CN112940440B

CN112940440B - Regenerated ABS material and preparation method and application thereof

Info

Publication number: CN112940440B
Application number: CN202110396629.2A
Authority: CN
Inventors: 杨圣月; 罗云; 唐晓寒; 陈龙; 秦邦保; 冯乐斐
Original assignee: Shijiazhuang Green Regeneration Resource Co ltd
Current assignee: Shijiazhuang Green Regeneration Resource Co ltd
Priority date: 2021-04-13
Filing date: 2021-04-13
Publication date: 2023-02-17
Anticipated expiration: 2041-04-13
Also published as: CN112940440A

Abstract

The invention provides a regenerated ABS material and application of the method in repairing waste ABS materials. The preparation raw materials of the regenerated ABS material comprise waste ABS, acrylate rubber powder, SAN resin, a lubricant, an optional antioxidant and an optional coupling agent. By adopting the method, the impact resistance of the waste ABS can be effectively repaired, and the weather resistance and the ageing resistance of the ABS are improved. The invention not only solves the problem of impact resistance reduction caused by aging of ABS, but also improves the weather resistance and aging resistance of ABS substantially, thereby greatly improving the utilization rate and the service time of waste ABS materials, having the advantages of cost saving, safety and environmental protection, and having greater popularization and application values.

Description

Regenerated ABS material and preparation method and application thereof

Technical Field

The invention relates to the field of material preparation, in particular to a regenerated ABS material and a preparation method and application thereof.

Background

Styrene-based plastic acrylonitrile-butadiene-styrene (ABS) is widely applied to various electronic and electrical products due to its excellent mechanical properties and processability. However, in the use process of ABS plastics, after long-time illumination, under the influence of environmental factors, the unsaturated double bond structure in the ABS rubber phase is aged and degraded, so that molecular chains are broken, the molecular weight is sharply reduced, the rubber phase is consumed, oxygen-containing groups such as hydroxyl (-OH), carboxyl (-COOH), ketone, aldehyde and the like are generated, then, the styrene-acrylonitrile copolymer (SAN phase) is further initiated to be degraded, and finally, the mechanical property of the waste ABS is degraded. For example, ABS liquid crystal front shells, television front shells, whose granules have only an impact strengthHas a density of 6.5-7.5 kJ/m ² . Therefore, the research on the aging degradation and recovery modification of the waste ABS is of great significance, and the purposes of saving resources, protecting the environment and changing waste into valuable can be achieved.

The invention patent with publication number CN108102282A discloses a regenerated ABS material with synchronous chain extension, toughening and interface repair and a preparation method thereof, the technology adopts a macromolecule chain extender to match with a chain extension accelerant without double bonds to chain extend, toughen and repair the interface of waste ABS, the essence is to prolong the molecular chain broken due to aging, and the aim of repair is achieved. However, the impact property of the recycled ABS is mainly affected by the consumption of the polybutadiene elastic phase, the rubber phase cannot be repaired by the technology, and the toughness of the material is not effectively repaired.

The invention discloses a modified ABS reclaimed material and a preparation method thereof, wherein the modified ABS reclaimed material with excellent strength and toughness is obtained by fully utilizing active functional groups existing in waste ABS and a proper amount of additional toughening agent to modify the waste ABS. However, the unsaturated double bond structure in the r-ABS polybutadiene rubber phase is still decomposed by heat and light in the using process, so that the ABS cannot radically improve the weather resistance of the ABS.

Disclosure of Invention

In view of the problems in the prior art, the invention provides a regenerated ABS material, a preparation method thereof and application of the method in repairing waste ABS materials. By adopting the method, the impact resistance of the waste ABS can be effectively repaired, and the weather resistance and the ageing resistance of the ABS are improved.

The invention provides a regenerated ABS material, which is prepared from raw materials including waste ABS, acrylate rubber powder, SAN resin, an optional lubricant, an optional antioxidant and an optional coupling agent.

In the invention, the waste ABS comprises unqualified products produced by ABS polymer, leftovers, nozzle materials, waste products and the like in the injection molding process; the ABS plastic also comprises a single component material of ABS recovered from various products used for a long time, such as automobile parts, television shells, liquid crystal front and back shells, air conditioner shells and other electric appliance shells, refrigerator liners, various tools and the like. The broken material of the waste ABS is generally adopted and is in an irregular shape with the size less than or equal to 5mm multiplied by 5mm, namely the length of a line section between two points farthest away on the contour of the broken material of the waste ABS is less than or equal to 5mm.

According to some preferred embodiments of the material according to the invention, the following amounts are given in parts by weight:

according to some preferred embodiments of the material, the weight ratio of the acrylate rubber powder to the SAN is 3 (1-3); preferably 3 (1-2).

According to some preferred embodiments of the material according to the present invention, the sum of the weight of the acrylate rubber powder, the SAN resin, the optional lubricant, the optional antioxidant and the optional coupling agent is 20 to 60%, preferably 30 to 50% of the weight of the recycled ABS material.

In the present invention, SAN resin means a copolymer of styrene acrylonitrile, which is commercially available.

According to some preferred embodiments of the material according to the present invention, the acrylate rubber powder is at least one selected from the group consisting of butyl acrylate rubber powder, methyl acrylate rubber powder, ethyl butyl acrylate rubber powder and 2-ethylhexyl butyl acrylate rubber powder, preferably butyl acrylate rubber powder.

In the invention, the particle size of the acrylate rubber powder is not particularly required, and the acrylate rubber powder with the particle size of micron is preferred.

According to some preferred embodiments of the material according to the present invention, the lubricant is selected from at least one of hexenylbisilamide (EBS), silicone oil, polyethylene wax, paraffin wax and magnesium stearate, preferably at least one of hexenylbisimide (EBS), polyethylene wax and paraffin wax.

According to some preferred embodiments of the material according to the present invention, the antioxidant is selected from at least one of antioxidant 1010, antioxidant 1076, antioxidant 2246, antioxidant DLTP and antioxidant 168, preferably at least one of antioxidant 1010, antioxidant 1076, antioxidant DLTP and antioxidant 168. In some embodiments of the present invention, the raw material for preparing the recycled ABS material comprises only one antioxidant, such as, but not limited to, antioxidant 1010, antioxidant 1076, and antioxidant 2246. In other embodiments of the present invention, the raw material for preparing the recycled ABS material comprises two antioxidants, such as, but not limited to, adding antioxidant 1010 or antioxidant 1076 when using antioxidant DLTP or antioxidant 168.

The coupling agent is selected from at least one of KH-550, KH-560, KH-570 and titanate-201 coupling agents, preferably at least one of KH-550, KH-570 and titanate-201 coupling agents.

The second aspect of the present invention provides a method for preparing the recycled ABS material, comprising:

mixing waste ABS, acrylic ester rubber powder, SAN resin, optional lubricant, optional antioxidant and optional coupling agent, extruding, drawing, cooling and pelletizing.

According to some preferred embodiments of the preparation method of the present invention, the waste ABS is pretreated ABS particles, preferably, the pretreatment conditions include: drying the ABS polymer until the water content is less than or equal to 0.1 percent.

According to some preferred embodiments of the production process according to the invention, the extrusion is carried out in a twin-screw extruder.

According to some preferred embodiments of the preparation method of the present invention, the process parameters of the twin-screw extruder include: the screw speed is 30-60 r/min, and more preferably 40-50 r/min; the mesh number of the screen is 40 to 200 meshes, and more preferably 60 to 120 meshes.

According to some preferred embodiments of the preparation method of the present invention, the process temperature of the twin-screw extruder is 180 ℃ to 230 ℃.

According to some preferred embodiments of the preparation method of the present invention, the process temperature of the twin-screw extruder from the feeding section to the die is 185-195 ℃, 190-200 ℃, 195-205 ℃, 200-210 ℃, 200-215 ℃, 200-225 ℃, 205-225 ℃ and 200-225 ℃ in sequence.

According to some preferred embodiments of the preparation method of the present invention, the process temperature of the twin-screw extruder from the feeding section to the die is 195 ℃,200 ℃,205 ℃,210 ℃,215 ℃,225 ℃,225 ℃,225 ℃,230 ℃ in sequence.

The third aspect of the invention provides the application of the preparation method in repairing the waste ABS material.

The invention has the beneficial effects that:

the invention aims to provide a regenerated ABS material and application of the method in repairing waste ABS materials. The consumed rubber phase is supplemented by utilizing the reaction of the active functional group existing in the waste ABS and the acrylate rubber powder, so that the impact property of the regenerated ABS is improved, the impact property of the regenerated ABS is effectively repaired, and the impact strength of the material reaches 20kJ/m ² The weather resistance and the aging resistance of the ABS are improved substantially, and the utilization rate and the service time of the waste ABS material are greatly improved. Meanwhile, the modified regenerated ABS greatly improves the ultraviolet light resistance and the capability of inhibiting color change. In addition, the regenerated ABS modified by the method can maintain the basic performance of the flame-retardant ABS resin, has the advantages of cost saving, safety and environmental protection, and has great popularization and application values.

Drawings

FIG. 1 is a process flow diagram for the preparation of recycled ABS material according to example 1 of the present invention.

Detailed Description

The present invention will be described in detail below with reference to examples, but the scope of the present invention is not limited to the following description.

The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available from commercial sources.

In the following embodiments, unless otherwise specified, the following methods are employed for the heat aging treatment of the material:

1. after the waste ABS material and the prepared regenerated ABS material are placed for 12 hours, injection molding is carried out by using granules of an injection molding machine, the temperature of the injection molding machine is 220 ℃, the injection pressure is set to be 20MPa, an impact sample for a cantilever beam notch impact strength test is prepared according to the requirements in GB/T1843-2008, a tensile sample for a tensile strength test is prepared according to the requirements in GB/T1040.1-2018, and a bending sample for a bending strength test is prepared according to the requirements in GB/T9341-2008.

2. And (3) placing the test piece in a ventilation type heat aging box at 110 ℃ for continuous heat drying for 48h, taking out and placing to normal temperature.

The performance of the material was tested by taking 5 sample bars per group and taking the average of 5 groups of data, the test results are shown in table 4:

1. notched izod impact strength: measuring the impact strength of a GB/T1843-2008 plastic cantilever beam;

2. tensile strength: measuring the tensile property of the GB/T1040.1-2018 plastic;

3. bending strength: and (3) determining the bending property of the GB/T9341-2008 plastic.

In the following examples, the starting materials were as shown in Table 1:

TABLE 1

Serial number	Name (R)	CAS#	Manufacturer of the product	Number plate
					1	Hexenyl bis stearamide	110-30-5	Lanzhou petrochemical Co Ltd	S-40
2	SAN resin	9003-54-7	Jilin petrochemical synthetic resin plant	SAN-2437
					3	Antioxidant 1010	6683-19-8	Nanjing Hualiming chemical Co., ltd	1010
4	Antioxidant 1076	2082-79-3	Nanjing Hualiming chemical Co., ltd	1076
					5	Antioxidant 2246	119-47-1	Chemical Co., ltd of Nanjing Hua Li Ming	2246
6	Coupling agent KH-550	919-30-2	Nanjing eosin organosilicon chemical Co Ltd	KH-550
					7	Coupling agent KH-570	3179-76-8	Nanjing eosin organosilicon chemical Co Ltd	KH-570
8	Titanate-201 coupling agent	67691-13-8	Nanjing eosin organosilicon chemical Co Ltd	NDZ-201
					9	EBS lubricant	110-30-5	GUANGZHOU DAYIN CHEMICAL TECHNOLOGY Co.,Ltd.	EBS
10	Polyethylene wax	9002-88-4	Guangzhou northern chemical Co Ltd	CH510

In addition, the butyl acrylate rubber powder is purchased from Beijing chemical research institute, and the median particle size of the butyl acrylate rubber powder is 50-100nm.

In the following examples, the used waste ABS materials were ABS broken materials of tv housings, liquid crystal front and rear housings, and air conditioner housings from which rubber and electric wires were removed. The waste ABS material is subjected to thermal aging treatment and then is subjected to performance test, and the specific results are shown in Table 2:

TABLE 2

[ examples 1 to 18 ]

The flow chart of the preparation process for preparing the regenerated ABS material is shown in figure 1.

S1, ABS pretreatment: drying the recovered ABS crushed material in a blowing drying oven at 80 ℃ for 3 hours to ensure that the water content of the ABS polymer is less than or equal to 0.1 percent; the size of the recovered ABS crushed material is not more than 5mm multiplied by 5mm in irregular shape;

s2, weighing the acrylate rubber powder, the SAN resin, the lubricant, the antioxidant and the coupling agent according to a formula ratio, and putting the materials into a high-speed batching machine to be mixed for 5min to obtain a mixed batching;

s3, mixing the waste ABS particles with the mixed ingredients, and putting the mixture into a high-speed ingredient machine for mixing for 3min to obtain a mixed raw material;

s4, feeding the mixed raw materials into a feeding system of a double-screw extruder through a vacuum suction machine, and then extruding, drawing, cooling and granulating, wherein the process parameters of the double-screw extruder are as follows: the screw speed is 50r/min, the mesh number of the screen is 80 meshes, and the working temperature of each section of the double-screw extruder is as follows:

granulating by a granulator to obtain the granules with the size of

The cylinder of (2) regenerates ABS granules.

The parts by weight of each material in examples 1-16 are shown in Table 3. Wherein the lubricant is hexenyl bis stearamide lubricant, the antioxidant is antioxidant 1010, and the coupling agent is KH-550.

[ example 17 ] to provide

Example 17 is essentially the same as example 1, except that: the EBS lubricant, the antioxidant 1076 and the coupling agent KH-570 are adopted.

[ example 18 ] A method for producing a polycarbonate

Example 18 is essentially the same as example 1, except that: polyethylene wax is used as a lubricant, an antioxidant 2246 and a titanate-201 coupling agent.

Comparative example 1

Comparative example 1 is substantially the same as example 1 except that: butyl acrylate rubber powder was not added.

Comparative example 2

Comparative example 2 is substantially the same as example 1 except that: no SAN resin was added.

TABLE 3

Examples	Waste ABS	Acrylate rubber powder	SAN resin	Lubricant agent	Antioxidant agent	Coupling agent
							1	100	30	10	0.8	0.5	2
2	100	27	12	0.8	0.5	2
							3	100	24	16	0.8	0.5	2
4	100	22.5	7.5	0.8	0.5	2
							5	100	37.5	12.5	0.8	0.5	2
6	100	21	9	0.5	0.3	1
							7	100	20	5	0.5	0	1
8	100	40	20	1	1	3
							9	100	40	26	2	2	3.5
10	100	10	2	0	0	0
							11	100	50	30	3	3	5
12	100	5	1.5	0	0	0
							13	100	60	35	5	5	7
14	100	30	7.5	0.8	0.5	2
							15	100	35	10	0.8	0.5	2
16	100	20	20	0.8	0.5	2

TABLE 4

As can be seen from Table 4, the mechanical properties of the modified ABS material are significantly improved, the impact properties are most significantly enhanced, and the aging resistance is also significantly improved. When the usage ratio of the acrylate rubber powder to the SAN resin is 3 (1-2), the whole lifting effect is best. The excessive use of one or both of the acrylate rubber powder and the SAN resin can cause residual reaction or excessive reaction to influence the modification effect, so that the mechanical property and the aging resistance of the acrylic rubber powder and the SAN resin cannot be obviously improved.

The regenerated ABS material obtained in example 1 has the optimal overall effect, the mechanical property of the modified material is obviously improved, the impact property is most obvious, and the impact strength is improved by nearly two times. After aging, the impact strength of unmodified regenerated ABS is lost by about 67%, while the impact strength of modified regenerated ABS is only lost by 34.5%, and the aging performance is obviously improved.

In addition, after the ABS materials obtained in the above examples and comparative examples are irradiated for 24h, 48h and 72h by ultraviolet lamp tubes with the central wavelength of 254 2pcs of 20W, the color difference change and the cracking phenomenon of the samples are contrastingly observed, and the result shows that the ultraviolet light resistance of the regenerated ABS prepared by the technical scheme provided by the application is obviously improved.

It should be noted that the above-mentioned embodiments are only for explaining the present invention, and do not constitute any limitation to the present invention. The present invention has been described in relation to an exemplary embodiment, and it is understood that the words which have been used herein are words of description and illustration, rather than words of limitation. The invention can be modified, as prescribed, within the scope of the claims and without departing from the scope and spirit of the invention. Although the invention has been described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, but rather extends to all other methods and applications having the same functionality.

Claims

1. A regenerated ABS material is prepared from raw materials including waste ABS, acrylate rubber powder, SAN resin, an optional lubricant, an optional antioxidant and an optional coupling agent;

the weight ratio of the acrylate rubber powder to the SAN resin is 3 (1-2).

2. The material according to claim 1, wherein the following components are used in parts by weight:

3. the material according to claim 2, wherein the acrylate rubber powder is 20 to 40 parts by weight; and/or 5-20 parts by weight of SAN resin; and/or 0.5-1 part by weight of the lubricant; and/or 0-1 part by weight of antioxidant; and/or 1-3 parts by weight of the coupling agent.

4. The material according to any one of claims 1 to 3, wherein the sum of the weight of the acrylate rubber powder, the SAN resin, the optional lubricant, the optional antioxidant and the optional coupling agent is 20 to 60 percent of the weight of the recycled ABS material.

5. The material of claim 4, wherein the sum of the weight of the acrylate rubber powder, the SAN resin, the optional lubricant, the optional antioxidant, and the optional coupling agent is 30-50% of the weight of the recycled ABS material.

6. A material according to any one of claims 1 to 3, wherein the acrylate rubber powder is selected from at least one of butyl acrylate rubber powder, methyl acrylate rubber powder, ethyl butyl acrylate rubber powder and 2-ethylhexyl butyl acrylate rubber powder; and/or

The lubricant is selected from at least one of hexenyl bis stearamide, silicone oil, polyethylene wax, solid paraffin and magnesium stearate; and/or

The antioxidant is selected from at least one of an antioxidant 1010, an antioxidant 1076, an antioxidant 2246, an antioxidant DLTP and an antioxidant 168; and/or

The coupling agent is at least one selected from KH-550, KH-560, KH-570 and titanate-201 coupling agents.

7. The material of claim 6, wherein the acrylate rubber crumb is butyl acrylate rubber crumb.

8. A material according to claim 6, wherein the lubricant is at least one of hexenyl bis stearamide, polyethylene wax and paraffin wax.

9. The material of claim 6, wherein the antioxidant is at least one of antioxidant 1010, antioxidant 1076, antioxidant DLTP, and antioxidant 168.

10. The material of claim 6, wherein the coupling agent is at least one of KH-550, KH-570, and titanate-201 coupling agents.

11. The method of producing a recycled ABS material of any one of claims 1 to 10, comprising:

mixing waste ABS, acrylate rubber powder, SAN resin, optional lubricant, optional antioxidant and optional coupling agent, extruding, drawing, cooling and pelletizing.

12. The method of claim 11, wherein the waste ABS is pre-treated ABS polymer particles.

13. The method of claim 12, wherein the pre-treating conditions include: drying the ABS polymer until the water content is less than or equal to 0.1 percent.

14. A method of manufacturing as claimed in any one of claims 11 to 13, wherein the extrusion is carried out in a twin screw extruder.

15. The method for preparing a compound according to claim 14, wherein the process parameters of the twin-screw extruder include: the screw speed is 30-60 r/min; the mesh number of the screen is 40-200 meshes.

16. The method of claim 15, wherein the screw speed is 40 to 50r/min.

17. The method according to claim 15, wherein the mesh number of the screen is 60 to 120 mesh.

18. The method of claim 14, wherein the twin screw extruder has a process temperature of 180 ℃ to 230 ℃.

19. The preparation method of claim 14, wherein the process temperature of the twin-screw extruder from the feeding section to the die head is 185-195 ℃, 190-200 ℃, 195-205 ℃, 200-210 ℃, 200-215 ℃, 200-225 ℃, 205-225 ℃ and 200-225 ℃ in sequence.

20. The method of any one of claim 14, wherein the process temperature of the twin screw extruder from the feeding section to the die is 195 ℃,200 ℃,205 ℃,210 ℃,215 ℃,225 ℃,225 ℃,225 ℃,230 ℃ in sequence.

21. Use of the process according to any one of claims 11 to 20 for the repair of waste ABS materials.