CN103044872B - Polylactic acid composition - Google Patents
Polylactic acid composition Download PDFInfo
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- CN103044872B CN103044872B CN201310030961.2A CN201310030961A CN103044872B CN 103044872 B CN103044872 B CN 103044872B CN 201310030961 A CN201310030961 A CN 201310030961A CN 103044872 B CN103044872 B CN 103044872B
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Abstract
The invention discloses a polylactic acid composition which comprises a polylactic acid mixture, a polymer blend, a nucleating agent and a compatible agent. The polylactic acid mixture comprises an L type polylactic acid material and a D type polylactic acid material, the polymer blend is a polyester type polymer blend or polyether type polymer blend, a polymer chain of the polymer blend has at least one functional group easily forming a hydrogen bond, the nucleating agent is selected from an aromatic acid salt compound, a fatty acid metal salt, an inorganic filler and a composition thereof, and the compatible agent contains peroxide or an unsaturated reactive functional group compound. The polylactic acid composition has high heat resistance without secondary processing, thereby saving time and cost; and the polylactic acid composition has high impact resistance, thereby expanding the applicable range.
Description
Technical field
The present invention system relates to a kind of raw matter plastics constituent, is specifically related to a kind of poly(lactic acid) constituent that has thermotolerance, shock-resistance and do not need the advantage of characteristic processing.
Background technology
It is made as raw material that traditional plastic material be take oil, because it has the characteristics such as lightweight, workability, weather resistance, obdurability, and is widely used in the every aspect of daily life.But the Stability Analysis of Structures of plastic material, is not easy to be subject to the impact of external environment factor and decomposes, make plastic refuse become a burden greatly of environment.The treatment process of plastic refuse is buried method and incineration method at present.After plastic refuse is buried, because it be difficult for to decompose, short-term can reduce the working life of landfill site, long-term can block the natural permeable layer of soil and make desertification of land, and then has a strong impact on environmental ecology.While processing with incineration method, although plastic refuse almost can disappear and not occupy soil, in incineration course, can produce as obnoxious flavoures such as dioxins, understand equally welding.
Along with environmental issue is watched attentively day by day, about use and the development of the Biodegradable plastics that can be decomposed by microorganism in physical environment, also extremely pay attention to.Wherein, poly(lactic acid) (polylactic acid, be called for short PLA, also be called polylactide), it can be by biolytic characteristic and not welding, it has characteristic easy to process and that mechanical properties is good simultaneously, and monomer whose can be completely by obtaining through conversion as renewable resourcess such as corn or beets except having, and needn't worry the source of raw material, its production cost is also comparatively cheap.
Yet the crystallization rate of poly(lactic acid) is slow, be difficult to crystallization in moulding process, make the heat-drawn wire of poly(lactic acid) finished product lower, and cause thermotolerance not enough, be difficult to be applicable in the environment of higher temperatures.If can effectively improve the degree of crystallinity of poly(lactic acid), can make the heat-drawn wire of poly(lactic acid) finished product improve and increase thermotolerance, and then expand the range of application of poly(lactic acid).
Particularly, see through the jetting formation process of general cold mould, the process-cycle of poly(lactic acid) can complete within 1 minute, but the heat-drawn wire of its products formed is only had an appointment 55 to 60 ℃, and Taiwan patent certificate discloses a kind of manufacture method of heat-resistance polylactic acid products formed for No. I364362, in polylactic acid raw material, add nucleator, make again just finished product, then this first finished product is heat-treated, to improve the degree of crystallinity of these pre-profiling product, and make a polylactic acid article with superior heat resistance, mainly by the means of secondary processing, reached the thermotolerance that improves poly(lactic acid).
But carry out secondary processing, need the time, also need extra cost payout, cause the shortcoming that integrated artistic is consuming time and cost increases, do not meet the demand in industry.
Summary of the invention
In view of above-mentioned prior art shortcoming, the object of the invention is to provide a kind of poly(lactic acid) constituent, and it has after moulding just can have better thermotolerance and shock-resistance without secondary processing, and then has advantages of the process time of saving and cost.
In order to reach aforementioned goal of the invention, the technique means that the present invention takes is for providing a kind of poly(lactic acid) constituent, and it comprises:
One poly-lactic acid mixture, is comprised of the L-type poly(lactic acid) material of 60 to 95 weight percents and the D type poly(lactic acid) material of 5 to 40 weight percents;
One poyblend be polyester type poyblend or polyether type high polymer blend, and its macromolecular chain has the functional group that at least one is easy to form hydrogen bond;
One nucleator, be selected from by aromatic acid salt compound, fatty acid metal salt, inorganic filler with and the group that formed of combination;
One compatibility agent, it contains superoxide or unsaturated reactive functional based compound.
Optical purity (optical purity): two mixtures that compound formed of optical isomeric compound each other, and the pure state of a compound in this mixture, the former ratio that revolves brightness that revolves brightness and the latter.
Furthermore, the described functional group who is easy to form hydrogen bond is carboxyl, alcohol radical, ether, amido or amide group.
Furthermore, this unsaturated reactive functional based compound is unsaturated carboxylic ester compound, epoxy compounds, polynary unsaturated polyester compound or polynary amides.
Preferably, take this poly-lactic acid mixture content as 100 weight parts, this additive level is 0.1 to 49 weight part, and this nucleator content is 0.1 to 15 weight part, and this compatibility agent content is 0.1 to 5 weight part.
Best, the content of this poly-lactic acid mixture of take is 100 weight parts, and the content of this additive is 0.5 to 15 weight part, and the content of this nucleator is 0.5 to 5 weight part, and the content of this compatibility agent is 0.2 to 2 weight part.
Preferably, in this poly-lactic acid mixture, L-type poly(lactic acid) material is to have the more than 95% L-type poly(lactic acid) of optical purity, and D type poly(lactic acid) material is to have the more than 95% D type poly(lactic acid) of optical purity.
Best, in this poly-lactic acid mixture, L-type poly(lactic acid) material is to have the more than 98% L-type poly(lactic acid) of optical purity, and D type poly(lactic acid) material is to have the more than 98% D type poly(lactic acid) of optical purity.
Preferably, this poly-lactic acid mixture molecular weight is between 80000 to 300000, and best, this poly-lactic acid mixture molecular weight is between 120000 to 200000.
Preferably, the L-type polylactic acid molecule amount of poly-lactic acid mixture L-type poly(lactic acid) material is between 100000 to 300000, and the D type polylactic acid molecule amount of poly-lactic acid mixture D type poly(lactic acid) material is between 60000 to 200000; Best, this L-type polylactic acid molecule amount is between 120000 to 200000, and this D type polylactic acid molecule amount is between 70000 to 150000.
Beneficial effect:
The advantage of poly (lactic acid) composition of the present invention is: do not need secondary processing just can have high heat resistance, thereby save time and cost, and can have high-impact simultaneously, the scope that can apply is more extensive.
embodiment:
Below in conjunction with embodiment, further set forth the present invention and reach the technique means that predetermined object is taked.
Poly(lactic acid) constituent of the present invention preferred embodiment includes a poly-lactic acid mixture, a poyblend, a nucleator and a compatibility agent.
Aforesaid poly-lactic acid mixture is comprised of the L-type poly(lactic acid) material of 60 to 95 weight percents and the D type poly(lactic acid) material of 5 to 40 weight percents, and this L-type poly(lactic acid) material is to have the more than 95% L-type poly(lactic acid) of optical purity, this D type poly(lactic acid) material is to have the more than 95% D type poly(lactic acid) of optical purity; Preferably, L-type poly(lactic acid) material is to have the more than 98% L-type poly(lactic acid) of optical purity, and D type poly(lactic acid) material is to have the more than 98% D type poly(lactic acid) of optical purity; Furthermore, D type poly(lactic acid) material adding proportion is higher, more easily form three-dimensional misfit thing (stereo-complex PLA), but relatively its process window is just narrower, difficulty of processing is just higher, and the optical purity of lifting L-type poly(lactic acid) and D type poly(lactic acid) can promote this solid misfit thing generating rate.
In addition,, when poly-lactic acid mixture is applied to different process, for taking into account in practical application and the upper required character of processing, its molecular weight need be between specific scope; For example, while being applied to extrusion molding technique, the molecular weight preferred range of poly-lactic acid mixture is between 80000 to 200000; If the molecular weight of poly-lactic acid mixture is lower than 80000, it is difficult to have needed character in realistic application, as: mechanical properties, heat-resisting character etc., and then make its products formed easily cracked; If poly-lactic acid mixture molecular weight is higher than 200000, its be difficult to have meet processing needed character (as: viscosity is too high), further, if adjust reluctantly machined parameters (as: processing temperature) to process, make its finished product produce other shortcoming (as: shortening in work-ing life); Best, the molecular weight of poly-lactic acid mixture is between 120000 to 200000.
Furthermore, the L-type polylactic acid molecule amount of the L-type poly(lactic acid) material of poly-lactic acid mixture is between 100000 to 300000, and the D type polylactic acid molecule amount of poly-lactic acid mixture D type poly(lactic acid) material is between 60000 to 200000; Best, this L-type polylactic acid molecule amount is between 120000 to 200000, and this D type polylactic acid molecule amount is between 70000 to 150000.
Aforementioned poyblend increases shock-resistance in order to strengthen the interaction force of each formula in composition, it is polyester type poyblend or polyether type high polymer blend, and its macromolecular chain has at least one functional group who is easy to form hydrogen bond, furthermore, the described functional group who is easy to form hydrogen bond is carboxyl, alcohol radical, ether, amido or amide group; For example, the polymer blended system poly butyric ester of polyester type (polyhydroxybutyrate, PHB), poly butylene succinate (polybutylenesuccinate, PBS), polycaprolactone (polycaprolactone, PCL) or poly-hexanodioic acid/butylene terephthalate (poly (butylene-adipate-co-terephthalate), PBAT), polyether type high polymer blend system Soxylat A 25-7 (polyethylene oxide, PEO) or polyphenylene oxide (polyphenylene oxide, PPO).
Aforementioned nucleator select free aromatic acid salt compound, fatty acid metal salt, inorganic filler with and the group that formed of combination, for example, described aromatic acid salt compound is aromatic sulfonate or aromatic base phosphoric acid salt etc.; Described fatty acid metal salt is Zinic stearas or calcium stearate etc.; Described inorganic filler is monomer nucleator, clay class, metal oxide, inorganic salts; I.e. how rice clay, graphite, kaolin, mica, polynite, silicon-dioxide, calcium carbonate, aluminium hydroxide, aluminum oxide, aluminium carbonate, calcium lactate, barium sulfate, glass fibre, oyster shell whiting etc.
Front compatibility agent is for linking any reagent of reactive force between the poly-lactic acid mixture in order to strengthening foundation poly (lactic acid) composition of the present invention and poyblend, avoiding poly-lactic acid mixture and polymer blended compound to produce is separated, can make compatible raising between formula, and then improve whole mechanical property, compatibility agent is for containing superoxide, unsaturated reactive functional based compound or polynary ester type compound, this unsaturated reactive functional group series of compounds unsaturated carboxylic ester compound (as: methyl acrylate compound) wherein, epoxy compounds (as: epoxy soybean oil, epoxy linseed oil etc.), polynary unsaturated polyester compound (as: different hydrogen acid ether) or polynary amides (as: stearylamide compound), furthermore, while containing polynary ester type compound, polynary unsaturated polyester compound or polynary amides in compatibility agent, this compatibility agent, except improving poly-lactic acid mixture and polymer blended compound compatibility, also can promote the crystallization of poly-lactic acid mixture.
It is finished product that reshaping after particle can be first made in this preferred embodiment, and facility for granulating can be used single shaft extruder, twin shaft extruder or other general plastic granulators, and can be via longitudinal stretching or cross directional stretch or biaxial stretch-formed and make needed poly(lactic acid) finished product.
The following example is for exemplary illustration the present invention.These embodiment are intended to limit the scope of the invention never in any form, but are used to indicate material of the present invention and the method how implemented.
Embodiment mono-
The present embodiment is first by poly(lactic acid) constituent mixing granulator of the present invention, and uses extrusion molding machine, and the poly(lactic acid) constituent particle making is given as security and made after sheet material, through single shaft or twin shaft, extends to finished product, and details are as follows for correlation parameter and step:
By the compatibility agent of the nucleator of the polyester type poyblend of the poly-lactic acid mixture of 100 weight parts, 0.5 weight part, 0.5 weight part and 0.2 weight part, be supplied to twin-screw mixer machine and carry out mixing granulator, and obtain the particle of poly (lactic acid) composition;
The D type poly(lactic acid) material that described poly-lactic acid mixture is 40 by L-type poly(lactic acid) material and the weight percent of weight percent 60 forms; The optical purity of the L-type poly(lactic acid) of L-type poly(lactic acid) material is more than 98%, and molecular weight is 200000, and the optical purity of the D type poly(lactic acid) of D type poly(lactic acid) material is more than 98%, and molecular weight is 150000;
Wherein, twin-screw mixer machine is provided by Taiwan Ya Jing is mechanical, and its screw rod long-width ratio (L/D) is 32, and compression ratio is 2.5:1, and working temperature is 160 to 180 ℃.
Then, the particle of poly (lactic acid) composition is dry at 90 ℃, its water content is down to below 250 ppm, be then supplied to extrusion molding machine, processing temperature is 170 to 190 ℃, through longitudinal stretching or cross directional stretch or double-axes fensile work, prepares poly(lactic acid) finished product.
Embodiment bis-
The poly-lactic acid mixture of the present embodiment be weight percentage 70 L-type poly(lactic acid) material and the D type poly(lactic acid) material of weight percent 30.
In addition, the poly-lactic acid mixture of the present embodiment is 100 weight parts, and the polyester type poyblend adding is that 6 weight parts, nucleator are that 3 weight parts and compatibility agent are 1.2 weight parts.
The method that the present embodiment is used, step and each composition are all identical with embodiment mono-, and detailed process repeats no more.
Embodiment tri-
The poly-lactic acid mixture of the present embodiment be weight percentage 80 L-type poly(lactic acid) material and the D type poly(lactic acid) material of weight percent 20.
In addition, the poly-lactic acid mixture of the present embodiment is 100 weight parts, and the polyester type poyblend adding is that 12 weight parts, nucleator are that 5 weight parts and compatibility agent are 1.8 weight parts.
The method that the present embodiment is used, step and each composition are all identical with embodiment mono-, and detailed process repeats no more.
Embodiment tetra-
The poly-lactic acid mixture of the present embodiment is heavily the amount L-type poly(lactic acid) material of per-cent 90 and the D type poly(lactic acid) material of weight percent 10.
In addition, the poly-lactic acid mixture of the present embodiment is 100 weight parts, and the polyester type poyblend adding is that 24 weight parts, nucleator are that 12 weight parts and compatibility agent are 2.4 weight parts.
The method that the present embodiment is used, step and each composition are all identical with embodiment mono-, and detailed process repeats no more.
Embodiment five
The poly-lactic acid mixture of the present embodiment be weight percentage 95 L-type poly(lactic acid) material and the D type poly(lactic acid) material of weight percent 5.
In addition, the poly-lactic acid mixture of the present embodiment is 100 weight parts, and the polyester type poyblend adding is that 48 weight parts, nucleator are that 15 weight parts and compatibility agent are 4.8 weight parts.
The method that the present embodiment is used, step and each composition are all identical with embodiment mono-, and detailed process repeats no more.
Comparative example
The commercially available polylactic acid plastic through granulation (Natureworks LLC company manufactures, and product are called 2003D), its heat-drawn wire, shock strength and elongation at break are as shown in Table 1.
Table 1 thermotolerance test technology parameter list
| Heat-drawn wire HDT (℃) | 55 |
| Shock strength (J/m) | 16 |
| Elongation (%) | 6 |
Use heat-drawn wire trier (HDT, Hong Da Instrument Ltd. manufactures) respectively embodiment mono-to five to be carried out to the measurement of heat-drawn wire, can record each embodiment thermotolerance, the heat-resisting character of the higher expression tested object of heat-drawn wire is better; Test result as shown in Table 2.
Processing parameter synopsis in table 2 embodiment of the present invention
If table one is with as shown in table two, the heat-drawn wire of comparative example is 55 ℃, the heat-drawn wire of embodiment mono-to five is followed successively by 126 ℃, 112 ℃, 105 ℃, 88 ℃ and 72 ℃, demonstrate each embodiment and all compared with comparative example, there is preferably thermotolerance, and each embodiment only passes through general moulding process, the stable on heating secondary processing of follow-up raising be can save, process time and cost saved.
Shock-resistance test
Use shock-testing machine (GT-7045, high ferro Science and Technology Co., Ltd. manufactures) respectively embodiment mono-to five to be carried out to shock strength (Izod impact strength) test, the shock-resistance of the higher expression tested object of shock strength is better; Test result as shown in Table 2.
If table one is with as shown in table two, the shock strength of comparative example is about 16J/m, the shock strength of embodiment mono-to five is sequentially 45 J/m, 216 J/m, 342 J/m, 398 J/m and 453J/m, demonstrate the shock strength of each embodiment all higher than the impact strength of comparative example, each embodiment has preferably shock-resistance.
Test of elongation rate
(Insrton 3369 to use tensile testing machine, U.S. Instron company manufactures) respectively embodiment mono-to five is carried out to tension test, record each embodiment elongation at break (elongation at break), elongation at break represents the length and length ratio originally that tested object can be stretched before fracture, conventionally with per-cent, represent, the ductility of the higher expression tested object of extension at break rate score is better, has preferably processing characteristics, and test result as shown in Table 2.
If table one is with as shown in table two, the elongation at break of comparative example is about 6%, the present embodiment one to five elongation is sequentially and is about 32%, 115%, 236%, 352% and 486%, demonstrates each embodiment elongation at break all higher than the elongation at break of comparative example, and each embodiment has better extensibility.
In sum, it is good thermotolerance that the present invention's poly(lactic acid) constituent does not need secondary processing just can have more commercially available poly(lactic acid), and can save time and cost, simultaneously, the present invention's poly(lactic acid) constituent also has preferably shock-resistance, and the scope that can apply is more extensive.
In addition,, for making poly (lactic acid) composition in the advantage that there is better thermotolerance, better shock-resistance and do not need secondary processing simultaneously, be further made as and in finished product technique, there is preferably processibility and convenient processing; And be made as and there is preferably product stability (as: work-ing life is longer) after finished product and can mass production, aforementioned each embodiment of take is example, preferably, take poly-lactic acid mixture during as 100 weight part, polyester type poyblend content is 0.5 to 25 weight part, nucleator content is 0.5 to 5 weight part, and compatibility agent content is 0.2 to 2 weight part.
Claims (7)
1. a poly (lactic acid) composition, it comprises:
One poly-lactic acid mixture, is comprised of the L-type poly(lactic acid) material of 60 to 95 weight percents and the D type poly(lactic acid) material of 5 to 40 weight percents;
One poyblend be polyester type poyblend or polyether type high polymer blend, and its macromolecular chain has the functional group that at least one is easy to form hydrogen bond;
One nucleator, be selected from aromatic acid salt compound, fatty acid metal salt, inorganic filler with and the group that formed of combination;
One compatibility agent, it contains superoxide, unsaturated reactive functional based compound or polynary ester type compound;
The L-type poly(lactic acid) material of described poly-lactic acid mixture is to have the more than 95% L-type poly(lactic acid) of optical purity; D type poly(lactic acid) material is to have the more than 95% D type poly(lactic acid) of optical purity;
The molecular weight of described poly-lactic acid mixture is 80000 to 300000;
The molecular weight of the L-type poly(lactic acid) of described poly-lactic acid mixture L-type poly(lactic acid) material is between 100000 to 300000; The molecular weight of the D type poly(lactic acid) of poly-lactic acid mixture D type poly(lactic acid) material is between 60000 to 200000.
2. poly (lactic acid) composition as claimed in claim 1, the functional group who is wherein easy to form hydrogen bond in poyblend is carboxyl, alcohol radical, ether, amido or amide group.
3. poly (lactic acid) composition as claimed in claim 1 or 2, wherein the unsaturated reactive functional based compound of compatibility agent is unsaturated carboxylic ester compound, epoxy compounds, polynary unsaturated polyester compound or polynary amides.
4. poly (lactic acid) composition as claimed in claim 1 or 2, wherein take poly-lactic acid mixture content as 100 weight parts, and macromolecule mixture additive level is 0.1 to 49 weight part.
5. poly (lactic acid) composition as claimed in claim 1 or 2, wherein take poly-lactic acid mixture content as 100 listed as parts by weight, and nucleator content is 0.1 to 15 weight part.
6. poly (lactic acid) composition as claimed in claim 1 or 2, wherein take poly-lactic acid mixture as content 100 listed as parts by weight, and compatibility agent content is 0.1 to 5 weight part.
7. poly (lactic acid) composition as claimed in claim 1 or 2, wherein the L-type poly(lactic acid) material of poly-lactic acid mixture is to have the more than 98% L-type poly(lactic acid) of optical purity, D type poly(lactic acid) material is to have the more than 98% D type poly(lactic acid) of optical purity.
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| CN104151799A (en) * | 2013-05-15 | 2014-11-19 | 允友成(宿迁)复合新材料有限公司 | Pressing-blowing type biodegradable plastic composition and application thereof |
| TWI500681B (en) * | 2013-07-02 | 2015-09-21 | Supla Material Technology Co Ltd | Multi-layer film, method of producing the same and application thereof |
| CN104341752A (en) * | 2013-07-31 | 2015-02-11 | 允友成(宿迁)复合新材料有限公司 | Heatproof biodegradable plastic and its preparation method |
| TWI504671B (en) * | 2014-01-06 | 2015-10-21 | Supla Material Technology Co Ltd | Polylactic acid composition and the molding product made therefrom |
| CN104988659A (en) * | 2015-06-23 | 2015-10-21 | 安徽皖翎羽绒制品有限公司 | High-durableness down feather composite warming material and preparation method of same |
| CN105002652A (en) * | 2015-06-23 | 2015-10-28 | 安徽皖翎羽绒制品有限公司 | Antimicrobial mildew-proof down composite warmth retention material and preparation method thereof |
| CN105040273A (en) * | 2015-06-23 | 2015-11-11 | 安徽皖翎羽绒制品有限公司 | Moth-proof down composite thermal material and preparation method thereof |
| CN104947315A (en) * | 2015-06-24 | 2015-09-30 | 安徽皖翎羽绒制品有限公司 | Down feather composite heat preservation material containing aloe fiber and preparation method of down feather composite heat preservation material |
| CN104911813A (en) * | 2015-06-24 | 2015-09-16 | 安徽皖翎羽绒制品有限公司 | Waterproof antifouling feather composite thermal insulation material and preparation method thereof |
| CN109777053B (en) * | 2019-01-11 | 2021-10-29 | 海南三碳科技有限公司 | Material containing calcium lactate and capable of controlling biodegradation rate |
| CN111005056B (en) * | 2019-12-24 | 2021-04-30 | 永嘉县开天饰品有限公司 | Composite long-life conductive hook for PCB electroplating and preparation method thereof |
| CN112480621A (en) * | 2020-12-04 | 2021-03-12 | 惠州莹光塑胶颜料有限公司 | Environment-friendly plastic master batch and preparation method thereof |
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| CN102241877A (en) * | 2010-05-12 | 2011-11-16 | 邹俊 | Polylactic acid modified material, and preparation method and application thereof |
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| CN102241877A (en) * | 2010-05-12 | 2011-11-16 | 邹俊 | Polylactic acid modified material, and preparation method and application thereof |
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