CN103013070B - Polylactic acid composite material and preparation method thereof - Google Patents
Polylactic acid composite material and preparation method thereof Download PDFInfo
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- CN103013070B CN103013070B CN201210531654.8A CN201210531654A CN103013070B CN 103013070 B CN103013070 B CN 103013070B CN 201210531654 A CN201210531654 A CN 201210531654A CN 103013070 B CN103013070 B CN 103013070B
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- 239000002131 composite material Substances 0.000 title claims abstract description 96
- 229920000747 poly(lactic acid) Polymers 0.000 title claims abstract description 92
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 239000004626 polylactic acid Substances 0.000 title claims abstract description 26
- 239000002994 raw material Substances 0.000 claims abstract description 42
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims abstract description 41
- 239000004970 Chain extender Substances 0.000 claims abstract description 37
- 238000000034 method Methods 0.000 claims abstract description 27
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 15
- 230000003712 anti-aging effect Effects 0.000 claims abstract description 13
- 229920000728 polyester Polymers 0.000 claims abstract description 13
- 239000012745 toughening agent Substances 0.000 claims abstract description 13
- -1 poly(lactic acid) Polymers 0.000 claims description 187
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 177
- 239000004310 lactic acid Substances 0.000 claims description 88
- 235000014655 lactic acid Nutrition 0.000 claims description 88
- 239000004902 Softening Agent Substances 0.000 claims description 55
- 229920001903 high density polyethylene Polymers 0.000 claims description 22
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- 238000001125 extrusion Methods 0.000 claims description 21
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- 239000012965 benzophenone Substances 0.000 claims description 11
- 238000005660 chlorination reaction Methods 0.000 claims description 11
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- 239000002184 metal Substances 0.000 claims description 9
- VXBMLRKDDFKUAD-UHFFFAOYSA-N CCCCCCCCCCCCCCCCCCOC(=O)C(C)C1=CC(C(C)(C)C)=CC(C(C)(C)C)=C1O Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C(C)C1=CC(C(C)(C)C)=CC(C(C)(C)C)=C1O VXBMLRKDDFKUAD-UHFFFAOYSA-N 0.000 claims description 8
- CAPNUXMLPONECZ-UHFFFAOYSA-N 3-(3,5-ditert-butyl-2-hydroxyphenyl)propanoic acid Chemical compound CC(C)(C)C1=CC(CCC(O)=O)=C(O)C(C(C)(C)C)=C1 CAPNUXMLPONECZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000003607 modifier Substances 0.000 claims description 7
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- GHKOFFNLGXMVNJ-UHFFFAOYSA-N Didodecyl thiobispropanoate Chemical compound CCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCC GHKOFFNLGXMVNJ-UHFFFAOYSA-N 0.000 claims description 6
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims description 6
- 239000012964 benzotriazole Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 4
- JBFHTYHTHYHCDJ-UHFFFAOYSA-N gamma-caprolactone Chemical compound CCC1CCC(=O)O1 JBFHTYHTHYHCDJ-UHFFFAOYSA-N 0.000 claims description 2
- 238000005469 granulation Methods 0.000 claims description 2
- 230000003179 granulation Effects 0.000 claims description 2
- 239000003963 antioxidant agent Substances 0.000 abstract description 15
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- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 60
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- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 14
- 150000001412 amines Chemical class 0.000 description 8
- 150000002989 phenols Chemical class 0.000 description 8
- 235000019260 propionic acid Nutrition 0.000 description 7
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 7
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Landscapes
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Abstract
The invention discloses a polylactic acid composite material and a preparation method thereof. Raw materials required in a preparing process of the polylactic acid composite material comprises polylactic acid, a polyester toughening agent, a chain extender, talcum powder, an anti-aging agent, an antioxidant and a plasticizer. Through the chain extender used in the raw materials for preparing the polylactic acid composite material, in a twin-screw extruding process, the chain extender reacts with a functional group on a polylactic acid chain, so that the polylactic acid molecular chain can form a long branched chain structure, the molecular weight of the polylactic acid can be increased, and the prepared polylactic acid composite material has improved toughness and better thermal stability and mechanical properties; and relative to the polylactic acid, the using amount of each additive in the raw materials used in the preparing process of the polylactic acid composite material is relatively small, so that the prepared polylactic acid composite material is obvious in toughening effect, high in transparency and high in tensile strength.
Description
Technical field
The invention belongs to field of polymer composite material, particularly a kind of lactic acid composite material and preparation method thereof.
Background technology
Along with the development of China's economy, the demand of wrapping material especially film based packaging material is also increasing.Conventional films based packaging material is mainly derived from the petroleum based material such as polypropylene, polyethylene, is difficult to processed after it is discarded.If adopt the mode process film based packaging material burned, then can produce by product poisonous in a large number; If adopt the mode process film based packaging material of burying, because conventional petroleum sill degradation cycle is very long, have even more than 100 years, this will bring serious " white pollution " problem.Therefore, develop environment amenable film based packaging material and become primary problem.
Poly(lactic acid) derives from the renewable farm crop such as corn, cassava, compared to other biological degradable polymer, has the advantage such as high strength, high-modulus.It can complete biodegradable in the short period of time when compost, and the product of degraded is carbonic acid gas and water, and can be absorbed by photosynthesis by renewable farm crop, complete and once circulate, the impact of whole process on environment is less.Because poly(lactic acid) has above advantage, it is widely used in a lot of fields, comprise medical treatment product, electronic product casing, textile product and wrapping material etc., wherein in wrapping material field, particularly film based packaging material field be applied to the focus studied in order to current poly(lactic acid).
Because poly(lactic acid) is semi-crystalline polymer, its second-order transition temperature is high, therefore causes its poor toughness, the shortcoming that fragility is large.For enabling poly(lactic acid) better be applied to real life, need to carry out Research on Toughening to it.Current production plasticizing polylactic acid film is mainly through the change of poly(lactic acid) complete processing and carry out modification realization to poly(lactic acid).Wherein, adopting two-way stretch technology to prepare polylactic acid film is one preferably working method.Shanghai Chemical Plant utilizes two-way stretch technology to produce BOPLA, and its tensile strength reaches 135MPa, and transmittance reaches 92%, and over-all properties, close to being even better than BOPET film, has reached the performance requriements of general film for packaging.But because two-way stretch investment in machinery and equipment is large, limit its widespread use to a certain extent.
Realizing the toughness reinforcing of poly(lactic acid) by modification is produce the modal method of plasticizing polylactic acid at present, and mainly comprise the method such as modification by copolymerization, blending and modifying, wherein blending and modifying is a kind of method of economical and efficient.Sichuan University, Guo Shaohua passes through polyoxyethylene glycol (PEG), triphenyl phosphite (TPPi), Uniflex DBS (DBS), citric acid dibutylester (TBC) and dibutyl phthalate (DOP) and polylactic acid blend, and the plasticizing polylactic acid film that adopted blow molding method to prepare, its maximum elongation at break is more than 400%.But in this blending modification method, the addition of properties-correcting agent is large, and the tensile strength of polylactic acid film can be made greatly to reduce, and affects the transparency of the polylactic acid film obtained.And due to the molecular weight of above-mentioned properties-correcting agent low, poor heat stability, As time goes on can produce volatilization or the situation such as ooze out, make polylactic acid film become fragility from toughness, therefore there is certain shortcoming in the practicality of film.
Summary of the invention
Technical problem to be solved by this invention is for above shortcomings in prior art, a kind of lactic acid composite material and preparation method thereof is provided, chainextender is added in preparation process, it can with the functional group reactions in polylactic acid chain, polylactic acid molecule chain formation long-branched structure can be made, increase its molecular weight simultaneously, the lactic acid composite material of final preparation not only greatly strengthen toughness, and has better thermostability and mechanical property.
The technical scheme that solution the technology of the present invention problem adopts is to provide a kind of lactic acid composite material, and the raw material needed in its preparation process comprises: poly(lactic acid), polyester toughner, chainextender, talcum powder, antiaging agent, oxidation inhibitor and softening agent.
Preferably, the described mass percent preparing the feed components of lactic acid composite material is closed and is:
Poly(lactic acid): 60% ~ 80%;
Polyester toughner: 5% ~ 25%;
Chainextender: 0.1% ~ 0.5%;
Talcum powder: 0.5% ~ 10%;
Antiaging agent: 0.1% ~ 1%;
Oxidation inhibitor: 0.1% ~ 1%;
Softening agent: 1% ~ 5%.
Preferably, described polylactic acid molecule amount is 8 ~ 300,000;
And/or described polyester toughner is for gathering (6-caprolactone) (PCL), poly butylene succinate (PBS), poly butyric ester (PHB), poly-hexanodioic acid/butylene terephthalate (PBAT) wherein one or more;
And/or described chainextender is diepoxy class chainextender;
And/or described talcum powder particle diameter is 500 ~ 2000 orders;
And/or described antiaging agent is one or more in suffocated amine antioxidant, Hinered phenols antioxidant, phosphite, metal passivator, benzophenone light stabilizer, benzotriazole light stabilizer;
And/or described oxidation inhibitor is four (β-(3,5 di-tert-butyl-hydroxy phenyls) propionic acid) pentaerythritol ester, (3,5-di-tert-butyl-hydroxy phenyl) propionic acid octadecyl ester, β-(3,5-di-tert-butyl-hydroxy phenyl) cyclohexyl propionate, one or more in Tyox B.
It is further preferred that described chainextender is the styrene/acrylic acid co-polymer oligopolymer containing epoxy-functional.
Preferably, the raw material needed in its preparation process also comprises: grafting toughening agent.
Preferably, the described mass percent preparing the feed components of lactic acid composite material is closed and is:
Poly(lactic acid): 50% ~ 80%;
Polyester toughner: 5% ~ 25%;
Grafting toughening agent: 0.1% ~ 10%;
Chainextender: 0.1% ~ 0.5%;
Talcum powder: 0.5% ~ 10%;
Antiaging agent: 0.1% ~ 1%;
Oxidation inhibitor: 0.1% ~ 1%;
Softening agent: 1% ~ 5%.
Preferably, described grafting toughening agent is maleic anhydride grafted ethene/octene thermoplastic elastomer (MAH-g-POE), one or more in acrylic ester grafted thing, glycidyl methacrylate graft polyolefine.
Preferably, the raw material needed in its preparation process also comprises: acrylic ester impact-resisting modifier.
Preferably, the described mass percent preparing the feed components of lactic acid composite material is closed and is:
Poly(lactic acid): 50% ~ 80%;
Polyester toughner: 5% ~ 25%;
Acrylic ester impact-resisting modifier: 5% ~ 20%;
Chainextender: 0.1% ~ 0.5%;
Talcum powder: 0.5% ~ 10%;
Antiaging agent: 0.1% ~ 1%;
Oxidation inhibitor: 0.1% ~ 1%;
Softening agent: 1% ~ 5%.
Preferably, the described mass percent preparing the feed components of lactic acid composite material is closed and is:
Poly(lactic acid): 50% ~ 80%;
Polyester toughner: 5% ~ 25%;
Grafting toughening agent: 0.1% ~ 10%;
Acrylic ester impact-resisting modifier: 5% ~ 20%;
Chainextender: 0.1% ~ 0.5%;
Talcum powder: 0.5% ~ 10%;
Antiaging agent: 0.1% ~ 1%;
Oxidation inhibitor: 0.1% ~ 1%;
Softening agent: 1% ~ 5%.
Preferably, described acrylic ester impact-resisting modifier is one or more in the IPN multipolymer (ACM) of methyl methacrylate-acrylate copolymer (ACR), the high density polyethylene(HDPE) of slight chlorination and acrylate, MBS (MBS).
The present invention also provides a kind of method preparing above-mentioned lactic acid composite material, comprises the following steps:
(1) the raw material mixing will needed in above-mentioned preparation process;
(2) raw material mixed is added twin screw extruder to melt extrude, wherein the highest extrusion temperature is 160 ~ 200 DEG C;
(3) granulation, dry, obtain described lactic acid composite material.
By using chainextender in the raw material preparing lactic acid composite material, in twin screw extrusion, chainextender can with the functional group reactions in polylactic acid chain, polylactic acid molecule chain formation long-branched structure can be made, increase its molecular weight simultaneously, the lactic acid composite material of final preparation not only greatly strengthen toughness, and has better thermostability and mechanical property.In the raw material used in the preparation process of lactic acid composite material, for poly(lactic acid), the amount that various additive uses is less, and make the lactic acid composite material toughening effect that finally prepares obvious, transparency is high, tensile strength is high.
Embodiment
For making those skilled in the art understand technical scheme of the present invention better, below in conjunction with embodiment, the present invention is described in further detail.
Embodiment 1
The present embodiment provides a kind of method preparing lactic acid composite material, comprises the following steps:
(1) by the vacuum-drying 3 ~ 8 hours at 60 DEG C respectively of poly(lactic acid), polyester toughner, chainextender, talcum powder, antiaging agent, oxidation inhibitor, stir pre-in homogenizer for dried above-mentioned substance 3 minutes, keep afterwards stirring, and constantly drip softening agent, make it mix with the material in stirrer, obtain the mixture of raw material.Wherein, the mass percent of each component of raw mixture is closed and is:
Poly(lactic acid): 60%;
Polyester toughner: 25%;
Chainextender: 0.3%;
Talcum powder: 10%;
Antiaging agent: 0.5%;
Oxidation inhibitor: 1%;
Softening agent: 3%.
(2) add in twin screw extruder by raw mixture again after dripping softening agent, extrude at the temperature of design, wherein, screw speed is 25rpm, and extruding zone each district temperature is respectively 140 DEG C, 160 DEG C, 180 DEG C, 185 DEG C, 190 DEG C, 195 DEG C, 200 DEG C, 190 DEG C, 185 DEG C, 185 DEG C, 180 DEG C.
(3) extrude tie rod to run on crawler belt pelletizing after by quenching, drying the lactic acid composite material that can obtain high tenacity film-grade.
By using chainextender in the raw material preparing lactic acid composite material, in twin screw extrusion, chainextender can with the functional group reactions in polylactic acid chain, polylactic acid molecule chain formation long-branched structure can be made, increase its molecular weight simultaneously, the lactic acid composite material of final preparation not only greatly strengthen toughness, and has better thermostability and mechanical property.In the raw material used in the preparation process of lactic acid composite material, for poly(lactic acid), the amount that various additive uses is less, and make the lactic acid composite material toughening effect that finally prepares obvious, transparency is high, tensile strength is high.
Embodiment 2
The present embodiment provides a kind of method preparing lactic acid composite material, comprises the following steps:
(1) be the poly(lactic acid) of 80,000 by molecular weight, poly butylene succinate, containing the styrene/acrylic acid co-polymer oligopolymer of epoxy-functional, particle diameter is 2000 object talcum powder, hindered amines four (β-(3, 5 di-tert-butyl-hydroxy phenyls) propionic acid) pentaerythritol ester, four (β-(3, 5 di-tert-butyl-hydroxy phenyls) propionic acid) pentaerythritol ester vacuum-drying 3 ~ 8 hours at 60 DEG C respectively, stir pre-in homogenizer for dried above-mentioned substance 3 minutes, keep afterwards stirring, and constantly drip softening agent, it is made to mix with the material in stirrer, obtain the mixture of raw material.Wherein, the mass percent of each component of raw mixture is closed and is:
Poly(lactic acid): 80%;
Poly butylene succinate: 10%;
Styrene/acrylic acid co-polymer oligopolymer containing epoxy-functional: 0.1%;
Talcum powder: 5%;
Hindered amines four (β-(3,5 di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol ester: 0.1%;
Four (β-(3,5 di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol ester: 0.5%;
Softening agent: 1%.
(2) again raw mixture is added in twin screw extruder after dripping softening agent, extrude at the temperature of design, wherein, screw speed is 100rpm, and extruding zone each district temperature is respectively 140 DEG C, 160 DEG C, 180 DEG C, 185 DEG C, 190 DEG C, 195 DEG C, 200 DEG C, 190 DEG C, 185 DEG C, 185 DEG C, 180 DEG C.
(3) extrude tie rod to run on crawler belt pelletizing after by quenching, drying the lactic acid composite material that can obtain high tenacity film-grade.
By using the styrene/acrylic acid co-polymer oligopolymer containing epoxy-functional as chainextender in the raw material preparing lactic acid composite material, in twin screw extrusion, styrene/acrylic acid co-polymer oligopolymer containing epoxy-functional can with the functional group reactions in polylactic acid chain, polylactic acid molecule chain formation long-branched structure can be made, increase its molecular weight simultaneously, the lactic acid composite material of final preparation not only greatly strengthen toughness, and has better thermostability and mechanical property.In the raw material used in the preparation process of lactic acid composite material, for poly(lactic acid), the amount that various additive uses is less, and make the lactic acid composite material toughening effect that finally prepares obvious, transparency is high, tensile strength is high.
Embodiment 3
The present embodiment provides a kind of method preparing lactic acid composite material, comprises the following steps:
(1) by molecular weight be 300,000 poly(lactic acid), poly butyric ester, diepoxy class chainextender, particle diameter be 500 object talcum powder, Hinered phenols antioxidant, (3,5-di-tert-butyl-hydroxy phenyl) vacuum-drying 3 ~ 8 hours at 60 DEG C respectively of propionic acid octadecyl ester, stir pre-in homogenizer for dried above-mentioned substance 3 minutes, keep afterwards stirring, and constantly drip softening agent, make it mix with the material in stirrer, obtain the mixture of raw material.Wherein, the mass percent of each component of raw mixture is closed and is:
Poly(lactic acid): 70%;
Poly butyric ester: 5%;
Diepoxy class chainextender: 0.5%;
Talcum powder: 0.5%;
Hinered phenols antioxidant: 1%;
(3,5-di-tert-butyl-hydroxy phenyl) propionic acid octadecyl ester: 0.1%;
Softening agent: 5%.
(2) again raw mixture is added in twin screw extruder after dripping softening agent, extrude at the temperature of design, wherein, screw speed is 180rpm, and extruding zone each district temperature is respectively 140 DEG C, 160 DEG C, 180 DEG C, 185 DEG C, 190 DEG C, 195 DEG C, 200 DEG C, 190 DEG C, 185 DEG C, 185 DEG C, 180 DEG C.
(3) extrude tie rod to run on crawler belt pelletizing after by quenching, drying the lactic acid composite material that can obtain high tenacity film-grade.
By using diepoxy class chainextender in the raw material preparing lactic acid composite material, in twin screw extrusion, diepoxy class chainextender can with the functional group reactions in polylactic acid chain, polylactic acid molecule chain formation long-branched structure can be made, increase its molecular weight simultaneously, the lactic acid composite material of final preparation not only greatly strengthen toughness, and has better thermostability and mechanical property.In the raw material used in the preparation process of lactic acid composite material, for poly(lactic acid), the amount that various additive uses is less, and make the lactic acid composite material toughening effect that finally prepares obvious, transparency is high, tensile strength is high.
Embodiment 4
The present embodiment provides a kind of method preparing lactic acid composite material, comprises the following steps:
(1) be the poly(lactic acid) of 100,000 by molecular weight, poly-hexanodioic acid/butylene terephthalate, maleic anhydride grafted ethene/octene thermoplastic elastomer, containing the styrene/acrylic acid co-polymer oligopolymer of epoxy-functional, particle diameter is 1200 object talcum powder, phosphite, β-(3, 5-di-tert-butyl-hydroxy phenyl) cyclohexyl propionate vacuum-drying 3 ~ 8 hours at 60 DEG C respectively, stir pre-in homogenizer for dried above-mentioned substance 3 minutes, keep afterwards stirring, and constantly drip softening agent, it is made to mix with the material in stirrer, obtain the mixture of raw material.Wherein, the mass percent of each component of raw mixture is closed and is:
Poly(lactic acid): 70%;
Poly-hexanodioic acid/butylene terephthalate: 5%;
Maleic anhydride grafted ethene/octene thermoplastic elastomer: 5%
Styrene/acrylic acid co-polymer oligopolymer containing epoxy-functional: 0.3%;
Talcum powder: 10%;
Phosphite: 0.5%;
β-(3,5-di-tert-butyl-hydroxy phenyl) cyclohexyl propionate: 0.1%;
Softening agent: 3%.
(2) again raw mixture is added in twin screw extruder after dripping softening agent, extrude at the temperature of design, wherein, screw speed is 100rpm, and extruding zone each district temperature is respectively 140 DEG C, 150 DEG C, 170 DEG C, 175 DEG C, 180 DEG C, 185 DEG C, 190 DEG C, 180 DEG C, 185 DEG C, 175 DEG C, 170 DEG C.
(3) extrude tie rod to run on crawler belt pelletizing after by quenching, drying the lactic acid composite material that can obtain high tenacity film-grade.
By using maleic anhydride grafted ethene/octene thermoplastic elastomer as grafting toughening agent in the raw material preparing lactic acid composite material, in twin screw extrusion, maleic anhydride grafted ethene/octene thermoplastic elastic physical efficiency strengthens the polarity of poly(lactic acid), thus make further poly(lactic acid) more easily and chainextender react, the toughening effect of the lactic acid composite material of final preparation is obvious, and there is better thermostability and mechanical property, substantially increase shock strength and the elongation at break of lactic acid composite material.
Embodiment 5
The present embodiment provides a kind of method preparing lactic acid composite material, comprises the following steps:
(1) by molecular weight be 230,000 poly(lactic acid), poly butylene succinate and the mixture of poly butyric ester, acrylic ester grafted thing, be the vacuum-drying 3 ~ 8 hours at 60 DEG C respectively of 600 object talcum powder, metal passivator, Tyox B containing the styrene/acrylic acid co-polymer oligopolymer of epoxy-functional, particle diameter, stir pre-in homogenizer for dried above-mentioned substance 3 minutes, keep afterwards stirring, and constantly drip softening agent, make it mix with the material in stirrer, obtain the mixture of raw material.Wherein, the mass percent of each component of raw mixture is closed and is:
Poly(lactic acid): 60%;
The mixture (wherein, the mass ratio of poly butylene succinate and poly butyric ester is 2: 1) of poly butylene succinate and poly butyric ester: 25%;
Acrylic ester grafted thing: 10%
Styrene/acrylic acid co-polymer oligopolymer containing epoxy-functional: 0.1%;
Talcum powder: 0.5%;
Metal passivator: 1%;
Tyox B: 1%;
Softening agent: 1%.
(2) add in twin screw extruder by raw mixture again after dripping softening agent, extrude at the temperature of design, wherein, screw speed is 25rpm, and extruding zone each district temperature is respectively 140 DEG C, 150 DEG C, 170 DEG C, 175 DEG C, 180 DEG C, 185 DEG C, 190 DEG C, 180 DEG C, 185 DEG C, 175 DEG C, 170 DEG C.
(3) extrude tie rod to run on crawler belt pelletizing after by quenching, drying the lactic acid composite material that can obtain high tenacity film-grade.
By using acrylic ester grafted thing as grafting toughening agent in the raw material preparing lactic acid composite material, in twin screw extrusion, acrylic ester grafted thing can strengthen the polarity of poly(lactic acid), thus make further poly(lactic acid) more easily and chainextender react, the toughening effect of the lactic acid composite material of final preparation is obvious, and there is better thermostability and mechanical property, substantially increase shock strength and the elongation at break of lactic acid composite material.
Embodiment 6
The present embodiment provides a kind of method preparing lactic acid composite material, comprises the following steps:
(1) be the poly(lactic acid) of 90,000 by molecular weight, poly-(6-caprolactone), glycidyl methacrylate graft polyolefine, diepoxy class chainextender, particle diameter is 1000 object talcum powder, benzophenone light stabilizer, (3, 5-di-tert-butyl-hydroxy phenyl) propionic acid octadecyl ester and β-(3, 5-di-tert-butyl-hydroxy phenyl) the mixture vacuum-drying 3 ~ 8 hours at 60 DEG C respectively of cyclohexyl propionate, stir pre-in homogenizer for dried above-mentioned substance 3 minutes, keep afterwards stirring, and constantly drip softening agent, it is made to mix with the material in stirrer, obtain the mixture of raw material.Wherein, the mass percent of each component of raw mixture is closed and is:
Poly(lactic acid): 80%;
Poly-(6-caprolactone): 10%;
Glycidyl methacrylate graft polyolefine: 0.1%
Diepoxy class chainextender: 0.5%;
Talcum powder: 1%;
Benzophenone light stabilizer: 0.1%;
(3,5-di-tert-butyl-hydroxy phenyl) propionic acid octadecyl ester and β-(3,5-di-tert-butyl-hydroxy phenyl) cyclohexyl propionate mixture (wherein, (3,5-di-tert-butyl-hydroxy phenyl) mass ratio of propionic acid octadecyl ester and β-(3,5-di-tert-butyl-hydroxy phenyl) cyclohexyl propionate is 1: 1): 0.5%;
Softening agent: 5%.
(2) add in twin screw extruder by raw mixture again after dripping softening agent, extrude at the temperature of design, wherein, screw speed is 180rpm, and the highest extrusion temperature is 200 DEG C.
(3) extrude tie rod to run on crawler belt pelletizing after by quenching, drying the lactic acid composite material that can obtain high tenacity film-grade.
Embodiment 7
The present embodiment provides a kind of method preparing lactic acid composite material, comprises the following steps:
(1) be the poly(lactic acid) of 300,000 by molecular weight, poly-hexanodioic acid/butylene terephthalate, acrylic ester grafted thing and the polyolefinic mixture of glycidyl methacrylate graft, containing the styrene/acrylic acid co-polymer oligopolymer of epoxy-functional, particle diameter is 1300 object talcum powder, benzotriazole light stabilizer, four (β-(3, 5 di-tert-butyl-hydroxy phenyls) propionic acid) pentaerythritol ester vacuum-drying 3 ~ 8 hours at 60 DEG C respectively, stir pre-in homogenizer for dried above-mentioned substance 3 minutes, keep afterwards stirring, and constantly drip softening agent, it is made to mix with the material in stirrer, obtain the mixture of raw material.Wherein, the mass percent of each component of raw mixture is closed and is:
Poly(lactic acid): 65%;
Poly-hexanodioic acid/butylene terephthalate: 15%;
Acrylic ester grafted thing and the polyolefinic mixture of glycidyl methacrylate graft (wherein, acrylic ester grafted thing and the polyolefinic mass ratio of glycidyl methacrylate graft are 1: 2): 6%
Styrene/acrylic acid co-polymer oligopolymer containing epoxy-functional: 0.4%;
Talcum powder: 5%;
Benzotriazole light stabilizer: 0.3%;
Four (β-(3,5 di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol ester: 0.8%;
Softening agent: 2%.
(2) add in twin screw extruder by raw mixture again after dripping softening agent, extrude at the temperature of design, wherein, screw speed is 100rpm, and the highest extrusion temperature is 180 DEG C.
(3) extrude tie rod to run on crawler belt pelletizing after by quenching, drying the lactic acid composite material that can obtain high tenacity film-grade.
List the performance test data of lactic acid composite material prepared by embodiment 2 ~ embodiment 7 in table 1., the lactic acid composite material prepared not only has good toughness, and has better thermostability and mechanical property.The lactic acid composite material prepared in each embodiment, comprehensive each performance perameter can find out that the overall performance of lactic acid composite material is significantly improved.
The performance test table of the lactic acid composite material of table 1. embodiment 2 ~ embodiment 7 preparation
Embodiment 8
The present embodiment provides a kind of method preparing lactic acid composite material, comprises the following steps:
(1) be the poly(lactic acid) of 130,000 by molecular weight, poly butylene succinate, methyl methacrylate-acrylate copolymer, diepoxy class chainextender, particle diameter is 1500 object talcum powder, the mixture of suffocated amine antioxidant and Hinered phenols antioxidant, (3, 5-di-tert-butyl-hydroxy phenyl) vacuum-drying 3 ~ 8 hours at 60 DEG C respectively of propionic acid octadecyl ester, stir pre-in homogenizer for dried above-mentioned substance 3 minutes, keep afterwards stirring, and constantly drip softening agent, it is made to mix with the material in stirrer, obtain the mixture of raw material.Wherein, the mass percent of each component of raw mixture is closed and is:
Poly(lactic acid): 60%;
Poly butylene succinate: 7%;
Methyl methacrylate-acrylate copolymer: 20%
Diepoxy class chainextender: 0.1%;
Talcum powder: 10%;
The mixture (wherein, the mass ratio of suffocated amine antioxidant and Hinered phenols antioxidant is 3: 2) of suffocated amine antioxidant and Hinered phenols antioxidant: 0.5%;
(3,5-di-tert-butyl-hydroxy phenyl) propionic acid octadecyl ester: 0.5%;
Softening agent: 1%.
(2) add in twin screw extruder by raw mixture again after dripping softening agent, extrude at the temperature of design, wherein, screw speed is 100rpm, and the highest extrusion temperature is 160 DEG C.
(3) extrude tie rod to run on crawler belt pelletizing after by quenching, drying the lactic acid composite material that can obtain high tenacity film-grade.
By using methyl methacrylate-acrylate copolymer as impact modifier in the raw material preparing lactic acid composite material, in twin screw extrusion, compared with small molecules softening agent, methyl methacrylate-acrylate copolymer itself is as polymeric plasticizer, generally can not separate out from poly(lactic acid) matrix, simultaneously, methyl methacrylate-acrylate copolymer enhances poly(lactic acid), poly butylene succinate, containing epoxy-functional styrene/acrylic acid co-polymer oligopolymer between consistency, poly(lactic acid) is made to be more prone to react with the styrene/acrylic acid co-polymer oligopolymer containing epoxy-functional, make the toughening effect of the lactic acid composite material of final preparation obvious.
Embodiment 9
The present embodiment provides a kind of method preparing lactic acid composite material, comprises the following steps:
(1) be the poly(lactic acid) of 150,000 by molecular weight, poly butyric ester, the high density polyethylene(HDPE) of slight chlorination and the IPN multipolymer of acrylate, containing the styrene/acrylic acid co-polymer oligopolymer of epoxy-functional, particle diameter is 1800 object talcum powder, suffocated amine antioxidant, four (β-(3, 5 di-tert-butyl-hydroxy phenyls) propionic acid) pentaerythritol ester vacuum-drying 3 ~ 8 hours at 60 DEG C respectively, stir pre-in homogenizer for dried above-mentioned substance 3 minutes, keep afterwards stirring, and constantly drip softening agent, it is made to mix with the material in stirrer, obtain the mixture of raw material.Wherein, the mass percent of each component of raw mixture is closed and is:
Poly(lactic acid): 80%;
Poly butyric ester: 5%;
The high density polyethylene(HDPE) of slight chlorination and the IPN multipolymer of acrylate: 5%
Styrene/acrylic acid co-polymer oligopolymer containing epoxy-functional: 0.2%;
Talcum powder: 5%;
Suffocated amine antioxidant: 0.3%;
Four (β-(3,5 di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol ester: 0.3%;
Softening agent: 3%.
(2) add in twin screw extruder by raw mixture again after dripping softening agent, extrude at the temperature of design, wherein, screw speed is 100rpm, and the highest extrusion temperature is 200 DEG C.
(3) extrude tie rod to run on crawler belt pelletizing after by quenching, drying the lactic acid composite material that can obtain high tenacity film-grade.
By the IPN multipolymer of the high density polyethylene(HDPE) and acrylate that use slight chlorination in the raw material preparing lactic acid composite material as impact modifier, in twin screw extrusion, compared with small molecules softening agent, the high density polyethylene(HDPE) of slight chlorination and the IPN multipolymer of acrylate itself are as polymeric plasticizer, generally can not separate out from poly(lactic acid) matrix, simultaneously, methyl methacrylate-acrylate copolymer enhances poly(lactic acid), poly butylene succinate, containing epoxy-functional styrene/acrylic acid co-polymer oligopolymer between consistency, poly(lactic acid) is made to be more prone to react with the styrene/acrylic acid co-polymer oligopolymer containing epoxy-functional, make the toughening effect of the lactic acid composite material of final preparation obvious.
Embodiment 10
The present embodiment provides a kind of method preparing lactic acid composite material, comprises the following steps:
(1) be the poly(lactic acid) of 250,000 by molecular weight, poly-hexanodioic acid/butylene terephthalate, MBS, containing the styrene/acrylic acid co-polymer oligopolymer of epoxy-functional, particle diameter is 500 object talcum powder, metal passivator, (3, 5-di-tert-butyl-hydroxy phenyl) vacuum-drying 3 ~ 8 hours at 60 DEG C respectively of propionic acid octadecyl ester, stir pre-in homogenizer for dried above-mentioned substance 3 minutes, keep afterwards stirring, and constantly drip softening agent, it is made to mix with the material in stirrer, obtain the mixture of raw material.Wherein, the mass percent of each component of raw mixture is closed and is:
Poly(lactic acid): 70%;
Poly-hexanodioic acid/butylene terephthalate: 12%;
MBS: 11%
Styrene/acrylic acid co-polymer oligopolymer containing epoxy-functional: 0.3%;
Talcum powder: 3%;
Metal passivator: 0.1%;
(3,5-di-tert-butyl-hydroxy phenyl) propionic acid octadecyl ester: 0.1%;
Softening agent: 2%.
(2) add in twin screw extruder by raw mixture again after dripping softening agent, extrude at the temperature of design, wherein, screw speed is 25rpm, and the highest extrusion temperature is 160 DEG C.
(3) extrude tie rod to run on crawler belt pelletizing after by quenching, drying the lactic acid composite material that can obtain high tenacity film-grade.
Embodiment 11
The present embodiment provides a kind of method preparing lactic acid composite material, comprises the following steps:
(1) be the poly(lactic acid) of 280,000 by molecular weight, poly-(6-caprolactone), the high density polyethylene(HDPE) of methyl methacrylate-acrylate copolymer and slight chlorination and the IPN copolymer mixture of acrylate, containing the styrene/acrylic acid co-polymer oligopolymer of epoxy-functional, particle diameter is 700 object talcum powder, benzophenone light stabilizer, four (β-(3, 5 di-tert-butyl-hydroxy phenyls) propionic acid) pentaerythritol ester vacuum-drying 3 ~ 8 hours at 60 DEG C respectively, stir pre-in homogenizer for dried above-mentioned substance 3 minutes, keep afterwards stirring, and constantly drip softening agent, it is made to mix with the material in stirrer, obtain the mixture of raw material.Wherein, the mass percent of each component of raw mixture is closed and is:
Poly(lactic acid): 60%;
Poly-(6-caprolactone): 25%;
The high density polyethylene(HDPE) of methyl methacrylate-acrylate copolymer and slight chlorination and the IPN copolymer mixture (wherein, the mass ratio of the high density polyethylene(HDPE) of methyl methacrylate-acrylate copolymer and slight chlorination and the IPN multipolymer of acrylate is 2: 3) of acrylate: 5%
Styrene/acrylic acid co-polymer oligopolymer containing epoxy-functional: 0.5%;
Talcum powder: 1%;
Benzophenone light stabilizer: 0.2%;
Four (β-(3,5 di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol ester: 0.2%;
Softening agent: 1%.
(2) add in twin screw extruder by raw mixture again after dripping softening agent, extrude at the temperature of design, wherein, screw speed is 180rpm, and the highest extrusion temperature is 200 DEG C.
(3) extrude tie rod to run on crawler belt pelletizing after by quenching, drying the lactic acid composite material that can obtain high tenacity film-grade.
Embodiment 12
The present embodiment provides a kind of method preparing lactic acid composite material, comprises the following steps:
(1) be the poly(lactic acid) of 230,000 by molecular weight, the mixture of poly-(6-caprolactone) and poly butylene succinate, glycidyl methacrylate graft polyolefine, MBS, containing the styrene/acrylic acid co-polymer oligopolymer of epoxy-functional, particle diameter is 2000 object talcum powder, benzotriazole light stabilizer, (3, 5-di-tert-butyl-hydroxy phenyl) vacuum-drying 3 ~ 8 hours at 60 DEG C respectively of propionic acid octadecyl ester, stir pre-in homogenizer for dried above-mentioned substance 3 minutes, keep afterwards stirring, and constantly drip softening agent, it is made to mix with the material in stirrer, obtain the mixture of raw material.Wherein, the mass percent of each component of raw mixture is closed and is:
Poly(lactic acid): 70%;
The mixture (wherein, the mass ratio of poly-(6-caprolactone) and poly butylene succinate is 3: 4) of poly-(6-caprolactone) and poly butylene succinate: 5%;
Glycidyl methacrylate graft polyolefine: 10%;
MBS: 10%
Styrene/acrylic acid co-polymer oligopolymer containing epoxy-functional: 0.3%;
Talcum powder: 0.5%;
Benzotriazole light stabilizer: 0.3%;
(3,5-di-tert-butyl-hydroxy phenyl) propionic acid octadecyl ester: 0.3%;
Softening agent: 2%.
(2) add in twin screw extruder by raw mixture again after dripping softening agent, extrude at the temperature of design, wherein, screw speed is 160rpm, and the highest extrusion temperature is 190 DEG C.
(3) extrude tie rod to run on crawler belt pelletizing after by quenching, drying the lactic acid composite material that can obtain high tenacity film-grade.
By using glycidyl methacrylate graft polyolefine as grafting toughening agent in the raw material preparing lactic acid composite material, MBS is as impact modifier, containing the styrene/acrylic acid co-polymer oligopolymer of epoxy-functional as chainextender, in twin screw extrusion, their common and poly(lactic acid) interact, grafting toughening agent adds the polarity of poly(lactic acid) matrix, make poly(lactic acid) more easily and chainextender react; Chainextender and poly(lactic acid) are reacted and are made poly(lactic acid) form long-branched structure, enhance thermostability and the mechanical property of the lactic acid composite material of preparation; Impact modifier adds the consistency between blended material.Simultaneously, in the raw material used in the preparation process of lactic acid composite material, for poly(lactic acid), the amount that various additive uses is less, make the lactic acid composite material toughening effect that finally prepares obvious, transparency is high, tensile strength is high, considerably increase the toughness of lactic acid composite material.
Embodiment 13
The present embodiment provides a kind of method preparing lactic acid composite material, comprises the following steps:
(1) be the poly(lactic acid) of 300,000 by molecular weight, poly butyric ester, the mixture of maleic anhydride grafted ethene/octene thermoplastic elastomer and acrylic ester grafted thing, methyl methacrylate-acrylate copolymer, containing the styrene/acrylic acid co-polymer oligopolymer of epoxy-functional, particle diameter is 1500 object talcum powder, the mixture of metal passivator and benzophenone light stabilizer, β-(3, 5-di-tert-butyl-hydroxy phenyl) cyclohexyl propionate vacuum-drying 3 ~ 8 hours at 60 DEG C respectively, stir pre-in homogenizer for dried above-mentioned substance 3 minutes, keep afterwards stirring, and constantly drip softening agent, it is made to mix with the material in stirrer, obtain the mixture of raw material.Wherein, the mass percent of each component of raw mixture is closed and is:
Poly(lactic acid): 80%;
Poly butyric ester: 6%;
The mixture (mass ratio of wherein, maleic anhydride grafted ethene/octene thermoplastic elastomer and acrylic ester grafted thing is 1: 1) of maleic anhydride grafted ethene/octene thermoplastic elastomer and acrylic ester grafted thing: 5%;
Methyl methacrylate-acrylate copolymer: 5%
Styrene/acrylic acid co-polymer oligopolymer containing epoxy-functional: 0.1%;
Talcum powder: 2%;
The mixture (wherein, the mass ratio of metal passivator and benzophenone light stabilizer is 1: 1) of metal passivator and benzophenone light stabilizer: 0.1%;
β-(3,5-di-tert-butyl-hydroxy phenyl) cyclohexyl propionate: 0.1%;
Softening agent: 1%.
(2) add in twin screw extruder by raw mixture again after dripping softening agent, extrude at the temperature of design, wherein, screw speed is 120rpm, and the highest extrusion temperature is 170 DEG C.
(3) extrude tie rod to run on crawler belt pelletizing after by quenching, drying the lactic acid composite material that can obtain high tenacity film-grade.
Embodiment 14
The present embodiment provides a kind of method preparing lactic acid composite material, comprises the following steps:
(1) be the poly(lactic acid) of 80,000 by molecular weight, poly-hexanodioic acid/butylene terephthalate, acrylic ester grafted thing, the high density polyethylene(HDPE) of slight chlorination and the IPN multipolymer of acrylate, containing the styrene/acrylic acid co-polymer oligopolymer of epoxy-functional, particle diameter is 1300 object talcum powder, Hinered phenols antioxidant, Tyox B vacuum-drying 3 ~ 8 hours at 60 DEG C respectively, stir pre-in homogenizer for dried above-mentioned substance 3 minutes, keep afterwards stirring, and constantly drip softening agent, it is made to mix with the material in stirrer, obtain the mixture of raw material.Wherein, the mass percent of each component of raw mixture is closed and is:
Poly(lactic acid): 60%;
Poly-hexanodioic acid/butylene terephthalate: 5%;
Acrylic ester grafted thing: 0.1%;
The high density polyethylene(HDPE) of slight chlorination and the IPN multipolymer of acrylate: 12%
Styrene/acrylic acid co-polymer oligopolymer containing epoxy-functional: 0.5%;
Talcum powder: 10%;
Hinered phenols antioxidant: 1%;
Tyox B: 1%;
Softening agent: 5%.
(2) add in twin screw extruder by raw mixture again after dripping softening agent, extrude at the temperature of design, wherein, screw speed is 120rpm, and the highest extrusion temperature is 200 DEG C.
(3) extrude tie rod to run on crawler belt pelletizing after by quenching, drying the lactic acid composite material that can obtain high tenacity film-grade.
Embodiment 15
The present embodiment provides a kind of method preparing lactic acid composite material, comprises the following steps:
(1) be the poly(lactic acid) of 140,000 by molecular weight, poly-hexanodioic acid/butylene terephthalate, maleic anhydride grafted ethene/octene thermoplastic elastomer, MBS, containing the styrene/acrylic acid co-polymer oligopolymer of epoxy-functional, particle diameter is 1900 object talcum powder, benzophenone light stabilizer, four (β-(3, 5 di-tert-butyl-hydroxy phenyls) propionic acid) pentaerythritol ester vacuum-drying 3 ~ 8 hours at 60 DEG C respectively, stir pre-in homogenizer for dried above-mentioned substance 3 minutes, keep afterwards stirring, and constantly drip softening agent, it is made to mix with the material in stirrer, obtain the mixture of raw material.Wherein, the mass percent of each component of raw mixture is closed and is:
Poly(lactic acid): 65%;
Poly-hexanodioic acid/butylene terephthalate: 5%;
Maleic anhydride grafted ethene/octene thermoplastic elastomer: 3%;
MBS: 20%
Styrene/acrylic acid co-polymer oligopolymer containing epoxy-functional: 0.1%;
Talcum powder: 0.5%;
Benzophenone light stabilizer: 0.5%;
Four (β-(3,5 di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol ester: 0.5%;
Softening agent: 3%.
(2) add in twin screw extruder by raw mixture again after dripping softening agent, extrude at the temperature of design, wherein, screw speed is 180rpm, and the highest extrusion temperature is 200 DEG C.
(3) extrude tie rod to run on crawler belt pelletizing after by quenching, drying the lactic acid composite material that can obtain high tenacity film-grade.
Embodiment 16
The present embodiment provides a kind of lactic acid composite material, and it is prepared by above-mentioned preparation method.
Be understandable that, the illustrative embodiments that above embodiment is only used to principle of the present invention is described and adopts, but the present invention is not limited thereto.For those skilled in the art, without departing from the spirit and substance in the present invention, can make various modification and improvement, these modification and improvement are also considered as protection scope of the present invention.
Claims (7)
1. a lactic acid composite material, is characterized in that, the raw material needed in its preparation process comprises: poly(lactic acid), polyester toughner, chainextender, talcum powder, antiaging agent, oxidation inhibitor and softening agent; Wherein, described antiaging agent is one or more in phosphite, metal passivator, benzophenone light stabilizer, benzotriazole light stabilizer; Described oxidation inhibitor is four (β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol ester, (3,5-di-tert-butyl-hydroxy phenyl) propionic acid octadecyl ester, β-(3,5-di-tert-butyl-hydroxy phenyl) cyclohexyl propionate, one or more in Tyox B;
The raw material needed in its preparation process also comprises: grafting toughening agent, and described grafting toughening agent is one or more in maleic anhydride grafted ethene/octene thermoplastic elastomer, acrylic ester grafted thing, glycidyl methacrylate graft polyolefine.
2. lactic acid composite material according to claim 1, is characterized in that,
Described polylactic acid molecule amount is 8 ~ 300,000;
And/or described polyester toughner is for gathering (6-caprolactone), poly butylene succinate, poly butyric ester, poly-hexanodioic acid/butylene terephthalate wherein one or more;
And/or described chainextender is diepoxy class chainextender;
And/or described talcum powder particle diameter is 500 ~ 2000 orders.
3. lactic acid composite material according to claim 1, is characterized in that, the described mass percent preparing the feed components of lactic acid composite material is closed and is:
Poly(lactic acid): 50% ~ 80%;
Polyester toughner: 5% ~ 25%;
Grafting toughening agent: 0.1% ~ 10%;
Chainextender: 0.1% ~ 0.5%;
Talcum powder: 0.5% ~ 10%;
Antiaging agent: 0.1% ~ 1%;
Oxidation inhibitor: 0.1% ~ 1%;
Softening agent: 1% ~ 5%.
4. lactic acid composite material according to claim 1, is characterized in that, the raw material needed in its preparation process also comprises: acrylic ester impact-resisting modifier.
5. lactic acid composite material according to claim 4, is characterized in that, the described mass percent preparing the feed components of lactic acid composite material is closed and is:
Poly(lactic acid): 50% ~ 80%;
Polyester toughner: 5% ~ 25%;
Grafting toughening agent: 0.1% ~ 10%;
Acrylic ester impact-resisting modifier: 5% ~ 20%;
Chainextender: 0.1% ~ 0.5%;
Talcum powder: 0.5% ~ 10%;
Antiaging agent: 0.1% ~ 1%;
Oxidation inhibitor: 0.1% ~ 1%;
Softening agent: 1% ~ 5%.
6. lactic acid composite material according to claim 4, it is characterized in that, described acrylic ester impact-resisting modifier is one or more in the IPN multipolymer of methyl methacrylate-acrylate copolymer, the high density polyethylene(HDPE) of slight chlorination and acrylate, MBS.
7. prepare a method for the lactic acid composite material in claim 1 ~ 6 described in any one, it is characterized in that, comprise the following steps:
(1) the raw material mixing will needed in the preparation process described in claim 1 ~ 6 any one;
(2) raw material mixed is added twin screw extruder to melt extrude, wherein the highest extrusion temperature is 160 ~ 200 DEG C;
(3) granulation, dry, obtain described lactic acid composite material.
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