CN114149642B

CN114149642B - High-rigidity and toughness vitreous ABS alloy material and preparation method and application thereof

Info

Publication number: CN114149642B
Application number: CN202111657846.9A
Authority: CN
Inventors: 汪文; 倪世茂; 王志鹏; 易亦华; 陶鹏
Original assignee: Guangzhou Shitian Material Technology Co ltd
Current assignee: Guangzhou Shitian Material Technology Co ltd
Priority date: 2021-12-31
Filing date: 2021-12-31
Publication date: 2023-08-01
Anticipated expiration: 2041-12-31
Also published as: CN114149642A

Abstract

The invention belongs to the technical field of polymers, and particularly relates to a high-rigidity and toughness vitreous ABS alloy material, and a preparation method and application thereof. The invention comprises the following steps: (1) Initiating cross-linking polymerization of the SBC and the first part of EAA in a molten state to form an SBC-EAA polymer with a grid structure; (2) Initiating cross-linking polymerization of SAN and a second part of EAA in a molten state to form SAN-EAA polymer with a grid structure; (3) And compositing the SBC-EAA polymer and the SAN-EAA polymer in a molten state through intermolecular forces to obtain an SBC-EAA-SAN blend polymer, namely the vitreous ABS alloy material. The ABS material is prepared from SAN, SBC and EAA by a step-by-step cross-linking polymerization and blending process, the same molecular chain segments are arranged between the SAN and the SBC, the molecular structure is similar, the structure of the EAA is similar to that of the SAN and the SBC, and the cross-linking structure is formed after the EAA, the SAN and the SBC are fused, so that the ABS material has the characteristics of ultrahigh fluidity, high rigidity, high transparency, wear resistance and the like, and has wide application prospect.

Description

High-rigidity and toughness vitreous ABS alloy material and preparation method and application thereof

Technical Field

The invention belongs to the technical field of polymers, and particularly relates to a high-rigidity and toughness vitreous ABS alloy material, and a preparation method and application thereof.

Background

The transparent acrylonitrile-butadiene-styrene (ABS) has high glossiness, good hand feeling and impact resistance, and can be widely applied to manufacturing of electric appliances, instruments, automobiles, medical appliances and electrons. While the production of ABS with high transparency is very demanding in terms of technology and equipment.

Generally, transparent ABS is prepared by grafting Methyl Methacrylate (MMA), styrene (St), acrylonitrile (AN) and other components onto polybutadiene or butene-benzene copolymer macromolecules by a graft blending method or by emulsion polymerization, controlling the particle size of the grafted polymer to be smaller than visible light wavelength, and obtaining a matrix resin with methyl methacrylate, styrene and acrylonitrile as main components by a suspension method or bulk polymerization. The two components are granulated by a melt blending method to prepare the transparent ABS material, and the method requires manufacturers to have polymerization capability, large production scale, complex process and single product.

With the continuous development of market demands, the market of high-transparency ABS alloy materials is gradually refined, and the demands of ABS composite materials with the characteristics of high rigidity and toughness, high fluidity, high impact resistance, high transparency, scratch resistance and the like are increased. Therefore, ABS materials with different performances are developed, the application of the materials is specialized, the added value of products is improved, the application range of the materials is enlarged, the market demand is met, and the ABS material is a main research and development direction of various manufacturers.

CN105008406B discloses transparent ABS resin and transparent ABS resin composition, the method of said transparent ABS resin comprising the steps of: adding butadiene monomer in batches to prepare polybutadiene rubber latex with gel content of 86-87%, swelling index of 16-18 and average particle size; to 50 to 60wt% of the polybutadiene rubber latex, 27 to 36wt% of methyl methacrylate monomer, 10 to 13wt% of styrene monomer and 2 to 6wt% of acrylonitrile monomer are continuously added, and at the same time, these monomers are graft polymerized in the presence of a reactive emulsifier and an oil-soluble polymerization initiator to prepare a transparent ABS resin. According to the technical scheme, the dipping degree of the styrene monomer into the polybutadiene rubber latex is minimized, and meanwhile, the styrene monomer forms a grafting shell, so that the grafting shell is effectively formed, and the transparent ABS resin is obtained, however, the requirement on raw materials is very high, the flexibility of production and preparation is insufficient, and there is room for improvement.

CN101935424B discloses an ABS thermoplastic resin and a preparation method thereof, and specifically discloses a thermoplastic resin prepared according to the weight portion ratio: 20-75 parts of SAN resin; 20-60 parts of PMMA resin; 2-25 parts of MBS resin; 0.2 to 0.4 part of antioxidant; 0.05 to 0.2 part of light stabilizer; 0.05 to 0.2 portion of whitening agent; 0.05 to 0.2 portion of lubricant. The ABS thermoplastic resin of the technical proposal has good surface glossiness and hardness, but there is room for improvement in transparency.

In view of the above, the prior art still lacks a method for preparing an ABS alloy material with flexible production, high rigidity and toughness and high transparency.

Disclosure of Invention

Aiming at the defects or improvement demands of the prior art, the invention provides a high-rigidity and toughness glass ABS alloy material and a preparation method thereof, and aims to prepare the high-rigidity and toughness glass ABS alloy material by a step-by-step cross-linking polymerization and blending process of SAN, SBC and EAA, so that the problems of low flowability, insufficient creep resistance, high injection pressure, high speed, high temperature, incapability of thin-wall injection molding and the like of the existing glass ABS alloy material are solved, the flexibility of production and preparation is improved, and the production and the preparation method is not limited by polymerization capacity and production scale.

In order to achieve the above object, according to one aspect of the present invention, there is provided a method for preparing a vitreous ABS alloy material, comprising the steps of:

(1) Initiating cross-linking polymerization of the SBC and the first part of EAA in a molten state to form an SBC-EAA polymer with a grid structure;

(2) Initiating cross-linking polymerization of SAN and a second part of EAA in a molten state to form SAN-EAA polymer with a grid structure;

(3) And compositing the SBC-EAA polymer and the SAN-EAA polymer in a molten state through intermolecular forces to obtain an SBC-EAA-SAN blend polymer, namely the vitreous ABS alloy material.

Preferably, the mass ratio of SAN, SBC and EAA is: (60-85): (10-30): (5-10), wherein the mass of EAA is the sum of the mass of the first portion EAA and the mass of the second portion EAA; preferably, the mass ratio of said SBC to said EAA is 3:1,

preferably, the mass ratio of the first portion EAA to the second portion EAA is (1-2): (1-2).

Preferably, the step (1) specifically comprises: after uniformly mixing SBC, a first part of EAA and an antioxidant, adding the mixture into a double screw from a main feeding port of a double screw extruder, adding an initiator into the double screw from a side feeding port, and carrying out melt cross-linking through the double screw extruder to obtain the final product.

Preferably, the step (2) specifically comprises: after uniformly mixing SBC, a first part of EAA, an antioxidant and a lubricant, adding the mixture into a double screw from a main feeding port of a double screw extruder, adding an initiator into the double screw from a side feeding port, and carrying out melt cross-linking through the double screw extruder to obtain the blend extrusion.

Preferably, the extrusion temperature of the double-screw extruder is 220-240 ℃, the screw rotating speed is 300-500rpm, and the vacuum degree is more than 0.04 MPa;

preferably, the antioxidant is at least one of hindered phenols, thioesters and phosphites, and the initiator is dicumyl peroxide DCP UN3110.

Preferably, the lubricant is at least one of stearate, fatty acid amide and ethylene bis-stearamide.

Preferably, the SAN is an acrylonitrile-styrene copolymer, and the melt index is more than 50g/10min under the test conditions of 220 ℃ and 10.0 KG;

preferably, the SBC is a styrene-butadiene copolymer, the melt index is 10-13g/10min under the test condition of 5.0KG at 200 ℃, and the transmissivity is 80-85%;

preferably, the EAA is an ethylene acrylic acid copolymer having a melt index of 5-8g/10min at 190℃under 2.16KG test.

According to another aspect of the present invention, there is provided a vitreous ABS alloy material prepared by the method of preparing a vitreous ABS alloy material.

According to another aspect of the present invention, there is provided the use of a vitreous ABS alloy material in an electrical appliance, instrument, automobile, medical device or electronic equipment.

The invention utilizes the existing commercial SAN, SBC, EAA and utilizes the same molecular chain segment (styryl) between SAN and SBC, the molecular structure is similar, and the compatibility between the SAN and the SBC is good; the structure of the acrylic polymer EAA is similar to that of the acrylic polymer EAA and the acrylic polymer EAA, the EAA has lower melt index, excellent transparency, adhesive force, toughness, stress crack resistance, creep resistance, water resistance, atomization resistance and other chemical resistance, and the refractive index of the material is similar to that of SAN and SBC. The polymerization proportion of SBC, EAA and SAN is adjusted to reduce the acrylonitrile content in the ABS material, so that the continuous phase refractive index of the ABS material is reduced, the crystalline phase refractive index of the assembled composite ABS material is consistent with the continuous phase refractive index, the reflection and the refraction are reduced as much as possible, and the ABS material has high rigidity and toughness and ultrahigh transparency.

Wherein the melt index of SAN (acrylonitrile-styrene copolymer) is more than 50g/10min, and the preferred SAN is Guangxi long-family SAN CN-4800.SAN is the main molecular chain of the ABS material, and the brand selection of the SAN depends on the application. SAN has high gloss, high transparency, high impact, good heat resistance and mechanical properties, and the elastic modulus is a higher one of the existing thermoplastics, and is not easy to generate internal stress cracking. In addition, polar groups (phenyl and cyano) on the side chains of SAN have the property of forming dipole forces, and are easily assembled to form supramolecules.

The SBC is a high-transmittance styrene-butadiene copolymer, the melt index is 10-13G/10min (under the test condition of 5.0KG at 200 ℃, the transmittance is 80-85%, and the SBC 2G66 is the preferred styrene collar. SBC is formed by copolymerization of styrene-butadiene, has high transparency and good glossiness, is a thermoplastic elastomer with rubber-plastic properties, has the characteristics of excellent tensile strength, good low-temperature performance, good processability and the like, is also a resin modifier, is blended with ABS, improves the impact resistance and flexibility of plastic parts, and is used for automobile materials, electric appliance elements and the like.

The EAA is a high acrylic ethylene-acrylic acid copolymer with a melt index of 5-8g/10min (at 190 ℃ C., 2.16KG test), preferably, the EAA is Dow 3004. The EAA has extremely strong adhesion among molecules, has extremely strong inhibition effect on crystal aggregation under the interaction of hydrogen bond and carboxyl, ensures that lattice nodes are step by step and uniform, breaks the linear structure of a main chain, and has good transparency, adhesion, toughness, chapping stress resistance, creep resistance and chemical resistance. Experiments show that after EAA, SAN and SBC are melted, a cross-linked structure is formed, the waterproof performance is very strong, the water absorption of materials is greatly reduced, water atomization of plastic parts is prevented, and the waterproof material is a key material for improving the transparency of a composite material.

In general, the above technical solutions conceived by the present invention, compared with the prior art, enable the following beneficial effects to be obtained:

(1) According to the invention, SAN, SBC and EAA are prepared into an ABS material through a step-by-step cross-linking polymerization and blending process, the same molecular chain segments are utilized between SAN and SBC, the molecular structure of EAA is similar to that of SAN and SBC, and after the EAA, SAN and SBC are fused, the SBC-EAA polymer and the SAN-EAA polymer are mutually attracted under the action of hydrogen bonds and Van der Waals forces existing between the similar structures under the fusion state, so that the SBC-EAA polymer and the SAN-EAA polymer are compounded through intermolecular forces to form an SBC-EAA-SAN blend polymer, and the ABS material has the characteristics of ultrahigh fluidity, high rigidity, high transparency, wear resistance and the like, and has wide application prospects.

(2) The polymerization proportion of SBC, EAA and SAN is adjusted to reduce the acrylonitrile content in the ABS material, so that the continuous phase refractive index of the ABS material is reduced, the crystalline phase refractive index of the assembled composite ABS material is consistent with the continuous phase refractive index, the reflection and the refraction are reduced as much as possible, and the ABS material has high rigidity and toughness and ultrahigh transparency.

(3) The invention forms a cross-linking structure by utilizing the intermolecular interaction force of EAA, SAN and SBC, has strong waterproof performance, greatly reduces the water absorption of materials, prevents plastic parts from water atomization, improves the transparency of composite materials,

Detailed Description

The present invention will be described in further detail with reference to the following examples in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention. In addition, the technical features of the embodiments of the present invention described below may be combined with each other as long as they do not collide with each other.

Example 1

The components of each material in the embodiment comprise the following components in parts by weight: SAN:80 parts of SBC:15 parts, EAA:5 parts, lubricant EBS:0.2 part of initiator DCP:0.2 parts of an antioxidant 1076:0.2 parts of an antioxidant 168:0.2 parts.

The high-rigidity and toughness vitreous ABS alloy material is prepared by the following steps:

(1) And (3) putting the SBC, 50% EAA and 10% antioxidant into a high-speed dispersion mixer, stirring for 8min, then putting the mixture obtained after stirring into a main feeding port of a double-screw extruder, adding a peroxide initiator DCP into the double-screw from a side feeding port through a high-precision micro metering pump, performing melt cross-linking on two materials through the double-screw extruder to form a melt state mixed cross-linking structure, and extruding and granulating to obtain a mixture-1. Technological conditions of the twin-screw extruder: extrusion temperature 240 ℃, host rotation speed 400rpm; the feeding frequency of the host machine is 9Hz; 10.0ml/min of high-precision micro metering pump;

(2) The SAN, 50% EAA and 10% antioxidant are put into a high-speed dispersion mixer to be stirred for 8min, then the molten state obtained after stirring is put into a main feeding port of a double-screw extruder, a peroxide initiator DCP is added into the double-screw from a side feeding port through a high-precision micro metering pump, and two materials are melted and crosslinked through the double-screw extruder to form a net structure, and then the mixture-2 is obtained through blending extrusion granulation. Technological conditions of the screw extruder: extrusion temperature 220 ℃, host rotation speed 400rpm; the feeding frequency of the host machine is 9Hz; 10.0ml/min of high-precision micro metering pump;

(3) And (3) putting the mixture-1, the mixture-2, 80% of antioxidant and lubricant into a high-speed dispersion mixer to be stirred for 5min, and then extruding, cooling, drying and granulating in a double-screw extruder (the process condition is that the extrusion temperature is 200 ℃ and the host rotation speed is 400 rpm) to obtain the high-rigidity and toughness vitreous ABS alloy material.

Example 2

The components of each material in the embodiment comprise the following components in parts by weight: SAN:74 parts, SBC:20 parts of EAA:6 parts, lubricant EBS:0.2 part of initiator DCP:0.2 parts of an antioxidant 1076:0.2 parts of an antioxidant 168:0.2 parts.

(1) And (3) putting the SBC, 50% EAA and 10% antioxidant into a high-speed dispersion mixer, stirring for 8min, then putting the mixture obtained after stirring into a main feeding port of a double-screw extruder, adding a peroxide initiator DCP into the double-screw from a side feeding port through a high-precision micro metering pump, and carrying out melt cross-linking on two materials through the double-screw extruder to form a net structure, and then blending, extruding and granulating to obtain the mixture-1. Technological conditions of the twin-screw extruder: extrusion temperature 240 ℃, host rotation speed 400rpm; the feeding frequency of the host machine is 9Hz; high-precision micro metering pump 10.0ml/min.

(2) The SAN, 50% EAA and 10% antioxidant are put into a high-speed dispersion mixer to be stirred for 8min, then the mixture obtained after stirring is put into a main feeding port of a double-screw extruder, a peroxide initiator DCP is added into the double-screw from a side feeding port through a high-precision micro metering pump, and two materials are melted and crosslinked through the double-screw extruder to form a net structure, and then the mixture-2 is obtained through blending extrusion granulation. Technological conditions of the screw extruder: extrusion temperature 240 ℃, host rotation speed 400rpm; the feeding frequency of the host machine is 9Hz; high-precision micro metering pump 10.0ml/min.

(3) And (3) putting the mixture (1), the mixture (2), 80% of antioxidant and lubricant into a high-speed dispersion mixer to be stirred for 5min, and then extruding, cooling, drying and granulating in a double-screw extruder (the process condition is that the extrusion temperature is 220 ℃ and the host rotation speed is 400 rpm) to obtain the high-rigidity and toughness vitreous ABS alloy material.

Example 3

The components of each material in the embodiment comprise the following components in parts by weight: SAN:67 parts, SBC:25 parts of EAA:8 parts, lubricant EBS:0.2 part of initiator DCP:0.2 parts of an antioxidant 1076:0.2 parts of an antioxidant 168:0.2 parts.

(3) And (3) putting the mixture-1, the mixture-2, 80% of antioxidant and lubricant into a high-speed dispersion mixer to be stirred for 5min, and then extruding, cooling, drying and granulating in a double-screw extruder (the process condition is that the extrusion temperature is 220 ℃ and the host rotation speed is 400 rpm) to obtain the high-rigidity and toughness vitreous ABS alloy material.

Example 4

The components of each material in the embodiment comprise the following components in parts by weight: SAN:60 parts of SBC:30 parts, EAA:10 parts of lubricant EBS:0.2 part of initiator DCP:0.2 parts of an antioxidant 1076:0.2 parts of an antioxidant 168:0.2 parts.

(1) And (3) putting the SBC, 50% EAA and 10% antioxidant into a high-speed dispersion mixer, stirring for 8min, then putting the mixture obtained after stirring into a main feeding port of a double-screw extruder, adding a peroxide initiator DCP into the double-screw from a side feeding port through a high-precision micro metering pump, and carrying out melt cross-linking on two materials through the double-screw extruder to form a net structure, and then blending, extruding and granulating to obtain the mixture-1. Technological conditions of the twin-screw extruder: extrusion temperature 220 ℃, host rotation speed 400rpm; the feeding frequency of the host machine is 9Hz; high-precision micro metering pump 10.0ml/min.

(2) The SAN, 50% EAA and 10% antioxidant are put into a high-speed dispersion mixer to be stirred for 8min, then the mixture obtained after stirring is put into a main feeding port of a double-screw extruder, a peroxide initiator DCP is added into the double-screw from a side feeding port through a high-precision micro metering pump, and two materials are melted and crosslinked through the double-screw extruder to form a net structure, and then the mixture-2 is obtained through blending extrusion granulation. Technological conditions of the screw extruder: extrusion temperature 220 ℃, host rotation speed 400rpm; the feeding frequency of the host machine is 9Hz; high-precision micro metering pump 10.0ml/min.

Comparative example 1

The components of each material in the embodiment comprise the following components in parts by weight: SAN:75 parts of SBC:15 parts, EAA:10 parts of lubricant EBS:0.2 parts of an antioxidant 1076:0.2 parts of an antioxidant 168:0.2 parts.

The preparation process of comparative example 1: weighing the materials in the raw material formula according to the weight ratio. The SAN, SBC, EAA, lubricant and antioxidant were mixed in proportion for 8 minutes. And then extruding, cooling, drying and granulating under the process conditions that the extrusion temperature of a double-screw extruder is 220 ℃ and the host rotation speed is 400rpm to obtain the transparent ABS material.

Comparative example 2

The components of each material in the embodiment comprise the following components in parts by weight: SAN:65 parts, SBC:30 parts, EAA:5 parts, lubricant EBS:0.2 parts of an antioxidant 1076:0.2 parts of an antioxidant 168:0.2 parts.

The preparation process of comparative example 2: weighing the materials in the raw material formula according to the weight ratio. The SAN, SBC, EAA, lubricant and antioxidant were mixed in proportion for 8 minutes. And then extruding, cooling, drying and granulating under the process conditions that the extrusion temperature of a double-screw extruder is 220 ℃ and the host rotation speed is 400rpm to obtain the transparent ABS material.

Test examples

Examples 1-4 and comparative examples 1-2 were tested and the test results are shown in Table 1.

1. Melt index: the detection conditions are as follows according to the national standard GB/T3682-2018 method: 220 ℃,10KG.

2. Notched Izod impact Strength: the detection conditions are as follows according to the national standard GB/T1843-2008 method: type a gap, 5.5J pendulum.

3. Flexural modulus and flexural strength: according to national standard GB/T9341.2008, the detection conditions are as follows: 2mm/min.

4. Transmittance: transparent plastic haze and transmittance test methods were as per ASTM D1003-2000.

5. Haze: haze meter CS-700, ASTM D1003-2013, clear Plastic light transmittance and haze test method.

TABLE 1 Main parameters and test results tables for examples 1-4 and comparative examples 1-2

As can be seen from Table 1, examples 1-4 show that the ABS material obtained by assembling and compounding the SBC-EAA polymer and the SAN-EAA polymer obtained by the initiator achieves high rigidity, toughness and ultra-high transparency. Comparative examples 1-2 did not use an initiator, and SAN, SBC and EAA did not undergo assembly compounding, and the haze of the singly fused ABS material was increased.

Further analysis shows that by adjusting the polymerization ratio of SBC, EAA and SAN, the acrylonitrile content in the ABS material is reduced, so that the continuous phase refractive index of the ABS material is reduced, the crystalline phase refractive index of the assembled composite ABS material is consistent with the continuous phase refractive index, and the reflection and the refraction are reduced as much as possible.

Among these, SAN has a large impact on melt index. The melt index is relatively low when the SAN usage is reduced; the impact strength, flexural modulus of flexural strength and transmittance slightly varied, with the difference not being great. The using amount of EAA has a certain influence on haze, and the key point is the waterproof and anti-fogging effects of the EAA, SAN and SBC.

It will be readily appreciated by those skilled in the art that the foregoing description is merely a preferred embodiment of the invention and is not intended to limit the invention, but any modifications, equivalents, improvements or alternatives falling within the spirit and principles of the invention are intended to be included within the scope of the invention.

Claims

1. The preparation method of the vitreous ABS alloy material is characterized by comprising the following steps of:

(3) The SBC-EAA polymer and the SAN-EAA polymer are compounded by intermolecular forces in a molten state to obtain an SBC-EAA-SAN blend polymer, namely the vitreous ABS alloy material,

wherein the mass ratio of SAN, SBC and EAA is (60-85): (10-30): (5-10), wherein the mass of EAA is the sum of the mass of first portion EAA and second portion EAA, and the ratio of the mass of first portion EAA to the mass of second portion EAA is (1-2): (1-2).

2. The method of claim 1, wherein the mass ratio of SBC to EAA is 3:1.

3. The preparation method according to claim 1, wherein the step (1) is specifically: after uniformly mixing SBC, a first part of EAA and an antioxidant, adding the mixture into a double screw from a main feeding port of a double screw extruder, adding an initiator into the double screw from a side feeding port, and carrying out melt cross-linking through the double screw extruder to obtain the final product.

4. The preparation method according to claim 1, wherein the step (2) is specifically: after uniformly mixing SBC, a first part of EAA, an antioxidant and a lubricant, adding the mixture into a double screw from a main feeding port of a double screw extruder, adding an initiator into the double screw from a side feeding port, and carrying out melt cross-linking through the double screw extruder to obtain the blend extrusion.

5. The method according to claim 3 or 4, wherein the twin-screw extruder has an extrusion temperature of 220 to 240 ℃, a screw rotation speed of 300 to 500rpm, and a vacuum degree of 0.04MPa or more.

6. The method according to claim 4, wherein the lubricant is at least one of stearate, fatty acid amide, and ethylene bis-stearamide.

7. The process of claim 4, wherein the SAN has a melt index of 50g/10min or greater at 220℃under 10.0KG test conditions.

8. The vitreous ABS alloy material according to any one of claims 1 to 7.

9. Use of the vitreous ABS alloy material according to claim 8 in electrical appliances, instruments, automobiles, medical devices or electronic devices.