Impact-resistant polypropylene composite material as well as production method and application thereof

Abstract

The invention relates to the technical field of high polymer materials, and discloses an impact-resistant polypropylene composite material as well as a production method and application thereof, and the impact-resistant polypropylene composite material comprises the following raw materials: polypropylene, maleic anhydride, impact-resistant SBS, a synergistic flame-retardant compound, a plasticizer, an antioxidant, an ultraviolet light absorber and a lubricant. The prepared impact-resistant SBS and the synergistic flame-retardant compound participate in the production process of the polypropylene composite material, so that the produced polypropylene composite material can have excellent impact resistance and flame retardance, stress change can be buffered when the polypropylene composite material is impacted, cracks and damage are not prone to being generated, the service life is effectively prolonged, and the polypropylene composite material is suitable for popularization and application. And meanwhile, the fire can be effectively prevented from spreading when a fire disaster occurs, and the use safety is extremely high.

Description

Technical Field

[0001] The present invention relates to the technical field of polymer materials, and particularly relates to an impact-resistant polypropylene composite material, a production method thereof, and an application thereof. Background Art

[0002] Polypropylene is a general-purpose plastic with excellent mechanical properties, low production costs, and good processing and molding capabilities. It is widely used in the automotive industry, building materials, electrical materials, packaging, and other fields. However, with the progress of industrial technology and the continuous expansion of application scenarios, the limitations of ordinary polypropylene materials in use have become increasingly prominent. In a complex stress environment, the impact resistance of ordinary polypropylene is average, and the material is prone to deformation and even cracking, resulting in structural failure. In addition, ordinary polypropylene does not have flame retardant properties, has a fast burning speed and a large amount of heat generation, and is accompanied by a melting droplet phenomenon during combustion, which is extremely likely to cause a fire and accelerate the spread of the fire. Therefore, in fields with high safety requirements such as electronics and transportation, there are great limitations in use.

[0003] The patent with the publication number CN117050454A discloses an impact-resistant polypropylene composite material and a preparation method thereof. This impact-resistant polypropylene composite material includes polypropylene, carbon fiber, unsaturated carboxylic acid monomers, initiators, cross-linking agents, and is prepared by a melt blending method, enabling the surface of the polypropylene composite material to interact with the carbon fiber through interfacial hydrogen bonds. The impact-resistant polypropylene composite material prepared by this patent has excellent impact resistance and tensile strength. However, the patent does not improve the flame retardant properties of the polypropylene composite material, and there is a risk of fire spread during a fire, posing a great safety hazard during use. Summary of the Invention

[0004] The purpose of the present invention is to provide an impact-resistant polypropylene composite material, a production method thereof, and an application thereof, and solve the following technical problems: (1) the problem that ordinary polypropylene materials have poor impact resistance and are prone to cracking and damage under stress; (2) the problem that ordinary polypropylene materials do not have flame retardant capabilities and pose safety hazards.

[0005] The purpose of the present invention can be achieved through the following technical solutions: An impact-resistant polypropylene composite material, comprising the following raw materials in parts by weight: 70-90 parts of polypropylene, 10-15 parts of maleic anhydride, 15-18 parts of impact-resistant SBS, 6-8 parts of synergistic flame retardant composite, 2-3 parts of plasticizer, 2-4 parts of antioxidant, 1-3 parts of ultraviolet absorber, and 1-3 parts of lubricant.

[0006] Further, the plasticizer is any one of dioctyl phthalate and diisononyl phthalate; the antioxidant is any one of antioxidant 1010, antioxidant 1076, and antioxidant 1135; the ultraviolet absorber is any one of ultraviolet absorber UV-P, ultraviolet absorber UV-360, and ultraviolet absorber UV-123; the lubricant is any one of stearic acid, zinc stearate, and white oil.

[0007] Further, the preparation method of the impact-resistant SBS comprises the following steps: S1: Place SBS in toluene, fully mix, add formic acid, heat up to 60 - 65 °C, dropwise add hydrogen peroxide solution, control the dropping rate at 0.5 - 0.6 ml / min, then add ethanol for coagulation, and after completion, filter, wash, and dry to obtain epoxidized SBS; S2: Place the epoxidized SBS in xylene, fully mix and stir, add hydroquinone di(2-hydroxyethyl) ether and a catalyst, heat up to 80 - 85 °C and react for 5 - 6 h, collect the product after vacuum distillation to obtain impact-resistant SBS.

[0008] In this solution, under the action of hydrogen peroxide and formic acid, SBS undergoes an oxidation reaction to obtain epoxidized SBS. Then, under the action of a catalyst, the epoxy group in the structure of epoxidized SBS undergoes a ring-opening reaction with the hydroxyl group in the structure of hydroquinone di(2-hydroxyethyl) ether and intertwines with the SBS long chain to obtain impact-resistant SBS. This kind of impact-resistant SBS uses the SBS long chain as the polymer backbone, has excellent impact resistance, and at the same time, the formed intertwined structure can generate cavities to release the stress brought by impact, further enhancing its impact resistance. When this kind of impact-resistant SBS participates in the preparation process of the polypropylene composite material, multiple hydroxyl groups in its structure can interact with the matrix of the polypropylene composite material, improving its compatibility in the polypropylene composite material, so that the prepared polypropylene composite material can have excellent impact resistance, is not easy to break, and extends its service life.

[0009] Further, in step S1, the concentration of the hydrogen peroxide solution is 30 - 35%.

[0010] Further, in step S2, the catalyst is boron trifluoride diethyl ether.

[0011] Further, the preparation method of the synergistic flame retardant composite comprises the following steps: SS1: Mix hydroxyethyl cellulose, vinylphosphonic acid, and cyclohexane evenly, heat up for reflux reaction, and collect the product after cooling to room temperature to obtain modified cellulose; SS2: Modified cellulose and diallylamine are placed in N,N-dimethylformamide, an initiator is added, the temperature is raised to 60-65°C for reaction for 6-8 hours, the solvent is removed by reduced pressure distillation, and the product is collected to obtain a synergistic flame retardant composite.

[0012] In this solution, under the action of the water-carrying agent cyclohexane, the hydroxyl group in the hydroxyethyl cellulose structure reacts with the phosphate group in the vinylphosphonic acid structure to obtain a modified cellulose having an alkenyl group in the structure. Then, under the action of an initiator, the alkenyl group in the modified cellulose structure undergoes a free radical polymerization reaction with the alkenyl group in the diallylamine structure to obtain a synergistic flame retardant composite. The synergistic flame retardant composite uses hydroxyethyl cellulose as a carbon source, vinylphosphonic acid as an acid source, and diallylamine as a gas source to form a synergistic flame retardant composite. When the composite is involved in the preparation process of a polypropylene composite material, the flame retardant ability of the material can be effectively improved. When a fire occurs, a non-combustible gas is generated to form a stable high-density carbon layer to isolate oxygen, so that the prepared polypropylene composite material has excellent flame retardant ability, which greatly improves safety during use.

[0013] Furthermore, in step SS1, the time of the temperature rising reflux reaction is 10-12h.

[0014] Furthermore, in step SS2, the initiator is any one of benzoyl peroxide and diisopropylbenzene peroxide.

[0015] A method for producing an impact-resistant polypropylene composite material comprises the following steps: Step 1: Place polypropylene, maleic anhydride, impact-resistant SBS, synergistic flame retardant compound, plasticizer, antioxidant, ultraviolet absorber, and stearic acid in a high-speed mixer, and mix and stir at a speed of 450-550 r / min for 1-1.5 hours to obtain a premix; Step 2: transfer the premix to a twin-screw extruder, set the screw speed to 300-350 r / min, the die temperature to 180-190° C., melt extrude and granulate to obtain a polypropylene composite material.

[0016] An impact-resistant polypropylene composite material is applied to the automotive industry, building materials, transportation, and electronic and electrical fields.

[0017] Beneficial effects of the present invention: The present invention prepares impact-resistant SBS and synergistic flame-retardant compounds and participates in the production process of polypropylene composite materials, so that the produced polypropylene composite materials can have excellent impact resistance and flame retardant properties, can buffer stress changes when impacted, are not prone to cracks and damage, and effectively extend the service life. At the same time, when a fire occurs, it can effectively prevent the spread of fire and has great safety in use.

[0018] Of course, any product implementing the present invention does not necessarily need to achieve all of the advantages described above at the same time. BRIEF DESCRIPTION OF THE DRAWINGS

[0019] In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the accompanying drawings required for describing the embodiments will be briefly introduced below. Obviously, the accompanying drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other accompanying drawings can be obtained based on these accompanying drawings without paying creative work.

[0020] Figure 1 The present invention is a production flow chart of the impact-resistant polypropylene composite material. DETAILED DESCRIPTION

[0021] The following will be combined with the drawings in 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.

[0022] The preparation methods of the impact-resistant SBS and synergistic flame-retardant composites in the following examples and comparative examples of the present invention are as follows: 1. Preparation of impact-resistant SBS S1: 3.2 g of SBS was placed in 60 ml of toluene, mixed thoroughly, and then 6 ml of formic acid was added. The temperature was raised to 60 °C, and 12 ml of 30% hydrogen peroxide solution was added dropwise at a rate of 0.5 ml / min. Then 6 ml of ethanol was added for condensation. After the condensation was completed, the epoxidized SBS was obtained after filtering, washing, and drying. S2: 3.6 g of epoxidized SBS was placed in 80 ml of xylene, and after sufficient mixing and stirring, 3 g of hydroquinone dihydroxyethyl ether and 0.6 g of boron trifluoride ether were added, and the temperature was raised to 80°C for reaction for 5 h. The product was collected after reduced pressure distillation to obtain impact-resistant SBS.

[0023] 2. Preparation of synergistic flame retardant compounds SS1: 4.6 g of hydroxyethyl cellulose, 3.8 g of vinylphosphonic acid and 5 g of cyclohexane were mixed evenly, heated and refluxed for 10 h, and the product was collected after cooling to room temperature to obtain modified cellulose; SS2: 5.5 g of modified cellulose and 5 g of diallylamine were placed in 80 ml of N,N-dimethylformamide, 0.6 g of benzoyl peroxide was added, the temperature was raised to 60°C for reaction for 6 h, the solvent was removed by vacuum distillation, and the product was collected to obtain a synergistic flame retardant composite.

[0024] Example 1

[0025] An impact-resistant polypropylene composite material, comprising the following raw materials in parts by weight: 70 parts of polypropylene, 10 parts of maleic anhydride, 15 parts of impact-resistant SBS, 6 parts of synergistic flame retardant composite, 2 parts of dioctyl phthalate, 2 parts of antioxidant 1010, 1 part of ultraviolet absorber UV-P, and 1 part of stearic acid; The production method of the impact-resistant polypropylene composite material comprises the following steps: Step 1: Place the polypropylene, maleic anhydride, impact-resistant SBS, synergistic flame retardant composite, dioctyl phthalate, antioxidant 1010, ultraviolet absorber UV-P, and stearic acid in parts by weight in a high-speed mixer, and mix and stir at a speed of 450 r / min for 1 h to obtain a premix; Step 2: Transfer the premix to a twin-screw extruder, set the screw speed to 300 r / min, and the head temperature to 180 °C, and melt and extrude into pellets to obtain a polypropylene composite material.

[0026] Example 2

[0027] An impact-resistant polypropylene composite material, comprising the following raw materials in parts by weight: 80 parts of polypropylene, 12 parts of maleic anhydride, 16 parts of impact-resistant SBS, 7 parts of synergistic flame retardant composite, 2.5 parts of diisononyl phthalate, 3 parts of antioxidant 1076, 2 parts of ultraviolet absorber UV-360, and 2 parts of zinc stearate; The production method of the impact-resistant polypropylene composite material comprises the following steps: Step 1: Place the polypropylene, maleic anhydride, impact-resistant SBS, synergistic flame retardant composite, diisononyl phthalate, antioxidant 1076, ultraviolet absorber UV-360, and zinc stearate in parts by weight in a high-speed mixer, and mix and stir at a speed of 500 r / min for 1.2 h to obtain a premix; Step 2: Transfer the premix to a twin-screw extruder, set the screw speed to 320 r / min, and the head temperature to 185 °C, and melt and extrude into pellets to obtain a polypropylene composite material.

[0028] Example 3

[0029] An impact-resistant polypropylene composite material, comprising the following raw materials in parts by weight: 90 parts of polypropylene, 15 parts of maleic anhydride, 18 parts of impact-resistant SBS, 8 parts of synergistic flame retardant composite, 3 parts of dioctyl phthalate, 4 parts of antioxidant 1135, 3 parts of ultraviolet absorber UV-123, and 3 parts of white oil; The production method of the impact-resistant polypropylene composite material comprises the following steps: Step 1: Put polypropylene, maleic anhydride, impact-resistant SBS, synergistic flame retardant composite, dioctyl phthalate, antioxidant 1135, ultraviolet absorber UV-123, and white oil in parts by weight into a high-speed mixer, and mix and stir at a speed of 550 r / min for 1.5 h to obtain a premix; Step 2: Transfer the premix to a twin-screw extruder, set the screw speed to 350 r / min, and the head temperature to 190 °C, and melt-extrude and pelletize to obtain a polypropylene composite material.

[0030] Comparative Example 1 A polypropylene composite material, comprising the following raw materials in parts by weight: 80 parts of polypropylene, 12 parts of maleic anhydride, 7 parts of synergistic flame retardant composite, 2.5 parts of diisononyl phthalate, 3 parts of antioxidant 1076, 2 parts of ultraviolet absorber UV-360, and 2 parts of zinc stearate; The production method of this polypropylene composite material includes the following steps: Step 1: Put polypropylene, maleic anhydride, synergistic flame retardant composite, diisononyl phthalate, antioxidant 1076, ultraviolet absorber UV-360, and zinc stearate in parts by weight into a high-speed mixer, and mix and stir at a speed of 500 r / min for 1.2 h to obtain a premix; Step 2: Transfer the premix to a twin-screw extruder, set the screw speed to 320 r / min, and the head temperature to 185 °C, and melt-extrude and pelletize to obtain a polypropylene composite material.

[0031] Comparative Example 2 A polypropylene composite material, comprising the following raw materials in parts by weight: 80 parts of polypropylene, 12 parts of maleic anhydride, 16 parts of impact-resistant SBS, 2.5 parts of diisononyl phthalate, 3 parts of antioxidant 1076, 2 parts of ultraviolet absorber UV-360, and 2 parts of zinc stearate; The production method of this polypropylene composite material includes the following steps: Step 1: Put polypropylene, maleic anhydride, impact-resistant SBS, diisononyl phthalate, antioxidant 1076, ultraviolet absorber UV-360, and zinc stearate in parts by weight into a high-speed mixer, and mix and stir at a speed of 500 r / min for 1.2 h to obtain a premix; Step 2: Transfer the premix to a twin-screw extruder, set the screw speed to 320 r / min, and the head temperature to 185 °C, and melt-extrude and pelletize to obtain a polypropylene composite material.

[0032] Comparative Example 3 A polypropylene composite material comprises the following raw materials in parts by weight: 80 parts of polypropylene, 12 parts of maleic anhydride, 16 parts of epoxidized SBS, 7 parts of synergistic flame retardant composite, 2.5 parts of diisononyl phthalate, 3 parts of antioxidant 1076, 2 parts of ultraviolet absorber UV-360, and 2 parts of zinc stearate; The production method of this polypropylene composite material comprises the following steps: Step 1: Place the polypropylene, maleic anhydride, epoxidized SBS, synergistic flame retardant composite, diisononyl phthalate, antioxidant 1076, ultraviolet absorber UV-360, and zinc stearate in parts by weight in a high-speed mixer, and mix and stir at a rotation speed of 500 r / min for 1.2 h to obtain a premix; Step 2: Transfer the premix to a twin-screw extruder, set the screw rotation speed to 320 r / min, and the head temperature to 185 °C, and melt and extrude into pellets to obtain the polypropylene composite material.

[0033] Performance testing Perform tablet pressing on the polypropylene composite materials prepared in Examples 1 - 3 and Comparative Examples 1 - 3 to make samples of composite specifications, and test the impact strength of the samples with reference to the standard GB / T1043.1 - 2008 to judge the impact resistance of the samples; test the flame retardant grade of the samples with reference to the UL-94 standard to judge the flame retardant performance of the samples; the specific test results are shown in the following table:

[0034] As can be seen from the above table, the samples prepared in Examples 1 - 3 all have excellent impact resistance and flame retardant effects. Among the samples prepared in Comparative Example 1, impact-resistant SBS was not added, so the impact resistance is poor. Among the samples prepared in Comparative Example 2, the synergistic flame retardant composite was not added, so the flame retardant ability is poor. Among the samples prepared in Comparative Example 3, epoxidized SBS was directly used, and the impact resistance is inferior to that of the examples. Because the synergistic flame retardant composite was added thereto, it has excellent flame retardant effects.

[0035] In the description of this specification, the description with reference to terms such as "one embodiment", "some embodiments", "example", "specific example", or "some examples" means that the specific features, structures, materials, or characteristics described in connection with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic representations of the above terms do not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials, or characteristics described can be combined in any one or more embodiments or examples in a suitable manner. In addition, without contradiction, those skilled in the art can combine and combine the different embodiments or examples described in this specification and the features of the different embodiments or examples.

[0036] The above content is only an example and illustration of the concept of the present invention. Those skilled in the art of the present technology can make various modifications or supplements to the described specific embodiments or use similar methods for substitution. As long as they do not deviate from the scope defined by the concept of the invention, they should all fall within the protection scope of the present invention.

Claims

1. An impact-resistant polypropylene composite material, characterized in that, The invention comprises the following raw materials in parts by weight: 70-90 parts of polypropylene, 10-15 parts of maleic anhydride, 15-18 parts of impact-resistant SBS, 6-8 parts of synergistic flame-retardant compound, 2-3 parts of plasticizer, 2-4 parts of antioxidant, 1-3 parts of ultraviolet absorber and 1-3 parts of lubricant.

2. The impact-resistant polypropylene composite material according to claim 1, wherein, The plasticizer is any one of dioctyl phthalate and diisononyl phthalate; the antioxidant is any one of antioxidant 1010, antioxidant 1076, and antioxidant 1135; the ultraviolet absorber is any one of ultraviolet absorber UV-P, ultraviolet absorber UV-360, and ultraviolet absorber UV-123; the lubricant is any one of stearic acid, zinc stearate, and white oil.

3. An impact-resistant polypropylene composite material according to claim 1, characterized in that, The preparation method of the impact-resistant SBS comprises the following steps: S1: Place SBS in toluene, mix thoroughly, add formic acid, heat to 60-65°C, drip hydrogen peroxide solution at a drip rate of 0.5-0.6 ml / min, and then add ethanol for condensation. After completion, filter, wash, and dry to obtain epoxidized SBS; S2: Place epoxidized SBS in xylene, mix and stir thoroughly, add hydroquinone dihydroxyethyl ether and a catalyst, heat to 80-85°C for reaction for 5-6h, and collect the product after reduced pressure distillation to obtain impact-resistant SBS.

4. An impact-resistant polypropylene composite material according to claim 3, wherein, In step S1, the concentration of the hydrogen peroxide solution is 30-35%.

5. An impact-resistant polypropylene composite material according to claim 3, characterized in that, In step S2, the catalyst is boron trifluoride etherate.

6. An impact-resistant polypropylene composite material according to claim 1, wherein, The preparation method of the synergistic flame retardant composite comprises the following steps: SS1: Mix hydroxyethyl cellulose, vinylphosphonic acid and cyclohexane evenly, heat up and reflux for reaction, and collect the product after cooling to room temperature to obtain modified cellulose; SS2: Modified cellulose and diallylamine are placed in N,N-dimethylformamide, an initiator is added, the temperature is raised to 60-65°C for reaction for 6-8 hours, the solvent is removed by reduced pressure distillation, and the product is collected to obtain a synergistic flame retardant composite.

7. An impact-resistant polypropylene composite material according to claim 6, characterized in that, In step SS1, the temperature rising and reflux reaction time is 10-12h.

8. An impact-resistant polypropylene composite material according to claim 6, characterized in that, In step SS2, the initiator is any one of benzoyl peroxide and diisopropylbenzene peroxide.

9. A production method of the impact-resistant polypropylene composite material as described in claim 1, characterized in that, The following steps are involved: Step 1: Place polypropylene, maleic anhydride, impact-resistant SBS, synergistic flame retardant compound, plasticizer, antioxidant, ultraviolet absorber, and stearic acid in a high-speed mixer, and mix and stir at a speed of 450-550 r / min for 1-1.5 hours to obtain a premix; Step 2: transfer the premix to a twin-screw extruder, set the screw speed to 300-350 r / min, the die temperature to 180-190° C., melt extrude and granulate to obtain a polypropylene composite material.

10. An impact-resistant polypropylene composite material as described in claim 1, characterized in that, The impact-resistant polypropylene composite material is applied to the automotive industry, building materials, transportation, and electronic and electrical fields.

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