CN114316504A

CN114316504A - Regenerated ABS resin composition and preparation method thereof

Info

Publication number: CN114316504A
Application number: CN202210027430.7A
Authority: CN
Inventors: 查超; 于云安; 汪策; 杨彦菊; 周霆
Original assignee: Shanghai Kumho Sunny Plastics Co Ltd
Current assignee: Shanghai Kumho Sunny Plastics Co Ltd
Priority date: 2022-01-11
Filing date: 2022-01-11
Publication date: 2022-04-12
Anticipated expiration: 2042-01-11
Also published as: CN114316504B

Abstract

The invention relates to a regenerated ABS resin composition and a preparation method thereof, wherein the resin composition comprises the following components in parts by weight: 85-94 parts of regenerated ABS, 2-8 parts of high-fluidity additive, 4-10 parts of impurity separant and 2-6 parts of SMA resin, mixing, and putting the mixture into a screw machine for melt extrusion and granulation to obtain the ABS alloy. Compared with the prior art, aiming at the characteristic that different impurities exist in the regenerated ABS, the high-fluidity additive, the impurity separant and the SMA resin are blended to prevent the impurity points from appearing on the surface of the regenerated ABS injection molding. The high-fluidity auxiliary agent has the polarity characteristics different from those of ABS and the high-fluidity characteristic, so that the high-fluidity auxiliary agent is easy to flow to the surface of a material in the injection molding process, uneven pits on the surface generated by impurity points are filled, and the size of the impurity points on the surface of the regenerated ABS is effectively reduced; the impurity separant can effectively isolate impurity points inside the material and is not easy to appear on the surface of the material.

Description

Regenerated ABS resin composition and preparation method thereof

Technical Field

The invention relates to the field of high polymer materials, in particular to a regenerated ABS resin composition and a preparation method thereof.

Background

ABS, an acrylonitrile-butadiene-styrene plastic, has excellent mechanical properties, processability and lacquer properties. Therefore, ABS is widely applied in the industries of household appliances, automobiles and the like. However, the amount of waste is also enormous. Because the material has no degradable property, the direct abandonment can bring great pollution to the environment. The waste plastics are recycled for treatment, and the method is a carbon-reducing and environment-friendly mode. The recovery of ABS is a mature technology, and generally, the regenerated ABS particles are obtained by recovering the shells of old home appliances, such as white home appliances, and performing the steps of crushing, washing many times, dehydrating, drying, etc.

The regenerated ABS particles have different performances according to different sources, and the mechanical performance of the regenerated ABS can meet most use scenes through simple modification. However, all regenerated ABS particles have a problem that impurities in the material are difficult to completely remove, many impurity spots are present inside the material, and the diameter of the impurity spots which cannot be removed is generally 5 μm or less. In some occasions with low requirements on appearance, the regenerated ABS can be directly used, but the wide use of the regenerated ABS is limited by the existence of impurity points when high-gloss parts are injection-molded. In addition, if the parts need to be painted, the existence of the foreign particles may enlarge the defects, and the painting yield is low (below 50%). Therefore, it is a significant problem to solve the problem of impurity contamination of regenerated ABS.

At present, in the industry, there are two conventional methods for solving the impurity points (pock points): 1. the parts are polished to remove impurities, but the process has low efficiency and high cost; 2. the addition of a certain proportion of new ABS material in the material reduces the concentration of impurity points and reduces the probability of pockmarks, but the two methods can not completely solve the problem of pockmarks.

Disclosure of Invention

The invention aims to solve the problem of impurity points existing in the use of regenerated ABS particles, and provides a regenerated ABS resin composition and a preparation method thereof.

The purpose of the invention is realized by the following technical scheme:

the regenerated ABS resin composition comprises the following components in parts by weight:

aiming at the characteristic that different impurities exist in the regenerated ABS, the high-fluidity additive, the impurity separant and the SMA resin are blended in the regenerated ABS, so that the impurity points are prevented from emerging on the surface of a regenerated ABS injection molding piece. The high-fluidity auxiliary agent has the polarity characteristics and the high-fluidity characteristics different from those of ABS (acrylonitrile-butadiene-styrene), so that the high-fluidity auxiliary agent can easily flow to the surface of a material in the injection molding process, uneven pits on the surface generated by impurity points are filled, and the size of the impurity points on the surface of the regenerated ABS is effectively reduced; the impurity separant can effectively isolate impurity points inside the material and is not easy to appear on the surface of the material, and the addition of the SAM improves the compatibility of the impurity separant.

As a preferable technical scheme, the regenerated ABS contains impurities with the size less than or equal to 5 mu m, and the impurity density of the surface is less than 5 pieces/cm². Wherein, the impurities comprise one or more of carbonization points, inorganic impurities and organic impurity points, and the carbonization points refer to a cross-linked carbon structure generated by carbonizing or partially carbonizing ABS through a high-temperature or multi-time thermal process; the inorganic impurity point comprises one or more of silicate impurities, silicon dioxide, calcium carbonate, barium sulfate and zinc oxide; the organic impurity point refers to a gel point generated by crosslinking of the ABS rubber.

As a preferable technical scheme, the melt index of the high-flow additive is more than or equal to 800g/10min at the temperature of 220 ℃ and under the condition of 10 kg.

In the present invention, it is further preferred that, for example, the high flow aid may be one or more of high flow Polystyrene (PS), polyethylene wax (PE wax), polypropylene wax (PP wax), hyperbranched flow aid.

The high-fluidity ABS/ABS alloy has high melt index, and because the high-fluidity ABS and the ABS have completely different polarity characteristics, when the high-fluidity ABS/ABS alloy is mixed with the regenerated ABS, the high-fluidity ABS alloy with high fluidity easily flows to the surface of a material in the injection molding process, and can fill out uneven pits on the surface generated by impurity points, thereby effectively reducing the impurity points on the surface of the regenerated ABS.

As a preferred technical scheme, the impurity separating agent is a block copolymer (PA-g-PEO) of polyamide and polyether.

The PA-g-PEO determined by the invention as an impurity separant plays an important role in further reducing the impurity point of regenerated ABS. After the isolating agent PA-g-PEO is added, impurity points can be effectively isolated inside the material, the impurity points are more easily dispersed at the interface of the PA-g-PEO and the ABS, and the compatibility of the PA-g-PEO and the ABS is further improved by adding the SAM resin, so that the island dispersed structure of the PA-g-PEO in the ABS matrix is smaller, the area of the interface of the PA-g-PEO and the ABS is obviously increased, the dispersion of the impurity points is more easily positioned at the interface, and the impurity points are isolated inside the material and are not easily appeared on the surface of the material, and the impurity points are effectively prevented from emerging on the surface of a regenerated ABS injection molding piece.

As a preferred technical scheme, the block copolymer of polyamide and polyether comprises one or more of PA6-g-PEO or PA 12-g-PEO.

As a preferable technical scheme, the density of the PA-g-PEO is 1.08-1.14 g/cm³. PA-g-PEO in this density range has a suitable PA ratio to achieve optimum compatibility with ABS.

As a preferable technical scheme, the SMA resin is a styrene-maleic anhydride copolymer, wherein the content of maleic anhydride is 8-20%.

A preparation method of a regenerated ABS resin composition comprises the following steps:

(1) preparing materials according to a formula: 85-94 parts of regenerated ABS, 2-8 parts of high-flow auxiliary agent, 4-10 parts of impurity separant and 2-6 parts of SMA resin;

(2) and (2) adding the components in the step (1) into a mixer for full mixing, then putting the mixture into a screw machine for melt extrusion, and cooling and granulating to obtain the regenerated ABS resin composition.

As a preferable technical scheme, the screw machine in the step (2) carries out melt extrusion under the conditions of extrusion temperature of 180-250 ℃ and screw rotation speed of 200-500 r/min.

Compared with the prior art, the technical means used by the invention effectively reduces impurity points (pock points) on the surface of the regenerated ABS injection molding piece, effectively reduces the number of the pock points and the size of the pock points, and improves the paint spraying yield from 20% to over 90%. The invention solves the industrial pain of the regenerated ABS, the obtained regenerated ABS resin has high surface gloss and paint spraying performance which are close to those of the new ABS material, the polishing process before painting of the regenerated ABS can be omitted, the production efficiency is greatly improved, and the application occasion of the regenerated ABS resin is effectively expanded.

Detailed Description

The present invention is described in detail below with reference to specific examples, but the present invention is not limited thereto in any way.

The specific method for defining the relevant indexes and testing the performance comprises the following steps:

1. surface pockmark density: in particular to the number of pockmarks per square centimeter on the surface of the high-gloss board; wherein the injection molding highlight plate has a size of 100mm 3mm, the number of pits on the surface is counted, and the number of pits is divided by 100cm²Equal to the surface pock density, and a total of 20 sample plates were evaluated for average.

2. The pit density on the painted surface is as follows: the surface pitting density of the sample after painting was evaluated by painting with commercially available paint, a high gloss board.

3. Paint spraying yield: and (4) performing paint spraying verification on 50 sample plates in each scheme, wherein no pockmark is a paint spraying good product, and the ratio of the number of the good products to the total paint spraying number is the paint spraying yield.

4. And (3) testing the material performance: the Charpy notched impact strength is measured according to ISO179-1:2010(E) standard, 4J of impact energy and 23 ℃ of test temperature.

Secondly, the raw material information of each component in the embodiment is as follows:

1. regenerated ABS

ABS 1-ABS 3 are commercially available regenerated ABS, ABS 4-ABS 9 are self-made new material ABS resins with different impurities, and the specific preparation method of the self-made ABS resin comprises the following steps: fully mixing the high-bridged petrochemical ABS8391 resin particles with different impurities (talcum powder, silicon dioxide, calcium carbonate, barium sulfate, zinc oxide and calcium carbonate), placing the mixture in a screw machine for melt extrusion (230 ℃), and cooling and granulating to obtain the required ABS with pits.

ABS 1-ABS 9 are as follows:

ABS 1: commercial recycled ABS with a surface pock density of 4.5/cm²The surface pit size is 0.3-1.3 μm, and the notch impact is 8kJ/m²；

ABS 2: commercial recycled ABS with a surface pock density of 2.1 dots/cm²The surface pit size is 0.5-5 μm, and the notch impact is 9kJ/m²；

ABS 3: commercial recycled ABS with a surface pock density of 12.3/cm²The surface pit size is 0.5-3 μm, and the notch impact is 12kJ/m²；

ABS 4: self-made ABS, 3 percent of talcum powder and 2.0 pits/cm of surface density²The surface pit size is 0.6-3 μm, and the notch impact is 8kJ/m²；

ABS 5: self-made ABS, containing 6 percent of silicon dioxide and having the surface pock density of 3.4/cm²The surface pit size is 1-3 μm, and the notch impact is 5kJ/m²；

ABS 6: self-made ABS, containing 13% calcium carbonate with small grain size and the surface pockmark density of 2.6/cm²The surface pit size is 0.6-0.9 μm, and the notch impact is 15kJ/m²；

ABS 7: self-made ABS, containing 6% barium sulfate, with surface pock density of 1.8/cm²The surface pit size is 1-1.8 μm, and the notch impact is 15kJ/m²；

ABS 8: self-made ABS, containing 15% zinc oxide, the surface pockmark density is 5.8/cm²The surface pockmark size is 0.1-06 μm, notched impact 12kJ/m²；

ABS 9: self-made ABS, containing 1 percent of calcium carbonate with large particle size and 2.5 pits/cm of surface density²The surface pit size is 2-8 μm, and the notch impact is 4kJ/m²；

2. High flow aid

ZJ 1: high flow aids, PE wax 3A, honeywell;

ZJ 2: hyperbranched flow aid, C100, wuhan hyperbranched resin technology ltd;

ZJ 3: high flow SAN, EMI200, melt index 1000g/10min (220 ℃, 10kg), good accessibility in Shanghai;

3. impurity isolating agent

GLJ 1: IonphaseU1, PA6-b-PEO, density 1.09g/cm³Eonfei Inc.;

GLJ 2: MH2030, PA-b-PEO, density 1.14g/cm, available from Akema;

GLJ 3: PELESTAT230, PP-b-PEO, density 1.08g/cm³Sanyo chemical Co;

4. SMA resin

SMA700, with an MAH content of 18%, chemical industry of Jiaxing Hua Wen.

The following are specific examples

When the regenerated ABS resin composition is prepared, the mixed components are added into a high-speed mixer, fully mixed and then placed into a screw machine, and melt extrusion is carried out at the extrusion temperature of 180-250 ℃ and the screw rotating speed of 200-500 r/min, and cooling granulation is carried out to obtain the regenerated ABS resin composition.

Example 1

The preparation method of the regenerated ABS resin composition comprises the following specific steps:

(1) preparing materials according to the following formula: 85 parts of ABS1, 2 parts of ZJ1, 10 parts of GLJ1 and 3 parts of SMA;

(2) and (2) adding the components in the step (1) into a high-speed mixer, fully mixing, putting into a screw machine for melt extrusion, cooling and granulating to obtain the regenerated ABS resin composition.

The specific formulation and performance test results are detailed in table 1.

Example 2

(1) preparing materials according to the following formula: 90 parts of ABS2, 3 parts of ZJ1, 5 parts of GLJ1 and 2 parts of SMA;

The specific formulation and performance test results are detailed in table 1.

Example 3

(1) preparing materials according to the following formula: 92 parts of ABS2, 2 parts of ZJ2, 4 parts of GLJ2 and 2 parts of SMA;

The specific formulation and performance test results are detailed in table 1.

Example 4

(1) preparing materials according to the following formula: 90 parts of ABS4, 3 parts of ZJ2, 5 parts of GLJ2 and 2 parts of SMA;

The specific formulation and performance test results are detailed in table 1.

Example 5

(1) preparing materials according to the following formula: 86 parts of ABS6, 4 parts of ZJ2, 4 parts of GLJ1 and 6 parts of SMA;

The specific formulation and performance test results are detailed in table 1.

Example 6

(1) preparing materials according to the following formula: 86 parts of ABS7, 6 parts of ZJ1, 6 parts of GLJ1 and 2 parts of SMA;

The specific formulation and performance test results are detailed in table 1.

Example 7

(1) preparing materials according to the following formula: 85 parts of ABS7, 8 parts of ZJ2, 3 parts of GLJ1 and 4 parts of SMA;

The specific formulation and performance test results are detailed in table 1.

Table 1 examples 1-7 formulation and performance test results

As can be seen from Table 1, in the examples of the present invention, there are no pits on the surface of the recycled ABS resin composition, or the density of the pits is at a low level, which indicates that the technical means used in the present invention effectively reduces the impurity points on the surface of the recycled ABS injection molded part, and effectively reduces the number of the pits and the size of the pits. The paint spraying yield is more than 90%, and the obtained regenerated ABS resin has high surface light performance and paint spraying performance similar to those of the new ABS material.

In addition, in order to further verify the effects of the components of the invention and further embody the technical effects of the technical scheme of the invention, the following comparative examples were developed, and the specific formulation and performance test results are detailed in table 2.

Comparative example 1

Compared to example 1, the high flow aid was removed: the size of the pits becomes large, and the paint spraying yield is reduced

Comparative example 2

Compared to example 1, the PA-b-PEO was removed: increased numb count

Comparative example 3

Compared to example 1, the SMA was removed: PA-b-PEO has larger domain and larger pit number

Comparative example 4

Compared with the example 1, the original ABS is replaced by the regenerated ABS with more pits, and the paint spraying yield is not high due to the excessive number of the pits

Comparative example 5

Compared with example 1, the SAN high flow aid was used to replace the PE wax, and the SAN was not able to flow to the surface to reduce the size of the pits due to its better compatibility with ABS.

Comparative example 6

Compared with the example 1, the PP-b-PEO is adopted to replace PA-b-PEO, and the PP-b-PEO has poor compatibility with ABS, so that the pit number is not reduced, and the spraying yield is low

Comparative example 7

The regenerated ABS from example 1 exhibited the most pockmarks and the lowest paint yield.

Comparative example 8

Compared with the example 1, the ABS8 with a large number of pits shows a certain improvement effect, but the number of pits is large, and the paint spraying yield is low.

Comparative example 9

Compared with the embodiment 1, the ABS9 with larger pit size is adopted, and the improvement effect is limited because the pit size is too large.

TABLE 2 COMPARATIVE EXAMPLES 1-9 COMPARATIVE EXAMPLES AND PERFORMANCES

As can be seen from Table 2, the technical scheme of the invention is very effective in reducing the size of the pits and reducing the number of the pits, and is especially obvious in improving the yield of the paint spraying.

The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.

Claims

1. The regenerated ABS resin composition is characterized by comprising the following components in parts by weight:

2. the recycled ABS resin composition of claim 1, wherein the recycled ABS contains impurities with a size of 5 μm or less, and the impurity density of the surface of the recycled ABS is less than 5/cm²。

3. The recycled ABS resin composition of claim 1, wherein the high flow aid has a melt index of 800g/10min or more at 220 ℃ under 10 kg.

4. The recycled ABS resin composition of claim 3, wherein the high flow additive comprises one or more of high flow polystyrene, polyethylene wax, polypropylene wax, and hyperbranched flow additives.

5. The recycled ABS resin composition according to claim 1, wherein the impurity segregation reducing agent is a block copolymer of polyamide and polyether.

6. The recycled ABS resin composition of claim 5, wherein the block copolymer of polyamide and polyether comprises one or more of PA6-g-PEO or PA 12-g-PEO.

7. The recycled ABS resin composition according to claim 5, wherein the density of the block copolymer of polyamide and polyether is 1.08-1.14 g/cm³。

8. The recycled ABS resin composition of claim 1, wherein the SMA resin is a styrene-maleic anhydride copolymer, wherein the maleic anhydride content is 8-20%.

9. The method for preparing a recycled ABS resin composition according to claim 1, comprising the steps of:

(1) preparing materials according to a formula;

10. The method for preparing recycled ABS resin composition as claimed in claim 9, wherein the screw extruder of step (2) is melt-extruded at an extrusion temperature of 180-250 ℃ and a screw rotation speed of 200-500 rpm.