CN103044872A - Polylactic acid composition - Google Patents
Polylactic acid composition Download PDFInfo
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- CN103044872A CN103044872A CN2013100309612A CN201310030961A CN103044872A CN 103044872 A CN103044872 A CN 103044872A CN 2013100309612 A CN2013100309612 A CN 2013100309612A CN 201310030961 A CN201310030961 A CN 201310030961A CN 103044872 A CN103044872 A CN 103044872A
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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 living 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
Traditional plastic material is made take oil as raw material, 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, so that plastic refuse becomes a large burden of environment.The treatment process of plastic refuse is buried method and incineration method at present.After plastic refuse was buried, because it be difficult for to decompose, short-term can reduce the working life of landfill site, and is long-term then can block the natural permeable layer of soil and make desertification of land, and then has a strong impact on environmental ecology.When processing with the incineration method, although plastic refuse almost can disappear and not occupy the soil, in incineration course, can produce such as obnoxious flavoures such as dioxins, understand equally welding.
Along with environmental issue is watched attentively day by day, also extremely pay attention to development about the use of the Biodegradable plastics that in physical environment, can be decomposed by microorganism.Wherein, poly(lactic acid) (polylactic acid, be called for short PLA, also be called polylactide), it can be by biolytic characteristic and not the welding, it has characteristic easy to process and that mechanical properties is good simultaneously, and monomer whose can be fully by obtaining through conversion such as renewable resourcess such as corn or beets except having, and needn't worry the source of raw material, then its production cost is also comparatively cheap.
Yet the crystallization rate of poly(lactic acid) is slow, is difficult to crystallization in moulding process, so that the heat-drawn wire of poly(lactic acid) finished product is lower, and causes thermotolerance not enough, is difficult to be applicable in the environment of higher temperatures.If the degree of crystallinity of energy Effective Raise poly(lactic acid) can make the heat-drawn wire of poly(lactic acid) finished product improve and increase thermotolerance, and then enlarge 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 finish within 1 minute, but the heat-drawn wire of its products formed is only had an appointment 55 to 60 ℃, and the Taiwan patent certificate discloses a kind of manufacture method of heat-resistance polylactic acid products formed for I364362 number, 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, the i.e. main thermotolerance that improves poly(lactic acid) that reached by the means of secondary processing.
Need the time but carry out secondary processing, also need extra cost payout, cause the shortcoming that integrated artistic is consuming time and cost increases, do not meet the demand on the 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 and need not secondary processing just can have better thermotolerance and shock-resistance after moulding, 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 consisted of of combination;
One compatibility agent, it contains superoxide or unsaturated reactive functional based compound.
Optical purity (optical purity): two mixtures that compound consisted of 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 is, take the content of this poly-lactic acid mixture as 100 weight parts, 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 L-type poly(lactic acid) of optical purity more than 95%, and D type poly(lactic acid) material is to have the D type poly(lactic acid) of optical purity more than 95%.
Best is, in this poly-lactic acid mixture, L-type poly(lactic acid) material is to have the L-type poly(lactic acid) of optical purity more than 98%, and D type poly(lactic acid) material is to have the D type poly(lactic acid) of optical purity more than 98%.
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 simultaneously high-impact, the scope that can use is more extensive.
Embodiment:
Further set forth the present invention below in conjunction with embodiment and reach the technique means that predetermined purpose 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 L-type poly(lactic acid) of optical purity more than 95%, and this D type poly(lactic acid) material is to have the D type poly(lactic acid) of optical purity more than 95%; Preferably, L-type poly(lactic acid) material is to have the L-type poly(lactic acid) of optical purity more than 98%, and D type poly(lactic acid) material is to have the D type poly(lactic acid) of optical purity more than 98%; 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 was applied to different process, for taking into account in the practical application and the upper required character of processing, its molecular weight needed between specific scope; For example, when 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, then it is difficult to have needed character in the realistic application, as: mechanical properties, heat-resisting character etc., and then make its products formed easily cracked; If the poly-lactic acid mixture molecular weight is higher than 200000, then 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, then 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 the interaction force of strengthening each prescription in the 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 be selected from by aromatic acid salt compound, fatty acid metal salt, inorganic filler with and the group that consisted of 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 in order to link any reagent of reactive force between the poly-lactic acid mixture of 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 the between prescription, and then the whole mechanical property of raising, compatibility agent is for containing superoxide, unsaturated reactive functional based compound or polynary ester type compound, wherein this unsaturated reactive functional group series of compounds unsaturated carboxylic ester compound (as: methyl acrylate compound), 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, when containing polynary ester type compound, polynary unsaturated polyester compound or polynary amides in the compatibility agent, this compatibility agent also can promote the crystallization of poly-lactic acid mixture except improving poly-lactic acid mixture and polymer blended compound compatibility.
This preferred embodiment can make first that reshaping is finished product behind the particle, and facility for granulating can use 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 used 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 one
The present embodiment is first with poly(lactic acid) constituent mixing granulator of the present invention, and uses the extrusion molding machine, with the poly(lactic acid) constituent particle that makes give as security make sheet material after, extend to finished product through single shaft or twin shaft, details are as follows for correlation parameter and step:
With the poly-lactic acid mixture of 100 weight parts, the polyester type poyblend of 0.5 weight part, the nucleator of 0.5 weight part and the compatibility agent of 0.2 weight part, be supplied to the twin-screw mixer machine and carry out mixing granulator, and obtain the particle of poly (lactic acid) composition;
Described poly-lactic acid mixture is that 40 D type poly(lactic acid) material forms by the L-type poly(lactic acid) material of weight percent 60 and weight percent; 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, the twin-screw mixer machine is provided by Taiwan Ya Jing machinery, 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, with the particle of poly (lactic acid) composition in 90 ℃ lower dry, its water content is down to below 250 ppm, then be supplied to the extrusion molding machine, processing temperature is 170 to 190 ℃, prepares the poly(lactic acid) finished product through longitudinal stretching or cross directional stretch or double-axes fensile work.
Embodiment two
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 that adds is that 6 weight parts, nucleator are that 3 weight parts and compatibility agent are 1.2 weight parts.
The employed method of the present embodiment, step and each composition are all identical with embodiment one, and detailed process repeats no more.
Embodiment three
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 that adds is that 12 weight parts, nucleator are that 5 weight parts and compatibility agent are 1.8 weight parts.
The employed method of the present embodiment, step and each composition are all identical with embodiment one, and detailed process repeats no more.
Embodiment four
The poly-lactic acid mixture of the present embodiment heavily is the L-type poly(lactic acid) material of amount 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 that adds is that 24 weight parts, nucleator are that 12 weight parts and compatibility agent are 2.4 weight parts.
The employed method of the present embodiment, step and each composition are all identical with embodiment one, 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 that adds is that 48 weight parts, nucleator are that 15 weight parts and compatibility agent are 4.8 weight parts.
The employed method of the present embodiment, step and each composition are all identical with embodiment one, and detailed process repeats no more.
Comparative example
Commercially available polylactic acid plastic through granulation (Natureworks LLC company makes, 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, the great Instr Ltd. that reaches makes) respectively embodiment one to five to be carried out 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 invention
Shown in table one and table two, the heat-drawn wire of comparative example is 55 ℃, the heat-drawn wire of embodiment one to five is followed successively by 126 ℃, 112 ℃, 105 ℃, 88 ℃ and 72 ℃, demonstrate each embodiment and all have better thermotolerance than comparative example, 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.
The shock-resistance test
Use shock-testing machine (GT-7045, high ferro Science and Technology Co., Ltd. makes) respectively embodiment one to five to be carried out 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.
Shown in table one and table two, the shock strength of comparative example is about 16J/m, the shock strength of embodiment one to five is sequentially 45 J/m, 216 J/m, 342 J/m, 398 J/m and 453J/m, the shock strength that demonstrates each embodiment all is higher than the impact strength of comparative example, and then each embodiment has better shock-resistance.
Test of elongation rate
(Insrton 3369 to use tensile testing machine, U.S. Instron company makes) respectively embodiment one to five is carried out 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, usually represent with per-cent, the ductility of the higher expression tested object of extension at break rate score is better, then has better processing characteristics, and test result as shown in Table 2.
Shown in table one and 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 the elongation at break that each embodiment elongation at break all is higher than comparative example, and then 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 better shock-resistance, and the scope that can use is more extensive.
In addition, for having better processibility in the finished product technique and convenient processing so that poly (lactic acid) composition in the advantage that has better thermotolerance, better shock-resistance and do not need secondary processing simultaneously, further is made as; And be made as have better product stability (as: work-ing life is longer) behind the finished product but and mass production, take aforementioned each embodiment as example, preferably, during take poly-lactic acid mixture 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 (10)
1. 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 consisted of of combination;
One compatibility agent, it contains superoxide, unsaturated reactive functional based compound or polynary ester type compound.
2. poly (lactic acid) composition as claimed in claim 1, the functional group who wherein is easy to form hydrogen bond in the 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, 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, nucleator content is 0.1 to 15 weight part.
6. poly (lactic acid) composition as claimed in claim 1 or 2,100 listed as parts by weight take poly-lactic acid mixture as content wherein, compatibility agent content is 0.1 to 5 weight part.
7. poly (lactic acid) composition as claimed in claim 1 or 2, wherein to have optical purity be L-type poly(lactic acid) more than 95 to the L-type poly(lactic acid) material of poly-lactic acid mixture, and D type poly(lactic acid) material to have optical purity be D type poly(lactic acid) more than 95%.
8. 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 L-type poly(lactic acid) of optical purity more than 98%, D type poly(lactic acid) material is to have the D type poly(lactic acid) of optical purity more than 98%.
9. poly (lactic acid) composition as claimed in claim 1 or 2, wherein the molecular weight of poly-lactic acid mixture is 80000 to 300000.
10. poly (lactic acid) composition as claimed in claim 1 or 2, wherein the molecular weight of the L-type poly(lactic acid) of poly-lactic acid mixture L-type poly(lactic acid) material is between 100000 to 300000, and 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.
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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 |
| 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 |
| 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 |
| TWI500681B (en) * | 2013-07-02 | 2015-09-21 | Supla Material Technology Co Ltd | Multi-layer film, method of producing the same and application 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 |
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| TWI504671B (en) * | 2014-01-06 | 2015-10-21 | Supla Material Technology Co Ltd | Polylactic acid composition and the molding product made therefrom |
| 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 |
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| CN109777053A (en) * | 2019-01-11 | 2019-05-21 | 海南绿袋子环保科技有限公司 | A kind of material of the rate of controllable biodegradable containing calcium lactate |
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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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| 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 |
| 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 |
| 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 |
| CN109777053A (en) * | 2019-01-11 | 2019-05-21 | 海南绿袋子环保科技有限公司 | A kind of material of the rate of controllable biodegradable containing calcium lactate |
| CN111005056A (en) * | 2019-12-24 | 2020-04-14 | 宁波革创新材料科技有限公司 | 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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