CN103013070A - Polylactic acid composite material and preparation method thereof - Google Patents
Polylactic acid composite material and preparation method thereof Download PDFInfo
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- CN103013070A CN103013070A CN2012105316548A CN201210531654A CN103013070A CN 103013070 A CN103013070 A CN 103013070A CN 2012105316548 A CN2012105316548 A CN 2012105316548A CN 201210531654 A CN201210531654 A CN 201210531654A CN 103013070 A CN103013070 A CN 103013070A
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- lactic acid
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- polylactic acid
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- 239000002131 composite material Substances 0.000 title claims abstract description 102
- 229920000747 poly(lactic acid) Polymers 0.000 title claims abstract description 94
- 238000002360 preparation method Methods 0.000 title claims abstract description 49
- 239000004626 polylactic acid Substances 0.000 title claims abstract description 26
- 239000002994 raw material Substances 0.000 claims abstract description 50
- 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 43
- 239000004970 Chain extender Substances 0.000 claims abstract description 39
- 238000000034 method Methods 0.000 claims abstract description 27
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 17
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 17
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 17
- 230000003712 anti-aging effect Effects 0.000 claims abstract description 15
- 229920000728 polyester Polymers 0.000 claims abstract description 15
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 189
- -1 poly(lactic acid) Polymers 0.000 claims description 187
- 239000004310 lactic acid Substances 0.000 claims description 94
- 235000014655 lactic acid Nutrition 0.000 claims description 94
- 239000004902 Softening Agent Substances 0.000 claims description 57
- 229920001903 high density polyethylene Polymers 0.000 claims description 22
- 239000004700 high-density polyethylene Substances 0.000 claims description 22
- 238000001125 extrusion Methods 0.000 claims description 21
- 239000004611 light stabiliser Substances 0.000 claims description 17
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 16
- 239000002245 particle Substances 0.000 claims description 16
- 229920001577 copolymer Polymers 0.000 claims description 15
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- 239000004631 polybutylene succinate Substances 0.000 claims description 15
- 239000003112 inhibitor Substances 0.000 claims description 14
- 230000003647 oxidation Effects 0.000 claims description 14
- 238000007254 oxidation reaction Methods 0.000 claims description 14
- WSQZNZLOZXSBHA-UHFFFAOYSA-N 3,8-dioxabicyclo[8.2.2]tetradeca-1(12),10,13-triene-2,9-dione Chemical compound O=C1OCCCCOC(=O)C2=CC=C1C=C2 WSQZNZLOZXSBHA-UHFFFAOYSA-N 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 12
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- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 11
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 11
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 11
- 239000012965 benzophenone Substances 0.000 claims description 11
- 238000005660 chlorination reaction Methods 0.000 claims description 11
- OBNCKNCVKJNDBV-UHFFFAOYSA-N ethyl butyrate Chemical compound CCCC(=O)OCC OBNCKNCVKJNDBV-UHFFFAOYSA-N 0.000 claims description 11
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 11
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 10
- 229920002725 thermoplastic elastomer Polymers 0.000 claims description 10
- MAMMVUWCKMOLSG-UHFFFAOYSA-N Cyclohexyl propionate Chemical compound CCC(=O)OC1CCCCC1 MAMMVUWCKMOLSG-UHFFFAOYSA-N 0.000 claims description 9
- 150000001412 amines Chemical class 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- YTXCAJNHPVBVDJ-UHFFFAOYSA-N octadecyl propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CC YTXCAJNHPVBVDJ-UHFFFAOYSA-N 0.000 claims description 9
- 150000002989 phenols Chemical class 0.000 claims description 9
- 239000003607 modifier Substances 0.000 claims description 8
- 235000019260 propionic acid Nutrition 0.000 claims description 8
- 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 claims description 8
- 229920000098 polyolefin Polymers 0.000 claims description 7
- 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
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 2
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- 238000005469 granulation Methods 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 10
- 239000000654 additive Substances 0.000 abstract description 6
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- 230000000996 additive effect Effects 0.000 abstract 1
- 239000012745 toughening agent Substances 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 62
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 60
- 229920002126 Acrylic acid copolymer Polymers 0.000 description 30
- 238000003756 stirring Methods 0.000 description 30
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- 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 description 6
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- 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 description 4
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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 the polymer composite field, particularly a kind of lactic acid composite material and preparation method thereof.
Background technology
Along with the development of China's economy, the wrapping material especially demand of film based packaging material are also increasing.The conventional films based packaging material is mainly derived from the petroleum base materials such as polypropylene, polyethylene, is difficult to processed after it is discarded.If adopt the mode of burning to process the film based packaging material, then can produce a large amount of poisonous by products; If adopt the mode bury to process the film based packaging material because traditional petroleum base material degradation cycle is very long, have in addition surpass 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, than the other biological degradable polymer, has the advantages such as high strength, high-modulus.Its complete biodegradable in the short period of time in the situation of compost, the product of degraded is carbonic acid gas and water, can be absorbed by photosynthesis by renewable farm crop, finishes once circulation, whole process is less on the impact of environment.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 the wrapping material field, particularly film based packaging material field is applied to focus at present poly(lactic acid) research.
Because poly(lactic acid) is semi-crystalline polymer, its second-order transition temperature is high, has therefore caused its poor toughness, the shortcoming that fragility is large.For making poly(lactic acid) can better be applied to real life, need to carry out Research on Toughening to it.Produce at present the plasticizing polylactic acid film and mainly carry out the modification realization by the change of poly(lactic acid) complete processing and to poly(lactic acid).Wherein, adopting the two-way stretch technology to prepare polylactic acid film is a kind of more excellent working method.Shanghai Chemical Plant utilizes the two-way stretch technology to produce BOPLA, and its tensile strength has reached 135MPa, and transmittance has reached 92%, and over-all properties approaches even is better than the BOPET film, has reached the performance requriements of general film for packaging.But because two-way stretch investment in machinery and equipment is large, limited to a certain extent its widespread use.
Realize that by modification the toughness reinforcing of poly(lactic acid) is to produce at present the modal method of plasticizing polylactic acid, mainly comprise the methods 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 adopting blow molding method to prepare the plasticizing polylactic acid film, its maximum elongation at break surpasses 400%.But the addition of properties-correcting agent is large in this blending modification method, and the tensile strength of polylactic acid film is reduced greatly, the transparency of the polylactic acid film that impact obtains.And because the molecular weight of above-mentioned properties-correcting agent is low, poor heat stability, the situation such as As time goes on can produce volatilization or ooze out, so that polylactic acid film becomes fragility by toughness, so 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 the prior art, a kind of lactic acid composite material and preparation method thereof is provided, in preparation process, add chainextender, its can with polylactic acid chain on functional group reactions, can be so that polylactic acid molecule chain formation long-branched structure, increase its molecular weight simultaneously, the lactic acid composite material of final preparation has not only strengthened toughness greatly, and has better thermostability and mechanical property.
The technical scheme that solution the technology of the present invention problem adopts provides a kind of lactic acid composite material, and the raw material that needs in its preparation process comprises: poly(lactic acid), polyester toughner, chainextender, talcum powder, antiaging agent, oxidation inhibitor and softening agent.
Preferably, the mass percent of each component of raw material of described preparation 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 for poly-(6-caprolactone) (PCL), poly butylene succinate (PBS), poly butyric ester (PHB), poly-wherein one or more of hexanodioic acid/butylene terephthalate (PBAT);
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 in suffocated amine antioxidant, Hinered phenols antioxidant, phosphite, metal passivator, benzophenone light stabilizer, the benzotriazole light stabilizer one or more;
And/or described oxidation inhibitor is four (β-(3,5 di-tert-butyl-hydroxy phenyls) propionic acid) pentaerythritol ester, (3, the 5-di-tert-butyl-hydroxy phenyl) one or more in propionic acid octadecyl ester, β-(3,5-di-tert-butyl-hydroxy phenyl) cyclohexyl propionate, the Tyox B.
More preferably, described chainextender is the styrene/acrylic acid co-polymer oligopolymer that contains epoxy-functional.
Preferably, the raw material that needs in its preparation process also comprises: grafting toughner.
Preferably, the mass percent of each component of raw material of described preparation lactic acid composite material is closed and is:
Poly(lactic acid): 50% ~ 80%;
Polyester toughner: 5% ~ 25%;
Grafting toughner: 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 toughner is maleic anhydride grafted ethene/octene thermoplastic elastomer (MAH-g-POE), one or more in acrylic ester grafted thing, the glycidyl methacrylate graft polyolefine.
Preferably, the raw material that needs in its preparation process also comprises: acrylic ester impact-resisting modifier.
Preferably, the mass percent of each component of raw material of described preparation 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 mass percent of each component of raw material of described preparation lactic acid composite material is closed and is:
Poly(lactic acid): 50% ~ 80%;
Polyester toughner: 5% ~ 25%;
Grafting toughner: 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 methyl methacrylate-acrylate copolymer (ACR), the high density polyethylene(HDPE) of slight chlorination and the IPN multipolymer (ACM) of acrylate, one or more in the MBS (MBS).
The present invention also provides a kind of method for preparing above-mentioned lactic acid composite material, may further comprise the steps:
(1) raw material that needs in the above-mentioned preparation process is mixed;
(2) raw material that mixes is added twin screw extruder and melt extrude, wherein the highest extrusion temperature is 160 ~ 200 ℃;
(3) granulation, drying obtains described lactic acid composite material.
By in the raw material of preparation lactic acid composite material, using chainextender, in twin screw extrusion, chainextender can with polylactic acid chain on functional group reactions, can be so that polylactic acid molecule chain formation long-branched structure, increase its molecular weight simultaneously, the lactic acid composite material of final preparation has not only strengthened toughness greatly, and has better thermostability and mechanical property.In the raw material that uses in the preparation process of lactic acid composite material, for poly(lactic acid), the amount that various additives use is less, so that the lactic acid composite material toughening effect that finally prepares is obvious, transparency is high, tensile strength is high.
Embodiment
For making those skilled in the art understand better technical scheme of the present invention, below in conjunction with embodiment the present invention is described in further detail.
Embodiment 1
Present embodiment provides a kind of method for preparing lactic acid composite material, may further comprise the steps:
(1) with poly(lactic acid), polyester toughner, chainextender, talcum powder, antiaging agent, oxidation inhibitor respectively 60 ℃ of lower vacuum-dryings 3 ~ 8 hours, with dried above-mentioned substance pre-stirring 3 minutes in homogenizer, keep afterwards stirring, and constantly drip softening agent, material in itself and the stirrer is mixed, obtain the mixture of raw material.Wherein, the mass percent of each component of raw mix 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) raw mix is added in the twin screw extruder after dripping softening agent again, extrude under the temperature of design, wherein, screw speed is 25rpm, and extruding zone is respectively distinguished temperature and is respectively 140 ℃, 160 ℃, 180 ℃, 185 ℃, 190 ℃, 195 ℃, 200 ℃, 190 ℃, 185 ℃, 185 ℃, 180 ℃.
(3) extrude tie rod on the operation crawler belt by quenching after pelletizing, oven dry can obtain the lactic acid composite material of high tenacity film-grade.
By in the raw material of preparation lactic acid composite material, using chainextender, in twin screw extrusion, chainextender can with polylactic acid chain on functional group reactions, can be so that polylactic acid molecule chain formation long-branched structure, increase its molecular weight simultaneously, the lactic acid composite material of final preparation has not only strengthened toughness greatly, and has better thermostability and mechanical property.In the raw material that uses in the preparation process of lactic acid composite material, for poly(lactic acid), the amount that various additives use is less, so that the lactic acid composite material toughening effect that finally prepares is obvious, transparency is high, tensile strength is high.
Embodiment 2
Present embodiment provides a kind of method for preparing lactic acid composite material, may further comprise the steps:
(1) with molecular weight is 80,000 poly(lactic acid), poly butylene succinate, the styrene/acrylic acid co-polymer oligopolymer that contains epoxy-functional, particle diameter is 2000 purpose 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 is respectively 60 ℃ of lower vacuum-dryings 3 ~ 8 hours, with dried above-mentioned substance pre-stirring 3 minutes in homogenizer, keep afterwards stirring, and constantly drip softening agent, material in itself and the stirrer is mixed, obtain the mixture of raw material.Wherein, the mass percent of each component of raw mix is closed and is:
Poly(lactic acid): 80%;
Poly butylene succinate: 10%;
The styrene/acrylic acid co-polymer oligopolymer that contains 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 mix is added in the twin screw extruder after dripping softening agent, under the temperature of design, extrude, wherein, screw speed is 100rpm, and extruding zone is respectively distinguished temperature and is respectively 140 ℃, 160 ℃, 180 ℃, 185 ℃, 190 ℃, 195 ℃, 200 ℃, 190 ℃, 185 ℃, 185 ℃, 180 ℃.
(3) extrude tie rod on the operation crawler belt by quenching after pelletizing, oven dry can obtain the lactic acid composite material of high tenacity film-grade.
Contain the styrene/acrylic acid co-polymer oligopolymer of epoxy-functional as chainextender by in the raw material of preparation lactic acid composite material, using, in twin screw extrusion, contain epoxy-functional the styrene/acrylic acid co-polymer oligopolymer can with polylactic acid chain on functional group reactions, can be so that polylactic acid molecule chain formation long-branched structure, increase its molecular weight simultaneously, the lactic acid composite material of final preparation has not only strengthened toughness greatly, and has better thermostability and mechanical property.In the raw material that uses in the preparation process of lactic acid composite material, for poly(lactic acid), the amount that various additives use is less, so that the lactic acid composite material toughening effect that finally prepares is obvious, transparency is high, tensile strength is high.
Embodiment 3
Present embodiment provides a kind of method for preparing lactic acid composite material, may further comprise the steps:
(1) be that 300,000 poly(lactic acid), poly butyric ester, diepoxy class chainextender, particle diameter are 500 purpose talcum powder, Hinered phenols antioxidant, (3 with molecular weight, the 5-di-tert-butyl-hydroxy phenyl) the propionic acid octadecyl ester is respectively 60 ℃ of lower vacuum-dryings 3 ~ 8 hours, with dried above-mentioned substance pre-stirring 3 minutes in homogenizer, keep afterwards stirring, and constantly drip softening agent, material in itself and the stirrer is mixed, obtain the mixture of raw material.Wherein, the mass percent of each component of raw mix 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 mix is added in the twin screw extruder after dripping softening agent, under the temperature of design, extrude, wherein, screw speed is 180rpm, and extruding zone is respectively distinguished temperature and is respectively 140 ℃, 160 ℃, 180 ℃, 185 ℃, 190 ℃, 195 ℃, 200 ℃, 190 ℃, 185 ℃, 185 ℃, 180 ℃.
(3) extrude tie rod on the operation crawler belt by quenching after pelletizing, oven dry can obtain the lactic acid composite material of high tenacity film-grade.
By in the raw material of preparation lactic acid composite material, using diepoxy class chainextender, in twin screw extrusion, diepoxy class chainextender can with polylactic acid chain on functional group reactions, can be so that polylactic acid molecule chain formation long-branched structure, increase its molecular weight simultaneously, the lactic acid composite material of final preparation has not only strengthened toughness greatly, and has better thermostability and mechanical property.In the raw material that uses in the preparation process of lactic acid composite material, for poly(lactic acid), the amount that various additives use is less, so that the lactic acid composite material toughening effect that finally prepares is obvious, transparency is high, tensile strength is high.
Embodiment 4
Present embodiment provides a kind of method for preparing lactic acid composite material, may further comprise the steps:
(1) with molecular weight is 100,000 poly(lactic acid), poly-hexanodioic acid/butylene terephthalate, maleic anhydride grafted ethene/octene thermoplastic elastomer, the styrene/acrylic acid co-polymer oligopolymer that contains epoxy-functional, particle diameter is 1200 purpose talcum powder, phosphite, β-(3, the 5-di-tert-butyl-hydroxy phenyl) cyclohexyl propionate is respectively 60 ℃ of lower vacuum-dryings 3 ~ 8 hours, with dried above-mentioned substance pre-stirring 3 minutes in homogenizer, keep afterwards stirring, and constantly drip softening agent, material in itself and the stirrer is mixed, obtain the mixture of raw material.Wherein, the mass percent of each component of raw mix is closed and is:
Poly(lactic acid): 70%;
Poly-hexanodioic acid/butylene terephthalate: 5%;
Maleic anhydride grafted ethene/octene thermoplastic elastomer: 5%
The styrene/acrylic acid co-polymer oligopolymer that contains 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 mix is added in the twin screw extruder after dripping softening agent, under the temperature of design, extrude, wherein, screw speed is 100rpm, and extruding zone is respectively distinguished temperature and is respectively 140 ℃, 150 ℃, 170 ℃, 175 ℃, 180 ℃, 185 ℃, 190 ℃, 180 ℃, 185 ℃, 175 ℃, 170 ℃.
(3) extrude tie rod on the operation crawler belt by quenching after pelletizing, oven dry can obtain the lactic acid composite material of high tenacity film-grade.
By in the raw material of preparation lactic acid composite material, using maleic anhydride grafted ethene/octene thermoplastic elastomer as grafting toughner, in twin screw extrusion, maleic anhydride grafted ethene/octene thermoplastic elastic physical efficiency strengthens the polarity of poly(lactic acid), thereby further so that poly(lactic acid) is easier and the chainextender reaction, the toughening effect of the lactic acid composite material of final preparation is obvious, and have better thermostability and mechanical property, greatly improved shock strength and the elongation at break of lactic acid composite material.
Embodiment 5
Present embodiment provides a kind of method for preparing lactic acid composite material, may further comprise the steps:
(1) be that mixture, acrylic ester grafted thing, the styrene/acrylic acid co-polymer oligopolymer that contains epoxy-functional, the particle diameter of 230,000 poly(lactic acid), poly butylene succinate and poly butyric ester is that 600 purpose talcum powder, metal passivator, Tyox B are respectively 60 ℃ of lower vacuum-dryings 3 ~ 8 hours with molecular weight, with dried above-mentioned substance pre-stirring 3 minutes in homogenizer, keep afterwards stirring, and constantly drip softening agent, material in itself and the stirrer is mixed, obtain the mixture of raw material.Wherein, the mass percent of each component of raw mix is closed and is:
Poly(lactic acid): 60%;
The mixture of poly butylene succinate and poly butyric ester (wherein, the mass ratio of poly butylene succinate and poly butyric ester is 2: 1): 25%;
Acrylic ester grafted thing: 10%
The styrene/acrylic acid co-polymer oligopolymer that contains epoxy-functional: 0.1%;
Talcum powder: 0.5%;
Metal passivator: 1%;
Tyox B: 1%;
Softening agent: 1%.
(2) raw mix is added in the twin screw extruder after dripping softening agent again, extrude under the temperature of design, wherein, screw speed is 25rpm, and extruding zone is respectively distinguished temperature and is respectively 140 ℃, 150 ℃, 170 ℃, 175 ℃, 180 ℃, 185 ℃, 190 ℃, 180 ℃, 185 ℃, 175 ℃, 170 ℃.
(3) extrude tie rod on the operation crawler belt by quenching after pelletizing, oven dry can obtain the lactic acid composite material of high tenacity film-grade.
By in the raw material of preparation lactic acid composite material, using acrylic ester grafted thing as grafting toughner, in twin screw extrusion, acrylic ester grafted thing can strengthen the polarity of poly(lactic acid), thereby further so that poly(lactic acid) is easier and the chainextender reaction, the toughening effect of the lactic acid composite material of final preparation is obvious, and have better thermostability and mechanical property, greatly improved shock strength and the elongation at break of lactic acid composite material.
Embodiment 6
Present embodiment provides a kind of method for preparing lactic acid composite material, may further comprise the steps:
(1) with molecular weight is 90,000 poly(lactic acid), poly-(6-caprolactone), the glycidyl methacrylate graft polyolefine, diepoxy class chainextender, particle diameter is 1000 purpose talcum powder, benzophenone light stabilizer, (3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid octadecyl ester and β-(3, the 5-di-tert-butyl-hydroxy phenyl) mixture of cyclohexyl propionate is respectively 60 ℃ of lower vacuum-dryings 3 ~ 8 hours, with dried above-mentioned substance pre-stirring 3 minutes in homogenizer, keep afterwards stirring, and constantly drip softening agent, material in itself and the stirrer is mixed, obtain the mixture of raw material.Wherein, the mass percent of each component of raw mix 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, the 5-di-tert-butyl-hydroxy phenyl) propionic acid octadecyl ester and β-(3, the 5-di-tert-butyl-hydroxy phenyl) mixture of cyclohexyl propionate (wherein, (3, the 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) raw mix is added in the twin screw extruder after dripping softening agent again, extrude under the temperature of design, wherein, screw speed is 180rpm, and the highest extrusion temperature is 200 ℃.
(3) extrude tie rod on the operation crawler belt by quenching after pelletizing, oven dry can obtain the lactic acid composite material of high tenacity film-grade.
Embodiment 7
Present embodiment provides a kind of method for preparing lactic acid composite material, may further comprise the steps:
(1) with molecular weight is 300,000 poly(lactic acid), poly-hexanodioic acid/butylene terephthalate, the polyolefinic mixture of acrylic ester grafted thing and glycidyl methacrylate graft, the styrene/acrylic acid co-polymer oligopolymer that contains epoxy-functional, particle diameter is 1300 purpose talcum powder, benzotriazole light stabilizer, four (β-(3,5 di-tert-butyl-hydroxy phenyls) propionic acid) pentaerythritol ester is respectively 60 ℃ of lower vacuum-dryings 3 ~ 8 hours, with dried above-mentioned substance pre-stirring 3 minutes in homogenizer, keep afterwards stirring, and constantly drip softening agent, material in itself and the stirrer is mixed, obtain the mixture of raw material.Wherein, the mass percent of each component of raw mix is closed and is:
Poly(lactic acid): 65%;
Poly-hexanodioic acid/butylene terephthalate: 15%;
The polyolefinic mixture of acrylic ester grafted thing and glycidyl methacrylate graft (wherein, the polyolefinic mass ratio of acrylic ester grafted thing and glycidyl methacrylate graft is 1: 2): 6%
The styrene/acrylic acid co-polymer oligopolymer that contains 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) raw mix is added in the twin screw extruder after dripping softening agent again, extrude under the temperature of design, wherein, screw speed is 100rpm, and the highest extrusion temperature is 180 ℃.
(3) extrude tie rod on the operation crawler belt by quenching after pelletizing, oven dry can obtain the lactic acid composite material of high tenacity film-grade.
Enumerated the performance test data of the lactic acid composite material of embodiment 2 ~ embodiment 7 preparations in the table 1., the lactic acid composite material for preparing not only has good toughness, and has better thermostability and mechanical property.The lactic acid composite material for preparing among each embodiment, comprehensively 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 preparations
Embodiment 8
Present embodiment provides a kind of method for preparing lactic acid composite material, may further comprise the steps:
(1) be that 130,000 poly(lactic acid), poly butylene succinate, methyl methacrylate-acrylate copolymer, diepoxy class chainextender, particle diameter are the mixture, (3 of 1500 purpose talcum powder, suffocated amine antioxidant and Hinered phenols antioxidant with molecular weight, the 5-di-tert-butyl-hydroxy phenyl) the propionic acid octadecyl ester is respectively 60 ℃ of lower vacuum-dryings 3 ~ 8 hours, with dried above-mentioned substance pre-stirring 3 minutes in homogenizer, keep afterwards stirring, and constantly drip softening agent, material in itself and the stirrer is mixed, obtain the mixture of raw material.Wherein, the mass percent of each component of raw mix 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 of suffocated amine antioxidant and Hinered phenols antioxidant (wherein, the mass ratio of suffocated amine antioxidant and Hinered phenols antioxidant is 3: 2): 0.5%;
(3,5-di-tert-butyl-hydroxy phenyl) propionic acid octadecyl ester: 0.5%;
Softening agent: 1%.
(2) raw mix is added in the twin screw extruder after dripping softening agent again, extrude under the temperature of design, wherein, screw speed is 100rpm, and the highest extrusion temperature is 160 ℃.
(3) extrude tie rod on the operation crawler belt by quenching after pelletizing, oven dry can obtain the lactic acid composite material of high tenacity film-grade.
By in the raw material of preparation lactic acid composite material, using methyl methacrylate-acrylate copolymer as impact modifier, in twin screw extrusion, compare with the small molecules softening agent, methyl methacrylate-acrylate copolymer itself is as polymeric plasticizer, generally can from the poly(lactic acid) matrix, not separate out, simultaneously, methyl methacrylate-acrylate copolymer has strengthened poly(lactic acid), poly butylene succinate, contain the consistency between the styrene/acrylic acid co-polymer oligopolymer of epoxy-functional, so that poly(lactic acid) is more prone to reaction with the styrene/acrylic acid co-polymer oligopolymer that contains epoxy-functional, so that the toughening effect of the lactic acid composite material of final preparation is obvious.
Embodiment 9
Present embodiment provides a kind of method for preparing lactic acid composite material, may further comprise the steps:
(1) with molecular weight is 150,000 poly(lactic acid), poly butyric ester, the high density polyethylene(HDPE) of slight chlorination and the IPN multipolymer of acrylate, the styrene/acrylic acid co-polymer oligopolymer that contains epoxy-functional, particle diameter is 1800 purpose talcum powder, suffocated amine antioxidant, four (β-(3,5 di-tert-butyl-hydroxy phenyls) propionic acid) pentaerythritol ester is respectively 60 ℃ of lower vacuum-dryings 3 ~ 8 hours, with dried above-mentioned substance pre-stirring 3 minutes in homogenizer, keep afterwards stirring, and constantly drip softening agent, material in itself and the stirrer is mixed, obtain the mixture of raw material.Wherein, the mass percent of each component of raw mix 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%
The styrene/acrylic acid co-polymer oligopolymer that contains 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) raw mix is added in the twin screw extruder after dripping softening agent again, extrude under the temperature of design, wherein, screw speed is 100rpm, and the highest extrusion temperature is 200 ℃.
(3) extrude tie rod on the operation crawler belt by quenching after pelletizing, oven dry can obtain the lactic acid composite material of high tenacity film-grade.
High density polyethylene(HDPE) by using slight chlorination in the raw material of preparation lactic acid composite material and the IPN multipolymer of acrylate are as impact modifier, in twin screw extrusion, compare with the 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 from the poly(lactic acid) matrix, not separate out, simultaneously, methyl methacrylate-acrylate copolymer has strengthened poly(lactic acid), poly butylene succinate, contain the consistency between the styrene/acrylic acid co-polymer oligopolymer of epoxy-functional, so that poly(lactic acid) is more prone to reaction with the styrene/acrylic acid co-polymer oligopolymer that contains epoxy-functional, so that the toughening effect of the lactic acid composite material of final preparation is obvious.
Embodiment 10
Present embodiment provides a kind of method for preparing lactic acid composite material, may further comprise the steps:
(1) with molecular weight is 250,000 poly(lactic acid), poly-hexanodioic acid/butylene terephthalate, MBS, the styrene/acrylic acid co-polymer oligopolymer that contains epoxy-functional, particle diameter is 500 purpose talcum powder, metal passivator, (3, the 5-di-tert-butyl-hydroxy phenyl) the propionic acid octadecyl ester is respectively 60 ℃ of lower vacuum-dryings 3 ~ 8 hours, with dried above-mentioned substance pre-stirring 3 minutes in homogenizer, keep afterwards stirring, and constantly drip softening agent, material in itself and the stirrer is mixed, obtain the mixture of raw material.Wherein, the mass percent of each component of raw mix is closed and is:
Poly(lactic acid): 70%;
Poly-hexanodioic acid/butylene terephthalate: 12%;
MBS: 11%
The styrene/acrylic acid co-polymer oligopolymer that contains 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) raw mix is added in the twin screw extruder after dripping softening agent again, extrude under the temperature of design, wherein, screw speed is 25rpm, and the highest extrusion temperature is 160 ℃.
(3) extrude tie rod on the operation crawler belt by quenching after pelletizing, oven dry can obtain the lactic acid composite material of high tenacity film-grade.
Embodiment 11
Present embodiment provides a kind of method for preparing lactic acid composite material, may further comprise the steps:
(1) with molecular weight is 280,000 poly(lactic acid), poly-(6-caprolactone), the high density polyethylene(HDPE) of methyl methacrylate-acrylate copolymer and slight chlorination and the IPN copolymer mixture of acrylate, the styrene/acrylic acid co-polymer oligopolymer that contains epoxy-functional, particle diameter is 700 purpose talcum powder, benzophenone light stabilizer, four (β-(3,5 di-tert-butyl-hydroxy phenyls) propionic acid) pentaerythritol ester is respectively 60 ℃ of lower vacuum-dryings 3 ~ 8 hours, with dried above-mentioned substance pre-stirring 3 minutes in homogenizer, keep afterwards stirring, and constantly drip softening agent, material in itself and the stirrer is mixed, obtain the mixture of raw material.Wherein, the mass percent of each component of raw mix 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 of acrylate (wherein, the mass ratio of the IPN multipolymer of the high density polyethylene(HDPE) of methyl methacrylate-acrylate copolymer and slight chlorination and acrylate is 2: 3): 5%
The styrene/acrylic acid co-polymer oligopolymer that contains 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) raw mix is added in the twin screw extruder after dripping softening agent again, extrude under the temperature of design, wherein, screw speed is 180rpm, and the highest extrusion temperature is 200 ℃.
(3) extrude tie rod on the operation crawler belt by quenching after pelletizing, oven dry can obtain the lactic acid composite material of high tenacity film-grade.
Embodiment 12
Present embodiment provides a kind of method for preparing lactic acid composite material, may further comprise the steps:
(1) with molecular weight is 230,000 poly(lactic acid), the mixture of poly-(6-caprolactone) and poly butylene succinate, the glycidyl methacrylate graft polyolefine, MBS, the styrene/acrylic acid co-polymer oligopolymer that contains epoxy-functional, particle diameter is 2000 purpose talcum powder, benzotriazole light stabilizer, (3, the 5-di-tert-butyl-hydroxy phenyl) the propionic acid octadecyl ester is respectively 60 ℃ of lower vacuum-dryings 3 ~ 8 hours, with dried above-mentioned substance pre-stirring 3 minutes in homogenizer, keep afterwards stirring, and constantly drip softening agent, material in itself and the stirrer is mixed, obtain the mixture of raw material.Wherein, the mass percent of each component of raw mix is closed and is:
Poly(lactic acid): 70%;
The mixture of poly-(6-caprolactone) and poly butylene succinate (wherein, the mass ratio of poly-(6-caprolactone) and poly butylene succinate is 3: 4): 5%;
Glycidyl methacrylate graft polyolefine: 10%;
MBS: 10%
The styrene/acrylic acid co-polymer oligopolymer that contains 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) raw mix is added in the twin screw extruder after dripping softening agent again, extrude under the temperature of design, wherein, screw speed is 160rpm, and the highest extrusion temperature is 190 ℃.
(3) extrude tie rod on the operation crawler belt by quenching after pelletizing, oven dry can obtain the lactic acid composite material of high tenacity film-grade.
By in the raw material of preparation lactic acid composite material, using the glycidyl methacrylate graft polyolefine as grafting toughner, MBS is as impact modifier, contain the styrene/acrylic acid co-polymer oligopolymer of epoxy-functional as chainextender, in twin screw extrusion, their common and poly(lactic acid) interactions, grafting toughner has increased the polarity of poly(lactic acid) matrix, reacts with chainextender so that poly(lactic acid) is easier; Chainextender and poly(lactic acid) reaction have strengthened thermostability and the mechanical property of the lactic acid composite material of preparation so that poly(lactic acid) forms the long-branched structure; Impact modifier has increased the consistency between the blended material.Simultaneously, in the raw material that in the preparation process of lactic acid composite material, uses, for poly(lactic acid), the amount that various additives use is less, so that the lactic acid composite material toughening effect that finally prepares is obvious, transparency is high, tensile strength is high, greatly increased the toughness of lactic acid composite material.
Embodiment 13
Present embodiment provides a kind of method for preparing lactic acid composite material, may further comprise the steps:
(1) with molecular weight is 300,000 poly(lactic acid), poly butyric ester, the mixture of maleic anhydride grafted ethene/octene thermoplastic elastomer and acrylic ester grafted thing, methyl methacrylate-acrylate copolymer, the styrene/acrylic acid co-polymer oligopolymer that contains epoxy-functional, particle diameter is 1500 purpose talcum powder, the mixture of metal passivator and benzophenone light stabilizer, β-(3, the 5-di-tert-butyl-hydroxy phenyl) cyclohexyl propionate is respectively 60 ℃ of lower vacuum-dryings 3 ~ 8 hours, with dried above-mentioned substance pre-stirring 3 minutes in homogenizer, keep afterwards stirring, and constantly drip softening agent, material in itself and the stirrer is mixed, obtain the mixture of raw material.Wherein, the mass percent of each component of raw mix is closed and is:
Poly(lactic acid): 80%;
Poly butyric ester: 6%;
The mixture of maleic anhydride grafted ethene/octene thermoplastic elastomer and acrylic ester grafted thing (wherein, the mass ratio of maleic anhydride grafted ethene/octene thermoplastic elastomer and acrylic ester grafted thing is 1: 1): 5%;
Methyl methacrylate-acrylate copolymer: 5%
The styrene/acrylic acid co-polymer oligopolymer that contains epoxy-functional: 0.1%;
Talcum powder: 2%;
The mixture of metal passivator and benzophenone light stabilizer (wherein, the mass ratio of metal passivator and benzophenone light stabilizer is 1: 1): 0.1%;
β-(3,5-di-tert-butyl-hydroxy phenyl) cyclohexyl propionate: 0.1%;
Softening agent: 1%.
(2) raw mix is added in the twin screw extruder after dripping softening agent again, extrude under the temperature of design, wherein, screw speed is 120rpm, and the highest extrusion temperature is 170 ℃.
(3) extrude tie rod on the operation crawler belt by quenching after pelletizing, oven dry can obtain the lactic acid composite material of high tenacity film-grade.
Embodiment 14
Present embodiment provides a kind of method for preparing lactic acid composite material, may further comprise the steps:
(1) with molecular weight is 80,000 poly(lactic acid), poly-hexanodioic acid/butylene terephthalate, acrylic ester grafted thing, the high density polyethylene(HDPE) of slight chlorination and the IPN multipolymer of acrylate, the styrene/acrylic acid co-polymer oligopolymer that contains epoxy-functional, particle diameter is 1300 purpose talcum powder, Hinered phenols antioxidant, Tyox B is respectively 60 ℃ of lower vacuum-dryings 3 ~ 8 hours, with dried above-mentioned substance pre-stirring 3 minutes in homogenizer, keep afterwards stirring, and constantly drip softening agent, material in itself and the stirrer is mixed, obtain the mixture of raw material.Wherein, the mass percent of each component of raw mix 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%
The styrene/acrylic acid co-polymer oligopolymer that contains epoxy-functional: 0.5%;
Talcum powder: 10%;
Hinered phenols antioxidant: 1%;
Tyox B: 1%;
Softening agent: 5%.
(2) raw mix is added in the twin screw extruder after dripping softening agent again, extrude under the temperature of design, wherein, screw speed is 120rpm, and the highest extrusion temperature is 200 ℃.
(3) extrude tie rod on the operation crawler belt by quenching after pelletizing, oven dry can obtain the lactic acid composite material of high tenacity film-grade.
Embodiment 15
Present embodiment provides a kind of method for preparing lactic acid composite material, may further comprise the steps:
(1) with molecular weight is 140,000 poly(lactic acid), poly-hexanodioic acid/butylene terephthalate, maleic anhydride grafted ethene/octene thermoplastic elastomer, MBS, the styrene/acrylic acid co-polymer oligopolymer that contains epoxy-functional, particle diameter is 1900 purpose talcum powder, benzophenone light stabilizer, four (β-(3,5 di-tert-butyl-hydroxy phenyls) propionic acid) pentaerythritol ester is respectively 60 ℃ of lower vacuum-dryings 3 ~ 8 hours, with dried above-mentioned substance pre-stirring 3 minutes in homogenizer, keep afterwards stirring, and constantly drip softening agent, material in itself and the stirrer is mixed, obtain the mixture of raw material.Wherein, the mass percent of each component of raw mix is closed and is:
Poly(lactic acid): 65%;
Poly-hexanodioic acid/butylene terephthalate: 5%;
Maleic anhydride grafted ethene/octene thermoplastic elastomer: 3%;
MBS: 20%
The styrene/acrylic acid co-polymer oligopolymer that contains 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) raw mix is added in the twin screw extruder after dripping softening agent again, extrude under the temperature of design, wherein, screw speed is 180rpm, and the highest extrusion temperature is 200 ℃.
(3) extrude tie rod on the operation crawler belt by quenching after pelletizing, oven dry can obtain the lactic acid composite material of high tenacity film-grade.
Embodiment 16
Present embodiment provides a kind of lactic acid composite material, and it is prepared by above-mentioned preparation method.
Be understandable that above embodiment only is the illustrative embodiments that adopts for principle of the present invention is described, yet 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 also are considered as protection scope of the present invention.
Claims (11)
1. a lactic acid composite material is characterized in that, the raw material that needs in its preparation process comprises: poly(lactic acid), polyester toughner, chainextender, talcum powder, antiaging agent, oxidation inhibitor and softening agent.
2. lactic acid composite material according to claim 1 is characterized in that, the mass percent of each component of raw material of described preparation 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%.
3. 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 poly-(6-caprolactone), poly butylene succinate, poly butyric ester, poly-wherein one or more of hexanodioic acid/butylene terephthalate;
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 in suffocated amine antioxidant, Hinered phenols antioxidant, phosphite, metal passivator, benzophenone light stabilizer, the benzotriazole light stabilizer one or more;
And/or described oxidation inhibitor is four (β-(3,5 di-tert-butyl-hydroxy phenyls) propionic acid) pentaerythritol ester, (3, the 5-di-tert-butyl-hydroxy phenyl) one or more in propionic acid octadecyl ester, β-(3,5-di-tert-butyl-hydroxy phenyl) cyclohexyl propionate, the Tyox B.
4. lactic acid composite material according to claim 1 is characterized in that, the raw material that needs in its preparation process also comprises: grafting toughner.
5. lactic acid composite material according to claim 4 is characterized in that, the mass percent of each component of raw material of described preparation lactic acid composite material is closed and is:
Poly(lactic acid): 50% ~ 80%;
Polyester toughner: 5% ~ 25%;
Grafting toughner: 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%.
6. lactic acid composite material according to claim 4, it is characterized in that described grafting toughner is one or more in maleic anhydride grafted ethene/octene thermoplastic elastomer, acrylic ester grafted thing, the glycidyl methacrylate graft polyolefine.
7. according to claim 1 or 4 described lactic acid composite materials, it is characterized in that the raw material that needs in its preparation process also comprises: acrylic ester impact-resisting modifier.
8. lactic acid composite material according to claim 7 is characterized in that, the mass percent of each component of raw material of described preparation 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%.
9. lactic acid composite material according to claim 7 is characterized in that, the mass percent of each component of raw material of described preparation lactic acid composite material is closed and is:
Poly(lactic acid): 50% ~ 80%;
Polyester toughner: 5% ~ 25%;
Grafting toughner: 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%.
10. lactic acid composite material according to claim 7, it is characterized in that described acrylic ester impact-resisting modifier is methyl methacrylate-acrylate copolymer, the high density polyethylene(HDPE) of slight chlorination and the IPN multipolymer of acrylate, one or more in the MBS.
11. a method for preparing the described lactic acid composite material of any one in the claim 1 ~ 10 is characterized in that, may further comprise the steps:
(1) raw material that needs in the described preparation process of claim 1 ~ 10 any one is mixed;
(2) raw material that mixes is added twin screw extruder and melt extrude, wherein the highest extrusion temperature is 160 ~ 200 ℃;
(3) granulation, drying obtains described lactic acid composite material.
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