A high temperature resistant flame retardant modified polypropylene material and preparation method thereof

Abstract

The present invention relates to the field of polymer materials, and in particular to a high temperature resistant flame retardant modified polypropylene material and a preparation method thereof. A high temperature resistant flame retardant modified polypropylene material, in terms of mass percentage, comprises raw materials including: 50-70% polypropylene matrix, 10-20% flame retardant additive, 1-5% functional additive, and the balance of flame retardant synergist. The high temperature resistant flame retardant modified polypropylene material provided in the present invention, in addition to having excellent high temperature resistance and flame retardant properties, can also further ensure its own excellent stability and weather resistance as well as waterproof and hygroscopic properties, solving the existing performance problems of flame retardant modified polypropylene materials in the domestic market, thereby greatly broadening the application field and application environment of polypropylene materials.

Description

Technical Field

[0001] The invention relates to the field of polymer materials, and in particular to a high temperature resistant flame retardant modified polypropylene material and a preparation method thereof. Background Art

[0002] Polypropylene is a general-purpose plastic with excellent comprehensive properties, which has been widely used in the fields of automobiles, packaging, home appliances, electronic products, furniture, etc. However, polypropylene material itself is a flammable material. Once a fire occurs, it will seriously endanger the safety of human life and property. Therefore, it is particularly important to modify polypropylene to be flame retardant.

[0003] At present, the domestic existing technology for the solution of the problem of flame retardant modification of polypropylene mainly focuses on the flame retardant modification of polypropylene using a flame retardant compounded with halogen-containing organic matter and antimony trioxide. As we all know, plastic products containing halogen flame retardants will generate a large amount of smoke and toxic and corrosive gases when burned, which will cause great harm to the environment and human body. And because some flame retardants are seriously agglomerated in polypropylene materials, the performance of polypropylene materials in terms of flame retardancy, waterproofness, mechanical properties, etc. is seriously degraded. For example, the intumescent flame retardant and the polypropylene matrix have opposite polarities and poor compatibility, so the intumescent flame retardant is seriously agglomerated in the polypropylene matrix, which leads to a significant performance degradation of the polypropylene material in terms of flame retardancy, thermal stability, weather resistance, and anti-hygroscopicity. Summary of the invention

[0004] In order to solve the above problems, the present invention provides a high temperature resistant flame retardant modified polypropylene material and a preparation method thereof. The prepared polypropylene material not only has excellent high temperature resistance and flame retardant properties, but also can further ensure its own excellent stability and weather resistance as well as waterproof and hygroscopic properties, thereby solving the existing performance problems of flame retardant modified polypropylene materials in the domestic market, thereby greatly broadening the application field and application environment of polypropylene materials.

[0005] The first aspect of the present invention provides a high temperature resistant flame retardant modified polypropylene material, wherein the raw materials include, by mass percentage: 50-75% polypropylene matrix, 10-20% flame retardant additive, 1-3% functional additive, and the balance of flame retardant synergist.

[0006] As a preferred solution, the polypropylene matrix is ​​a composition of copolymer polypropylene and homopolypropylene.

[0007] As a preferred solution, the mass ratio of the copolymer polypropylene to the homopolypropylene is (2-4):(0.5-1.5).

[0008] As a preferred solution, the mass ratio of the copolymer polypropylene to the homopolypropylene is (2.5-3):(1-1.2).

[0009] As a preferred solution, the mass ratio of the copolymer polypropylene to the homopolypropylene is 2.8:1.2.

[0010] As a preferred solution, the melt index of the copolymerized polypropylene is 1 to 15 g / min, and the test conditions are: 230° C. / 2.16 kg.

[0011] As a preferred solution, the melt index of the copolymerized polypropylene is 3 to 8 g / min, and the test conditions are: 230° C. / 2.16 kg.

[0012] As a preferred solution, the flame retardant auxiliary agent is a nitrogen-phosphorus composite flame retardant.

[0013] As a preferred scheme, the preparation method of the nitrogen-phosphorus composite flame retardant comprises the following steps, measured by mass: S1: adding 5 to 10 parts of polyphosphoric acid into a reaction container, then adding 3 to 6 parts of melamine and 60 to 80 parts of deionized water, and stirring evenly at 100 to 200 r / min; S2: adding 5 to 6 parts of hydroquinone and 3 to 4 parts of propylene glycol, heating to 50 to 60°C, and stirring at 100 to 200 r / min for 3 to 4 hours; S3: after the reaction is completed, cooling to room temperature and adding a pH regulator to adjust the pH to 6 to 6.5, then filtering and washing to obtain a solid material; S4: mixing the solid material with melamine pyrophosphate and pentaerythritol and pulverizing them evenly to obtain a nitrogen-phosphorus composite flame retardant.

[0014] As a preferred solution, the mass ratio of the solid material to melamine pyrophosphate and pentaerythritol is (10-20):(3-8):(4-6).

[0015] As a preferred solution, the mass ratio of the solid material to melamine pyrophosphate and pentaerythritol is 14.5:4.5:5.

[0016] As a preferred solution, the mass ratio of the polypropylene matrix to the flame retardant additive is (65-70):(14-18).

[0017] As a preferred solution, the mass ratio of the polypropylene matrix to the flame retardant additive is 70:15.

[0018] As a preferred solution, the functional additive is at least one of an antioxidant, a lubricant, a dispersant, a water-proofing agent, an anti-ultraviolet agent, a stabilizer, a toughening agent, and a solubilizing agent.

[0019] As a preferred solution, the functional additives are antioxidants and lubricants.

[0020] As a preferred solution, the antioxidant is at least one of a hindered phenol antioxidant and a phosphite antioxidant.

[0021] As a preferred solution, the antioxidant is a hindered phenol antioxidant and a phosphite antioxidant, and the mass ratio of the two is (1-3): (1-3).

[0022] As a preferred solution, the lubricant is EBS lubricant.

[0023] As a preferred solution, the mass ratio of the flame retardant auxiliary agent to the flame retardant synergist is (14-18): (8-14).

[0024] As a preferred solution, the flame retardant synergist is modified barium sulfate and modified silicon powder.

[0025] As a preferred solution, the mass ratio of the modified barium sulfate to the modified silicon micropowder is (4-5): (1-2).

[0026] As a preferred solution, the average particle size of the modified barium sulfate is 4000-5000 mesh.

[0027] As a preferred solution, the average particle size of the modified barium sulfate is 4000-4500 mesh.

[0028] As a preferred solution, the preparation method of the modified barium sulfate comprises the following steps: S1: mixing barium sulfate with ammonia water and ethanol, and then heating to 40-60° C. and keeping warm for 30-60 min; S2: uniformly mixing tetraethyl orthosilicate and ethanol at 50-60° C. and dripping into the mixed solution of S1, and the dripping reaction time is 2-2.5 h; S3: dripping 10wt% sodium hydroxide aqueous solution to maintain the pH at 8-8.5 and keeping warm for 1-1.5 h to obtain the modified barium sulfate.

[0029] As a preferred solution, the mass ratio of barium sulfate to tetraethyl orthosilicate is (3-5):(2-4).

[0030] As a preferred solution, the mass ratio of barium sulfate to tetraethyl orthosilicate is (4-5): (2-2.5).

[0031] In the present invention, by adopting a compound combination of modified barium sulfate and nitrogen-phosphorus composite flame retardant, it is possible to ensure excellent flame retardant properties while further ensuring the self-stability, mechanical properties and waterproof properties of the polypropylene material. This is mainly because the addition of modified barium sulfate can accelerate the collision frequency with the effective molecules of the nitrogen-phosphorus composite flame retardant through its extremely low surface energy in the system, thereby promoting the uniform dispersion of the nitrogen-phosphorus composite flame retardant, and further reducing the segregation movement speed of the nitrogen-phosphorus composite flame retardant, so that it can exist stably in the polypropylene material; on the other hand, the modified barium sulfate can form a gradient distributed waterproof site in the polypropylene material system through the surface amorphous coating layer, so that water molecules are concentrated on the surface of the polypropylene material, and the path length and movement rate of the water molecules that continue to penetrate into the interior are increased, thereby making the polypropylene material have good waterproofness and self-stability.

[0032] As a preferred scheme, the preparation method of the modified silicon micropowder includes the following steps: S1: mixing and stirring an organic acid anhydride and a surface modifier with silicon micropowder, and then adding them together into an organic solvent and stirring evenly to obtain a silicon micropowder mixed solution; S2: heating the silicon micropowder mixed solution to 60-70°C and heating it for 2-2.5h to obtain a suspension, and centrifuging it to collect the precipitate, washing and drying it to obtain pretreated silicon micropowder; S3: adding the pretreated silicon micropowder, chromium nitrate nonahydrate, terephthalic acid, and acetic acid to deionized water, heating it to 180-220°C in a closed reactor, stirring and reacting for 6-12h, and then washing, filtering, and drying to obtain modified silicon micropowder.

[0033] As a preferred solution, the mass ratio of the pretreated silicon powder to chromium nitrate nonahydrate and terephthalic acid is (1-3): (3-4): (1-2.5).

[0034] As a preferred solution, the average particle size of the silicon micropowder is 3000-4000 mesh.

[0035] In the present invention, the addition of modified silicon micropowder can not only help enhance the flame retardant performance, but also have excellent mechanical strengthening effect. This is mainly because the surface of the modified silicon micropowder is loaded with more framework particles due to bonding. The presence of these particles increases the segregation degree of silicon micropowder particles in the polypropylene system, so that in the prepared polypropylene material, most of them are distributed on the surface of the polypropylene material, and the modified silicon micropowder particles can be used as surface adsorption sites to adsorb surface moisture. Water molecules will remain inside the modified particles without staying on the surface or overflowing, and the rough surface peak-valley structure formed by them can form a good blocking effect on the surface, thereby maintaining good waterproof and hygroscopic properties in a specific humid environment. When subjected to high temperature, the moisture will release a large amount of water vapor from the inside of the particles due to heat, taking away a large amount of heat, thereby having excellent flame retardant and high temperature resistant effects.

[0036] The second aspect of the present invention provides a method for preparing the above-mentioned high temperature resistant flame retardant modified polypropylene material, the preparation method comprising the following steps: S1: adding a polypropylene matrix, a flame retardant additive, a functional additive, and a flame retardant synergist to a high-speed mixer in sequence and mixing them evenly; S2: transferring the mixture in S1 to an extruder, extruding, cooling, and granulating to obtain a high temperature resistant flame retardant modified polypropylene material.

[0037] Beneficial effects:

[0038] 1. The present invention provides a high temperature resistant flame retardant modified polypropylene material. The prepared polypropylene material not only has excellent high temperature resistance and flame retardant properties, but also can further ensure its own excellent stability and weather resistance as well as waterproof and hygroscopic properties, thus solving the existing performance problems of flame retardant modified polypropylene materials in the domestic market, thereby greatly broadening the application field and application environment of polypropylene materials.

[0039] 2. A high temperature resistant flame retardant modified polypropylene material provided in the present invention can ensure excellent flame retardant properties while further ensuring the stability, mechanical properties and waterproof properties of the polypropylene material itself by adopting a compound combination of modified barium sulfate and nitrogen-phosphorus composite flame retardant; the addition of modified barium sulfate can accelerate the collision frequency between it and the effective molecules of the nitrogen-phosphorus composite flame retardant in the system through its extremely low surface energy, thereby promoting the uniform dispersion of the nitrogen-phosphorus composite flame retardant, and further reducing the segregation movement speed of the nitrogen-phosphorus composite flame retardant, so that it can exist stably in the polypropylene material; on the other hand, the modified barium sulfate can form a gradient distributed waterproof site in the polypropylene material system through the surface amorphous coating layer, so that water molecules are concentrated on the surface of the polypropylene material, while increasing the path length and movement rate of the water molecules continuing to penetrate into the interior, thereby obtaining good waterproof and anti-hygroscopic properties.

[0040] 3. The high temperature resistant flame retardant modified polypropylene material provided in the present invention can not only help enhance the flame retardant performance by adding modified silicon powder, but also have excellent mechanical strengthening effect; the modified silicon powder can be mostly distributed on the surface of the polypropylene material, and the modified silicon powder particles can be used as surface adsorption sites to adsorb surface moisture, and the water molecules will be retained inside the modified particles without staying on the surface or overflowing, and the rough surface peak-valley structure formed by it can form a good blocking effect on the surface, thereby maintaining good waterproof and anti-hygroscopic properties in a specific humid environment. When subjected to high temperature, the moisture will release a large amount of water vapor from the inside of the particles due to heat, taking away a large amount of heat, thereby having excellent flame retardant and high temperature resistant effects.

[0041] 4. The high temperature resistant flame retardant modified polypropylene material provided in the present invention has a simple preparation method, does not involve complex chemical reactions, and does not have serious corrosion reactions on the preparation equipment. Therefore, it can effectively reduce the labor cost and equipment maintenance cost of the production of polypropylene materials. BRIEF DESCRIPTION OF THE DRAWINGS

[0042] Figure 1 This is an electron microscope image of the high temperature resistant flame retardant modified polypropylene material prepared in Example 1 of the present invention. DETAILED DESCRIPTION

[0043] The following will further illustrate and demonstrate the technical solutions in the above invention content of the present invention in the form of specific implementation schemes. The following embodiments are only practical examples used to illustrate and explain the contents of the technical solutions in the specification, and should not limit the scope of the claims to be protected by the present invention. All technical products based on the technical solutions described in the invention content of the present invention should be included in the scope to be protected by the present invention.

[0044] In the following examples, unless otherwise specified, the raw materials are all commercially available products, or can be prepared by methods well known to those skilled in the art.

[0045] Example 1

[0046] Embodiment 1 The first aspect provides a high temperature resistant flame retardant modified polypropylene material, wherein the raw materials include, by mass percentage: 70% polypropylene matrix, 15% flame retardant additive, 3% functional additive, and the balance of flame retardant synergist.

[0047] The polypropylene matrix is ​​a composition of copolymer polypropylene and homopolypropylene; the mass ratio of the copolymer polypropylene to the homopolypropylene is 2.8:1.2.

[0048] The copolymer polypropylene is 7032E3, the melt index of the copolymer polypropylene is 4 g / min, and the test conditions are: 230° C. / 2.16 kg.

[0049] Homopolymer polypropylene was purchased from 578N homopolymer polypropylene sold by Shanghai Hongsu Plastic Chemical Co., Ltd.

[0050] The flame retardant auxiliary agent is a nitrogen-phosphorus composite flame retardant; the preparation method of the nitrogen-phosphorus composite flame retardant, calculated by mass, comprises the following steps: S1: adding 6 parts of polyphosphoric acid into a reaction container, and then adding 4 parts of melamine and 80 parts of deionized water, and stirring at 150 r / min; S2: adding 5 parts of hydroquinone and 4 parts of propylene glycol, heating to 60°C, and stirring at 200 r / min for 3.5 hours;

[0051] S3: After the reaction is completed, cool to room temperature and add hydrochloric acid to adjust the pH to 6, then filter and wash to obtain a solid material; S4: 14.5 parts of the solid material, 4.5 parts of melamine pyrophosphate and 5 parts of pentaerythritol are mixed and evenly crushed to obtain a nitrogen-phosphorus composite flame retardant.

[0052] The functional additives are antioxidants and lubricants; the antioxidants are hindered phenol antioxidants and phosphite antioxidants, and the mass ratio of the antioxidants is 1:1; the hindered phenol antioxidant is antioxidant 1010; and the phosphite antioxidant is antioxidant 168.

[0053] The lubricant is EBS lubricant.

[0054] The flame retardant synergist is modified barium sulfate and modified silicon micropowder; the mass ratio of the modified barium sulfate to the modified silicon micropowder is 4:1.5.

[0055] The average particle size of the modified barium sulfate is 4200 mesh.

[0056] The preparation method of modified barium sulfate includes the following steps, calculated by mass: S1: 4.2 parts of barium sulfate are mixed with 10 parts of ammonia water and 60 parts of ethanol, and then the temperature is raised to 50°C and kept warm for 40 minutes; S2: 2.5 parts of tetraethyl orthosilicate and 30 parts of ethanol are mixed evenly at 55°C and added dropwise to the mixed solution of S1, and the reaction time of the addition is 2 hours; S3: 10wt% sodium hydroxide aqueous solution is added dropwise to maintain the pH at 8.5 and keep warm for 1 hour to obtain the modified barium sulfate.

[0057] The preparation method of modified silicon micropowder includes the following steps, calculated by mass: S1: 5 parts of succinic anhydride and 3 parts of (3-aminopropyl)triethoxysilane are mixed with 2 parts of silicon micropowder, and then added into 80 parts of DMF, stirred evenly, and obtained a silicon micropowder mixed solution; S2: The silicon micropowder mixed solution is heated to 65°C for 2 hours to obtain a suspension, and the precipitate is collected by centrifugation, washed and dried to obtain pretreated silicon micropowder; S3: 2 parts of pretreated silicon micropowder, 3.5 parts of chromium nitrate nonahydrate, 1.4 parts of terephthalic acid, and 0.45 parts of acetic acid are added to 60 parts of deionized water, heated to 190°C in a closed reactor, stirred for reaction for 11 hours, and then washed, filtered and dried to obtain modified silicon micropowder.

[0058] The average particle size of silica powder is 3500 mesh.

[0059] The second aspect of this embodiment provides a method for preparing the above-mentioned high temperature resistant flame retardant modified polypropylene material, and the preparation method comprises the following steps: S1: adding a polypropylene matrix, a flame retardant additive, a functional additive, and a flame retardant synergist to a high-speed mixer in sequence and mixing them evenly; S2: transferring the mixture in S1 into an extruder, extruding, cooling, and granulating to obtain a high temperature resistant flame retardant modified polypropylene material.

[0060] Example 2

[0061] Embodiment 2 The first aspect provides a high temperature resistant flame retardant modified polypropylene material, in which the raw materials include, by mass percentage: 70% polypropylene matrix, 15% flame retardant additive, 3% functional additive, and the balance of flame retardant synergist.

[0062] The polypropylene matrix is ​​a composition of copolymer polypropylene and homopolypropylene; the mass ratio of the copolymer polypropylene to the homopolypropylene is 3:1.

[0063] The copolymer polypropylene is 7032E3, the melt index of the copolymer polypropylene is 4 g / min, and the test conditions are: 230° C. / 2.16 kg.

[0064] Homopolymer polypropylene was purchased from 578N homopolymer polypropylene sold by Shanghai Hongsu Plastic Chemical Co., Ltd.

[0065] The flame retardant auxiliary agent is a nitrogen-phosphorus composite flame retardant; the preparation method of the nitrogen-phosphorus composite flame retardant, calculated by mass, comprises the following steps: S1: adding 6 parts of polyphosphoric acid into a reaction container, and then adding 4 parts of melamine and 80 parts of deionized water, and stirring at 150 r / min; S2: adding 5 parts of hydroquinone and 4 parts of propylene glycol, heating to 60°C, and stirring at 200 r / min for 3.5 hours;

[0066] S3: After the reaction is completed, cool to room temperature and add hydrochloric acid to adjust the pH to 6, then filter and wash to obtain a solid material; S4: 16 parts of the solid material, 6 parts of melamine pyrophosphate and 4 parts of pentaerythritol are mixed and evenly crushed to obtain a nitrogen-phosphorus composite flame retardant.

[0067] The functional additives are antioxidants and lubricants; the antioxidants are hindered phenol antioxidants and phosphite antioxidants, and the mass ratio of the antioxidants is 1:1; the hindered phenol antioxidant is antioxidant 1010; and the phosphite antioxidant is antioxidant 168.

[0068] The lubricant is EBS lubricant.

[0069] The flame retardant synergist is modified barium sulfate and modified silicon micropowder; the mass ratio of the modified barium sulfate to the modified silicon micropowder is 5:1.

[0070] The average particle size of the modified barium sulfate is 4200 mesh.

[0071] The preparation method of modified barium sulfate includes the following steps, calculated by mass: S1: 4.2 parts of barium sulfate are mixed with 10 parts of ammonia water and 60 parts of ethanol, and then the temperature is raised to 50°C and kept warm for 40 minutes; S2: 2.5 parts of tetraethyl orthosilicate and 30 parts of ethanol are mixed evenly at 55°C and added dropwise to the mixed solution of S1, and the reaction time of the addition is 2 hours; S3: 10wt% sodium hydroxide aqueous solution is added dropwise to maintain the pH at 8.5 and keep warm for 1 hour to obtain the modified barium sulfate.

[0072] The preparation method of modified silicon micropowder includes the following steps, calculated by mass: S1: 5 parts of succinic anhydride and 3 parts of (3-aminopropyl)triethoxysilane are mixed with 2 parts of silicon micropowder, and then added into 80 parts of DMF, stirred evenly, and obtained a silicon micropowder mixed solution; S2: The silicon micropowder mixed solution is heated to 65°C for 2 hours to obtain a suspension, and the precipitate is collected by centrifugation, washed and dried to obtain pretreated silicon micropowder; S3: 2 parts of pretreated silicon micropowder, 3.5 parts of chromium nitrate nonahydrate, 1.4 parts of terephthalic acid, and 0.45 parts of acetic acid are added to 60 parts of deionized water, heated to 190°C in a closed reactor, stirred for reaction for 11 hours, and then washed, filtered and dried to obtain modified silicon micropowder.

[0073] The average particle size of silica powder is 3500 mesh.

[0074] The second aspect of this embodiment provides a method for preparing the above-mentioned high temperature resistant flame retardant modified polypropylene material, and the preparation method comprises the following steps: S1: adding a polypropylene matrix, a flame retardant additive, a functional additive, and a flame retardant synergist to a high-speed mixer in sequence and mixing them evenly; S2: transferring the mixture in S1 into an extruder, extruding, cooling, and granulating to obtain a high temperature resistant flame retardant modified polypropylene material.

[0075] Example 3

[0076] Embodiment 3 The first aspect provides a high temperature resistant flame retardant modified polypropylene material, in which the raw materials include, by mass percentage: 70% polypropylene matrix, 15% flame retardant additive, 3% functional additive, and the balance of flame retardant synergist.

[0077] The polypropylene matrix is ​​a composition of copolymer polypropylene and homopolypropylene; the mass ratio of the copolymer polypropylene to the homopolypropylene is 2.5:1.5.

[0078] The copolymer polypropylene is 7032E3, the melt index of the copolymer polypropylene is 4 g / min, and the test conditions are: 230° C. / 2.16 kg.

[0079] Homopolymer polypropylene was purchased from 578N homopolymer polypropylene sold by Shanghai Hongsu Plastic Chemical Co., Ltd.

[0080] The flame retardant auxiliary agent is a nitrogen-phosphorus composite flame retardant; the preparation method of the nitrogen-phosphorus composite flame retardant, calculated by weight, comprises the following steps: S1: adding 5 parts of polyphosphoric acid to a reaction container, then adding 5 parts of melamine and 80 parts of deionized water, and stirring evenly at 120 r / min; S2: adding 3 parts of hydroquinone and 5 parts of propylene glycol, heating to 60°C, and stirring at 200 r / min for 3.5 hours;

[0081] S3: After the reaction is completed, cool to room temperature and add hydrochloric acid to adjust the pH to 6, then filter and wash to obtain a solid material; S4: 14.5 parts of the solid material, 4.5 parts of melamine pyrophosphate and 5 parts of pentaerythritol are mixed and evenly crushed to obtain a nitrogen-phosphorus composite flame retardant.

[0082] The functional additives are antioxidants and lubricants; the antioxidants are hindered phenol antioxidants and phosphite antioxidants, and the mass ratio of the antioxidants is 1:1; the hindered phenol antioxidant is antioxidant 1010; and the phosphite antioxidant is antioxidant 168.

[0083] The lubricant is EBS lubricant.

[0084] The flame retardant synergist is modified barium sulfate and modified silicon micropowder; the mass ratio of the modified barium sulfate to the modified silicon micropowder is 5:1.5.

[0085] The average particle size of the modified barium sulfate is 4000 mesh.

[0086] The preparation method of modified barium sulfate includes the following steps, measured by mass: S1: 4 parts of barium sulfate are mixed with 10 parts of ammonia water and 60 parts of ethanol, and then the temperature is raised to 50°C and kept warm for 40 minutes; S2: 2 parts of ethyl orthosilicate and 30 parts of ethanol are mixed evenly at 55°C and added dropwise to the mixed solution of S1, and the dropwise reaction time is 2 hours; S3: 10wt% sodium hydroxide aqueous solution is added dropwise to maintain the pH at 8.5 and keep warm for 1 hour to obtain the product.

[0087] The preparation method of modified silicon micropowder includes the following steps, calculated by mass: S1: 5 parts of succinic anhydride and 3 parts of (3-aminopropyl)triethoxysilane are mixed with 2 parts of silicon micropowder, and then added into 80 parts of DMF, stirred evenly, and obtained a silicon micropowder mixed solution; S2: The silicon micropowder mixed solution is heated to 65°C for 2 hours to obtain a suspension, and the precipitate is collected by centrifugation, washed and dried to obtain pretreated silicon micropowder; S3: 2 parts of pretreated silicon micropowder, 3.5 parts of chromium nitrate nonahydrate, 1.4 parts of terephthalic acid, and 0.45 parts of acetic acid are added to 60 parts of deionized water, heated to 190°C in a closed reactor, stirred for reaction for 11 hours, and then washed, filtered and dried to obtain modified silicon micropowder.

[0088] The average particle size of silica powder is 3500 mesh.

[0089] The second aspect of this embodiment provides a method for preparing the above-mentioned high temperature resistant flame retardant modified polypropylene material, and the preparation method comprises the following steps: S1: adding a polypropylene matrix, a flame retardant additive, a functional additive, and a flame retardant synergist to a high-speed mixer in sequence and mixing them evenly; S2: transferring the mixture in S1 into an extruder, extruding, cooling, and granulating to obtain a high temperature resistant flame retardant modified polypropylene material.

[0090] Comparative Example 1

[0091] Comparative Example 1 The first aspect provides a high temperature resistant flame retardant modified polypropylene material, in which the raw materials include, by mass percentage: 70% polypropylene matrix, 15% flame retardant additive, 3% functional additive, and the balance of flame retardant synergist.

[0092] The polypropylene matrix is ​​a composition of copolymer polypropylene and homopolypropylene; the mass ratio of the copolymer polypropylene to the homopolypropylene is 2.8:1.2.

[0093] The copolymer polypropylene is 7032E3, the melt index of the copolymer polypropylene is 4 g / min, and the test conditions are: 230° C. / 2.16 kg.

[0094] Homopolymer polypropylene was purchased from 578N homopolymer polypropylene sold by Shanghai Hongsu Plastic Chemical Co., Ltd.

[0095] The flame retardant auxiliary agent is a nitrogen-phosphorus composite flame retardant; the preparation method of the nitrogen-phosphorus composite flame retardant, calculated by mass, comprises the following steps: S1: adding 6 parts of polyphosphoric acid into a reaction container, and then adding 4 parts of melamine and 80 parts of deionized water, and stirring at 150 r / min; S2: adding 5 parts of hydroquinone and 4 parts of propylene glycol, heating to 60°C, and stirring at 200 r / min for 3.5 hours;

[0096] S3: After the reaction is completed, cool to room temperature and add hydrochloric acid to adjust the pH to 6, then filter and wash to obtain a solid material; S4: 14.5 parts of the solid material, 4.5 parts of melamine pyrophosphate and 5 parts of pentaerythritol are mixed and evenly crushed to obtain a nitrogen-phosphorus composite flame retardant.

[0097] The functional additives are antioxidants and lubricants; the antioxidants are hindered phenol antioxidants and phosphite antioxidants, and the mass ratio of the antioxidants is 1:1; the hindered phenol antioxidant is antioxidant 1010; and the phosphite antioxidant is antioxidant 168.

[0098] The lubricant is EBS lubricant.

[0099] The flame retardant synergist is modified barium sulfate and modified silicon micropowder; the mass ratio of the modified barium sulfate to the modified silicon micropowder is 2:1.5.

[0100] The average particle size of the modified barium sulfate is 3500 mesh.

[0101] The preparation method of modified barium sulfate includes the following steps, calculated by mass: S1: 5 parts of barium sulfate are mixed with 8 parts of ammonia water and 60 parts of ethanol, and then the temperature is raised to 50°C and kept warm for 40 minutes; S2: 1 part of ethyl orthosilicate is mixed with 15 parts of ethanol at 55°C and added dropwise to the mixed solution of S1, and the reaction time of the addition is 1 hour; S3: 10wt% sodium hydroxide aqueous solution is added dropwise to maintain the pH at 8 and keep warm for 1 hour to obtain the modified barium sulfate.

[0102] The preparation method of modified silicon micropowder includes the following steps, calculated by mass: S1: 5 parts of succinic anhydride and 3 parts of (3-aminopropyl)triethoxysilane are mixed with 2 parts of silicon micropowder, and then added into 80 parts of DMF, stirred evenly, and obtained a silicon micropowder mixed solution; S2: The silicon micropowder mixed solution is heated to 65°C for 2 hours to obtain a suspension, and the precipitate is collected by centrifugation, washed and dried to obtain pretreated silicon micropowder; S3: 2 parts of pretreated silicon micropowder, 3.5 parts of chromium nitrate nonahydrate, 1.4 parts of terephthalic acid, and 0.45 parts of acetic acid are added to 60 parts of deionized water, heated to 190°C in a closed reactor, stirred for reaction for 11 hours, and then washed, filtered and dried to obtain modified silicon micropowder.

[0103] The average particle size of silica powder is 3500 mesh.

[0104] The second aspect of this embodiment provides a method for preparing the above-mentioned high temperature resistant flame retardant modified polypropylene material, and the preparation method comprises the following steps: S1: adding a polypropylene matrix, a flame retardant additive, a functional additive, and a flame retardant synergist to a high-speed mixer in sequence and mixing them evenly; S2: transferring the mixture in S1 into an extruder, extruding, cooling, and granulating to obtain a high temperature resistant flame retardant modified polypropylene material.

[0105] Comparative Example 2

[0106] Comparative Example 2 The first aspect provides a high temperature resistant flame retardant modified polypropylene material, in which the raw materials include, by mass percentage: 70% polypropylene matrix, 15% flame retardant additive, 3% functional additive, and the balance of flame retardant synergist.

[0107] The polypropylene matrix is ​​a composition of copolymer polypropylene and homopolypropylene; the mass ratio of the copolymer polypropylene to the homopolypropylene is 2.8:1.2.

[0108] The copolymer polypropylene is 7032E3, the melt index of the copolymer polypropylene is 4 g / min, and the test conditions are: 230° C. / 2.16 kg.

[0109] Homopolymer polypropylene was purchased from 578N homopolymer polypropylene sold by Shanghai Hongsu Plastic Chemical Co., Ltd.

[0110] The flame retardant auxiliary agent is a nitrogen-phosphorus composite flame retardant; the preparation method of the nitrogen-phosphorus composite flame retardant, calculated by mass, comprises the following steps: S1: adding 6 parts of polyphosphoric acid into a reaction container, and then adding 4 parts of melamine and 80 parts of deionized water, and stirring at 150 r / min; S2: adding 5 parts of hydroquinone and 4 parts of propylene glycol, heating to 60°C, and stirring at 200 r / min for 3.5 hours;

[0111] S3: After the reaction is completed, cool to room temperature and add hydrochloric acid to adjust the pH to 6, then filter and wash to obtain a solid material; S4: 14.5 parts of the solid material, 4.5 parts of melamine pyrophosphate and 5 parts of pentaerythritol are mixed and evenly crushed to obtain a nitrogen-phosphorus composite flame retardant.

[0112] The functional additives are antioxidants and lubricants; the antioxidants are hindered phenol antioxidants and phosphite antioxidants, and the mass ratio of the antioxidants is 1:1; the hindered phenol antioxidant is antioxidant 1010; and the phosphite antioxidant is antioxidant 168.

[0113] The lubricant is EBS lubricant.

[0114] The flame retardant synergists are barium sulfate and modified silicon micropowder; the mass ratio of barium sulfate to modified silicon micropowder is 4:1.5.

[0115] The average particle size of barium sulfate is 3000 mesh.

[0116] The preparation method of modified silicon micropowder includes the following steps, calculated by mass: S1: 5 parts of succinic anhydride and 3 parts of (3-aminopropyl)triethoxysilane are mixed with 2 parts of silicon micropowder, and then added into 80 parts of DMF, stirred evenly, and obtained a silicon micropowder mixed solution; S2: The silicon micropowder mixed solution is heated to 65°C for 2 hours to obtain a suspension, and the precipitate is collected by centrifugation, washed and dried to obtain pretreated silicon micropowder; S3: 2 parts of pretreated silicon micropowder, 3.5 parts of chromium nitrate nonahydrate, 1.4 parts of terephthalic acid, and 0.45 parts of acetic acid are added to 60 parts of deionized water, heated to 190°C in a closed reactor, stirred for reaction for 11 hours, and then washed, filtered and dried to obtain modified silicon micropowder.

[0117] The average particle size of silica powder is 3500 mesh.

[0118] The second aspect of this embodiment provides a method for preparing the above-mentioned high temperature resistant flame retardant modified polypropylene material, and the preparation method comprises the following steps: S1: adding a polypropylene matrix, a flame retardant additive, a functional additive, and a flame retardant synergist to a high-speed mixer in sequence and mixing them evenly; S2: transferring the mixture in S1 into an extruder, extruding, cooling, and granulating to obtain a high temperature resistant flame retardant modified polypropylene material.

[0119] Comparative Example 3

[0120] Comparative Example 3 The first aspect provides a high temperature resistant flame retardant modified polypropylene material, in which the raw materials include, by mass percentage: 70% polypropylene matrix, 15% flame retardant additive, 3% functional additive, and the balance of flame retardant synergist.

[0121] The polypropylene matrix is ​​a composition of copolymer polypropylene and homopolypropylene; the mass ratio of the copolymer polypropylene to the homopolypropylene is 2.8:1.2.

[0122] The copolymer polypropylene is 7032E3, the melt index of the copolymer polypropylene is 4 g / min, and the test conditions are: 230° C. / 2.16 kg.

[0123] Homopolymer polypropylene was purchased from 578N homopolymer polypropylene sold by Shanghai Hongsu Plastic Chemical Co., Ltd.

[0124] The flame retardant auxiliary agent is a nitrogen-phosphorus composite flame retardant; the preparation method of the nitrogen-phosphorus composite flame retardant, calculated by mass, comprises the following steps: S1: adding 6 parts of polyphosphoric acid into a reaction container, and then adding 4 parts of melamine and 80 parts of deionized water, and stirring at 150 r / min; S2: adding 5 parts of hydroquinone and 4 parts of propylene glycol, heating to 60°C, and stirring at 200 r / min for 3.5 hours;

[0125] S3: After the reaction is completed, cool to room temperature and add hydrochloric acid to adjust the pH to 6, then filter and wash to obtain a solid material; S4: 14.5 parts of the solid material, 4.5 parts of melamine pyrophosphate and 5 parts of pentaerythritol are mixed and evenly crushed to obtain a nitrogen-phosphorus composite flame retardant.

[0126] The functional additives are antioxidants and lubricants; the antioxidants are hindered phenol antioxidants and phosphite antioxidants, and the mass ratio of the antioxidants is 1:1; the hindered phenol antioxidant is antioxidant 1010; and the phosphite antioxidant is antioxidant 168.

[0127] The lubricant is EBS lubricant.

[0128] The flame retardant synergist is modified barium sulfate and modified silicon micropowder; the mass ratio of the modified barium sulfate to the modified silicon micropowder is 4:1.5.

[0129] The average particle size of the modified barium sulfate is 4200 mesh.

[0130] The preparation method of modified barium sulfate includes the following steps, calculated by mass: S1: 4.2 parts of barium sulfate are mixed with 10 parts of ammonia water and 60 parts of ethanol, and then the temperature is raised to 50°C and kept warm for 40 minutes; S2: 2.5 parts of tetraethyl orthosilicate and 30 parts of ethanol are mixed evenly at 55°C and added dropwise to the mixed solution of S1, and the reaction time of the addition is 2 hours; S3: 10wt% sodium hydroxide aqueous solution is added dropwise to maintain the pH at 8.5 and keep warm for 1 hour to obtain the modified barium sulfate.

[0131] The preparation method of modified silicon micropowder includes the following steps, calculated by mass: S1: 5 parts of succinic anhydride and 3 parts of (3-aminopropyl)triethoxysilane are mixed with 2 parts of silicon micropowder, and then added into 80 parts of DMF, stirred evenly, and obtained a silicon micropowder mixed solution; S2: The silicon micropowder mixed solution is heated to 65°C for 2 hours to obtain a suspension, and the precipitate is collected by centrifugation, washed and dried to obtain pretreated silicon micropowder; S3: 2 parts of pretreated silicon micropowder, 2 parts of chromium nitrate nonahydrate, 0.5 parts of terephthalic acid, and 0.45 parts of acetic acid are added to 40 parts of deionized water, heated to 190°C in a closed reactor, stirred and reacted for 8 hours, and then washed, filtered and dried to obtain modified silicon micropowder.

[0132] The average particle size of silica powder is 2800 mesh.

[0133] The second aspect of this embodiment provides a method for preparing the above-mentioned high temperature resistant flame retardant modified polypropylene material, and the preparation method comprises the following steps: S1: adding a polypropylene matrix, a flame retardant additive, a functional additive, and a flame retardant synergist to a high-speed mixer in sequence and mixing them evenly; S2: transferring the mixture in S1 into an extruder, extruding, cooling, and granulating to obtain a high temperature resistant flame retardant modified polypropylene material.

[0134] Comparative Example 4

[0135] Comparative Example 4 The first aspect provides a high temperature resistant flame retardant modified polypropylene material, in which the raw materials include, by mass percentage: 70% polypropylene matrix, 15% flame retardant additive, 3% functional additive, and the balance of flame retardant synergist.

[0136] The polypropylene matrix is ​​a composition of copolymer polypropylene and homopolypropylene; the mass ratio of the copolymer polypropylene to the homopolypropylene is 2.8:1.2.

[0137] The copolymer polypropylene is 7032E3, the melt index of the copolymer polypropylene is 4 g / min, and the test conditions are: 230° C. / 2.16 kg.

[0138] Homopolymer polypropylene was purchased from 578N homopolymer polypropylene sold by Shanghai Hongsu Plastic Chemical Co., Ltd.

[0139] The flame retardant auxiliary agent is a nitrogen-phosphorus composite flame retardant; the preparation method of the nitrogen-phosphorus composite flame retardant, measured by mass, comprises the following steps: S1: adding 6 parts of polyphosphoric acid into a reaction container, then adding 4 parts of melamine and 80 parts of deionized water, and stirring evenly at 150r / min; S2: adding 5 parts of hydroquinone and 4 parts of propylene glycol, heating to 60°C, and stirring at 200r / min for 3.5h; S3: after the reaction is completed, cooling to room temperature and adding hydrochloric acid to adjust the pH to 6, then filtering and washing to obtain a solid material; S4: mixing 14.5 parts of the solid material with 4.5 parts of melamine pyrophosphate and 5 parts of pentaerythritol and pulverizing them evenly to obtain a nitrogen-phosphorus composite flame retardant.

[0140] The functional additives are antioxidants and lubricants; the antioxidants are hindered phenol antioxidants and phosphite antioxidants, and the mass ratio of the antioxidants is 1:1; the hindered phenol antioxidant is antioxidant 1010; and the phosphite antioxidant is antioxidant 168.

[0141] The lubricant is EBS lubricant.

[0142] The flame retardant synergist is modified barium sulfate and modified silicon micropowder; the mass ratio of the modified barium sulfate to the modified silicon micropowder is 4:1.5.

[0143] The average particle size of the modified barium sulfate is 4200 mesh.

[0144] The preparation method of modified barium sulfate includes the following steps, calculated by mass: S1: 4.2 parts of barium sulfate are mixed with 10 parts of ammonia water and 60 parts of ethanol, and then the temperature is raised to 50°C and kept warm for 40 minutes; S2: 2.5 parts of tetraethyl orthosilicate and 30 parts of ethanol are mixed evenly at 55°C and added dropwise to the mixed solution of S1, and the reaction time of the addition is 2 hours; S3: 10wt% sodium hydroxide aqueous solution is added dropwise to maintain the pH at 8.5 and keep warm for 1 hour to obtain the modified barium sulfate.

[0145] The preparation method of modified silicon micropowder includes the following steps, calculated by mass: S1: adding 2 parts of silicon micropowder, 3.5 parts of chromium nitrate nonahydrate, 1.4 parts of terephthalic acid, and 0.45 parts of acetic acid to 60 parts of deionized water, heating to 190°C in a closed reactor, stirring and reacting for 11 hours, then washing, filtering and drying to obtain modified silicon micropowder.

[0146] The average particle size of silica powder is 2900 mesh.

[0147] The second aspect of this embodiment provides a method for preparing the above-mentioned high temperature resistant flame retardant modified polypropylene material, and the preparation method comprises the following steps: S1: adding a polypropylene matrix, a flame retardant additive, a functional additive, and a flame retardant synergist to a high-speed mixer in sequence and mixing them evenly; S2: transferring the mixture in S1 into an extruder, extruding, cooling, and granulating to obtain a high temperature resistant flame retardant modified polypropylene material.

[0148] Morphological characterization

[0149] The morphology of the high temperature resistant flame retardant modified polypropylene material prepared in Example 1 of the present invention was characterized by scanning electron microscopy (SEM). Figure 1 It can be clearly seen that the modified barium sulfate and modified silicon powder are evenly distributed in the high temperature resistant flame retardant modified polypropylene material.

[0150] Performance Evaluation

[0151] Flame retardancy: The flame retardancy test was performed on the polypropylene materials obtained in the examples and comparative examples with reference to the UL94 standard. The test condition was 3.2 mm. The results are recorded in Table 1.

[0152] Moisture and moisture absorption resistance: The polypropylene material samples prepared in the embodiments and comparative examples were kept at 50°C and 100% humidity for 30 days before testing, and then flame retardant tests were performed according to the UL94 standard. The test conditions were 3.2 mm. If the flame retardant grade was V-0, it was qualified, otherwise it was unqualified. 100 samples were tested, and the number of qualified samples was recorded. The results are recorded in Table 1.

[0153] Mechanical properties: The tensile strength and elongation at break of the polypropylene materials obtained in the examples and comparative examples were tested with reference to ASTM-D638 standard. The samples were kept at 50°C and 100% humidity for 30 days before testing. The average values ​​of 10 times were recorded in Table 1.

[0154] Table 1 Performance test results of polypropylene materials obtained in Examples and Comparative Examples

[0155]

[0156]

[0157] From the examples of the present invention and the comparative examples and the data results in Table 1, it can be seen that the examples 1 to 3 using the specific technical solution of the present invention have achieved excellent results in terms of flame retardancy, moisture resistance and mechanical properties. However, because the comparative examples 1 to 4 do not use the specific technical solution of the present invention, the polypropylene materials obtained therefrom have poor surface waterproofness and self-stability, which ultimately affects the overall flame retardancy, and further proves the necessity of the specific technical solution of the present invention for the corresponding technical effect.

[0158] The applicant declares that the above is only a specific implementation mode of the present invention, but the protection scope of the present invention is not limited thereto. Those skilled in the art should understand that any changes or substitutions that can be easily thought of by those skilled in the art within the technical scope disclosed by the present invention shall fall within the protection scope and disclosure scope of the present invention.

Claims

1. A high temperature resistant flame retardant modified polypropylene material, characterized in that: In terms of mass percentage, the raw materials include: 50-70% of polypropylene matrix, 10-20% of flame retardant additive, 1-5% of functional additive, and the balance of flame retardant synergist; The polypropylene matrix is ​​a composition of copolymer polypropylene and homopolymer polypropylene; The mass ratio of the copolymer polypropylene to the homopolymer polypropylene is (2-4): (0.5-1.5); The melt index of the copolymerized polypropylene is 1 to 15 g / min, and the test conditions are: 230° C. / 2.16 kg; The flame retardant auxiliary agent is a nitrogen-phosphorus composite flame retardant; The preparation method of the nitrogen-phosphorus composite flame retardant comprises the following steps, calculated by mass: S1: adding 5 to 10 parts of polyphosphoric acid into a reaction container, then adding 3 to 6 parts of melamine and 60 to 80 parts of deionized water, and stirring evenly at 100 to 200 r / min; S2: adding 5 to 6 parts of hydroquinone and 3 to 4 parts of propylene glycol, heating to 50 to 60° C., and stirring at 100 to 200 r / min for 3 to 4 hours; S3: after the reaction is completed, cooling to room temperature and adding a pH regulator to adjust the pH to 6 to 6.5, then filtering and washing to obtain a solid material; S4: mixing the solid material with melamine pyrophosphate and pentaerythritol and pulverizing them evenly to obtain a nitrogen-phosphorus composite flame retardant; The flame retardant synergist is modified barium sulfate and modified silicon micropowder; the mass ratio of the modified barium sulfate and the modified silicon micropowder is (4-5): (1-2); The preparation method of the modified barium sulfate comprises the following steps: S1: mixing barium sulfate with ammonia water and ethanol, and then heating to 40-60° C. and keeping the temperature for 30-60 minutes; S2: uniformly mixing tetraethyl orthosilicate and ethanol at 50-60° C. and dripping into the mixed solution of S1, and the dripping reaction time is 2-2.5 hours; S3: dripping 10wt% sodium hydroxide aqueous solution to maintain the pH at 8-8.5 and keeping the temperature for 1-1.5 hours to obtain; The mass ratio of barium sulfate to tetraethyl orthosilicate is (3-5):(2-4); The preparation method of modified silicon micropowder comprises the following steps: S1: mixing and stirring an organic acid anhydride and a surface modifier with silicon micropowder, and then adding them together into an organic solvent and stirring them evenly to obtain a silicon micropowder mixed solution; S2: heating the silicon micropowder mixed solution to 60-70° C. and heating it for 2-2.5 hours to obtain a suspension, and centrifuging and collecting the precipitate, washing and drying it to obtain pretreated silicon micropowder; S3: adding the pretreated silicon micropowder, chromium nitrate nonahydrate, terephthalic acid, and acetic acid into deionized water, heating the mixture to 180-220° C. in a closed reactor, stirring and reacting for 6-12 hours, and then washing, filtering, and drying it to obtain modified silicon micropowder; The mass ratio of the pretreated silicon powder to chromium nitrate nonahydrate and terephthalic acid is (1-3): (3-4): (1-2.5); The average particle size of the silicon powder is 3000-4000 meshes.

2. The high temperature resistant flame retardant modified polypropylene material according to claim 1, characterized in that: The mass ratio of the solid material to melamine pyrophosphate and pentaerythritol is (10-20):(3-8):(4-6).

3. The high temperature resistant flame retardant modified polypropylene material according to claim 2, characterized in that: The mass ratio of the polypropylene matrix to the flame retardant additive is (60-68):(14-18).

4. The high temperature resistant flame retardant modified polypropylene material according to claim 3, characterized in that: The functional additive is at least one of an antioxidant, a lubricant, a dispersant, a waterproofing agent, an anti-ultraviolet agent, a stabilizer, a toughening agent, and a solubilizing agent.

5. The high temperature resistant flame retardant modified polypropylene material according to claim 4, characterized in that: The functional additives are antioxidants and lubricants; the antioxidant is at least one of hindered phenol antioxidants and phosphite antioxidants.

6. The high temperature resistant flame retardant modified polypropylene material according to claim 5, characterized in that: The mass ratio of the flame retardant auxiliary agent to the flame retardant synergist is (14-18): (8-14).

7. A method for preparing a high temperature resistant flame retardant modified polypropylene material according to any one of claims 1 to 6, characterized in that: The preparation method comprises the following steps: S1: Add polypropylene matrix, flame retardant additive, functional additive and flame retardant synergist into a high-speed mixer in sequence and mix them evenly; S2: The mixed material in S1 is transferred into an extruder for extrusion, cooling and granulation to obtain a high temperature resistant flame retardant modified polypropylene material.

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