Impact-resistant polypropylene composite material and its production method and use

Abstract

The application 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.The impact-resistant polypropylene composite material comprises the following raw materials: polypropylene, maleic anhydride, impact-resistant SBS, synergistic flame-retardant composite, plasticizer, antioxidant, ultraviolet absorber and lubricant.The impact-resistant SBS and the synergistic flame-retardant composite are prepared and used in the production process of the polypropylene composite material, so that the produced polypropylene composite material has excellent impact resistance and flame retardation, can buffer stress change when impacted, is not prone to crack damage, effectively prolongs the service life, can effectively prevent fire spreading when a fire occurs, and has great use safety.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of high polymer materials, in particular to an impact-resistant polypropylene composite material and a production method and application thereof. BACKGROUND

[0002] Polypropylene is a general-purpose plastic with excellent mechanical properties, low production cost and good processing and molding capability, and is widely used in the fields of automobile industry, building materials, electrical materials and packaging. However, with the progress of industrial technology and the continuous expansion of application scenarios, the limitations of ordinary polypropylene materials in use are increasingly prominent. In a complex stress environment, ordinary polypropylene has poor impact resistance, and the material is prone to deformation and even cracking, leading to structural failure. In addition, ordinary polypropylene does not have flame retardant properties, burns quickly and generates a large amount of heat, and the combustion process is accompanied by melt dripping, which can easily cause fires and accelerate the spread of fire. Therefore, in the fields of electronic appliances, transportation and other safety-critical fields, there are great limitations in use.

[0003] Patent No. CN117050454A discloses an impact-resistant polypropylene composite material and a preparation method thereof. The impact-resistant polypropylene composite material comprises polypropylene, carbon fiber, unsaturated carboxylic acid monomer, initiator, crosslinking agent, and is prepared by a melt blending method. The surface of the polypropylene composite material and the carbon fiber interact through interfacial hydrogen bonds. The impact-resistant polypropylene composite material prepared by the patent has excellent impact resistance and tensile strength. However, the flame retardant properties of the polypropylene composite material are not improved in the patent, and there is a risk of fire spreading in the event of a fire, which poses a great safety hazard when used. SUMMARY

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

[0005] The object of the present application can be achieved by the following technical solutions:

[0006] An impact-resistant polypropylene composite material comprises the following raw materials 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.

[0007] Further, the plasticizer is any one of dioctyl phthalate, diisononyl phthalate; the antioxidant is any one of antioxidant 1010, antioxidant 1076, antioxidant 1135; the ultraviolet absorber is any one of ultraviolet absorber UV-P, ultraviolet absorber UV-360, ultraviolet absorber UV-123; the lubricant is any one of stearic acid, zinc stearate, white oil.

[0008] Further, the preparation method of the impact-resistant SBS comprises the following steps:

[0009] S1: Put SBS in toluene, mix well, then add formic acid, heat to 60-65℃, drop hydrogen peroxide solution, control the drop rate to 0.5-0.6ml / min, then add ethanol for condensation, filter, wash and dry to obtain epoxidized SBS;

[0010] S2: Put epoxidized SBS in toluene, mix well and stir, then add p-benzenediol dihydroxyethyl ether and catalyst, heat to 80-85℃ and react for 5-6h, then collect the product by distillation under reduced pressure to obtain impact-resistant SBS.

[0011] In this scheme, SBS undergoes oxidation reaction under the action of hydrogen peroxide and formic acid to obtain epoxidized SBS, and then the epoxy group in the structure of epoxidized SBS undergoes ring-opening reaction with the hydroxyl group in the structure of p-benzenediol dihydroxyethyl ether under the action of catalyst, and is intertwined with the long chain of SBS to obtain impact-resistant SBS. The impact-resistant SBS has excellent impact resistance with the long chain of SBS as the high molecular skeleton, and the intertwined structure can produce cavities to release the stress caused by impact, further enhancing its impact resistance. The impact-resistant SBS is involved in the preparation process of polypropylene composite material, and the multiple hydroxyl groups in the structure of the impact-resistant SBS can interact with the matrix of the polypropylene composite material to improve its compatibility in the polypropylene composite material, so that the prepared polypropylene composite material can have excellent impact resistance and long service life.

[0012] Further, in step S1, the concentration of the hydrogen peroxide solution is 30-35%.

[0013] Further, in step S2, the catalyst is boron trifluoride ether.

[0014] Further, the preparation method of the synergistic flame-retardant composite comprises the following steps:

[0015] SS1: Mix hydroxyethyl cellulose, vinyl phosphonic acid and cyclohexane uniformly, heat to reflux, cool to room temperature, and collect the product to obtain modified cellulose;

[0016] SS2: the modified cellulose and diallyl amine are placed in N,N-dimethylformamide, an initiator is added, the temperature is raised to 60-65 DEG C and reacted for 6-8 hours, the solvent is removed by distillation under reduced pressure, and the product is collected to obtain the synergistic flame-retardant composite.

[0017] In the scheme, under the action of the water-carrying agent cyclohexane, the hydroxyl group in the structure of hydroxyethyl cellulose and the phosphoric acid group in the structure of vinyl phosphonic acid react to obtain modified cellulose with an alkenyl group in the structure, and then under the action of an initiator, the alkenyl group in the structure of the modified cellulose and the alkenyl group in the structure of diallyl amine undergo a free radical polymerization reaction to obtain a synergistic flame-retardant composite. The synergistic flame-retardant composite takes hydroxyethyl cellulose as a carbon source, vinyl phosphonic acid as an acid source, and diallyl amine as a gas source to form a synergistic flame-retardant composite, which is involved in the preparation process of a polypropylene composite material, so that the flame-retardant capacity of the material can be effectively improved. In the event of a fire, 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 capacity and greatly improves the safety in use.

[0018] Further, in step SS1, the temperature reflux reaction time is 10-12 hours.

[0019] Further, in step SS2, the initiator is any one of benzoyl peroxide and dicumyl peroxide.

[0020] A production method of an impact-resistant polypropylene composite material, comprising the following steps:

[0021] Step one, polypropylene, maleic anhydride, impact-resistant SBS, synergistic flame-retardant composite, plasticizer, antioxidant, ultraviolet absorber, stearic acid are placed in a high-speed mixer, mixed and stirred at a speed of 450-550 r / min for 1-1.5 h to obtain a premix;

[0022] Step two, the premix is transferred to a twin-screw extruder, the screw speed is set to 300-350 r / min, the die head temperature is 180-190 DEG C, and the melt extrusion granulation is carried out to obtain a polypropylene composite material.

[0023] An impact-resistant polypropylene composite material, which is applied to the automobile industry, building materials, transportation and electronic and electrical fields.

[0024] The beneficial effects of the present application are:

[0025] The application is prepared by preparing the impact-resistant SBS and the synergistic flame-retardant compound into the production process of the polypropylene composite material, so that the produced polypropylene composite material can have excellent impact resistance and flame retardance, can buffer stress change when impacted, is not easy to crack and damage, effectively prolongs the service life, and effectively prevents fire spread when fire occurs, and has great use safety.

[0026] Of course, it is not necessary for any product implementing the present application to achieve all the advantages mentioned above at the same time. BRIEF DESCRIPTION OF DRAWINGS

[0027] In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings needed for the description of the embodiments will be briefly introduced as follows. Obviously, the drawings in the following description are only some embodiments of the present application, and other drawings can be obtained by those skilled in the art without creative labor.

[0028] Figure 1 The production flow chart of the impact-resistant polypropylene composite material of the present application. DETAILED DESCRIPTION

[0029] The technical solutions in the embodiments of the present application will be described clearly and completely in combination with the drawings in the embodiments of the present application. Obviously, the described embodiments are only some embodiments of the present application, not all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor are within the protection scope of the present application.

[0030] The preparation method of the impact-resistant SBS and the synergistic flame-retardant compound in the following embodiments and comparative examples of the present application is as follows:

[0031] I. Preparation of impact-resistant SBS

[0032] S1: 3.2g of SBS was placed in 60ml of toluene, mixed thoroughly, 6ml of formic acid was added, heated to 60℃, 12ml of 30% hydrogen peroxide solution was added dropwise at a rate of 0.5ml / min, 6ml of ethanol was added for condensation, and then filtered, washed and dried to obtain epoxidized SBS;

[0033] S2: 3.6g of epoxidized SBS was placed in 80ml of dimethylbenzene, mixed and stirred thoroughly, 3g of p-phenylenediamine dihydroxyethyl ether and 0.6g of boron trifluoride ether were added, heated to 80℃ for 5h, and then the product was collected by distillation under reduced pressure to obtain impact-resistant SBS.

[0034] II. Preparation of synergistic flame-retardant compound

[0035] SS1: 4.6g of hydroxyethyl cellulose, 3.8g of vinyl phosphonic acid and 5g of cyclohexane were mixed uniformly, and the mixture was heated to reflux for 10h. After cooling to room temperature, the product was collected to obtain the modified cellulose;

[0036] SS2: 5.5g of the modified cellulose and 5g of diallylamine were placed in 80ml of N,N-dimethylformamide, 0.6g of benzoyl peroxide was added, and the mixture was heated to 60℃ for 6h. After distillation under reduced pressure, the solvent was removed, and the product was collected to obtain the synergistic flame-retardant composite.

[0037] Example 1

[0038] An impact-resistant polypropylene composite material, comprising the following raw materials 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.

[0039] The production method of the impact-resistant polypropylene composite material comprises the following steps:

[0040] Step one, the polypropylene, maleic anhydride, impact-resistant SBS, synergistic flame-retardant composite, dioctyl phthalate, antioxidant 1010, ultraviolet absorber UV-P, and stearic acid were placed in a high-speed mixer and mixed and stirred at a speed of 450r / min for 1h to obtain a premix;

[0041] Step two, the premix was transferred to a twin-screw extruder, the screw speed was set to 300r / min, and the die head temperature was set to 180℃. The mixture was melt-extruded and granulated to obtain the polypropylene composite material.

[0042] Example 2

[0043] An impact-resistant polypropylene composite material, comprising the following raw materials 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.

[0044] The production method of the impact-resistant polypropylene composite material comprises the following steps:

[0045] Step one, the polypropylene, maleic anhydride, impact-resistant SBS, synergistic flame-retardant composite, diisononyl phthalate, antioxidant 1076, ultraviolet absorber UV-360, and zinc stearate were placed in a high-speed mixer and mixed and stirred at a speed of 500r / min for 1.2h to obtain a premix;

[0046] Step two, the premix is transferred to a twin-screw extruder, the screw speed is set to 320 r / min, the die head temperature is 185℃, and the polypropylene composite material is obtained by melt extrusion granulation.

[0047] Example 3

[0048] An impact-resistant polypropylene composite material, comprising the following raw materials 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;

[0049] The production method of the impact-resistant polypropylene composite material comprises the following steps:

[0050] Step one, the polypropylene, maleic anhydride, impact-resistant SBS, synergistic flame-retardant composite, dioctyl phthalate, antioxidant 1135, ultraviolet absorber UV-123, and white oil are placed in a high-speed mixer and mixed and stirred at a speed of 550 r / min for 1.5 h to obtain a premix;

[0051] Step two, the premix is transferred to a twin-screw extruder, the screw speed is set to 350 r / min, the die head temperature is 190℃, and the polypropylene composite material is obtained by melt extrusion granulation.

[0052] Comparative Example 1

[0053] A polypropylene composite material, comprising the following raw materials 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;

[0054] The production method of the polypropylene composite material comprises the following steps:

[0055] Step one, the polypropylene, maleic anhydride, synergistic flame-retardant composite, diisononyl phthalate, antioxidant 1076, ultraviolet absorber UV-360, and zinc stearate are placed in a high-speed mixer and mixed and stirred at a speed of 500 r / min for 1.2 h to obtain a premix;

[0056] Step two, the premix is transferred to a twin-screw extruder, the screw speed is set to 320 r / min, the die head temperature is 185℃, and the polypropylene composite material is obtained by melt extrusion granulation.

[0057] Comparative Example 2

[0058] A polypropylene composite material, comprising the following raw materials by weight: 80 parts of polypropylene, 12 parts of maleic anhydride, 16 parts of impact SBS, 2.5 parts of diisononyl phthalate, 3 parts of antioxidant 1076, 2 parts of ultraviolet absorber UV-360, 2 parts of zinc stearate;

[0059] The production method of the polypropylene composite material comprises the following steps:

[0060] Step one, put the polypropylene, maleic anhydride, impact SBS, diisononyl phthalate, antioxidant 1076, ultraviolet absorber UV-360, and zinc stearate by weight into a high-speed mixer, mix and stir at a speed of 500 r / min for 1.2 h to obtain a premix;

[0061] Step two, transfer the premix to a twin-screw extruder, set the screw speed to 320 r / min, and the die head temperature to 185℃, melt extrude and granulate to obtain the polypropylene composite material.

[0062] Comparative Example 3

[0063] A polypropylene composite material, comprising the following raw materials by weight: 80 parts of polypropylene, 12 parts of maleic anhydride, 16 parts of impact SBS, 2.5 parts of diisononyl phthalate, 3 parts of antioxidant 1076, 2 parts of ultraviolet absorber UV-360, 2 parts of zinc stearate;

[0064] The production method of the polypropylene composite material comprises the following steps:

[0065] Step one, put the polypropylene, maleic anhydride, impact SBS, diisononyl phthalate, antioxidant 1076, ultraviolet absorber UV-360, and zinc stearate by weight into a high-speed mixer, mix and stir at a speed of 500 r / min for 1.2 h to obtain a premix;

[0066] Step two, transfer the premix to a twin-screw extruder, set the screw speed to 320 r / min, and the die head temperature to 185℃, melt extrude and granulate to obtain the polypropylene composite material.

[0067] Performance detection

[0068] The polypropylene composite materials prepared in Examples 1-3 and Comparative Examples 1-3 were subjected to tabletting treatment to prepare samples of composite specifications, the impact strength of the samples was tested according to the standard GB / T1043.1-2008 to determine the impact resistance of the samples, and the flame retardant grade of the samples was tested according to the UL-94 standard to determine the flame retardant performance of the samples, and the specific test results are shown in the following table:

[0069]

[0070] From the above table, it can be seen that the samples prepared in Examples 1-3 have excellent impact resistance and flame retardant effect. The sample prepared in Comparative Example 1 has poor impact resistance because no impact-resistant SBS is added. The sample prepared in Comparative Example 2 has poor flame retardant effect because no synergistic flame-retardant compound is added. The sample prepared in Comparative Example 3 has poorer impact resistance than Examples because it directly uses epoxidized SBS, but has excellent flame retardant effect because the synergistic flame-retardant compound is added.

[0071] In the description of the present specification, the description of the terms "one embodiment", "some embodiments", "an example", "a specific example", or "some examples" and the like 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 application. In the present specification, the illustrative description of the above terms does not necessarily refer to the same embodiment or example. Also, the specific features, structures, materials or characteristics described can be combined in any appropriate manner in any one or more embodiments or examples. In addition, the person skilled in the art can combine and combine the different embodiments or examples described in the present specification and the features of the different embodiments or examples without contradiction.

[0072] The above is only an example and description of the concept of the present application, and those skilled in the art can make various modifications or supplements to the described specific embodiments or use similar ways to replace, as long as they do not deviate from the scope defined by the concept of the application, which shall belong to the protection scope of the present application.

Claims

1. An impact resistant polypropylene composite, characterized in that, The raw materials include the following weight parts: 70-90 parts of polypropylene, 10-15 parts of maleic anhydride, 15-18 parts of impact 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; The preparation method of the impact SBS comprises the following steps: S1: SBS is placed in toluene, mixed thoroughly, formic acid is added, the temperature is raised to 60-65 DEG C, hydrogen peroxide solution is added dropwise, the drop speed is controlled to be 0.5-0.6 ml / min, ethanol is added for condensation, after completion, filtration, washing and drying, the epoxidized SBS is obtained; S2: the epoxidized SBS is placed in xylene, mixed and stirred thoroughly, p-benzenediol dihydroxyethyl ether and a catalyst are added, the temperature is raised to 80-85 DEG C and reacted for 5-6 h, the product is collected after distillation under reduced pressure, and the impact SBS is obtained; The preparation method of the synergistic flame-retardant compound comprises the following steps: SS1: hydroxyethyl cellulose, vinyl phosphonic acid and cyclohexane are uniformly mixed, the temperature is raised to reflux, the product is collected after the temperature is lowered to room temperature, and the modified cellulose is obtained; SS2: the modified cellulose and diallylamine are placed in N,N-dimethylformamide, an initiator is added, the temperature is raised to 60-65 DEG C and reacted for 6-8 h, the solvent is removed after distillation under reduced pressure, and the synergistic flame-retardant compound is obtained.

2. An impact polypropylene composite material according to claim 1, characterized in that, 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; and the lubricant is any one of stearic acid, zinc stearate and white oil.

3. The impact polypropylene composite material according to claim 1, characterized in that, In step S1, the concentration of the hydrogen peroxide solution is 30-35%.

4. The impact polypropylene composite material according to claim 1, wherein, In step S2, the catalyst is boron trifluoride etherate.

5. The impact polypropylene composite material according to claim 1, wherein, In step SS1, the temperature reflux reaction time is 10-12 h.

6. The impact polypropylene composite material according to claim 1, wherein, In step SS2, the initiator is any one of benzoyl peroxide and dicumyl peroxide.

7. A process for the production of an impact polypropylene composite as claimed in claim 1, characterized in that, The method comprises the following steps: Step one, polypropylene, maleic anhydride, impact SBS, synergistic flame-retardant compound, plasticizer, antioxidant, ultraviolet absorber and stearic acid are placed in a high-speed mixer, mixed and stirred at a speed of 450-550 r / min for 1-1.5 h, and a premix is obtained; Step two, the premix is transferred to a twin-screw extruder, the screw speed is set to be 300-350 r / min, the die head temperature is set to be 180-190 DEG C, and the premix is melt-extruded and granulated to obtain a polypropylene composite material.

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