CN102276895B - Biodegradable polyethylene composite material and preparation method thereof - Google Patents
Biodegradable polyethylene composite material and preparation method thereof Download PDFInfo
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- CN102276895B CN102276895B CN2011101682324A CN201110168232A CN102276895B CN 102276895 B CN102276895 B CN 102276895B CN 2011101682324 A CN2011101682324 A CN 2011101682324A CN 201110168232 A CN201110168232 A CN 201110168232A CN 102276895 B CN102276895 B CN 102276895B
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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
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/04—Particle-shaped
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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
-
- 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
- B29C48/78—Thermal treatment of the extrusion moulding material or of preformed parts or layers, e.g. by heating or cooling
- B29C48/875—Thermal treatment of the extrusion moulding material or of preformed parts or layers, e.g. by heating or cooling for achieving a non-uniform temperature distribution, e.g. using barrels having both cooling and heating zones
-
- 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
-
- 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
-
- 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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- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to a biodegradable polyethylene composite material and a preparation method thereof. The polyethylene composite material comprises the following raw materials in parts by weight: 100 parts of high-density polyethylene (HDPE), 3-50 parts of polylactic acid (PLA), 1-40 parts of ethylene copolymer, 0.01-10 parts of organometallic compound and 0.1-1.5 parts of functional auxiliary. The biodegradable polyethylene composite material is prepared from the raw materials by the steps of mixing, refining, extruding and pelletizing. The biodegradable polyethylene composite material and the preparation method thereof are economic and practical. Due to the adoption of the biodegradable polyethylene composite material and the preparation method thereof, the mechanical property and the biodegradability of an HDPE and PLA blend can be effectively improved.
Description
Technical field
The present invention relates to a kind of eco-friendly polymeric material, more particularly, the present invention relates to a kind of biodegradable composite polyethylene material and preparation method thereof.
Background technology
High density polyethylene is that a kind of degree of crystallinity is high, nonpolar, nontoxic, tasteless, the white granular thermoplastic resin of odorless, it has good mechanical property and good chemical stability, and available very wide different processing methods are made great majority life and chemicals for industrial use, comprise such as sheet extrusion, film extrude, tubing or profile extrusion, and based articles such as other blowing, injection moulding.Because people fully trust its biological safety, nontoxicity in daily life, so HDPE is used widely.Yet this resin can not be degraded, and its waste still can bring serious pollution to environment.
On the other hand, polylactic acid PLA is a kind of novel high polymer material of nontoxic fully biodegradable, along with improvement, production-scale expansion, the decline of cost and the rise of oil price of synthesis technique in recent years, poly(lactic acid) is entering more extensively general plastics market, part has substituted the plastics such as polyethylene, polyester and polystyrene, therefore alleviated the conventional plastic pollution on the environment, expected that its application in macromolecular material related products field will be fast-developing.Yet PLA not only property is crisp, and shock resistance is also low, has limited greatly it and has applied.
A kind of feasible method in conjunction with both advantages with HDPE and PLA blend, yet, between these two kinds of polymkeric substance, relatively poor consistency causes their blend appearance phenomenon of phase separation clearly, thereby reduces significantly the mechanical property of blend, has restricted its practical application.
Therefore, be necessary to provide a kind of economical and practical, have HDPE and the mechanical property of PLA blend and the method for biological degradability and products thereof improved.
Summary of the invention
Above-mentioned shortcoming for prior art, the objective of the invention is to provide a kind of biodegradable composite polyethylene material and preparation method thereof, and it has following advantage: this composite polyethylene material and preparation method are economical and practical and can effectively improve mechanical property and the biological degradability of HDPE and PLA blend.
For this reason, one of technical solution of the present invention is a kind of biodegradable composite polyethylene material, and this composite polyethylene material adopts the raw material of following weight part:
High density polyethylene: 100 parts,
Polylactic acid PLA: 3～50 parts,
Ethylene copolymer: 1～40 part,
Organometallic compound: 0.01～10 part,
Functional agent: 0.1～1.5 part;
Above-mentioned raw materials makes described biodegradable composite polyethylene material through mixed refining, extruding pelletization.
matrix material of the present invention adopts organometallic compound as the catalyzer of blend effect between HDPE and PLA originally, improving the HDPE biological degradability simultaneously, successfully solve the not good problem of mechanical property of itself and PLA blend, and, for making mechanical property, the all good matrix materials of biodegradability, the mechanical property such as the toughness that matrix material of the present invention allows to adopt ethylene copolymer to improve blend and be aided with functional agent, and, these ethylene copolymers, functional agent can also improve blend compatibility, stability, make goods be not easy during use to separate out monomer and element, guarantee to use safety.By the measured result of back as seen: on above-mentioned formula basis, except obtaining eco-friendly performance, can also fully keep HDPE extensive flexibility of operation originally, can carry out polytype plastic workings such as injection moulding, plastic uptake or blowing, make the qualified different goods of mechanical property.
For further improving stability, the reliability of the multiple superperformance of material of the present invention, the present invention improves and also comprises:
The molecular weight of described high density polyethylene(HDPE) is 4～500,000, and the melt flow rate (MFR) under 200 ℃ and 2.16kg is 0.02～50g/10min; The molecular weight of described polylactic resin is 5～500,000.
Described ethylene copolymer is that ethylene-olefin copolymer, ethene-unsaturated ester multipolymer, ethylene-acrylic acid copolymer are wherein at least a.
Described ethylene-olefin copolymer is that ethylene-propylene copolymer, ethylene-butene copolymer are wherein at least a; Described ethene-unsaturated ester multipolymer is ethylene-vinyl acetate copolymer.
Described organometallic compound is combined with atoms metal and is formed by alkyl, and comprises key between carbon-metal; Described alkyl is one of alkyl, aromatic base; Atoms metal be lithium, sodium, magnesium, calcium, zinc, aluminium, tin one of them.
Described functional agent is that hard esteramides, oleylamide, stearate soap series lubricant agent, carbodiimide class hydrolysis inhibitor are wherein at least a.
Multiple superperformance for further overall equilbrium material of the present invention improves its processing characteristics, use properties, and the present invention improves and also comprises:
Described composite polyethylene material has following mechanics and degradation property: tensile strength＞15MPa, elongation at break＞20%, Izod notched Izod impact strength＞5KJ/m
2, the melt flow rate (MFR) under 200 ℃ and 2.16Kg is 0.05-30g/10min, 28 ℃ and 90%RH (relative humidity) time pellet mildew area occupation ratio of 28 days are 25%.Like this, what matrix material of the present invention made moulds goods because having the surface-area larger than pellet, easier to be mouldy after discarding, grow a lot of holes and expose very high surface area, the discarded goods accelerated degradation significantly under the effects such as mushroom, ultraviolet ray of moulding that these increase exposed areas significantly increases the environmental friendliness performance that matrix material is discarded goods.
Correspondingly, another technical solution of the present invention is a kind of preparation method of biodegradable composite polyethylene material as mentioned above, and it comprises the steps:
A) mixing raw material: at normal temperatures, adopt stirring mixer, will be extremely even by the various raw material stirring that predetermined proportion prepares;
B) double-screw extruding pelletizing: the raw material that mixes is put into twin screw extruder carry out extruding pelletization, extrusion condition is: 100-140 ℃ of one section feeding section, two, three sections compression section 150-180 ℃, four sections melt zone 170-190 ℃, five sections conversion zone 170-190 ℃, six sections metering zone 170-190 ℃, seven sections head 175-185 ℃.
Preparation method of the present invention determines appropriate process on main raw material is filled a prescription the basis, make mechanical property, all good matrix materials of biodegradability, and apparent, the inventive method technique is simple, the energy consumption saving, and is economical and practical, is convenient to promote.
Provide multiple processing characteristics and adaptive product class for further bringing into play the potential processing characteristics of material prescription of the present invention, producing, the inventive method is improved and is also comprised:
Described steps A comprises: according to the required different melt flow rate range of injection moulding, plastic uptake or blowing, adjust the proportioning of various raw materials.
For further improving working (machining) efficiency, the quality product of the inventive method, the inventive method is improved and is also comprised:
Described preparation method comprises one of following steps at least: A0) pre-treatment: under 50 ℃～80 ℃ conditions, with the various raw materials of vacuum drying oven oven dry, then send steps A;
C) aftertreatment: under 50～70 ℃ of conditions, dry the pellet made from vacuum drying oven.
Below in conjunction with specific embodiment, technical solution of the present invention is described further.
Embodiment
Embodiment 1 (injection-molded item)
(1) composition and content form: take by weight high density polyethylene(HDPE) (Period In Maoming petrochemical iy produced, model is HHM5502) 100 parts, (Nature Work produces poly(lactic acid), model is 3251D) 30 parts, 10 parts of ethylene-vinyl acetate copolymers (EVA) (Arkema company produce), lithium methide (CH
3Li) 2 parts, 0.5 part of functional agent Zinic stearas.
(2) raw-material pre-treatment:
1. dry: in vacuum drying oven, the drying temperature of HDPE, PLA and EVA respectively is 55 ℃, 50 ℃, 80 ℃, and the time is 6 hours;
2. the mixing of raw material: at normal temperatures, will mix in stirring mixer in each starting material that predetermined ratio prepares to evenly;
(3) double-screw extruding pelletizing:
1. each section of twin screw extruder temperature (totally 7 sections): one section 120 ℃, two sections 150 ℃, three sections 170 ℃, four sections 180 ℃; Five sections 185 ℃, six sections 185 ℃, 180 ℃ of heads;
2. screw speed: 90r/min;
3. granulation aftertreatment: dry under 70 ℃ of conditions with the pellet that vacuum drying oven will be made.
(4) after above-mentioned pellet drying treatment on general injection moulding machine machine-shaping obtain injection-molded item such as cup etc., wherein:
1. each section of injection moulding machine temperature (totally 4 sections): one section 150 ℃, two sections 170 ℃, three sections 185 ℃, four sections 195 ℃;
2. injection pressure is 80-100MPa, and speed is 40-60;
3. be 30-40 second cooling time.
Embodiment 2 (Blister product)
(1) composition and content form: take by weight high density polyethylene(HDPE) (Period In Maoming petrochemical iy produced, model is HHM5502) 100 parts, (Nature Work produces poly(lactic acid), model is 4032D) 20 parts, 20 parts of ethylene-vinyl acetate copolymers (EVA) (Arkema company produce), n-Butyl Lithium (n-C
4H
9Li) 1.5 parts, 0.5 part of functional agent oleylamide.
(2) raw-material pre-treatment:
1. dry: in vacuum drying oven, the drying temperature of HDPE, PLA and EVA respectively is 55 ℃, 50 ℃, 80 ℃, and the time is 6 hours;
2. the mixing of raw material: at normal temperatures, will mix in stirring mixer in each starting material that predetermined ratio prepares to evenly;
(3) double-screw extruding pelletizing:
1. each section of twin screw extruder temperature (totally 7 sections): one section 120 ℃, two sections 150 ℃, three sections 175 ℃, four sections 185 ℃; Five sections 185 ℃, six sections 185 ℃, 180 ℃ of heads;
2. screw speed: 120r/min;
3. granulation aftertreatment: dry under 70 ℃ of conditions with the pellet that vacuum drying oven will be made.
(4) first prepare sheet material after above-mentioned pellet drying treatment on general plastics sheet forcing machine, then produce on plastic suction forming apparatus and obtain Blister product such as medical detection cup, lunch box, food trays etc., wherein:
1. each section of sheet extruder temperature (totally 7 sections): one section 120 ℃, two sections 150 ℃, three sections 170 ℃, four sections 180 ℃; Five sections 185 ℃, six sections 185 ℃, 180 ℃ of heads, three roll temperatures be, 40 ℃ of top rolls, 60 ℃ of central rolls, 50 ℃ of lower rolls;
2. the sheet material that makes is processed into goods on plastic suction forming apparatus, the preheating temperature during plastic uptake is 180-200 ℃, and be 3-10 minute warm up time.
Embodiment 3 (Blow Molded Articles)
(1) composition and content form: take by weight high density polyethylene(HDPE) (Period In Maoming petrochemical iy produced, model is HHM5502) 100 parts, (Nature Work produces poly(lactic acid), model is 7001D) 20 parts, 15 parts of ethylene-acrylic acid copolymers (EAA) (Arkema company produce), n-Butyl Lithium (n-C
4H
9Li) 1.5 parts, 0.3 part of functional agent Zinic stearas.
(2) raw-material pre-treatment:
1. dry: in vacuum drying oven, the drying temperature of HDPE, PLA and EAA respectively is 55 ℃, 50 ℃, 80 ℃, and the time is 6 hours;
2. the mixing of raw material: at normal temperatures, will mix in stirring mixer in each starting material that predetermined ratio prepares to evenly;
(3) double-screw extruding pelletizing:
1. each section of twin screw extruder temperature (totally 7 sections): one section 120 ℃, two sections 150 ℃, three sections 175 ℃, four sections 185 ℃; Five sections 185 ℃, six sections 185 ℃, 180 ℃ of heads;
2. screw speed: 80r/min;
3. granulation aftertreatment: dry under 70 ℃ of conditions with the pellet that vacuum drying oven will be made.
(4) prepare the plastic container bottle etc. of different shape after above-mentioned pellet drying treatment on general hollow blow molding equipment, wherein:
1. each section of blow molding machine temperature (totally 4 sections): one section 140 ℃, two sections 170 ℃, three sections 185 ℃, four sections 190 ℃;
2. blow-up ratio is 2.
The main performance testing results that the various embodiments described above are processed the pellet that obtains sees the following form 1:
Table 1
Annotate: the melting index test condition is 200 ℃, 2.16Kg.
Claims (8)
1. biodegradable composite polyethylene material, this composite polyethylene material adopts the raw material of following weight part: high density polyethylene: 100 parts,
Polylactic acid PLA: 3～50 parts,
Ethylene copolymer: 1～40 part,
Organometallic compound: 0.01～10 part,
Functional agent: 0.1～1.5 part;
Described ethylene copolymer is that ethylene-olefin copolymer, ethene-unsaturated ester multipolymer, ethylene-acrylic acid copolymer are wherein at least a; Described organometallic compound is combined with atoms metal and is formed by alkyl, and comprises key between carbon-metal; Described alkyl is one of alkyl, aromatic base; Atoms metal be lithium, sodium, magnesium, calcium, zinc, aluminium, tin one of them;
Above-mentioned raw materials makes described biodegradable composite polyethylene material through mixed refining, extruding pelletization.
2. biodegradable composite polyethylene material as claimed in claim 1, it is characterized in that: the molecular weight of described high density polyethylene(HDPE) is 4～500,000, the melt flow rate (MFR) under 200 ℃ and 2.16kg is 0.02～50g/10min; The molecular weight of described polylactic resin is 5～500,000.
3. biodegradable composite polyethylene material as claimed in claim 1, it is characterized in that: described ethylene-olefin copolymer is that ethylene-propylene copolymer, ethylene-butene copolymer are wherein at least a; Described ethene-unsaturated ester multipolymer is ethylene-vinyl acetate copolymer.
4. biodegradable composite polyethylene material as claimed in claim 1 is characterized in that: described functional agent is that hard esteramides, oleylamide, stearate soap series lubricant agent, carbodiimide class hydrolysis inhibitor are wherein at least a.
5. biodegradable composite polyethylene material as claimed in claim 4, it is characterized in that: described composite polyethylene material has following mechanics and degradation property: tensile strength＞15MPa, elongation at break＞20%, Izod notched Izod impact strength＞5KJ/m
2, the melt flow rate (MFR) under 200 ℃ and 2.16 Kg is 0.05-30g/10min, under 28 ℃ and 90%RH, the pellet mildew area occupation ratio of 28 days is 25%.
6. preparation method as biodegradable composite polyethylene material as described in one of claim 1-5, it comprises the steps: A) mixing raw material: at normal temperatures, adopt stirring mixer, the various raw material stirring that will prepare by predetermined proportion are to evenly;
B) double-screw extruding pelletizing: the raw material that mixes is put into twin screw extruder carry out extruding pelletization, extrusion condition is: 100-140 ℃ of one section feeding section, two, three sections compression section 150-180 ℃, four sections melt zone 170-190 ℃, five sections conversion zone 170-190 ℃, six sections metering zone 170-190 ℃, seven sections head 175-185 ℃.
7. the preparation method of biodegradable composite polyethylene material as claimed in claim 6, it is characterized in that: described steps A comprises: according to the required different melt flow rate range of injection moulding, plastic uptake or blowing, adjust the proportioning of various raw materials.
8. the preparation method of biodegradable composite polyethylene material as claimed in claim 6, it is characterized in that: described preparation method comprises one of following steps at least: A0) pre-treatment: under 50 ℃～80 ℃ conditions, with the various raw materials of vacuum drying oven oven dry, then send steps A;
C) aftertreatment: under 50～70 ℃ of conditions, dry the pellet made from vacuum drying oven.
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| CN105694478A (en) * | 2016-03-31 | 2016-06-22 | 青岛百瑞吉生物工程有限公司 | Preparation method of degradable biological medical composite material |
| CN108359230B (en) * | 2017-10-09 | 2019-05-14 | 同济大学 | A kind of degradable laminated film of PLA/PPC and preparation method thereof |
| NL2020686B1 (en) | 2018-03-29 | 2019-10-07 | De Patent B V | Scratch resistant polymer composition |
| CN109467777A (en) * | 2018-10-09 | 2019-03-15 | 嘉善欣达胶业有限公司 | A kind of degradable PLA biomaterial of suction pipe manufacture and preparation method thereof |
| CN114163710A (en) * | 2021-12-20 | 2022-03-11 | 中金辐照武汉有限公司 | Composite material crosslinked by gamma ray irradiation and preparation method thereof |
| CN117777584A (en) * | 2024-02-28 | 2024-03-29 | 石家庄市明联电力科技有限公司 | Degradable cable composite material, preparation method thereof and cable |
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| CN101250295A (en) * | 2008-04-15 | 2008-08-27 | 开原市升达塑料彩印厂 | Degradable plastic film |
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Address after: No. 49, Wuhe South Road, Buji Bantian, Shenzhen, Guangdong 518112 Patentee after: Shenzhen Lihe Technology Innovation Co.,Ltd. Patentee after: SHENZHEN WEIMING BEIKE ENVIRONMENTAL MATERIAL Co.,Ltd. Patentee after: PEKING University SHENZHEN GRADUATE SCHOOL Address before: No. 49, Wuhe South Road, Buji Bantian, Shenzhen, Guangdong 518112 Patentee before: SHENZHEN BEAUTY STAR Co.,Ltd. Patentee before: SHENZHEN WEIMING BEIKE ENVIRONMENTAL MATERIAL Co.,Ltd. Patentee before: PEKING University SHENZHEN GRADUATE SCHOOL |
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| TR01 | Transfer of patent right |
Effective date of registration: 20210705 Address after: No. 1001, Longgang Avenue, Pingxi community, Pingdi street, Longgang District, Shenzhen, Guangdong 518000 Patentee after: Shenzhen TONGCHAN Lixing Technology Group Co.,Ltd. Patentee after: SHENZHEN WEIMING BEIKE ENVIRONMENTAL MATERIAL Co.,Ltd. Patentee after: PEKING University SHENZHEN GRADUATE SCHOOL Address before: No. 49, Wuhe South Road, Buji Bantian, Shenzhen, Guangdong 518112 Patentee before: Shenzhen Lihe Technology Innovation Co.,Ltd. Patentee before: SHENZHEN WEIMING BEIKE ENVIRONMENTAL MATERIAL Co.,Ltd. Patentee before: PEKING University SHENZHEN GRADUATE SCHOOL |