WO2023098497A1 - Halogen-free high-gloss flame-retardant polystyrene material, and preparation method therefor and application thereof - Google Patents

Abstract

The present invention relates to a halogen-free high-gloss flame-retardant polystyrene material, and a preparation method therefor and an application thereof. The polystyrene material comprises the following components in parts by weight: 27-38 parts of a polyphenylether resin, 5-33 parts of a polystyrene resin, 15-20 parts of a phosphorus-based flame retardant, 5-8 parts of a nitrogen-based flame retardant, 1-5 parts of low-melting-point glass powder, 12-22 parts of a toughener, and 2-5 parts of a polyolefin graft. The polystyrene material has good flame retardance, glossiness, and toughness.

Description

A kind of halogen-free high-gloss flame-retardant polystyrene material and its preparation method and application technical field

The invention belongs to the technical field of engineering plastics, in particular to a halogen-free high-gloss flame-retardant polystyrene material and its preparation method and application.

Background technique

Polyphenylene ether (PPE) is a high-performance thermoplastic engineering plastic, non-toxic, transparent, low relative density, excellent mechanical strength, electrical properties, stress relaxation resistance, creep resistance, heat resistance, water resistance, water resistance Vapor resistance, dimensional stability. However, its melt viscosity is high, its fluidity is poor, and it is difficult to process and form, so it is difficult to use alone. At present, most of PPE is blended with polystyrene (PS) to form polyphenylene ether/polystyrene alloy, which can greatly improve processing performance, improve stress crack resistance and impact performance, and greatly reduce costs. Various excellent performances, and flame retardant can also be achieved by adding bromine-based, phosphorus-nitrogen-based flame retardants, and can be widely used in electrical appliances, auto parts, office equipment, home appliances and other fields.

However, the existing polyphenylene ether/polystyrene alloy materials are basically high-impact polystyrene (HIPS) compounded with PPE, and most of the tougheners use traditional styrene/butadiene/styrene block copolymerization. (SBS), styrene/isoprene/styrene block copolymer (SIS) and styrene/ethylene/butylene/styrene block copolymer (SEBS), etc., due to the gloss itself of HIPS and SBS It is very poor, resulting in poor appearance of the obtained alloy material, thereby limiting its application field. For example, Chinese patent CN107903608A discloses a halogen-free flame-retardant high-temperature-resistant polyphenylene ether alloy material including polyphenylene ether, polystyrene, toughening agent, compound flame retardant, thermoplastic polyimide, compatibilizer, antioxidant, Among them, the compound flame retardant is composed of phosphorus flame retardant and nitrogen flame retardant, and the toughening agent is styrene-butadiene-styrene copolymer. The alloy material has high strength, high impact resistance and high temperature resistance. , high flame retardancy and excellent comprehensiveness, but the flame retardancy of the alloy material needs to be further improved, and the appearance of the alloy material is not good.

Contents of the invention

The technical problem to be solved by the present invention is to provide a halogen-free high-gloss flame-retardant polystyrene material and its preparation method and application, so as to overcome the defects of poor flame retardancy and gloss of polyphenylene ether alloy materials in the prior art.

The invention provides a halogen-free high-gloss flame-retardant polystyrene material. The material components include:

The glass powder is a low-melting glass powder, and the melting temperature of the low-melting glass powder is 350-600°C;

The toughening agent includes one or more of ABS grafted rubber powder, ethylene-propylene-diene rubber, and acrylic resin.

Preferably, the polyphenylene ether resin includes poly(2,6-dimethyl-1,4-phenylene) ether, poly(2,6-diethyl-1,4-phenylene) ether, Poly(2,6-dipropyl-1,4-phenylene) ether, poly(2-methyl-6-ethyl-1,4-phenylene) ether, poly(2-methyl-6 - one or more of propyl-1,4-phenylene) ether, 2,6-dimethylphenol/2,3,6-trimethylphenol copolymer.

Preferably, the intrinsic viscosity of the polyphenylene ether resin is 35-45 cm ³ /g. The test standard for intrinsic viscosity is GB/T1632-1993 (30°C, chloroform solution).

Preferably, the polystyrene resin is a polymer synthesized by free radical addition polymerization of styrene monomers.

Preferably, the polystyrene resin has a melt flow rate of 6-10 g/10 min under the condition of 200° C./5 kg. The test standard for melt flow rate is ISO 1133-1-2011.

Preferably, the phosphorus-based flame retardant includes triphenyl phosphate, bisphenol A-bis(diphenyl phosphate), resorcinol-bis(diphenyl phosphate), hydroquinone bis(diphenyl Phosphate), one or more of resorcinol bis[bis(2,6-dimethylphenyl)phosphate].

Preferably, the nitrogen-based flame retardant includes tris (2-hydroxyethyl) isocyanurate, triglycidyl isocyanurate, melamine cyanurate, melamine polyphosphate, dicyandiamide, ammonium polyphosphate, One or more of amine borate and dicyandiamide formaldehyde resin.

Preferably, the particle size D50 of the low-melting point glass powder is 0.5-7 μm.

Preferably, the average rubber particle size of the toughening agent is 250-500nm. In order to achieve a high-gloss effect, a toughening agent with a reasonable rubber particle size must be selected. The average particle size is less than 200nm, and the toughening effect is not obvious. The average particle size is greater than 500nm, which will seriously affect the gloss of the material.

Preferably, the polyolefin graft includes PP grafted with maleic anhydride; the grafting rate of the maleic anhydride is 1-2%.

Preferably, the test method of the grafting rate of maleic anhydride comprises: PP grafted maleic anhydride is heated to reflux 2h with dimethylbenzene (analytically pure, commercially available), pours it into a beaker while it is hot, and uses acetone (analytical Pure, commercially available) precipitation, suction filtration, continued washing with acetone twice and suction filtration, and finally dried in a vacuum oven at 90°C for 6 hours. The refined PP grafted with maleic anhydride was placed in a 500ml Erlenmeyer flask, poured into xylene, refluxed for more than 20min until the grafts were dissolved, and added KOH/ethanol after cooling (KOH, analytically pure, commercially available; ethanol, Analytical pure, commercially available) solution, reheating and reflux until the precipitate dissolves, after cooling, use phenolphthalein as indicator (analytical pure, commercially available), and titrate the unreacted KOH with acetic acid (analytical pure, commercially available)/xylene solution , record the amount of acid consumed, and calculate the grafting rate according to the following formula:

G——grafting rate, %;

C ₁ ——concentration of KOH/ethanol standard solution, mol/L;

V ₁ ——the volume of excess KOH/ethanol standard solution added, ml;

C ₂ —concentration of acetic acid/xylene solution, mol/L;

V ₂ ——the volume of acetic acid/xylene standard solution consumed in the titration process, ml;

M—mass of refined sample of polyolefin graft, g.

Preferably, the polyphenylene ether resin is 28-35 parts by weight; the polystyrene resin is 10-30 parts by weight; the phosphorus-based flame retardant is 17-19 parts by weight; the nitrogen-based flame retardant is 6-7 parts by weight; 2-3 parts by weight of low melting point glass powder; 13-18 parts by weight of toughening agent; 3-4 parts by weight of polyolefin graft.

Preferably, the material further includes 0-2 parts of processing aids.

Preferably, the processing aids include one or more of anti-dripping agents, antioxidants, lubricants, weather-resistant agents, and colorants.

Preferably, the weight part of the anti-dripping agent is 0.1-2 parts.

Preferably, the anti-dripping agent includes one or more of polytetrafluoroethylene, polytetrafluoroethylene coated with styrene-acrylonitrile, and polytetrafluoroethylene coated with acrylate.

Preferably, the antioxidant is 0.1-1 part by weight.

Preferably, the antioxidant includes one or both of organic hindered phenolic antioxidants and phosphite antioxidants.

Preferably, the organic hindered phenolic antioxidant is antioxidant 1010 (tetrakis[methyl-β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate] pentaerythritol ester), so The phosphite antioxidant is antioxidant 168 (tris [2.4-di-tert-butylphenyl] phosphite).

Preferably, the lubricant is 0.1-2 parts by weight.

Preferably, the lubricant includes one or more of amide lubricants, stearate lubricants, ester lubricants, and silicone lubricants.

Preferably, the weight part of the weather resistance agent is 0.1-2 parts.

Preferably, the weather resistance agent includes one or more of benzophenone ultraviolet absorbers, benzotriazole ultraviolet absorbers and hindered amine light stabilizers.

Preferably, the weight part of the colorant is 0.1-2 parts.

Preferably, the colorant includes one or more of titanium dioxide, cadmium-based pigments, iron red, ultramarine blue, carbon black, phthalocyanine-based and quinacridone-based organic pigments.

The present invention also provides a method for preparing a halogen-free high-gloss flame-retardant polystyrene material, including:

(1) Mix low-melting glass powder and silicone oil at a ratio of 0.8-1.5 g: 0.3-1.2 mL to obtain a low-melting glass powder mixture;

(2) In parts by weight, 27-38 parts of polyphenylene ether resin, 5-33 parts of polystyrene resin, 15-20 parts of phosphorus-based flame retardant, 5-8 parts of nitrogen-based flame retardant, and 12 parts of toughening agent ~22 parts and 2~5 parts of polyolefin grafts are pre-mixed, and the obtained mixture is added to the twin-screw extruder, and the low-melting point glass powder mixture in step (1) is added to the twin-screw extruder, extruded and granulated , to obtain a halogen-free high-gloss flame-retardant polystyrene material, wherein the parts by weight of the low-melting point glass powder are 1-5 parts.

Preferably, 0-2 parts of processing aids are added during premixing in the step (2).

Preferably, in the step (2), the pre-mixing speed is 100-800 rpm, and the pre-mixing time is 1-6 minutes.

Preferably, in the step (2), the low-melting glass powder mixture is added to the twin-screw extruder at the fifth section of the screw barrel.

Preferably, in the step (2), the temperature of each section of the twin-screw extruder is 180-300° C., the aspect ratio is 30-45, and the screw speed is 200-500 rpm.

The present invention also provides an application of a halogen-free high-gloss flame-retardant polystyrene material in household appliances, office supplies, or information and communication appliances, such as the rear shell of a TV set, the electric control box shell of a refrigerator, and the toner cartridge assembly of a laser printer. And display case etc.

Beneficial effect

The present invention uses low-melting point glass powder to compound with phosphorus-based flame retardants and nitrogen-based flame retardants to synergistically make the flame-retardant effect of polystyrene materials reach V-0 or higher, and at the same time, low-melting point glass powder can significantly improve the performance of styrene materials. Gloss.

In the present invention, the low-melting glass powder is pre-dispersed in silicone oil, and then added into the fifth section of the screw barrel through a liquid filling pump, thereby strengthening the dispersion of the low-melting glass powder, thereby improving the synergistic flame-retardant effect and gloss of the low-melting glass powder Effect.

In the invention, there is a synergistic effect between the polyolefin graft and the toughening agent to improve the toughness of the styrene material.

Detailed ways

Below in conjunction with specific embodiment, further illustrate the present invention. It should be understood that these examples are only used to illustrate the present invention and are not intended to limit the scope of the present invention. In addition, it should be understood that after reading the teachings of the present invention, those skilled in the art can make various changes or modifications to the present invention, and these equivalent forms also fall within the scope defined by the appended claims of the present application.

Raw material source:

PPE LXR040: polyphenylene ether, intrinsic viscosity is about 38-42cm ³ /g, Nantong Xingchen Synthetic Materials Co., Ltd.;

PPE LXR050: polyphenylene ether, intrinsic viscosity is 48-53cm ³ /g, Nantong Xingchen Synthetic Materials Co., Ltd.;

GP1441: Polystyrene resin with a melt flow rate of 8g/10min (200℃/5kg, ISO 1133-1-2011), Total Corporation;

GPPS-251: Polystyrene resin with a melt flow rate of 2.4g/10min (200℃/5kg, ISO 1133-1-2011), Shanghai Secco Petrochemical Co., Ltd.;

WSFR-BDP: bisphenol A-bis(diphenyl phosphate), Zhejiang Wansheng Co., Ltd.;

WSFR-RDP: Resorcinol-bis(diphenyl phosphate), Zhejiang Wansheng Co., Ltd.;

FP-2200S: Ammonium polyphosphate, Adike Fine Chemicals (Shanghai) Co., Ltd.;

HT-211: Melamine cyanurate, Shandong Taixing New Material Co., Ltd.;

D250: Low-melting point glass powder, melting temperature 500°C, particle size D50 is about 6.5μm, Anmi Micro-Nano New Materials (Guangzhou) Co., Ltd.;

GS-1500: Low melting point glass powder, melting temperature 700℃, particle size D50 about 6.5μm, Shanggao County Mingzheng Plastic Chemical Co., Ltd.;

C4051: Low melting point glass powder, melting temperature 500℃, particle size D50 about 7.5μm, Foshan Youhe Chemical Technology Co., Ltd.;

ABS POW HR181: ABS grafted rubber powder, the average rubber particle size is 320-350nm, Korea Kumho Petrochemical Co., Ltd.;

ABS 60P: ABS grafted rubber powder, the average rubber particle size is about 300nm, Guoqiao Petrochemical Co., Ltd.;

E700N: EPDM rubber toughening agent, the average rubber particle size is 350nm, Guangzhou Runfeng Chemical Co., Ltd.;

XC640: acrylic resin, the average rubber particle size is 380-440nm, Korea Kumho Petrochemical Company;

ABS PA-757K: ABS grafted rubber powder and AS resin blend (ABS resin), Zhenjiang Chimei Chemical Co., Ltd.;

YH-792E: Styrene/butadiene/styrene block copolymer, the average rubber particle size is about 1 μm, Sinopec Baling Petrochemical Co., Ltd.;

PS 350K: high-impact polystyrene, with an average rubber particle size of 0.8-2μm, Guoqiao Petrochemical Co., Ltd.;

AP5000H: ABS grafted rubber powder, the average rubber particle size is about 200nm, Thailand Petrochemical Industry Company;

AP6007: ABS grafted rubber powder, the average rubber particle size is about 800nm, Thailand Petrochemical Industry Company;

CMG5701: PP grafted with maleic anhydride, the grafting rate of maleic anhydride is about 1.1%, Jiayirong Polymer (Shanghai) Co., Ltd.;

CMG9801: PP grafted with maleic anhydride, the grafting rate of maleic anhydride is about 0.7%, Jiayirong Polymer (Shanghai) Co., Ltd.;

PP-g-MAH-1020: PP grafted with maleic anhydride, the maleic anhydride graft ratio is about 2.3%, self-made, the method is: 100 parts by weight of polypropylene homopolymer (T30S, Fushun Ethylene Chemical Co., Ltd.), 3.5 parts by weight of maleic anhydride (maleic anhydride, Zibo Qixiang Tengda Chemical Co., Ltd.), 0.15 parts by weight of hindered phenols and phosphite antioxidants (antioxidant 1010 and antioxidant 168 mass ratio 1 :2, commercially available) and a small amount of white oil are mixed evenly, add length-to-diameter ratio through the main feeding port and be the co-rotating twin-screw extruder of 52:1; Will contain 0.2 weight part divinylbenzene (industrial grade, Wuhan Jixin Yibang Biotechnology Co., Ltd.), 0.11 parts by weight of dibenzoyl peroxide (industrial grade, Jiangsu Yuanyang Pharmaceutical Co., Ltd.) and a small amount of white oil are added from the feeding port on the side of the third section of the screw barrel in the extruder. Adjust the temperature of the reaction extruder to 190-230°C, and the rotation speed to 100-400rpm, and obtain the PP grafted maleic anhydride through traction, granulation and post-treatment processes;

POLY TS 30X: Polytetrafluoroethylene anti-dripping agent coated with styrene-acrylonitrile, Korea Pacific International Chemical Co., Ltd. (PIC);

Antioxidant: Antioxidant 1010, Antioxidant 168, commercially available;

EBS: Ethylene bis stearic acid amide lubricant, commercially available.

The preparation method of polystyrene material in embodiment 1-13,15-17 and comparative example 1-10:

(1) Mix low-melting-point glass powder with methyl silicone oil (201-10, Qingdao Zhongbao Silicon Material Technology Co., Ltd.) at a ratio of 1g: 0.6mL to obtain a low-melting-point glass powder mixture;

(2) According to the formula in Table 1, Table 2 or Table 3, add other components except low-melting point glass powder into the mixer for pre-mixing in turn, the speed is 100-800 rpm, the mixing time is 1-6 minutes, and then The mixture is delivered to the twin-screw extruder through the plunger pump, and the low-melting glass powder mixture in step (1) is added to the twin-screw extruder in the fifth section of the screw barrel through the liquid addition pump, and each section of the extruder The temperature of the screw is controlled between 180-300°C, the length-to-diameter ratio of the twin-screw extruder is 30-45, and the screw speed is 200-500 rpm. Under the shearing, mixing and conveying of the screw, the material can be fully Melting, compounding, extrusion granulation, and drying to obtain styrene materials.

The components in Example 14 were prepared according to the above-mentioned styrene material, instead of mixing methyl silicone oil with low-melting glass powder, the low-melting glass powder was directly added to the twin-screw extruder in the fifth section of the screw barrel, and the rest were The same as above-mentioned preparation method, obtain styrene material.

Styrene material in the embodiment and the comparative example is injection-molded into the standard sample bar (glossiness test adopts 100*100*2.5mm square plate test) of testing by standard size earlier, carries out each performance test by following standard then:

(1) Flame retardant grade test: thickness 2.0mm, according to the standard UL94-2018, the flame retardant grades from high to low are 5VA, V-0, V-1, V-2 and HB.

(2) Izod notched impact strength: According to the standard ISO 180-2000, the test condition is 23°C, A-type notch.

(3) Gloss: According to the standard ASTM D523-2018, the test condition is 60° angle.

Table 1 Embodiment 1-11 proportioning (parts by weight)

Table 2 Embodiment 12-17 proportioning (parts by weight)

Table 3 comparative ratio proportioning (parts by weight)

It can be seen from Table 1-3 that no nitrogen-based flame retardant was added in Comparative Example 3, no phosphorus-based flame retardant was added in Comparative Example 4, no low-melting glass powder was added in Comparative Example 5, and the polystyrene material in Comparative Example 3-5 was flame retardant The flammability is obviously lower than that of Example 1. In Comparative Example 6, ammonium polyphosphate flame retardant was used to replace the combination of phosphorus-based flame retardant and nitrogen-based flame retardant, and the flame retardancy of the polystyrene material was lower than that of Example 1. Comparative Example 10 uses glass powder with a melting temperature higher than 600° C., and its flame retardancy is lower than that of Example 1. It can be seen that the compounding of low-melting point glass powder, phosphorus-based flame retardants and nitrogen-based flame retardants can synergistically improve the flame-retardant effect, and the flame-retardant effect can reach V-0 level or above, so as to meet the needs of TV rear shells and router shells. The needs of the household appliances industry and the office supplies industry such as the front panel of the optical printer. Comparative Example 5 does not add low melting point glass powder, the glossiness is obviously lower than that of Example 1, and the glossiness cannot reach more than 70, which cannot meet the requirements of household appliances industries such as TV rear casings, router casings, and office supplies industries such as optical printer front panels. need.

In the preparation method of Example 14, the low-melting point glass powder is not pre-dispersed in methyl silicone oil, and the flame retardancy and toughness of the prepared polystyrene material are lower than that of Example 1. It can be seen that methyl silicone oil will strengthen the dispersion of low melting point glass, thereby improving the synergistic flame retardant effect and gloss effect of low melting point glass powder.

In Comparative Example 1, PP grafted maleic anhydride was not added, and in Comparative Example 2, no toughening agent was added. The notched Izod impact strength of the polystyrene material in Comparative Example 1 and Comparative Example 2 was significantly lower than that of Example 1. It can be seen that the combination of PP grafted maleic anhydride and toughening agent can synergistically increase the toughness of styrene materials, and the notched impact strength of the cantilever beam can reach ^more than 7.0kJ/m2, so as to meet the needs of TV rear shells, routers, etc. Housing and other household appliances industry and optical printer front panel and other office supplies industry demand.

Comparative Example 7 was toughened with general-purpose ABS resin, and Comparative Examples 8 and 9 used conventional toughening agents. The polystyrene material had poor toughness and average gloss. The reason may be that the general-purpose ABS has poor compatibility with the base resin. .

Claims (10)

1. A halogen-free high-gloss flame-retardant polystyrene material, characterized in that the material components include:

   

   The glass powder is a low-melting glass powder, and the melting temperature of the low-melting glass powder is 350-600°C;

   The toughening agent includes one or more of ABS grafted rubber powder, ethylene-propylene-diene rubber, and acrylic resin.
2. The polystyrene material according to claim 1, wherein the polyphenylene ether resin comprises poly(2,6-dimethyl-1,4-phenylene) ether, poly(2,6-bis Ethyl-1,4-phenylene) ether, poly(2,6-dipropyl-1,4-phenylene) ether, poly(2-methyl-6-ethyl-1,4-phenylene) phenyl) ether, poly(2-methyl-6-propyl-1,4-phenylene) ether, 2,6-dimethylphenol/2,3,6-trimethylphenol copolymer One or several kinds; the intrinsic viscosity of polyphenylene ether resin is 35-45 cm ³ /g; the melt flow rate of polystyrene resin under the condition of 200°C/5kg is 6-10g/10min.
3. The polystyrene material according to claim 1, wherein the phosphorus-based flame retardant comprises triphenyl phosphate, bisphenol A-bis(diphenyl phosphate), resorcinol-bis(diphenyl phosphate) phenyl ester), hydroquinone bis (diphenyl phosphate), resorcinol bis [bis (2,6-dimethylphenyl) phosphate] or one or more; nitrogen flame retardant Agents include tris (2-hydroxyethyl) isocyanurate, triglycidyl isocyanurate, melamine cyanurate, melamine polyphosphate, dicyandiamide, ammonium polyphosphate, amine borate, dicyandiamide formaldehyde resin one or more of.
4. The polystyrene material according to claim 1, characterized in that, the particle size D50 of the low-melting point glass powder is 0.5-7 μm; the average rubber particle size of the toughening agent is 250-500 nm.
5. The polystyrene material according to claim 1, wherein the polyolefin graft comprises PP grafted with maleic anhydride; the grafting rate of the maleic anhydride is 1-2%.
6. The polystyrene material according to claim 1, wherein the weight portion of the polyphenylene ether resin is 28 to 35 parts; the weight portion of the polystyrene resin is 10 to 30 parts; the weight portion of the phosphorus-based flame retardant is 17-19 parts by weight; 6-7 parts by weight of nitrogen-based flame retardant; 2-3 parts by weight of low-melting glass powder; 13-18 parts by weight of toughening agent; 3 parts by weight of polyolefin graft ~ 4 servings.
7. The polystyrene material according to claim 1, characterized in that, the material also includes 0 to 2 parts of processing aids; the processing aids include anti-dripping agents, antioxidants, lubricants, weather-resistant agents, One or more of the colorants.
8. A method for preparing a halogen-free high-gloss flame-retardant polystyrene material according to any one of claims 1 to 6, comprising:

   (1) Mix low-melting glass powder and silicone oil at a ratio of 0.8-1.5 g: 0.3-1.2 mL to obtain a low-melting glass powder mixture;

   (2) In parts by weight, 27-38 parts of polyphenylene ether resin, 5-33 parts of polystyrene resin, 15-20 parts of phosphorus-based flame retardant, 5-8 parts of nitrogen-based flame retardant, and 12 parts of toughening agent ~22 parts and 2~5 parts of polyolefin grafts are pre-mixed, and the obtained mixture is added to the twin-screw extruder, and the low-melting point glass powder mixture in step (1) is added to the twin-screw extruder, extruded and granulated , to obtain a halogen-free high-gloss flame-retardant polystyrene material, wherein the parts by weight of the low-melting point glass powder are 1-5 parts.
9. The preparation method according to claim 8, characterized in that 0 to 2 parts of processing aids are added during pre-mixing in the step (2); the low melting point glass powder mixture is added to the twin-screw extruder in the fifth section of the screw extruder. Barrel; the screw temperature of each section of the twin-screw extruder is 180-300°C, the aspect ratio is 30-45, and the screw speed is 200-500 rpm.
10. An application of the polystyrene material according to any one of claims 1 to 6 in household appliances, office supplies or information and communication appliances.