CN110894331A - Environment-friendly low-smoke flame-retardant HIPS material and preparation method thereof - Google Patents

Abstract

The invention provides an environment-friendly low-smoke flame-retardant HIPS material and a preparation method thereof, which are characterized by comprising the following raw materials by weight: HIPS resin: 60-85 parts; bis (4-allyloxy-3, 5-dibromophenyl) sulfone: 6-15 parts; a compound of antimony trioxide and molybdenum trioxide: 3-7 parts; an organic silicon toughening agent: 3-15 parts; ferrocenealkynone: 3-6 parts; lubricant: 0.1-1 part; antioxidant: 0.1-2 parts. The environment-friendly low-smoke flame-retardant HIPS material has a good low-smoke flame-retardant effect.

Description

Environment-friendly low-smoke flame-retardant HIPS material and preparation method thereof

Technical Field

The invention relates to the technical field of polymer modification, in particular to an environment-friendly low-smoke flame-retardant HIPS material and a preparation method thereof.

Background

Polystyrene is the third major variety of general-purpose plastics, has the advantages of transparency, good formability, good rigidity, easy dyeing, low moisture absorption, low price and the like, and is widely applied to the industries of packaging, electronics, buildings, automobile household appliances, instruments, daily necessities, toys and the like. But polystyrene is brittle and has low impact strength. Therefore, increasing the toughness has been an important issue for PS modification. In addition, polystyrene is a flammable material. Therefore, it is usually necessary to add a certain amount of flame retardant to impart good flame retardant properties to the material. However, since the styrene polymer contains benzene rings and unsaturated double bonds, a large amount of smoke is generated during combustion, and although the halogen-antimony flame retardant material can resist flame, the smoke generation amount is much higher. At present, the high polymer material has gone into every corner of our life, and our clothes and people can not leave the high polymer material, but the high polymer material brings convenience to our lives and brings an unstable factor. In use, it has been found that the main factor responsible for the mass casualties of a fire incident is the mass production of smoke during combustion, rather than a fire. The generation of smoke and toxic gas can not only cause oxygen deficiency asphyxia, but also cause low visibility in dangerous areas, is not beneficial to rescue, and causes casualties and property loss. Therefore, the development of an environment-friendly low-smoke flame-retardant HIPS material is very important, and the material has a huge market space.

Disclosure of Invention

The invention aims to provide an environment-friendly low-smoke flame-retardant HIPS material and a preparation method thereof. The environment-friendly low-smoke flame-retardant HIPS material has a good low-smoke flame-retardant effect.

In order to achieve the purpose, the invention provides an environment-friendly low-smoke flame-retardant HIPS material which comprises the following raw materials in parts by weight: HIPS resin: 60-85 parts; bis (4-allyloxy-3, 5-dibromophenyl) sulfone: 6-15 parts; a compound of antimony trioxide and molybdenum trioxide: 3-7 parts; an organic silicon toughening agent: 3-15 parts; ferrocenealkynone: 3-6 parts; lubricant: 0.1-1 part; antioxidant: 0.1-2 parts;

the HIPS resin is high impact polystyrene, and the melt flow rate is 3 at 200 ℃ and 5kg6g/10min, notched Izod impact Strength>9kJ/m²。

The HIPS material has a good low-smoke flame-retardant effect. The resin of the present invention is High Impact Polystyrene (HIPS) which is produced by adding polybutyl rubber particles to polystyrene, wherein micron-sized rubber particles are added to the polystyrene product in order to link the polystyrene and the rubber particles together. Polystyrene belongs to the group of polyolefins and is obtained by radical polymerization of styrene. The invention selects the bis (4-allyloxy-3, 5-dibromophenyl) sulfone as the flame retardant, and the bis (4-allyloxy-3, 5-dibromophenyl) sulfone and the polystyrene simultaneously contain unsaturated double bonds, so that the bis (4-allyloxy-3, 5-dibromophenyl) sulfone can be better dissolved and diffused in the polystyrene, an overall effective filling of polystyrene is formed, especially with a melting point of 180 ℃ and the resin processing temperature in the present invention is 180 ℃ to 230 ℃, before which the bis (4-allyloxy-3, 5-dibromophenyl) sulfone has melted to a homogeneous dispersion, therefore, the flame retardant is miscible with the HIPS material, does not delaminate or suck out, can be firmly keyed into the HIPS resin matrix, and has better flame retardant effect and less smoke generation. In order to further retard flame and smoke, the invention adds a compound of antimony trioxide and molybdenum trioxide as a flame-retardant synergist. Since polystyrene in High Impact Polystyrene (HIPS) is polymerized by free radicals, toxic smoke generating substances such as benzene and toluene are generated once combustion occurs, molybdenum trioxide promotes the production of a carbon layer and reduces the smoke amount by Lewis acid, and the addition of molybdenum trioxide is helpful for forming a relatively stable pi-aromatic complex and reducing the production of benzene and toluene, thereby reducing the smoke amount; and the antimony trioxide forms a molten state at the initial combustion stage of the HIPS material, so that a protective film is formed on the surface of the HIPS material to isolate air, the combustion temperature is reduced through internal endothermic reaction, the antimony trioxide can be gasified at high temperature, the oxygen concentration in the air is diluted, the flame retardant effect is achieved, and the smoke generation amount is reduced again. In addition, the molybdenum trioxide and the antimony trioxide belong to inorganic substances, the molybdenum trioxide and the antimony trioxide have better compatibility, the compounding and combination are more stable, and the molybdenum trioxide and the antimony trioxide are compounded to play a role of a flame retardant synergist and also play a role of a smoke suppressant. In addition, the invention also adds ferroceneacetylenic ketone as a smoke suppressant, the addition of the bis (4-allyloxy-3, 5-dibromophenyl) sulfone has the effects of smoke suppression and flame retardance, but smoke is generated when the ferrocene acetylenic ketone burns, and the ferrocene acetylenic ketone can form FeX4(X is halogen) with the bis (4-allyloxy-3, 5-dibromophenyl) sulfone during the combustion process of the bis (4-allyloxy-3, 5-dibromophenyl) sulfone to promote carbonization, so that the bis (4-allyloxy-3, 5-dibromophenyl) sulfone is subjected to flame retardance and smoke suppression. Through the synergistic cooperation of the compound of bis (4-allyloxy-3, 5-dibromophenyl) sulfone, antimony trioxide and molybdenum trioxide and ferrocene alkynone, the HIPS material has a better low-smoke flame retardant effect.

Further, the ratio of the antimony trioxide to the molybdenum trioxide in the compound of the antimony trioxide and the molybdenum trioxide is 3: 1-1: 3.

Further, the organic silicon toughening agent is polysiloxane rubber.

Further, the lubricant is silicone oil.

Further, the antioxidant is a phenolic antioxidant.

Further, the phenolic antioxidant is one or a mixture of more of 2, 4, 6-tri-tert-butylphenol, 4-methyl-6-tert-butylphenol and pentaerythritol tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ].

Preferably, the raw materials comprise the following weight portions: HIPS resin: 65-80 parts; bis (4-allyloxy-3, 5-dibromophenyl) sulfone: 8-13 parts; a compound of antimony trioxide and molybdenum trioxide: 4-6 parts; an organic silicon toughening agent: 6-12 parts; ferrocenealkynone: 4-5 parts; lubricant: 0.2-0.8 part; antioxidant: 0.2 to 1.8 portions.

On the other hand, the invention also provides a preparation method of the environment-friendly low-smoke flame-retardant HIPS material, which comprises the following steps:

step 1: adding HIPS resin, bis (4-allyloxy-3, 5-dibromophenyl) sulfone, a compound of antimony trioxide and molybdenum trioxide, an organosilicon toughening agent, ferrocene alkynone, a lubricant and an antioxidant into a high-speed mixer according to a ratio, and mixing for 10-60 minutes to obtain a mixture;

step 2: conveying the mixture obtained in the step 1 into a double-screw extruder for shearing and mixing to obtain a mixture in a molten state, wherein the temperature of each section of screw of the double-screw extruder is 180-230 ℃, the length-diameter ratio of the double-screw extruder is 25-40, and the rotating speed of the screw is 200-800 revolutions per minute;

and step 3: extruding, granulating and drying the mixture in the molten state in the step 2 to obtain a granular environment-friendly low-smoke flame-retardant HIPS material;

and 4, step 4: adding the granular environment-friendly low-smoke flame-retardant HIPS material obtained in the step 3 into an injection molding machine to be processed into sample strips, wherein the injection molding conditions are as follows: the temperature of the charging barrel is 190 ℃ and 240 ℃, the temperature of the die is 60-70 ℃, and the injection pressure is 6-10 MPa.

Further, in the step 2, the temperature of each section of the screw of the twin-screw extruder is 190-210 ℃, the length-diameter ratio of the twin-screw extruder is 30-35, and the rotation speed of the screw is 400-.

The toughness of the invention is effectively improved. High Impact Polystyrene (HIPS) resins are inherently brittle and have low impact strength. Therefore, the organic silicon toughening agent is added, and the polysiloxane rubber can play three roles in the formula, wherein the first role is as follows: under the impact of external force, the rubber in the multipolymer can keep good deformation and movement capability, and can still initiate a large amount of silver lines and shear bands on the HIPS matrix, thereby improving the toughness of the material. Secondly, smoke suppression: upon combustion, the organosilicon-rich layer formed upon migration of the organosilicon to the surface of the material produces an inorganic oxygen-and heat-insulating protective layer containing Si bonds and/or Si-C bonds, which is characteristic of polysiloxanes. This not only prevents the combustion decomposition product from escaping, but also inhibits the thermal decomposition of the high molecular material, and achieves the purposes of flame retardance, low smoke, low toxicity, etc. Thirdly, scratch resistance: migration of the silicone to the surface can improve the stick-slip behavior of the material, thereby enhancing the scratch resistance of the material.

The lubricant is silicone oil; the addition of the silicone oil can improve the lubricating effect of the material and also play a role in smoke suppression and scraping resistance.

The phenolic antioxidant suitable for the system is 2, 4, 6-tri-tert-butylphenol, 2 methylene bis (4-methyl-6-tert-butylphenol) or tetra [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester, and the antioxidant is added for the purposes of improving the thermal stability of the composite material and preventing the composite material from being degraded in the processes of extrusion granulation or injection molding of a product and improving the long-term aging resistance of the composite.

The invention has the advantages and positive effects that:

(1) the invention relates to an environment-friendly low-smoke flame-retardant HIPS material; in the formula, except that the ferrocenyl alkynone has a smoke suppression effect, the compound of bis (4-allyloxy-3, 5-dibromophenyl) sulfone, the organosilicon toughening agent, antimony trioxide and molybdenum trioxide and the lubricant have the smoke suppression effect, so that the components cooperate to suppress smoke, and the smoke density of the material is extremely low; the smoke density is reduced by 70 percent compared with the commercial flame-retardant HIPS.

(2) Through tests, the flame retardant grade of the environment-friendly low-smoke flame-retardant HIPS material reaches V-0 grade, and the HIPS material has the characteristics of excellent mechanical property, low smoke density, high elongation at break, high oxygen index, scratch resistance and the like.

(3) The environment-friendly low-smoke flame-retardant HIPS material is simple and easy to prepare, easy to process and very suitable for popularization and application in the fields of household appliances, electric appliances and instruments, building industry, traffic industry, security industry and the like.

The preparation components and content of the environment-friendly low-smoke flame-retardant HIPS material are selected, and the beneficial effects of the preparation method of the environment-friendly low-smoke flame-retardant HIPS material are described by giving specific experimental data through embodiments.

Detailed Description

Unless defined otherwise, technical terms used in the following examples have the same meanings as commonly understood by one of ordinary skill in the art to which the present invention belongs. The test reagents used in the following examples, unless otherwise specified, are all conventional biochemical reagents; the experimental methods are conventional methods unless otherwise specified. The invention is described in detail below with reference to the following examples and accompanying tables.

In the invention, the HIPS is selected from the Yashi-De HIPS MA 5210; the antimony trioxide is S-05N of Yunnan Murray antimony industry Co., Ltd, and the molybdenum trioxide is molybdenum trioxide of Xingbang molybdenum industry; the organic silicon toughening agent selects acrylic acid-polysiloxane rubber-acrylonitrile styrene multipolymer, and the specific mark is Tailong chemical S-1720; the lubricant is silicone oil; the antioxidant is a blend of 1010 and 168 of basf.

Example 1: step 1: HIPS resin, bis (4-allyloxy-3, 5-dibromophenyl) sulfone, a compound of antimony trioxide and molybdenum trioxide, acrylic acid-polysiloxane rubber-acrylonitrile styrene multipolymer, ferrocenyl acetylenic ketone, a lubricant and an antioxidant are added into a high-speed mixer according to the proportion and mixed to obtain a mixture, the mixing time is 10 minutes, and the specific component proportion is shown in Table 1. Step 2: and (3) conveying the mixture obtained in the step (1) into a double-screw extruder for shearing and mixing to obtain a mixture in a molten state, wherein the temperature of each section of screw of the double-screw extruder is 180 ℃, the length-diameter ratio of the double-screw extruder is 30, and the rotating speed of the screw is 600 revolutions per minute. And step 3: and (3) extruding, granulating and drying the mixture in the molten state in the step (2) to obtain the granular environment-friendly low-smoke flame-retardant HIPS material. And 4, step 4: adding the granular environment-friendly low-smoke flame-retardant HIPS material obtained in the step 3 into an injection molding machine to be processed into sample strips, wherein the injection molding conditions are as follows: the charging barrel temperature is 200 ℃, the die temperature is 70 ℃, and the injection molding pressure is 10 MPa.

Example 2: step 1: HIPS resin, bis (4-allyloxy-3, 5-dibromophenyl) sulfone, a compound of antimony trioxide and molybdenum trioxide, acrylic acid-polysiloxane rubber-acrylonitrile styrene multipolymer, ferrocenyl acetylenic ketone, a lubricant and an antioxidant are added into a high-speed mixer according to the proportion and mixed to obtain a mixture, the mixing time is 50 minutes, and the specific component proportion is shown in Table 1. Step 2: and (3) conveying the mixture obtained in the step (1) into a double-screw extruder for shearing and mixing to obtain a mixture in a molten state, wherein the temperature of each section of screw of the double-screw extruder is 220 ℃, the length-diameter ratio of the double-screw extruder is 40, and the rotating speed of the screw is 800 revolutions per minute. And step 3: and (3) extruding, granulating and drying the mixture in the molten state in the step (2) to obtain the granular environment-friendly low-smoke flame-retardant HIPS material. And 4, step 4: adding the granular environment-friendly low-smoke flame-retardant HIPS material obtained in the step 3 into an injection molding machine to be processed into sample strips, wherein the injection molding conditions are as follows: the temperature of the charging barrel is 220 ℃, the temperature of the die is 70 ℃, and the injection pressure is 6 MPa.

Example 3: step 1: HIPS resin, bis (4-allyloxy-3, 5-dibromophenyl) sulfone, a compound of antimony trioxide and molybdenum trioxide, acrylic acid-polysiloxane rubber-acrylonitrile styrene multipolymer, ferrocenyl acetylenic ketone, a lubricant and an antioxidant are added into a high-speed mixer according to the proportion and mixed to obtain a mixture, the mixing time is 30 minutes, and the specific component proportion is shown in Table 1. Step 2: and (3) conveying the mixture obtained in the step (1) into a double-screw extruder for shearing and mixing to obtain a mixture in a molten state, wherein the temperature of each section of screw of the double-screw extruder is 180 ℃, the length-diameter ratio of the double-screw extruder is 40, and the rotating speed of the screw is 500 revolutions per minute. And step 3: and (3) extruding, granulating and drying the mixture in the molten state in the step (2) to obtain the granular environment-friendly low-smoke flame-retardant HIPS material. And 4, step 4: adding the granular environment-friendly low-smoke flame-retardant HIPS material obtained in the step 3 into an injection molding machine to be processed into sample strips, wherein the injection molding conditions are as follows: the charging barrel temperature is 200 ℃, the die temperature is 60 ℃, and the injection molding pressure is 10 MPa.

Example 4: step 1: HIPS resin, bis (4-allyloxy-3, 5-dibromophenyl) sulfone, a compound of antimony trioxide and molybdenum trioxide, an acrylic acid-polysiloxane rubber-acrylonitrile styrene multipolymer, ferrocenyl acetylenic ketone, a lubricant and an antioxidant are added into a high-speed mixer according to the proportion and mixed to obtain a mixture, the mixing time is 20 minutes, and the specific component proportion is shown in Table 1. Step 2: and (3) conveying the mixture obtained in the step (1) into a double-screw extruder for shearing and mixing to obtain a mixture in a molten state, wherein the temperature of each section of screw of the double-screw extruder is 230 ℃, the length-diameter ratio of the double-screw extruder is 40, and the rotating speed of the screw is 300 revolutions per minute. And step 3: and (3) extruding, granulating and drying the mixture in the molten state in the step (2) to obtain the granular environment-friendly low-smoke flame-retardant HIPS material. And 4, step 4: adding the granular environment-friendly low-smoke flame-retardant HIPS material obtained in the step 3 into an injection molding machine to be processed into sample strips, wherein the injection molding conditions are as follows: the charging barrel temperature is 200 ℃, the die temperature is 60 ℃, and the injection molding pressure is 8 MPa.

Comparative example 1: step 1: the HIPS resin, the compound of bis (4-allyloxy-3, 5-dibromophenyl) sulfone, antimony trioxide and molybdenum trioxide and the antioxidant are added into a high-speed mixer according to the proportion and mixed to obtain a mixture, the mixing time is 20 minutes, and the specific component proportion is shown in Table 1. Step 2: and (3) conveying the mixture obtained in the step (1) into a double-screw extruder for shearing and mixing to obtain a mixture in a molten state, wherein the temperature of each section of screw of the double-screw extruder is 190 ℃, the length-diameter ratio of the double-screw extruder is 25, and the rotating speed of the screw is 200 revolutions per minute. And step 3: and (3) extruding, granulating and drying the mixture in the molten state in the step (2). And 4, step 4: adding the HIPS material extruded, granulated and dried in the step 3 into an injection molding machine to be processed into sample strips, wherein the injection molding conditions are as follows: the temperature of the charging barrel is 240 ℃, the temperature of the die is 50 ℃, and the injection pressure is 10 MPa.

The products obtained in the examples and the comparative examples are tested for relevant properties by adopting an ISO standard; the UL-94 vertical burner used to test the flame retardant rating was ATLAS HVUL-2, USA; the plastic particles prepared in the above examples and comparative examples were injection molded into test standard specimens in standard sizes, and performance tests were performed according to the test standards, and the test results are shown in Table 1.

TABLE 1 specific ratios of components and performance test data for examples and comparative examples

As can be seen from the test results of the examples and comparative examples in Table 1, the smoke density of the example HIPS material is very low and can be reduced by 70% at the minimum while maintaining higher toughness as compared with the comparative example 1. From example 2, it can be seen that when the ratio of bis (4-allyloxy-3, 5-dibromophenyl) sulfone to ferroceneynone is 4:1, the two act synergistically and have lower smoke density. The environment-friendly low-smoke flame-retardant HIPS material can be applied to household appliances, electric appliances and instruments, the building industry, the traffic industry, the security industry and the like.

The above description is only for the purpose of illustrating the preferred embodiments of the present invention and should not be taken as limiting the invention, so that any modifications, equivalents, improvements and the like, which are within the spirit and principle of the present invention, should be included in the scope of the present invention.

Claims (9)

1. An environment-friendly low-smoke flame-retardant HIPS material is characterized by comprising the following raw materials by weight: HIPS resin: 60-85 parts; bis (4-allyloxy-3, 5-dibromophenyl) sulfone: 6-15 parts; a compound of antimony trioxide and molybdenum trioxide: 3-7 parts; an organic silicon toughening agent: 3-15 parts; ferrocenealkynone: 3-6 parts; lubricant: 0.1-1 part; antioxidant: 0.1-2 parts;

the HIPS resin is high impact polystyrene, the melt flow rate is 3-6g/10min under the conditions of 200 ℃ and 5kg, and the notched impact strength of a cantilever beam>9kJ/m²。

2. The environment-friendly low-smoke flame-retardant HIPS material as set forth in claim 1, wherein the ratio of the antimony trioxide to the molybdenum trioxide in the compound of the antimony trioxide and the molybdenum trioxide is 3: 1-1: 3.

3. The environment-friendly, low-smoke, flame-retardant HIPS material of claim 1, wherein the organosilicon toughening agent is a polysiloxane rubber.

4. The environment-friendly, low-smoke, flame-retardant HIPS material of claim 1, wherein the lubricant is silicone oil.

5. The environment-friendly, low-smoke, flame-retardant HIPS material of claim 1, wherein the antioxidant is a phenolic antioxidant.

6. The environment-friendly, low-smoke and flame-retardant HIPS material as set forth in claim 5, wherein the phenolic antioxidant is one or a mixture of 2, 4, 6-tri-tert-butylphenol, 4-methyl-6-tert-butylphenol, and pentaerythritol tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ].

7. The environment-friendly low-smoke flame-retardant HIPS material as set forth in claim 6, which comprises the following raw materials by weight: HIPS resin: 65-80 parts; bis (4-allyloxy-3, 5-dibromophenyl) sulfone: 8-13 parts; a compound of antimony trioxide and molybdenum trioxide: 4-6 parts; an organic silicon toughening agent: 6-12 parts; ferrocenealkynone: 4-5 parts; lubricant: 0.2-0.8 part; antioxidant: 0.2 to 1.8 portions.

8. A method for preparing the environment-friendly low-smoke flame-retardant HIPS material as defined in any one of claims 1 to 7, wherein: the method comprises the following steps:

step 1: adding HIPS resin, bis (4-allyloxy-3, 5-dibromophenyl) sulfone, a compound of antimony trioxide and molybdenum trioxide, an organosilicon toughening agent, ferrocene alkynone, a lubricant and an antioxidant into a high-speed mixer according to a ratio, and mixing for 10-60 minutes to obtain a mixture;

step 2: conveying the mixture obtained in the step 1 into a double-screw extruder for shearing and mixing to obtain a mixture in a molten state, wherein the temperature of each section of screw of the double-screw extruder is 180-230 ℃, the length-diameter ratio of the double-screw extruder is 25-40, and the rotating speed of the screw is 200-800 revolutions per minute;

and step 3: extruding, granulating and drying the mixture in the molten state in the step 2 to obtain a granular environment-friendly low-smoke flame-retardant HIPS material;

and 4, step 4: adding the granular environment-friendly low-smoke flame-retardant HIPS material obtained in the step 3 into an injection molding machine to be processed into sample strips, wherein the injection molding conditions are as follows: the temperature of the charging barrel is 190 ℃ and 240 ℃, the temperature of the die is 60-70 ℃, and the injection pressure is 6-10 MPa.

9. The method for preparing the environment-friendly low-smoke flame-retardant HIPS material as claimed in claim 8, wherein: in the step 2, the temperature of each section of the screw of the double-screw extruder is 190-210 ℃, the length-diameter ratio of the double-screw extruder is 30-35, and the rotation speed of the screw is 400-600 revolutions per minute.