CN103571105A - Environment-friendly polyvinyl chloride resin composition and preparation method thereof - Google Patents
Environment-friendly polyvinyl chloride resin composition and preparation method thereof Download PDFInfo
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- CN103571105A CN103571105A CN201310547351.XA CN201310547351A CN103571105A CN 103571105 A CN103571105 A CN 103571105A CN 201310547351 A CN201310547351 A CN 201310547351A CN 103571105 A CN103571105 A CN 103571105A
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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
- B29C48/92—Measuring, controlling or regulating
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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
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
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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
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92819—Location or phase of control
- B29C2948/92857—Extrusion unit
- B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
- B29C2948/92885—Screw or gear
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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
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92819—Location or phase of control
- B29C2948/92857—Extrusion unit
- B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
- B29C2948/92895—Barrel or housing
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Abstract
The invention discloses an environment-friendly polyvinyl chloride resin composition and a preparation method thereof. The environment-friendly polyvinyl chloride resin composition is prepared from the following raw materials in parts by weight: 80-100 parts of polyvinyl chloride resin, 20-80 parts of ester polymer, 1-5 parts of thermal stabilizer and 1-10 parts of auxiliary thermal stabilizer. The environment-friendly polyvinyl chloride resin composition obtained according to the preparation method can be used for obviously improving the toughness and melt fluidity of the polyvinyl chloride resin. The polyvinyl chloride resin composition is environment-friendly and has superior comprehensive performance; the preparation method of the composition is simple and is easy for realizing industrialization.
Description
Technical field
The present invention relates to technical field of polymer materials, particularly relate to a kind of environmental protection polyvinyl chloride resin combination and preparation method thereof.
Background technology
Polyvinyl chloride, is called for short PVC, is the thermoplastic resin being formed by chloroethylene polymerization, and the multipolymer of ryuron and vinylchlorid is referred to as polyvinyl chloride (PVC) RESINS, i.e. polyvinyl chloride resin.PVC is only second to polyethylene and the resins for universal use that occupies world wide production second, is widely used in the fields such as tubing, bar, film, insulating material, material of construction.Yet polyvinyl chloride resin self also exists many defects to restrict its forming process and in the application in some field:
(1) poor heat stability: pure PVC easily decomposes when melt-processed, causes variable color and performance degradation.Therefore, need to add stablizer to improve its thermostability, add softening agent to improve its fluidity of molten simultaneously.Conventional plasticizers, as phthalic ester plasticizer, tritolyl phosphate and trioctyl trimellitate etc. have good plasticization effect.But easily there is migration and ecotope and HUMAN HEALTH worked the mischief in these softening agent.In recent years, epoxy soybean oil, hexanodioic acid dibutyl ester, citrate etc. are used to substitute or the alternative conventional plasticizers of part in the polyvinyl chloride resin course of processing.It is material modified that Chinese invention patent CN102453291A discloses a kind of property environment-friendly type PVC that comprises hexanodioic acid dibutyl ester/epoxy soybean oil composite elasticizer.This system softening agent is little to harm, but consumption is large.
(2) poor toughness: polyvinyl chloride resin has notch sensitivity, its notched Izod impact strength is about 3KJ/m
2, can not be used as structured material.Current toughness reinforcing two kinds of methods, i.e. chemical toughening modifying and the physics toughening modifying of mainly containing to PVC.Chemistry toughening modifying is by methods such as grafting, copolymerization, to change the molecular structure of polyvinyl chloride resin, introduces soft segment in PVC molecule, plays toughening effect.Chemical modification, because complex process, equipment requirements are high, is difficult to realize at polyvinyl chloride resin processed user end.Physics toughening modifying be by with toughner blend, improve its toughness.The good plasticized modifier of effect has ethylene vinyl acetate, paracril, styrene-butadiene rubber(SBR), acrylonitrile-butadiene-styrene (ABS) elastomerics, urethane, chlorinatedpolyethylene and styrene copolymer etc.Chinese invention patent CN102453291A discloses a kind of composition that utilizes ultrafine powder paracril toughening PVC; A kind of composition that adopts Polyurethane Thermoplastic Elastomer and the common toughening PVC of anti-impact processing aid is disclosed in Chinese invention patent CN101948596A; A kind of composition that adopts softening agent and the common toughening PVC of phenylethylene thermoplastic elastomer is disclosed in Chinese patent CN103059464A; A kind of high tenacity polychloroethylene pipes that contains the components such as chlorinated polyethylene resin, urethane, styrene-butadiene rubber(SBR), Chlorinated Polypropylene III acid-butadiene-styrene copolymer is disclosed in Chinese invention patent CN102850696A; In Chinese invention patent CN102898752A, adopt powdered fluororubber, nano level auxiliary agent, the common toughening PVC of processing aid to prepare a kind of high-performance PVC (polyvinyl chloride) tubing.In patent and report, PVC plasticized modifier is of a great variety, but mostly is petroleum base and not biodegradable elastomerics or elastomeric material at present.
(3) PVC poor in processability: conventionally need to add a large amount of softening agent to improve its melt flow rate (MFR).
Polyvinyl chloride resin and conventional plasticizers thereof and toughner mostly come from oil and not biodegradable, so its production and use to ecotope is caused certain pollution and oil is had to dependency.In addition, there is migration problem in the small molecules softening agent (as phthalate) using in polyvinyl chloride resin product, and human body and environment are produced to harm, seriously restricted PVC in some field, such as the application of the aspects such as toy for children.At present both at home and abroad about adopting research and the technology of bio-based and biodegradable polyesters material modification polyvinyl chloride resin to rarely have report.Therefore, use bio-based and biodegradable polyesters to carry out modification to PVC, avoid using or with non-environment-friendly type auxiliary agent, to prepare eco-friendly polyvinyl chloride resin material, there is innovation and novelty less as far as possible.
Summary of the invention
In view of this, the object of the invention is to propose a kind of environmental protection polyvinyl chloride resin combination and preparation method thereof, to improve toughness, processing fluidity, biomass or the biodegradable component concentration of polyvinyl chloride resin material, avoid using a large amount of softening agent simultaneously.
Based on above-mentioned purpose, a kind of environmental protection polyvinyl chloride resin combination provided by the invention, is characterized in that, by following raw material according to respectively having weight part proportioning group of one's own: polyvinyl chloride (PVC) RESINS 80-100 part, esters polymer 20-80 part, thermo-stabilizer 1-5 part, auxiliary heat stabilizer 1-10 part.
Alternatively, described polyvinyl chloride (PVC) RESINS is SG0-SG9 type, preferably SG2-SG6 type.
Alternatively, described esters polymer is selected from least one in succinic acid-butanediol ester multipolymer, tetramethylene adipate-mutual-phenenyl two acid bromide two alcohol ester multipolymer, succinic acid-butanediol ester-tetramethylene adipate multipolymer, 3 hydroxybutyric acid ester homopolymers, 3 butyric ester-3 hydroxyl pentanoate copolymers, 3 butyric ester-4 hydroxybutyric acid ester copolymers and 3 butyric ester-3 hydroxycaproic acid ester copolymers.
Alternatively, described thermo-stabilizer is at least one in organic tin stablizer and calcium zinc stabilizer.
Preferably, described auxiliary heat stabilizer is epoxy soybean oil.
The present invention also provides a kind of method of preparing described environmental protection polyvinyl chloride resin combination, comprises the following steps:
First polyvinyl chloride (PVC) RESINS, esters polymer, thermo-stabilizer and auxiliary heat stabilizer are at room temperature mixed and obtained pre-composition by homogenizer according to proportioning, again above-mentioned pre-composition is passed through to rotor Banbury mixer melt blending, obtain described environmental protection polyvinyl chloride resin combination.Wherein, melt blending temperature is 140-190 ℃, and the blend time is 2-20 minute, and closed-smelting machine rotor rotating speed is 20-100 rev/min.
The present invention also provides the method for the described environmental protection polyvinyl chloride resin combination of another kind of preparation, comprises the following steps:
First polyvinyl chloride (PVC) RESINS, esters polymer, thermo-stabilizer and auxiliary heat stabilizer are at room temperature mixed and obtained pre-composition by homogenizer according to proportioning, again above-mentioned pre-composition is extruded by screw extrusion press melt blending, obtained described environmental protection polyvinyl chloride resin combination.Wherein, screw extrusion press feeding section temperature is 30-80 ℃, and all the other each section of temperature are 140-190 ℃, and the screw speed of screw extrusion press is 80-500 rev/min, preferably 90-300 rev/min.
As can be seen from above, the environmental protection polyvinyl chloride resin combination obtaining according to preparation method provided by the invention can significantly improve toughness and the fluidity of molten of polyvinyl chloride resin, there is higher bio-based or biodegradable component concentration, avoid using a large amount of softening agent simultaneously, can be directly used in extrude, injection moulding, mold pressing and the various environment-friendly type plastic material products of calendering formation.Its preparation method simply, is easily realized industrialization.In addition, add trace or a small amount of functional aid in described environmental protection polyvinyl chloride resin combination or its preparation process, for example oxidation inhibitor, lubricant, tinting material, mineral filler, processing aid, can not affect the basic mechanical property of said composition.
Embodiment
For making the object, technical solutions and advantages of the present invention clearer, below in conjunction with specific embodiment, the present invention is described in more detail.
Embodiment 1
By polyvinyl chloride (PVC-SG5, Group Co.,Ltd of Xingjiang Tianye Co. product) 100 parts, (4 butyric ester monomer molar content are 10% to 3 butyric ester-4 hydroxybutyric acid ester copolymers, Shenzhen Yi Ke Man product) 30 parts, methyl mercaptan tin heat stabilizer (NX-128, Nantong Ai Dewang Chemical Co., Ltd. product) 4 parts and epoxy soybean oil (Yueling City lucky star additives for plastics factory product) are 4 parts, in high-speed mixer, mix and obtain pre-composition, this pre-composition blend 4min in Haake Banbury mixer is obtained to a kind of environmental protection polyvinyl chloride resin combination.Wherein rotor speed is that 50rpm, temperature are 160 ℃.This poly (vinyl chloride) resin composition is pressed into sheet material for stretching and impact experiment by vulcanizing press, and the tensile strength that records this environmental protection polyvinyl chloride resin combination sheet material is 38MPa, and elongation at break is 250%, and notched Izod impact strength is 4.5kJ/m
2, melting index is 1.5g/10min.
Embodiment 2
By polyvinyl chloride (PVC-SG5, Group Co.,Ltd of Xingjiang Tianye Co. product) 100 parts, (4 butyric ester monomer molar content are 10% to 3 butyric ester-4 hydroxybutyric acid ester copolymers, Shenzhen Yi Ke Man product) 40 parts, calcium zinc heat stabilizer (CZ-7311, Huizhou Guang Xu plastics company limited product) 4 parts and epoxy soybean oil (Yueling City lucky star additives for plastics factory product) are 5 parts, in high-speed mixer, mix and obtain pre-composition, this pre-composition blend 5min in Haake Banbury mixer is obtained to a kind of environmental protection polyvinyl chloride resin combination.Wherein rotor speed is that 40rpm, temperature are 160 ℃.This poly (vinyl chloride) resin composition is pressed into sheet material for stretching and impact experiment by vulcanizing press, and the tensile strength that records this environmental protection polyvinyl chloride resin combination sheet material is 45MPa, and elongation at break is 300%, and notched Izod impact strength is 8.5kJ/m
2, melting index is 4.0g/10min.
Embodiment 3
By polyvinyl chloride (PVC-SG5, Group Co.,Ltd of Xingjiang Tianye Co. product) 105 parts, (4 butyric ester monomer molar content are 13% to 3 butyric ester-4 hydroxybutyric acid ester copolymers, Shenzhen Yi Ke Man product) 40 parts, calcium zinc heat stabilizer (CZ-7311, Huizhou Guang Xu plastics company limited product) 4 parts and epoxy soybean oil (Yueling City lucky star additives for plastics factory product) are 6 parts, in high-speed mixer, mix and obtain pre-composition, this pre-composition blend 3.5min in Haake Banbury mixer is obtained to a kind of environmental protection polyvinyl chloride resin combination.Wherein rotor speed is that 60rpm, temperature are 160 ℃.This poly (vinyl chloride) resin composition is pressed into sheet material for stretching and impact experiment by vulcanizing press, and the tensile strength that records this environmental protection polyvinyl chloride resin combination sheet material is 37MPa, and elongation at break is 270%, and notched Izod impact strength is 8.0kJ/m
2, melting index is 4.5g/10min.
Embodiment 4
By polyvinyl chloride (PVC-SG6, Group Co.,Ltd of Xingjiang Tianye Co. product) 72 parts of the 3 butyric ester-3 hydroxycaproic acid ester copolymers that 110 parts, 3 hydroxycaproic ester monomer molar content are 7% (Japanese Kaneka company product), calcium zinc heat stabilizer (CZ-7311, Huizhou Guang Xu plastics company limited product) 5 parts and epoxy soybean oil (Yueling City lucky star additives for plastics factory product) are 6 parts, in high-speed mixer, mix and obtain pre-composition, this pre-composition blend 5min in Haake Banbury mixer is obtained to a kind of environmental protection polyvinyl chloride resin combination.Wherein rotor speed is that 40rpm, temperature are 160 ℃.This poly (vinyl chloride) resin composition is pressed into sheet material for stretching and impact experiment by vulcanizing press, and the tensile strength that records this environmental protection polyvinyl chloride resin combination sheet material is 36MPa, and elongation at break is 320%, and notched Izod impact strength is 13.5kJ/m
2, melting index is 9.5g/10min.
Embodiment 5
By polyvinyl chloride (PVC-SG5, Group Co.,Ltd of Xingjiang Tianye Co. product) 95 parts, tetramethylene adipate-mutual-phenenyl two acid bromide two alcohol ester multipolymer (PBAT, Hangzhou Xin Fu medicine company limited-liability company product) 30 parts, calcium zinc heat stabilizer (CZ-7311, Huizhou Guang Xu plastics company limited product) 3 parts and epoxy soybean oil (Yueling City lucky star additives for plastics factory product) are 6 parts, in high-speed mixer, mix and obtain pre-composition, this pre-composition is melt extruded by twin screw extruder, obtain a kind of environmental protection polyvinyl chloride resin combination, wherein forcing machine is respectively 30 ℃ from feeding section to a mouthful temperature for mould section, 140 ℃, 145 ℃, 155 ℃ and 165 ℃, screw speed is 150rpm.This poly (vinyl chloride) resin composition is pressed into sheet material for stretching and impact experiment by vulcanizing press, and the tensile strength that records this environmental protection polyvinyl chloride resin combination sheet material is 40MPa, and elongation at break is 250%, and notched Izod impact strength is 7.5kJ/m
2, melting index is 2.0g/10min.
Embodiment 6
By polyvinyl chloride (PVC-SG4, Group Co.,Ltd of Xingjiang Tianye Co. product) 90 parts, succinic acid-butanediol ester-tetramethylene adipate multipolymer (EnPol G4460, Korea S Li Lai KCC product) 30 parts, methyl mercaptan tin heat stabilizer (NX-128, Nantong Ai Dewang Chemical Co., Ltd. product) 3.5 parts and epoxy soybean oil (Yueling City lucky star additives for plastics factory product) are 5 parts, in high-speed mixer, mix and obtain pre-composition, this pre-composition is melt extruded by twin screw extruder, obtain a kind of environmental protection polyvinyl chloride resin combination, wherein forcing machine is respectively 30 ℃ from feeding section to a mouthful temperature for mould section, 145 ℃, 150 ℃, 155 ℃ and 165 ℃, screw speed is 120rpm.This poly (vinyl chloride) resin composition is pressed into sheet material for stretching and impact experiment by vulcanizing press, and the tensile strength that records this environmental protection polyvinyl chloride resin combination sheet material is 42MPa, and elongation at break is 250%, and notched Izod impact strength is 7.0kJ/m
2, melting index is 4.0g/10min.
Embodiment 7
By polyvinyl chloride (PVC-SG6, Group Co.,Ltd of Xingjiang Tianye Co. product) 100 parts, 3 hydroxybutyric acid ester homopolymer (PHB, Ningbo Tianan Biological Material Co., Ltd.'s product) 10 parts, (4 butyric ester monomer molar content are 15% to 3 butyric ester-4 hydroxybutyric acid ester copolymers, Shenzhen Yi Ke Man product) 30 parts, methyl mercaptan tin heat stabilizer (NX-128, Nantong Ai Dewang Chemical Co., Ltd. product) 3 parts and epoxy soybean oil (Yueling City lucky star additives for plastics factory product) are 6 parts, in high-speed mixer, mix and obtain pre-composition, this pre-composition is melt extruded by single screw extrusion machine, obtain a kind of environmental protection polyvinyl chloride resin combination, wherein forcing machine is respectively 30 ℃ from feeding section to a mouthful temperature for mould section, 145 ℃, 150 ℃, 155 ℃ and 165 ℃, screw speed is 120rpm.This poly (vinyl chloride) resin composition is pressed into sheet material for stretching and impact experiment by vulcanizing press, and the tensile strength that records this environmental protection polyvinyl chloride resin combination sheet material is 37MPa, and elongation at break is 280%, and notched Izod impact strength is 5.5kJ/m
2, melting index is 6.0g/10min.
Comparative example 1
By polyvinyl chloride (PVC-SG5, Group Co.,Ltd of Xingjiang Tianye Co. product) 100 parts, calcium zinc heat stabilizer (CZ-7311, Huizhou Guang Xu plastics company limited product) 4 parts and epoxy soybean oil (Yueling City lucky star additives for plastics factory product) are 5 parts, in high-speed mixer, mix and obtain pre-composition, this pre-composition blend 5min in Haake Banbury mixer is obtained to a kind of environmental protection polyvinyl chloride resin combination.Wherein rotor speed is that 40rpm, temperature are 160 ℃.This poly (vinyl chloride) resin composition is pressed into sheet material for stretching and impact experiment by vulcanizing press, and the tensile strength that records this environmental protection polyvinyl chloride resin combination sheet material is 41MPa, and elongation at break is 70%, and notched Izod impact strength is 2.0kJ/m
2, melting index is 0.5g/10min.
Comparative example 2
By polyvinyl chloride (PVC-SG5, Group Co.,Ltd of Xingjiang Tianye Co. product) 100 parts, dioctyl phthalate (DOP) (DOP, Chemical Reagent Co., Ltd., Sinopharm Group's product) 30 parts, calcium zinc heat stabilizer (CZ-7311, Huizhou Guang Xu plastics company limited product) 4 parts and epoxy soybean oil (Yueling City lucky star additives for plastics factory product) are 5 parts, in high-speed mixer, mix and obtain pre-composition, this pre-composition blend 5min in Haake Banbury mixer is obtained to a kind of environmental protection polyvinyl chloride resin combination.Wherein rotor speed is that 40rpm, temperature are 160 ℃.This poly (vinyl chloride) resin composition is pressed into sheet material for stretching experiment by vulcanizing press, and the tensile strength that records this environmental protection polyvinyl chloride resin combination sheet material is 21MPa, and elongation at break is 230%, and melting index is 2.0g/10min.Because this poly (vinyl chloride) resin composition plasticizer loading is high, matter is soft should not carry out notch shock experiment.
It should be noted that, the method of prepared environmental protection polyvinyl chloride resin combination compacting sheet material comprises: first prepared environmental protection polyvinyl chloride resin combination is put into mould and (160 ℃ of the hot pressing temperatures of hot pressing on vulcanizing press, hot pressing time 4min, hot pressing pressure 10MPa) colding pressing, (time 5min colds pressing again, pressure 10MPa colds pressing), make the sheet material that thickness is 1mm and 4mm, be respectively used to stretch and impact experiment.
Umber described in embodiment is weight fraction; Vacuum-drying 8 hours at 60 ℃ before polyvinyl chloride used and esters polymer are used; The tensile strength of described environmental protection polyvinyl chloride resin combination and elongation adopt Shenzhen WDT-10 of Kai Qiangli Machinery Co., Ltd. tensile testing machine to record according to GB/T1040-2006 standard, and rate of extension is 10mm/min; Notched Izod impact strength adopts the MZ-2056 shock-testing machine of Jiangdu Mingzhu Testing Machinery Co., Ltd. to test according to ASTM D256; Melting index adopts the XNR-400B fusion index instrument of Chengde Jin Jian detecting instrument company limited to record according to GB/T3682-2000 standard, and test condition is 190 ℃ * 5.00kg.
The environmental protection polyvinyl chloride resin combination obtaining in embodiment 1-7 has the features such as intensity is high, good toughness, environmental friendliness.With do not adopt the comparative example 1 of esters polymer modification in the poly (vinyl chloride) resin composition that obtains compare, the environmental protection polyvinyl chloride resin combination obtaining in embodiment 1-7 is not only given polyvinyl chloride (PVC) RESINS material bio-based or biodegradable new features, and has significantly improved its elongation at break, notched Izod impact strength and melting index.With use the comparative example 2 of dioctyl phthalate (DOP) in the poly (vinyl chloride) resin composition that obtains compare, the environmental protection polyvinyl chloride resin combination obtaining in embodiment 1-7 is avoided using to environment and the harmful small molecules softening agent of human body, and can improve the processing fluidity of polyvinyl chloride (PVC) RESINS, significantly improve its tensile strength and elongation at break simultaneously.Visible, the environmental protection polyvinyl chloride resin combination obtaining according to preparation method provided by the invention is not only environmentally friendly, has also significantly improved mechanical property and the melt processability of poly (vinyl chloride) resin composition.
The present invention utilizes easy this characteristic of degraded that occurs in bio-based and biodegradable esters polymer melt-processed process to carry out comprehensive modification to polyvinyl chloride resin, and becoming fraud is profit.After the degraded of biodegradable polyesters moderate-heat, molecular weight distribution broadens, the part that wherein molecular weight is lower produces plasticising to polyvinyl chloride resin, the part that molecular weight is higher has toughness reinforcing effect to polyvinyl chloride resin, therefore the environmental protection polyvinyl chloride resin combination that utilizes bio-based and Biodegradable high-molecular modification to obtain has very excellent mechanical property and melt processability, for example excellent intensity, toughness and fluidity of molten.And the second-order transition temperature of described esters polymer is below room temperature, good with polyvinyl chloride resin consistency, therefore, the structure of described environmental protection polyvinyl chloride resin combination is fine and smooth, be easy to control.In addition, micro-or a small amount of functional aid, as oxidation inhibitor, tinting material, softening agent etc. can not affect the fundamental property of this environmental protection polyvinyl chloride resin combination.
As can be seen here, PHA matrix material provided by the invention and preparation method thereof has following characteristics:
(1) environmental protection type polyvinyl chloride composition of preparing by method provided by the invention has excellent mechanical property, as high in tensile strength, elongation at break is high, impelling strength good.
(2) environmental protection polyvinyl chloride resin combination provided by the invention can be avoided the use of non-environment-friendly plasticizer, increase the content of biomass and biodegradable component in polyvinyl chloride (PVC) RESINS material, be conducive to alleviate many problems that energy scarcity and white pollution bring.
(3) the present invention adopts esters polymer to significantly improve the melting index of polyvinyl chloride resin composition, has improved the melt flowability of polyvinyl chloride resin composition.
(4) preparation method's technique of environmental protection polyvinyl chloride resin combination provided by the invention simple, with short production cycle, can on existing polyvinyl chloride resin processing units, implement, be easy to realize industrialization.
(5) environmental protection polyvinyl chloride resin combination provided by the invention is of many uses, can be used for extruding, the various goods of moulding such as injection moulding, mold pressing and calendering.
Those of ordinary skill in the field are to be understood that: the foregoing is only specific embodiments of the invention and oneself; be not limited to the present invention; within the spirit and principles in the present invention all, any modification of making, be equal to replacement, improvement etc., within all should being included in protection scope of the present invention.
Claims (10)
1. an environmental protection polyvinyl chloride resin combination, is characterized in that, consists of: polyvinyl chloride (PVC) RESINS 80-100 part, esters polymer 20-80 part, thermo-stabilizer 1-5 part, auxiliary heat stabilizer 1-10 part following raw material according to weight part proportioning separately.
2. environmental protection polyvinyl chloride resin combination according to claim 1, is characterized in that, described polyvinyl chloride (PVC) RESINS is SG0-SG9 type, preferably SG2-SG6 type.
3. environmental protection polyvinyl chloride resin combination according to claim 1, it is characterized in that, described esters polymer is selected from least one in succinic acid-butanediol ester multipolymer, tetramethylene adipate-mutual-phenenyl two acid bromide two alcohol ester multipolymer, succinic acid-butanediol ester-tetramethylene adipate multipolymer, 3 hydroxybutyric acid ester homopolymers, 3 butyric ester-3 hydroxyl pentanoate copolymers, 3 butyric ester-4 hydroxybutyric acid ester copolymers and 3 butyric ester-3 hydroxycaproic acid ester copolymers.
4. environmental protection polyvinyl chloride resin combination according to claim 1, is characterized in that, described thermo-stabilizer is at least one in organic tin stablizer and calcium zinc stabilizer.
5. environmental protection polyvinyl chloride resin combination according to claim 1, is characterized in that, described auxiliary heat stabilizer is epoxy soybean oil.
6. prepare according to a method for the environmental protection polyvinyl chloride resin combination described in any one in claim 1-5, it is characterized in that, said method comprising the steps of:
First polyvinyl chloride (PVC) RESINS, esters polymer, thermo-stabilizer and auxiliary heat stabilizer are at room temperature mixed and obtained pre-composition by homogenizer according to proportioning, again above-mentioned pre-composition is passed through to rotor Banbury mixer melt blending, obtain described environmental protection polyvinyl chloride resin combination.
7. the preparation method of environmental protection polyvinyl chloride resin combination according to claim 6, is characterized in that, melt blending temperature is 140-190 ℃, and the blend time is 2-20 minute, and closed-smelting machine rotor rotating speed is 20-100 rev/min.
8. prepare according to a method for the environmental protection polyvinyl chloride resin combination described in any one in claim 1-5, it is characterized in that, said method comprising the steps of:
First polyvinyl chloride (PVC) RESINS, esters polymer, thermo-stabilizer and auxiliary heat stabilizer are at room temperature mixed and obtained pre-composition by homogenizer according to proportioning, again above-mentioned pre-composition is extruded by screw extrusion press melt blending, obtained described environmental protection polyvinyl chloride resin combination.
9. the preparation method of environmental protection polyvinyl chloride resin combination according to claim 8, is characterized in that, screw extrusion press feeding section temperature is 30-80 ℃, and all the other each section of temperature are 130-190 ℃.
10. the preparation method of environmental protection polyvinyl chloride resin combination according to claim 8, is characterized in that, the screw speed of screw extrusion press is 80-500 rev/min, preferably 90-300 rev/min.
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| CN103865194A (en) * | 2014-02-28 | 2014-06-18 | 广东若天新材料科技有限公司 | Application of environment-friendly calcium-zinc stabilizer on heavy-caliber PVC tubular product and PVC tubular product prepared by using stabilizer |
| CN104987620A (en) * | 2015-07-13 | 2015-10-21 | 金宝丽科技（苏州）有限公司 | Fiber-reinforced composite PVC (polyvinyl chloride) material and preparation method thereof |
| CN106459544A (en) * | 2014-03-27 | 2017-02-22 | 梅塔玻利克斯公司 | Highly filled polymer systems |
| WO2018072747A1 (en) * | 2016-10-21 | 2018-04-26 | 中国石油化工股份有限公司 | Polyester composition and preparation method therefor |
| US10030135B2 (en) | 2012-08-17 | 2018-07-24 | Cj Cheiljedang Corporation | Biobased rubber modifiers for polymer blends |
| CN109016047A (en) * | 2018-08-21 | 2018-12-18 | 中山市宝润木业有限公司 | A kind of production technology of timber |
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| US10030135B2 (en) | 2012-08-17 | 2018-07-24 | Cj Cheiljedang Corporation | Biobased rubber modifiers for polymer blends |
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| CN109553882A (en) * | 2017-09-27 | 2019-04-02 | 江南大学 | A kind of polyvinyl chloride anti-biotic material and its preparation method and application |
| CN109016047A (en) * | 2018-08-21 | 2018-12-18 | 中山市宝润木业有限公司 | A kind of production technology of timber |
| CN110978450A (en) * | 2019-12-28 | 2020-04-10 | 李玫 | Polyvinyl chloride molding formula and polyvinyl chloride molding method |
| CN112759897A (en) * | 2020-12-07 | 2021-05-07 | 金发科技股份有限公司 | ACS/PBAT alloy material and preparation method and application thereof |
| CN113248850A (en) * | 2021-07-05 | 2021-08-13 | 上海氯碱化工股份有限公司 | Plasticizer composition, chlorine-containing polymer and preparation method thereof |
| CN113619060A (en) * | 2021-07-30 | 2021-11-09 | 广东省鼎诚聚力环保科技有限公司 | Preparation method and application of high-strength composite plastic steel plate |
| CN113619060B (en) * | 2021-07-30 | 2023-10-03 | 广东省鼎诚聚力环保科技有限公司 | Preparation method and application of high-strength composite plastic steel plate |
| CN113462103A (en) * | 2021-08-26 | 2021-10-01 | 北京化工大学 | Medical antibacterial light-resistant and emigration-resistant PVC composite material and preparation method thereof |
| WO2023139498A1 (en) * | 2022-01-18 | 2023-07-27 | Proquinal S.A.S. | Bioblends of pvc |
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