a twin-screw extruder. Under the action of twin-screw conveying and shearing, the mixture is fully melted and plasticized. Then, it is stretched, cooled, and pelletized to obtain the high-transparency flame-retardant bio-based polyamide material.

7. The preparation method according to claim 6, characterized in that: The twin-screw extruder operates at a speed of 300-500 rpm and a processing temperature of 250-290℃.

8. The use of the high-transparency flame-retardant bio-based polyamide material according to any one of claims 1-4 in the preparation of electronic, electrical or automotive housing covers.

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