Spraying-free ABS / PMMA alloy material for piano black and preparation method of spraying-free ABS / PMMA alloy material

Abstract

The invention relates to the technical field of materials, and discloses a piano black spraying-free ABS / PMMA alloy material and a preparation method thereof.The piano black spraying-free ABS / PMMA alloy material is prepared by stirring and mixing ABS resin, PMMA, self-made ABS grafted powder, a phosphonitrilic chloride-based flame retardant, an antioxidant 1010, a phosphite antioxidant 168, organic black powder and a calcium stearate processing aid; the preparation method comprises the following steps: mixing ABS and PMMA, adding the mixture into a main feeding bin of an engaged co-rotating twin-screw extruder, extruding, rotating a main machine, and carrying out melt extrusion, cooling, granulation and drying treatment to obtain the piano black spraying-free ABS / PMMA alloy material. By adopting the self-made ABS double-monomer grafted copolymer, the toughness of the material can be effectively improved under the condition that a small amount of ABS double-monomer grafted copolymer is added, and the glossiness of the material is not reduced. Efficient organic black powder is adopted for dyeing, the organic black powder can be uniformly dispersed in the material, and the piano black effect is truly achieved.

Description

Technical Field

[0001] The invention relates to the technical field of materials, and in particular to a piano black spray-free ABS / PMMA alloy material and a preparation method thereof. Background Art

[0002] Existing piano black plastic parts need to be sprayed with high-brightness black paint to achieve a good appearance, but the large amount of solvents used in the painting process have adverse effects on the health of operators and the environment; the painting process is complicated and the scrap rate is high; because the paint is a thermosetting material, it is difficult to melt again, and the recycling performance of plastic products after painting is poor, which affects their reuse. However, the ABS / PMMA alloy treated with dyeing can achieve high black and high brightness effects without spraying, achieving a perfect combination of environmental protection and aesthetics.

[0003] ABS is a commonly used thermoplastic engineering plastic made from the polymerization of three monomers: acrylonitrile, butadiene and styrene. It can still maintain good impact strength at -40°C, and has good dimensional stability and good insulation. It is widely used in home appliances, automobiles and communication equipment. However, pure ABS resin also has some defects, such as high melt viscosity, poor fluidity, poor weather resistance, low hardness, etc., which limit its further application. PMMA is an atactic polymer made by free radical polymerization of methyl methacrylate monomer. It has the characteristics of high surface hardness, good heat resistance and excellent gloss performance. It has been widely used in construction, medical and automotive fields. Since ABS resin contains side phenyl, cyano and unsaturated double bonds, and PMMA has polar side methyl and ester groups, ABS and PMMA have good compatibility in theory. Summary of the invention

[0004] 1. Technical issues to be solved

[0005] In view of the deficiencies in the prior art, the present invention provides a piano black spray-free ABS / PMMA alloy material and a preparation method thereof, which has good flame retardancy and tensile properties.

[0006] (II) Technical solution

[0007] To achieve the above object, the present invention provides the following technical solution: a piano black spray-free ABS / PMMA alloy material, comprising the following components by weight: 35-65 parts by weight of ABS resin, 15-40 parts by weight of PMMA, 15-20 parts by weight of homemade ABS grafted powder, 5-10 parts by weight of hexachlorophosphazene-based flame retardant, 1-2 parts by weight of antioxidant 1010, 0.8-1 parts by weight of phosphite antioxidant 168, 1.5-2 parts by weight of organic black powder, and 1-1.3 parts by weight of calcium stearate processing aid;

[0008] The organic black powder is a water-soluble aniline black powder, which is synthesized from aniline compounds through oxidation, amination, coupling, acylation and other reaction steps, with a maximum wavelength of 570nm;

[0009] The self-made ABS graft powder is an ABS dual-monomer graft copolymer obtained by using maleic anhydride and butyl methacrylate as graft monomers; the preparation method of the self-made ABS graft powder is as follows: ABS, MAH, BMA and dicumyl peroxide are placed in a vacuum drying oven at 80-90°C and dried for 2-3 hours, then ABS, MAH, BMA and DCP are mixed in a ratio of 100:2:1:0.1, the raw materials are mixed evenly and then added into a twin-screw extruder, and after melt extrusion, cooling, drying and pelletizing, an ABS dual-monomer graft copolymer with a graft rate of 1.5% is obtained.

[0010] Preferably, the preparation method of the hexachlorophosphazene-based flame retardant is:

[0011] (1) dissolving 4-(2-methylpropenyl)carbonyloxyphenylboronic acid in deionized water, adding hexachlorophosphazene to an acetone solvent, stirring to dissolve, and adding 4-(2-methylpropenyl)carbonyloxyphenylboronic acid dropwise under a nitrogen atmosphere. After the addition is complete, reacting at 60-80° C. for 2-4 hours. After the reaction is complete, rotary evaporation is performed to obtain boron-modified hexachlorophosphazene;

[0012] (2) Adding boron-modified hexachlorophosphazene, 2-aminothiazole-4-acetic acid, and sodium ethoxide catalyst to N,N-dimethylformamide solvent, stirring and mixing, reacting at 25-35° C. for 1-2 h, filtering, washing, and drying after the reaction to obtain intermediate 1;

[0013] (3) The intermediate 1 and 4-hydroxymethyl caged bicyclic phosphate are added to N,N-dimethylformamide solvent, stirred evenly, and p-toluenesulfonic acid catalyst is continuously added thereto, and the reaction is carried out for 5-8 hours. After the reaction is completed, the mixture is distilled under reduced pressure, washed and dried to obtain a hexachlorophosphazene-based flame retardant.

[0014] Preferably, the mass ratio of 4-(2-methylpropenyl)carbonyloxyphenylboronic acid to hexachlorophosphazene in (1) is 1.3-2.2:1.

[0015] Preferably, the mass ratio of the boron-modified hexachlorophosphazene, 2-aminothiazole-4-acetic acid, and sodium ethoxide catalyst in (2) is 1:1.2-1.6:0.02-0.03.

[0016] Preferably, the mass ratio of the intermediate 1, 4-hydroxymethyl caged bicyclic phosphate, and p-toluenesulfonic acid catalyst in (3) is 1.2-1.3:1:0.03-0.05.

[0017] Preferably, the reaction temperature in (3) is 55-70°C.

[0018] Preferably, the preparation method of the piano black spray-free ABS / PMMA alloy material is: ABS resin, PMMA, homemade ABS grafted powder, hexachlorophosphazene-based flame retardant, antioxidant 1010, phosphite antioxidant 168, organic black powder, and calcium stearate processing aid are stirred and mixed, and after drying, placed in the main feeding bin of an intermeshing co-rotating twin-screw extruder, and added into the barrel of the extruder through the feeding screw, and the temperature is set to: 170°C, 170°C, 180°C, 190°C, 195°C, 190°C, 190°C, and the main engine is rotated. After melt extrusion, cooling, granulation, and drying, the piano black spray-free ABS / PMMA alloy material is obtained.

[0019] Preferably, the main engine has a rotation speed of 250-300 rpm.

[0020] (III) Beneficial technical effects

[0021] The present invention is to mix ABS resin, PMMA, self-made ABS graft powder, hexachlorophosphazene-based flame retardant, antioxidant 1010, phosphite antioxidant 168, organic black powder, and calcium stearate processing aid, and then place them in the main feeding bin of an intermeshing co-rotating twin-screw extruder after drying, and then add them into the barrel of the extruder through the feeding screw, and then rotate the main machine, and then melt-extrude, cool, granulate, and dry to obtain a piano black spray-free ABS / PMMA alloy material. The traditional ABS / PMMA alloy solution has always had the technical problem of low toughness. The toughness of the material can only be increased slightly by a compatibilizer such as MBS and EMA, and the glossiness of the material will also decrease rapidly with the addition of the compatibilizer, which greatly limits the use range of the material. The present invention adopts a self-made ABS double-monomer graft copolymer, which can effectively improve the toughness of the material when a small amount of addition is added, and the glossiness of the material is not reduced. The present invention adopts efficient organic black powder dyeing, which can be evenly dispersed in the material, and truly achieves a piano black effect. The phosphorus, boron and sulfur elements in the hexachlorophosphazene-based flame retardant all have good flame retardant effects and together constitute a flame retardant system. DETAILED DESCRIPTION

[0022] Styrene-butadiene-acrylonitrile (ABS) resin is prepared by bulk method. Under the test conditions of 220° C. and 10 kg, its melt index is 8-30 g / 10 min, and acrylonitrile is ≤24%.

[0023] PMMA resin is ultrafine PMMA powder, and under the test conditions of 220°C and 10Kg, its melt index is 20-50g / 10min.

[0024] Example 1

[0025] Organic black powder is a water-soluble aniline black powder, which is synthesized from aniline compounds through oxidation, amination, coupling, acylation and other reaction steps, with a maximum wavelength of 570nm;

[0026] The self-made ABS graft powder is an ABS dual-monomer graft copolymer obtained by using maleic anhydride and butyl methacrylate as graft monomers; the preparation method of the self-made ABS graft powder is as follows: ABS, MAH, BMA and dicumyl peroxide are placed in a vacuum drying oven at 80°C and dried for 2 hours, then ABS, MAH, BMA and DCP are mixed in a ratio of 100:2:1:0.1, the raw materials are mixed evenly and then added into a twin-screw extruder, and after melt extrusion, cooling, drying and pelletizing, an ABS dual-monomer graft copolymer with a graft rate of 1.5% is obtained.

[0027] (1) dissolving 4-(2-methylpropenyl)carbonyloxyphenylboronic acid in deionized water, adding hexachlorophosphazene to an acetone solvent, wherein the mass ratio of 4-(2-methylpropenyl)carbonyloxyphenylboronic acid to hexachlorophosphazene is 1.3:1, stirring to dissolve, and adding 4-(2-methylpropenyl)carbonyloxyphenylboronic acid dropwise under a nitrogen atmosphere. After the addition is complete, reacting at 60° C. for 2 h. After the reaction is complete, rotary evaporation is performed to obtain boron-modified hexachlorophosphazene;

[0028] (2) adding boron-modified hexachlorophosphazene, 2-aminothiazole-4-acetic acid, and sodium ethoxide catalyst to N,N-dimethylformamide solvent, wherein the mass ratio of boron-modified hexachlorophosphazene, 2-aminothiazole-4-acetic acid, and sodium ethoxide catalyst is 1:1.2:0.02, stirring and mixing, reacting at 25°C for 1 hour, filtering, washing, and drying after the reaction to obtain intermediate 1;

[0029] (3) adding intermediate 1 and 4-hydroxymethyl caged bicyclic phosphate to N,N-dimethylformamide solvent, stirring evenly, and continuing to add p-toluenesulfonic acid catalyst thereto, wherein the mass ratio of intermediate 1, 4-hydroxymethyl caged bicyclic phosphate, and p-toluenesulfonic acid catalyst is 1.2:1:0.03, reacting at 55° C. for 5 h, and then performing reduced pressure distillation after completion, washing, and drying to obtain a hexachlorophosphazene-based flame retardant;

[0030] (4) 35 parts by weight of ABS resin, 15 parts by weight of PMMA, 15 parts by weight of homemade ABS grafted powder, 5 parts by weight of hexachlorophosphazene-based flame retardant, 1 part by weight of antioxidant 1010, 0.8 parts by weight of phosphite antioxidant 168, 1.5 parts by weight of organic black powder, and 1 part by weight of calcium stearate processing aid were stirred and mixed, dried, placed in the main feeding bin of an intermeshing co-rotating twin-screw extruder, and added into the barrel of the extruder through the feeding screw. The temperatures were set to 170°C, 170°C, 180°C, 190°C, 195°C, 190°C, and 190°C. The main engine speed was 250 rpm. After melt extrusion, cooling, granulation, and drying, a piano black spray-free ABS / PMMA alloy material was obtained.

[0031] Example 2

[0032] Organic black powder is a water-soluble aniline black powder, which is synthesized from aniline compounds through oxidation, amination, coupling, acylation and other reaction steps, with a maximum wavelength of 570nm;

[0033] The self-made ABS graft powder is an ABS dual-monomer graft copolymer obtained by using maleic anhydride and butyl methacrylate as graft monomers; the preparation method of the self-made ABS graft powder is as follows: ABS, MAH, BMA and dicumyl peroxide are placed in a vacuum drying oven at 90°C and dried for 3 hours, then ABS, MAH, BMA and DCP are mixed in a ratio of 100:2:1:0.1, the raw materials are mixed evenly and then added into a twin-screw extruder, and after melt extrusion, cooling, drying and pelletizing, an ABS dual-monomer graft copolymer with a grafting rate of 1.5% is obtained.

[0034] (1) dissolving 4-(2-methylpropenyl)carbonyloxyphenylboronic acid in deionized water, adding hexachlorophosphazene to an acetone solvent, wherein the mass ratio of 4-(2-methylpropenyl)carbonyloxyphenylboronic acid to hexachlorophosphazene is 1.3-2.2:1, stirring to dissolve, and adding 4-(2-methylpropenyl)carbonyloxyphenylboronic acid dropwise under a nitrogen atmosphere. After the addition is complete, reacting at 80° C. for 4 hours. After the reaction is completed, rotary evaporation is performed to obtain boron-modified hexachlorophosphazene;

[0035] (2) adding boron-modified hexachlorophosphazene, 2-aminothiazole-4-acetic acid, and sodium ethoxide catalyst to N,N-dimethylformamide solvent, wherein the mass ratio of boron-modified hexachlorophosphazene, 2-aminothiazole-4-acetic acid, and sodium ethoxide catalyst is 1:1.6:0.03, stirring and mixing, reacting at 35°C for 2h, filtering, washing, and drying after the reaction to obtain intermediate 1;

[0036] (3) adding intermediate 1 and 4-hydroxymethyl caged bicyclic phosphate to N,N-dimethylformamide solvent, stirring evenly, and continuing to add p-toluenesulfonic acid catalyst thereto, wherein the mass ratio of intermediate 1, 4-hydroxymethyl caged bicyclic phosphate, and p-toluenesulfonic acid catalyst is 1.3:1:0.05, reacting at 70° C. for 8 h, and then performing reduced pressure distillation after completion, washing and drying to obtain a hexachlorophosphazene-based flame retardant;

[0037] (4) 65 parts by weight of ABS resin, 40 parts by weight of PMMA, 20 parts by weight of homemade ABS grafted powder, 10 parts by weight of hexachlorophosphazene-based flame retardant, 2 parts by weight of antioxidant 1010, 1 part by weight of phosphite antioxidant 168, 2 parts by weight of organic black powder, and 1.3 parts by weight of calcium stearate processing aid were stirred and mixed, dried and placed in the main feeding bin of an intermeshing co-rotating twin-screw extruder, and then added into the barrel of the extruder through the feeding screw. The temperatures were set to 170°C, 170°C, 180°C, 190°C, 195°C, 190°C, and 190°C. The main engine speed was 300 rpm. After melt extrusion, cooling, granulation, and drying, a piano black spray-free ABS / PMMA alloy material was obtained.

[0038] Example 3

[0039] Organic black powder is a water-soluble aniline black powder, which is synthesized from aniline compounds through oxidation, amination, coupling, acylation and other reaction steps, with a maximum wavelength of 570nm;

[0040] The self-made ABS graft powder is an ABS dual-monomer graft copolymer obtained by using maleic anhydride and butyl methacrylate as graft monomers; the preparation method of the self-made ABS graft powder is as follows: ABS, MAH, BMA and dicumyl peroxide are placed in a vacuum drying oven at 85°C and dried for 2.5 hours, then ABS, MAH, BMA and DCP are mixed in a ratio of 100:2:1:0.1, the raw materials are mixed evenly and then added into a twin-screw extruder, and after melt extrusion, cooling, drying and pelletizing, an ABS dual-monomer graft copolymer with a graft rate of 1.5% is obtained.

[0041] (1) dissolving 4-(2-methylpropenyl)carbonyloxyphenylboronic acid in deionized water, adding hexachlorophosphazene to an acetone solvent, wherein the mass ratio of 4-(2-methylpropenyl)carbonyloxyphenylboronic acid to hexachlorophosphazene is 1.9:1, stirring to dissolve, and adding 4-(2-methylpropenyl)carbonyloxyphenylboronic acid dropwise under a nitrogen atmosphere. After the addition is complete, reacting at 70° C. for 3 h. After the reaction is complete, rotary evaporation is performed to obtain boron-modified hexachlorophosphazene;

[0042] (2) adding boron-modified hexachlorophosphazene, 2-aminothiazole-4-acetic acid, and sodium ethoxide catalyst to N,N-dimethylformamide solvent, wherein the mass ratio of boron-modified hexachlorophosphazene, 2-aminothiazole-4-acetic acid, and sodium ethoxide catalyst is 1:1.4:0.025, stirring and mixing, reacting at 30° C. for 1 h, filtering, washing, and drying after the reaction is completed to obtain intermediate 1;

[0043] (3) adding intermediate 1 and 4-hydroxymethyl caged bicyclic phosphate to N,N-dimethylformamide solvent, stirring evenly, and continuing to add p-toluenesulfonic acid catalyst thereto, wherein the mass ratio of intermediate 1, 4-hydroxymethyl caged bicyclic phosphate, and p-toluenesulfonic acid catalyst is 1.25:1:0.04, reacting at 65° C. for 6 hours, and then distilling under reduced pressure after completion, washing and drying to obtain a hexachlorophosphazene-based flame retardant;

[0044] (4) 50 parts by weight of ABS resin, 25 parts by weight of PMMA, 18 parts by weight of homemade ABS grafted powder, 8 parts by weight of hexachlorophosphazene-based flame retardant, 1 part by weight of antioxidant 1010, 0.8 parts by weight of phosphite antioxidant 168, 1.5 parts by weight of organic black powder, and 1 part by weight of calcium stearate processing aid were stirred and mixed, dried, placed in the main feeding bin of an intermeshing co-rotating twin-screw extruder, and fed into the barrel of the extruder through the feeding screw. The temperatures were set to 170° C., 170° C., 180° C., 190° C., 195° C., 190° C., and 190° C. The main engine speed was 270 rpm. After melt extrusion, cooling, granulation, and drying, a piano black spray-free ABS / PMMA alloy material was obtained.

[0045] Comparative Example 1

[0046] Compared with Example 3, this comparative example is different in that no hexachlorophosphazene-based flame retardant is added.

[0047] Use an oxygen index tester to test the oxygen index of the material.

[0048] The combustion level of the material is tested using a horizontal vertical combustion tester.

[0049] Table 1: Flame retardancy tests.

[0050] project Oxygen index (%) UL-94 Example 1 28.9 V-0 Example 2 30.2 V-0 Example 3 29.3 V-0 Example 4 28.1 V-0 Comparative Example 1 22.7 V-1

[0051] It can be seen from Table 1 that Examples 1-4 of the present invention have better flame retardant effects than Comparative Example 1.

[0052] Table 2: Test results of piano black non-spraying ABS / PMMA alloy material.

[0053]

[0054] It can be seen from Table 2 that the alloy material of the present invention has good tensile strength and glossiness.

[0055] The preferred embodiments of the present invention disclosed above are only used to help illustrate the present invention. The preferred embodiments do not describe all the details in detail, nor do they limit the invention to the specific implementation methods described. Obviously, many modifications and changes can be made according to the content of this specification. This specification selects and specifically describes these embodiments in order to better explain the principles and practical applications of the present invention, so that those skilled in the art can understand and use the present invention well. The present invention is limited only by the claims and their full scope and equivalents.

Claims

1. A piano black spray-free ABS / PMMA alloy material, characterized in that: The invention comprises the following components by weight: 35-65 parts by weight of ABS resin, 15-40 parts by weight of PMMA, 15-20 parts by weight of self-made ABS grafted powder, 5-10 parts by weight of hexachlorophosphazene-based flame retardant, 1-2 parts by weight of antioxidant 1010, 0.8-1 parts by weight of phosphite antioxidant 168, 1.5-2 parts by weight of organic black powder, and 1-1.3 parts by weight of calcium stearate processing aid; The organic black powder is a water-soluble aniline black powder, which is synthesized from aniline compounds through oxidation, amination, coupling, acylation and other reaction steps, with a maximum wavelength of 570nm; The self-made ABS graft powder is an ABS dual-monomer graft copolymer obtained by using maleic anhydride and butyl methacrylate as graft monomers; the preparation method of the self-made ABS graft powder is as follows: ABS, MAH, BMA and dicumyl peroxide are placed in a vacuum drying oven at 80-90°C and dried for 2-3 hours, then ABS, MAH, BMA and DCP are mixed in a ratio of 100:2:1:0.1, the raw materials are mixed evenly and then added into a twin-screw extruder, and after melt extrusion, cooling, drying and pelletizing, an ABS dual-monomer graft copolymer with a graft rate of 1.5% is obtained.

2. The piano black spray-free ABS / PMMA alloy material according to claim 1, characterized in that: The preparation method of the hexachlorophosphazene-based flame retardant is: (1) dissolving 4-(2-methylpropenyl)carbonyloxyphenylboronic acid in deionized water, adding hexachlorophosphazene to an acetone solvent, stirring to dissolve, and adding 4-(2-methylpropenyl)carbonyloxyphenylboronic acid dropwise under a nitrogen atmosphere. After the addition is complete, reacting at 60-80° C. for 2-4 hours. After the reaction is complete, rotary evaporation is performed to obtain boron-modified hexachlorophosphazene; (2) Adding boron-modified hexachlorophosphazene, 2-aminothiazole-4-acetic acid, and sodium ethoxide catalyst to N,N-dimethylformamide solvent, stirring and mixing, reacting at 25-35° C. for 1-2 h, filtering, washing, and drying after the reaction to obtain intermediate 1; (3) The intermediate 1 and 4-hydroxymethyl caged bicyclic phosphate are added to N,N-dimethylformamide solvent, stirred evenly, and p-toluenesulfonic acid catalyst is continuously added thereto, and the reaction is carried out for 5-8 hours. After the reaction is completed, the mixture is distilled under reduced pressure, washed and dried to obtain a hexachlorophosphazene-based flame retardant.

3. The piano black spray-free ABS / PMMA alloy material according to claim 2, characterized in that: The mass ratio of 4-(2-methylpropenyl)carbonyloxyphenylboronic acid to hexachlorophosphazene in (1) is 1.3-2.2:

1.

4. The piano black spray-free ABS / PMMA alloy material according to claim 2, characterized in that: The mass ratio of the boron-modified hexachlorophosphazene, 2-aminothiazole-4-acetic acid and sodium ethoxide catalyst in (2) is 1:1.2-1.6:0.02-0.

03.

5. The piano black spray-free ABS / PMMA alloy material according to claim 2, characterized in that: The mass ratio of the intermediate 1, 4-hydroxymethyl caged bicyclic phosphate, and p-toluenesulfonic acid catalyst in (3) is 1.2-1.3:1:0.03-0.

05.

6. The piano black spray-free ABS / PMMA alloy material according to claim 2, characterized in that: The reaction temperature in (3) is 55-70°C.

7. A method for preparing a piano black spray-free ABS / PMMA alloy material according to any one of claims 1 to 6, characterized in that: The preparation method of the piano black spray-free ABS / PMMA alloy material comprises the following steps: mixing ABS resin, PMMA, homemade ABS grafted powder, hexachlorophosphazene-based flame retardant, antioxidant 1010, phosphite antioxidant 168, organic black powder, and calcium stearate processing aid, placing the mixture in a main feeding bin of an intermeshing co-rotating twin-screw extruder after drying, adding the mixture into a barrel of the extruder through a feeding screw, setting the temperature to 170° C., 170° C., 180° C., 190° C., 195° C., 190° C., and 190° C., rotating the main machine, and subjecting the mixture to melt extrusion, cooling, granulation, and drying to obtain the piano black spray-free ABS / PMMA alloy material.

8. The piano black spray-free ABS / PMMA alloy material according to claim 7, characterized in that: The main engine has a rotation speed of 250-300 rpm.

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