CN112745615B - A kind of PMMA/ASA material and preparation method thereof - Google Patents

Abstract

The invention discloses a PMMA/ASA material and a preparation method thereof. ~1 part, 0.1-0.5 parts of heat stabilizer, 0.1-0.5 parts of lubricant and 0.5-2 parts of toner and dye are prepared according to parts by weight. The ASA glue content of the ASA high rubber powder is ≥60% and the particle size <350nm. The present invention adds a brightener to the PMMA/ASA material to form an effect similar to a paint film on the surface of the part, improves the brightness of the material, and resists the selection of an impact modifier to make it excellent in low-temperature impact toughness.

Description

A kind of PMMA/ASA material and preparation method thereof

technical field

The invention belongs to the technical field of polymer alloy materials, and in particular relates to a PMMA/ASA material and a preparation method thereof.

Background technique

Compared with traditional ABS resin, acrylonitrile-styrene-acrylate terpolymer (ASA) replaces butadiene rubber with acrylate rubber without double bonds, so that it can be used in mechanical and processing properties. It is comparable to ABS resin, and its weather resistance has been substantially improved, so its application is becoming more and more extensive, especially for outdoor parts.

Polymethyl methacrylate (PMMA) has excellent light transmittance and good weather resistance. After alloying with other resins, its weather resistance and surface gloss will be improved, but its impact toughness will be somewhat inferior Satisfactory. PMMA/ASA alloy is a promising material in the industry because of its excellent weather resistance and surface gloss. Although the conventional alloys of the two can meet the general appearance requirements of parts, the impact toughness of the alloy is compromised. Although it is better than PMMA The impact toughness of the raw material resin should be high, but the existing PMMA/ASA alloy cannot meet the requirements for the occasions where the appearance is extremely black and bright and the low temperature impact toughness is high, which limits its application.

Contents of the invention

Based on this, the present invention provides a PMMA/ASA material, which solves the problem that the existing PMMA/ASA alloy materials cannot meet the high black and bright appearance and low-temperature impact toughness at the same time. The present invention adds a brightener to the PMMA/ASA material to make the parts The surface forms a paint film-like effect, which improves the brightness of the material, and at the same time resists the selection of impact modifiers, making it excellent in low-temperature impact toughness.

In order to achieve the above object, the present invention adopts the following technical solutions:

A PMMA/ASA material is prepared by the following components in parts by weight:

The ASA high-glue powder has an ASA content of ≥60% and a particle size of <350nm. When the rubber powder content increases, it helps to improve the impact resistance of the material, but not any ASA with a high rubber powder content can satisfy the ultimate goal of the present invention (reaching a high black and bright effect), so only a small particle size (< 350nm) special rubber powder, in order to meet the requirements of high black and bright appearance on the basis of increasing impact performance.

Further, the impact modifier is an AN/St grafted silicone-acrylic acid type high weather resistance impact modifier. AN/St grafted silicon-acrylic acid high weather resistance and impact modifier mainly has the characteristics of chemical resistance, coloring and good fluidity, and the physical properties of silicon-containing tougheners contribute to the low temperature impact resistance of the material. Adding it to the composite material can significantly improve the low temperature impact toughness of the material.

Further, the brightening agent is polyvinyl acetate.

Further, the heat stabilizer is selected from at least one of hindered amine heat stabilizers, hindered phenol heat stabilizers and triphenyl phosphite heat stabilizers.

Further, the lubricant is a silicone masterbatch with AS as the carrier.

Further, the toner dye is a compound of transparent red, transparent yellow and transparent blue. The proportions of the three are not limited in the present invention. It can be understood that those skilled in the art can adjust according to actual requirements, and compared with black powder or black masterbatch, organic dyes have stronger dyeability, and the material The matching blackness should be darker, and the hue should be adjusted according to the needs, not just the single color of black powder or black masterbatch.

Another object of the present invention is to provide a kind of preparation method of above-mentioned PMMA/ASA material, comprise the following steps:

a. Mixing polymethyl methacrylate, ASA high rubber powder, impact modifier, brightener, heat stabilizer, lubricant and toner dye uniformly according to the proportion by weight to obtain a mixed material;

b. Send the mixed material into a twin-screw extruder, and obtain PMMA/ASA material through full melting, compounding, extrusion, stranding, cooling and pelletizing.

Further, the screw temperature of each section of the twin-screw extruder is 220-250° C., and the screw speed is 100-500 rpm.

Preferably, the screw temperature of each section of the twin-screw extruder is preferably 230-240° C., and the screw speed is 400-500 rpm.

Compared with the prior art, the present invention has the following beneficial effects:

Conventionally, if PMMA is used as the main body, the impact toughness of the material will decrease. How to ensure the impact toughness of the material without affecting the high black and bright appearance is the key. In this invention, in order to ensure the black and bright appearance of the material, a suitable ASA was selected Rubber powder (that is, the particle size should be less than 350nm), and at the same time properly add brightener, silicone masterbatch with AS as the carrier, and dye with high blackness; in addition, in order to ensure the impact toughness of the material, the present invention uses Rubber powder with a rubber content greater than 60%; use a certain amount of silicon-containing impact modifier (to be controlled within an appropriate range, otherwise it will affect the appearance of the material). Therefore, the problem that the impact toughness of PMMA as the main material decreases is solved. .

The PMMA/ASA material in the present invention is prepared by a twin-screw extrusion process, which has the advantages of simple and continuous process, high production efficiency and stable product quality.

The appearance of the PMMA/ASA material of the present invention has high black brightness and high gloss.

The PMMA/ASA material of the present invention maintains good mechanical properties at the same time, especially low-temperature impact toughness is very beneficial, and can be used in product fields that not only require high black appearance and brightness, but also high low-temperature toughness.

Detailed ways

In order to facilitate understanding of the present invention, the present invention will be described more fully below in conjunction with specific embodiments. However, the present invention can be embodied in many different forms and is not limited to the embodiments described herein. On the contrary, the purpose of providing these embodiments is to make the disclosure of the present invention more thorough and comprehensive.

Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the technical field of the invention. The terminology used herein in the description of the present invention is only for the purpose of describing specific embodiments, and is not intended to limit the present invention.

All substances in the embodiments of the present invention are known commercially available products, and its unit is parts by weight, specifically including:

The PMMA resin is PMMA-CM211 from Taiwan Chimei;

ASA high rubber powder is A-960A of Chemtura;

The impact modifier is Mitsubishi Rayon's SX006;

Brightening agent is polyvinyl acetate (commercially available);

The heat stabilizer is hindered phenolic antioxidant 1076 [ie CIBA's Irganox 1076β-(3,5-di-tert-butyl-4-hydroxyphenyl) n-octadecyl propionate] and triphenyl phosphite antioxidant Oxygen agent 168 [ie CIBA's Irganox168 tris (2,4-di-tert-butylphenyl) phosphite];

The lubricant is Dow Corning MB50-008 silicone masterbatch;

The toner dyes are clear red, clear yellow and clear blue (commercially available).

Example 1

With 60 parts of PMMA-CM211 resin, 35 parts of ASA high rubber powder A-960A, 5 parts of impact modifier SX006, 0.5 part of brightener polyvinyl acetate, 0.5 part of light and heat stabilizer (1076:168=1: 2, mass ratio) and 0.3 parts of lubricant silicone masterbatch MB50-008 and 0.8 parts of toner dye (transparent red: transparent yellow: transparent blue = 1:1:1.5, mass ratio) after high-speed stirring and mixing, send into the twin-screw extruder, wherein the working temperature of each section of the twin-screw extruder is: the temperature of the first zone is 230°C, the temperature of the second zone is 230°C, the temperature of the third zone is 235°C, the temperature of the fourth zone is 235°C, and the temperature of the fifth zone is 240°C , the temperature in the sixth zone is 240°C, the temperature in the seventh zone is 230°C, the temperature of the head is 225°C, and the screw speed is 450r/min. Head extrusion, strand drawing, cooling, and pelletizing to obtain high-black and bright PMMA/ASA materials with good low-temperature impact resistance.

The prepared PMMA/ASA material was injection-molded into a standard sample bar for testing according to the standard size, and tested according to the physical performance test standard in Table 1, and the performance test results are shown in Table 2.

Example 2

With 65 parts of PMMA-CM211 resin, 25 parts of ASA high rubber powder A-960A, 10 parts of impact modifier SX006, 0.5 part of brightener polyvinyl acetate, 0.3 part of light and heat stabilizer (1076:168=1: 2, mass ratio) and 0.2 parts of lubricant silicone masterbatch MB50-008 and 1 part of toner dye (transparent red: transparent yellow: transparent blue = 1:1:1.5, mass ratio) after mixing evenly at high speed, send into the twin-screw extruder, wherein the working temperature of each section of the twin-screw extruder is: the temperature of the first zone is 230°C, the temperature of the second zone is 230°C, the temperature of the third zone is 235°C, the temperature of the fourth zone is 235°C, and the temperature of the fifth zone is 240°C , the temperature in the sixth zone is 240°C, the temperature in the seventh zone is 230°C, the temperature of the head is 225°C, and the screw speed is 450r/min. Head extrusion, strand drawing, cooling, and pelletizing to obtain high-black and bright PMMA/ASA materials with good low-temperature impact resistance.

The prepared PMMA/ASA material was injection-molded into a standard sample bar for testing according to the standard size, and tested according to the physical performance test standard in Table 1, and the performance test results are shown in Table 2.

Example 3

With 70 parts of PMMA-CM211 resin, 25 parts of ASA high rubber powder A-960A, 5 parts of impact modifier SX006, 0.5 part of brightener polyvinyl acetate, 0.2 part of light and heat stabilizer (1076:168=1: 2, mass ratio) and 0.5 parts of lubricant silicone masterbatch MB50-008 and 2 parts of toner dye (transparent red: transparent yellow: transparent blue = 2:1:1, mass ratio) after mixing evenly at high speed, send into the twin-screw extruder, wherein the working temperature of each section of the twin-screw extruder is: the temperature of the first zone is 230°C, the temperature of the second zone is 230°C, the temperature of the third zone is 235°C, the temperature of the fourth zone is 235°C, and the temperature of the fifth zone is 240°C , the temperature in the sixth zone is 240°C, the temperature in the seventh zone is 230°C, the temperature of the head is 225°C, and the screw speed is 450r/min. Head extrusion, strand drawing, cooling, and pelletizing to obtain high-black and bright PMMA/ASA materials with good low-temperature impact resistance.

The prepared PMMA/ASA material was injection-molded into a standard sample bar for testing according to the standard size, and tested according to the physical performance test standard in Table 1, and the performance test results are shown in Table 2.

Example 4

With 60 parts of PMMA-CM211 resin, 35 parts of ASA high rubber powder A-960A, 5 parts of impact modifier SX006, 1 part of brightener polyvinyl acetate, 0.1 part of light and heat stabilizer (1076:168=1: 2, mass ratio) and 0.2 parts of lubricant silicone masterbatch MB50-008 and 0.5 parts of toner dye (transparent red: transparent yellow: transparent blue = 1:1:1.5, mass ratio) after mixing evenly at high speed, send into the twin-screw extruder, wherein the working temperature of each section of the twin-screw extruder is: the temperature of the first zone is 230°C, the temperature of the second zone is 230°C, the temperature of the third zone is 235°C, the temperature of the fourth zone is 235°C, and the temperature of the fifth zone is 240°C , the temperature in the sixth zone is 240°C, the temperature in the seventh zone is 230°C, the temperature of the head is 225°C, and the screw speed is 450r/min. Head extrusion, strand drawing, cooling, and pelletizing to obtain high-black and bright PMMA/ASA materials with good low-temperature impact resistance.

The prepared PMMA/ASA material was injection-molded into a standard sample bar for testing according to the standard size, and tested according to the physical performance test standard in Table 1, and the performance test results are shown in Table 2.

Example 5

With 65 parts of PMMA-CM211 resin, 25 parts of ASA high rubber powder A-960A, 10 parts of impact modifier SX006, 1 part of brightener polyvinyl acetate, 0.4 part of light and heat stabilizer (1076:168=1: 2, mass ratio) and 0.1 part of lubricant silicone masterbatch MB50-008 and 0.9 part of toner dye (transparent red: transparent yellow: transparent blue = 1:1:1.5, mass ratio) after mixing evenly at high speed, send into the twin-screw extruder, wherein the working temperature of each section of the twin-screw extruder is: the temperature of the first zone is 230°C, the temperature of the second zone is 230°C, the temperature of the third zone is 235°C, the temperature of the fourth zone is 235°C, and the temperature of the fifth zone is 240°C , the temperature in the sixth zone is 240°C, the temperature in the seventh zone is 230°C, the temperature of the head is 225°C, and the screw speed is 450r/min. Head extrusion, strand drawing, cooling, and pelletizing to obtain high-black and bright PMMA/ASA materials with good low-temperature impact resistance.

The prepared PMMA/ASA material was injection-molded into a standard sample bar for testing according to the standard size, and tested according to the physical performance test standard in Table 1, and the performance test results are shown in Table 2.

Example 6

With 70 parts of PMMA-CM211 resin, 25 parts of ASA high rubber powder A-960A, 5 parts of impact modifier SX006, 1 part of brightener polyvinyl acetate, 0.2 part of light and heat stabilizer (1076:168=1: 2, mass ratio) and 0.2 parts of lubricant silicone masterbatch MB50-008 and 1 part of toner dye (transparent red: transparent yellow: transparent blue = 2:1:1, mass ratio) after mixing evenly at high speed, send into the twin-screw extruder, wherein the working temperature of each section of the twin-screw extruder is: the temperature of the first zone is 230°C, the temperature of the second zone is 230°C, the temperature of the third zone is 235°C, the temperature of the fourth zone is 235°C, and the temperature of the fifth zone is 240°C , the temperature in the sixth zone is 240°C, the temperature in the seventh zone is 230°C, the temperature of the head is 225°C, and the screw speed is 450r/min. Head extrusion, strand drawing, cooling, and pelletizing to obtain high-black and bright PMMA/ASA materials with good low-temperature impact resistance.

The prepared PMMA/ASA material was injection-molded into a standard sample bar for testing according to the standard size, and tested according to the physical performance test standard in Table 1, and the performance test results are shown in Table 2.

Comparative example 1

60 parts of PMMA-CM211 resin, 35 parts of ASA high rubber powder XC-500 (rubber powder content 50-52%), 5 parts of impact modifier SX006, 0.5 parts of brightener polyvinyl acetate, 0.5 parts of photothermal Stabilizer (1076:168=1:2, mass ratio) and 0.3 parts of lubricant silicone masterbatch MB50-008 and 0.8 parts of toner dye (transparent red: transparent yellow: transparent blue = 1:1:1.5, mass ratio ) after high-speed stirring and mixing evenly, it is sent into the twin-screw extruder. The temperature is 235°C, the temperature in the fifth zone is 240°C, the temperature in the sixth zone is 240°C, the temperature in the seventh zone is 230°C, the temperature of the head is 225°C, the screw speed is 450r/min, under the conveying and shearing action of the screw of the twin-screw extruder , the material is fully melted and compounded, and then extruded through the machine head, drawn, cooled, and pelletized to obtain PMMA/ASA material.

The prepared PMMA/ASA material was injection-molded into a standard sample bar for testing according to the standard size, and tested according to the physical performance test standard in Table 1, and the performance test results are shown in Table 2.

Comparative example 2

With 65 parts of PMMA-CM211 resin, 25 parts of ASA high rubber powder A-960A, 10 parts of MBS toughening agent, 0.5 part of brightener polyvinyl acetate, 0.3 part of light and heat stabilizer (1076:168=1:2 , mass ratio) and 0.2 parts of lubricant silicone masterbatch MB50-008 and 1 part of toner dye (transparent red: transparent yellow: transparent blue = 1:1:1.5, mass ratio) are mixed evenly by high-speed stirring, and then sent into In the twin-screw extruder, the working temperature of each section of the twin-screw extruder is: the temperature of the first zone is 230°C, the temperature of the second zone is 230°C, the temperature of the third zone is 235°C, the temperature of the fourth zone is 235°C, the temperature of the fifth zone is 240°C, The temperature in the sixth zone is 240°C, the temperature in the seventh zone is 230°C, the temperature of the head is 225°C, and the screw speed is 450r/min. Head extrusion, strand drawing, cooling, pelletizing to obtain PMMA/ASA material.

The prepared PMMA/ASA material was injection-molded into a standard sample bar for testing according to the standard size, and tested according to the physical performance test standard in Table 1, and the performance test results are shown in Table 2.

Comparative example 3

60 parts of PMMA-CM211 resin, 35 parts of ASA high rubber powder A-960A, 5 parts of impact modifier SX006, 0.1 part of light and heat stabilizer (1076:168=1:2, mass ratio) and 0.2 part of lubricant A-C540A (ethylene acrylic acid copolymer) and 0.5 parts of toner dye (transparent red: transparent yellow: transparent blue = 1:1:1.5, mass ratio) are mixed evenly by high-speed stirring, and then sent into the twin-screw extruder. Among them, the working temperature of each section of the twin-screw extruder is: the temperature of the first zone is 230°C, the temperature of the second zone is 230°C, the temperature of the third zone is 235°C, the temperature of the fourth zone is 235°C, the temperature of the fifth zone is 240°C, the temperature of the sixth zone is 240°C, and the temperature of the seventh zone is 240°C. The zone temperature is 230°C, the head temperature is 225°C, and the screw speed is 450r/min. Under the conveying and shearing action of the screw of the twin-screw extruder, the materials are fully melted and compounded, and then extruded through the head, drawn, Cool and pelletize to obtain PMMA/ASA material.

The prepared PMMA/ASA material was injection-molded into a standard sample bar for testing according to the standard size, and tested according to the physical performance test standard in Table 1, and the performance test results are shown in Table 2.

Comparative example 4

With 65 parts of PMMA-CM211 resin, 25 parts of ASA high rubber powder A-960A, 10 parts of impact modifier SX006, 1 part of brightener polyvinyl acetate, 0.4 part of light and heat stabilizer (1076:168=1: 2, mass ratio) and 0.1 parts of lubricant silicone masterbatch MB50-008 and 10 parts of black masterbatch-2014 (Cabot) are mixed evenly at high speed, and then sent into the twin-screw extruder, wherein the twin-screw extruder The working temperature of each section of the machine is: the temperature of the first zone is 230°C, the temperature of the second zone is 230°C, the temperature of the third zone is 235°C, the temperature of the fourth zone is 235°C, the temperature of the fifth zone is 240°C, the temperature of the sixth zone is 240°C, and the temperature of the seventh zone is 230°C , the head temperature is 225°C, the screw speed is 450r/min, under the conveying and shearing action of the screw of the twin-screw extruder, the material is fully melted and compounded, and then extruded through the head, drawn, cooled, and pelletized , to obtain high black and bright PMMA/ASA material with good impact resistance at low temperature.

The prepared PMMA/ASA material was injection-molded into a standard sample bar for testing according to the standard size, and tested according to the physical performance test standard in Table 1, and the performance test results are shown in Table 2.

Table 1

Table 2

table 3

It can be seen from Table 2 and Table 3 that by properly controlling the ratio adjustment and selection of the various components (the lubricant uses AS carrier silicone masterbatch, it not only plays the role of lubrication and surface brightening, but also has the effect of blending with the matrix The compatibility of the resin is good, and other lubricants can play a lubricating role, but the compatibility is relatively poor, and it is easy to produce fogging on the surface of the part under the condition of high temperature injection molding; compared with the traditional black masterbatch, the toner dye , its black dyeing power is greatly enhanced, and the blackening effect is greatly improved visually, and the blackness value (L value) is also greatly reduced. The toughening agent chooses AN/St grafted silicon-acrylic acid type impact resistance The modifier not only has good compatibility with the base material, but also greatly increases the low-temperature impact resistance of the material. During the molding process, polyvinyl acetate can be precipitated on the surface of the workpiece, making it similar to coating the surface of the workpiece, increasing the The brightness of the parts), so that compared with the existing black and bright PMMA/ASA materials, the material’s mechanical properties can be maintained, the low-temperature impact toughness is higher, and the low-temperature impact resistance is better. On the other hand, the material’s The black brightness is high, and the blackness and hue can be adjusted according to the different actual requirements of the parts. It can be used in occasions with high low-temperature impact toughness, high black and bright appearance requirements, and high gloss requirements.

The technical features of the above-mentioned embodiments can be combined arbitrarily. To make the description concise, all possible combinations of the technical features in the above-mentioned embodiments are not described. However, as long as there is no contradiction in the combination of these technical features, should be considered as within the scope of this specification.

The above-mentioned embodiments only express several implementation modes of the present invention, and the descriptions thereof are relatively specific and detailed, but should not be construed as limiting the patent scope of the invention. It should be noted that, for those skilled in the art, several modifications and improvements can be made without departing from the concept of the present invention, and these all belong to the protection scope of the present invention. Therefore, the protection scope of the patent for the present invention should be based on the appended claims.

Claims (7)

1. A PMMA/ASA material, characterized in that, is prepared by the following components in parts by weight: 60-70 parts of polymethyl methacrylate, 25-35 parts of ASA high-glue powder, Impact modifier 5~10 parts, Brightener 0.5~1 part, Heat stabilizer 0.1～0.5 parts, Lubricant 0.1～0.5 parts, 0.5-2 parts of toner dye; The ASA high rubber powder has an ASA glue content ≥ 60% and a particle size < 350nm; the impact modifier is an AN/St grafted silicon-acrylic acid type high weather resistance impact modifier; the brightening The agent is polyvinyl acetate. 2. PMMA/ASA material as claimed in claim 1, is characterized in that, described heat stabilizer is selected from hindered amine heat stabilizer, hindered phenol heat stabilizer and triphenyl phosphite heat stabilizer at least one of . 3. PMMA/ASA material as claimed in claim 1, is characterized in that, described lubricant is the silicone masterbatch with AS as carrier. 4. PMMA/ASA material as claimed in claim 1 is characterized in that, described toner dyestuff is the composite of transparent red, transparent yellow and transparent blue three. 5. a preparation method of the PMMA/ASA material as described in any one of claims 1 to 4, is characterized in that, comprises the following steps: a. Mix polymethyl methacrylate, ASA high rubber powder, impact modifier, brightener, heat stabilizer, lubricant and toner dye evenly to obtain a mixed material according to the ratio of parts by weight; b. Send the mixed material into a twin-screw extruder, and obtain PMMA/ASA material through full melting, compounding, extrusion, stranding, cooling and pelletizing. 6 . The preparation method according to claim 5 , wherein the screw temperature of each section of the twin-screw extruder is 220-250° C., and the screw speed is 100-500 rpm. 7. The preparation method according to claim 6, characterized in that, the screw temperature of each section of the twin-screw extruder is preferably 230-240°C, and the screw speed is 400-500 rpm.