Low odor flame retardant polypropylene composite and method of making same

Abstract

This invention belongs to the field of polymer composite materials technology, and provides a low-odor flame-retardant polypropylene composite material and its preparation method. The preparation of this composite material includes the following steps: mixing polypropylene, a flame retardant, a lubricant, an antioxidant, and a defoamer to obtain a premix; mixing the premix and an odor inhibitor to obtain an intermediate product; and melt-extruding and granulating the intermediate product to obtain the low-odor flame-retardant polypropylene composite material. This invention eliminates odorous volatile substances generated during the preparation of the premix by heating, defoaming with a defoamer, and vacuuming. Furthermore, after eliminating the odorous volatile substances, an odor inhibitor is added to further suppress the generation of unpleasant odors. The resulting polypropylene composite material has advantages such as low odor and high flame retardancy.

Description

Technical Field

[0001] This invention relates to the field of polymer composite materials technology, and in particular to a low-odor flame-retardant polypropylene composite material and its preparation method. Background Technology

[0002] Polypropylene (PP) materials are characterized by their light weight, high strength, good impact resistance, and good dimensional stability. In recent years, with the advancement of automotive lightweighting, PP materials have become increasingly widely used in the automotive industry as a primary material for replacing steel, due to their high cost-effectiveness. Applications include instrument panel frames, air ducts, and multi-functional brackets. Automotive parts made of flame-retardant PP materials have comparable performance to steel parts, but flame-retardant PP automotive parts also possess flame-retardant properties and are more than 40% lighter, resulting in better economic efficiency. However, in the automotive industry, existing flame-retardant PP materials often contain flame retardants, wetting agents, compatibilizers, and other substances with unpleasant odors, resulting in relatively unpleasant smells in flame-retardant PP material parts.

[0003] With rising living standards, people have increasingly higher demands for automobiles. As the main materials for automotive interior components, polymer materials and polymer composites significantly impact the odor of the vehicle interior. Strong odors not only severely affect the user experience but also negatively impact the health of passengers. Therefore, OEMs are placing greater emphasis on in-vehicle air quality and have imposed higher requirements on the odor characteristics of automotive materials, especially plastic materials used in interior trim. Consequently, developing a low-odor, highly flame-retardant polypropylene composite material has become a pressing issue for those skilled in the art. Summary of the Invention

[0004] In view of this, the present invention provides a low-odor flame-retardant polypropylene composite material and its preparation method. Its purpose is to solve the technical problems such as poor odor in existing flame-retardant polypropylene material components.

[0005] To achieve the above objectives, the present invention adopts the following technical solution:

[0006] This invention provides a low-odor flame-retardant polypropylene composite material, prepared from raw materials comprising the following parts by weight:

[0007] 50-100 parts polypropylene, 1-10 parts odor inhibitor, 1-10 parts flame retardant, 0.1-5 parts lubricant, 0.2-0.5 parts antioxidant, and 1-5 parts defoamer;

[0008] The odor inhibitor comprises zinc ricinoleate, zeolite, tartaric acid, and citric acid, wherein the mass ratio of zinc ricinoleate, zeolite, tartaric acid, and citric acid is 10–20:30–50:10–20:10–20.

[0009] Furthermore, the flame retardant is one or more of nitrogen-based flame retardants, phosphorus-based flame retardants, bromine-based flame retardants, chlorine-based flame retardants, and inorganic flame retardants.

[0010] Furthermore, the lubricant is one or more of silicone, EBS, PE wax, and PETS.

[0011] Furthermore, the antioxidant is one or more of antioxidant 168, antioxidant 1098, antioxidant 1076, antioxidant 1010 and antioxidant H11.

[0012] Furthermore, the defoamer is one or more of silicone oil, polyethylene glycol, and tributyl phosphate.

[0013] This invention also provides a method for preparing the above-mentioned low-odor flame-retardant polypropylene composite material, comprising the following steps:

[0014] S1. Polypropylene, flame retardant, lubricant, antioxidant and defoamer are mixed to obtain a premixed material;

[0015] S2. Mix the premixed material and the odor inhibitor to obtain an intermediate product;

[0016] S3. The intermediate product is melt-extruded and granulated to obtain a low-odor flame-retardant polypropylene composite material.

[0017] Furthermore, in step S1, the mixing temperature is 90–150°C, the mixing time is 5–20 min, and the mixing vacuum degree is ≤0.05 MPa.

[0018] Furthermore, in step S2, the mixing temperature is 50–90°C, and the mixing time is 5–20 min.

[0019] Furthermore, in step S3, the temperature of melt extrusion granulation is 150–200°C.

[0020] As can be seen from the above technical solution, compared with the prior art, the beneficial effects of the present invention are as follows:

[0021] This invention eliminates odorous volatile substances generated during the preparation of premixed materials through heating, defoaming with an antifoaming agent, and vacuuming. Furthermore, after eliminating the odorous volatile substances, an odor inhibitor is added to further suppress the generation of unpleasant odors. This dual deodorization method effectively reduces the odor of flame-retardant polypropylene composite materials.

[0022] The zeolite used in this invention has a porous structure, which can effectively absorb odor molecules, achieving a significant deodorizing effect. When odor molecules come into contact with zinc ricinoleate, zinc ions act as a catalyst, further decomposing the odor molecules into harmless substances. Citric acid and tartaric acid inhibit bacterial growth, thereby removing odors. Furthermore, citric acid can neutralize alkaline substances in the air, thus neutralizing odors. Therefore, the odor inhibitor used in this invention can remove odors from multiple aspects, resulting in excellent deodorizing effects. Detailed Implementation

[0023] This invention provides a low-odor flame-retardant polypropylene composite material, prepared from raw materials comprising the following parts by weight:

[0024] 50-100 parts polypropylene, 1-10 parts odor inhibitor, 1-10 parts flame retardant, 0.1-5 parts lubricant, 0.2-0.5 parts antioxidant, and 1-5 parts defoamer;

[0025] The odor inhibitor comprises zinc ricinoleate, zeolite, tartaric acid, and citric acid, wherein the mass ratio of zinc ricinoleate, zeolite, tartaric acid, and citric acid is 10–20:30–50:10–20:10–20, preferably 12–18:34–46:12–18:12–18, and more preferably 14–16:38–40:14–16:14–16.

[0026] In this invention, the amount of polypropylene used is preferably 60 to 90 parts, and more preferably 70 to 80 parts.

[0027] In this invention, the amount of odor inhibitor is preferably 2 to 8 parts, and more preferably 4 to 6 parts.

[0028] In this invention, the amount of flame retardant used is preferably 2 to 8 parts, and more preferably 4 to 6 parts.

[0029] In this invention, the amount of lubricant used is preferably 1 to 4 parts, and more preferably 2 to 3 parts.

[0030] In this invention, the amount of antioxidant is preferably 0.3 to 0.4 parts, and more preferably 0.35 parts.

[0031] In this invention, the amount of defoamer used is preferably 2 to 4 parts, and more preferably 3 parts.

[0032] In this invention, the flame retardant is one or more of nitrogen-based flame retardants, phosphorus-based flame retardants, brominated flame retardants, chlorinated flame retardants, and inorganic flame retardants; the nitrogen-based flame retardant is preferably melamine and / or melamine cyanurate, more preferably melamine; the phosphorus-based flame retardant is preferably one or more of phosphate esters, phosphites, and phosphonates, more preferably phosphate esters; the brominated flame retardant is preferably one or more of brominated polystyrene, tetrabromobisphenol A, and decabromodiphenyl ethane, more preferably brominated polystyrene; the chlorinated flame retardant is preferably chlorinated paraffin and / or methyl pentachlorostearate, more preferably chlorinated paraffin; the inorganic flame retardant is preferably aluminum hydroxide and / or magnesium hydroxide, more preferably aluminum hydroxide.

[0033] In this invention, the lubricant is one or more of silicone, EBS, PE wax and PETS, preferably one or more of silicone, PE wax and PETS, and more preferably PE wax and / or PETS.

[0034] In this invention, the antioxidant is one or more of antioxidant 168, antioxidant 1098, antioxidant 1076, antioxidant 1010 and antioxidant H11, preferably one or more of antioxidant 168, antioxidant 1098, antioxidant 1076 and antioxidant H11, and more preferably one or more of antioxidant 168, antioxidant 1076 and antioxidant H11.

[0035] In this invention, the defoamer is one or more of silicone oil, polyethylene glycol and tributyl phosphate, preferably silicone oil and / or polyethylene glycol, and more preferably silicone oil.

[0036] This invention also provides a method for preparing the above-mentioned low-odor flame-retardant polypropylene composite material, comprising the following steps:

[0037] S1. Polypropylene, flame retardant, lubricant, antioxidant and defoamer are mixed to obtain a premixed material;

[0038] S2. Mix the premixed material and the odor inhibitor to obtain an intermediate product;

[0039] S3. The intermediate product is melt-extruded and granulated to obtain a low-odor flame-retardant polypropylene composite material.

[0040] In this invention, in step S1, the mixing temperature is 90-150°C, preferably 100-140°C, and more preferably 110-120°C; the mixing time is 5-20 min, preferably 8-16 min, and more preferably 10-12 min; the mixing vacuum degree is ≤0.05 MPa, preferably ≤0.03 MPa, and more preferably ≤0.01 MPa.

[0041] In this invention, in step S2, the mixing temperature is 50-90°C, preferably 60-80°C, and more preferably 70°C; the mixing time is 5-20 min, preferably 8-16 min, and more preferably 10-12 min.

[0042] In this invention, in step S3, the temperature of melt extrusion granulation is 150-200°C, preferably 160-190°C, and more preferably 170-180°C.

[0043] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0044] Example 1

[0045] The low-odor flame-retardant polypropylene composite material prepared in this embodiment comprises the following raw materials in parts by weight:

[0046] 60 parts polypropylene, 9 parts odor inhibitor (1 part zinc ricinoleate, 5 parts zeolite, 2 parts tartaric acid and 1 part citric acid), 4 parts flame retardant (2 parts each of phosphate ester and aluminum hydroxide), 2 parts silicone, 0.3 parts antioxidant 168, and 3 parts silicone oil.

[0047] The specific preparation steps are as follows:

[0048] Polypropylene, phosphate ester, aluminum hydroxide, silicone, antioxidant 168 and silicone oil are mixed at 0.01 MPa, heated to 120°C, and stirred for 10 min to make them evenly mixed to obtain a premixed material.

[0049] The premixed materials, zinc ricinoleate, zeolite and tartaric acid were mixed at 70°C and stirred for 10 min to obtain the intermediate product;

[0050] The intermediate product is fed into a parallel twin-screw extruder for melting and extrusion granulation to obtain a low-odor flame-retardant polypropylene composite material, wherein the extruder barrel temperature is 190℃.

[0051] Example 2

[0052] The low-odor flame-retardant polypropylene composite material prepared in this embodiment comprises the following raw materials in parts by weight:

[0053] 70 parts polypropylene, 6 parts odor inhibitor (1 part zinc ricinoleate, 3 parts zeolite, 1 part tartaric acid and 1 part citric acid), 4 parts flame retardant (2 parts melamine and 2 parts chlorinated paraffin), 3 parts EBS, 0.4 parts antioxidant 1010, and 3 parts polyethylene glycol.

[0054] The specific preparation steps are as follows:

[0055] Polypropylene, melamine, chlorinated paraffin, EBS, antioxidant 1010 and polyethylene glycol are mixed at 0.02 MPa, heated to 120°C, and stirred for 15 min to make them evenly mixed to obtain a premixed material.

[0056] The premixed materials, zinc ricinoleate, zeolite and citric acid were mixed at 60°C and stirred for 15 min to obtain the intermediate product;

[0057] The intermediate product is fed into a parallel twin-screw extruder for melting and extrusion granulation to obtain a low-odor flame-retardant polypropylene composite material, wherein the extruder barrel temperature is 200℃.

[0058] Example 3

[0059] The low-odor flame-retardant polypropylene composite material prepared in this embodiment comprises the following raw materials in parts by weight:

[0060] 55 parts polypropylene, 8 parts odor inhibitor (2 parts zinc ricinoleate, 3 parts zeolite, 1 part tartaric acid and 2 parts citric acid), 6 parts flame retardant (2 parts each of phosphonate, tetrabromobisphenol A and chlorinated paraffin), 1 part PETS, 0.2 parts antioxidant 1098, and 1 part tributyl phosphate.

[0061] The specific preparation steps are as follows:

[0062] Polypropylene, phosphonate, tetrabromobisphenol A, chlorinated paraffin, PETS, antioxidant 1098 and tributyl phosphate are mixed at 0.03 MPa, heated to 130°C, and stirred for 8 minutes to make them evenly mixed to obtain a premixed material.

[0063] The premixed materials, zinc ricinoleate, zeolite and citric acid were mixed at 50°C and stirred for 20 min to obtain the intermediate product;

[0064] The intermediate product is fed into a parallel twin-screw extruder for melting and extrusion granulation to obtain a low-odor flame-retardant polypropylene composite material, wherein the extruder barrel temperature is 180℃.

[0065] Example 4

[0066] The low-odor flame-retardant polypropylene composite material prepared in this embodiment comprises the following raw materials in parts by weight:

[0067] 80 parts polypropylene, 7 parts odor inhibitor (2 parts zinc ricinoleate, 3 parts zeolite, 1 part tartaric acid and 1 part citric acid), 7 parts flame retardant (2 parts melamine cyanurate and 5 parts methyl pentachlorostearate), 4 parts PE wax, 0.3 parts antioxidant H11, and 1 part silicone oil.

[0068] The specific preparation steps are as follows:

[0069] Polypropylene, melamine cyanurate, methyl pentachlorostearate, PE wax, antioxidant H11 and silicone oil are mixed at 0.04 MPa, heated to 125°C, and stirred for 12 min to make them evenly mixed to obtain a premixed material.

[0070] The premixed materials, zinc ricinoleate, zeolite and citric acid were mixed at 70°C and stirred for 8 minutes to obtain the intermediate product;

[0071] The intermediate product is fed into a parallel twin-screw extruder for melting and extrusion granulation to obtain a low-odor flame-retardant polypropylene composite material, wherein the extruder barrel temperature is 190℃.

[0072] Example 5

[0073] The low-odor flame-retardant polypropylene composite material prepared in this embodiment comprises the following raw materials in parts by weight:

[0074] 90 parts polypropylene, 10 parts odor inhibitor (2 parts zinc ricinoleate, 4 parts zeolite, 2 parts tartaric acid and 2 parts citric acid), 6 parts flame retardant (2 parts each of decabromodiphenyl ethane, magnesium hydroxide and chlorinated paraffin), 4 parts silicone, 0.5 parts antioxidant 1076, and 2 parts silicone oil.

[0075] The specific preparation steps are as follows:

[0076] Polypropylene, decabromodiphenyl ethane, magnesium hydroxide, chlorinated paraffin, silicone, antioxidant 1076 and silicone oil are mixed at 0.05 MPa, heated to 135°C, and stirred for 5 minutes to make them evenly mixed to obtain a premixed material.

[0077] The premixed materials, zinc ricinoleate, zeolite and citric acid were mixed at 60°C and stirred for 15 min to obtain the intermediate product;

[0078] The intermediate product is fed into a parallel twin-screw extruder for melting and extrusion granulation to obtain a low-odor flame-retardant polypropylene composite material, wherein the extruder barrel temperature is 170℃.

[0079] Comparative Example 1

[0080] The raw materials and steps are the same as in Example 1, except that zinc ricinoleate was not added.

[0081] Comparative Example 2

[0082] The raw materials and steps are the same as in Example 1, except that zeolite is not added.

[0083] Comparative Example 3

[0084] The raw materials and steps are the same as in Example 1, except that tartaric acid is not added.

[0085] Comparative Example 4

[0086] The raw materials and steps are the same as in Example 1, except that citric acid is not added.

[0087] Comparative Example 5

[0088] Replace the odor inhibitor in Example 1 with odor-eliminating masterbatch, and the other steps are the same.

[0089] The main performance indicators of the low-odor flame-retardant polypropylene composites prepared in Examples 1-5 are shown in Table 1, and the odor properties of the low-odor flame-retardant polypropylene composites prepared in Comparative Examples 1-5 are shown in Table 2.

[0090] Table 1. Main performance indicators of the low-odor flame-retardant polypropylene composite materials prepared in Examples 1-5

[0091]

[0092] Table 2 Odor properties of low-odor flame-retardant polypropylene composites prepared in Comparative Examples 1–5

[0093] performance Test Standards Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Odor PV3900 3.5 4.0 3.0 3.0 3.5

[0094] As can be seen from Tables 1 and 2, the low-odor flame-retardant polypropylene composite material prepared by the present invention has the advantages of low odor and high flame retardancy while maintaining mechanical properties.

[0095] The above description is only a preferred embodiment of the present invention. It should be noted that for those skilled in the art, several improvements and modifications can be made without departing from the principle of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. A low-odor, flame-retardant polypropylene composite material, characterized in that, It is prepared from raw materials comprising the following parts by weight: 50-100 parts polypropylene, 1-10 parts odor inhibitor, 1-10 parts flame retardant, 0.1-5 parts lubricant, 0.2-0.5 parts antioxidant, and 1-5 parts defoamer; The odor inhibitor comprises zinc ricinoleate, zeolite, tartaric acid, and citric acid, wherein the mass ratio of zinc ricinoleate, zeolite, tartaric acid, and citric acid is 10–20:30–50:10–20:10–20.

2. The low-odor flame-retardant polypropylene composite material according to claim 1, characterized in that, The flame retardant is one or more of nitrogen-based flame retardants, phosphorus-based flame retardants, bromine-based flame retardants, chlorine-based flame retardants, and inorganic flame retardants.

3. The low-odor flame-retardant polypropylene composite material according to claim 2, characterized in that, The lubricant is one or more of silicone, EBS, PE wax and PETS.

4. The low-odor flame-retardant polypropylene composite material according to any one of claims 1 to 3, characterized in that, The antioxidant is one or more of antioxidant 168, antioxidant 1098, antioxidant 1076, antioxidant 1010 and antioxidant H11.

5. The low-odor flame-retardant polypropylene composite material according to claim 4, characterized in that, The defoamer is one or more of silicone oil, polyethylene glycol, and tributyl phosphate.

6. The method for preparing the low-odor flame-retardant polypropylene composite material according to any one of claims 1 to 5, characterized in that, Includes the following steps: S1. Polypropylene, flame retardant, lubricant, antioxidant and defoamer are mixed to obtain a premixed material; S2. Mix the premixed material and the odor inhibitor to obtain an intermediate product; S3. The intermediate product is melt-extruded and granulated to obtain a low-odor flame-retardant polypropylene composite material.

7. The preparation method according to claim 6, characterized in that, In step S1, the mixing temperature is 90–150°C, the mixing time is 5–20 min, and the mixing vacuum degree is ≤0.05 MPa.

8. The preparation method according to claim 7, characterized in that, In step S2, the mixing temperature is 50–90°C and the mixing time is 5–20 min.

9. The preparation method according to any one of claims 6 to 8, characterized in that, In step S3, the temperature of melt extrusion granulation is 150–200°C.

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