CN102492255A - ABS/PMMA (Acrylonitrile Butadiene Styrene/Polymethyl Methacrylate) composite material and preparation method thereof - Google Patents
ABS/PMMA (Acrylonitrile Butadiene Styrene/Polymethyl Methacrylate) composite material and preparation method thereof Download PDFInfo
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Abstract
The invention relates to the technical field of high-performance and multifunctional modification of macromolecular engineering plastics, in particular to an ABS/PMMA (Acrylonitrile Butadiene Styrene/Polymethyl Methacrylate) composite material and a preparation method thereof. The ABS/PMMA composite material is formed by melt blending the following raw materials in parts by weight: 20-70 parts of ABS resin, 20-60 parts of PMMA resin, 2-25 parts of MBS (Methacrylate Butadiene Styrene) resin and 1-5 parts of coloring masterbatch, wherein the difference value between the refractive indexes of the ABS resin and the PMMA resin is not more than 0.1. The ABS/PMMA composite material prepared by the preparation method provided by the invention has excellent hardness (the hardness can reach H level and can reach 3H level to the maximum), translucency (the transmittance is 32-40%) and mechanical properties (the tensile strength is 40-65 Mpa, and the bending strength is 48-80 Mpa) and can be applied to a flat-panel television and a surface frame and a base of a liquid crystal display.
Description
Technical field
The present invention relates to macromolecule engineering plastics high performance, multifunction modification technology field, be specifically related to ABS/PMMA matrix material and preparation method thereof.
Background technology
Vinyl cyanide--divinyl--styron (ABS) is a kind of novel universal thermoplastic engineering plastic of the exploitation forties in 20th century; It is the phenylethylene terpolymer, is a kind of thermoplastics that is formed by vinylbenzene (St) and vinyl cyanide (AN), the monomer-grafted copolymerization of divinyl (Bu).It has good electrical property, chemical resistant properties, shock-resistance, low temperature tolerance characteristics, tinctorial property and dimensional stability, is easy to machine-shaping, the rich excellent glossiness of goods, and have toughness and flexibility concurrently.Therefore, ABS resin is widely used in household electrical appliance, industrial spare and accessory parts, shells of electronics and driving member, office appliance, instrument and other field etc.
But the ABS goods are on the low side than some plastic product surface hardness, limited its application in some fields.In addition, constantly bring forth new ideas along with the continuous progress of industrial design and state of the art and to what product appearance designed, industries such as electronic apparatus, instrument and automobile automobile fitting increase the research and the application of translucent material gradually; At present, ABS or its multipolymer that people have special construction through polyreaction preparation often prepare the translucent thermoplastic resin material to substrate coloring then as base material, and its preparation process is complicated, complex operation.
Summary of the invention
The present invention is directed to above-mentioned defective, a kind of ABS/PMMA matrix material with high firmness and translucency is provided, this ABS/PMMA matrix material is to be formed by following materials of weight proportions melt blending:
20～70 parts of ABS resins;
20～60 parts of PMMA resins;
2～25 parts of MBS resins;
1～5 part of color master-batch;
Wherein, said ABS and PMMA resin refractive index difference≤0.1.
Preferably, this ABS/PMMA matrix material is to be formed by following materials of weight proportions melt blending:
35～70 parts of ABS resins;
20～50 parts of PMMA resins;
4～20 parts of MBS resins;
2～4 parts of color master-batchs.
Preferably, the refractive index of said PMMA resin is 1.4～1.6, and the refractive index of ABS resin is 1.5～1.7.
Preferably, the content of vinyl cyanide is 10～26% in the said ABS resin, and Vicat softening point is 100 ℃-120 ℃.
Preferably, the Vicat softening point of said PMMA resin is 100 ℃-125 ℃, and under the condition of 200 ℃/5Kg, its melting index is at 1.5～3.5g/min.
Preferably, the weight percent content of methyl acrylate is 5～45% in the said MBS resin, and the weight percent content of divinyl is 10～40%, and cinnamic weight percent content is 15～60%.
Preferably, said color master-batch is at least a in mineral dye, pigment dyestuff, the dyestuff.
ABS/PMMA matrix material of the present invention also can comprise other additive, such as inhibitor, and photostabilizer, whitening agent, lubricant etc.
Preferably, above-mentioned ABS/PMMA matrix material is to be formed by following materials of weight proportions melt blending:
20～70 parts of ABS resins;
20～60 parts of PMMA resins;
2～25 parts of MBS resins;
1～5 part of color master-batch;
0.2～0.4 part of inhibitor;
0.05～0.2 part of photostabilizer;
0.05～0.2 part in whitening agent;
0.05～0.2 part of lubricant.
Preferred, above-mentioned ABS/PMMA matrix material is to be formed by following materials of weight proportions melt blending:
35～70 parts of ABS resins;
20～50 parts of PMMA resins;
4～20 parts of MBS resins;
2～4 parts of color master-batchs;
0.2～0.3 part of inhibitor;
0.05～0.1 part of photostabilizer;
0.05～0.1 part in whitening agent;
0.05～0.1 part of lubricant.
Preferably, said inhibitor is a hindered phenol antioxidant;
Said photostabilizer is that sebacic acid is two 2,2,6,6-tetramethyl piperidine alcohol ester, two (1,2; 2,6,6-pentamethyl--4-piperidines) sebate, 1-methyl-8-(1,2,2; 6,6-pentamethyl--4-piperidines) sebate, 2,2,6, at least a in the 6-tetramethyl piperidine nitrogen oxygen free radical;
Said whitening agent be 2.2 '-(4.4 '-diphenylethyllene-) two benzoxazoles (white dyes OB-1), 2.5-two-(the 5-tertiary butyl-2-benzoxazolyl) thiophene (white dyes OBC), 4, at least a in two (5 methyl-2-benzoxazolyl) toluylene (white dyes KSN) of 4-, two (benzoxazolyl-2-yl) naphthalenes (white dyes KCB) of 1.4-, 2.5-pair-(the 5-tertiary butyl-2-benzoxazolyl) thiophene derivant (white dyes OBS);
Said lubricant is Triple Pressed Stearic Acid, butyl stearate, oleylamide, ethylene bis stearamide, native paraffin, whiteruss (white oil), at least a in microcrystalline wax, polyethylene wax, the low-molecular-weight polypropylene.
Preferred, said inhibitor comprises main anti-oxidant and auxilliary inhibitor, and the weight ratio of main anti-oxidant and auxilliary inhibitor is 3: 1; Wherein main anti-oxidant is that model is 1010 hindered phenol antioxidant, and auxilliary inhibitor is that model is 168 hindered phenol antioxidant;
Said photostabilizer is that sebacic acid is two 2,2,6,6-tetramethyl piperidine alcohol ester; Said whitening agent is white dyes OB-1; Said lubricant is an ethylene bis stearamide.
The present invention also provides the preparation method of above-mentioned ABS/PMMA matrix material, is specially: according to said ratio said raw materials melt blend is promptly made the ABS/PMMA matrix material.
Preferably, adopt forcing machine to carry out blend in the aforesaid method, Heating temperature is 160～245 ℃, and the head extrusion temperature is 210～220 ℃, main-machine screw rotating speed 450～550r/min, reinforced rotating speed 45～55r/min; The blend time is 1～6 minute; Preferred 2 minutes.
Beneficial effect of the present invention:
The present invention passes through in ABS, to add the PMMA resin, thereby has improved the hardness of ABS resin, has widened its Application Areas; In addition; The present invention rationally controls the ratio and the composition of each component in the prescription; Adopt the method for blending and modifying, the ABS/PMMA matrix material for preparing possesses good hardness (hardness can reach the H rank, reaches as high as the 3H level), translucency (transmittance is 32-40%), (tensile strength is 40-65Mpa to mechanical property; Flexural strength is 48-80Mpa; Modulus in flexure is 2000-2900Mpa) and moulding processability (under the condition of 220 ℃/10Kg, its melt flow rate(MFR) is 20-30g/10min), can be used on the face frame and base of flat panel TV and liquid-crystal display.
Embodiment
The invention provides a kind of ABS/PMMA matrix material with high firmness and translucency, this ABS/PMMA matrix material is to be formed by following materials of weight proportions melt blending:
20～70 parts of ABS resins;
20～60 parts of PMMA resins;
2～25 parts of MBS resins;
1～5 part of color master-batch;
Wherein, said ABS and PMMA resin refractive index difference≤0.1.Adopt the ABS and the PMMA of refractive index difference≤0.1; Thereby make disperse phase (rubber composition; Divinyl among the MBS) and between the external phase (matrix resin, ABS and PMMA resin) at the interface the refraction of light and diffusion be reduced to minimumly, guaranteed the transparency of gained matrix material.
Preferably, this ABS/PMMA matrix material is to be formed by following materials of weight proportions melt blending:
35～70 parts of ABS resins;
20～50 parts of PMMA resins;
4～20 parts of MBS resins;
2～4 parts of color master-batchs.
Preferably, the refractive index of said PMMA resin is 1.4～1.6, and the refractive index of ABS resin is 1.5～1.7.
Preferably, the content of vinyl cyanide is 10～26% in the said ABS resin, 100 ℃-120 ℃ of Vicat softening points.
Preferably, 100 ℃-125 ℃ of the Vicat softening points of said PMMA resin, under the condition of 200 ℃/5Kg, its melting index is at 1.5～3.5g/min.The Vicat softening point that limits ABS and PMMA among the present invention is better in order to ensure the better transparent and resistance toheat of products obtained therefrom in above-mentioned scope.
Preferably, the weight percent content of methyl acrylate is 5～45% in the said MBS resin, and butadiene content is 10～40%, and styrene content is 15～60%.
Preferably, said color master-batch is at least a in mineral dye, pigment dyestuff, the dyestuff; Pigment dyestuff more preferably.Can adopt mineral dye among the present invention, but because its dispersing property in resin is relatively poor, the gained translucent material is fair; The preferred pigment dyestuff that adopts, because it has good dispersing property in ABS, PMMA, the better quality of gained translucent material.
ABS/PMMA matrix material of the present invention also comprises other additive, such as inhibitor, and photostabilizer, whitening agent, lubricant etc.
Preferably, above-mentioned ABS/PMMA matrix material is to be formed by following materials of weight proportions melt blending:
20～70 parts of ABS resins;
20～60 parts of PMMA resins;
2～25 parts of MBS resins;
1～5 part of color master-batch;
0.2～0.4 part of inhibitor;
0.05～0.2 part of photostabilizer;
0.05～0.2 part in whitening agent;
0.05～0.2 part of lubricant.
Preferred, this ABS/PMMA matrix material is to be formed by following materials of weight proportions melt blending:
35～70 parts of ABS resins;
20～50 parts of PMMA resins;
4～20 parts of MBS resins;
2～4 parts of color master-batchs;
0.2～0.3 part of inhibitor;
0.05～0.1 part of photostabilizer;
0.05～0.1 part in whitening agent;
0.05～0.1 part of lubricant.
Said inhibitor is a hindered phenol antioxidant; Said photostabilizer is that sebacic acid is two 2,2,6,6-tetramethyl piperidine alcohol ester, two (1,2; 2,6,6-pentamethyl--4-piperidines) sebate, 1-methyl-8-(1,2,2; 6,6-pentamethyl--4-piperidines) sebate, 2,2,6, at least a in the 6-tetramethyl piperidine nitrogen oxygen free radical; Said whitening agent is at least a among white dyes OB-1, white dyes OBC, white dyes KSN, white dyes KCB, the white dyes OBS; Said lubricant is Triple Pressed Stearic Acid, butyl stearate, oleylamide, ethylene bis stearamide, native paraffin, whiteruss (white oil), at least a in microcrystalline wax, polyethylene wax, the low-molecular-weight polypropylene.
Preferably, said inhibitor comprises main anti-oxidant and auxilliary inhibitor, and the weight ratio of main anti-oxidant and auxilliary inhibitor is 3: 1; Wherein main anti-oxidant is that model is 1010 hindered phenol antioxidant, and auxilliary inhibitor is that model is 168 hindered phenol antioxidant; Said photostabilizer is that sebacic acid is two 2,2,6,6-tetramethyl piperidine alcohol ester; Said whitening agent is white dyes OB-1; Said lubricant is an ethylene bis stearamide.
The present invention also provides the preparation method of above-mentioned ABS/PMMA matrix material, is specially: according to said ratio said raw materials melt blend (promptly the temperature more than the fusing point of ABS and PMMA, below the decomposition temperature is carried out mechanical blending) is promptly made the ABS/PMMA matrix material.
Preferably, adopt forcing machine to carry out blend in the aforesaid method, Heating temperature is 160～245 ℃, and the head extrusion temperature is 210～220 ℃, is preferably 215 ℃; Main-machine screw rotating speed 450～550r/min, reinforced rotating speed 45～55r/min; The blend time is 1～6 minute; Preferred 2 minutes.
Preferably, in the aforesaid method, before mixing ABS resin, PMMA resin and MBS resin are carried out drying, drying temperature is 70～90 ℃, is preferably 80 ℃, 3～6 hours time of drying.
Through embodiment the present invention is specifically described below; It is important to point out that embodiment only is used for further specifying of the present invention; Can not be interpreted as the restriction to protection domain of the present invention, these those skilled in the art can make some nonessential improvement and adjustment according to the present invention.
The preparation and the performance thereof of embodiment 1ABS/PMMA matrix material
Take by weighing various raw materials according to table 1 composition of raw materials, wherein (weight percent content of methyl acrylate is 25% to the MBS resin, and butadiene content is 15%; Styrene content is 60%), (refractive index is 1.492 to the PMMA resin; Vicat softening point is 115| ℃, and under the condition of 200 ℃/5Kg, its melting index is 2.0g/min), (refractive index is 1.56 to ABS resin; The content of vinyl cyanide is 20%, and Vicat softening point is 108 ℃); MBS resin, PMMA resin, ABS resin are under 80 ℃ of conditions dry 3 hours respectively before using, and various raw materials (comprising auxiliary material) are added the high-speed mixer high speed mixed low speed discharging again 2 minutes.Material behind the mixing gets high firmness, translucent ABS/PMMA matrix material through fusing and pelleting, and product property detects data and sees table 2.The melt pelletization condition is: twin screw extruder screw speed 500r/min, and reinforced rotating speed 50r/min, the Heating temperature section is set at: 1 section/170 ℃; 2 sections/190 ℃, 3 sections/200 ℃, 4 sections/215 ℃; 5 sections/225 ℃, 6 sections/235 ℃, 7 sections/225 ℃; 8 sections/215 ℃, 9 sections/210 ℃, head extrusion temperature: 215 ℃.
The preparation and the performance thereof of embodiment 2-5ABS/PMMA matrix material
The preparation method of embodiment 2～5 is identical with embodiment 1, and concrete proportioning raw materials is seen table 1; The product of 4 embodiment is tested according to GB, and performance data is as shown in table 2.
The preparation of Comparative Examples 1ABS/PMMA matrix material and performance thereof
The preparation method of Comparative Examples 1 is identical with embodiment 1, and concrete proportioning raw materials is seen table 1; Products obtained therefrom is tested according to GB, and performance data is as shown in table 2.Can know that by table 2 when the color concentrate addition surpassed 5wt%, the products obtained therefrom transmittance sharply descended, and can not get corresponding translucent product.
Comparative Examples 2 polyreactions obtain the performance of product
In the prior art vinyl cyanide, divinyl, vinylbenzene and MMA MONOMER prepared the copolymerization product of acrylonitrile-butadiene-styrene (ABS)-TEB 3K through polyreaction; Again to the corresponding translucent product of the painted preparation of this multipolymer; The products obtained therefrom performance is as shown in table 2; Utilize the performance of this method products obtained therefrom close with the inventive method products obtained therefrom performance; But a large amount of polymerization equipment of needs when preparing translucent material, and there are shortcomings such as complex operation, long reaction time through monomer polymerization reactions.
The performance of Comparative Examples 3ABS material
The ABS material that we adopt embodiment 1-5 has carried out transmittance test and pencil hardness test, and the transmittance of ABS is 88%, and pencil hardness is HB.Show and adopt set of dispense of the present invention method when, can obtain translucent product, and gained translucent material hardness is higher.
The proportioning raw materials unit of table 1ABS/PMMA matrix material: kilogram
In the table 1; Inhibitor is antioxidant 1010 (four [β-(3; The 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester) and the compound of inhibitor 168 (tricresyl phosphite (24-di-tert-butyl-phenyl) ester), antioxidant 1010: oxidation inhibitor 168=3: 1 by weight.
Table 2ABS/PMMA performance of composites
In the foregoing description, tensile strength is tested according to GB GB/T1040.2-2006; Flexural strength, modulus in flexure are tested according to GB GB/T9341-2000; The socle girder notched Izod impact strength is tested according to GB GB/T1843-2008; Heat-drawn wire is tested according to GB GB/T1634.2-2004; Melt flow rate(MFR) is tested according to GB GB/T3682-2000; Transmittance is tested according to GB GB/T2410-2008; Pencil hardness is tested according to GB GB/T6739-1996, and wherein, the grade of pencil hardness is followed successively by from low to high: 6B, 5B, 4B, 3B, 2B, B, HB, F, H, 2H, 3H, 4H, 5H, 6H, 7H, 8H, 9H.
From table 2, can find out; Ratio and composition through each component in the reasonable control prescription; Add the transmittance that effectively to control the gained thermoplastic resin composition under the situation of a certain amount of color master-batch; The ABS/PMMA matrix material for preparing possesses good hardness (hardness can reach the H rank, reaches as high as the 3H level), translucency (transmittance is 32-40%), (tensile strength is 40-65Mpa to mechanical property, and flexural strength is 48-80Mpa; Modulus in flexure is 2000-2900Mpa) and moulding processability (under the condition of 220 ℃/10Kg, its melt flow rate(MFR) is 20-30g/10min).In addition; Through relatively Comparative Examples 2 and embodiments of the invention, can see, prepare translucent material through polyreaction in the method that the present invention prepares high firmness, translucent ABS/PMMA matrix material and the prior art and compare; Method of the present invention is simple to operate; Time spent is short, and required starting material are easy to get, and can prepare the translucent material of different colours according to the color that demand changes color master-batch.
Claims (10)
1.ABS/PMMA matrix material, this ABS/PMMA matrix material are to be formed by following materials of weight proportions melt blending:
20～70 parts of ABS resins;
20～60 parts of PMMA resins;
2～25 parts of MBS resins;
1～5 part of color master-batch;
Wherein, said ABS and PMMA resin refractive index difference≤0.1.
2. ABS/PMMA matrix material according to claim 1 is characterized in that, this ABS/PMMA matrix material is to be formed by following materials of weight proportions melt blending:
35～70 parts of ABS resins;
20～50 parts of PMMA resins;
4～20 parts of MBS resins;
2～4 parts of color master-batchs.
3. ABS/PMMA matrix material according to claim 1 and 2 is characterized in that, the refractive index of said PMMA resin is 1.4～1.6, and the refractive index of ABS resin is 1.5～1.7.
4. according to each described ABS/PMMA matrix material of claim 1-3, it is characterized in that the weight percent content of vinyl cyanide is 10～26% in the said ABS resin, Vicat softening point is 100 ℃-120 ℃.
5. according to each described ABS/PMMA matrix material of claim 1-4, it is characterized in that the Vicat softening point of said PMMA resin is 100 ℃-125 ℃, under the condition of 200 ℃/5Kg, its melting index is at 1.5～3.5g/min.
6. according to each described ABS/PMMA matrix material of claim 1-5; It is characterized in that; The weight percent content of methyl acrylate is 5～45% in the said MBS resin, and the weight percent content of divinyl is 10～40%, and cinnamic weight percent content is 15～60%.
7. according to each described ABS/PMMA matrix material of claim 1-6, it is characterized in that said color master-batch is at least a in mineral dye, pigment dyestuff, the dyestuff.
8. according to each described ABS/PMMA matrix material of claim 1-7, it is characterized in that this ABS/PMMA matrix material is to be formed by following materials of weight proportions melt blending:
20～70 parts of ABS resins;
20～60 parts of PMMA resins;
2～25 parts of MBS resins;
1～5 part of color master-batch;
0.2～0.4 part of inhibitor;
0.05～0.2 part of photostabilizer;
0.05～0.2 part in whitening agent;
0.05～0.2 part of lubricant.
9. ABS/PMMA matrix material according to claim 8 is characterized in that,
Said inhibitor is a hindered phenol antioxidant;
Said photostabilizer is that sebacic acid is two 2,2,6,6-tetramethyl piperidine alcohol ester, two (1,2; 2,6,6-pentamethyl--4-piperidines) sebate, 1-methyl-8-(1,2,2; 6,6-pentamethyl--4-piperidines) sebate, 2,2,6, at least a in the 6-tetramethyl piperidine nitrogen oxygen free radical;
Said whitening agent be 2.2 '-(4.4 '-diphenylethyllene-) two benzoxazoles, 2.5-two-(the 5-tertiary butyl-2-benzoxazolyl) thiophene, 4, at least a in two (5 methyl-2-benzoxazolyl) toluylene of 4-, two (benzoxazolyl-2-yl) naphthalenes of 1.4-, 2.5-pair-(the 5-tertiary butyl-2-benzoxazolyl) thiophene derivant;
Said lubricant is Triple Pressed Stearic Acid, butyl stearate, oleylamide, ethylene bis stearamide, native paraffin, whiteruss, at least a in microcrystalline wax, polyethylene wax, the low-molecular-weight polypropylene.
10. the preparation method of each described ABS/PMMA matrix material of claim 1-9, be specially: each raw materials melt blend promptly makes the ABS/PMMA matrix material.
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| CN103214776A (en) * | 2013-04-12 | 2013-07-24 | 深圳Tcl新技术有限公司 | Anti-scraping material, television front shell and preparation method of anti-scraping material |
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| CN103756238A (en) * | 2013-12-27 | 2014-04-30 | 吴江市东泰电力特种开关有限公司 | Enhanced ABS (Acrylonitrile Butadiene Styrene)/PMMA (Polymethyl Methacrylate) alloy material |
| CN106009476A (en) * | 2016-07-25 | 2016-10-12 | 金田集团（桐城）塑业有限公司 | High-hardness and anti-impact PMMA/ABS (Polymethyl Methacrylate/Acrylonitrile Butadiene Styrene) composite sheet material |
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| CN106009476A (en) * | 2016-07-25 | 2016-10-12 | 金田集团（桐城）塑业有限公司 | High-hardness and anti-impact PMMA/ABS (Polymethyl Methacrylate/Acrylonitrile Butadiene Styrene) composite sheet material |
| CN106398094A (en) * | 2016-08-31 | 2017-02-15 | 佛山市顺德区美的洗涤电器制造有限公司 | ABS (acrylonitrile-butadiene-styrene copolymer) resin material, application and household appliances |
| CN107778747A (en) * | 2017-11-15 | 2018-03-09 | 昆山飞奔塑胶模具有限公司 | A kind of high light wearable ABS/PMMA composites and preparation method thereof |
| CN108510779A (en) * | 2018-03-26 | 2018-09-07 | 中国电子科技集团公司第三十六研究所 | It is a kind of to multiply board and bus stop board for leading for smart electronics bus stop board |
| CN111849115A (en) * | 2020-07-15 | 2020-10-30 | 海信（山东）空调有限公司 | Novel high polymer material and display mask of cabinet air conditioner prepared from same |
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Application publication date: 20120613 |