Functional plastic based on polymer material and preparation process thereof

Abstract

The invention relates to the technical field of polymer materials, and discloses a functional plastic based on polymer materials and a preparation process thereof. The functional plastic comprises the following raw materials: polypropylene, a flame retardant additive, a smoke suppression functional component, a filler, a stabilizer, an antioxidant, and a lubricant; wherein the flame retardant additive is xylan containing a nitrogen-phosphorus flame retardant in its structure; and the smoke suppression functional component is prepared by complexing iron ions on the surface of kaolin. The functional plastic prepared by the invention has good flame retardancy and smoke suppression performance, and can significantly reduce the spread speed of flames and the generation of toxic smoke when a fire occurs, thereby reducing the destructiveness of the fire and the risk of casualties, ensuring the applicability and safety of the plastic under various environmental conditions, and being conducive to broadening the application field of the plastic.

Description

Technical Field

[0001] The invention relates to the technical field of polymer materials, and in particular to a functional plastic based on polymer materials and a preparation process thereof. Background Art

[0002] With the development of science and technology and the improvement of people's living standards, people's demand for various materials has gradually increased, and various plastic products have gradually come into people's view. Plastics are polymer compounds made of monomers through addition polymerization or condensation polymerization. They are mainly composed of synthetic resins and various additives. Among many polymer materials, polypropylene has become one of the preferred materials in plastic production because of its good chemical stability, low density, good electrical insulation, odorless and non-toxic characteristics. It is widely used in home appliances, packaging, medical, automotive and other fields.

[0003] In recent years, with the continuous promotion and expansion of the application scope of plastic products, the requirements for plastic performance have become higher and higher. Adding diversified functionality to plastics has become a topic of in-depth research by many experts and scholars. Due to the frequent occurrence of fire accidents in recent years, the fire resistance of plastic products has attracted people's attention. However, polypropylene is a flammable material. It will quickly ignite when exposed to open flames or high temperatures, which is prone to fire and poses great safety hazards. In addition, polypropylene will produce a large amount of heat, smoke and toxic gases during the combustion process, which not only threatens human life and property safety, but also has a serious impact on the environment. In addition, the fast burning speed, accompanied by the phenomenon of molten dripping, further increases the destructiveness of the fire. Therefore, polypropylene plastics still have certain shortcomings in practical applications.

[0004] In the prior art, functional additives are often used to fill and modify polypropylene plastics in order to improve the performance of polypropylene plastics. For example, the invention patent with the announcement number CN103467852B discloses a polypropylene flame retardant plastic, which is prepared by adding a flame retardant to a polypropylene matrix. The flame retardant is composed of dimethyl trimethylsilylmethylphosphonate, melamine cyanurate, magnesium hydroxide and aluminum hydroxide, so that the prepared polypropylene plastic has good flame retardant properties. Therefore, polypropylene plastics with good flame retardant and smoke suppression properties can be prepared by adding optimized components in the matrix. Summary of the invention

[0005] In order to solve the problems mentioned in the background technology, the purpose of the present invention is to provide a functional plastic based on polymer materials and a preparation process thereof.

[0006] The purpose of the present invention can be achieved through the following technical solutions:

[0007] A preparation process of a functional plastic based on a polymer material, the functional plastic comprising the following raw materials in parts by weight: 45 to 55 parts of polypropylene, 5 to 7 parts of a flame retardant additive, 4 to 6 parts of a smoke suppression functional component, 5 to 15 parts of a filler, 2 to 4 parts of a stabilizer, 1 to 2 parts of an antioxidant, and 1 to 3 parts of a lubricant;

[0008] The preparation process comprises the following steps:

[0009] (1) Add polypropylene, flame retardant additives, smoke suppression functional components, fillers, stabilizers, antioxidants and lubricants into a high-speed mixer, set the mixer speed to 600-800 r / min, increase the temperature to 90-100°C, stir for 1-3 hours, wait for the material to cool naturally, discharge the material, and obtain a premix;

[0010] (2) The premix is ​​passed through a feeder into a twin-screw extruder, the screw speed is set to 200-400 r / min, the working temperature of the extrusion section is set to 170-190°C, and melt extrusion is performed, followed by cooling and granulation to obtain functional plastics.

[0011] Furthermore, the method for preparing the flame retardant additive comprises the following steps:

[0012] D1: Add xylan into dimethyl sulfoxide, mix well, add folic acid and esterification catalyst under continuous nitrogen conditions, after addition, raise the temperature to 90-110°C, stir for 5-8 hours under this temperature condition, stop heating and remove nitrogen, cool to room temperature and then discharge to obtain modified xylan;

[0013] D2: Add modified xylan and N,N-dimethylformamide into a reaction kettle, stir mechanically for uniformity, pass nitrogen, exhaust the air, add 2-chloro-2-oxo-1,3,2-dioxaphospholane and an acid binding agent, stir at room temperature for 4 to 6 hours, and remove the solvent by vacuum distillation to obtain a flame retardant additive.

[0014] Furthermore, in step D1, the esterification catalyst is any one of tetrabutyl titanate, tetraethyl titanate or tetraisopropyl titanate.

[0015] Furthermore, in step D2, the acid binding agent is any one of triethylamine or pyridine.

[0016] Furthermore, in step D1, the mass ratio of the xylan, folic acid, esterification catalyst and dimethyl sulfoxide is 10:2.4:0.1:100; in step D2, the mass ratio of the modified xylan, 2-chloro-2-oxo-1,3,2-dioxaphospholane, acid binding agent and N,N-dimethylformamide is 10:1:0.08:100.

[0017] The principle of the above technical solution is: in step D1, the structure of xylan contains active hydroxyl groups, which can undergo esterification reaction with the carboxyl groups in the folic acid structure under the action of an esterification catalyst, thereby grafting folic acid into the structure of xylan to obtain modified xylan; in step D2, the structure of the modified xylan contains amino groups, and the structure of 2-chloro-2-oxo-1,3,2-dioxaphospholane contains highly active phosphoryl chloride groups, which can undergo amidation condensation reaction with each other to obtain a flame retardant additive.

[0018] Furthermore, the preparation method of the smoke suppression functional component comprises the following steps:

[0019] DD1: Kaolin and N-methylpyrrolidone were stirred and mixed to form a uniform dispersion. 3,4-dihydroxyphenylpropionic acid and tetrabutyl titanate were added to the dispersion under nitrogen protection. After the addition, heating was turned on. After the system temperature reached 90-110°C, constant temperature stirring was performed for 5-8h. The solid material was separated by filtration, washed and vacuum dried to obtain modified kaolin.

[0020] DD2: Under nitrogen protection, add ferric nitrate nonahydrate and modified kaolin to anhydrous ethanol, stir mechanically for 0.5 to 1.5 hours, then add Tris-HCL buffer solution, adjust the pH value of the system to 7 to 9, stir at room temperature for 1 to 3 hours, centrifuge, collect the product, wash the product, and vacuum dry it to obtain the smoke suppression functional component.

[0021] Furthermore, in step DD1, the mass ratio of kaolin, 3,4-dihydroxyphenylpropionic acid, tetrabutyl titanate and N-methylpyrrolidone is 5:1.2:0.05:50; in step DD2, the mass ratio of ferric nitrate nonahydrate, modified kaolin and anhydrous ethanol is 3.6:5:50.

[0022] Furthermore, in step DD1, the average particle size of the kaolin is 4 μm; and in step DD2, the mass fraction of the Tris-HCL buffer is 20%.

[0023] The principle of the above technical scheme is: in step DD1, since the surface of kaolin contains hydroxyl groups, it can react with the carboxyl groups in the structure of 3,4-dihydroxyphenylpropionic acid under the catalytic action of tetrabutyl titanate, thereby introducing catechol groups on the surface of kaolin to obtain modified kaolin; in step DD2, the surface of modified kaolin is rich in catechol groups. When the pH value of the system is 7-9, the catechol groups can coordinate and complex with iron ions, thereby stably fixing the iron ions on the surface of kaolin to obtain smoke suppression functional components.

[0024] Furthermore, the filler is any one of calcium carbonate, talc or titanium dioxide; the stabilizer is any one of barium zinc stabilizer or calcium zinc stabilizer; the antioxidant is any one of antioxidant 1076, antioxidant 168 or antioxidant 2246; the lubricant is any one of paraffin or polyethylene wax.

[0025] A functional plastic based on polymer material is made by adopting the above preparation process.

[0026] Beneficial effects of the present invention:

[0027] (1) The present invention adds the prepared flame retardant additive and smoke suppression functional component into the preparation process of plastics, so that the prepared plastics have good flame retardant and smoke suppression properties. When a fire occurs, the spread of flames can be significantly reduced, and the generation of toxic smoke can be reduced, thereby reducing the destructiveness of the fire and the risk of casualties, ensuring its applicability and safety under various environmental conditions, and broadening the application field of plastics.

[0028] (2) The present invention prepares a flame retardant additive as a filler modifier for polypropylene plastic. Since the flame retardant additive is an intumescent flame retardant that integrates an acid source, a carbon source, and a gas source, the prepared plastic has good flame retardant properties. When a fire occurs, the "three sources" undergo chemical changes in a coordinated manner to quickly form a dense carbon layer on the surface of the material, shielding heat transfer, significantly reducing the heat release rate, preventing the diffusion of flammable gases, and inhibiting further combustion of the material. At the same time, the released non-combustible gases such as ammonia and nitrogen can dilute the concentration of combustible volatiles in the air, reduce the effective combustion heat, and ultimately prevent the spread and propagation of flames, thereby reducing the potential harm of fire to people and property.

[0029] (3) The present invention obtains a smoke suppression functional component by complexing iron ions on the surface of kaolin. On the one hand, after organic modification, the interfacial properties of kaolin in the polypropylene matrix are enhanced, which helps to evenly disperse the kaolin in the matrix and avoid the phase separation phenomenon caused by the interface problem between the two phases. In addition, due to its special layered structure, it can form a physical barrier layer after even dispersion, which can not only insulate and block the migration of flammable gases to the combustion surface, but also reduce the temperature of the combustion surface, thereby producing a synergistic effect with the flame retardant additive to further improve the flame retardant properties of the plastic. On the other hand, iron is a smoke suppression element. By introducing iron, the smoke suppression properties of the plastic can be effectively improved, avoiding the toxic smoke released during the combustion process from endangering human life and property safety, while reducing the negative impact on the environment.

[0030] 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

[0031] 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.

[0032] Figure 1 This is an infrared spectrum test chart of the flame retardant additive prepared by the present invention.

[0033] Figure 2 This is an infrared spectrum test chart of the modified kaolin and smoke suppression functional components prepared in the present invention. DETAILED DESCRIPTION

[0034] 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.

[0035] The flame retardant additives and smoke suppression functional components in the examples and comparative examples of the present invention are prepared by the following method:

[0036] 1. Preparation of flame retardant additives

[0037] D1: Add 10 g of xylan into 100 g of dimethyl sulfoxide, mix well, add 2.4 g of folic acid and 0.1 g of tetrabutyl titanate under continuous nitrogen conditions, raise the temperature to 100°C, stir for 6 h at this temperature, stop heating and remove nitrogen, cool to room temperature and then discharge to obtain modified xylan;

[0038] D2: Add 10g of modified xylan and 100g of N,N-dimethylformamide into the reactor, stir mechanically to evenly, pass nitrogen, exhaust the air, add 1g of 2-chloro-2-oxo-1,3,2-dioxaphospholane and 0.08g of triethylamine, stir at room temperature for 5h, and remove the solvent by vacuum distillation to obtain a flame retardant additive with a purity of 99.1%.

[0039] The flame retardant additives were analyzed by infrared spectroscopy using Nicolet 6700 Fourier transform infrared spectrometer produced by Thermo Corporation of the United States. Figure 1 As shown by Figure 1 It can be seen that in the infrared spectrum of flame retardant additives, The absorption peak of ether bond COC appears at The absorption peak of the ester group C=O appears at The absorption peak of C=O in amide appears at The absorption peak of the carbon-hydrogen bond in the benzene ring appears at The absorption peak of NH appears at The absorption peak of CN appears at The absorption peak of C=N appears at The absorption peak of POC appears at The absorption peak of NP appears at The absorption peak of P=O appears at

[0040] 2. Preparation of smoke suppression functional components

[0041] DD1: 5 g of kaolin with an average particle size of 4 μm was mixed with 50 g of N-methylpyrrolidone to form a uniform dispersion. Under nitrogen protection, 1.2 g of 3,4-dihydroxyphenylpropionic acid and 0.05 g of tetrabutyl titanate were added to the dispersion. After the addition, heating was turned on. After the system temperature reached 100°C, constant temperature stirring was performed for 7 hours. The solid material was separated by filtration, washed and vacuum dried to obtain modified kaolin.

[0042] DD2: Under nitrogen protection, add 3.6g of ferric nitrate nonahydrate and 5g of modified kaolin to 50g of anhydrous ethanol, stir mechanically for 1h, then add 20% by mass of Tris-HCL buffer, adjust the pH value of the system to 8, stir at room temperature for 2h, centrifuge, collect the product, wash the product, and vacuum dry to obtain a smoke suppression functional component with a purity of 99.3%.

[0043] The modified kaolin and smoke suppression functional components were analyzed by infrared spectroscopy using Nicolet 6700 Fourier transform infrared spectrometer produced by Thermo Corporation of the United States. Figure 2 As shown by Figure 2 It can be seen that in the infrared spectrum of modified kaolin, The absorption peak of the ester group C=O appears at The absorption peak of the carbon-hydrogen bond in the benzene ring appears at The absorption peak of OH in the hydroxyl group appears at , and in the infrared spectrum of the smoke suppression functional component, the absorption peak of the hydroxyl group becomes broadened and moves to This is due to the influence of the metal ions connected by coordination bonds. Example 1

[0044] Preparation of functional plastics

[0045] (1) Add 45g polypropylene, 5g flame retardant additive, 4g smoke suppression functional component, 5g calcium carbonate, 2g calcium zinc stabilizer, 1g antioxidant 168, and 1g paraffin into a high-speed mixer, set the mixer speed to 600r / min, increase the temperature to 90°C, stir for 1h, wait for the material to cool naturally, discharge the material, and obtain a premix;

[0046] (2) The premix is ​​passed through a feeder into a twin-screw extruder. The screw speed is set to 200 r / min and the operating temperature of the extrusion section is set to 170°C. Melt extrusion is performed and the premix is ​​cooled and granulated to obtain functional plastics. Example 2

[0047] Preparation of functional plastics

[0048] (1) Add 50g polypropylene, 6g flame retardant additive, 5g smoke suppression functional component, 10g calcium carbonate, 3g calcium zinc stabilizer, 1.5g antioxidant 168, and 2g paraffin into a high-speed mixer, set the mixer speed to 700r / min, increase the temperature to 95°C, stir for 2h, wait for the material to cool naturally, discharge the material, and obtain a premix;

[0049] (2) The premix is ​​passed through a feeder into a twin-screw extruder. The screw speed is set to 300 r / min and the operating temperature of the extrusion section is set to 180°C. Melt extrusion is performed and cooled to granulate to obtain functional plastics. Example 3

[0050] Preparation of functional plastics

[0051] (1) Add 55g polypropylene, 7g flame retardant additive, 6g smoke suppression functional component, 15g calcium carbonate, 4g calcium zinc stabilizer, 2g antioxidant 168, and 3g paraffin into a high-speed mixer, set the mixer speed to 800r / min, increase the temperature to 100°C, stir for 3h, wait for the material to cool naturally, discharge the material, and obtain a premix;

[0052] (2) The premix is ​​passed through a feeder into a twin-screw extruder. The screw speed is set to 400 r / min and the operating temperature of the extrusion section is set to 190°C. Melt extrusion is performed and the premix is ​​cooled and granulated to obtain functional plastics.

[0053] Comparative Example 1

[0054] Preparation of functional plastics

[0055] (1) Add 50g polypropylene, 6g flame retardant additive, 10g calcium carbonate, 3g calcium zinc stabilizer, 1.5g antioxidant 168, and 2g paraffin into a high-speed mixer, set the mixer speed to 700r / min, increase the temperature to 95°C, stir for 2h, wait for the material to cool naturally, discharge the material, and obtain a premix;

[0056] (2) The premix is ​​passed through a feeder into a twin-screw extruder. The screw speed is set to 300 r / min and the operating temperature of the extrusion section is set to 180°C. Melt extrusion is performed and cooled to granulate to obtain functional plastics.

[0057] Comparative Example 2

[0058] Preparation of functional plastics

[0059] (1) Add 50g polypropylene, 5g smoke suppression functional component, 10g calcium carbonate, 3g calcium zinc stabilizer, 1.5g antioxidant 168, and 2g paraffin into a high-speed mixer, set the mixer speed to 700r / min, increase the temperature to 95°C, stir for 2h, wait for the material to cool naturally, discharge the material, and obtain a premix;

[0060] (2) The premix is ​​passed through a feeder into a twin-screw extruder. The screw speed is set to 300 r / min and the operating temperature of the extrusion section is set to 180°C. Melt extrusion is performed and the premix is ​​cooled and granulated to obtain functional plastics.

[0061] Comparative Example 3

[0062] Preparation of functional plastics

[0063] (1) Add 50g polypropylene, 6g flame retardant additive, 5g kaolin, 10g calcium carbonate, 3g calcium zinc stabilizer, 1.5g antioxidant 168, and 2g paraffin into a high-speed mixer, set the mixer speed to 700r / min, increase the temperature to 95°C, stir for 2h, wait for the material to cool naturally, discharge the material, and obtain a premix;

[0064] (2) The premix is ​​passed through a feeder into a twin-screw extruder. The screw speed is set to 300 r / min and the operating temperature of the extrusion section is set to 180°C. Melt extrusion is performed and the premix is ​​cooled and granulated to obtain functional plastics.

[0065] Comparative Example 4

[0066] Preparation of functional plastics

[0067] (1) Add 50g polypropylene, 10g calcium carbonate, 3g calcium zinc stabilizer, 1.5g antioxidant 168, and 2g paraffin into a high-speed mixer, set the mixer speed to 700r / min, increase the temperature to 95°C, stir for 2h, wait for the material to cool naturally, discharge the material, and obtain a premix;

[0068] (2) The premix is ​​passed through a feeder into a twin-screw extruder. The screw speed is set to 300 r / min and the operating temperature of the extrusion section is set to 180°C. Melt extrusion is performed and cooled to granulate to obtain functional plastics.

[0069] Performance testing:

[0070] The functional plastics prepared in Examples 1 to 3 of the present invention and Comparative Examples 1 to 4 were tabletted to prepare samples that met the specifications. The samples were tested for combustion performance according to GB / T 2406.2-2009 "Determination of Combustion Behavior of Plastics by Oxygen Index Method Part 2: Room Temperature Test" to evaluate the flame retardant properties of the plastics. The samples were tested for smoke density according to GB / T 8323.2-2008 "Plastic Smoke Generation Part 2: Single Chamber Method for Determination of Smoke Density Test" to evaluate the smoke suppression properties of the plastics. The lower the maximum specific optical density values ​​with and without flames are, the better the smoke suppression performance is. The specific test results are shown in Table 1:

[0071] ;

[0072] As can be seen from Table 1, the functional plastics prepared in Examples 1 to 3 all have good flame retardant and smoke suppression properties, which is presumably because the added flame retardant additives and smoke suppression functional components have good flame retardant and smoke suppression effects; the functional plastic prepared in Comparative Example 1 does not add the smoke suppression functional component, and compared with the example, the smoke suppression performance of the plastic is poor; the functional plastic prepared in Comparative Example 2 does not add the flame retardant additive, and the flame retardant performance of the plastic is not as good as that of the example. It is presumed that this is because it can only rely on the smoke suppression functional component for flame retardancy and cannot exert the synergistic flame retardant effect, resulting in a decrease in the flame retardant performance of the plastic; flame retardant additives and kaolin are added to the functional plastic prepared in Comparative Example 3, and compared with the example, the flame retardant performance of the plastic is general, and the smoke suppression performance is poor. It is presumed that this is because the added kaolin has not been organically modified, and it has agglomerated in the matrix, and no iron element has been introduced, resulting in a decrease in the flame retardant and smoke suppression performance of the plastic; flame retardant additives and smoke suppression functional components are not added to the functional plastic prepared in Comparative Example 4, so the performance of each sample is the worst.

[0073] The above contents are merely examples and explanations of the concept of the present invention. The technicians in this technical field may make various modifications or additions to the specific embodiments described or replace them in a similar manner. As long as they do not deviate from the concept of the invention or exceed the scope defined by the claims, they should all fall within the protection scope of the present invention.

Claims

1. A process for preparing functional plastics based on polymer materials, characterized in that: The functional plastic comprises the following raw materials in parts by weight: 45 to 55 parts of polypropylene, 5 to 7 parts of flame retardant additives, 4 to 6 parts of smoke suppression functional components, 5 to 15 parts of fillers, 2 to 4 parts of stabilizers, 1 to 2 parts of antioxidants, and 1 to 3 parts of lubricants; The preparation process comprises the following steps: (1) Add polypropylene, flame retardant additives, smoke suppression functional components, fillers, stabilizers, antioxidants and lubricants into a high-speed mixer, set the mixer speed to 600-800 r / min, increase the temperature to 90-100°C, stir for 1-3 hours, wait for the material to cool naturally, discharge the material, and obtain a premix; (2) The premix is ​​passed through a feeder into a twin-screw extruder, the screw speed is set to 200-400 r / min, the extrusion section operating temperature is set to 170-190°C, and melt extrusion is performed, and cooling and granulation are performed to obtain functional plastics; The preparation method of the flame retardant additive comprises the following steps: D1: Add xylan into dimethyl sulfoxide, mix well, add folic acid and esterification catalyst under continuous nitrogen conditions, after addition, raise the temperature to 90-110°C, stir for 5-8 hours under this temperature condition, stop heating and remove nitrogen, cool to room temperature and then discharge to obtain modified xylan; The esterification catalyst is any one of tetrabutyl titanate, tetraethyl titanate or tetraisopropyl titanate; The mass ratio of xylan to folic acid is 10:2.4; D2: Add modified xylan and N,N-dimethylformamide into a reaction kettle, stir mechanically to make it uniform, pass nitrogen, exhaust the air, add 2-chloro-2-oxo-1,3,2-dioxaphospholane and an acid binding agent, stir at room temperature for 4 to 6 hours, and remove the solvent by distillation under reduced pressure to obtain a flame retardant additive; the acid binding agent is any one of triethylamine or pyridine; The preparation method of the smoke suppression functional component comprises the following steps: DD1: Kaolin and N-methylpyrrolidone were stirred and mixed to form a uniform dispersion. 3,4-dihydroxyphenylpropionic acid and tetrabutyl titanate were added to the dispersion under nitrogen protection. After the addition, heating was turned on. After the system temperature reached 90-110°C, constant temperature stirring was performed for 5-8h. The solid material was separated by filtration, washed and vacuum dried to obtain modified kaolin. The average particle size of the kaolin is 4 μm; DD2: Under nitrogen protection, add ferric nitrate nonahydrate and modified kaolin to anhydrous ethanol, stir mechanically for 0.5 to 1.5 hours, then add Tris-HCL buffer, adjust the pH value of the system to 7 to 9, stir at room temperature for 1 to 3 hours, centrifuge, collect the product, wash the product, and vacuum dry it to obtain a smoke suppression functional component; The mass fraction of the Tris-HCL buffer is 20%.

2. The process for preparing a functional plastic based on a polymer material according to claim 1, characterized in that: The filler is any one of calcium carbonate, talc or titanium dioxide; the stabilizer is any one of barium zinc stabilizer or calcium zinc stabilizer; the antioxidant is any one of antioxidant 1076, antioxidant 168 or antioxidant 2246; the lubricant is any one of paraffin or polyethylene wax.

3. A functional plastic based on polymer materials, characterized in that: The method is prepared by the preparation process as claimed in claim 1.

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