CN116120725A - Environment-friendly spraying-free ABS/PLA alloy material and preparation method thereof - Google Patents

Abstract

The invention relates to an environment-friendly spraying-free ABS/PLA alloy material and a preparation method thereof, wherein the environment-friendly spraying-free ABS/PLA alloy material is prepared from the following raw materials: MMA-ABS resin, polylactic acid resin, toughening agent, organic metal effect toner, dispersing agent and antioxidant. According to the invention, the metal effect toner is modified by the silane coupling agent, so that the compatibility of the metal effect toner and the resin base material is improved; the problem of poor compatibility of ABS and PLA is solved by MMA-ABS resin, and the metal effect of the spraying-free material is improved. Therefore, the environment-friendly spraying-free ABS/PLA alloy material prepared by the invention has excellent mechanical and processing properties, has excellent metal spraying-free effect, has fewer flow mark and weld mark defects in the processing process, and can be used for appearance parts with higher color requirements.

Description

Environment-friendly spraying-free ABS/PLA alloy material and preparation method thereof

Technical Field

The invention relates to the field of high polymer materials, in particular to an environment-friendly spraying-free ABS/PLA alloy material and a preparation method thereof.

Background

Acrylonitrile-butadiene-styrene (ABS) has high gloss, good chemical stability and processability, and low price, and is widely used in the fields of home appliances, kitchen appliances, electronic appliances, automobiles, toys, and the like. For aesthetic purposes, ABS is usually dyed, sprayed or electroplated, but the solvents and dust in the production process are harmful to the environment and human body.

Polylactic acid PLA is an environment-friendly biodegradable material, and synthetic monomers thereof can be obtained by fermenting biomass raw materials such as corn, starch, straw and the like, and can be decomposed into water and carbon dioxide by microorganisms after the service life is finished, so that the polylactic acid PLA is nontoxic and harmless to the environment.

The global carbon dioxide is continuously discharged, the greenhouse effect is gradually enhanced, and under the background of the global climate problem, the carbon dioxide discharge amount of the synthetic 1KG ABS resin is about 3.12KG, and the carbon dioxide discharge amount of the synthetic 1KG PLA is only 0.5KG, so that the carbon discharge of the material can be reduced by adding PLA into ABS.

Currently, some research is done in the prior art on ABS/PLA materials, such as: chinese patent CN 102617977a discloses a bio-plastic alloy material with excellent performance, which comprises the following components in percentage by weight: 50-70% of ABS resin, 5-30% of PMMA resin, 5-70% of PLA resin, 0.5-2% of thermo-oxidative stabilizer and 0.5-1% of lubricant, and the compatibility of the alloy material is improved by taking PMMA as a bridge of an ABS/PMMA/PLA product, so that the composite material with the advantages of three components of ABS/PMMA/PLA is obtained.

Chinese patent CN 104945837a discloses an ABS/PLA alloy resin composition for 3D printing, which consists of, by mass, 30 to 70 parts of ABS resin, 30 to 70 parts of PLA resin, 0.1 to 1.0 part of cross-linking agent, and 0.5 to 1.5 parts of processing aid, wherein active free radicals generated by peroxides react with ABS and PLA during extrusion, improving compatibility between ABS and PLA.

Chinese patent CN 105001586a discloses a conductive ABS/PLA composite material for 3D printed wires, which comprises 15-30% of ABS by mass percent; 15-30% of emulsion ABS; 1 to 10 percent of styrene-acrylonitrile-glycidyl methacrylate copolymer; 0.01 to 0.05 percent of butyl triphenylphosphine bromide; 5-15% of metal nickel powder; 30-50% of polylactic acid; 1-5% of multi-wall carbon nano tube; 1-5% of graphene microplates; the conductivity of the ABS/PLA material is improved through nickel powder, carbon nano tube micro-plates and graphene plates, and the composite material for 3D printing is prepared.

Chinese patent CN 103965599a discloses a polylactic acid/ABS alloy material and a preparation method thereof, wherein the polylactic acid accounts for 5-95% of the total mass of the polylactic acid and ABS, the ABS accounts for 95-5% of the total mass of the polylactic acid and ABS, the third component accounts for 0.5-15% of the total mass of the polylactic acid and ABS, and the compatibility and toughness of the two components are improved by the linear copolymer or comb-shaped graft copolymer of the third component.

However, the above patent improves the compatibility of two components of ABS and PLA by adding a third component such as PMMA, peroxide, epoxy compound, linear or comb copolymer, but the third component has the disadvantages of difficult control of dispersion and reactive crosslinking during processing, complicated production process, difficult processing, and the like.

Disclosure of Invention

Based on this, it is necessary to provide an ABS/PLA material which can have good glossiness, heat resistance and fluidity of ABS, PMMA high hardness, high gloss, PLA low carbon, high rigidity, and no need of adding a third component compatibilizer, and which can be applied to fields of home appliances, electronic appliances, toy cases, and the like.

In order to achieve the above purpose, the present invention provides the following technical solutions:

the environment-friendly spraying-free ABS/PLA alloy material is prepared from the following raw materials in parts by weight:

the further scheme is that the compound is prepared from the following raw materials in parts by weight:

further, the organic metal effect toner is obtained by modifying metal effect toner by a silane coupling agent. The silane coupling agent is hydrolyzed to generate silanol, which can form hydrogen bond with hydroxyl on the surface of metal powder or pearl powder and shrink into-SiO-bond, and the unsaturated bond at the other end of the silane coupling agent can react with carboxyl end of PLA resin, i.e. the unsaturated double bond can form crosslinking point with the resin, thereby improving the compatibility of the metal effect toner and the resin.

Preferably, the metal effect toner comprises aluminum powder, copper powder, zinc powder and pearlescent pigment; the silane coupling agent is gamma-glycidoxypropyl trimethoxysilane (KH 560) or gamma-methacryloxypropyl trimethoxysilane (KH 570).

Further, the MMA-ABS resin is methyl methacrylate-acrylonitrile-butadiene-styrene copolymer, and the preparation steps are as follows:

(1) Adding styrene, acrylonitrile and methyl methacrylate into a solvent one by one for mixing, then adding the crushed butadiene rubber, and stirring until the butadiene rubber is completely dissolved;

(2) Respectively adding an initiator and a chain transfer agent into the mixed solution in the step (1), introducing nitrogen for protection, sealing, and stirring for reaction under the condition of circulating oil bath;

(3) Filtering the product after the reaction, extruding and granulating by a double-screw extruder, and devolatilizing by a vacuum oven to obtain the MMA-ABS resin.

The MMA chain segment in MMA-ABS has better compatibility with PLA, so that the compatibility between PLA and ABS resin is improved.

The preparation method is characterized in that the mass ratio of styrene, acrylonitrile and methyl methacrylate is 6.5-8: 20.5 to 23:57.5 to 64.5, the mass ratio of the total mass of the styrene, the acrylonitrile and the methyl methacrylate to the solvent is 7:3, the mass ratio of butadiene rubber is 5-15%;

the initiator in the step (2) is di-tert-butyl peroxide, the addition amount of the initiator is 0.05 to 0.1 weight percent, the chain transfer agent is tert-dodecyl mercaptan, and the addition amount of the chain transfer agent is 0.15 to 0.3 weight percent

The circulating oil bath is heated to 130 ℃ at a speed of 2-5 ℃/min, and stirred for reacting for 4-8h at a speed of 100-200 r/min;

the step (3) of devolatilization in the vacuum oven means that the vacuum oven is used for devolatilization for 12 to 20 hours under the condition of the temperature of 80 to 90 ℃/vacuum degree of-0.06 to-1 MPa.

In a further preferred embodiment, the mass ratio of styrene, acrylonitrile and methyl methacrylate is 7.5:22.5:63, the mass ratio of the total mass of styrene, acrylonitrile and methyl methacrylate to the solvent is 7:3, the mass ratio of butadiene rubber is 7%;

the initiator in the step (2) is di-tert-butyl peroxide, the addition amount of the initiator is 0.05wt percent, the chain transfer agent is tert-dodecyl mercaptan, and the addition amount of the initiator is 0.15wt percent

The circulating oil bath is heated to 130 ℃ at 2 ℃/min and stirred for reaction for 4-8h at 150 r/min;

the step (3) of devolatilization in the vacuum oven means that the vacuum oven is used for devolatilization for 12 hours under the condition of the temperature of 85 ℃/vacuum degree of-1 MPa.

Further scheme, the melting point of the polylactic acid resin is 140-150 ℃ and the crystallinity is 0-20%; the low-light pure PLA has low crystallinity, better transparency and glossiness, low molecular chain regularity and easy improvement of compatibility when being compounded with other resins.

The dispersing agent is pentaerythritol stearate;

the antioxidant is beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid n-stearyl alcohol ester and tris [2, 4-di-tert-butylphenyl ] phosphite ester with the mass ratio of 1:2, and a compound of 2.

Further scheme, the toughening agent is methyl methacrylate-butadiene-styrene (MBS) and ethylene-butyl acrylate-glycidyl methacrylate (EMA-GMA) according to the mass ratio of 3-5: 2-5.

The invention also aims to provide a preparation method of the environment-friendly spraying-free ABS/PLA alloy material, which comprises the following steps:

(1) Dispersing a silane coupling agent in an ethanol solution with the concentration of 25wt%, regulating the pH value to 4-5 by using acid, and magnetically stirring to obtain a mixed solution A;

magnetically stirring the metal effect toner in an ethanol solution until the metal effect toner is uniformly dispersed to obtain a mixed solution B;

slowly adding the mixed solution A into the mixed solution B, magnetically stirring for reaction, after the reaction is finished, carrying out suction filtration, flushing with ethanol until the pH value of the filtrate is 7, and drying to obtain the toner with the organic metal effect;

(2) Adding the dried MMA-ABS resin, polylactic acid resin, a toughening agent, organic metal effect toner, a dispersing agent and an antioxidant into a high-speed stirrer according to parts by weight, and mixing to obtain a mixture C;

(3) And (3) putting the mixture C into a double-screw extruder, and granulating after melt extrusion to obtain the ABS/PLA alloy material.

Further, the technological parameters of the twin-screw extruder are as follows: first area 40-50deg.C, second area 170-190 deg.C, third area 175-195 deg.C, fourth area 185-195 deg.C, fifth area 185-200 deg.C, sixth area 195-205 deg.C, seventh area 185-200 deg.C, eighth area 175-195 deg.C, ninth area 170-190 deg.C, tenth area 170-190 deg.C, eleventh area 170-190 deg.C, twelfth area 170-190 deg.C, thirteenth area 195-205 deg.C, fourteen area 195-205 deg.C;

the double-screw extruder is a parallel double-screw extruder, and the length-diameter ratio of the screw is L/D and is 48-52; the temperature of the head of the twin-screw extruder is 195-205 ℃, the rotating speed is set to 250-400 rpm, and the vacuum degree is set to-0.05-0.08 Mpa.

The traditional spraying-free ABS/PLA material is obtained by directly blending inorganic toner with resin and granulating after twin-screw or banburying, but the toner has poor compatibility with a resin matrix, so that defects such as flow marks, welding marks and the like are easy to generate in the subsequent forming process, and the physical property and luster of the material are influenced. In order to solve the problems, the invention modifies the metal effect toner through gamma-glycidol ether oxypropyl trimethoxy silane KH560 or gamma-methacryloxy propyl trimethoxy silane KH570, and the surface of the metal effect toner is grafted with unsaturated double bonds or epoxy groups, so that the metal effect toner can react with carboxyl end groups of PLA resin, the compatibility of the metal effect toner and resin base material is improved, and the metal effect toner can participate in resin flowing in the processing process.

The presently disclosed ABS/PLA alloy materials all have improved compatibility of ABS and PLA by adding a third resin component or cross-linking agent. The invention obtains MMA-ABS resin by the bulk copolymerization of methacrylic acid, styrene, acrylonitrile and butadiene, wherein MMA component has good close compatibility with PLA solubility parameter, can be directly mixed with PLA for granulation, can effectively solve the problems of poor compatibility of ABS and PLA, does not need to additionally add compatilizer and the like, and MMA-ABS can obtain transparent resin by controlling synthesis conditions, is compounded with low-light pure transparent PLA resin, and is beneficial to improving the metal effect of the spraying-free material. And simultaneously, the compatibility among the toner, MMA-ABS and PLA is further improved by adding the toughening agent methyl methacrylate-butadiene-styrene and ethylene-butyl acrylate-glycidyl methacrylate, and the toughness of the composite material is improved.

Compared with the prior art, the invention has the following advantages:

(1) The environment-friendly spraying-free ABS/PLA alloy material prepared by the invention has excellent mechanical and processing properties, has excellent metal spraying-free effect, has fewer flow mark and weld mark defects in the processing process, and can be used for appearance parts with higher color requirements;

(2) The environment-friendly spraying-free ABS/PLA alloy material disclosed by the invention is simple in processing technology, a third component compatilizer is not required to be added, and PLA sources and biomass fermentation have low carbon properties, so that the carbon footprint of the material can be reduced, and the environment protection is facilitated.

Detailed Description

In order that the invention may be understood more fully, a more particular description of the invention will be rendered by reference to specific embodiments thereof which are illustrated in the appended claims. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. These embodiments are provided so that this disclosure will be thorough and complete.

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.

Specific information of each raw material used in the examples and comparative examples of the present invention is as follows:

MMA-ABS resin: selected from Mitsubishi chemical industry raw materials (Shanghai) Limited

Styrene: selected from Jilin petrochemical synthetic resin plants

Acrylonitrile: selected from Jilin petrochemical synthetic resin plants

Butadiene rubber: selected from North Huajin chemical group

Polylactic acid resin: selected from Anhuifeng Proc group Co., ltd

Methyl methacrylate-butadiene-styrene MBS: selected from Korean LG company

Ethylene-butyl acrylate-glycidyl methacrylate EMA-GMA: selected from the company Amara France

The dispersing agent is pentaerythritol stearate;

the toughening agents are methyl methacrylate-butadiene-styrene (MBS) and ethylene-butyl acrylate-glycidyl methacrylate (EMA-GMA);

the antioxidant is beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid n-stearyl alcohol ester and tris [2, 4-di-tert-butylphenyl ] phosphite ester with the mass ratio of 1: 2;

the MMA-ABS resin in each example is a methyl methacrylate-acrylonitrile-butadiene-styrene copolymer prepared as follows:

(1) Styrene, acrylonitrile and methyl methacrylate with the mass ratio of 7.5:22.5:63 are added into toluene solvent one by one for mixing, then 7wt percent of butadiene rubber is added after being sheared, and the mixture is stirred until the butadiene rubber is completely dissolved;

(2) Adding 0.05wt% of initiator di-tert-butyl peroxide and 0.15wt% of chain transfer agent tert-dodecyl mercaptan into the mixed solution in the step (1), introducing nitrogen for protection, sealing, heating to 130 ℃ at 2 ℃/min under the condition of circulating oil bath, and stirring and reacting for 4-8h at 150 r/min;

(3) Filtering the product after the reaction, extruding and granulating by a double-screw extruder, and devolatilizing for 12 hours by using a vacuum oven at the temperature of 85 ℃/vacuum degree of-1 MPa to obtain the MMA-ABS resin.

Example 1:

the environment-friendly spraying-free ABS/PLA alloy material is prepared from the following raw materials in parts by weight:

the preparation method of the environment-friendly spraying-free ABS/PLA alloy material comprises the following steps:

(1) Dispersing KH560 in 25wt% ethanol solution, regulating pH to 4-5 with acetic acid, magnetically stirring for 1h to obtain mixed solution A, magnetically stirring metallic effect toner pearlescent pigment in proper amount of ethanol solution for 1h to uniformly disperse to obtain mixed solution B, slowly adding the mixed solution A into the mixed solution B, magnetically stirring at 60 ℃ for reacting for 1h, filtering after the reaction is finished, flushing with ethanol until the pH of filtrate is 7, and drying at 60 ℃ to obtain organic metallic effect toner;

(2) Mixing the dried MMA-ABS resin, PLA resin, a toughening agent, organic metal effect toner, a dispersing agent and an antioxidant on a high-speed stirrer according to the parts by weight to obtain a mixture C;

(3) The mixture C was fed into a parallel twin-screw extruder, and pelletized after melt extrusion. The technological parameters are as follows: the rotation speed of the twin-screw extruder is set to 250rpm, and the vacuum degree is set to-0.08 MPa.

The double-screw extruder is a parallel double-screw extruder, and the ratio L/D of the screw length L to the screw diameter D is 48.

Example 2:

the environment-friendly spraying-free ABS/PLA alloy material is prepared from the following raw materials in parts by weight:

the preparation method of the environment-friendly spraying-free ABS/PLA alloy material comprises the following steps:

(1) Dispersing KH560 in 25wt% ethanol solution, regulating pH to 4-5 with acetic acid, magnetically stirring for 1h to obtain mixed solution A, magnetically stirring metallic effect toner pearlescent pigment in proper amount of ethanol solution for 1h to uniformly disperse to obtain mixed solution B, slowly adding the mixed solution A into the mixed solution B, magnetically stirring at 60 ℃ for reacting for 1h, filtering after the reaction is finished, flushing with ethanol until the pH of filtrate is 7, and drying at 60 ℃ to obtain organic metallic effect toner;

(2) Mixing the dried MMA-ABS resin, PLA resin, a toughening agent, organic metal effect toner, a dispersing agent and an antioxidant on a high-speed stirrer according to the parts by weight to obtain a mixture C;

(3) The mixture C was fed into a parallel twin-screw extruder, and pelletized after melt extrusion. The process parameters are as follows: the rotation speed of the twin-screw extruder is set to 250rpm, and the vacuum degree is set to-0.08 MPa.

The double-screw extruder is a parallel double-screw extruder, and the ratio L/D of the screw length L to the screw diameter D is 48.

Example 3:

the environment-friendly spraying-free ABS/PLA alloy material is prepared from the following raw materials in parts by weight:

the preparation method of the environment-friendly spraying-free ABS/PLA alloy material comprises the following steps:

(1) Dispersing KH560 in 25wt% ethanol solution, regulating pH to 4-5 with acetic acid, magnetically stirring for 1h to obtain mixed solution A, magnetically stirring metal effect toner aluminum powder in proper amount of ethanol solution for 1h to uniformly disperse to obtain mixed solution B, slowly adding the mixed solution A into the mixed solution B, magnetically stirring at 60 ℃ for reaction for 1h, filtering after the reaction is finished, flushing with ethanol until the pH of filtrate is 7, and drying at 60 ℃ to obtain the organic metal effect toner;

(2) Mixing the dried MMA-ABS resin, PLA resin, a toughening agent, organic metal effect toner, a dispersing agent and an antioxidant on a high-speed stirrer according to the parts by weight to obtain a mixture C;

(3) The mixture C was fed into a parallel twin-screw extruder, and pelletized after melt extrusion. The process parameters are as follows: the rotation speed of the twin-screw extruder is set to 300rpm, and the vacuum degree is set to-0.08 MPa, wherein the rotation speed of the twin-screw extruder is set to 50 ℃ in the first region, 185 ℃ in the second region, 185 ℃ in the third region, 195 ℃ in the fourth region, 195 ℃ in the fifth region, 200 ℃ in the sixth region, 195 ℃ in the seventh region, 195 ℃ in the eighth region, 190 ℃ in the ninth region, 185 ℃ in the tenth region, 185 ℃ in the eleventh region, 185 ℃ in the twelve region, 200 ℃ in the thirteenth region, 200 ℃ in the fourteenth region, 205 ℃ in the nose.

The double-screw extruder is a parallel double-screw extruder, and the ratio L/D of the screw length L to the screw diameter D is 48.

Example 4:

the environment-friendly spraying-free ABS/PLA alloy material is prepared from the following raw materials in parts by weight:

the preparation method of the environment-friendly spraying-free ABS/PLA alloy material comprises the following steps:

(1) Dispersing KH570 in 25wt% ethanol solution, regulating pH to 4-5 with acetic acid, magnetically stirring for 1h to obtain mixed solution A, magnetically stirring metal effect toner aluminum powder in proper amount of ethanol solution for 1h to uniformly disperse to obtain mixed solution B, slowly adding the mixed solution A into the mixed solution B, magnetically stirring at 60 ℃ for reaction for 1h, filtering after the reaction is finished, flushing with ethanol until the pH of filtrate is 7, and drying at 60 ℃ to obtain the organic metal effect toner;

(2) Mixing the dried MMA-ABS resin, PLA resin, a toughening agent, organic metal effect toner, a dispersing agent and an antioxidant on a high-speed stirrer according to the parts by weight to obtain a mixture C;

(3) The mixture C was fed into a parallel twin-screw extruder, and pelletized after melt extrusion. The process parameters are as follows: the rotation speed of the twin-screw extruder is set to 300rpm, and the vacuum degree is set to-0.08 MPa, wherein the rotation speed of the twin-screw extruder is set to 50 ℃ in the first region, 185 ℃ in the second region, 185 ℃ in the third region, 195 ℃ in the fourth region, 195 ℃ in the fifth region, 200 ℃ in the sixth region, 195 ℃ in the seventh region, 195 ℃ in the eighth region, 190 ℃ in the ninth region, 185 ℃ in the tenth region, 185 ℃ in the eleventh region, 185 ℃ in the twelve region, 200 ℃ in the thirteenth region, 200 ℃ in the fourteenth region, 205 ℃ in the nose.

The double-screw extruder is a parallel double-screw extruder, and the ratio L/D of the screw length L to the screw diameter D is 48.

Example 5:

the environment-friendly spraying-free ABS/PLA alloy material is prepared from the following raw materials in parts by weight:

the preparation method of the environment-friendly spraying-free ABS/PLA alloy material comprises the following steps:

(1) Dispersing KH570 in 25wt% ethanol solution, regulating pH to 4-5 with acetic acid, magnetically stirring for 1h to obtain mixed solution A, magnetically stirring metal effect toner copper powder in proper amount of ethanol solution for 1h to uniformly disperse to obtain mixed solution B, slowly adding the mixed solution A into the mixed solution B, magnetically stirring at 60 ℃ for reaction for 1h, filtering after the reaction is finished, flushing with ethanol until the pH of filtrate is 7, and drying at 60 ℃ to obtain the organic metal effect toner;

(2) Mixing the dried MMA-ABS resin, PLA resin, a toughening agent, organic metal effect toner, a dispersing agent and an antioxidant on a high-speed stirrer according to the parts by weight to obtain a mixture C;

(3) The mixture C was fed into a parallel twin-screw extruder, and pelletized after melt extrusion. The process parameters are as follows: the rotation speed of the twin-screw extruder is set to 300rpm, and the vacuum degree is set to-0.08 MPa, wherein the rotation speed of the twin-screw extruder is set to 50 ℃ in the first region, 185 ℃ in the second region, 185 ℃ in the third region, 195 ℃ in the fourth region, 195 ℃ in the fifth region, 200 ℃ in the sixth region, 195 ℃ in the seventh region, 195 ℃ in the eighth region, 190 ℃ in the ninth region, 185 ℃ in the tenth region, 185 ℃ in the eleventh region, 185 ℃ in the twelve region, 200 ℃ in the thirteenth region, 200 ℃ in the fourteenth region, 205 ℃ in the nose.

The double-screw extruder is a parallel double-screw extruder, and the ratio L/D of the screw length L to the screw diameter D is 48.

Example 6:

the environment-friendly spraying-free ABS/PLA alloy material is prepared from the following raw materials in parts by weight:

the preparation method of the environment-friendly spraying-free ABS/PLA alloy material comprises the following steps:

(1) Dispersing KH560 in 25wt% ethanol solution, regulating pH to 4-5 with acetic acid, magnetically stirring for 1h to obtain mixed solution A, magnetically stirring metal effect toner copper powder in proper amount of ethanol solution for 1h to uniformly disperse to obtain mixed solution B, slowly adding the mixed solution A into the mixed solution B, magnetically stirring at 60 ℃ for reaction for 1h, filtering after the reaction is finished, flushing with ethanol until the pH of filtrate is 7, and drying at 60 ℃ to obtain the organic metal effect toner;

(2) Mixing the dried MMA-ABS resin, PLA resin, a toughening agent, organic metal effect toner, a dispersing agent and an antioxidant on a high-speed stirrer according to the parts by weight to obtain a mixture C;

(3) The mixture C was fed into a parallel twin-screw extruder, and pelletized after melt extrusion. The process parameters are as follows: the rotation speed of the twin-screw extruder is set to 400rpm, and the vacuum degree is set to-0.08 MPa, wherein the rotation speed of the twin-screw extruder is set to 50 ℃ in the first region, 190 ℃ in the second region, 195 ℃ in the fourth region, 205 ℃ in the fifth region, 205 ℃ in the sixth region, 200 ℃ in the seventh region, 195 ℃ in the eighth region, 190 ℃ in the ninth region, 185 ℃ in the tenth region, 185 ℃ in the eleventh region, 185 ℃ in the twelfth region, 200 ℃ in the thirteenth region, 200 ℃ in the fourteenth region, 205 ℃ in the nose, and 205 ℃.

The double-screw extruder is a parallel double-screw extruder, and the ratio L/D of the screw length L to the screw diameter D is 52.

Example 7:

the environment-friendly spraying-free ABS/PLA alloy material is prepared from the following raw materials in parts by weight:

the preparation method of the environment-friendly spraying-free ABS/PLA alloy material comprises the following steps:

(1) Dispersing KH570 in 25wt% ethanol solution, regulating pH to 4-5 with acetic acid, magnetically stirring for 1h to obtain mixed solution A, magnetically stirring metal effect toner copper powder in proper amount of ethanol solution for 1h to uniformly disperse to obtain mixed solution B, slowly adding the mixed solution A into the mixed solution B, magnetically stirring at 60 ℃ for reaction for 1h, filtering after the reaction is finished, flushing with ethanol until the pH of filtrate is 7, and drying at 60 ℃ to obtain the organic metal effect toner;

(2) Mixing the dried MMA-ABS resin, PLA resin, a toughening agent, organic metal effect toner, a dispersing agent and an antioxidant on a high-speed stirrer according to the parts by weight to obtain a mixture C;

(3) The mixture C was fed into a parallel twin-screw extruder, and pelletized after melt extrusion. The process parameters are as follows: the rotation speed of the twin-screw extruder is set to 300rpm, and the vacuum degree is set to-0.08 MPa, wherein the rotation speed of the twin-screw extruder is set to 50 ℃ in the first region, 185 ℃ in the second region, 185 ℃ in the third region, 195 ℃ in the fourth region, 195 ℃ in the fifth region, 200 ℃ in the sixth region, 195 ℃ in the seventh region, 195 ℃ in the eighth region, 190 ℃ in the ninth region, 185 ℃ in the tenth region, 185 ℃ in the eleventh region, 185 ℃ in the twelfth region, 200 ℃ in the thirteenth region, 205 ℃ in the fourteenth region, 205 ℃ in the nose temperature 205 ℃.

The double-screw extruder is a parallel double-screw extruder, and the ratio L/D of the screw length L to the screw diameter D is 52.

Example 8:

the environment-friendly spraying-free ABS/PLA alloy material is prepared from the following raw materials in parts by weight:

the preparation method of the environment-friendly spraying-free ABS/PLA alloy material comprises the following steps:

(1) Dispersing KH560 in 25wt% ethanol solution, regulating pH to 4-5 with acetic acid, magnetically stirring for 1h to obtain mixed solution A, magnetically stirring metal effect toner in proper amount of ethanol solution for 1h to uniformly disperse to obtain mixed solution B, slowly adding the mixed solution A into the mixed solution B, magnetically stirring at 60 ℃ for reacting for 1h, filtering after the reaction is finished, flushing with ethanol until the pH of the filtrate is 7, and drying at 60 ℃ to obtain the organic metal effect toner;

(2) Mixing the dried MMA-ABS resin, PLA resin, a toughening agent, organic metal effect toner, a dispersing agent and an antioxidant on a high-speed stirrer according to the parts by weight to obtain a mixture C;

(3) The mixture C was fed into a parallel twin-screw extruder, and pelletized after melt extrusion. The process parameters are as follows: the rotation speed of the twin-screw extruder is set to 300rpm, and the vacuum degree is set to-0.08 MPa, wherein the rotation speed of the twin-screw extruder is 50 ℃ in the first region, 185 ℃ in the second region, 190 ℃ in the third region, 195 ℃ in the fourth region, 200 ℃ in the fifth region, 205 ℃ in the sixth region, 200 ℃ in the seventh region, 195 ℃ in the eighth region, 190 ℃ in the ninth region, 190 ℃ in the tenth region, 190 ℃ in the eleventh region, 190 ℃ in the twelfth region, 205 ℃ in the thirteenth region, 205 ℃ in the fourteenth region, 205 ℃ in the nose temperature, and 205 ℃.

The double-screw extruder is a parallel double-screw extruder, and the ratio L/D of the screw length L to the screw diameter D is 48.

Comparative example 1:

the environment-friendly spraying-free ABS/PLA alloy material is prepared from the following raw materials in parts by weight:

the preparation method of the environment-friendly spraying-free ABS/PLA alloy material comprises the following steps:

(1) Dispersing KH560 in 25wt% ethanol solution, regulating pH to 4-5 with acetic acid, magnetically stirring for 1h to obtain mixed solution A, magnetically stirring metallic effect toner pearlescent pigment in proper amount of ethanol solution for 1h to uniformly disperse to obtain mixed solution B, slowly adding the mixed solution A into the mixed solution B, magnetically stirring at 60 ℃ for reacting for 1h, filtering after the reaction is finished, flushing with ethanol until the pH of filtrate is 7, and drying at 60 ℃ to obtain organic metallic effect toner;

(2) Mixing the dried ABS resin, PMMA resin, PLA resin, a toughening agent, organic metal effect toner, a dispersing agent and an antioxidant on a high-speed stirrer according to the parts by weight to obtain a mixture C;

(3) The mixture C was fed into a parallel twin-screw extruder, and pelletized after melt extrusion. The process parameters are as follows: the rotation speed of the twin-screw extruder is set to 300rpm, and the vacuum degree is set to-0.08 MPa, wherein the rotation speed of the twin-screw extruder is set to 50 ℃ in the first region, 185 ℃ in the second region, 185 ℃ in the third region, 195 ℃ in the fourth region, 195 ℃ in the fifth region, 200 ℃ in the sixth region, 195 ℃ in the seventh region, 195 ℃ in the eighth region, 190 ℃ in the ninth region, 185 ℃ in the tenth region, 185 ℃ in the eleventh region, 185 ℃ in the twelve region, 200 ℃ in the thirteenth region, 200 ℃ in the fourteenth region, 205 ℃ in the nose.

The double-screw extruder is a parallel double-screw extruder, and the ratio L/D of the screw length L to the screw diameter D is 52.

Comparative example 2:

the environment-friendly spraying-free ABS/PLA alloy material is prepared from the following raw materials in parts by weight:

the preparation method of the environment-friendly spraying-free ABS/PLA alloy material comprises the following steps:

(1) Mixing the dried MMA-ABS resin, PLA resin, a toughening agent, unorganized metal effect toner, a dispersing agent and an antioxidant on a high-speed stirrer;

(2) And (3) putting the raw materials uniformly mixed in the step (2) into a parallel double-screw extruder, and granulating after melt extrusion. The process parameters are as follows: the rotation speed of the twin-screw extruder is set to 300rpm, and the vacuum degree is set to-0.08 MPa, wherein the rotation speed of the twin-screw extruder is set to 50 ℃ in the first region, 185 ℃ in the second region, 185 ℃ in the third region, 195 ℃ in the fourth region, 195 ℃ in the fifth region, 200 ℃ in the sixth region, 195 ℃ in the seventh region, 195 ℃ in the eighth region, 190 ℃ in the ninth region, 185 ℃ in the tenth region, 185 ℃ in the eleventh region, 185 ℃ in the twelve region, 200 ℃ in the thirteenth region, 200 ℃ in the fourteenth region, 205 ℃ in the nose.

The double-screw extruder is a parallel double-screw extruder, and the ratio L/D of the screw length L to the screw diameter D is 52.

The following is a list of the raw material compositions of examples and comparative examples.

Table 1 list of the raw materials in parts by weight for examples and comparative examples

The environment-friendly spraying-free ABS/PLA alloy material prepared by the above examples and comparative examples is subjected to the following performance tests:

the notched impact strength of the cantilever beam is tested according to the GB/T1843 standard, and the toughness of the material is represented.

The melt index was measured according to GB/T3682-2000 standard at 200℃under a load of 5kg.

Flexural modulus the stiffness of the material was characterized according to the GB/T9341-2008 standard test.

The glossiness is tested according to the GB/T8807-1988 standard, the incident angle is 60 degrees, the surface effect of the polymer is represented, and the larger the numerical value is, the better the surface effect is.

The results of the performance test are shown in Table 2.

Table 2 performance lists of the environmentally friendly spray-free ABS/PLA alloy materials of examples and comparative examples

	Impact Strength (kJ/m) 2 )	Melt finger (g/10 min)	Flexural modulus (MPa)	Gloss 60 °
					Example 1	8	45	3174	83
Example 2	10	43	2904	87
					Example 3	13	38	2642	90
Example 4	15	36	2478	92
					Example 5	17	32	2389	96
Example 6	20	27	2315	98
					Example 7	21	25	2435	99
Example 8	11	20	2788	101
					Comparative example 1	23	15	2059	87
Comparative example 2	15	25	2401	80

Examples 1-8 are prepared by adjusting the addition ratio of MMA-ABS resin, PLA resin, toughening agent and toner, and it can be seen from the table that the impact of PLA material is lower, the impact performance of the material is gradually improved along with the reduction of the PLA ratio, and the impact increase approaches to the extreme value when the PLA addition amount is 20-30%; in addition, the glossiness is gradually improved along with the increase of the proportion of MMA-ABS. By contrast, the combination properties of examples 6 and 7 are optimal, and PLA has low carbon properties, which can reduce carbon emissions of ABS materials, and can be applied to the fields of household appliances, electronic appliances, toy shells and the like.

Example 6 the use of PMMA as the third component in comparative example 1 improved ABS to PLA compatibility, the higher impact was associated with the selection of bulk ABS (about 20%) with butadiene levels higher than MMA-ABS (7%) but the lower flowability, flexural modulus and gloss, and the use of unorganized metallic toners in comparative example 6 gave lower impact and gloss, poor compatibility with the resin, poor impact resistance, and a tendency for the toner to block flow during molding to float on the resin surface resulting in reduced gloss of the material compared to comparative example 2.

The technical features of the above-described embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above-described embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.

The above examples illustrate only a few embodiments of the invention, which are described in detail and are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.

Claims (10)

1. The environment-friendly spraying-free ABS/PLA alloy material is characterized by being prepared from the following raw materials in parts by weight:

2. the environment-friendly spraying-free ABS/PLA alloy material according to claim 1, which is characterized by being prepared from the following raw materials in parts by weight:

3. the environment-friendly spraying-free ABS/PLA alloy material according to claim 1 or 2, wherein the organic metal effect toner is obtained by modifying metal effect toner by a silane coupling agent.

4. An environmentally friendly spray-free ABS/PLA alloy material according to claim 3, wherein the metallic effect toner comprises aluminum powder, copper powder, zinc powder, pearlescent pigment; the silane coupling agent is gamma-glycidol ether oxygen propyl trimethoxy silane or gamma-methacryloxy propyl trimethoxy silane.

5. The environment-friendly spray-free ABS/PLA alloy material according to claim 1 or 2, wherein the MMA-ABS resin is methyl methacrylate-acrylonitrile-butadiene-styrene copolymer, and the preparation steps are as follows:

(1) Adding styrene, acrylonitrile and methyl methacrylate into a solvent one by one for mixing, then adding the crushed butadiene rubber, and stirring until the butadiene rubber is completely dissolved;

(2) Respectively adding an initiator and a chain transfer agent into the mixed solution in the step (1), introducing nitrogen for protection, sealing, and stirring for reaction under the condition of circulating oil bath;

(3) Filtering the product after the reaction, extruding and granulating by a double-screw extruder, and devolatilizing by a vacuum oven to obtain the MMA-ABS resin.

6. The environment-friendly spray-free ABS/PLA alloy material as claimed in claim 5, wherein the mass ratio of styrene, acrylonitrile and methyl methacrylate is 6.5-8: 20.5 to 23:57.5 to 64.5, the mass ratio of the total mass of the styrene, the acrylonitrile and the methyl methacrylate to the solvent is 7:3, the mass ratio of butadiene rubber is 5-15%;

the initiator in the step (2) is di-tert-butyl peroxide, the addition amount of the initiator is 0.05 to 0.1 weight percent, the chain transfer agent is tert-dodecyl mercaptan, and the addition amount of the chain transfer agent is 0.15 to 0.3 weight percent

The circulating oil bath is heated to 130 ℃ at a speed of 2-5 ℃/min, and stirred for reacting for 4-8h at a speed of 100-200 r/min;

the step (3) of devolatilization in the vacuum oven means that the vacuum oven is used for devolatilization for 12 to 20 hours under the condition of the temperature of 80 to 90 ℃/vacuum degree of-0.06 to-1 MPa.

7. The environment-friendly spraying-free ABS/PLA alloy material according to claim 1 or 2, wherein the melting point of the polylactic acid resin is 140-150 ℃ and the crystallinity is 0-20%;

the dispersing agent is pentaerythritol stearate;

the antioxidant is beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid n-stearyl alcohol ester and tris [2, 4-di-tert-butylphenyl ] phosphite ester with the mass ratio of 1:2, and a compound of 2.

8. The environment-friendly spraying-free ABS/PLA alloy material according to claim 1 or 2, wherein the toughening agent is methyl methacrylate-butadiene-styrene and ethylene-butyl acrylate-glycidyl methacrylate with a mass ratio of 3-5: 2-5.

9. A method for preparing an environment-friendly spraying-free ABS/PLA alloy material according to claim 1 or 2, comprising the steps of:

(1) Dispersing a silane coupling agent in a 25wt% ethanol solution, adjusting the pH value to 4-5 by using acid, and magnetically stirring to obtain a mixed solution A;

magnetically stirring the metal effect toner in an ethanol solution until the metal effect toner is uniformly dispersed to obtain a mixed solution B;

slowly adding the mixed solution A into the mixed solution B, magnetically stirring for reaction, after the reaction is finished, carrying out suction filtration, flushing with ethanol until the pH value of the filtrate is 7, and drying to obtain the toner with the organic metal effect;

(2) Adding the dried MMA-ABS resin, polylactic acid resin, a toughening agent, organic metal effect toner, a dispersing agent and an antioxidant into a high-speed stirrer according to parts by weight, and mixing to obtain a mixture C;

(3) And (3) putting the mixture C into a double-screw extruder, and granulating after melt extrusion to obtain the ABS/PLA alloy material.

10. The method of claim 9, wherein the twin screw extruder process parameters are as follows: first area 40-50deg.C, second area 170-190 deg.C, third area 175-195 deg.C, fourth area 185-195 deg.C, fifth area 185-200 deg.C, sixth area 195-205 deg.C, seventh area 185-200 deg.C, eighth area 175-195 deg.C, ninth area 170-190 deg.C, tenth area 170-190 deg.C, eleventh area 170-190 deg.C, twelfth area 170-190 deg.C, thirteenth area 195-205 deg.C, fourteen area 195-205 deg.C;

the double-screw extruder is a parallel double-screw extruder, and the length-diameter ratio of the screw is L/D and is 48-52; the temperature of the head of the twin-screw extruder is 195-205 ℃, the rotating speed is set to 250-400 rpm, and the vacuum degree is set to-0.05-0.08 Mpa.