CN106939112B - High-gloss HIPS/recycled PET bottle flake composite material and preparation method thereof - Google Patents
High-gloss HIPS/recycled PET bottle flake composite material and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/04—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
Abstract
The invention relates to the technical field of high polymer materials, in particular to a composite material and a preparation method thereof. A high gloss HIPS/recycled PET bottle flake composite material comprises the following raw materials in parts by weight: 100 parts of HIPS, 10-40 parts of recycled PET bottle flakes, 2-20 parts of compatilizer, 5-25 parts of flexibilizer, 0.1-1 part of antioxidant and 0.1-1 part of lubricant. The invention not only enlarges the application range of the recycled PET bottle flakes, but also improves the surface gloss of HIPS, simultaneously reduces the cost of HIPS composite material, and the composite material is environment-friendly and low-carbon, and can be widely applied to the preparation of shells of electronic and electric appliance parts and the like.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a composite material and a preparation method thereof.
Background
Polyethylene terephthalate (PET) is widely used in fiber applications because of its excellent combination of chemical and physical properties and low cost, and is used in beverage bottles in a considerable amount. With the wide application of PET in the field of edible liquid flexible packaging, the problem of recycling a large number of waste beverage bottles is brought. As the amount of PET used was gradually increased, the amount of PET bottles recovered was also gradually increased. According to statistics, the average recycling rate of the PET bottles is 20.4%, the countries with high recycling rate such as Swiss, Germany and Japan are 100%, 49% and 46%, respectively, and China is only 1.7%. Most of the recycled PET bottle chips are degraded and utilized and are used for producing low-grade fibers, films, non-edible packaging bottles and the like; and the upgraded utilization rate of the high-performance engineering plastic only accounts for about 8.4 percent. Recycled PET bottle chips are used primarily for spinning short fibers of some low-grade Polyester (PET). Therefore, for the bottle flakes of recycled PET, it is necessary to further expand the application fields and products thereof and to improve the added value of the products thereof.
Polystyrene homopolymers are generally rather brittle resins with poor impact strength. The HIPS resin with good toughness is obtained by introducing rubber component units into the molecular chain. However, this also results in a significant reduction in the surface gloss of the resin, which limits its widespread use in applications requiring a certain surface gloss, such as telephones, computers and other consumer electronics.
The patent CN1256699A discloses that modified HIPS with certain gloss is prepared by a continuous bulk polymerization method, but the preparation process and equipment are complex, the technical requirement is high, and the industrial production difficulty is high.
Disclosure of Invention
The invention aims to provide a high-gloss HIPS/recycled PET bottle flake composite material to solve the technical problem.
The invention also aims to provide a preparation method of the high-gloss HIPS/recycled PET bottle flake composite material, so as to solve the technical problems.
The technical problem solved by the invention can be realized by adopting the following technical scheme:
a high gloss HIPS/recycled PET bottle flake composite material comprises the following raw materials in parts by weight:
the raw materials with the following parts by weight are preferably adopted:
the invention adoptsThe method has the advantages that a certain amount of recycled PET bottle flakes are added into HIPS (high impact polystyrene), so that the high added value utilization of the recycled PET bottle flakes is realized again, limited resources are saved, the recycling application range of recycled PET bottle flake materials is expanded, the cost of the HIPS composite material is reduced, the glossiness of the surface of the material is improved, the composite material has excellent toughness, chemical resistance, electrical property, high mechanical strength and good dimensional stability, and the application field of the HIPS is further expanded. The tensile strength of the invention adopting the formula reaches 40MPa to 55MPa, the bending strength reaches 60MPa to 70MPa, and the Izod notch impact strength is 8.5KJ/m2-9.5KJ/m2The glossiness reaches more than 90, and the surface has no incompatibility phenomena of layering and skinning. The composite material of the invention can be widely applied to the fields of electronic and electric appliance shells and transmission parts, office equipment, instruments and meters, sports equipment and the like.
The HIPS has a relative density of 1.05 and a number average molecular weight of 6-15 ten thousand; izod notched impact Strength of 8.5KJ/m2-9.5KJ/m2Preferably 9.0KJ/m2-9.5KJ/m2。
The recycled PET bottle sheet is preferably white transparent sheet, and the intrinsic viscosity of the recycled PET bottle sheet is 0.68dl/g-0.78dl/g, preferably 0.70dl/g-0.75 dl/g. The recycled PET bottle flakes with the intrinsic viscosity are easy to process and have high strength.
The compatilizer is terpolymer, preferably styrene-propylene-glycidyl methacrylate, has a melt index of 6-9g/10min (200 ℃/5Kg), and contains 1.8% -2.2% of GMA (glycidyl methacrylate) in the total amount of the compatilizer.
The toughening agent is a styrene-butadiene-methyl acrylate copolymer which is a transparent material, and the rubber content in the toughening agent is 50-70%, preferably 50-60% of the total amount of the toughening agent. It has great influence on the mechanical property of the material. The method has the advantages that the interfacial tension of the HIPS and the recycled PET is reduced, the interfacial thickness is increased, the system forms a thermodynamically stable phase structure with the characteristics of a macroscopic uniform microscopic phase separation system, and the composite material keeps good mechanical properties.
The antioxidant consists of a main antioxidant and an auxiliary antioxidant, wherein the weight ratio of the main antioxidant to the auxiliary antioxidant is 2: 1-3: 1, proportioning;
the primary antioxidant is antioxidant 1010 or antioxidant 1098, preferably antioxidant 1010;
the auxiliary antioxidant is antioxidant 168. The antioxidant ensures the stability of the appearance color of the composite material in the processing process and is suitable for different use requirements.
The lubricant is at least one selected from ethylene bis stearamide, calcium stearate, polyethylene oxide wax or TAF. The lubricant is preferably ethylene bis stearamide.
The HIPS (high impact polystyrene) molecular chain of the invention obtains good toughness due to the introduction of rubber component units. But the surface gloss of the resin is greatly reduced, after the preferable scheme is adopted, the gloss of the material can be obviously improved while the good toughness of the material is kept, so that the material has good gloss and good toughness, and meanwhile, the recycled PET bottle flakes are low in cost and can be effectively utilized, so that the preferable scheme has important significance for environmental protection and accords with the development trend of environmental protection in the current society.
A preparation method of a high gloss HIPS/recycled PET bottle flake composite material comprises the following steps:
1) drying the recovered PET bottle flakes;
2) the HIPS, the recycled PET bottle flakes, the compatilizer, the flexibilizer, the antioxidant and the lubricant are uniformly mixed according to the proportion to prepare a mixture;
3) and adding the mixture into a double-screw extruder through a main feeding port of the double-screw extruder, carrying out melt extrusion, and cooling, air-drying, granulating and drying the extruded material to obtain the high-gloss HIPS/recycled PET bottle flake composite material.
In the step 1), drying the recovered PET bottle chips in a vacuum oven; preferably, the drying is carried out in two stages, wherein the first stage is drying for 3h to 5h, preferably 3.5h to 4.5h at the temperature of 75 ℃ to 80 ℃; the second stage is drying at 135-145 deg.c for 7-10 hr, preferably 8-9 hr.
In the step 2), the raw materials are mixed for 10-15 minutes to prepare a mixture.
In the step 3), the temperature setting range of the double-screw extruder is 240-265 ℃, the rotating speed of a screw is 200-500 rpm, and the vacuum degree is-0.6 Kgf/cm2-1.0Kgf/cm2。
The double-screw extruder adopts seven-zone temperature regulation, and the temperature of each zone is as follows:
temperature in the first zone: 240-245 ℃,
temperature in the second zone: 245-250 ℃,
three-zone temperature: at the temperature of 250-255 ℃,
temperature in the fourth zone: at the temperature of 255-260 ℃,
temperature in the fifth zone: 260-265 ℃ of the temperature of the reaction kettle,
temperature in the six zones: 260-265 ℃ of the temperature of the reaction kettle,
temperature in the seven zones: 260-258 ℃.
Has the advantages that: compared with the prior art, the invention has the following advantages:
(1) the high-gloss HIPS/recycled PET bottle flake composite material provided by the invention not only expands the application range of recycled PET bottle flakes, but also improves the surface gloss of the HIPS, and simultaneously reduces the cost of the HIPS composite material, and the composite material is environment-friendly and low-carbon, and can be widely applied to the preparation of shells of electronic and electrical equipment parts and the like.
(2) The high-gloss HIPS/recycled PET bottle flake composite material provided by the invention has good mechanical property, the tensile strength reaches 50MPa, the bending strength can reach 60MPa, and the notch impact strength can reach 8.5KJ/m2And the mechanical property of the material is not greatly different from that of a pure HIPS material.
(3) The preparation method of the high-gloss HIPS/recycled PET bottle flake composite material provided by the invention has the advantages of simple compounding process and processing process and easiness in processing and preparation.
Detailed Description
In order to make the technical means, the creation characteristics, the achievement purposes and the effects of the invention easy to understand, the invention is further explained below.
A high gloss HIPS/recycled PET bottle flake composite material comprises the following raw materials in parts by weight: 100 parts of HIPS, 10-40 parts of recycled PET bottle flakes, 2-20 parts of compatilizer, 5-25 parts of flexibilizer, 0.1-1 part of antioxidant and 0.1-1 part of lubricant. The raw materials with the following parts by weight are preferably adopted: 100 parts of HIPS, 15-30 parts of recycled PET bottle chips, 4-10 parts of compatilizer, 10-15 parts of toughener, 0.2-0.5 part of antioxidant and 0.2-0.5 part of lubricant.
In the raw materials, the relative density of the HIPS is 1.05, and the number average molecular weight is 6-15 ten thousand; izod notched impact Strength of 8.5KJ/m2-9.5KJ/m2Preferably 9.0KJ/m2-9.5KJ/m2. The recycled PET bottle chips are preferably white transparent chips in appearance color, and the intrinsic viscosity of the recycled PET bottle chips is 0.68dl/g to 0.78dl/g, preferably 0.70dl/g to 0.75 dl/g. The compatibilizer is terpolymer, preferably styrene-propylene glycidyl methacrylate, has melt index of 6-9g/10min (200 deg.C/5 Kg), and contains GMA 1.8-2.2% of the total amount of compatibilizer. The toughening agent is a styrene-butadiene-methyl acrylate copolymer which is a transparent material, and the rubber content in the toughening agent is 50-70%, preferably 50-60% of the total amount of the toughening agent. The antioxidant consists of a main antioxidant and an auxiliary antioxidant, wherein the main antioxidant and the auxiliary antioxidant are mixed according to the weight ratio of 2: 1-3: 1 proportion. The primary antioxidant is antioxidant 1010 or antioxidant 1098, preferably antioxidant 1010. The auxiliary antioxidant is antioxidant 168. The antioxidant ensures the stability of the appearance color of the composite material in the processing process and is suitable for different use requirements. The lubricant is at least one selected from ethylene bis stearamide, calcium stearate, polyethylene oxide wax or TAF. The lubricant is preferably ethylene bis stearamide.
A preparation method of a high gloss HIPS/recycled PET bottle flake composite material comprises the following steps:
1) the recovered PET bottle flakes were dried in a vacuum oven. Preferably, the drying is carried out in two stages, wherein the first stage is drying at a temperature of 75 ℃ to 80 ℃ for 3h to 5h, preferably 3.5h to 4.5 h. The second stage is drying at 135-145 deg.c for 7-10 hr, preferably 8-9 hr.
2) Mixing the HIPS, the recycled PET bottle flakes, the compatilizer, the flexibilizer, the antioxidant and the lubricant for 10 to 15 minutes according to the proportion to prepare a mixture.
3) And adding the mixture into a double-screw extruder through a main feeding port of the double-screw extruder, carrying out melt extrusion, and cooling, air-drying, granulating and drying the extruded material to obtain the composite material of the high-gloss HIPS/recycled PET bottle flake composite material.
The temperature setting range of the double screw extruder is 240-265 ℃, the screw rotating speed is 200-500 rpm, and the vacuum degree is-0.6 Kgf/cm2-1.0Kgf/cm2. The double-screw extruder adopts seven zones for temperature regulation, and the temperature of each zone is as follows: temperature in the first zone: 240 ℃ to 245 ℃, temperature in the second zone: 245-250 ℃, three-zone temperature: 250 ℃ to 255 ℃, four-zone temperature: 255-260 ℃, and the temperature of the five zones: 260-265 ℃, and six-zone temperature: 260-265 ℃, temperature in seven zones: 260-258 ℃.
Example 1:
the high gloss HIPS/recycled PET bottle flake composite material comprises the following components in Table 1:
table 1: unit (kg)
| HIPS | Recycled PET bottle flake | Compatilizer | Toughening agent | Antioxidant agent | Lubricant agent |
| 100 | 15 | 5 | 10 | 0.25 | 0.35 |
Wherein the HIPS has a relative density of 1.05 and a number average molecular weight of 10 ten thousand; izod notched impact Strength of 8.5KJ/m2；
The intrinsic viscosity of the recovered PET bottle piece is 0.72 dl/g;
the compatibilizer is styrene-propylene-glycidyl methacrylate (its melt index is 8g/10min (200 deg.C/5 Kg), GMA content is 2.0%, such as SAG-02 of QINXINNI GmbH;
the toughening agent is styrene-butadiene-methyl acrylate copolymer, is transparent material, and has rubber content of 60%, such as Mitsubishi company C223A;
the antioxidant is compounded by 1010 antioxidant and 168 antioxidant, and the weight ratio is 1: 2;
the lubricant is TAF.
Example 2:
the high gloss HIPS/recycled PET bottle flake composite material comprises the following components in percentage by weight as shown in Table 2:
table 2: unit (kg)
| HIPS | Recycled PET bottle flake | Compatilizer | Toughening agent | Antioxidant agent | Lubricant agent |
| 100 | 20 | 6 | 10 | 0.25 | 0.30 |
Wherein the HIPS has a relative density of 1.05 and a number average molecular weight of 10 ten thousand; izod notched impact Strength of 8.5KJ/m2；
The intrinsic viscosity of the recovered PET bottle piece is 0.75 dl/g;
the compatibilizer is styrene-propylene-glycidyl methacrylate (its melt index is 8g/10min (200 deg.C/5 Kg), GMA content is 2.0%, such as SAG-02 of QINXINNI GmbH;
the toughening agent is styrene-butadiene-methyl acrylate copolymer, is transparent material, and has rubber content of 60%, such as Mitsubishi company C223A;
the antioxidant is compounded by 1010 antioxidant and 168 antioxidant, and the weight ratio is 1: 2.5;
the lubricant is a polyethylene oxide wax.
Example 3:
the high gloss HIPS/recycled PET bottle flake composite material of the invention has the composition shown in Table 3:
table 3: unit (kg)
| HIPS | Recycled PET bottle flake | Compatilizer | Toughening agent | Antioxidant agent | Lubricant agent |
| 100 | 18 | 5 | 10 | 0.25 | 0.30 |
Wherein the HIPS has a relative density of 1.05 and a number average molecular weight of 10 ten thousand; izod notched impact Strength of 8.5KJ/m2；
The intrinsic viscosity of the recovered PET bottle piece is 0.75 dl/g;
the toughening agent is styrene-butadiene-methyl acrylate copolymer, is transparent material, and has rubber content of 60%, such as Mitsubishi company C223A;
the compatibilizer is styrene-propylene-glycidyl methacrylate (its melt index is 8g/10min (200 deg.C/5 Kg), GMA content is 2.0%, such as SAG-02 of QINXINNI GmbH;
the antioxidant is compounded by 1010 antioxidant and 168 antioxidant, and the weight ratio is 1: 2.45 of;
the lubricant is ethylene bis stearamide.
The composite materials of examples 1-3 were prepared by the following methods:
1) drying the recovered PET bottle flakes in a vacuum oven, wherein the drying is carried out in two stages, and the first stage is drying for 3 hours at the temperature of 80 ℃; the second stage is drying for 7h at the temperature of 145 ℃;
2) the HIPS, the recycled PET bottle flakes, the toughening agent, the compatilizer, the antioxidant and the lubricant are uniformly mixed according to the proportion to prepare a mixture, and the mixing time is 10 minutes;
3) and adding the mixture into a double-screw extruder through a main feeding port of the double-screw extruder, carrying out melt extrusion, and cooling, air-drying, granulating and drying the extruded material to obtain the sheet composite material.
The screw rotation speed of the twin-screw extruder was 400rpm, and the vacuum degree was-0.6 Kgf/cm2The temperatures in the zones of the twin-screw extruder were:
temperature in the first zone: 240-245 ℃,
temperature in the second zone: 245-250 ℃,
three-zone temperature: at the temperature of 250-255 ℃,
temperature in the fourth zone: at the temperature of 255-260 ℃,
temperature in the fifth zone: 260-265 ℃ of the temperature of the reaction kettle,
temperature in the six zones: 260-265 ℃ of the temperature of the reaction kettle,
temperature in the seven zones: 260-258 ℃.
Compared with the pure HIPS material in the prior art, the physical properties of the high-gloss HIPS/recycled PET bottle flake composite material prepared by the preparation method disclosed by the invention are shown in Table 4:
table 4:
| tensile Strength (MPa) | Degree of gloss | Flexural Strength (MPa) | Notched impact Strength (KJ/m)2) | |
| HIPS | 41 | 70 | 64 | 8.5 |
| Example 1 | 45 | 90 | 66 | 8.5 |
| Example 2 | 48 | 96 | 68 | 8.6 |
| Example 3 | 43 | 94 | 65 | 8.8 |
As can be seen from the above table, the high gloss HIPS/recycled PET bottle flake composite material prepared by the raw material combination and the preparation method of the invention has good mechanical properties, the bending strength can reach more than 60MPa, and the notch impact strength can reach 8.5KJ/m2And the mechanical property of the material is not greatly different from that of a pure HIPS material.
The foregoing shows and describes the general principles and broad features of the present invention and advantages thereof. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (4)
1. The high-gloss HIPS/recycled PET bottle flake composite material is characterized by comprising the following raw materials in parts by weight:
HIPS100 parts by weight
10-40 parts by weight of recycled PET bottle flakes
2-20 parts of compatilizer
5-25 parts of toughening agent
0.1 to 1 weight portion of antioxidant
0.1 to 1 weight portion of lubricant
The HIPS has a relative density of 1.05 and a number average molecular weight of 6-15 ten thousand; izod notched impact Strength of 8.5KJ/m2-9.5KJ/m2(ii) a The intrinsic viscosity of the recovered PET bottle sheet is 0.68dl/g-0.78 dl/g; the compatilizer is styrene-acrylonitrile-glycidyl methacrylate, the melt index of the compatilizer is 6-9g/10min under the test condition of 200 ℃/5Kg, and the content of GMA in the compatilizer is 1.8-2.2% of the total amount of the compatilizer; the toughening agent is a styrene-butadiene-methyl acrylate copolymer which is a transparent material, and the rubber content in the toughening agent is 50-70% of the total amount of the toughening agent; the antioxidant consists of a main antioxidant and an auxiliary antioxidant, and the main antioxidant and the auxiliary antioxidant are mixed according to the weight ratio of 2: 1-3: 1; the primary antioxidant is antioxidant 1010 or antioxidant 1098; the auxiliary antioxidant is antioxidant 168; the lubricant is at least one selected from ethylene bis stearamide, calcium stearate, polyethylene oxide wax or TAF.
2. The preparation method for preparing the high-gloss HIPS/recycled PET bottle flake composite material as claimed in claim 1, is characterized by comprising the following steps:
1) drying the recovered PET bottle flakes;
2) the HIPS, the recycled PET bottle flakes, the compatilizer, the flexibilizer, the antioxidant and the lubricant are uniformly mixed according to the proportion to prepare a mixture;
3) and adding the mixture into a double-screw extruder through a main feeding port of the double-screw extruder, carrying out melt extrusion, and cooling, air-drying, granulating and drying the extruded material to obtain the high-gloss HIPS/recycled PET bottle flake composite material.
3. The method for preparing the high gloss HIPS/recycled PET bottle flake composite material according to claim 2, wherein in the step 1), the drying of the recycled PET bottle flakes is performed in a vacuum oven; drying in two stages, wherein the first stage is drying at 75-80 deg.C for 3-5 h; the second stage is drying at 135-145 deg.c for 7-10 hr.
4. The method for preparing the high gloss HIPS/recycled PET bottle flake composite material according to claim 2, wherein the temperature setting range of the twin-screw extruder in the step 3) is 240-265 ℃, the screw rotation speed is 200-500 rpm, and the vacuum degree is-0.6 Kgf/cm2-1.0Kgf/cm2；
The double-screw extruder adopts seven-zone temperature regulation, and the temperature of each zone is as follows: temperature in the first zone: 240 ℃ to 245 ℃, temperature in the second zone: 245-250 ℃, three-zone temperature: 250 ℃ to 255 ℃, four-zone temperature: 255-260 ℃, and the temperature of the five zones: 260-265 ℃, and six-zone temperature: 260-265 ℃, temperature in seven zones: 260-258 ℃.
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| CN111849085A (en) * | 2020-07-28 | 2020-10-30 | 青岛福尔蒂新材料有限公司 | High-impact PS/PET resin composition |
| CN111925622A (en) * | 2020-08-25 | 2020-11-13 | 佳易容聚合物(上海)有限公司 | HIPS (high impact polystyrene) composite material with excellent chemical resistance and preparation method thereof |
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| Title |
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| Burning Rate, Mechanical and Rheological Properties of HIPS-PET and Clay Nanocomposites;Sanchez-Olivares, G等;《INTERNATIONAL JOURNAL OF POLYMERIC MATERIALS》;20081231;第57卷(第5期);第417-428页 * |
| In Situ Compatibilization of PET/ PS Blends through Reactive Copolymers;CHYN-TEIN MAA等;《JOURNAL OF APPLIED POLYMER SCIENCE》;19930805;第49卷;第913-924页，尤其涉及摘要，第913页右侧第2段，第914页左侧第3段，第918页表1，第919页左栏第1段 * |
| Sanchez-Olivares, G.等.Burning Rate, Mechanical and Rheological Properties of HIPS-PET and Clay Nanocomposites.《INTERNATIONAL JOURNAL OF POLYMERIC MATERIALS》.2008,第57卷第417-428页，尤其涉及第419页第3段，第420页图1. * |
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