CN112266537A - Marine recycled PP/PET alloy - Google Patents

Marine recycled PP/PET alloy Download PDF

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Publication number
CN112266537A
CN112266537A CN202011243288.7A CN202011243288A CN112266537A CN 112266537 A CN112266537 A CN 112266537A CN 202011243288 A CN202011243288 A CN 202011243288A CN 112266537 A CN112266537 A CN 112266537A
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marine
recycled
polypropylene
polyethylene terephthalate
pet alloy
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Chinese (zh)
Inventor
刘贵臻
赵庆祥
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Shandong Xingda New Materials Co ltd
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Shandong Xingda New Materials Co ltd
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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
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/12—Polypropene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
    • 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
    • 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
    • C08L2205/06—Polymer mixtures characterised by other features having improved processability or containing aids for moulding methods
    • 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
    • C08L2205/08—Polymer mixtures characterised by other features containing additives to improve the compatibility between two polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/04—Thermoplastic elastomer

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention discloses a marine recycled PP/PET alloy, which belongs to the technical field of high polymer material modification and regeneration, and comprises polypropylene, polyethylene terephthalate, a compatilizer, a flexibilizer, a colorant and an antioxidant, wherein the polypropylene and the polyethylene terephthalate adopt the polypropylene and the polyethylene terephthalate which are recycled in the sea, so that the recycling of the polypropylene and the polyethylene terephthalate in marine garbage can be realized, the marine recycled PP/PET alloy with good mechanical property can be prepared, and the marine recycled PP/PET alloy is applied to the fields of automobiles, household appliances, toys, machinery and the like and has wide application prospect.

Description

Marine recycled PP/PET alloy
Technical Field
The invention belongs to the technical field of high polymer material modification and regeneration, relates to a PP/PET (polypropylene/polyethylene terephthalate) regenerated alloy, and particularly relates to a PP/PET alloy regenerated by using marine garbage.
Background
The marine garbage is one of main factors threatening the marine ecosystem and the navigation safety, the marine garbage mainly comprises plastic bags, cigarette ends, plastic foam snack boxes, fishing nets, glass bottles and the like, and in order to treat the marine garbage, the marine garbage is usually subjected to harmless treatment after being recovered.
The plastic products in the marine garbage comprise Polycarbonate (PC), polypropylene (PP), polyethylene terephthalate (PET) and the like, wherein the PC has the characteristics of high strength, elastic coefficient, high impact strength, wide use temperature range, high transparency, free dyeing property, low forming shrinkage, good size stability and the like, but has the defects of low hydrolysis resistance and stability, sensitivity to notches, poor scratch resistance and the like; PP has excellent properties of light weight, no toxicity, electric insulation property, good chemical stability, easy processing and forming and the like, is widely applied to various fields of industrial production, but has the defects of low-temperature brittleness, low mechanical strength, low hardness, large forming shrinkage and the like; PET has excellent properties such as wear resistance, heat resistance, good electrical insulation, and chemical resistance, and is mainly used for synthetic fibers, biaxially stretched films, hollow containers, and the like. However, since the glass transition temperature and melting point of PET are relatively high, the crystallization rate is relatively slow at ordinary processing temperatures, and the impact toughness is poor.
In order to reduce the marine pollution and improve the recycling of the marine garbage, the recycling of PP and PET in the marine garbage can be considered, and the PP and the PET can be modified by combining the defects of the PET and the PP and blending the PET and the PP, so that the performance of the PET and the PET is further optimized: the strength, modulus, heat resistance and surface hardness of the PP are improved by using the PET; the PP is utilized to improve the performances of processing, impact, environmental stress cracking resistance, barrier and the like of the PET.
Disclosure of Invention
The invention aims to solve the problem of recycling marine pollutants, and the polypropylene and the polyethylene terephthalate in the marine pollutants are recycled, modified and regenerated to obtain the PP/PET alloy material with good physical property and chemical property.
Based on the above purposes, the invention provides the following technical scheme:
the marine regenerated PP/PET alloy comprises polypropylene, polyethylene terephthalate, a compatilizer, a toughening agent, a colorant and an antioxidant, and the weight percentage of each raw material is as follows:
polypropylene: 15% -55%;
polyethylene terephthalate: 15% -55%;
a compatilizer: 2% -8%;
a toughening agent: 10% -25%;
colorant: 0.5% -5%;
antioxidant: 0.1 to 2 percent.
Preferably, the marine recycled PP/PET alloy comprises the following raw materials in percentage by mass:
polypropylene: 25% -55%;
polyethylene terephthalate: 15% -35%;
a compatilizer: 2% -8%;
a toughening agent: 10% -25%;
colorant: 0.5% -5%;
antioxidant: 0.1 to 2 percent.
Preferably, the marine recycled PP/PET alloy comprises the following raw materials in percentage by mass:
polypropylene: 15% -35%;
polyethylene terephthalate: 25% -55%;
a compatilizer: 2% -8%;
a toughening agent: 10% -25%;
colorant: 0.5% -5%;
antioxidant: 0.1 to 2 percent.
Further preferably, the raw material in the marine recycled PP/PET alloy further comprises a deodorant, and the content of the deodorant in the marine recycled PP/PET alloy is 0.5% -2% by mass percent.
Preferably, the odor eliminating agent is aluminosilicate having a porous structure.
Preferably, the polypropylene is freshly prepared polypropylene particles or marine recycled polypropylene particles.
Further preferably, the polypropylene is a mixture of freshly prepared polypropylene particles and marine recycled polypropylene particles, and the mixing ratio of the polypropylene to the marine recycled polypropylene particles is 5 (2-5).
Preferably, the polyethylene terephthalate is freshly made polyethylene terephthalate particles or marine recycled polyethylene terephthalate particles.
Further preferably, the polyethylene terephthalate is a mixture of freshly prepared polyethylene terephthalate particles and marine recycled polyethylene terephthalate particles in a mixing ratio of 5:
(2-5)。
preferably, the marine recycled polypropylene particles are prepared by centrifugally cleaning, drying and crushing marine recycled polypropylene, extruding the crushed marine recycled polypropylene by a double-screw extruder, cooling, drying and granulating the crushed marine recycled polypropylene.
Preferably, the marine recycled polyethylene terephthalate particles are prepared by centrifugally cleaning, drying and crushing marine recycled polyethylene terephthalate, extruding by a double-screw extruder, cooling, drying and granulating.
Preferably, the compatilizer is at least one of polypropylene grafted maleimide (PP-g-MI), polypropylene grafted glycidyl methacrylate (PP-g-GMA) and maleic anhydride grafted styrene-ethylene-butadiene-styrene block copolymer (SEBS-g-MAH).
Further preferably, the compatilizer is polypropylene grafted glycidyl methacrylate (PP-g-GMA).
Preferably, the toughening agent is a thermoplastic elastomer toughening agent.
Further preferably, the thermoplastic elastomer type toughening agent is at least one of a styrene-butadiene thermoplastic elastomer, an acrylonitrile-butadiene-styrene copolymer, a methyl methacrylate-butadiene-styrene terpolymer and an ethylene-vinyl acetate copolymer.
Preferably, the colorant is at least one of titanium dioxide, zinc powder, cadmium red, ferric oxide, carbon black, chrome yellow, zinc yellow and hansha yellow.
Preferably, the antioxidant is at least one of hindered phenol antioxidant and phosphate antioxidant.
More preferably, the antioxidant is at least one of antioxidant 1010, antioxidant 1076, antioxidant 168, antioxidant MB and antioxidant DLTP.
The invention has the beneficial effects that: according to the invention, PP and PET recovered from ocean are modified and regenerated to prepare the PP/PET blended alloy material, so that on one hand, harmless recovery and reutilization of ocean garbage are realized; on the other hand, the PP/PET alloy improves the compatibilization effect of the PP/PET alloy and improves the toughness of the PP/PET alloy under the action of the compatilizer, the flexibilizer and the antioxidant, has excellent bending property, can be widely applied to the fields of automobiles, household appliances, toys, machinery and the like, and has wide application prospect.
Detailed Description
The present invention will be described in further detail with reference to specific examples. The starting materials used in the examples are, unless otherwise specified, commercially available from conventional sources.
Example 1
The marine regenerated PP/PET alloy comprises the following components in percentage by mass:
fresh polypropylene: 48.5 percent;
mixture of freshly made polyethylene terephthalate and marine recycled polyethylene terephthalate (mixing ratio 5: 2): 27.8 percent;
PP-g-GMA：7.6％；
styrene-butadiene thermoplastic elastomer: 14.6 percent;
carbon black: 1.2 percent;
antioxidant 1010: 0.3 percent.
The preparation method of the marine recycled PP/PET alloy in the embodiment comprises the following steps:
(1) blending fresh polyethylene terephthalate and marine regenerated polyethylene terephthalate by a double-screw extruder;
(2) blending a compatilizer PP-g-GMA and a toughening agent styrene-butadiene thermoplastic elastomer through a double-screw extruder;
(3) the mixture obtained in (1) and (2) is blended with fresh polypropylene and other auxiliary agents by a twin-screw extruder, and the marine recycled PP/PET alloy in the embodiment is obtained by extrusion.
Example 2
The marine regenerated PP/PET alloy comprises the following components in percentage by mass:
fresh polypropylene: 48.5 percent;
marine recycled polyethylene terephthalate: 27.8 percent;
PP-g-GMA：7.6％；
styrene-butadiene thermoplastic elastomer: 14.6 percent;
carbon black: 1.2 percent;
antioxidant 1010: 0.3 percent.
The preparation method of the marine recycled PP/PET alloy in the embodiment comprises the following steps:
(1) blending a compatilizer PP-g-GMA and a toughening agent styrene-butadiene thermoplastic elastomer through a double-screw extruder;
(2) blending the mixture obtained in the step (1) with fresh polypropylene, marine recycled polyethylene terephthalate and other auxiliary agents through a double-screw extruder, and extruding to obtain the marine recycled PP/PET alloy in the embodiment.
Comparative example 1
The PP/PET alloy comprises the following components in percentage by mass:
fresh polypropylene: 48.5 percent;
fresh polyethylene terephthalate: 27.8 percent;
PP-g-GMA：7.6％；
styrene-butadiene thermoplastic elastomer: 14.6 percent;
carbon black: 1.2 percent;
antioxidant 1010: 0.3 percent.
The preparation method of the marine recycled PP/PET alloy in the comparative example comprises the following steps:
(1) blending a compatilizer PP-g-GMA and a toughening agent styrene-butadiene thermoplastic elastomer through a double-screw extruder;
(2) and (3) blending the mixture obtained in the step (1) with fresh polypropylene, fresh polyethylene terephthalate and other auxiliary agents through a double-screw extruder, and extruding to obtain the PP/PET alloy in the comparative example.
Example 3
The marine regenerated PP/PET alloy comprises the following components in percentage by mass:
blend of freshly made polypropylene and marine recycled polypropylene (5: 3 mix ratio): 19.6 percent;
fresh polyethylene terephthalate: 50.2 percent;
PP-g-MI：7.3％；
acrylonitrile-butadiene-styrene copolymer: 19.8 percent;
titanium dioxide: 2.1 percent;
antioxidant 168: 0.2 percent;
odor removing agent: 0.8 percent.
The preparation method of the marine recycled PP/PET alloy in the embodiment comprises the following steps:
(1) blending the newly-prepared polypropylene and the marine regenerated polypropylene by a double-screw extruder;
(2) blending a compatilizer PP-g-MI and a toughening agent acrylonitrile-butadiene-styrene copolymer through a double-screw extruder;
(3) the mixture obtained in (1) and (2) is blended with fresh polyethylene terephthalate and other auxiliary agents by a twin-screw extruder, and the marine recycled PP/PET alloy in the embodiment is obtained by extrusion.
Example 4
The marine regenerated PP/PET alloy comprises the following components in percentage by mass:
marine recycled polypropylene: 19.6 percent;
fresh polyethylene terephthalate: 50.2 percent;
PP-g-MI：7.3％；
acrylonitrile-butadiene-styrene copolymer: 19.8 percent;
titanium dioxide: 2.1 percent;
antioxidant 168: 0.2 percent;
odor removing agent: 0.8 percent.
The preparation method of the marine recycled PP/PET alloy in the embodiment comprises the following steps:
(1) blending a compatilizer PP-g-MI and a toughening agent acrylonitrile-butadiene-styrene copolymer through a double-screw extruder;
(2) blending the mixture obtained in the step (1) with marine recycled polypropylene, fresh polyethylene terephthalate and other auxiliary agents through a double-screw extruder, and extruding to obtain the marine recycled PP/PET alloy in the embodiment.
Comparative example 2
The PP/PET alloy comprises the following components in percentage by mass:
fresh polypropylene: 19.6 percent;
fresh polyethylene terephthalate: 50.2 percent;
PP-g-MI：7.3％；
acrylonitrile-butadiene-styrene copolymer: 19.8 percent;
titanium dioxide: 2.1 percent;
antioxidant 168: 0.2 percent;
odor removing agent: 0.8 percent.
The preparation method of the marine recycled PP/PET alloy in the comparative example comprises the following steps:
(1) blending a compatilizer PP-g-MI and a toughening agent acrylonitrile-butadiene-styrene copolymer through a double-screw extruder;
(2) and (3) blending the mixture obtained in the step (1) with fresh polypropylene, fresh polyethylene terephthalate and other auxiliary agents through a double-screw extruder, and extruding to obtain the PP/PET alloy in the comparative example.
The PP/PET alloy materials obtained in the examples and the comparative examples were tested, and the test results are shown in Table 1.
TABLE 1 PP/PET alloy materials test results
Figure BDA0002769062090000071
By comparing the test data of the example 1, the example 2 and the comparative example 1 and the test data of the example 3, the example 4 and the comparative example 2, it can be seen that the addition of the marine recycled polyethylene terephthalate and the marine recycled polypropylene leads the test data of the PP/PET alloy material to be generally higher than the test data of the PP/PET alloy material which is completely prepared by adopting the novel polyethylene terephthalate and the polypropylene under the formulas of the example and the comparative example. The marine recycled PP/PET alloy prepared in the recycling process of the marine polypropylene and the polyethylene terephthalate has good application performance, and can replace the newly prepared PP/PET alloy to be applied to the fields of automobiles, household appliances, toys, machinery and the like. The method not only can solve the pollution problem in the ocean, but also can change waste into valuable, fully recycles the garbage in the ocean, and has wide market prospect and application prospect.
The foregoing illustrates and describes the principles, general features, and advantages of the present invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, and the embodiments and descriptions given above are only illustrative of the principles of the present invention, and various changes and modifications may be made without departing from the spirit and scope of the invention, which fall within the scope of the claims. The scope of the invention is defined by the appended claims and equivalents thereof.

Claims (9)

1. The marine regenerated PP/PET alloy is characterized by comprising the following raw materials in percentage by mass:
polypropylene: 15% -55%;
polyethylene terephthalate: 15% -55%;
a compatilizer: 2% -8%;
a toughening agent: 10% -25%;
colorant: 0.5% -5%;
antioxidant: 0.1 to 2 percent.
2. The marine recycled PP/PET alloy of claim 1, wherein the polypropylene is at least one of freshly made polypropylene particles and marine recycled polypropylene particles.
3. The marine recycled PP/PET alloy of claim 1, wherein the polyethylene terephthalate is at least one of freshly made polyethylene terephthalate pellets and marine recycled polyethylene terephthalate pellets.
4. The marine recycled PP/PET alloy of claim 2, wherein the marine recycled polypropylene particles are prepared by centrifugally cleaning, drying, crushing, extruding by a double-screw extruder, cooling, drying and granulating the marine recycled polypropylene.
5. The marine recycled PP/PET alloy of claim 3, wherein the marine recycled polyethylene terephthalate particles are prepared by centrifugally cleaning, drying, crushing, extruding by a double-screw extruder, cooling, drying and granulating the marine recycled polyethylene terephthalate.
6. The marine recycled PP/PET alloy of claim 1, wherein the compatibilizer is at least one of polypropylene grafted maleimide (PP-g-MI), polypropylene grafted glycidyl methacrylate (PP-g-GMA), and maleic anhydride grafted styrene-ethylene-butadiene-styrene block copolymer (SEBS-g-MAH).
7. The marine recycled PP/PET alloy of claim 1, wherein the toughening agent is a thermoplastic elastomer based toughening agent.
8. The marine recycled PP/PET alloy of claim 1, wherein the colorant is at least one of titanium dioxide, zinc powder, cadmium red, ferric oxide, carbon black, chrome yellow, zinc yellow, and hansa yellow.
9. The marine recycled PP/PET alloy of claim 1, wherein the antioxidant is at least one of a hindered phenolic antioxidant and a phosphate antioxidant.
CN202011243288.7A 2020-11-10 2020-11-10 Marine recycled PP/PET alloy Pending CN112266537A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114874544A (en) * 2022-05-10 2022-08-09 东莞市国亨塑胶科技有限公司 Impact-resistant marine recycled polypropylene recycled material and preparation method thereof

Citations (3)

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Publication number Priority date Publication date Assignee Title
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CN108948524A (en) * 2018-06-22 2018-12-07 苏州上车新材料科技有限公司 MODIFIED PP/PET alloy die casting collet and preparation method thereof
CN110093024A (en) * 2019-04-19 2019-08-06 山东星达新材料有限公司 Ocean regenerative PET is modified PC/ABS alloy

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Publication number Priority date Publication date Assignee Title
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CN108948524A (en) * 2018-06-22 2018-12-07 苏州上车新材料科技有限公司 MODIFIED PP/PET alloy die casting collet and preparation method thereof
CN110093024A (en) * 2019-04-19 2019-08-06 山东星达新材料有限公司 Ocean regenerative PET is modified PC/ABS alloy

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114874544A (en) * 2022-05-10 2022-08-09 东莞市国亨塑胶科技有限公司 Impact-resistant marine recycled polypropylene recycled material and preparation method thereof

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Application publication date: 20210126