CN103497423A - High melt strength polypropylene (PP) composition and preparation method thereof - Google Patents
High melt strength polypropylene (PP) composition and preparation method thereof Download PDFInfo
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- CN103497423A CN103497423A CN201310431560.8A CN201310431560A CN103497423A CN 103497423 A CN103497423 A CN 103497423A CN 201310431560 A CN201310431560 A CN 201310431560A CN 103497423 A CN103497423 A CN 103497423A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B9/00—Making granules
- B29B9/02—Making granules by dividing preformed material
- B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
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- 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
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
- B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
- B29C48/402—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders the screws having intermeshing parts
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- 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
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/50—Details of extruders
- B29C48/505—Screws
- B29C48/625—Screws characterised by the ratio of the threaded length of the screw to its outside diameter [L/D ratio]
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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
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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
- C08L23/14—Copolymers of propene
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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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides a high melt strength polypropylene (PP) composition. The composition is prepared from the following raw materials in parts by weight: 100 parts of PP (A), 1-30 parts of ethylene-acrylic acid copolymer (B), 0.5-5 parts of accelerant (C), 0.01-1 part of initiator (D), 0.1-0.5 part of antioxidant (E) and 0.1-2 parts of lubricating agent (F). The composition has the beneficial effects that the ethylene-acrylic acid polymer is adopted as the graft monomer of PP, thus avoiding the defect that conjugated diene compounds are easy to crosslink; the produced high melt strength PP is free from crosslinking and has an excellent extrusion property.
Description
Technical field
The invention belongs to technical field of plastic, be specifically related to a kind of non-crosslinked high melt strength, propylene containing long branched chain structure and preparation method thereof.
Background technology
Polypropylene (PP) molecular chain is the linear straight chain structure, lacks long-chain branch, can not produce the secondary activity center, cause the shortcomings such as the low and Sag Resistance of its melt strength is poor, under molten state, polypropylene does not have strain hardening effect, has therefore greatly limited polyacrylic range of application.In addition, polypropylene or a kind of partially crystalline polymer, softening temperature and fusing point are very approaching, after surpassing fusing point, melt strength descends rapidly, cause when thermoforming container wall thickness inhomogeneous, occur edge curl, contraction during extrusion coated calendering, the abscess problem such as subside during extrusion foaming.Overcome the above problems, effective means is to improve polyacrylic melt strength.Because high melt strength, propylene technology wide application, added value of product are high, many countries conducting in-depth research aspect the exploitation high melt strength, propylene, have obtained breakthrough, thereby have enlarged polyacrylic Application Areas in recent years.
Preparing high melt strength, propylene (HMSPP) can be by improving polyacrylic relative molecular mass, increasing the methods such as molecular weight distribution, grafting long-chain branch.Specific implementation method has the methods such as blending and modifying, chemically crosslinked, radiation crosslinking, solution graft copolymerization, fusion-grafting and original flavor polymerization.
Japanese Patent JP5531807 discloses a kind of method of PP, HDPE, LDPE, EPR blend raising melt strength, and the producing foamed material; Chinese patent CN1775851A discloses the method that PP, grafting PP, PE and aminated compounds blending extrusion prepare high melt strength, propylene; U.S. Pat 4365004 improves melt strength by CPP and LDPE blend.Only adopt simple blend to be difficult to arrive molecular level dispersed, product melt strength and mechanical property are undesirable.
Meng Daier company has been introduced in activity keto concentration is less than 15% environment at Chinese patent of invention ZL94116148, with energy beam, homopolymerization and Co-polypropylene or other compositions are carried out to radiation in 1 hour, thereby and then make the free radical inactivation of radiation obtain the method for the high melt strength, propylene of branching.It is said that this method can obtain not containing the high melt strength, propylene of gel, melt elasticity is high and obvious stress hardening phenomenon arranged, aspect foaming and Extrusion Coating, having wide practical use, thereby the main drawback of method for radio-grafting is the facility investment that produces energetic ray causes greatly the high melt strength, propylene of preparation expensive, has limited its widespread use.
Chinese patent ZL200510043675.5 discloses the preparation method of partial cross-linked high melt strength, propylene, and it adopts the grafting preparation under extrusion condition such as unsaturated silane, alcoholysis agent and superoxide.CN 102329405 A, CN1341670A have also introduced similar method.Add unsaturated the second monomer, although limited polyacrylic degraded, easily produce crosslinkedly to improve melt strength, crosslinking degree is difficult to control.And crosslinked polypropylene easily produces gel, in the post-treatment process, can bring a large amount of problems to production.
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Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, provide a kind of melt flow rate (MFR) wide, gel-free, simple high melt strength, propylene of preparation technology and preparation method thereof.
The objective of the invention is to be achieved through the following technical solutions:
A kind of high melt strength, propylene based on graft reaction, the parts by weight that its raw material forms are:
Polypropylene (A) 100 weight parts
Ethylene acrylic acid co polymer (B) 1-30 weight part, preferably 5-25% weight part
Promotor (C) 0.5-5%
Initiator (D) 0.01～1 weight part
Oxidation inhibitor (E) 0.1-0.5 weight part
Lubricant (F) 0.1-2 weight part.
Described polypropylene is homo-polypropylene, Co-polypropylene, atactic copolymerized polypropene or its combination, and requiring the melt polypropylene flow rate is 1.0-10g/10min.
Described ethylene acrylic acid co polymer is that the polymerization degree is 1000-10000, acrylic acid content 6-15%, the preferably ethylene acrylic acid co polymer of acrylic acid content 9-11%.Ethylene acrylic acid co polymer, under metal-salt or metal oxide effect, forms the star-like grafts of ethylene acrylic, and this grafts with polypropylene grafted, forms the polypropylene long-chain branch under peroxidation, thereby produces high melt strength, propylene.
Described promotor is metal oxide, metal hydroxides and stearate composition thereof, is specially zinc oxide, calcium oxide, magnesium oxide, aluminum oxide, calcium hydroxide, magnesium hydroxide, aluminium hydroxide, Zinic stearas, calcium stearate, Magnesium Stearate, aluminum stearate and combination thereof.
Described initiator is selected from peroxide, azo radical initiator or its combination; Be specially BP, dicumyl peroxide, di-t-butyl peroxide, Diisopropyl azodicarboxylate or its combination.
Described oxidation inhibitor is 3,5-di-t-butyl-4-hydroxy phenylpropionic acid octadecyl ester, 2,6-tert-butyl-4-methyl-Phenol, 2, the 6-tertiary butyl-a-dimethylin Pyrogentisinic Acid, three (2, the 4-tert-butyl-phenyl) phosphorous acid ester, four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester
With one or more compounds in the thio-2 acid dilaurate.
Described lubricant is one or more compounds in single stearic acid glycerine lipoprotein, erucicamide, stearic acid, ethylene bis stearamide, ethylene dilaurate acid amides.
Containing the high melt strength, propylene preparation method of long-chain branch, its step is as follows:
1) mix: take in proportion each component, put into homogenizer and fully mix 5-6 minute, guarantee that mixing temperature is not less than 50 degree.
2) cooling and absorbing: by the cooling placement at least 24 hours under the environment of sealing of mixed raw material.
3) extruding pelletization: mixture is added in single screw rod or twin screw extruder, preferred twin screw extruder, rotating speed 40-300r/min, twin screw extruder is the 170-240 degree from the transportation section to the die temperature, the reaction extruding pelletization, obtain high melt strength, propylene.
Beneficial effect: the present invention prepares polypropylene melt with high melt strength strength ratio raw material and improves 2-8 doubly.The present invention adopts the standby high melt strength, propylene of extruding pelletization legal system, and the method is simple, convenient, enhances productivity, and reduces production costs.The present invention adopts the ethylene, propylene acid polymer as polyacrylic grafted monomer, has avoided easily crosslinked shortcoming of conjugated diene compound, and the high melt strength, propylene of production, without crosslinked, extrudes the processing characteristics excellence.
Major equipment of the present invention is homogenizer and forcing machine, and facility investment is few, and technique is simple, easily controls, with low cost.The products obtained therefrom melt strength obviously improves, and can be used for the goods such as extrusion coated, thermoforming, foaming, blowing.
The accompanying drawing explanation
Fig. 1 does the abscess microphotograph of foam sheet by Comparative Examples
Fig. 2 makes the abscess microphotograph of foamed material of embodiment 7
Fig. 3 is the infrared colour spectrogram of Comparative Examples and embodiment 7
Fig. 4 is that the shearing rate of Comparative Examples and embodiment 7 compares graph of a relation with Die Swell
Claims (6)
1. a high melt strength, propylene composition consists of following raw material in weight fraction:
Polypropylene (A) 100
Ethylene acrylic acid co polymer (B) 1-30
Promotor (C) 0.5-5
Initiator (D) 0.01-1
Oxidation inhibitor (E) 0.1-0.5
Lubricant (F) 0.1-2,
Described polypropylene is homo-polypropylene, Co-polypropylene, atactic copolymerized polypropene or its combination, and melt flow rate (MFR) is 1.0-10g/10min;
The described ethylene acrylic acid co polymer polymerization degree is 1000-10000, and the vinylformic acid weight percentage is 6-15%;
Described promotor is metal oxide, metal hydroxides and stearate composition thereof and combination thereof;
Described initiator is selected from peroxide, azo radical initiator or its combination; Be specially BP, dicumyl peroxide, di-t-butyl peroxide, Diisopropyl azodicarboxylate or its combination;
Described oxidation inhibitor is 3,5-di-t-butyl-4-hydroxy phenylpropionic acid octadecyl ester, 2,6-tert-butyl-4-methyl-Phenol, 2, the 6-tertiary butyl-a-dimethylin Pyrogentisinic Acid, three (2, the 4-tert-butyl-phenyl) one or more compounds in phosphorous acid ester, four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester and thio-2 acid dilaurate;
Described lubricant is one or more compounds in single stearic acid glycerine lipoprotein, erucicamide, stearic acid, ethylene bis stearamide, ethylene dilaurate acid amides.
2. high melt strength, propylene composition according to claim 1, the acrylic acid content that it is characterized in that ethylene acrylic acid co polymer is 9-11%.
3. high melt strength, propylene composition according to claim 2, the content that it is characterized in that ethylene acrylic acid co polymer is 5-25.
4. described high melt strength, propylene composition according to claim 2, is characterized in that promotor is zinc oxide, calcium oxide, magnesium oxide, aluminum oxide, calcium hydroxide, magnesium hydroxide, aluminium hydroxide, Zinic stearas, calcium stearate, Magnesium Stearate, aluminum stearate and combination thereof.
5. high melt strength, propylene composition according to claim 1, the preparation method is as follows:
1) mix: take in proportion each component, put into homogenizer and fully mix 5-6 minute, mixing temperature is not less than 50 degree;
2) cooling and absorbing: by the cooling placement at least 24 hours under the environment of sealing of mixed raw material;
3) extruding pelletization: mixture is added in twin screw extruder, rotating speed 40-300r/min, twin screw extruder is the 170-240 degree from the transportation section to the die temperature, the reaction extruding pelletization, obtain high melt strength, propylene.
6. the preparation method of high melt strength, propylene composition according to claim 5, is characterized in that twin screw extruder is for leading to the rotation engagement type, screw diameter 45mm, length-to-diameter ratio is 44:1, speed control by frequency variation, adopt nine sections to add control temp, the 8th section of forcing machine, carries out vacuum exhaust.
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| CN201310431560.8A CN103497423A (en) | 2013-09-22 | 2013-09-22 | High melt strength polypropylene (PP) composition and preparation method thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104231445A (en) * | 2014-09-04 | 2014-12-24 | 广州树德科技股份有限公司 | High-melt-strength polypropylene composition and preparation method thereof |
| CN105801757A (en) * | 2016-03-24 | 2016-07-27 | 中国石油化工股份有限公司 | Long-chain-branch high-melt-strength polypropylene resin and preparation method thereof |
| CN113480805A (en) * | 2021-08-13 | 2021-10-08 | 贵州省材料产业技术研究院 | High-performance, antibacterial and corrosion-resistant screen material and preparation method thereof |
| CN113549272A (en) * | 2021-08-13 | 2021-10-26 | 贵州省材料产业技术研究院 | Durable hydrophilic polypropylene separation net material and preparation method thereof |
| CN116041855A (en) * | 2023-01-03 | 2023-05-02 | 青岛海泰科新材料科技有限公司 | High-melt-strength micro-foaming polypropylene composite material and preparation method thereof |
-
2013
- 2013-09-22 CN CN201310431560.8A patent/CN103497423A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104231445A (en) * | 2014-09-04 | 2014-12-24 | 广州树德科技股份有限公司 | High-melt-strength polypropylene composition and preparation method thereof |
| CN105801757A (en) * | 2016-03-24 | 2016-07-27 | 中国石油化工股份有限公司 | Long-chain-branch high-melt-strength polypropylene resin and preparation method thereof |
| CN113480805A (en) * | 2021-08-13 | 2021-10-08 | 贵州省材料产业技术研究院 | High-performance, antibacterial and corrosion-resistant screen material and preparation method thereof |
| CN113549272A (en) * | 2021-08-13 | 2021-10-26 | 贵州省材料产业技术研究院 | Durable hydrophilic polypropylene separation net material and preparation method thereof |
| CN113549272B (en) * | 2021-08-13 | 2023-08-29 | 贵州省材料产业技术研究院 | Durable hydrophilic polypropylene separation net material and preparation method thereof |
| CN116041855A (en) * | 2023-01-03 | 2023-05-02 | 青岛海泰科新材料科技有限公司 | High-melt-strength micro-foaming polypropylene composite material and preparation method thereof |
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Application publication date: 20140108 |