Polyolefin resin film material and preparation method thereof

Abstract

The invention discloses a polyolefin resin film material and a preparation method thereof. The polyolefin resin film material comprises the following raw materials in parts by mass: 60-70 parts of polyolefin resin, 10-20 parts of a Si-P-N-C quaternary hybrid flame retardant, 10-15 parts of chlorinated polyvinyl chloride, 2-5 parts of antimony trioxide and 2-3 parts of a triazine carbon-forming agent. The Si-P-N-C quaternary hybrid flame retardant, the antimony trioxide and the triazine carbon-forming agent are introduced at the same time, and through synergistic flame retardance of the three, the flame retardance of the material is remarkably improved.

Description

Technical Field

[0001] The present invention belongs to the technical field of polymer materials, and particularly relates to a polyolefin resin film material and a preparation method thereof. Background Art

[0002] Polyolefin resins are widely used in building materials, automotive parts, packaging materials, agricultural materials, outer shell materials of household appliances, toys, etc. due to their excellent chemical and mechanical properties. However, polyolefin resins are combustible substances, so flame retardants are essential. Currently used flame retardants include halogen-based flame retardants, inorganic phosphorus-based flame retardants composed of multi-phosphorus-based flame retardants such as red phosphorus and ammonium polyphosphate, organic phosphorus-based flame retardants represented by triaryl phosphate compounds, metal hydroxides represented by flame retardants, antimony oxide, etc. Flame retardant aids and melamine compounds can be used alone or in combination.

[0003] In polyolefin resin materials, most flame retardants need to be blended at a relatively high concentration. When the prepared resin material is used for a film, only a film with low physical properties can be obtained, and it is impossible to balance the flame retardant effect and mechanical properties. Summary of the Invention

[0004] The purpose of the present invention is to provide a polyolefin resin film material and a preparation method thereof that can ensure the mechanical properties of the material while improving the flame retardant effect in view of the above problems existing in the prior art.

[0005] To achieve the above purpose, the technical solution of the present invention is as follows:

[0006] In the first aspect, the present invention provides a polyolefin resin film material, and its raw material composition and mass ratio include: 60 - 70 parts of polyolefin resin, 10 - 20 parts of Si-P-N-C quaternary hybrid flame retardant, 10 - 15 parts of chlorinated polyvinyl chloride, 2 - 5 parts of antimony trioxide, and 2 - 3 parts of triazine charring agent.

[0007] The raw material composition and mass ratio of the Si-P-N-C quaternary hybrid flame retardant include: 5 - 8 parts of nitrogen and phosphorus-based flame retardant grafted with graphene oxide, 3 - 5 parts of thermoplastic resin grafted with graphene oxide, 88 - 95 parts of modified wollastonite, and 1 - 1.2 parts of silane coupling agent;

[0008] The modified wollastonite is obtained by high-speed mixing of wollastonite fibers and a silane coupling agent.

[0009] The raw material composition of the nitrogen and phosphorus-based flame retardant grafted with graphene oxide includes a graphene oxide suspension, a nitrogen and phosphorus-based flame retardant, and a silane coupling agent. The mass ratio of the nitrogen and phosphorus-based flame retardant to the silane coupling agent is 5 - 8:1 - 1.2, and the addition ratio of the nitrogen and phosphorus-based flame retardant to the graphene oxide suspension is 5 - 8 g:0.5 L;

[0010] The raw material composition of the graphene oxide grafted thermoplastic resin includes graphene oxide suspension, thermoplastic resin, and silane coupling agent. The mass ratio of the thermoplastic resin to the silane coupling agent is 2 - 4:1 - 1.2, and the addition ratio of the thermoplastic resin to the graphene oxide suspension is 2 - 4 g:0.5 L;

[0011] The concentration of the graphene oxide suspension is 5 - 8 g / L.

[0012] The nitrogen - phosphorus - based flame retardant is any one of 9,10 - dihydro - 9 - oxa - 10 - phosphaphenanthrene - 10 - oxide, melamine polyphosphate, and piperazine pyrophosphate;

[0013] The thermoplastic resin is any one of polyether ether ketone and MQ resin;

[0014] The silane coupling agent is any one of KH - 550, KH - 560, KH - 570, and KH - 590.

[0015] The raw material composition of the material further includes ammonium polyphosphate and decabromodiphenylethane. The mass ratio of ammonium polyphosphate, decabromodiphenylethane to polyolefin resin is 1 - 2:3:60 - 70.

[0016] Second, the present invention provides a preparation method of a polyolefin resin film material, including:

[0017] S1. Prepare the Si - P - N - C quaternary hybrid flame retardant;

[0018] S2. Mix polyolefin resin, Si - P - N - C quaternary hybrid flame retardant, chlorinated polyvinyl chloride, antimony trioxide, and triazine char - forming agent in the required proportions and then extrude and mold them.

[0019] The raw material composition and mass parts ratio of the Si - P - N - C quaternary hybrid flame retardant include: 5 - 8 parts of graphene oxide grafted nitrogen - phosphorus - based flame retardant, 3 - 5 parts of graphene oxide grafted thermoplastic resin, and 88 - 95 parts of modified wollastonite;

[0020] S1 includes: first, prepare graphene oxide grafted nitrogen - phosphorus - based flame retardant and graphene oxide grafted thermoplastic resin separately, and then mix graphene oxide grafted nitrogen - phosphorus - based flame retardant, graphene oxide grafted thermoplastic resin, and modified wollastonite in the required proportions to obtain the Si - P - N - C quaternary hybrid flame retardant.

[0021] The raw material composition of the graphene oxide grafted nitrogen - phosphorus - based flame retardant includes graphene oxide suspension, nitrogen - phosphorus - based flame retardant, and silane coupling agent. The mass ratio of the nitrogen - phosphorus - based flame retardant to the silane coupling agent is 5 - 8:1 - 1.2, and the addition ratio of the nitrogen - phosphorus - based flame retardant to the graphene oxide suspension is 5 - 8 g:0.5 L;

[0022] The preparation of the graphene oxide grafted nitrogen-phosphorus based flame retardant includes: adding a nitrogen-phosphorus based flame retardant and a silane coupling agent to a graphene oxide suspension, and obtaining the graphene oxide grafted nitrogen-phosphorus based flame retardant through a functionalization reaction;

[0023] The raw material composition of the graphene oxide grafted thermoplastic resin includes a graphene oxide suspension, a thermoplastic resin, and a silane coupling agent. The mass ratio of the thermoplastic resin to the silane coupling agent is 2-4:1-1.2, and the addition ratio of the thermoplastic resin to the graphene oxide suspension is 2-4 g:0.5 L;

[0024] The preparation of the graphene oxide grafted thermoplastic resin includes: adding a thermoplastic resin and a silane coupling agent to a graphene oxide suspension, and obtaining the graphene oxide grafted thermoplastic resin through a functionalization reaction. The conditions of the functionalization reaction are: refluxing for 10-12 h at 73-80 °C under a nitrogen atmosphere;

[0025] The concentration of the graphene oxide suspension is 5-8 g / L.

[0026] The raw material composition of the material further includes ammonium polyphosphate and decabromodiphenylethane. The weight ratio of ammonium polyphosphate, decabromodiphenylethane to the polyolefin resin is 1-2:3:60-70;

[0027] S2 includes: mixing polyolefin resin, Si-P-N-C quaternary hybrid flame retardant, chlorinated polyvinyl chloride, antimony trioxide, triazine charring agent, ammonium polyphosphate, and decabromodiphenylethane in the required proportions and then extruding and molding.

[0028] In S2, the blending temperature is 105-120 °C, and the extrusion temperature conditions are 180-220 °C.

[0029] Compared with the prior art, the beneficial effects of the present invention are:

[0030] 1. The raw material composition and mass ratio of a polyolefin resin film material of the present invention include: 60-70 parts of polyolefin resin, 10-20 parts of Si-P-N-C quaternary hybrid flame retardant, 10-15 parts of chlorinated polyvinyl chloride, 2-5 parts of antimony trioxide, and 2-3 parts of triazine charring agent. By introducing the Si-P-N-C quaternary hybrid flame retardant, antimony trioxide and triazine charring agent simultaneously, on the one hand, the triazine charring agent synergistically acts with antimony trioxide and the Si-P-N-C quaternary hybrid flame retardant, which can effectively improve the gas barrier performance of chlorinated polyvinyl chloride when combustible gas is formed, especially when macromolecules decompose into combustible gas at 200-300°C; on the other hand, antimony chloride is formed when antimony trioxide and high-polyvinyl chloride burn, covering the surface of the material to prevent combustion. On this basis, due to the lack of oxygen on the surface after carbonization, the triazine charring agent can better form a carbon layer on the surface of the organic material; at the same time, Si, P, N, and C synergistically retard the flame, improving the flame retardancy of the material.

[0031] 2. The raw material composition and mass ratio of the Si-P-N-C quaternary hybrid flame retardant in a polyolefin resin film material of the present invention include: 5-8 parts of nitrogen-phosphorus-based flame retardant grafted with graphene oxide, 3-5 parts of thermoplastic resin grafted with graphene oxide, 88-95 parts of modified wollastonite, and 1-1.2 parts of silane coupling agent. On the basis of modified wollastonite, the nitrogen-phosphorus-based flame retardant, thermoplastic resin and graphene oxide are introduced by using the silane coupling agent. On the one hand, due to the silane coupling agent having various active functional groups such as amino, epoxy, and vinyl groups, the obtained system composition has good compatibility with the polymer matrix, thus having better mechanical properties and processing properties.

[0032] 3. The polyolefin resin film material of the present invention also adds ammonium polyphosphate and decabromodiphenylethane. The combination of ammonium polyphosphate and triazine charring agent can better promote carbonization, especially when the mass ratio of ammonium polyphosphate to triazine charring agent is 1:3; decabromodiphenylethane and antimony trioxide synergistically retard the flame, and can form antimony bromide to cover the surface tissue to prevent combustion and form a carbon layer, further improving the flame retardancy of the material. Description of the Drawings

[0033] Figure 1 It is a schematic structural diagram of the nitrogen-phosphorus-based flame retardant grafted with graphene oxide of the present invention.

[0034] Figure 2 It is a schematic structural diagram of the thermoplastic resin grafted with graphene oxide of the present invention.

[0035] Figure 3 It is a schematic structural diagram of the Si-P-N-C quaternary hybrid flame retardant system composition of the present invention. Detailed Embodiments

[0036] The present invention will be further described in detail below in conjunction with specific embodiments and the accompanying drawings.

[0037] The present invention provides a polyolefin resin film material. Through the synergistic flame retardancy of Si-P-N-C quaternary hybrid flame retardant, chlorinated polyvinyl chloride, antimony trioxide, triazine charring agent, ammonium polyphosphate, and decabromodiphenylethane, the flame retardancy grade of the prepared film reaches A2 level. At the same time, this film material has good mechanical properties and processing properties, and can be used in vegetable greenhouses or as a waterproof and fireproof outer covering film (for logistics). Among them, Si-C in the Si-P-N-C quaternary hybrid flame retardant and the triazine charring agent can quickly form carbon, and the non-combustible gas generated by P-N at about 300 °C can capture and drive away oxygen and combustible gas free radicals; antimony trioxide and halogen form halogen antimony, covering the material surface to prevent combustion; ammonium polyphosphate promotes the carbonization of the triazine charring agent.

[0038] Example 1:

[0039] A polyolefin resin film material, the raw material composition and mass ratio are as follows: polyolefin resin 65, Si-P-N-C quaternary hybrid flame retardant 15, chlorinated polyvinyl chloride 13, antimony trioxide 4, triazine charring agent 2.5; the raw material composition and mass ratio of the Si-P-N-C quaternary hybrid flame retardant are: graphene oxide grafted nitrogen-phosphorus based flame retardant 5, graphene oxide grafted thermoplastic resin 3, modified wollastonite 90, silane coupling agent 1; the raw material composition of the graphene oxide grafted nitrogen-phosphorus based flame retardant includes graphene oxide suspension, nitrogen-phosphorus based flame retardant 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO), silane coupling agent KH-550, the mass ratio of the nitrogen-phosphorus based flame retardant to the silane coupling agent is 5:1, and the addition ratio of the nitrogen-phosphorus based flame retardant to the graphene oxide suspension is 5 g:0.5 L; the raw material composition of the graphene oxide grafted thermoplastic resin includes graphene oxide suspension, thermoplastic resin polyetheretherketone, silane coupling agent, the mass ratio of the thermoplastic resin to the silane coupling agent is 3:1, and the addition ratio of the thermoplastic resin to the graphene oxide suspension is 3 g:0.5 L; the concentration of the graphene oxide suspension is 5 g / L.

[0040] The preparation method of the above material is carried out successively according to the following steps:

[0041] S1. Suspend graphene oxide in tetrahydrofuran solvent and treat it in an ultrasonic bath for 30 min to obtain graphene oxide suspension.

[0042] S2. While stirring, add the nitrogen-phosphorus based flame retardant and silane coupling agent to the graphene oxide suspension, and then reflux at 75 °C under a nitrogen atmosphere for 12 h for functionalization reaction to obtain a reaction product. Then dry the reaction product in vacuum at 80 °C overnight to remove the solvent, and obtain a structure asFigure 1 The graphene oxide grafted nitrogen-phosphorus based flame retardant as shown; adding a thermoplastic resin and a silane coupling agent to the graphene oxide suspension, refluxing for 12 h at 75 °C under a nitrogen atmosphere for a functionalization reaction to obtain a reaction product, and then drying the reaction product in vacuo overnight at 80 °C to remove the solvent, obtaining the thermoplastic resin grafted with graphene oxide as shown in Figure 2 Figure

[0043] S3. First, wollastonite fibers and a silane coupling agent are placed in a high-speed mixer according to a mass ratio of 100:1, and the modified wollastonite is obtained after high-speed stirring. Then, the graphene oxide grafted nitrogen-phosphorus based flame retardant, the thermoplastic resin grafted with graphene oxide and the modified wollastonite are mixed, and then the silane coupling agent is added dropwise to obtain the Si-P-N-C quaternary hybrid flame retardant system composition as shown in Figure 3 Figure

[0044] S4. The polyolefin resin, the Si-P-N-C quaternary hybrid flame retardant, chlorinated polyvinyl chloride, antimony trioxide, and triazine charring agent are blended in the required proportions and then extruded into a film to obtain the polyolefin resin film material, where the blending temperature is 110 °C and the extrusion temperature condition is 200 °C.

[0045] Example 2:

[0046] The difference from Example 1 is that:

[0047] The raw material composition and mass fraction ratio of the polyolefin resin film material are: polyolefin resin 60, Si-P-N-C quaternary hybrid flame retardant 12, chlorinated polyvinyl chloride 10, antimony trioxide 2, triazine charring agent 2; the raw material composition and mass fraction ratio of the Si-P-N-C quaternary hybrid flame retardant are: graphene oxide grafted nitrogen-phosphorus based flame retardant 6.5, thermoplastic resin grafted with graphene oxide 4, modified wollastonite 95, silane coupling agent 1.2; the raw material composition of the graphene oxide grafted nitrogen-phosphorus based flame retardant includes graphene oxide suspension, nitrogen-phosphorus based flame retardant piperazine pyrophosphate, and silane coupling agent KH-560, the mass ratio of the nitrogen-phosphorus based flame retardant to the silane coupling agent is 8:1.2, and the addition ratio of the nitrogen-phosphorus based flame retardant to the graphene oxide suspension is 8 g:0.5 L; the raw material composition of the thermoplastic resin grafted with graphene oxide includes graphene oxide suspension, thermoplastic resin MQ resin, and silane coupling agent, the mass ratio of the thermoplastic resin to the silane coupling agent is 4:1.2, and the addition ratio of the thermoplastic resin to the graphene oxide suspension is 4 g:0.5 L; the concentration of the graphene oxide suspension is 6 g / L.

[0048] Example 3:

[0049] The difference from Example 1 is that:

[0050] The raw material composition and mass ratio of the polyolefin resin film material are as follows: 68 parts by mass of polyolefin resin, 16 parts by mass of Si-P-N-C quaternary hybrid flame retardant, 14 parts by mass of chlorinated polyvinyl chloride, 4 parts by mass of antimony trioxide, and 3 parts by mass of triazine charring agent; The raw material composition and mass ratio of the Si-P-N-C quaternary hybrid flame retardant are as follows: 8 parts by mass of nitrogen-phosphorus based flame retardant grafted with graphene oxide, 5 parts by mass of thermoplastic resin grafted with graphene oxide, 88 parts by mass of modified wollastonite, and 1.1 parts by mass of silane coupling agent; The raw material composition of the nitrogen-phosphorus based flame retardant grafted with graphene oxide includes graphene oxide suspension, nitrogen-phosphorus based flame retardant melamine polyphosphate, and silane coupling agent KH-570. The mass ratio of the nitrogen-phosphorus based flame retardant to the silane coupling agent is 6:1.2, and the addition ratio of the nitrogen-phosphorus based flame retardant to the graphene oxide suspension is 6 g:0.5 L; The raw material composition of the thermoplastic resin grafted with graphene oxide includes graphene oxide suspension, thermoplastic resin MQ resin, and silane coupling agent. The mass ratio of the thermoplastic resin to the silane coupling agent is 2:1.1, and the addition ratio of the thermoplastic resin to the graphene oxide suspension is 2 g:0.5 L; The concentration of the graphene oxide suspension is 8 g / L.

[0051] Example 4:

[0052] The difference from Example 1 is:

[0053] The raw material composition and mass ratio of the polyolefin resin film material are as follows: 70 parts by mass of polyolefin resin, 18 parts by mass of Si-P-N-C quaternary hybrid flame retardant, 15 parts by mass of chlorinated polyvinyl chloride, 5 parts by mass of antimony trioxide, and 2 parts by mass of triazine charring agent; The raw material composition and mass ratio of the Si-P-N-C quaternary hybrid flame retardant are as follows: 7 parts by mass of nitrogen-phosphorus based flame retardant grafted with graphene oxide, 5 parts by mass of thermoplastic resin grafted with graphene oxide, 90 parts by mass of modified wollastonite, and 1 part by mass of silane coupling agent; The raw material composition of the nitrogen-phosphorus based flame retardant grafted with graphene oxide includes graphene oxide suspension, nitrogen-phosphorus based flame retardant melamine polyphosphate, and silane coupling agent KH-590. The mass ratio of the nitrogen-phosphorus based flame retardant to the silane coupling agent is 6:1, and the addition ratio of the nitrogen-phosphorus based flame retardant to the graphene oxide suspension is 6 g:0.5 L; The raw material composition of the thermoplastic resin grafted with graphene oxide includes graphene oxide suspension, thermoplastic resin MQ resin, and silane coupling agent. The mass ratio of the thermoplastic resin to the silane coupling agent is 4:1, and the addition ratio of the thermoplastic resin to the graphene oxide suspension is 4 g:0.5 L.

[0054] Example 5:

[0055] The difference from Example 1 is:

[0056] The raw material composition of the polyolefin resin film material further includes ammonium polyphosphate, and the mass ratio of ammonium polyphosphate to polyolefin resin is 1.5:65.

[0057] Example 6:

[0058] The difference from Example 3 is that:

[0059] The raw material composition of the polyolefin resin film material further includes ammonium polyphosphate, and the mass ratio of ammonium polyphosphate to polyolefin resin is 1:68.

[0060] Example 7:

[0061] The difference from Example 3 is that:

[0062] The raw material composition of the polyolefin resin film material further includes ammonium polyphosphate and decabromodiphenylethane, and the mass ratio of ammonium polyphosphate, decabromodiphenylethane to polyolefin resin is 1:3:68.

[0063] Comparative Example 1:

[0064] The difference from Example 1 is that:

[0065] The raw material composition and mass ratio of the polyolefin resin film material are: 65 parts of polyolefin resin, 15 parts of Si-P-N-C quaternary hybrid flame retardant, 13 parts of chlorinated polyvinyl chloride, and 4 parts of antimony trioxide.

[0066] Comparative Example 2:

[0067] The difference from Example 1 is that:

[0068] The raw material composition and mass ratio of the polyolefin resin film material are: 65 parts of polyolefin resin, 15 parts of Si-P-N-C quaternary hybrid flame retardant, and 13 parts of chlorinated polyvinyl chloride.

[0069] Comparative Example 3:

[0070] The difference from Example 1 is that:

[0071] The raw material composition and mass ratio of the polyolefin resin film material are: 65 parts of polyolefin resin, 15 parts of Si-P-N-C quaternary hybrid flame retardant, 13 parts of chlorinated polyvinyl chloride, and 2.5 parts of triazine char former.

[0072] Comparative Example 4:

[0073] The difference from Example 1 is that:

[0074] The raw material composition and mass ratio of the polyolefin resin film material are: 65 parts of polyolefin resin, 13 parts of chlorinated polyvinyl chloride, 2.5 parts of triazine char former, and 4 parts of antimony trioxide.

[0075] Comparative Example 5:

[0076] A Si-P-N-C quaternary mixture, the preparation method of which includes:

[0077] First, wollastonite fibers and a silane coupling agent are placed in a high-speed mixer according to a mass ratio of 100:1. After high-speed stirring, modified wollastonite is obtained. Then, 5 g of the nitrogen-phosphorus-based flame retardant DOPO, 3 g of the thermoplastic resin polyether ether ketone, 0.5 g of graphene oxide, and 90 g of the modified wollastonite are added to the high-speed mixer for mixing. Then, 1 g of the silane coupling agent is added dropwise. After high-speed stirring, a Si-P-N-C quaternary mixture is obtained.

[0078] Comparative Example 6:

[0079] A Si-P-N-C quaternary mixture, and its preparation method includes:

[0080] First, wollastonite fibers and a silane coupling agent are placed in a high-speed mixer according to a mass ratio of 100:1. After high-speed stirring, modified wollastonite is obtained. Then, 5 g of the nitrogen-phosphorus-based flame retardant DOPO, 3 g of the thermoplastic resin polyether ether ketone, and 90 g of the modified wollastonite are added to the high-speed mixer for mixing. Then, 1 g of the silane coupling agent is added dropwise. After high-speed stirring, a Si-P-N-C quaternary mixture is obtained.

[0081] Performance verification:

[0082] (1) To investigate the flame retardancy of the polyolefin resin film material of the present invention, the flame retardancy of Examples 1, 3, 5-7 and Comparative Examples 1-4 was tested respectively. The test method was GB / T 2406.2-2009 "Plastics - Determination of burning behavior by the oxygen index method - Part 2: Ambient temperature test". The oxygen index was used as the final criterion for evaluating the flame retardancy. The results are shown in Table 1:

[0083] Table 1 Test results of the flame retardancy of the film material

[0084] Oxygen index Example 1 26 Example 3 26 Example 5 27 Example 6 28 Example 7 36 Comparative example 1 24 Comparative example 2 22 Comparative example 3 24 Comparative example 4 22

[0085] As can be seen from Table 1, the present invention can effectively improve the flame retardancy of the film material, and the oxygen index of the film material obtained in Example 7 can reach 36.

[0086] (2) To investigate the mechanical properties and flame retardancy of the Si-P-N-C quaternary hybrid flame retardant of the present invention, in 100 parts by mass of polypropylene (melt flow rate at a load of 2.16 kg and 230 °C measured according to JIS K7210 = 8 g / 10 min), 0.1 part by mass of calcium stearate (organic nucleating agent), 0.1 part by mass of tetrakis [3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate methyl] methane (phenolic antioxidant), 0.1 part by mass of tris(2,4-di-tert-butylphenyl) phosphite (phosphorus antioxidant), and 0.3 part by mass of glycerol monostearate (lubricant), the products of Examples 1-4 and Comparative Examples 5-6 were added respectively to obtain a flame-retardant synthetic resin composition. In the obtained flame-retardant synthetic resin composition, the mass ratios of the products of Examples 1-4 and Comparative Examples 1-2 were both 35%. The obtained flame-retardant synthetic resin composition was pressed at 220 °C and 5-15 MPa for 15 min under pressing processing conditions to obtain test pieces. Surface detection, flame retardancy experiments, and oxygen index detection were carried out on the test pieces.

[0087] Surface detection: According to whether the surface of the test piece is smooth and whether there are white spots, the compatibility of the nitrogen-phosphorus flame retardant, modified wollastonite, graphene oxide, and the polypropylene resin matrix was judged.

[0088] Flame retardancy experiment: The test piece was made into a spline with a length of 127 mm, a width of 12.7 mm, and a thickness of 1.6 mm. The spline was placed vertically and contacted with the flame of the lower burner for 10 seconds, then the flame was removed, and the time for the fire on the spline to go out was measured. Then, after the first fire went out, the second flame contact was carried out for 10 seconds, and the time for the fire on the spline to go out was measured; in addition, whether the cotton below the spline was ignited by the falling fire was evaluated. According to the combustion times of the first and second times, whether the cotton was on fire, etc., the combustion grade was determined according to the UL-94V standard. For the combustion grade, V-0 is the highest, and the flame retardancy decreases in the order of V-1 and V-2.

[0089] Oxygen index detection: The test piece was made into a spline with a length of 150 mm, a width of 10 mm, and a thickness of 4 mm. A line was drawn at 50 mm at one end, and the other end was inserted into the sample clamp of the combustion cylinder. The concentrations of nitrogen and oxygen were adjusted, and then the top of the sample was ignited with a lighter for no more than 30 s. The lighter was removed and timing was started immediately. The lowest oxygen concentration required for the sample to just burn for 3 min or go out naturally after burning 50 mm was the oxygen index.

[0090] The test results are shown in Table 2:

[0091] Table 2 Test results of surface detection, flame retardancy experiment, and oxygen index detection

[0092]

[0093] From Table 2, taking the Si-P-N-C quaternary hybrid flame retardant system composition prepared in Examples 1-4 as the flame retardant and adding it to the polypropylene resin composition at an addition amount of 35 parts by mass, the obtained test pieces all passed the UL-94 flame retardancy test, the oxygen index was greater than 34, and the surface of the test pieces was smooth without white spots, indicating that it has good flame retardancy and processability. For the test pieces obtained by adding the comparative examples 1-2 as the flame retardant to the polypropylene resin composition at an addition amount of 35 parts by mass, they failed to pass the UL-94 flame retardancy test, the oxygen index was only 27 and 28, and the surface of the test pieces was relatively rough with white spots, indicating that their flame retardancy and processability were worse than those of Examples 1-4. The above results show that the Si-P-N-C quaternary hybrid flame retardant system composition prepared in the present invention has more excellent flame retardancy, and also has more excellent mechanical properties and processability.

Claims

1. A polyolefin resin film material, characterized in that: The raw material composition and mass ratio of the material include: 60 - 70 parts of polyolefin resin, 10 - 20 parts of Si - P - N - C quaternary hybrid flame retardant, 10 - 15 parts of chlorinated polyvinyl chloride, 2 - 5 parts of antimony trioxide, and 2 - 3 parts of triazine charring agent.

2. The polyolefin resin film material according to claim 1, characterized in that: The raw material composition and mass ratio of the Si - P - N - C quaternary hybrid flame retardant include: 5 - 8 parts of graphene oxide - grafted nitrogen - phosphorus - based flame retardant, 3 - 5 parts of graphene oxide - grafted thermoplastic resin, 88 - 95 parts of modified wollastonite, and 1 - 1.2 parts of silane coupling agent; The modified wollastonite is obtained by high - speed mixing of wollastonite fiber and silane coupling agent.

3. The polyolefin resin film material according to claim 2, characterized in that: The raw material composition of the graphene oxide - grafted nitrogen - phosphorus - based flame retardant includes graphene oxide suspension, nitrogen - phosphorus - based flame retardant, and silane coupling agent. The mass ratio of the nitrogen - phosphorus - based flame retardant to the silane coupling agent is 5 - 8:1 - 1.2, and the addition ratio of the nitrogen - phosphorus - based flame retardant to the graphene oxide suspension is 5 - 8 g:0.5 L; The raw material composition of the graphene oxide - grafted thermoplastic resin includes graphene oxide suspension, thermoplastic resin, and silane coupling agent. The mass ratio of the thermoplastic resin to the silane coupling agent is 2 - 4:1 - 1.2, and the addition ratio of the nitrogen - phosphorus - based flame retardant to the graphene oxide suspension is 2 - 4 g:0.5 L; The concentration of the graphene oxide suspension is 5 - 8 g / L.

4. The polyolefin resin film material according to claim 3, characterized in that: The nitrogen - phosphorus - based flame retardant is any one of 9,10 - dihydro - 9 - oxa - 10 - phosphaphenanthrene - 10 - oxide, melamine polyphosphate, and piperazine pyrophosphate; The thermoplastic resin is any one of polyetheretherketone and MQ resin; The silane coupling agent is any one of KH - 550, KH - 560, KH - 570, and KH - 590.

5. The polyolefin resin film material according to claim 1 or 2, characterized in that: The raw material composition of the material further includes ammonium polyphosphate and decabromodiphenylethane. The mass ratio of ammonium polyphosphate, decabromodiphenylethane to polyolefin resin is 1 - 2:3:60 - 70.

6. A preparation method of the polyolefin resin film material according to claim 1, characterized in that: The preparation method includes: S1. Prepare the Si - P - N - C quaternary hybrid flame retardant; S2. Mix the polyolefin resin, Si - P - N - C quaternary hybrid flame retardant, chlorinated polyvinyl chloride, antimony trioxide, and triazine charring agent in the required proportion and then extrude and mold.

7. The preparation method of a polyolefin resin film material according to claim 6, characterized in that: The raw material composition and mass ratio of the Si - P - N - C quaternary hybrid flame retardant include: 5 - 8 parts of graphene oxide - grafted nitrogen - phosphorus - based flame retardant, 3 - 5 parts of graphene oxide - grafted thermoplastic resin, 88 - 95 parts of modified wollastonite; The S1 includes: respectively preparing a nitrogen-phosphorus-based flame retardant grafted with graphene oxide and a thermoplastic resin grafted with graphene oxide first, and then mixing the nitrogen-phosphorus-based flame retardant grafted with graphene oxide, the thermoplastic resin grafted with graphene oxide, and modified wollastonite in a required proportion to obtain the Si-P-N-C quaternary hybrid flame retardant.

8. The preparation method of a polyolefin resin film material according to claim 7, characterized in that: The raw material composition of the nitrogen-phosphorus-based flame retardant grafted with graphene oxide includes a graphene oxide suspension, a nitrogen-phosphorus-based flame retardant, and a silane coupling agent. The mass ratio of the nitrogen-phosphorus-based flame retardant to the silane coupling agent is 5-8:1-1.2, and the addition ratio of the nitrogen-phosphorus-based flame retardant to the graphene oxide suspension is 5-8 g:0.5 L; The preparation of the nitrogen-phosphorus-based flame retardant grafted with graphene oxide includes: adding a nitrogen-phosphorus-based flame retardant and a silane coupling agent to the graphene oxide suspension, and obtaining the nitrogen-phosphorus-based flame retardant grafted with graphene oxide through a functionalization reaction; The raw material composition of the thermoplastic resin grafted with graphene oxide includes a graphene oxide suspension, a thermoplastic resin, and a silane coupling agent. The mass ratio of the thermoplastic resin to the silane coupling agent is 2-4:1-1.2, and the addition ratio of the nitrogen-phosphorus-based flame retardant to the graphene oxide suspension is 2-4 g:0.5 L; The preparation of the thermoplastic resin grafted with graphene oxide includes: adding a thermoplastic resin and a silane coupling agent to the graphene oxide suspension, and obtaining the thermoplastic resin grafted with graphene oxide through a functionalization reaction. The conditions of the functionalization reaction are: refluxing for 10-12 h at 73-80 °C under a nitrogen atmosphere; The concentration of the graphene oxide suspension is 5-8 g / L.

9. The preparation method of a polyolefin resin film material according to claim 8, characterized in that: In the S2, the blending temperature is 105-120 °C, and the extrusion temperature condition is 180-220 °C.

10. The preparation method of a polyolefin resin film material according to claim 6, characterized in that: The raw material composition of the material further includes ammonium polyphosphate and decabromodiphenylethane. The weight ratio of ammonium polyphosphate, decabromodiphenylethane to the polyolefin resin is 1-2:3:60-70; The S2 includes: blending polyolefin resin, Si-P-N-C quaternary hybrid flame retardant, chlorinated polyvinyl chloride, antimony trioxide, triazine charring agent, ammonium polyphosphate, and decabromodiphenylethane in a required proportion and then extruding and molding.

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