CN107266786A - A kind of polypropylene halogen-free flame-retardant master batch and preparation method thereof - Google Patents

Abstract

The invention discloses a polypropylene halogen-free flame-retardant masterbatch and a preparation method thereof. The polypropylene halogen-free flame-retardant masterbatch adopts piperazine diphosphate, pentaerythritol diphosphate melamine salt, melamine cyanurate and triphenyl phosphate Ester constitutes a halogen-free composite flame retardant system. The flame retardant system has good flame retardant synergy and good high temperature resistance. It is not easy to be decomposed by water in the process.

Description

A kind of polypropylene halogen-free flame-retardant masterbatch and preparation method thereof

technical field

The invention relates to a polymer material processing aid and a preparation method thereof, in particular to a polypropylene halogen-free flame-retardant masterbatch and a preparation method thereof.

Background technique

Polypropylene is widely used in the manufacture of components such as electronic appliances, auto parts, and modern office supplies due to its good heat resistance, low water absorption, and high comprehensive mechanical properties. However, due to the disadvantage of flammability of polypropylene, its application in some fields is limited.

Currently used flame retardant polypropylene materials include halogen/antimony flame retardant polypropylene and halogen-free flame retardant polypropylene materials. The former type of flame-retardant polypropylene is prone to secondary disasters due to thermal cracking and a large amount of corrosive toxic gases and smoke generated during combustion. Therefore, according to the application and development trend of flame-retardant polymer materials in the international market, the use of halogen-free flame-retardant polypropylene materials is advocated, especially in the electronic appliances and auto parts industries.

At present, modified halogen-containing or halogen-free flame-retardant polypropylene materials are mainly used in the market. The production cost is high, and the flexibility of polypropylene products meeting different flame-retardant requirements is low.

Contents of the invention

One of the purposes of the present invention is to solve the above problems, to provide a simple and flexible method of use, which can meet different flame-retardant requirements for the production of polypropylene flame-retardant products, and at the same time have better flame-retardant properties, mechanical properties and water-resistant desorption properties. , a polypropylene halogen-free flame retardant masterbatch with low production cost and simple production process. The polypropylene halogen-free flame retardant masterbatch can be directly applied to the production of flame retardant polypropylene products by simply mixing with polypropylene raw materials in a certain proportion.

Another object of the present invention is to provide a method for preparing the above-mentioned polypropylene halogen-free flame-retardant masterbatch.

The polypropylene halogen-free flame retardant masterbatch to be protected in this application consists of the following components by weight: 10-30 parts of polypropylene resin, 60-80 parts of halogen-free composite flame retardant, 3-15 parts of dispersant, Composite antioxidant 0.1-0.4 parts.

The preferred polypropylene halogen-free flame retardant masterbatch to be protected in this application consists of the following components by weight: 20.72 parts of polypropylene resin, 74 parts of halogen-free composite flame retardant, 5 parts of dispersant, composite antioxidant 0.28 servings.

The halogen-free composite flame retardant of the polypropylene halogen-free flame-retardant master batch to be protected by this application consists of the following components by weight: 30-50 parts of piperazine bisphosphate, 15-25 parts of pentaerythritol diphosphate melamine salt , 8-15 parts of melamine cyanurate, and 2-6 parts of triphenyl phosphate.

The preferred halogen-free composite flame retardant of the polypropylene halogen-free flame-retardant masterbatch to be protected in this application consists of the following components by weight: 40 parts of piperazine diphosphate, 20 parts of pentaerythritol diphosphate melamine salt, melamine 10 parts of cyanurate, 4 parts of triphenyl phosphate.

The dispersant of the polypropylene halogen-free flame retardant masterbatch to be protected in this application is preferably ethylene bis fatty acid acyl compound, which is derived from the powdery product code TAS-2A produced by Suzhou Xingtai Photochemical Auxiliary Co., Ltd. agent.

The composite antioxidant of the polypropylene halogen-free flame-retardant masterbatch to be protected in this application is preferably composed of antioxidant 1076 and antioxidant DLTDP in a weight ratio of 1-4:0.3-0.7.

The preparation method of the polypropylene halogen-free flame retardant masterbatch to be protected in this application comprises the following steps:

(1) Weighing polypropylene resin, halogen-free composite flame retardant, dispersant and composite antioxidant according to the formula, and mixing them in a high-speed mixer to obtain a mixture;

(2) Melt and extrude the mixed material obtained in step (1), die-cut the extruded strip, cool and dry to obtain polypropylene halogen-free flame-retardant masterbatch.

The preferred preparation method of the polypropylene halogen-free flame retardant masterbatch to be protected in this application comprises the following steps:

(1) Weigh the polypropylene resin, halogen-free composite flame retardant, dispersant and composite antioxidant according to the formula, and mix them in a high-speed mixer until the friction heat generated by the mixing makes the temperature of the materials rise to 80°C~ 90°C, the discharged material is cooled to obtain the cooled mixture;

(2) Feed the cooled mixture into a twin-screw extruder for melt extrusion. The temperature in each zone of the twin-screw extruder is T ₁ =130-140°C, T ₂ =140-150°C, T ₃ = 150-160°C, T ₄ =170-180°C, T ₅ =180-190°C, T ₆ =190-200°C, T ₇ =190-200°C, T ₈ =200-205°C, T ₉ =190- 200°C, T _die = 180-190°C, cut the extruded strands into pellets, cool and dry to obtain polypropylene halogen-free flame retardant masterbatch.

The positive technical effect that the present invention has:

1. The polypropylene halogen-free flame-retardant masterbatch of the present invention uses piperazine diphosphate, pentaerythritol diphosphate melamine salt, melamine cyanurate and triphenyl phosphate to form a halogen-free composite flame-retardant system. The combustion system has the following advantages:

(1) Good flame retardant synergy, good flame retardant effect can be obtained with less dosage (oxygen index greater than 31%, vertical combustion V-0 level), while ensuring that the mechanical properties are not affected.

(2) Good hydrolysis resistance can be obtained without any treatment, so that the flame retardant system is not easy to hydrolysis during the molding process, thereby ensuring that the flame retardant performance is not affected.

(3) Good high temperature resistance, its thermal decomposition temperature is greater than 260°C, which ensures the stability of manufacturing and molding processing of halogen-free flame-retardant polypropylene materials.

2. The polypropylene halogen-free flame retardant of the present invention adopts the ethylene bis fatty acid acyl compound TAS-2A with high-efficiency dispersion, which ensures that the composite halogen-free flame retardant has the advantages in the manufacture and application of polypropylene flame-retardant masterbatches. Good uniform dispersion is beneficial to improve the flame retardant effect of polypropylene materials.

detailed description

Example 1

The polypropylene halogen-free flame retardant masterbatch of this embodiment is made of the following components by weight:

20.72kg of polypropylene resin, 74kg of halogen-free composite flame retardant (composed of 40kg of piperazine diphosphate, 20kg of pentaerythritol diphosphate melamine salt, 10kg of melamine cyanurate, 4kg of triphenyl phosphate), dispersed Antioxidant 5kg, compound antioxidant 0.28kg (made up of the antioxidant DLTDP of the antioxidant 1076 of 0.2kg and 0.08kg);

The preparation method of the above-mentioned polypropylene halogen-free flame retardant masterbatch has the following steps:

(1) The above-mentioned components will be weighed according to the formula, and mixed in a high-speed mixer until the friction heat generated by the mixing makes the temperature of the material rise to 80 ° C ~ 90 ° C, and the material is discharged to cool;

(2) Feed the cooled mixture into the twin-screw extruder for melt extrusion. The temperature of each zone of the twin-screw extruder is: T ₁ =130-140°C, T ₂ =140-150°C, T ₃ ＝ ₁₅₀ ～160℃, _T4 ＝170～180℃, T5＝180～190℃, _T6 ＝190～200℃, _T7 ＝190～200℃, _T8 ＝200～205℃, _T9 ＝190 ~200°C, T _die =180~190°C, the extruded strands are cut into pellets by the die head, cooled by water, and dried to obtain the polypropylene halogen-free flame retardant masterbatch.

Embodiment 2 to Embodiment 6

The preparation method of the halogen-free flame-retardant polypropylene material of each example is the same as that of Example 1, the difference lies in the weight ratio of each component, see Table 1 for details.

Table 1: each component formula of embodiment

Mix the polypropylene halogen-free flame retardant masterbatch prepared in Examples 1 to 6 with the copolymerized polypropylene resin in a ratio of 35:65, and use an injection molding machine to inject a standard sample, and the standard sample according to the national standard The mechanical properties and flame retardant properties were tested, and the test results are shown in Table 2.

Table 2: Test results of mechanical properties and flame retardant properties of Examples 1 to 6

Comparative application example

The preparation method of the halogen-free flame-retardant polypropylene material of each comparative example is the same as that of Example 1, the difference is that the prepared polypropylene halogen-free flame-retardant masterbatch and the copolymerized polypropylene resin are mixed evenly in a ratio of 40:60, and injection molding is used to The standard specimens were injection-molded by the molding machine, and the mechanical properties and flame-retardant properties of the test were shown in Table 3 for details. The application comparison test is mainly to illustrate the differences in flame retardant performance and other mechanical properties of different ratios of flame retardant masterbatch and PP.

Table 3: Test results of mechanical properties and flame retardant properties of Comparative Examples 1-6

Claims (8)

1. A polypropylene halogen-free flame retardant masterbatch, characterized in that the flame retardant masterbatch is composed of the following components by weight: 10-30 parts of polypropylene resin, 60-80 parts of halogen-free composite flame retardant parts, dispersant 3-15 parts, composite antioxidant 0.1-0.4 parts. 2. The polypropylene halogen-free flame-retardant masterbatch according to claim 1, wherein the flame-retardant masterbatch is composed of the following components by weight: 20.72 parts of polypropylene resin, halogen-free composite flame retardant 74 parts, 5 parts of dispersant, 0.28 parts of composite antioxidant. 3. The polypropylene halogen-free flame retardant masterbatch according to claim 1, wherein the halogen-free composite flame retardant is composed of the following components by weight: 30-50 parts of piperazine diphosphate, 15-25 parts of pentaerythritol diphosphate melamine salt, 8-15 parts of melamine cyanurate, and 2-6 parts of triphenyl phosphate. 4. The polypropylene halogen-free flame-retardant masterbatch according to claim 3, wherein the halogen-free composite flame retardant is composed of the following components by weight: 40 parts of piperazine diphosphate, pentaerythritol bis 20 parts of melamine phosphate, 10 parts of melamine cyanurate, and 4 parts of triphenyl phosphate. 5. The polypropylene halogen-free flame retardant masterbatch according to claim 1, characterized in that: the dispersant is ethylene bis fatty acid acyl compound. 6. The polypropylene halogen-free flame retardant masterbatch according to claim 1, characterized in that the composite antioxidant is composed of antioxidant 1076 and antioxidant DLTDP in a weight ratio of 1-4:0.3-0.7 composition. 7. The preparation method of the polypropylene halogen-free flame-retardant masterbatch according to any one of claims 1-6, characterized in that it comprises the following steps: (1) Weighing polypropylene resin, halogen-free composite flame retardant, dispersant and composite antioxidant according to the formula, and mixing them in a high-speed mixer to obtain a mixture; (2) Melt and extrude the mixed material obtained in step (1), die-cut the extruded strip, cool and dry to obtain polypropylene halogen-free flame-retardant masterbatch. 8. The preparation method of the polypropylene halogen-free flame retardant masterbatch according to claim 7, characterized in that it comprises the following steps: (1) Weigh the polypropylene resin, halogen-free composite flame retardant, dispersant and composite antioxidant according to the formula, and mix them in a high-speed mixer until the friction heat generated by the mixing makes the temperature of the materials rise to 80°C~ 90°C, the discharged material is cooled to obtain the cooled mixture; (2) Feed the cooled mixture into a twin-screw extruder for melt extrusion. The temperature in each zone of the twin-screw extruder is T ₁ =130-140°C, T ₂ =140-150°C, T ₃ = 150-160°C, T ₄ =170-180°C, T ₅ =180-190°C, T ₆ =190-200°C, T ₇ =190-200°C, T ₈ =200-205°C, T ₉ =190- 200°C, T _die = 180-190°C, cut the extruded strands into pellets, cool and dry to obtain polypropylene halogen-free flame retardant masterbatch.