CN107286610A - A kind of PLA oil bottle closure and preparation method thereof - Google Patents

A kind of PLA oil bottle closure and preparation method thereof Download PDF

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Publication number
CN107286610A
CN107286610A CN201710485627.4A CN201710485627A CN107286610A CN 107286610 A CN107286610 A CN 107286610A CN 201710485627 A CN201710485627 A CN 201710485627A CN 107286610 A CN107286610 A CN 107286610A
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China
Prior art keywords
pla
oil bottle
parts
bottle closure
acid
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Pending
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CN201710485627.4A
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Chinese (zh)
Inventor
佟毅
李义
吴延东
颜祥禹
刘志刚
王文玲
唐明勋
肖洋
王金枝
武丽达
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Jilin COFCO Bio Chemical Co Ltd
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Jilin COFCO Bio Chemical Co Ltd
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Priority to CN201710485627.4A priority Critical patent/CN107286610A/en
Publication of CN107286610A publication Critical patent/CN107286610A/en
Pending legal-status Critical Current

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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
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
    • 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
    • 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]
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/06—Biodegradable
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/10—Applications used for bottles
    • 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
    • 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
    • C08L2205/03—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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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Chemical & Material Sciences (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 present invention relates to a kind of PLA oil bottle closure, belong to polymeric material field.It is made up of following parts by weight raw material：20~80 parts of PLA, 14.5~71.5 parts of toughener, 1~3 part of plasticizer, 0.4~1 part of chain extender, 0.2~4 part of antioxidant, 1~2.5 part of opening agent.Advantage is using the biodegradable plastics such as PLA production PLA oil bottle closure, especially closure draw ring opening force can reach the closure tearing strength that polythene material is made, PLA is extended as packaging product applications, green, environmental protection improve the market competitiveness.

Description

A kind of PLA oil bottle closure and preparation method thereof
Technical field
The present invention relates to polymeric material field, and in particular to a kind of PLA oil bottle closure and preparation method thereof.
Background technology
PLA is a kind of biodegradable resin, and it is using lactic acid as monomer, by lactic acid polycondensation or the dimerization by lactic acid Body-lactide ring-opening polymerisation is formed, and PLA has good Biodegradable, 100 days i.e. degradable 80% under composting conditionses More than.
Conventional polymer material largely uses non-renewable petroleum resources, and discarded object is to severe environmental pollution.It is poly- Lactic acid（Abbreviation PLA）It is a kind of polymer with excellent biocompatibility and biodegradable, it is from renewable Resource crops, its most prominent advantage is biodegradability, can completely be decomposed by nature microorganism, ultimately generate dioxy Change carbon and water, it is free from environmental pollution.But PLA has the shortcomings that very important, material fragility is larger, significantly limit PLA work For the application of packaging material.Although many for the document of PLA toughness reinforcing, plasticising, while plasticising, toughness reinforcing is reached, Especially in PLA oil bottle closure in draw ring opening process, due between product molecular entanglement firmly, interface fusion compared with It is good；And after a period of time is placed, due to cold crystallization, there is being not readily separated caused by crystallization is induced in draw ring junction, and causes Draw ring opens intensity increase, and easily openable, does not limit the use as oil bottle closure.
The content of the invention
The present invention provides a kind of PLA oil bottle closure and preparation method thereof, to solve PLA bottle cap impact strength It is low, the problem of closure draw ring is difficult to open.
The present invention takes the technical scheme to be：It is made up of the raw material of following parts by weight：20~80 parts of PLA, toughener 14.5 ~71.5 parts, 1~3 part of plasticizer, 0.4~1 part of chain extender, 0.2~4 part of antioxidant, 1~2.5 part of opening agent.
Described PLA is mixed type PLA, and PLA number-average molecular weight 10~200,000, wherein PLLA are accounted for 98.6%, poly- L-lactic acid 1.4%；Or PLLA accounts for 95.75%, poly- L-lactic acid 4.25%.
Described toughener is glycerin monostearate（GMS）, poly- hexanedioic acid mutual-phenenyl two acid bromide two alcohol ester（PBAT）, it is poly- Succinic acid fourth diester (PBS), poly (propylene carbonate)（PPC）, polycaprolactone（PCL）In two kinds.
Described plasticizer is one kind in ATBC, glycerine, epoxidized soybean oil.
Described chain extender is one in isocyanates, epoxy radicals Tissuemat E, styrene-propene acid glycidyl ester Kind.
Described antioxidant be four [β-（3,5- di-tert-butyl-hydroxy phenyls）Propionic acid] pentaerythritol ester, bis--uncles of 2,6- Butyl -4- methylphenols, three [2,4- di-tert-butyl-phenyls] phosphite esters, β -（3,5- di-tert-butyl-hydroxy phenyls）Propionic acid Positive octadecanol ester one kind therein.
Described opening agent is oleamide, ethylene bis stearamide, erucyl amide one kind therein.
A kind of preparation method of PLA oil bottle closure, comprises the following steps：
20~80 parts of PLA, 14.5~71.5 parts of toughener, 1~3 part of plasticizer, 0.4~1 part of chain extender, antioxidant 0.2~ 4 parts, 1~2.5 part of opening agent is weighed, double screw extruder is granulated using metering weighing system, is molded after drying through injection machine, Obtain finished product.
The screw slenderness ratio of described double screw extruder is 52:1, melt blending temperature is 170~195 DEG C.
The invention has the advantages that：
1）The present invention uses the biodegradable plastics such as PLA production PLA oil bottle closure, especially closure draw ring opening force The closure tearing strength that polythene material is made can be reached, extend PLA as packaging product applications, green, Environmental protection, improves the market competitiveness.
2）The present invention has considered seal cap sealing performance and draw ring opens performance, a variety of auxiliary agents has been played collaboration effect Should, and using the big twin-screw extrusion processing of draw ratio, strengthen reactive blending effect, main is in glycerin monostearate （GMS）While addition, change between molecule the cohesive force serious performance deficiency such as by force, solve the draw ring openability of product Can, it is ensured that use requirement of the product in the supporting bottle cap of oil bottle.Especially in container auxiliary package field, alternative PE, PP etc., city Field has a extensive future.The need for the industrialization of PLA is conducive to the energy and material resources long term growth, deep processing of farm products is promoted, The dependence to oil is reduced, white pollution is solved, the development of Novel environment-friendlymaterial material industry is promoted, with great economic and society Meaning.
Embodiment
Embodiment 1
Weigh the raw material of following number：
50 parts of PLAs after drying, NatureWorks 4032D, mixed type PLA, PLLA accounts for 98.6%, poly- dextrorotation Lactic acid 1.4%, PLA number-average molecular weight 10~200,000；
27 parts of polyadipate mutual-phenenyl two acid bromide two alcohol esters (PBAT)；
16 parts of glycerin monostearates（GMS）
1.0 parts of ATBCs；
0.4 part of isocyanates；
0.2 part four [β-（3,5- di-tert-butyl-hydroxy phenyls）Propionic acid] pentaerythritol ester；
1.0 parts of ethylene bis stearamides；
PLA and PBAT, ATBC are first mixed, other raw materials is then added and is well mixed, obtain mixed thing Material；Mixed material is added into double screw extruder melt blending, each area's temperature of equipment be followed successively by 170 DEG C, 175 DEG C, 180 DEG C, 185 DEG C, 190 DEG C, 195 DEG C, 190 DEG C, then tie rod, pelletizing obtains granular hybrid resin；Will be granular mixed Resin carries out water removal drying process, and it is resin dedicated to obtain bottle cap PLA, and product, mould temperature are obtained through injection machine injection after drying Machine design temperature is between 45 DEG C~60 DEG C, the screw slenderness ratio of the double screw extruder of selection is 52:1, exist for ease of product It is stripped on mould, adjustment mold releasability gradient increases by 1 °, obtains finished product.
Embodiment 2
Weigh the raw material of following number：
80 parts of PLAs after drying, NatureWorks 4032D, mixed type PLA, PLLA accounts for 98.6%, poly- dextrorotation Lactic acid 1.4%, PLA number-average molecular weight 10~200,000；
13 parts of carbon dioxide copolymers (PPC)；
1.5 parts of glycerin monostearates（GMS）
2.0 parts of glycerine；
0.7 part of epoxy radicals Tissuemat E；
2 parts of 2,6- di-t-butyl -4- methylphenols;
1.8 parts of oleamides；
PLA and PPC, glycerine are first mixed, other raw materials is then added and is well mixed, obtain mixed material；Will mixing Material afterwards adds into double screw extruder melt blending, each area's temperature of equipment be followed successively by 170 DEG C, 175 DEG C, 180 DEG C, 185 DEG C, 190 DEG C, 195 DEG C, 190 DEG C, then tie rod, pelletizing obtains granular hybrid resin；Granular hybrid resin is entered Row water removal drying process, it is resin dedicated to obtain bottle cap PLA, and product, die heater setting temperature are obtained through injection machine injection after drying Spend for 45 DEG C, the screw slenderness ratio of the double screw extruder of selection is 52:1.
Embodiment 3
Weigh the raw material of following number：
65 parts of PLAs after drying, NatureWorks 2003D, mixed type PLA, PLLA 95.75%, poly- dextrorotation breast Acid 4.25%, PLA number-average molecular weight 10~200,000；
26.5 parts of poly-succinic fourth diester PBS；
1.5 parts of glycerin monostearates（GMS）;
3.0 parts of epoxidized soybean oils；
1.0 parts of styrene-propene acid glycidyl esters；
4 part of three [2,4- di-tert-butyl-phenyls] phosphite ester；
2.5 parts of erucyl amides；
PLA and PBS, epoxidized soybean oil are first mixed, other raw materials is then added and is well mixed, obtain mixed material； Mixed material is added into double screw extruder melt blending, each area's temperature of equipment be followed successively by 170 DEG C, 175 DEG C, 180 DEG C, 185 DEG C, 190 DEG C, 195 DEG C, 190 DEG C, then tie rod, pelletizing obtains granular hybrid resin；By granular mixing Resin carries out water removal drying process, and it is resin dedicated to obtain bottle cap PLA, and product, die heater are obtained through injection machine injection after drying Design temperature is 45 DEG C, and the screw slenderness ratio of the double screw extruder of selection is 52:1.
Embodiment 4
Weigh the raw material of following number：
20 parts of PLAs after drying, NatureWorks 2003D, mixed type PLA, PLLA 95.75%, poly- dextrorotation breast Acid 4.25%, PLA number-average molecular weight 10~200,000；
71.5 part polycaprolactone（PCL）
1.5 parts of glycerin monostearates（GMS）；
3.0 parts of ATBCs；
1.0 parts of styrene-propene acid glycidyl esters；
0.5 part of β-（3,5- di-tert-butyl-hydroxy phenyls）The positive octadecanol ester of propionic acid；
2.5 parts of ethylene bis stearamides；
PLA and PCL, POE are first mixed, other raw materials is then added and is well mixed, obtain mixed material；Will mixing Material afterwards adds into double screw extruder melt blending, each area's temperature of equipment be followed successively by 170 DEG C, 175 DEG C, 180 DEG C, 185 DEG C, 190 DEG C, 195 DEG C, 190 DEG C, then tie rod, pelletizing obtains granular hybrid resin；Granular hybrid resin is entered Row water removal drying process, it is resin dedicated to obtain bottle cap PLA, and product, die heater setting temperature are obtained through injection machine injection after drying Spend for 45 DEG C, the screw slenderness ratio of the double screw extruder of selection is 52:1.
Embodiment 5
Weigh the raw material of following number：
100 parts of polyethylene（PE）, PE is obtained into product through injection machine injection.
Embodiment 1~5 is obtained into oil bottle closure, tear test, its test result such as institute of table 1 are carried out using puller system Show.
Table 1
Test index Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4 Comparative example 5
Draw ring opening force/N 69.1 71.5 70.2 71.2 70.8
The closure produced as can be seen from Table 1 using closure draw ring opening force produced by the invention and PE materials opens performance Quite, draw ring opens better performances.

Claims (9)

1. a kind of PLA oil bottle closure, it is characterised in that：It is made up of following parts by weight raw material：20~80 parts of PLA, 14.5~71.5 parts of toughener, 1~3 part of plasticizer, 0.4~1 part of chain extender, 0.2~4 part of antioxidant, 1~2.5 part of opening agent.
2. a kind of PLA oil bottle closure according to claim 1, it is characterised in that：Described PLA is mixed type PLA, wherein PLA number-average molecular weight 10~200,000, PLLA 98.6%, poly- L-lactic acid 1.4%；Or gather left-handed breast Acid 95.75%, poly- L-lactic acid 4.25%.
3. a kind of PLA oil bottle closure according to claim 1, it is characterised in that：Described toughener is single stearic Acid glyceride GMS, poly- hexanedioic acid mutual-phenenyl two acid bromide two alcohol ester PBAT, poly-succinic fourth diester PBS, poly (propylene carbonate) PPC, Two kinds in polycaprolactone (PCL).
4. a kind of PLA oil bottle closure according to claim 1, it is characterised in that：Described plasticizer is citric acid One kind in tributyl, glycerine, epoxidized soybean oil.
5. a kind of PLA oil bottle closure according to claim 1, it is characterised in that：Described chain extender is isocyanic acid One kind in ester, epoxy radicals Tissuemat E, styrene-propene acid glycidyl ester.
6. a kind of PLA oil bottle closure according to claim 1, it is characterised in that：Described antioxidant be four [β- （3,5- di-tert-butyl-hydroxy phenyls）Propionic acid] pentaerythritol ester, 2,6- di-t-butyl -4- methylphenols, the three [uncles of 2,4- bis- Butyl phenyl] phosphite ester, β-（3,5- di-tert-butyl-hydroxy phenyls）The positive octadecanol ester one kind therein of propionic acid.
7. a kind of PLA oil bottle closure according to claim 1, it is characterised in that：Described opening agent is oleic acid acyl Amine, ethylene bis stearamide, erucyl amide one kind therein.
8. the preparation method of the PLA oil bottle closure according to any one of claim 1~7, it is characterised in that including Following steps：
20~80 parts of PLA, 14.5~71.5 parts of toughener, 1~3 part of plasticizer, 0.4~1 part of chain extender, antioxidant 0.2~ 4 parts, 1~2.5 part of opening agent is weighed, double screw extruder is granulated using metering weighing system, is molded after drying through injection machine.
9. the preparation method of PLA oil bottle closure according to claim 8, it is characterised in that：Described twin-screw is squeezed The screw slenderness ratio for going out machine is 52:1, melt blending temperature is 170~195 DEG C.
CN201710485627.4A 2017-06-23 2017-06-23 A kind of PLA oil bottle closure and preparation method thereof Pending CN107286610A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112063141A (en) * 2020-08-14 2020-12-11 安徽丰原生物新材料有限公司 Cellulose polyester composite material and preparation method thereof
CN113930065A (en) * 2021-11-20 2022-01-14 郑州市彦峰塑料包装有限公司 High-strength degradable packaging bag and preparation method thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102618003A (en) * 2012-04-13 2012-08-01 中国科学院长春应用化学研究所 Polylactic acid composition and polylactic acid product
CN106519618A (en) * 2016-11-23 2017-03-22 吉林中粮生化有限公司 High-polylactic acid-content film and preparation method thereof

Patent Citations (2)

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Publication number Priority date Publication date Assignee Title
CN102618003A (en) * 2012-04-13 2012-08-01 中国科学院长春应用化学研究所 Polylactic acid composition and polylactic acid product
CN106519618A (en) * 2016-11-23 2017-03-22 吉林中粮生化有限公司 High-polylactic acid-content film and preparation method thereof

Non-Patent Citations (1)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112063141A (en) * 2020-08-14 2020-12-11 安徽丰原生物新材料有限公司 Cellulose polyester composite material and preparation method thereof
CN112063141B (en) * 2020-08-14 2022-08-02 安徽丰原生物新材料有限公司 Cellulose polyester composite material and preparation method thereof
CN113930065A (en) * 2021-11-20 2022-01-14 郑州市彦峰塑料包装有限公司 High-strength degradable packaging bag and preparation method thereof
CN113930065B (en) * 2021-11-20 2022-12-02 郑州市彦峰塑料包装有限公司 High-strength degradable packaging bag and preparation method thereof

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Application publication date: 20171024