Flame-retardant high polymer material and preparation method thereof

Abstract

The invention relates to the technical field of flame-retardant materials, and provides a flame-retardant high polymer material and a preparation method thereof. The flame-retardant high polymer material comprises the following components in parts by weight: 50-80 parts of a high polymer material and 3-45 parts of a flame retardant, the flame retardant is prepared from the following components in parts by weight: 1 to 25 parts of diisobutyl aluminum hypophosphite, 1 to 15 parts of bromotriazine and 1 to 5 parts of antimony flame retardant. According to the technical scheme, the problems of insufficient flame retardance and lower strength of a high polymer material in the related technology are solved.

Description

Technical Field

[0001] The present invention relates to the technical field of flame retardant materials, and in particular to a flame retardant polymer material and a preparation method thereof. Background Art

[0002] Polymer materials have been widely used in construction, electronics, transportation, aerospace, and daily necessities due to their excellent properties, such as light weight, convenient processing, corrosion resistance, and low cost. However, polymer materials are mostly composed of organic compounds, which are inherently flammable, which greatly limits their application in many specific scenarios. Once polymer products encounter a fire source, they are extremely easy to burn and spread the fire quickly. In order to effectively reduce the flammability of polymer materials, flame retardant technology has emerged and has become one of the key hotspots in the current polymer material research field, but the flame retardancy of existing flame-retardant polymer materials is still insufficient to cope with more stringent application scenarios. At the same time, the interaction between the molecular chains of many polymer materials is relatively weak. When subjected to external impact force, the molecular chains are difficult to effectively transmit and disperse stress, which makes it easy for stress to concentrate in local areas, thereby causing cracks, fractures, and other damage phenomena in the material. Especially in some application scenarios that need to withstand high impact forces, such as car bumpers, sports equipment, etc., the low strength of polymer materials limits their performance and service life. Therefore, it is necessary to obtain a polymer material with excellent flame retardant properties and high strength. Summary of the invention

[0003] The invention provides a flame retardant polymer material and a preparation method thereof, which solves the problems of insufficient flame retardancy and low strength of the polymer material in the related art.

[0004] The technical solution of the present invention is as follows: The present invention provides a flame retardant polymer material, comprising the following components in parts by weight: 50~80 parts of polymer materials, 3~45 parts of flame retardants; The flame retardant comprises the following components in parts by weight: 1 to 25 parts of diisobutyl aluminum hypophosphite, 1 to 15 parts of bromotriazine, and 1 to 5 parts of antimony-based flame retardant.

[0005] As a further technical solution, the polymer material includes a thermoplastic polymer material; The thermoplastic polymer material includes one or more of ABS, PP, PE, PA, PVC, and PC; The antimony-based flame retardant includes one or more of antimony trioxide, antimony pentoxide, antimony trichloride, and antimony pentachloride.

[0006] In the present invention, the antimony flame retardant can work synergistically with other flame retardants to show a more excellent flame retardant effect. Under high temperature environment, for example, antimony trioxide is compounded with diisobutyl aluminum hypophosphite and bromotriazine, which has the characteristics of high boiling point and low vapor pressure, and can capture free radicals in the gas phase, thereby interrupting the chain propagation of the combustion reaction, achieving the purpose of flame retardancy, and making the polymer material have excellent flame retardancy.

[0007] In the present invention, ABS is acrylonitrile-butadiene-styrene copolymer, PP is polypropylene, PE is polyethylene, PA is polyamide, PVC is polyvinyl chloride, and PC is polycarbonate.

[0008] As a further technical solution, the invention comprises the following components in parts by weight: 50~80 parts of polymer materials, 9~43 parts of flame retardants; The flame retardant comprises the following components in parts by weight: 5 to 25 parts of diisobutyl aluminum hypophosphite, 3 to 15 parts of bromotriazine, and 1 to 3 parts of antimony-based flame retardant.

[0009] As a further technical solution, the mass ratio of the diisobutyl aluminum hypophosphite, bromotriazine and antimony flame retardant is 5-10:4:1.

[0010] In the present invention, the flame retardant in the polymer material adopts diisobutyl aluminum hypophosphite, bromotriazine and antimony flame retardant in a mass ratio of 5-10:4:1, thereby improving the strength of the polymer material.

[0011] As a further technical solution, the flame retardant further comprises aryl phosphite; the mass ratio of the diisobutyl aluminum phosphite, bromotriazine, antimony flame retardant and aryl phosphite is 10:4:1:2-5.

[0012] In the present invention, in addition to diisobutyl aluminum hypophosphite, bromotriazine and antimony flame retardant, aryl hypophosphite is introduced into the flame retardant, thereby improving the flame retardancy and strength of the polymer material.

[0013] As a further technical solution, the aryl phosphite includes one or more of phenyl aluminum phosphite, phenyl zinc phosphite, and phenyl sodium phosphite.

[0014] In the present invention, an aryl hypophosphite is introduced, and the aryl hypophosphite can be one or more of phenyl hypophosphite aluminum, phenyl hypophosphite zinc, and phenyl hypophosphite sodium. The aryl hypophosphite, by virtue of its unique molecular structure, not only improves the flame retardant properties of polymer materials, but also plays a key role in improving the strength of polymer materials. The aryl hypophosphite has a stronger binding force with the polymer material matrix, which is beneficial to the improvement of the strength and flame retardancy of the polymer material. Among them, the aryl hypophosphite is preferably phenyl hypophosphite aluminum and phenyl hypophosphite zinc.

[0015] As a further technical solution, the following components are also included in parts by weight: 2 to 5 parts of a toughening agent and 0.2 to 0.5 parts of an antioxidant.

[0016] As a further technical solution, the toughening agent includes one or both of a rubber toughening agent and a thermoplastic elastomer toughening agent; the antioxidant includes one or both of an amine antioxidant and a phenolic antioxidant.

[0017] In the present invention, the addition of the toughening agent can form a dispersed phase in the polymer material matrix. When the material is impacted by an external force, the dispersed phase can induce silver streaks and shear bands and absorb a large amount of energy.

[0018] In the present invention, the antioxidant can inhibit the performance degradation of the polymer material caused by oxidation during processing, storage and use, and can effectively extend the service life of the polymer material and maintain the stability of its various properties. The model of the antioxidant can be, for example, antioxidant 445, antioxidant 264, etc.

[0019] As a further technical solution, the antimony flame retardant is prepared by modification with a coupling agent and 2-propylene acrylic acid; The modification method comprises the following steps: ball milling the antimony flame retardant and the coupling agent solution for the first time, adding 2-propylene acrylic acid solution for the second time, and drying.

[0020] As a further technical solution, the mass volume ratio of the antimony flame retardant and the coupling agent solution is 1g:1~1.5mL; The mass volume ratio of the antimony flame retardant and the 2-propylene acrylic acid solution is 1g:0.8-1.2mL; The mass fraction of the coupling agent in the coupling agent solution is 2% to 5%; The mass fraction of 2-propylene acrylic acid in the 2-propylene acrylic acid solution is 1% to 3%.

[0021] In the present invention, since the antimony flame retardant is an inorganic flame retardant, in order to improve its compatibility with the polymer matrix, the antimony flame retardant is modified by using a coupling agent and 2-propylene acrylic acid, thereby improving the strength of the polymer material.

[0022] The present invention also provides a method for preparing the flame retardant polymer material, comprising the following steps: The components of the flame retardant polymer material are mixed, extruded and granulated to obtain the flame retardant polymer material.

[0023] The working principle and beneficial effects of the present invention are: In the present invention, since the polymer material is usually composed of a large amount of hydrocarbon elements and lacks flame retardant elements or has a low content of flame retardant elements, the polymer material is flammable. Therefore, the present invention uses the polymer material as a matrix, adds diisobutyl aluminum hypophosphite, bromotriazine and antimony flame retardant therein for compounding, synergistic flame retardancy, and improves the flame retardancy and strength of the polymer material. DETAILED DESCRIPTION

[0024] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0025] In the following examples and comparative examples, the model of ABS is PA-777D, the model of PC is CH8225, the model of PA6 is YH400, the model of bromotriazine is FR-245, the model of ethylene-vinyl acetate copolymer is 1533, and the model of coupling agent is KH-570.

[0026] Example 1 The flame retardant polymer material comprises the following components in parts by weight: ABS 40 parts, PC 10 parts, flame retardant 3 parts; The flame retardant includes the following components in parts by weight: 1 part of diisobutyl aluminum hypophosphite, 1 part of bromotriazine, and 1 part of antimony trioxide; The method for preparing a flame retardant polymer material comprises the following steps: The components of the flame retardant polymer material are mixed, extruded and granulated to obtain the flame retardant polymer material.

[0027] Example 2 The flame retardant polymer material comprises the following components in parts by weight: ABS 70 parts, PA6 10 parts, flame retardant 45 parts; The flame retardant includes the following components in parts by weight: 25 parts of diisobutyl aluminum hypophosphite, 15 parts of bromotriazine, 2 parts of antimony trioxide, and 3 parts of antimony pentoxide; The method for preparing a flame retardant polymer material comprises the following steps: The components of the flame retardant polymer material are mixed, extruded and granulated to obtain the flame retardant polymer material.

[0028] Example 3 The flame retardant polymer material comprises the following components in parts by weight: ABS 50 parts, flame retardant 9 parts; The flame retardant includes the following components in parts by weight: 5 parts of diisobutyl aluminum hypophosphite, 3 parts of bromotriazine, and 1 part of antimony trioxide; The method for preparing a flame retardant polymer material comprises the following steps: The components of the flame retardant polymer material are mixed, extruded and granulated to obtain the flame retardant polymer material.

[0029] Example 4 The flame retardant polymer material comprises the following components in parts by weight: ABS 80 parts, flame retardant 43 parts, ethylene-vinyl acetate copolymer 2 parts, antioxidant 445 0.3 parts, antioxidant 264 0.2 parts; The flame retardant includes the following components in parts by weight: 25 parts of diisobutyl aluminum hypophosphite, 15 parts of bromotriazine, and 3 parts of antimony trioxide; The method for preparing a flame retardant polymer material comprises the following steps: The components of the flame retardant polymer material are mixed, extruded and granulated to obtain the flame retardant polymer material.

[0030] Example 5 The flame retardant polymer material comprises the following components in parts by weight: ABS 80 parts, flame retardant 18 parts, ethylene-vinyl acetate copolymer 5 parts, antioxidant 264 0.2 parts; The flame retardant includes the following components in parts by weight: 8 parts of diisobutyl aluminum hypophosphite, 8 parts of bromotriazine, and 2 parts of antimony trioxide; The method for preparing a flame retardant polymer material comprises the following steps: The components of the flame retardant polymer material are mixed, extruded and granulated to obtain the flame retardant polymer material.

[0031] Example 6 The only difference between this embodiment and embodiment 5 is that the flame retardant is diisobutyl aluminum hypophosphite, bromotriazine and antimony trioxide in a mass ratio of 11:4:1.

[0032] Example 7 The only difference between this embodiment and embodiment 5 is that the flame retardant is diisobutyl aluminum hypophosphite, bromotriazine and antimony trioxide in a mass ratio of 5:4:1.

[0033] Example 8 The only difference between this embodiment and embodiment 5 is that the flame retardant is diisobutyl aluminum hypophosphite, bromotriazine and antimony trioxide in a mass ratio of 10:4:1.

[0034] Example 9 The only difference between this embodiment and embodiment 8 is that the flame retardant is diisobutyl aluminum hypophosphite, bromotriazine, antimony trioxide and phenyl aluminum hypophosphite in a mass ratio of 10:4:1:2.

[0035] Example 10 The only difference between this embodiment and embodiment 8 is that the flame retardant is diisobutyl aluminum hypophosphite, bromotriazine, antimony trioxide, phenyl aluminum hypophosphite and phenyl zinc hypophosphite in a mass ratio of 20:8:2:5:5.

[0036] Embodiment 11 The difference between this embodiment and embodiment 10 is that antimony trioxide is prepared after being modified by a coupling agent and stearic acid; The modified preparation method comprises the following steps: ball milling antimony trioxide and a coupling agent solution for the first time, adding a stearic acid solution for the second time, and drying; Among them, the mass volume ratio of antimony trioxide and coupling agent solution is 1g:1.5mL; the mass volume ratio of antimony trioxide and stearic acid solution is 1g:0.8mL; the mass fraction of coupling agent in coupling agent solution is 2%; the mass fraction of stearic acid in stearic acid solution is 1%; the solvent in coupling agent solution and 2-propylene acrylic acid solution is ethanol.

[0037] Example 12 The only difference between this example and Example 11 is that stearic acid is replaced by 2-propenylacrylic acid.

[0038] Embodiment 13 The difference between this example and Example 11 is that antimony trioxide is prepared after being modified with a coupling agent and 2-propylene acrylic acid; The modified preparation method comprises the following steps: ball milling antimony trioxide and a coupling agent solution for the first time, adding 2-propylene acrylic acid solution for the second time, and drying; Among them, the mass volume ratio of antimony trioxide and coupling agent solution is 1g:1mL; the mass volume ratio of antimony trioxide and 2-propylene acrylic acid solution is 1g:1.2mL; the mass fraction of coupling agent in coupling agent solution is 5%; the mass fraction of 2-propylene acrylic acid in 2-propylene acrylic acid solution is 3%; the solvents in coupling agent solution and 2-propylene acrylic acid solution are both ethanol.

[0039] Comparative Example 1 The difference between this comparative example and Example 1 is that diisobutyl aluminum hypophosphite is replaced by aluminum hypophosphite.

[0040] Comparative Example 2 The difference between this comparative example and Example 1 is that diisobutyl aluminum hypophosphite is replaced by diethyl aluminum hypophosphite.

[0041] Comparative Example 3 The only difference between this comparative example and Example 1 is that the flame retardant includes the following components in parts by weight: 1.5 parts of diisobutyl aluminum hypophosphite and 1.5 parts of antimony trioxide.

[0042] Comparative Example 4 The only difference between this comparative example and Example 1 is that the flame retardant includes the following components in parts by weight: 1.5 parts of diisobutyl aluminum hypophosphite and 1.5 parts of bromotriazine.

[0043] Comparative Example 5 The only difference between this comparative example and Example 1 is that the flame retardant comprises the following components in parts by weight: 1.5 parts of bromotriazine and 1.5 parts of antimony trioxide.

[0044] Experimental Example 1 The flame retardant polymer materials prepared in Examples 1 to 4, Examples 7 to 10 and Comparative Examples 1 to 5 were respectively subjected to flame retardancy tests: According to the UL94 test method, the flame retardant grade of the sample with a thickness of 1.6 mm was tested, and the results are shown in Table 1 below.

[0045] Table 1 Flame retardant performance test results

[0046] Compared with Comparative Examples 1 to 5, the flame retardant grade of the polymer materials obtained in Examples 1 to 4 and Examples 7 to 10 is higher, indicating that the present invention uses a polymer material as a matrix, adds diisobutyl aluminum hypophosphite, bromotriazine and antimony flame retardant thereto for compounding, and also introduces aromatic hypophosphite for synergistic flame retardancy, thereby improving the flame retardancy of the polymer material.

[0047] Experimental Example 2 The flame retardant polymer materials prepared in Examples 1 to 13 and Comparative Examples 1 to 5 were respectively subjected to a simple supported beam notched impact strength test: the flame retardant polymer materials were subjected to a simple supported beam notched impact strength test according to the standard GB / T 1043.1-2008 "Determination of Simple Supported Beam Impact Properties of Plastics Part 1: Non-Instrumented Impact Test", the specimen type was type 1 specimen, the notch type was type A, and each group had 5 specimens. The test results were averaged, and the results are shown in Table 2; Table 2 Results of simply supported beam notched impact strength test

[0048] Compared with Comparative Examples 1 to 5, the polymer materials prepared in Examples 1 to 13 have higher simply supported beam notched impact strength, indicating that the present invention adds diisobutyl aluminum hypophosphite, bromotriazine and antimony-based flame retardant to the polymer material matrix for compounding, and further improves the strength of the polymer material by adjusting the mass ratio of the flame retardant, introducing aromatic hypophosphite and modifying the antimony-based flame retardant.

[0049] The above are only preferred embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention should be included in the protection scope of the present invention.

Claims

1. A flame retardant polymer material, characterized in that: The composition comprises the following components in parts by weight: 50~80 parts of polymer materials, 3~45 parts of flame retardants; The flame retardant comprises the following components in parts by weight: 1 to 25 parts of diisobutyl aluminum hypophosphite, 1 to 15 parts of bromotriazine, and 1 to 5 parts of antimony-based flame retardant.

2. A flame retardant polymer material according to claim 1, characterized in that: The polymer material includes a thermoplastic polymer material; The thermoplastic polymer material includes one or more of ABS, PP, PE, PA, PVC, and PC; The antimony-based flame retardant includes one or more of antimony trioxide, antimony pentoxide, antimony trichloride, and antimony pentachloride.

3. A flame retardant polymer material according to claim 1, characterized in that: The composition comprises the following components in parts by weight: 50~80 parts of polymer materials, 9~43 parts of flame retardants; The flame retardant comprises the following components in parts by weight: 5 to 25 parts of diisobutyl aluminum hypophosphite, 3 to 15 parts of bromotriazine, and 1 to 3 parts of antimony-based flame retardant.

4. A flame retardant polymer material according to claim 3, characterized in that: The mass ratio of the diisobutyl aluminum hypophosphite, bromotriazine and antimony flame retardant is 5-10:4:

1.

5. A flame retardant polymer material according to claim 4, characterized in that: The flame retardant also includes aryl phosphite; the mass ratio of diisobutyl aluminum phosphite, bromotriazine, antimony flame retardant and aryl phosphite is 10:4:1:2-5.

6. A flame retardant polymer material according to claim 5, characterized in that: The aryl phosphite includes one or more of phenyl aluminum phosphite, phenyl zinc phosphite, and phenyl sodium phosphite.

7. The flame retardant polymer material according to claim 3, characterized in that: The invention also comprises the following components in parts by weight: 2 to 5 parts of a toughening agent and 0.2 to 0.5 parts of an antioxidant.

8. The flame retardant polymer material according to claim 5, characterized in that: The antimony flame retardant is prepared by modification with a coupling agent and 2-propylene acrylic acid; The modification method comprises the following steps: ball milling the antimony flame retardant and the coupling agent solution for the first time, adding 2-propylene acrylic acid solution for the second time, and drying.

9. The flame retardant polymer material according to claim 8, characterized in that: The mass volume ratio of the antimony flame retardant and the coupling agent solution is 1g:1~1.5mL; The mass volume ratio of the antimony flame retardant and the 2-propylene acrylic acid solution is 1g:0.8-1.2mL; The mass fraction of the coupling agent in the coupling agent solution is 2% to 5%; The mass fraction of 2-propylene acrylic acid in the 2-propylene acrylic acid solution is 1% to 3%.

10. The method for preparing a flame retardant polymer material according to any one of claims 1 to 9, characterized in that: The following steps are involved: The components of the flame retardant polymer material are mixed, extruded and granulated to obtain the flame retardant polymer material.

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