Transparent high-impact PP / ABS alloy material and preparation method thereof

Abstract

The invention relates to the technical field of high-molecular compounds, and particularly discloses a transparent and high-impact PP / ABS alloy material and a preparation method thereof. According to the invention, the high-transparency high-impact co-polypropylene powder and the rubber-phase transparent ABS with small particle size are selected as raw materials, and the use amount of the PP nucleating agent is optimized to control the size of spherocrystals, so that the transparency of the alloy is improved; meanwhile, maleic anhydride grafted transparent PP is used as a compatilizer, so that the compatibility of the alloy is improved, the influence of the compatilizer on the transparency of the alloy is reduced, and the PP / ABS alloy with both transparency and high impact is prepared.

Description

Technical Field

[0001] The invention relates to the technical field of polymer compounds, and particularly discloses a transparent, high-impact PP / ABS alloy material and a preparation method thereof. Background Art

[0002] Polypropylene (PP) is a high-performance general-purpose plastic with advantages such as light weight, good toughness, and chemical resistance, but it also suffers from poor rigidity and high shrinkage. Acrylonitrile-butadiene-styrene copolymer (ABS), one of the most widely used engineering plastics, offers advantages such as high strength and low shrinkage, but suffers from disadvantages such as poor heat and weather resistance. PP / ABS alloys, made from PP and ABS, combine the advantages of both, forming a complementary structure with excellent overall performance. They have been widely used in the automotive, home appliance, packaging, construction, and medical fields.

[0003] Currently, research on general-purpose PP / ABS alloys focuses on modifications for reinforcement, flame retardancy, heat resistance, aging resistance, and antistatic properties, such as those in CN104672746A, CN105462152A, CN106084446A, CN111793283A, CN108192199A, and CN107345031A. Driven by consumption upgrades, production process improvements, and product upgrades, transparent PP and transparent ABS are demonstrating broad application potential in a wide range of fields, including automotive and home appliances. Many well-known petrochemical companies (such as Basell, ExxonMobil, Sinopec, and North China Huajin) produce transparent PP, and my country's transparent PP production capacity alone has reached 2.5 million tons. Transparent ABS technology is primarily mastered by foreign chemical companies such as LG, Chi Mei, and Asahi Kasei. They have launched a variety of transparent ABS products, but these are currently priced relatively high. Domestic companies such as Guangxi Changke and North Huajin have already tackled the technical challenges of transparent ABS, breaking the long-standing foreign monopoly and potentially achieving domestic production. However, there have been no reports on research into transparent PP / ABS alloys. This is due to the significant difference in refractive index between transparent PP and transparent ABS, as well as their poor compatibility, making it difficult to achieve both transparency and high impact resistance.

[0004] With the development of the global manufacturing industry, the increasing demand of consumers for product appearance and functionality, and the reduction of transparent ABS cost, the demand for transparent PP / ABS alloy will increase sharply in the future. Therefore, it is of great significance to prepare a transparent, high-impact PP / ABS alloy. Summary of the Invention

[0005] The technical problem to be solved by the present invention is that the current development and modification of PP / ABS alloys mainly use general-purpose PP and ABS as raw materials. The prepared PP / ABS alloys have low transparency and poor impact performance, which cannot meet the market demand for highly transparent and high-impact products.

[0006] The technical solution adopted in the present invention is as follows:

[0007] In a first aspect, the present invention provides a method for preparing a transparent, high-impact PP / ABS alloy material, comprising the following steps:

[0008] S1. Weigh 20-50 parts of transparent PP powder, 30-80 parts of transparent ABS, 5-15 parts of a compatibilizer, 0.4-0.8 parts of a lubricant, 0.1-0.2 parts of a transparent nucleating agent, and 0.2-0.5 parts of an antioxidant;

[0009] The transparent PP powder is any one or more of homopolymer polypropylene and copolymer polypropylene, and has a melt index of 15-60 g / 10 min at 230° C. / 2.16 kg.

[0010] The transparent ABS has a rubber content of 5-30%, an acrylonitrile content of 20-30%, a styrene content of 40-60%, and a melt index of 10-40 g / 10 min at 220°C / 10 kg.

[0011] The compatibilizer is one or more of maleic anhydride grafted polypropylene (PP-g-MAH), maleic anhydride grafted hydrogenated styrene-butadiene block copolymer (SEBS-g-MAH), and maleic anhydride grafted polyolefin elastomer (POE-g-MAH), wherein the maleic anhydride grafting rate is ≥1%;

[0012] S2. Mix the materials weighed in S1 evenly;

[0013] S3 S2 mixed material was melt mixed by a twin-screw extruder, extruded and granulated to obtain a transparent PP / ABS alloy modified material;

[0014] The processing temperature of the twin-screw extruder is 200-250° C., and the screw speed is 250-500 rpm.

[0015] Preferably, the transparent ABS is prepared by a bulk method or an emulsion method.

[0016] Preferably, the lubricant is one or a mixture of white oil, silicone oil, silicone powder, paraffin, stearic acid, butyl stearate, oleamide or ethylene bisstearamide.

[0017] Preferably, the transparent nucleating agent is selected from one or more of sorbitol transparent nucleating agents, aromatic phosphate transparent nucleating agents, carboxylic acid metal salt transparent nucleating agents, dehydrogenated polar acid and its salt transparent nucleating agents, branched acid amine transparent nucleating agents, and polymer transparent nucleating agents.

[0018] Preferably, the antioxidant is one or more of hindered phenol antioxidants and phosphite antioxidants.

[0019] Preferably, in step S3, the feeding speed is 5-15 Hz.

[0020] In a second aspect, the present invention provides a transparent, high-impact PP / ABS alloy material prepared by the method described in the first aspect.

[0021] The beneficial effects achieved by the present invention are:

[0022] The present invention solves the problem of poor compatibility between transparent PP and transparent ABS due to the large difference in refractive index, and the significant impact of adding a common compatibilizer on the alloy's transparency. The resulting PP / ABS alloy struggles to achieve both transparency and high impact. The present invention utilizes high-transparency, high-impact copolymerized polypropylene powder and transparent ABS with a small rubber phase particle size as raw materials, optimizes the dosage of a PP nucleating agent to control the size of spherulites, thereby improving the transparency of the alloy. Furthermore, the present invention uses transparent PP grafted with maleic anhydride as a compatibilizer, improving the alloy's compatibility while reducing the compatibilizer's impact on the alloy's transparency. This results in a PP / ABS alloy that achieves both transparency and high impact. DETAILED DESCRIPTION

[0023] In order to make the purpose, technical solutions and advantages of the present invention more clear and distinct, the present invention is further described in detail with reference to the following examples. It should be noted that the present invention is not limited to the following examples.

[0024] Table 1 Examples and Comparative Examples Raw Materials

[0025]

[0026] The preparation methods of the two homemade raw materials No. 5 and 8 are as follows:

[0027] Preparation of transparent ABS:

[0028] At 30°C, 10wt% styrene-butadiene rubber particles, 11wt% acrylonitrile, 25wt% styrene, 35wt% methyl methacrylate, and 15wt% ethylbenzene are fully stirred in a sol kettle to form a uniform raw rubber solution. The dissolved raw rubber solution is sequentially transported to four plug flow reactors for bulk polymerization, and finally devolatilization and extrusion granulation are performed to obtain transparent ABS. Specifically, 1500ppm of tert-butyl diperoxide-cyclohexane (initiator) is added at the inlet of the first plug flow reactor, and the reactor temperature is 100°C; 1500ppm of n-dodecyl mercaptan (chain transfer agent) is added at the inlet of the second plug flow reactor, and the reactor temperature is 110°C; 1000ppm of silicone oil and 4wt% of ethylbenzene are added at the inlet of the third plug flow reactor, and the reactor temperature is 130°C; 1500ppm of n-dodecyl mercaptan and ethylbenzene are added at the inlet of the fourth plug flow reactor, and the reactor temperature is approximately 160°C.

[0029] Preparation of PP-g-MAH:

[0030] PP-g-MAH was prepared by a melt grafting method. Transparent polypropylene RC-20M, maleic anhydride (MAH) monomer, dicumyl peroxide (DCP) initiator, and tetramethylthiuram disulfide (TMTD) activator were accurately weighed in a mass ratio of 97:2.5:0.3:0.2 and thoroughly mixed in a high-speed mixer. The mixed materials were then extruded in a twin-screw extruder at a screw temperature of 230°C, a feed rate of 6 Hz, and a screw speed of 200 rpm. PP-g-MAH was obtained after drawing, cooling, pelletizing, and drying.

[0031] Example 1

[0032] Weigh 20 parts of transparent PP powder RC-20M, 74.1 parts of transparent ABS TR-558AI, 5 parts of compatibilizer PP-g-MAH KT-1, 0.5 parts of silicone oil, 0.1 parts of transparent nucleating agent NX8000, 0.1 parts of antioxidant 1010, 0.1 parts of antioxidant 1076, and 0.1 parts of antioxidant 168 in parts by mass; pour the weighed materials into a high-speed mixer and mix and stir at high speed for 2 minutes; melt-mix the mixed materials through a twin-screw extruder with a maximum temperature of 230° C., a feed rate of 6 Hz, and a screw speed of 300 rpm. After extrusion and granulation, a transparent PP / ABS alloy modified material is obtained, which is dried for later use.

[0033] Example 2

[0034] Weigh 20 parts of transparent PP powder RC-20M, 74.1 parts of homemade transparent ABS, 5 parts of compatibilizer PP-g-MAHKT-1, 0.5 parts of silicone oil, 0.1 parts of transparent nucleating agent NA-98, 0.1 parts of antioxidant 1010, 0.1 parts of antioxidant 1076, and 0.1 parts of antioxidant 168 in parts by mass; pour the weighed materials into a high-speed mixer and mix and stir at high speed for 2 minutes; melt-mix the mixed materials through a twin-screw extruder with a maximum temperature of 240°C, a feeding rate of 12 Hz, and a screw speed of 400 rpm. After extrusion and granulation, a transparent PP / ABS alloy modified material is obtained, which is dried for later use.

[0035] Example 3

[0036] Weigh 20 parts of transparent PP powder RC-20M, 71.08 parts of transparent ABS PA-758, 8 parts of homemade compatibilizer PP-g-MAH, 0.5 parts of EBS, 0.12 parts of transparent nucleating agent NA-98, 0.1 parts of antioxidant 1010, 0.1 parts of antioxidant 1076, and 0.1 parts of antioxidant 168 in parts by mass; pour the weighed materials into a high-speed mixer and mix and stir at high speed for 2 minutes; melt-mix the mixed materials through a twin-screw extruder with a maximum temperature of 220°C, a feeding rate of 8 Hz, and a screw speed of 350 rpm. After extrusion and granulation, a transparent PP / ABS alloy modified material is obtained, which is dried for later use.

[0037] Example 4

[0038] Weigh 25 parts of transparent PP powder RC-20M, 62.05 parts of transparent ABS PA-758, 12 parts of compatibilizer SEBS-g-MAH, 0.5 parts of EBS, 0.15 parts of transparent nucleating agent NX8000, 0.1 parts of antioxidant 1010, 0.1 parts of antioxidant 1076, and 0.1 parts of antioxidant 168 in parts by mass; pour the weighed materials into a high-speed mixer and mix and stir at high speed for 2 minutes; melt-mix the mixed materials through a twin-screw extruder with a maximum temperature of 230°C, a feed rate of 8 Hz, and a screw speed of 350 rpm. After extrusion and granulation, a transparent PP / ABS alloy modified material is obtained, which is dried for later use.

[0039] Example 5

[0040] Weigh 25 parts of transparent PP powder RC-20M, 64.08 parts of homemade transparent ABS, 10 parts of homemade compatibilizer PP-g-MAH, 0.5 parts of EBS, 0.12 parts of transparent nucleating agent NX8000, 0.1 parts of antioxidant 1010, 0.1 parts of antioxidant 1076, and 0.1 parts of antioxidant 168 by mass; pour the weighed materials into a high-speed mixer and stir at high speed for 2 minutes; melt-mix the mixed materials through a twin-screw extruder with a maximum temperature of 240°C, a feeding rate of 6 Hz, and a screw speed of 300 rpm. After extrusion and granulation, a transparent PP / ABS alloy modified material is obtained, which is dried for later use.

[0041] Example 6

[0042] Weigh 30 parts of transparent PP powder RC-20M, 54.08 parts of transparent ABS TR-558AI, 15 parts of compatibilizer SEBS-g-MAH, 0.5 parts of silicone oil, 0.12 parts of transparent nucleating agent NA-98, 0.1 parts of antioxidant 1010, 0.1 parts of antioxidant 1076, and 0.1 parts of antioxidant 168 in parts by mass; pour the weighed materials into a high-speed mixer and mix and stir at high speed for 2 minutes; melt-mix the mixed materials through a twin-screw extruder with a maximum temperature of 240°C, a feed rate of 9 Hz, and a screw speed of 450 rpm. After extrusion and granulation, a transparent PP / ABS alloy modified material is obtained, which is dried for later use.

[0043] Comparative Example 1

[0044] Weigh 20 parts by mass of transparent PP powder HJ9060, 74.1 parts of transparent ABS TR-558AI, 5 parts of compatibilizer PP-g-MAH KT-1, 0.5 parts of silicone oil, 0.1 parts of transparent nucleating agent NX8000, 0.1 parts of antioxidant 1010, 0.1 parts of antioxidant 1076, and 0.1 parts of antioxidant 168; pour the weighed materials into a high-speed mixer and mix and stir at high speed for 2 minutes; melt-mix the mixed materials through a twin-screw extruder with a maximum temperature of 250° C., a feed rate of 6 Hz, and a screw speed of 300 rpm. After extrusion and granulation, a transparent PP / ABS alloy modified material is obtained, which is dried for later use.

[0045] Comparative Example 2

[0046] Weigh 20 parts of transparent PP powder HJ9060, 68.95 parts of homemade transparent ABS, 10 parts of homemade compatibilizer PP-g-MAH, 0.6 parts of EBS, 0.15 parts of transparent nucleating agent NA-98, 0.1 parts of antioxidant 1010, 0.1 parts of antioxidant 1076, and 0.1 parts of antioxidant 168 by mass; pour the weighed materials into a high-speed mixer and stir at high speed for 2 minutes; melt-mix the mixed materials through a twin-screw extruder with a maximum temperature of 240°C, a feeding rate of 8 Hz, and a screw speed of 400 rpm. After extrusion and granulation, a transparent PP / ABS alloy modified material is obtained, which is dried for later use.

[0047] Comparative Example 3

[0048] Weigh 20 parts of transparent PP powder RC-20M, 70.95 parts of transparent ABS TR-558AI, 8 parts of homemade compatibilizer PP-g-MAH, 0.6 parts of EBS, 0.15 parts of transparent nucleating agent NX8000, 0.1 parts of antioxidant 1010, 0.1 parts of antioxidant 1076, and 0.1 parts of antioxidant 168 in parts by mass; pour the weighed materials into a high-speed mixer and mix and stir at high speed for 2 minutes; melt-mix the mixed materials through a twin-screw extruder with a maximum temperature of 230°C, a feeding rate of 10 Hz, and a screw speed of 450 rpm. After extrusion and granulation, a transparent PP / ABS alloy modified material is obtained, which is dried for later use.

[0049] Table 2 Test results of examples and comparative examples

[0050]

[0051] Test standard:

[0052] (1) Melt index: measured according to GB / T 3682.1-2018;

[0053] (2) Tensile strength: measured according to GB / T 1040.1-2018;

[0054] (3) Flexural modulus: measured according to GB / T 9341-2008;

[0055] (4) Impact strength: measured according to GB / T 1043.1-2008;

[0056] (5) Vicat softening temperature: measured according to GB / T 1633-2000;

[0057] (6) Light transmittance: measured according to GB / T 2410-2008;

[0058] (7) Haze: measured according to GB / T 2410-2008.

[0059] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the technical principles of the present invention. These improvements and modifications should also be regarded as the scope of protection of the present invention.

Claims

1. A method for preparing a transparent, high-impact PP / ABS alloy material, characterized in that: The following steps are involved: S1. Weigh 20-50 parts of transparent PP powder, 30-80 parts of transparent ABS, 5-15 parts of a compatibilizer, 0.4-0.8 parts of a lubricant, 0.1-0.2 parts of a transparent nucleating agent, and 0.2-0.5 parts of an antioxidant; The transparent PP powder is any one or more of homopolymer polypropylene and copolymer polypropylene, and has a melt index of 15-60 g / 10 min at 230° C. / 2.16 kg. The transparent ABS has a rubber content of 5-30%, an acrylonitrile content of 20-30%, a styrene content of 40-60%, and a melt index of 10-40 g / 10 min at 220°C / 10 kg. The compatibilizer is one or more of maleic anhydride grafted polypropylene (PP-g-MAH), maleic anhydride grafted hydrogenated styrene-butadiene block copolymer (SEBS-g-MAH), and maleic anhydride grafted polyolefin elastomer (POE-g-MAH), wherein the maleic anhydride grafting rate is ≥1%; S2. Mix the materials weighed in S1 evenly; S3 S2 mixed material was melt mixed by a twin-screw extruder, extruded and granulated to obtain a transparent PP / ABS alloy modified material; The processing temperature of the twin-screw extruder is 200-250° C., and the screw speed is 250-500 rpm.

2. The method for preparing a transparent, high-impact PP / ABS alloy material according to claim 1, characterized in that: The transparent ABS is prepared by a bulk method or an emulsion method.

3. The method for preparing a transparent, high-impact PP / ABS alloy material according to claim 2, characterized in that: The transparent ABS preparation method comprises the following steps: fully stirring 10 wt% of styrene-butadiene rubber particles, 11 wt% of acrylonitrile, 25 wt% of styrene, 35 wt% of methyl methacrylate, and 15 wt% of ethylbenzene in a sol kettle to obtain a uniform raw rubber solution; sequentially conveying the dissolved raw rubber solution to four plug flow reactors for bulk polymerization reaction; and finally performing devolatilization and extrusion granulation to obtain the transparent ABS.

4. The method for preparing a transparent, high-impact PP / ABS alloy material according to claim 3, characterized in that 1500 ppm of tert-butyl diperoxide-cyclohexane (initiator) was added to the inlet of the first plug flow reactor, and the temperature of the reactor was 100°C; 1500 ppm of n-dodecyl mercaptan (chain transfer agent) was added to the inlet of the second plug flow reactor, and the temperature of the reactor was 110°C; 1000 ppm of silicone oil and 4 wt% of ethylbenzene were added to the inlet of the third plug flow reactor, and the temperature of the reactor was 130°C; 1500 ppm of n-dodecyl mercaptan and ethylbenzene were added to the inlet of the fourth plug flow reactor, and the temperature of the reactor was 160°C.

5. The method for preparing a transparent, high-impact PP / ABS alloy material according to claim 1, characterized in that: The preparation method of PP-g-MAH is as follows: transparent polypropylene RC-20M, monomer maleic anhydride (MAH), initiator diisopropyl peroxide (DCP) and activator tetramethylthiuram disulfide (TMTD) are weighed in a mass ratio of 97:2.5:0.3:0.2 and then thoroughly mixed; the mixed materials are added to a twin-screw extruder for extrusion reaction at a screw temperature of 230°C, a feed rate of 6 Hz, and a screw speed of 200 rpm. PP-g-MAH is obtained by drawing, cooling, pelletizing, and drying.

6. The method for preparing a transparent, high-impact PP / ABS alloy material according to claim 1, characterized in that: The lubricant is one or a mixture of white oil, silicone oil, silicone powder, paraffin, stearic acid, butyl stearate, oleamide or ethylene bisstearamide.

7. The method for preparing a transparent, high-impact PP / ABS alloy material according to claim 1, characterized in that: The transparent nucleating agent is selected from one or more of sorbitol transparent nucleating agents, aromatic phosphate transparent nucleating agents, carboxylic acid metal salt transparent nucleating agents, dehydrogenated polar acid and its salt transparent nucleating agents, branched acid amine transparent nucleating agents, and polymer transparent nucleating agents.

8. The method for preparing a transparent, high-impact PP / ABS alloy material according to claim 1, characterized in that: The antioxidant is one or more of hindered phenol antioxidants and phosphite antioxidants.

9. The method for preparing a transparent, high-impact PP / ABS alloy material according to claim 1, characterized in that: In step S3, the feeding speed is 5-15 Hz.

10. A transparent, high-impact PP / ABS alloy material prepared by the method according to any one of claims 1 to 9.

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