CN101402786B - Toughening polythene-polylactic acid composition - Google Patents
Toughening polythene-polylactic acid composition Download PDFInfo
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- CN101402786B CN101402786B CN2008102027126A CN200810202712A CN101402786B CN 101402786 B CN101402786 B CN 101402786B CN 2008102027126 A CN2008102027126 A CN 2008102027126A CN 200810202712 A CN200810202712 A CN 200810202712A CN 101402786 B CN101402786 B CN 101402786B
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- lactic acid
- impact modifier
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Abstract
The invention relates to a toughening polyethylene-polylactic resin combination which comprises polyethylene, polylactic resin and an impact modifier. The impact modifier comprises a copolymer impact modifier composed of monomers (a), (b) and (c), wherein, the (a) is ethylene and the (b) is a kind or many kinds of alkene with a general formula CH2=CR<1>, wherein, the R<1> is an alkyl which comprises 3 to 9 carbon atoms like propyl, butyl or amyl; the (c) is a type or many types of alkene with a general formula CH2=C(R<2>)CO2R<3>, wherein, R<2> is hydrogen or an alkyl which comprises 1 to 5 carbon atoms like methyl and R<3> is glycidyl. The combination is characterized by favorable impact resistance and tractility, higher rigidity and being environmentally-friendly.
Description
Technical field
The present invention relates to a kind of toughened polyethylene and poly (lactic acid) composition.More particularly, the present invention relates to thermoplastic compounds, comprise polyethylene and poly(lactic acid), adopt the copolymer impact modifier that comprises glycidyl toughness reinforcing.
Background technology
Poly(lactic acid) is a kind of macromolecular material of complete biodegradable, and the enzyme effect eventual degradation by microorganisms in physical environment becomes inorganic substance such as water and carbonic acid gas.In degradable thermoplastic polyester type macromolecular material, poly(lactic acid) has the highest fusing point, and therefore the highest second-order transition temperature and mechanical strength have better heat-resisting.Especially, owing to poly(lactic acid) is the renewable resources that is come by W-Gum production, it is environment-friendly material, therefore poly(lactic acid) becomes and is used for auto parts and electronic industrial products and other application product, replaces traditional plastics that derive from oil, Sweet natural gas to have very important significance and the potential using value.But there are shortcomings such as poor toughness, processing temperature scope be narrower in poly(lactic acid), and its application is very limited, and particularly requires the field with higher toughness.By improving the toughness of poly(lactic acid) to a certain extent with the softening agent blend.Can be with extruding through the plastifying poly(lactic acid), injection moulding, curtain coating, blowing, spinning, multiple mode such as biaxial stretch-formed is processed.But the system structure that softening agent is toughness reinforcing and the less stable of performance, softening agent can be in time growth and separate out.
Polyethylene is a kind of high tenacity, has the polymkeric substance of rapid crystallization ability, and cheap.By the effect of impact modifier, can in melt, be dispersed into enough little particle, with solid-state fully bonding, make stress can transmit basal body interface then with matrix, improve the shock resistance of matrix.
Chinese patent CN 1367189A utilizes the method for free radical grafting polyvinyl alcohol, vinylformic acid etc. to be grafted on the main chain of poly(lactic acid), has obviously improved the snappiness of poly(lactic acid).This method all belongs to chemical modification, has complex process, the more high shortcoming of cost.Chinese patent CN 00112783.7 relates to a kind of plasticized poly lactic acid material that is applied to medical anti-adhesive film, and used softening agent comprises water-soluble plasticizer such as polyoxyethylene glycol and oil soluble softening agent such as oleic acid, stearic acid, capric acid, ethyl oleate in this material.Chinese patent CN 02123145.1 relates to a kind of bio-degradable plastics product of the 5-50% of containing weight part Polyglycerine acetic ester plasticized poly lactic acid.Chinese patent CN 03117482.5 relates to the poly (lactic acid) composition film of the medical softening agent of a kind of 2-15% of containing, and used softening agent is polyoxyethylene glycol, tributyl citrate, tributyl acetylcitrate, oligomeric poly(lactic acid).The polyol ester class, the polyester softening agent respectively has relative merits to the plasticization effect of poly(lactic acid) at aspects such as thermotolerance, resistance to migration, consistencies, and result of use can not be satisfactory separately.Chinese patent CN 200410011366.5 relates to two classes or the above composite softening agent of two classes that comprises in polyol ester class, oligomeric polyester class and the citric acid ester plasticizer, has improved the comprehensive use properties of poly(lactic acid).But the problem that has resistance to migration, consistency aspect equally.Chinese patent CN 200510119120.4 relates to the micromolecular polyol ester class of employing, oligomeric polyester class and citric acid ester plasticizer as Plasticising system, adopts the method introducing of cross-linking radiation crosslinked, to obtain the poly-lactic acid material of structure and stable performance.But there is complicated operation, mechanical means is required height, be difficult for industrialized shortcoming.Chinese patent CN 200480000758.X relates to the blend of a kind of polyoxymethylene and poly(lactic acid), and used impact modifier is a kind ofly to contain ethene, acrylate or vinyl ester and contain the ethylene copolymer that glycidyl single group system is made, and is easy to industrial applications.But, from reducing cost, improve ductility, improve the over-all properties angle of composition, the formation of composition, the structure of impact modifier can also further be improved, to realize better composition.
Summary of the invention
At the defective of prior art, the invention provides a kind of biodegradable resin combination, said composition has the high-impact performance, and high ductibility also has higher rigidity.
The present invention is achieved by the following technical solutions.
A kind of toughening polythene-polylactic acid composition, described composition comprises following component:
A poly(lactic acid) 5～95wt%,
B polyethylene 1～90wt% and
C impact modifier 1～50wt%,
Wherein, the weight percentage of poly(lactic acid), polyethylene and impact modifier is a benchmark in the gross weight of poly(lactic acid), polyethylene and impact modifier;
The number-average molecular weight of described poly(lactic acid) is 3,000-1, and 000,000,
Described poly number-average molecular weight is 100,000-1, and 000,000,
Described component C impact modifier, its number-average molecular weight are 100,000-1, and 000,000, comprise following monomer copolymerization deutero-multipolymer:
(a) ethene of 20～90wt%;
(b) one or more general formulas of 8～70wt% are CH
2=CR
1Alkene, R wherein
1Be contain 3～9 carbon atoms alkyl group and
(c) one or more general formulas of 1～20wt% are CH
2=C (R
2) CO
2R
3Alkenyl compound, R wherein
2Be hydrogen or the alkyl group that contains 1～5 carbon atom, R
3It is glycidyl;
Wherein, the weight percentage of (a) and (b), (c) is a benchmark in the gross weight of impact modifier;
By melt blending, 2～45 minutes blend time, 150～230 ℃ of temperature promptly make described composition with said components A, B, C.
The component of the preferred version of technique scheme is:
A poly(lactic acid) 8～95wt%, number-average molecular weight is 10,000-700,000
B polyethylene 2～75wt%, number-average molecular weight is 300,000-700,000 and
C impact modifier 1～45wt%.
Poly(lactic acid) in the present invention (PLA) refers to the poly(lactic acid) homopolymer or contains the multipolymer derived from the repeating unit of lactic acid or derivatives thereof of mol ratio 50% at least, with and composition thereof, its number-average molecular weight is 3,000-1,000,000, or be preferably 5,000-900,000, more preferably 10,000-700,000.As preferably, the poly(lactic acid) of Ying Yonging contains the repeating unit of 70mol% derived from lactic acid or derivatives thereof (for example making by the lactic acid or derivatives thereof) at least in the present invention.Poly(lactic acid) homopolymer of Ying Yonging and multipolymer can be derived from D-lactic acid, L-lactic acid or its mixtures in the present invention.It can be the mixture of two or more polylactic acid polymers.Poly(lactic acid) generally by the benzilate dimerization of lactic acid, is called " rac-Lactide ", the catalysis ring-opening polymerization prepare.Therefore, poly(lactic acid) is also referred to as " polylactide ".Poly(lactic acid) also can be equipped with by the active bio system such as bacterium, perhaps, prepares from the plant material that comprises corn and sweet potato etc.The multipolymer of lactic acid generally prepares with one or more cyclic esters and/or benzilate dimerization catalyzed copolymerization by rac-Lactide or other lactic acid derivatives.Preferred poly(lactic acid) accounts for the about 5～about 95wt% of the present composition, more preferably accounts for about 7～about 95wt%, perhaps also more preferably accounts for 8～95wt%, and total composition is the benchmark meter.
The polyethylene (PE) that the present invention uses can be one or more homopolymer, multipolymer, or its mixture.Multipolymer can comprise one or more comonomers that generally is applied to prepare modified poly ethylene.The general comonomer of using comprises the compound that contains carbon carbon unsaturated double-bond, as vinyl silanes, vinylformic acid (AA) and methacrylic acid (MMA) and ester class, vinyl cyanide, vinylbenzene and homologue thereof, glycidyl methacrylate (GMA), maleic anhydride (MAH) and fumaric acid (FA) etc.If the selection multipolymer, the amount of comonomer usually is not more than 30wt% so, preferably is not more than 20wt%, more preferably no more than 5wt%.Preferred comonomer is vinylformic acid and methacrylic acid and ester class, glycidyl methacrylate and maleic anhydride, wherein more preferably glycidyl methacrylate and maleic anhydride.
The polyethylene that is used for the present composition can be one or both or a multiple mixture of new LDPE (film grade), medium-density polyethylene, high density polyethylene(HDPE), linear low density polyethylene, polyethylene and ethylene copolymers, general number-average molecular weight is 100,000-1,000,000, be preferably 200,000-800,000, more preferably 300,000-700,000.The preferably about 1～about 90wt% of polymerized ethylene content, 1～about 80wt% more preferably from about, preferred more again 2～75wt% is a benchmark in the total amount of polyethylene and poly(lactic acid).
" copolymer impact modifier " of the present invention refers to derived from (for example certainly synthetic) ethene and two kinds of other polymer of monomers at least.
Being used for copolymer impact modifier of the present invention is to comprise the polymkeric substance that following monomer polymerization is made: a) ethene; (b) one or more general formulas are CH
2=CR
1Alkene, R wherein
1Be the alkyl group that contains 3～9 carbon atoms, as propyl group, butyl or amyl group; (c) one or more general formulas are CH
2=C (R
2) CO
2R
3Alkene, R wherein
2Be hydrogen or the alkyl group that contains 1～5 carbon atom, methyl for example, R
3It is glycidyl.Account for about 10～about 98wt% of copolymer impact modifier gross weight from monomer (a) repeat units derived, preferably account for about 15～about 95wt%, or more preferably account for 20～90wt%.Preferably account for about 2～about 80wt% of copolymer impact modifier gross weight from monomer (b) repeat units derived, or more preferably account for 5～about 75wt%, or more preferably account for 8～70wt%.Preferably account for about 0.4～about 30wt% of copolymer impact modifier gross weight from monomer (c) repeat units derived, or more preferably account for 0.6～25wt%, or also more preferably account for 1～20wt%.Its number-average molecular weight is 100,000-1,000,000.
The amount of impact modifier is preferably about 1～about 50wt% in the present composition, and 1～about 45wt% more preferably from about, even 1～about 40wt% more preferably from about are benchmark in the gross weight of poly(lactic acid), polyethylene and impact modifier.
The present composition also can be chosen wantonly and also comprise other additive, 0.5～about 10wt% softening agent according to appointment, about 0.1～about 5wt% oxidation inhibitor and stablizer, about 3～about 40wt% filler, about 5～about 40wt% toughener, the nano combined toughener of about 0.5～about 10wt%, and/or about 0.5～about 30wt% fire retardant.Suitable filler comprises glass fibre, vegetable fibre and mineral such as talcum, precipitated chalk and wollastonite etc.
Composition of the present invention is that described component is passed through melt blending, and not delamination prepares during until their visual inspection homodisperse and in injection moulding.Blend can obtain by adopting any melting mixing method known in the art that each component materials is mixed.For example: 1) each component materials can adopt melt mixer such as list or uniform mixing such as twin screw extruder, kneader, Banbury mixer, torque rheometer and mill, obtains resin combination; Or 2) the part component materials is mixed in melt mixer, then with the sequential adding of all the other component materials, melting mixing is until evenly again.The time of blend and temperature range are decided according to the blending equipment that adopts.As list or twin screw extruder, rotating speed is 100～500 rev/mins, and machine barrel and head temperature are 150～230 ℃, and the blend times such as Banbury mixer, torque rheometer and mill are 2～45 minutes, and temperature is 150～230 ℃.
Adopt any suitable melt-processed technology the present composition can be molded as goods, the melt molding method of preferred general application known in the art, for example injection moulding, extrusion molding and blowing.More preferably injection moulding.The present composition can prepare cast film and inflation film formation film and sheet material by extrusion molding.These sheet materials can further be thermoformed into goods and structure, and they can be orientated from melt or the step of the back that composition is processed.The present composition also can be used for shaped fibers and long filament, and they can be orientated from melt or the step of the back of processing compositions.Can include, but not limited to knop (button), button, disposable tableware and thermoset sheet material etc. from the example of composition formation goods of the present invention.The present invention also can be applicable to electronic industrial products such as mobile telephone, computer etc. and automotive field.
Beneficial effect
1, adopt component of the present invention, can prepare required composition by simple melt blending, can improve erosion-resisting characteristics greatly, ductility also has higher rigidity, and technology is simple, and cost is low;
2, owing to poly(lactic acid) is the renewable resources that is come by W-Gum production, be environment-friendly material.So high tenacity polyethylene-polylactic acid resin composition provided by the invention, can be used for auto parts and electronic industrial products and other application product, replace plastics traditional, that derive from oil or Sweet natural gas, fibre product and other structure or engineering materials, embody favorable social and economic benefits, have very high potential using value.
Embodiment
Embodiment
The invention will be further described below in conjunction with embodiment, but protection scope of the present invention is not limited to this.
Embodiment 1
Press polylactic resin 65 grams, polyethylene 15 grams, polymkeric substance impact modifier 20 grams are filled a prescription, in Banbury mixer, carried out melting mixing 5 minutes, 165 ℃ of hybrid process temperature are pressed into the thick thin slice of 4mm with mixed material in oil press, 175 ℃ of press temperatures; The plasticizing polylactic acid that compacting obtains carries out Mechanics Performance Testing.The result who obtains: tensile strength 45MPa, elongation at break 320%, notched Izod impact strength 71kJ/m
2, modulus in flexure 2206MPa, flexural strength 56MPa.
Embodiment 2
Press polylactic resin 60 grams, polyethylene 20 grams, polymkeric substance impact modifier 20 grams are filled a prescription, in Banbury mixer, carried out melting mixing 5 minutes, 165 ℃ of hybrid process temperature are pressed into the thick thin slice of 4mm with mixed material in oil press, 175 ℃ of press temperatures; The plasticizing polylactic acid that compacting obtains carries out Mechanics Performance Testing.The result who obtains: tensile strength 41MPa, elongation at break 268%, notched Izod impact strength 69kJ/m
2, modulus in flexure 2116MPa, flexural strength 54MPa.
Embodiment 3
Press polylactic resin 50 grams, polyethylene 25 grams, polymkeric substance impact modifier 25 grams are filled a prescription, in Banbury mixer, carried out melting mixing 5 minutes, 165 ℃ of hybrid process temperature are pressed into the thick thin slice of 4mm with mixed material in oil press, 175 ℃ of press temperatures; The plasticizing polylactic acid that compacting obtains carries out Mechanics Performance Testing.The result who obtains: tensile strength 39MPa, elongation at break 260%, notched Izod impact strength 72kJ/m
2, modulus in flexure 2012MPa, flexural strength 52MPa.
Embodiment 4
Press polylactic resin 65 grams, polyethylene 15 grams, polymkeric substance impact modifier 20 grams are filled a prescription, behind the parallel dual-screw extruding machine extruding pelletization, injection moulding.Carry out Mechanics Performance Testing.Extruder screw nominal diameter 35mm, length-to-diameter ratio (L/D) 48, machine barrel and head are heated to 200 ℃.Injection pressure 90psi, injection speed 60mm/s, 80 ℃ of mould temperature.The plasticizing polylactic acid batten that injection moulding is made carries out Mechanics Performance Testing.The result who obtains: tensile strength 42MPa, elongation at break 246%, notched Izod impact strength 69kJ/m
2, modulus in flexure 2287MPa, flexural strength 53MPa.
Embodiment 5
Press polylactic resin 60 grams, polyethylene 20 grams, polymkeric substance impact modifier 20 grams are filled a prescription, behind the parallel dual-screw extruding machine extruding pelletization, injection moulding.Carry out Mechanics Performance Testing.Extruder screw nominal diameter 35mm, length-to-diameter ratio (L/D) 48, machine barrel and head are heated to 200 ℃.Injection pressure 90psi, injection speed 60mm/s, 85 ℃ of mould temperature.The plasticizing polylactic acid batten that injection moulding is made carries out Mechanics Performance Testing.The result who obtains: tensile strength 40MPa, elongation at break 263%, notched Izod impact strength 76kJ/m
2, modulus in flexure 2118MPa, flexural strength 51MPa.
Embodiment 6
Press polylactic resin 50 grams, polyethylene 25 grams, polymkeric substance impact modifier 25 grams are filled a prescription, behind the parallel dual-screw extruding machine extruding pelletization, injection moulding.Carry out Mechanics Performance Testing.Extruder screw nominal diameter 35mm, length-to-diameter ratio (L/D) 48, machine barrel and head are heated to 200 ℃.Injection pressure 90psi, injection speed 60mm/s, 90 ℃ of mould temperature.The plasticizing polylactic acid batten that injection moulding is made carries out Mechanics Performance Testing.The result who obtains: tensile strength 46MPa, elongation at break 318%, notched Izod impact strength 81kJ/m
2, modulus in flexure 2084MPa, flexural strength 46MPa.
The polylactic resin that adopts in embodiment 1, example 3, the example 5 is a NatureWorks LLC company product, and the polymkeric substance impact modifier is the product that directly adds initiator and properties-correcting agent and the copolymerization of ethylene-octene copolymer fusion-grafting on forcing machine.Polylactic resin in embodiment 2, example 4, the example 6 is that Shenzhen China light great achievement Industrial Co., Ltd. provides, and the polymkeric substance impact modifier is an Exxon Mobil oil company product.All polyethylene all come from Nanjing multiple star polymer company limited among the embodiment.
Claims (2)
1. a toughening polythene-polylactic acid composition is characterized in that, described composition comprises following component:
A poly(lactic acid) 5～95wt%,
B polyethylene 1～90wt% and
C impact modifier 1～50wt%,
Wherein, the weight percentage of poly(lactic acid), polyethylene and impact modifier is a benchmark in the gross weight of poly(lactic acid), polyethylene and impact modifier;
The number-average molecular weight of described poly(lactic acid) is 3,000-1, and 000,000,
Described poly number-average molecular weight is 100,000-1, and 000,000,
Described component C impact modifier, its number-average molecular weight are 100,000-1, and 000,000, comprise following monomer copolymerization deutero-multipolymer:
(a) ethene of 20～90wt%;
(b) one or more general formulas of 8～70wt% are CH
2=CR
1Alkene, R wherein
1Be contain 3～9 carbon atoms alkyl group and
(c) one or more general formulas of 1～20wt% are CH
2=C (R
2) CO
2R
3Alkenyl compound, R wherein
2Be hydrogen or the alkyl group that contains 1～5 carbon atom, R
3It is glycidyl;
Wherein, the weight percentage of (a) and (b), (c) is a benchmark in the gross weight of impact modifier;
By melt blending, 2～45 minutes blend time, 150～230 ℃ of temperature promptly make described composition with said components A, B, C.
2. polythene-polylactic acid composition as claimed in claim 1 is characterized in that, the component of described composition is as follows:
A poly(lactic acid) 8～95wt%, number-average molecular weight is 10,000-700,000
B polyethylene 2～75wt%, number-average molecular weight is 300,000-700,000 and
C impact modifier 1～45wt%.
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| CN101402786B true CN101402786B (en) | 2011-05-18 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2550320A4 (en) * | 2010-03-22 | 2017-03-29 | Clear Lam Packaging, Inc. | Additive for performance enhancement of biopolymer articles |
| CN101875764B (en) * | 2010-06-30 | 2012-08-15 | 中国蓝星（集团）股份有限公司 | Formable polylactic resin composition and preparation method for plastic strip thereof |
| CN102276895B (en) * | 2011-06-21 | 2013-06-12 | 深圳市通产丽星股份有限公司 | Biodegradable polyethylene composite material and preparation method thereof |
| CN114752134B (en) * | 2022-06-15 | 2022-09-09 | 河北上东包装科技有限公司 | Polyethylene easily-torn film |
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| CN1701082A (en) * | 2003-05-13 | 2005-11-23 | 纳幕尔杜邦公司 | Toughened polyoxymethylene-poly(lactic acid) compositions |
| CN1894338A (en) * | 2003-12-12 | 2007-01-10 | E.I.内穆尔杜邦公司 | Toughened poly(lactic acid) compositions |
| WO2007144529A1 (en) * | 2006-06-16 | 2007-12-21 | Arkema France | Poly(lactic acid) composition with improved impact resistance |
| EP1911807A1 (en) * | 2005-08-04 | 2008-04-16 | Toray Industries, Inc. | Resin composition and molded article comprising the same |
| CN101275011A (en) * | 2007-03-29 | 2008-10-01 | 东丽纤维研究所（中国）有限公司 | High-shock-resistance polylactic acid composite material, preparation thereof and use thereof |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1701082A (en) * | 2003-05-13 | 2005-11-23 | 纳幕尔杜邦公司 | Toughened polyoxymethylene-poly(lactic acid) compositions |
| CN1894338A (en) * | 2003-12-12 | 2007-01-10 | E.I.内穆尔杜邦公司 | Toughened poly(lactic acid) compositions |
| EP1911807A1 (en) * | 2005-08-04 | 2008-04-16 | Toray Industries, Inc. | Resin composition and molded article comprising the same |
| WO2007144529A1 (en) * | 2006-06-16 | 2007-12-21 | Arkema France | Poly(lactic acid) composition with improved impact resistance |
| CN101275011A (en) * | 2007-03-29 | 2008-10-01 | 东丽纤维研究所（中国）有限公司 | High-shock-resistance polylactic acid composite material, preparation thereof and use thereof |
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