CN106700237A - Enhanced modified polypropylene reclaimed material and preparation method thereof - Google Patents

Enhanced modified polypropylene reclaimed material and preparation method thereof Download PDF

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Publication number
CN106700237A
CN106700237A CN201510778973.2A CN201510778973A CN106700237A CN 106700237 A CN106700237 A CN 106700237A CN 201510778973 A CN201510778973 A CN 201510778973A CN 106700237 A CN106700237 A CN 106700237A
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polypropylene
parts
reclaimed materials
modified polypropene
antioxidant
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杨桂生
方永炜
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Hefei Genius New Materials Co Ltd
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Hefei Genius New Materials Co Ltd
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Priority to CN201510778973.2A priority Critical patent/CN106700237A/en
Publication of CN106700237A publication Critical patent/CN106700237A/en
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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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/92—Measuring, controlling or regulating
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
    • C08J5/043—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with glass fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92504—Controlled parameter
    • B29C2948/92704—Temperature
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/003—Additives being defined by their diameter
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
    • 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
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • 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
    • C08L2207/20—Recycled plastic

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention provides an enhanced modified polypropylene reclaimed material and a preparation method thereof. The enhanced modified polypropylene reclaimed material is prepared by mixing, extruding and granulating 30 to 75 parts of polypropylene reclaimed material, 10 to 30 parts of polypropylene, 5 to 15 parts of polypropylene grafted maleic anhydride, 10 to 25 parts of medium-alkali glass fibers, 0.2 to 1 part of antioxidant and 0.5 to 2 parts of bis(tert-butyl peroxy)diisopropyl benzene. By introducing the polypropylene grafted maleic anhydride into the polypropylene reclaimed material, a group with high polarity and reactiveness is introduced, so that the material is high in polarity and reactiveness, and the compatibility of the polypropylene and fibers is greatly improved; and meanwhile, the cross-linking degree of the material is increased by virtue of the bis(tert-butylperoxy)diisopropyl benzene, the dispersity and compatibility are excellent, the rigidness and flexibility balance is excellent, and the enhanced modified polypropylene reclaimed material can be used for producing a product with high requirement on the balance of the rigidness and flexibility.

Description

One kind enhancing modified polypropene reclaimed materials and preparation method thereof
Technical field
The invention belongs to field of high polymer material modification and processing technique field, and in particular to one kind enhancing modified polypropene reclaimed materials and preparation method thereof.
Background technology
Polypropylene is a kind of thermoplastic, and its light specific gravity, elasticity are high, and finished product case hardness is big, the features such as also have heat resistance, chemical stability, good insulating properties in addition, is widely used in fields such as auto parts and components, household electrical appliance.But with industrial expansion, polyacrylic discarded amount increases year by year, in recent years, the recovery problem of waste or used plastics increasingly obtains everybody concern, and many enterprises proceed by being modified again for reclaimed materials.
Laundry machine barrel is generally COPP material and is made, its filling less, high melt index, shock resistance it is high.The washing machine of millions of is scrapped per annual meeting by China, and is being increased with average annual 20% speed.If resulting laundry machine barrel waste material can be recycled rationally, can economize on resources, environmental protection is reduced and wasted.
The polypropylene material of recovery causes its performance substantially to decay because of aging, degraded etc., and in the granulation process again of reclaimed materials, polypropylene segment can again be destroyed and degraded.Therefore in order to preferably utilize reclaimed materials, typically it can be again modified, to improve polyacrylic intensity and ageing-resistant performance.
Glass fibre to the humidification of plastics clearly, and be widely used in the enhancing of plastics it is modified in.Alkali-free glass fiber has excellent chemical stability, electrical insulating property and mechanical property, is mainly used in reinforced plastics, and alkali-free glass fiber RPP material has been used widely on automobile at present.The alkali metal content of medium-alkali glass fiber is higher than alkali-free glass fiber, its mechanical strength is not so good as alkali-free glass fiber, but it is its abundance, cheap, alkali-free glass fiber RPP material is substituted with medium-alkali glass fiber modified polypropylene material, can be with reduces cost, and strengthen the use of modified polypropene reclaimed materials, and material cost can be further reduced, bring profit to enterprise.
The content of the invention
It is an object of the invention to provide one kind enhancing modified polypropene reclaimed materials and preparation method thereof.
Technical scheme is as follows：
The invention provides one kind enhancing modified polypropene reclaimed materials, the material is made up of the component of following weight portion：
Polypropylene reclaimed material：30 ~ 75 parts,
Polypropylene：10 ~ 30 parts,
Polypropylene grafted maleic anhydride：5 ~ 15 parts,
Medium-alkali glass fiber：10 ~ 25 parts,
Antioxidant：0.2 ~ 1 part,
Double tert-butyl peroxy base diisopropylbenzene (DIPB)s：0.5 ~ 2 part.
The polypropylene 230 DEG C in the case of 2.16Kg melt index be 40 ~ 100 g/10min。
The polypropylene reclaimed material is waste and old polypropylene laundry machine barrel reclaimed materials, and its ash content is that 2 ~ 10%, density is 0.91 ~ 0.98g/cm3, 230 DEG C in the case of 2.16Kg melt index be 10 ~ 40g/10min.
Grafting rate >=1% of the polypropylene grafted maleic anhydride, weight average molecular weight >=30000.
Described antioxidant includes primary antioxidant and auxiliary anti-oxidant.Described primary antioxidant can select in hindered phenol and sulphur ester antioxidant one or several, preferably antioxidant 1010, chemical name：Four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol esters, and antioxidant 1076, chemical name：β-(4 '-hydroxyl -3 ', 5 '-di-tert-butyl-phenyl) propionic acid octadecyl.Described auxiliary anti-oxidant is selected from one or several in phosphite and esters antioxidant, preferably irgasfos 168, chemical name：Three (2,4- di-tert-butyl-phenyls) phosphite esters.
The medium-alkali glass fiber is middle alkali long glass fibres, and its filament diameter is 20 ~ 30 microns.
Described double 46 DEG C of tert-butyl peroxy base diisopropylbenzene (DIPB) fusing points.
The preparation method of enhancing modified polypropene reclaimed materials of the invention is comprised the following steps, the double tert-butyl peroxy base diisopropylbenzene (DIPB)s of 30 ~ 75 parts of polypropylene reclaimed materials, 10 ~ 30 parts of polypropylene, 5 ~ 15 parts of polypropylene grafted maleic anhydrides, 0.2 ~ 1 part of antioxidant and 0.5 ~ 2 portion are put into high-speed mixer and are mixed 3 ~ 5 minutes, then in feeding the mixture into extruder, 10 ~ 25 parts of medium-alkali glass fibers are added from glass fiber opening simultaneously, extrusion pelletizing obtains required medium-alkali glass fiber enhancing enhancing modified polypropene reclaimed materials.
Described extruder is double screw extruder, and the barrel temperature of extruder is 180 ~ 220 DEG C.
Beneficial effects of the present invention：
1st, the present invention adds polypropylene grafted maleic anhydride to introduce highly polar reactive group by polypropylene reclaimed material, material is had polarity and reactivity high, greatly improves the compatibility of polypropylene and fiber；
2nd, on the one hand the double tert-butyl peroxy base diisopropylbenzene (DIPB)s in the present invention can be significantly increased the degree of cross linking of polypropylene reclaimed material, increase composition melt index, improve the physics characteristic of composition；On the other hand reached with polypropylene grafted maleic anhydride collective effect and combined closely with polymer, significantly improve intensity, cohesion, dispersive property of material etc., most making obtained composition after all has good dispersiveness, compatibility, excellent rigid-tough balance, can be used to having higher requirements rigid-tough balance the making of product, and such as arrangements for automotive doors is marked time body.
3rd, the present invention makes it rationally be recycled using machine barrel waste material of doing washing, and can economize on resources, environmental protection, reduces and wastes.
Specific embodiment
The present invention is further illustrated with reference to embodiments.
Tensile strength of the comprehensive mechanical property of material as obtained by test, bending strength, the numerical value of impact strength and density are judged that the performance test results are shown in Table 1.
Embodiment 1
By 75 parts of polypropylene reclaimed materials, 10 parts of polypropylene, 5 parts of polypropylene grafted maleic anhydrides, 0.2 part of antioxidant（Antioxidant 1010 and irgasfos 168）It is put into together in high-speed mixer with 0.5 portion of double tert-butyl peroxy base diisopropylbenzene (DIPB) and is mixed 3 minutes, then fed the mixture into extruder, 10 parts of medium-alkali glass fibers are added from glass fiber opening, extrusion pelletizing obtains strengthening modified polypropene reclaimed materials.
Each zone temperatures of barrel of double screw extruder are respectively set to：One 180 DEG C of area, 185 DEG C of 2nd area, 195 DEG C of 3rd area, 195 DEG C of 4th area, 200 DEG C of 5th area, 200 DEG C of 6th area, 205 DEG C of head.Extrusion bar is cooled to room temperature by circulating water chennel, is granulated into pelleter by after hair-dryer drying.
Embodiment 2
By 30 parts of polypropylene reclaimed materials, 30 parts of polypropylene, 15 parts of polypropylene grafted maleic anhydrides, 0.4 part of antioxidant（Antioxidant 1010, antioxidant 1076 and irgasfos 168）It is put into high-speed mixer with 1.3 portions of double tert-butyl peroxy base diisopropylbenzene (DIPB)s and is mixed 4 minutes, then fed the mixture into extruder, 25 parts of medium-alkali glass fibers are added from glass fiber opening, extrusion pelletizing obtains strengthening modified polypropene reclaimed materials.
Each zone temperatures of barrel of double screw extruder are respectively set to：One 180 DEG C of area, 185 DEG C of 2nd area, 195 DEG C of 3rd area, 195 DEG C of 4th area, 210 DEG C of 5th area, 220 DEG C of 6th area, 205 DEG C of head.Extrusion bar is cooled to room temperature by circulating water chennel, is granulated into pelleter by after hair-dryer drying.
Embodiment 3
By 52 parts of polypropylene reclaimed materials, 20 parts of polypropylene, 10 parts of polypropylene grafted maleic anhydrides, 1 part of antioxidant（Antioxidant 1010 and irgasfos 168）It is put into together in high-speed mixer with 2 portions of double tert-butyl peroxy base diisopropylbenzene (DIPB)s and is mixed 5 minutes, then fed the mixture into extruder, 18 parts of medium-alkali glass fibers are added from glass fiber opening, extrusion pelletizing obtains strengthening modified polypropene reclaimed materials.
Each zone temperatures of barrel of double screw extruder are respectively set to：One 180 DEG C of area, 185 DEG C of 2nd area, 195 DEG C of 3rd area, 195 DEG C of 4th area, 200 DEG C of 5th area, 200 DEG C of 6th area, 205 DEG C of head.Extrusion bar is cooled to room temperature by circulating water chennel, is granulated into pelleter by after hair-dryer drying.
Enhancing modified polypropene reclaimed materials prepared by above-described embodiment 1-3 is molded into batten through standard, and performance is as shown in table 1.Simultaneously will it is existing 230 DEG C in the case of 2.16Kg melt index be 40 ~ 100 The polypropylene and waste and old polypropylene of g/10min do washing machine barrel reclaimed materials as comparative example, are equally molded into batten and detect its performance, as shown in table 1 below.
Table 1
Test event Embodiment 1 Embodiment 2 Embodiment 3 Polypropylene Polypropylene reclaimed material Examination criteria
Density（g/cm3） 0.97 1.08 1.03 0.9 1.10 GB/T 1033
Tensile strength（MPa） 81 89 83 28 16 GB/T 1040
Bending strength（MPa） 112 132 129 42 23 GB/T 9341
Bending modulus（MPa） 4123 4350 4199 1852 986 GB/T 9341
Simply supported beam notch impact strength（KJ/m2） 21 26 25 14 9 GB/T 1043
Simply supported beam unnotched impact strength（KJ/m2） 78 94 80 54 26 GB/T 1043
Be can be seen that from upper table 1, the mechanical performance such as tensile strength, bending strength of enhancing modified polypropene reclaimed materials prepared by the present invention is significantly better than common polypropylene reclaimed material, is also significantly better than polypropylene material.So enhancing modified polypropene reclaimed materials prepared by the present invention has excellent rigidity-toughness balanced performance.
The above-mentioned description to embodiment is to be understood that and apply the present invention for ease of those skilled in the art.Person skilled in the art obviously can easily make various modifications to these embodiments, and General Principle described herein is applied in other embodiment without by performing creative labour.Therefore, the invention is not restricted to embodiment here, those skilled in the art's announcement of the invention, does not depart from improvement that scope made and modification all should be within protection scope of the present invention.

Claims (9)

  1. It is 1. a kind of to strengthen modified polypropene reclaimed materials, it is characterised in that：It is prepared from by weight by following components：
    Polypropylene reclaimed material：30 ~ 75 parts,
    Polypropylene：10 ~ 30 parts,
    Polypropylene grafted maleic anhydride：5 ~ 15 parts,
    Medium-alkali glass fiber：10 ~ 25 parts,
    Antioxidant：0.2 ~ 1 part,
    Double tert-butyl peroxy base diisopropylbenzene (DIPB)s：0.5 ~ 2 part.
  2. It is 2. according to claim 1 to strengthen modified polypropene reclaimed materials, it is characterised in that：The polypropylene 230 DEG C in the case of 2.16Kg melt index be 40 ~ 100 g/10min.
  3. It is 3. according to claim 1 to strengthen modified polypropene reclaimed materials, it is characterised in that：The polypropylene reclaimed material is waste and old polypropylene laundry machine barrel reclaimed materials, and its ash content is that 2 ~ 10%, density is 0.91 ~ 0.98g/cm3, 230 DEG C in the case of 2.16Kg melt index be 10 ~ 40g/10min.
  4. It is 4. according to claim 1 to strengthen modified polypropene reclaimed materials, it is characterised in that：Grafting rate >=1% of the polypropylene grafted maleic anhydride, weight average molecular weight >=30000.
  5. It is 5. according to claim 1 to strengthen modified polypropene reclaimed materials, it is characterised in that：The antioxidant is made up of primary antioxidant and auxiliary anti-oxidant mixing, and wherein primary antioxidant selects one or several in hindered phenol and sulphur ester antioxidant；Auxiliary anti-oxidant be selected from phosphite and esters antioxidant in one or several.
  6. It is 6. according to claim 5 to strengthen modified polypropene reclaimed materials, it is characterised in that：The primary antioxidant is preferably four [β-(3,5- di-tert-butyl-hydroxy phenyls) propionic acid] pentaerythritol esters or β-(4 '-hydroxyl -3 ', 5 '-di-tert-butyl-phenyl) propionic acid octadecyl；The auxiliary anti-oxidant is preferably three (2,4- di-tert-butyl-phenyls) phosphite esters.
  7. It is 7. according to claim 1 to strengthen modified polypropene reclaimed materials, it is characterised in that：The medium-alkali glass fiber is middle alkali long glass fibres, and its filament diameter is 20 ~ 30 microns.
  8. It is 8. according to claim 1 to strengthen modified polypropene reclaimed materials, it is characterised in that：Described double 46 DEG C of tert-butyl peroxy base diisopropylbenzene (DIPB) fusing points.
  9. 9. as described in claim any one of 1-8 enhancing modified polypropene reclaimed materials preparation method, it is characterised in that：First the double tert-butyl peroxy base diisopropylbenzene (DIPB)s of 30 ~ 75 parts of polypropylene reclaimed materials, 10 ~ 30 parts of polypropylene, 5 ~ 15 parts of polypropylene grafted maleic anhydrides, 0.2 ~ 1 part of antioxidant and 0.5 ~ 2 portion are put into high-speed mixer together and are mixed 3 ~ 5 minutes；Then feed the mixture into extruder, while 10 ~ 25 parts of medium-alkali glass fibers are added from glass fiber opening, extrusion, pelletizing obtain final product enhancing modified polypropene reclaimed materials；Described extruder is double screw extruder, and its barrel temperature is 180 ~ 220 DEG C.
CN201510778973.2A 2015-11-15 2015-11-15 Enhanced modified polypropylene reclaimed material and preparation method thereof Pending CN106700237A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113845727A (en) * 2021-10-25 2021-12-28 成都金发科技新材料有限公司 High-rigidity high-thermal-aging-resistance polypropylene composite material and preparation method thereof
CN115386163A (en) * 2022-07-29 2022-11-25 广州汽车集团股份有限公司 Polypropylene reclaimed material and preparation method and application thereof

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101638493A (en) * 2009-08-27 2010-02-03 惠东美化塑胶实业有限公司 Long glass fiber reinforced recycled polypropylene material and preparation method thereof

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101638493A (en) * 2009-08-27 2010-02-03 惠东美化塑胶实业有限公司 Long glass fiber reinforced recycled polypropylene material and preparation method thereof

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113845727A (en) * 2021-10-25 2021-12-28 成都金发科技新材料有限公司 High-rigidity high-thermal-aging-resistance polypropylene composite material and preparation method thereof
CN113845727B (en) * 2021-10-25 2023-12-12 成都金发科技新材料有限公司 Polypropylene composite material with high rigidity and high thermal aging resistance and preparation method thereof
CN115386163A (en) * 2022-07-29 2022-11-25 广州汽车集团股份有限公司 Polypropylene reclaimed material and preparation method and application thereof

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