A weather-resistant and flame-retardant reinforced ABS polymer and its preparation method

Abstract

This invention relates to a weather-resistant, flame-retardant reinforced ABS polymer and its preparation method. The ABS polymer components, by weight, include: 29-57 parts ABS resin; 10-35 parts glass fiber surface-treated with 2,3-dibromosuccinic anhydride; 3-8 parts toughening agent; 18-25 parts flame retardant; and 3-10 parts flame retardant synergist. This ABS polymer exhibits good initial impact strength and flame retardancy, as well as good retention of impact strength and flame retardancy after aging.

Description

Technical Field

[0001] This invention belongs to the field of general plastics, and specifically relates to a weather-resistant and flame-retardant reinforced ABS polymer and its preparation method. Background Technology

[0002] Styrene-butadiene-acrylonitrile (ABS) resin combines the rigidity and heat resistance of acrylonitrile, the gloss and processability of polystyrene, and the impact resistance of polybutadiene. It is widely used in household appliances, office equipment, instruments, transportation, building materials, daily necessities, and packaging materials. To further expand its applications, researchers have modified ABS materials in various ways, such as using glass fiber reinforcement to further improve the strength and heat resistance of the composite material; adding flame retardants to impart fire-resistant properties; and adding heat-resistant agents to improve the heat resistance of ABS materials, etc.

[0003] In recent years, with increasingly stringent safety regulations in the home appliance and electronics industries, especially for certain outdoor components, higher requirements have been placed on the long-term performance of ABS materials, such as toughness and flame retardancy. For example, air conditioner outdoor unit components require that after 1000 hours of xenon lamp aging, key performance indicators, such as notched impact strength, retain at least 75% of their performance before and after aging, and the flame retardancy rating must not decrease. However, ABS itself has generally poor weather resistance. Adding flame retardants and glass fiber further reduces the material's weather resistance, making it prone to decreased toughness and flame retardancy instability due to issues such as flame retardant dispersion and the "wick effect" of glass fiber after long-term aging. Summary of the Invention

[0004] The technical problem to be solved by the present invention is to provide a weather-resistant and flame-retardant reinforced ABS polymer and its preparation method, so as to overcome the defects of poor toughness and flame retardancy of ABS materials after aging in the prior art.

[0005] This invention provides a weather-resistant and flame-retardant reinforced ABS polymer, wherein the ABS polymer components comprise, by weight parts:

[0006] The toughening agent is chlorinated polyethylene;

[0007] The flame retardant is an EP-type brominated epoxy.

[0008] Preferably, the ABS polymer component comprises, by weight parts:

[0009]

[0010]

[0011] Preferably, the D50 particle size of the ABS resin rubber is 650-1500 nm. The D50 particle size of this rubber in the ABS polymer is the same as that of the raw ABS rubber. Since the main function of the twin-screw extruder is macroscopic plasticization and dispersion of different materials, it has virtually no impact on the microscopic rubber phase with a particle size of only 650-1500 nm. Therefore, after extrusion by the twin-screw extruder, the rubber diameter remains essentially unchanged. The particle size testing method is as follows: Take 3-4 ABS resin particles, dissolve them in 10 mL of DMF, sonicate for 15 min, and after the particles are completely dissolved, drop them into the sample cell of a JL9200 laser particle size analyzer and record the particle size test results.

[0012] Preferably, the butadiene weight percentage in the ABS resin is 19%-35%. The method for testing the butadiene weight percentage is as follows: Weigh approximately 10g of ABS resin, add 50-100ml of acetone, shake on a HY-200 type variable speed shaker for 2 hours, then centrifuge on a GL-21M type ultracentrifuge at 15000r / min for 30 minutes. After removing the supernatant, repeat the dissolution and separation process once. The resulting precipitate is placed in a vacuum oven and dried under vacuum at 80℃ for 6 hours, then weighed. The weight of the dried precipitate divided by 10g gives the butadiene weight percentage.

[0013] More preferably, the butadiene in the ABS resin is 20%-26% by weight.

[0014] Preferably, the 2,3-dibromosuccinic anhydride accounts for 0.5%-2% of the weight of the glass fiber in the 2,3-dibromosuccinic anhydride-treated glass fiber.

[0015] Preferably, the glass fibers in the 2,3-dibromosuccinic anhydride-treated glass fibers are type E alkali-free glass fibers.

[0016] Preferably, the preparation method of the 2,3-dibromosuccinic anhydride surface-treated glass fiber includes: immersing type E alkali-free glass fiber in an acidic aqueous solution and drying it; then immersing the treated glass fiber in a 2,3-dibromosuccinic anhydride solution, stirring, and drying it to obtain the glass fiber. The method for testing the weight ratio of 2,3-dibromosuccinic anhydride to the glass fiber is as follows: weigh the 2,3-dibromosuccinic anhydride surface-treated glass fiber and record its weight as a; place the treated glass fiber in a muffle furnace, ignite it at 500°C for 2 hours, remove it, cool it, weigh it, and record its weight as b; the weight ratio of 2,3-dibromosuccinic anhydride to the glass fiber is [(ab) / a]×100%.

[0017] Preferably, the acidic aqueous solution includes one or more of sulfuric acid aqueous solution, hydrochloric acid aqueous solution, nitric acid aqueous solution, and acetic acid aqueous solution.

[0018] Preferably, the acidic aqueous solution has a mass fraction of 7%-20%.

[0019] More preferably, the acidic aqueous solution is a hydrochloric acid aqueous solution with a mass fraction of 7%-20%.

[0020] Preferably, the solvent for the 2,3-dibromosuccinic anhydride solution is ethyl acetate with a concentration of 0.5-2 mol / L.

[0021] Preferably, the soaking temperature is room temperature and the soaking time is 0.3-1 hour.

[0022] Preferably, the drying temperature is 100-120℃.

[0023] Preferably, the stirring temperature is 70-80℃ and the stirring time is 2-3 hours.

[0024] The EP-type brominated epoxy involved in this invention is a polymer synthesized by reacting tetrabromobisphenol A and epichlorohydrin. The molecular chain has epoxy groups at both ends, and its structural formula is as follows:

[0025]

[0026] In the formula, n is 0-3;

[0027] The molecular weight of the EP-type brominated epoxy corresponding to the above structural formula is generally 656 to 2456.

[0028] Preferably, the weight-average molecular weight of the EP-type brominated epoxy is 1200-2000.

[0029] Preferably, the flame retardant synergist comprises an antimony compound, a polysiloxane, and an inorganic powder, wherein the antimony compound comprises 20-80% by weight in the flame retardant synergist.

[0030] Preferably, the polysiloxane in the flame retardant synergist has a weight percentage of 10-20%.

[0031] Preferably, the inorganic powder has a weight percentage of 10-70% in the flame retardant synergist.

[0032] Preferably, the antimony compound includes one or more of antimony trioxide, colloidal antimony pentoxide, sodium antimonate, antimony trichloride, antimony pentachloride, antimony phosphite, antimony polyphosphate, and complexed antimony.

[0033] Preferably, the polysiloxane includes one or more of methyl polysiloxane, phenyl polysiloxane, vinyl polysiloxane, amide polysiloxane, epoxy polysiloxane, isobutyl polysiloxane, styrene polysiloxane, and cyclic polysiloxane.

[0034] Preferably, the inorganic powder includes one or more of the following: talc powder, magnesium carbonate, barium sulfate, marble powder, mica powder, natural silica, wollastonite powder, kaolin, sepiolite, whiskers, montmorillonite, and feldspar powder.

[0035] Preferably, the ABS polymer further includes 0-2 parts of other additives.

[0036] Preferably, the other additives include one or more of the following: anti-dripping agents, antioxidants, lubricants, weather-resistant agents, and colorants.

[0037] Preferably, the anti-dripping agent is present in an amount of 0.1-0.3 parts by weight.

[0038] Preferably, the anti-dripping agent comprises SAN-coated polytetrafluoroethylene.

[0039] Preferably, the antioxidant is present in 0.1-0.5 parts by weight.

[0040] Preferably, the antioxidant includes an organic hindered phenolic antioxidant and / or a phosphite antioxidant, wherein the organic hindered phenolic antioxidant includes pentaerythritol tetrakis[methyl-β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], and the phosphite antioxidant includes tris[2,4-di-tert-butylphenyl]phosphite.

[0041] Preferably, the lubricant is present in a weight ratio of 0.3-1.5 parts.

[0042] Preferably, the lubricant includes one or more of amide lubricants, stearate lubricants, ester lubricants, and silicone lubricants.

[0043] Preferably, the weathering agent is present in 0.3-0.5 parts by weight.

[0044] Preferably, the weathering agent includes one or more of benzophenone-based ultraviolet absorbers, benzotriazole-based ultraviolet absorbers, and hindered amine light stabilizers.

[0045] Preferably, the colorant is present in 0.1-0.3 parts by weight.

[0046] Preferably, the colorant includes one or more of titanium dioxide, cadmium-based pigments, iron oxide red, ultramarine, carbon black, phthalocyanine-based pigments, and quinacridone-based organic pigments.

[0047] This invention also provides a method for preparing weather-resistant and flame-retardant reinforced ABS polymer, comprising:

[0048] All components except for the 2,3-dibromosuccinic anhydride-treated glass fiber and toughening agent are mixed. The resulting mixture is then added to a twin-screw extruder. The 2,3-dibromosuccinic anhydride-treated glass fiber and toughening agent are added via side feeding. The mixture is then extruded and granulated to obtain a weather-resistant and flame-retardant reinforced ABS polymer.

[0049] Preferably, the 2,3-dibromosuccinic anhydride-treated glass fiber and toughening agent are added to the sixth zone of the screw via side feeding.

[0050] Preferably, the feeding speed of the twin-screw extruder is 200-400 rpm; the screw temperature of each section of the twin-screw extruder is 190-270℃, and the screw speed is 200-400 rpm.

[0051] More preferably, the screw temperatures of the twin-screw extruder from the feed port to the die head are as follows: Zone 1: 195-205℃; Zone 2: 225-235℃; Zone 3: 235-245℃; Zone 4: 235-245℃; Zone 5: 235-245℃; Zone 6: 245-255℃; Zone 7: 245-255℃; Zone 8: 245-255℃; Zone 9: 245-255℃; and Die head temperature: 255-265℃.

[0052] This invention also provides an application of weather-resistant and flame-retardant reinforced ABS polymer in household appliances or electronic appliances, such as for air conditioner outdoor unit handles, induction cooker control boxes, LED light back covers, etc.

[0053] This invention utilizes EP-type brominated epoxy, which exhibits superior initial flame retardancy, flame retardancy after aging, and impact strength retention compared to other traditional brominated flame retardants. This is likely due to the strong polarity of the epoxy structures at both ends of the EP-type brominated epoxy molecular chain, resulting in relatively low compatibility with ABS. Consequently, it tends to distribute around glass fibers containing a large number of hydroxyl groups. Simultaneously, the epoxy groups at both ends of its molecular chain possess strong reactivity, reacting with the Si-OH groups on the glass fiber surface, acting as a "coupling agent" and reducing the adverse effects of the "wick effect." Furthermore, the glass fiber surface is treated with 2,3-dibromosuccinic anhydride, allowing the anhydride to distribute on the glass fiber surface through chemical and physical processes. This reduces the wick effect caused by the glass fiber being directly exposed on the material surface during combustion, thereby improving the material's initial flame retardancy and its flame retardant stability after aging.

[0054] The toughening agent chlorinated polyethylene used in this invention can improve the compatibility of flame retardants and flame retardant synergists with ABS resin. Simultaneously, chlorinated polyethylene does not contain double bonds, is not easily oxidized, and exhibits stable toughening effects after long-term aging. Therefore, the compounding of chlorinated polyethylene with EP-type brominated epoxy can give the ABS polymer higher initial impact strength and flame retardancy, while also ensuring more stable impact strength and flame retardancy after aging.

[0055] Beneficial effects

[0056] This invention utilizes a compound of EP-type brominated epoxy, 2,3-dibromosuccinic anhydride-surface-treated glass fiber, and chlorinated polyethylene as a toughening agent. This compound significantly improves the impact strength retention and flame retardancy of ABS polymers after aging, while also enhancing their initial impact strength and flame retardancy. The initial impact strength of the ABS polymer is 8.7-10.4 kJ / m. 2 The flame retardancy reaches 2.0mm 5VA-2.0mm V-0, and the impact strength retention rate after 1000 hours of xenon lamp aging is over 80%, with no significant decrease in flame retardancy. Detailed Implementation

[0057] The present invention will be further illustrated below with reference to specific embodiments. It should be understood that these embodiments are for illustrative purposes only and are not intended to limit the scope of the invention. Furthermore, it should be understood that after reading the teachings of this invention, those skilled in the art can make various alterations or modifications to the invention, and these equivalent forms also fall within the scope defined by the appended claims.

[0058] Reagent source:

[0059] ABS Resin 1: Rubber D50 particle size is 750nm, butadiene weight percentage is 20.22%, ABS 8391, Sinopec Shanghai Gaoqiao Petrochemical Co., Ltd.;

[0060] ABS Resin 2: Rubber D50 particle size is 1300nm, butadiene weight percentage is 25.99%, ABS 3504, Sinopec Shanghai Gaoqiao Petrochemical Co., Ltd.;

[0061] ABS Resin 3: Rubber D50 particle size is 500nm, butadiene weight percentage is 34.10%, ABS AG10NP, Taiwan Chemical Fiber Co., Ltd.;

[0062] ABS Resin 4: Rubber D50 particle size is 1600nm, butadiene weight percentage is 19.57%, ABS 275, Liaoning Huajin Chemical (Group) Co., Ltd.;

[0063] 2,3-Dibromosuccinic anhydride surface-treated glass fiber: The weight ratio of 2,3-dibromosuccinic anhydride to glass fiber is 1.6%. The preparation method is as follows: Glass fiber 960A (China Jushi Co., Ltd.) is immersed in a hydrochloric acid aqueous solution (mass fraction 15%) for 0.5 hours at room temperature and then dried at 100-120℃; then the treated glass fiber is immersed in a 2,3-dibromosuccinic anhydride solution (solvent is ethyl acetate, concentration 1 mol / L), stirred at 70℃ for 3 hours, and dried at 100-120℃ to obtain the final product. The 2,3-dibromosuccinic anhydride was purchased from Beijing Taiyajie Technology Co., Ltd.

[0064] 2,3-Dibromosuccinic anhydride-treated glass fiber: The weight ratio of 2,3-dibromosuccinic anhydride to glass fiber is 0.6%. The preparation method is as follows: Glass fiber 960A (China Jushi Co., Ltd.) is immersed in a sulfuric acid aqueous solution (mass fraction 10%) for 0.5 hours at room temperature and then dried at 100-120℃; then the treated glass fiber is immersed in a 2,3-dibromosuccinic anhydride solution (solvent is ethyl acetate, concentration 0.5mol / L), stirred at 75℃ for 2 hours, and dried at 100-120℃ to obtain the final product. The 2,3-dibromosuccinic anhydride was purchased from Beijing Taiyajie Technology Co., Ltd.

[0065] Fiberglass: 960A (China Jushi Co., Ltd.);

[0066] Toughening agent 1: Chlorinated polyethylene, CPE135C, Hangzhou Keli Chemical Co., Ltd.;

[0067] Toughening agent 2: SAN-type toughening agent grafted with rubber powder, HR181, Kumho Petrochemical Co., Ltd., South Korea;

[0068] Flame retardant 1: EP type brominated epoxy, weight average molecular weight is 1400, EP-1400, Jiangsu Xingsheng Chemical Co., Ltd.;

[0069] Flame retardant 2: EP type brominated epoxy, weight average molecular weight is 1600, EP-1600, Jiangsu Xingsheng Chemical Co., Ltd.;

[0070] Flame retardant 3: EP type brominated epoxy, weight average molecular weight is 2000, EP-2000, Jiangsu Xingsheng Chemical Co., Ltd.;

[0071] Flame retardant 4: EC type brominated epoxy, weight average molecular weight 1400, F-3014, Israel Chemicals Ltd.;

[0072] Flame retardant 5: Tris(tribromophenoxy)triazine, FR-245, Israel Chemicals Ltd.;

[0073] Flame retardant synergist: a mixture of talc, dimethyl polysiloxane, and antimony trioxide, prepared by mixing 60g of talc, 15g of dimethyl polysiloxane, and 25g of antimony trioxide in a high-speed mixer for 20 minutes; wherein the antimony trioxide was purchased from Huachang Antimony Industry Co., Ltd., the talc used was HTP Ultra 5L purchased from IMIFABI, Italy, and the dimethyl polysiloxane was purchased from Sigma-Aldrich (Shanghai) Trading Co., Ltd.

[0074] Other adjuvants:

[0075] Anti-dripping agent: SAN-coated polytetrafluoroethylene, commercially available;

[0076] Antioxidant: A mixture of antioxidant 1010 (organic hindered phenolic antioxidant) and antioxidant 168 (phosphite antioxidant) in a weight ratio of 1:2, commercially available;

[0077] Lubricant: Ethylene bis-stearamide type lubricant, commercially available;

[0078] Unless otherwise specified, any component (e.g., anti-dripping agent, antioxidant, lubricant) in the parallel embodiments and comparative examples of this invention is the same commercially available product.

[0079] The preparation method of ABS polymer includes: according to the proportions in Tables 1, 2, and 3, mixing all components except for the 2,3-dibromosuccinic anhydride surface-treated glass fiber (or glass fiber) and toughening agent in a high-speed mixer until homogeneous; feeding the mixture into a twin-screw extruder, wherein the 2,3-dibromosuccinic anhydride surface-treated glass fiber (or glass fiber) and toughening agent are added via side feeding in the sixth zone of the screw; under the conveying and shearing action of the twin-screw extruder, the mixture is fully melted, plasticized, kneaded, and mixed, and then processed. The product is obtained by extrusion, stranding, cooling, pelletizing, and drying. The feeding speed of the twin-screw extruder is 200-400 rpm. The preferred screw temperatures from the feed port to the die head are 200℃ for zone 1, 230℃ for zone 2, 240℃ for zone 3, 240℃ for zone 4, 240℃ for zone 5, 250℃ for zone 6, 250℃ for zone 7, 250℃ for zone 8, 250℃ for zone 9, and 260℃ for the die head. The screw speed is 300 rpm.

[0080] After drying, the ABS polymers of the examples and comparative examples were injection molded into standard test strips using a precision injection molding machine (injection temperature 180-210℃) for performance testing.

[0081] (1) Impact strength of cantilever beam notched beam: tested according to test standard ISO 180-2000 (Type A notch, thickness 4mm, temperature 23℃);

[0082] (2) Flame retardancy rating test: Tested according to the test standard UL94-2018 (thickness 2.0mm);

[0083] (3) Performance retention rate after aging: The above standard test specimens were subjected to artificial accelerated climate aging test for 1000 hours according to standard ISO4892-2:1994 (xenon lamp, method A / cycle 1), and the performance before and after aging was compared. Among them, the retention rate of cantilever beam notched impact strength was (cantilever beam notched impact strength after aging / cantilever beam notched impact strength before aging × 100%).

[0084] Table 1. Formulation ratios (parts by weight) for Examples 1-8

[0085]

[0086]

[0087]

[0088] Table 2. Formulation ratios (parts by weight) for Examples 9-12

[0089]

[0090] Table 3 Comparative proportions (parts by weight)

[0091]

[0092]

[0093] As shown in Tables 1-3, Comparative Example 1 used untreated glass fiber, Comparative Example 2 used SAN-type toughening agent grafted with adhesive powder, Comparative Example 3 used EC-type brominated epoxy, Comparative Example 4 used tris(tribromophenoxy)triazine, and the amount of 2,3-dibromosuccinic anhydride-treated glass fiber added in Comparative Example 5 exceeded the scope of this invention. The cantilever beam notched impact strength, cantilever beam notched impact strength retention rate, and flame retardancy before and after aging of the ABS polymers in Comparative Examples 1-5 were not as good as those in Example 1. Therefore, this invention, using EP-type brominated epoxy, 2,3-dibromosuccinic anhydride-treated glass fiber, and chlorinated polyethylene as a toughening agent, can significantly improve the impact strength retention rate and flame retardancy of ABS polymers after aging, while also improving the initial impact strength and flame retardancy of the ABS polymers.

Claims

1. A weather-resistant and flame-retardant reinforced ABS polymer, characterized in that, The ABS polymer component comprises, by weight parts: The toughening agent is chlorinated polyethylene; The flame retardant is an EP-type brominated epoxy, and the EP-type brominated epoxy molecular chain has epoxy groups at both ends.

2. The weather-resistant and flame-retardant reinforced ABS polymer according to claim 1, characterized in that, The ABS polymer component comprises, by weight parts:

3. The weather-resistant and flame-retardant reinforced ABS polymer according to claim 1, characterized in that, The ABS resin rubber D50 has a particle size of 650-1500nm.

4. The weather-resistant and flame-retardant reinforced ABS polymer according to claim 1, characterized in that, The weight-average molecular weight of the EP-type brominated epoxy is 1200-2000; the weight ratio of 2,3-dibromosuccinic anhydride in the glass fiber surface-treated with 2,3-dibromosuccinic anhydride is 0.5%-2%.

5. The weather-resistant and flame-retardant reinforced ABS polymer according to claim 1, characterized in that, The flame retardant synergist comprises antimony compound, polysiloxane and inorganic powder, wherein the antimony compound comprises 20-80% by weight in the flame retardant synergist.

6. The weather-resistant and flame-retardant reinforced ABS polymer according to claim 5, characterized in that, The antimony compounds include one or more of antimony trioxide, colloidal antimony pentoxide, sodium antimonate, antimony trichloride, antimony pentachloride, antimony phosphite, antimony polyphosphate, and complexed antimony; the polysiloxanes include one or more of methyl polysiloxane, phenyl polysiloxane, vinyl polysiloxane, amide polysiloxane, epoxy polysiloxane, isobutyl polysiloxane, styrene polysiloxane, and cyclic polysiloxane; the inorganic powders include one or more of talc, magnesium carbonate, barium sulfate, marble powder, mica powder, natural silica, wollastonite powder, kaolin, sepiolite, whiskers, montmorillonite, and feldspar powder.

7. The weather-resistant and flame-retardant reinforced ABS polymer according to claim 1, characterized in that, The ABS polymer also includes 0-2 parts of other additives; the other additives include one or more of the following: anti-dripping agents, antioxidants, lubricants, weathering agents, and colorants.

8. A method for preparing the weather-resistant and flame-retardant reinforced ABS polymer as described in any one of claims 1-7, comprising: All components except for the 2,3-dibromosuccinic anhydride-treated glass fiber and toughening agent are mixed. The resulting mixture is then added to a twin-screw extruder. The 2,3-dibromosuccinic anhydride-treated glass fiber and toughening agent are added via side feeding. The mixture is then extruded and granulated to obtain a weather-resistant and flame-retardant reinforced ABS polymer.

9. The preparation method according to claim 8, characterized in that, The feeding speed of the twin-screw extruder is 200-400 rpm; the screw temperature of each section of the twin-screw extruder is 190-270℃, and the screw speed is 200-400 rpm.

10. The application of the weather-resistant and flame-retardant reinforced ABS polymer as described in any one of claims 1-7 in household appliances or electronic appliances.

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