CN103772878A - Completely biodegradable material and preparation method thereof and cosmetics container - Google Patents
Completely biodegradable material and preparation method thereof and cosmetics container Download PDFInfo
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Abstract
The invention provides a completely biodegradable material, a preparation method thereof, and a cosmetics container. The completely biodegradable material comprises the following components in parts by weight: 100 parts of completely biodegradable polymer, 0.1 to 10 parts of nucleating agent, 0 to 0.2 part of radical initiator, 0 to 2 parts of maleic anhydride, and 0.5 to 10 parts of other auxiliaries. The completely biodegradable material has the characteristics of being outstanding in mechanical property, resistant to heat and low in cost. The completely biodegradable material can replace PE (Polyethylene), PP (Polypropylene), PVC (Polyvinyl Chloride) and the like to prepare various environment-friendly plastic products, and particularly has a wide market prospect in the high-end cosmetics containers (like eye shadow container, liquid foundation container, pressed powder container and lip gloss container), food packing, household appliances, auto and other fields.
Description
Technical field
The present invention relates to plastic material field, particularly relate to a kind of Biodegradable Materials and preparation method thereof and cosmetic packaging box.
Background technology
Take fossil resources such as oil as raw-material polypropylene (PP), polyethylene (PE), polystyrene (PS), polyvinyl chloride (PVC), synthetic glass and polycarbonate etc. be widely used in the fields such as food product pack, electrochemical goods, industrial equipment.After this class materials'use, be difficult to recycle, caused more serious " white pollution " problem at present, and this class resource of oil be non-renewable, a large amount of unreasonable uses has brought serious shortage of resources problem to the mankind.The raw-material recyclability of the appearance of biodegradable material, especially degradable material provides effective means for addressing this problem.Wherein, raw material sources, in the complete biodegradable resin of biomass, are more paid close attention to as poly(lactic acid) (PLA), poly-succinic fourth diester (PBS), polyhydroxyalkanoate (PHA) etc. are subject to people.
PLA is that a class is take renewable biological source as raw material, by biological fermentation and chemical synthesis process preparation, the bio-based degradation material of acquisition widespread use.PLA has good mechanical property, nontoxic, relative density is low, easily machine-shaping under normal temperature, can degrade by all biological, the good characteristics such as relative low price, have now become the kind that in bio-based plastics, rate of growth is the fastest, output is maximum, new product development enlivens the most, can be widely used in chemical industry, light industry, household electrical appliances, wrapping material etc.But compared with the conventional general-purpose plastics such as PE, PP, PS, pure PLA plastics exist that poor heat resistance (55～58 ℃ of heat-drawn wires), crystallization velocity are slow, the forming process cycle long, goods gloss and the bad shortcoming of the transparency, and this is restricted its range of application to a certain extent.
PBS resin is creamy white, odorless tasteless, is easily decomposed by the enzyme in natural multiple-microorganism or animal and plant body, is typical fully biodegradable polymer materials.Its synthetic source can be both petroleum resources, also can be fermented and be obtained by Biological resources.But PBS relative molecular mass is low, and melting index is high, and mechanical property is poor.
PHA compounds is directed to biological fermentation.In the time that the alkyl side chain in PHA is methyl, this material is called poly 3-hydroxy butyrate (PHB).In Ta Shi PHA family, exist the extensivelyst, find the earliest and the most deep one of research.PHB is hard and crisp thermoplastic polymer, and its mechanical property and PP and PS are suitable at normal temperatures.Compared with PP, PHB has similar ambient temperature mechanical properties, close melt temperature, lower solvent resistance and good ultraviolet aging resistance performance.But also there is obvious shortcoming: first its melt temperature (approximately 170～180 ℃) approaches with decomposition temperature (205 ℃), and machine-shaping can only be carried out in a narrow temperature range near 190 ℃.The more important thing is, its resistance to impact shock is low, and elongation at break is almost than low two orders of magnitude of PP.Therefore, PHB often will with other plastic blend modifications.
Summary of the invention
An object of the present invention is to provide a kind of Biodegradable Materials of good heat resistance.
Further object of the present invention is the preparation method that a kind of this material will be provided.
Another further object of the present invention is that a kind of cosmetic packaging box will be provided.
On the one hand, the invention provides a kind of Biodegradable Materials, the content of its component and component is:
Complete biodegradable polymkeric substance 100 weight parts;
Nucleator 0.1～10 weight part;
Radical initiator 0～0.2 weight part;
Maleic anhydride 0～2 weight part;
Other auxiliary agent 0.5～10 weight parts.
In one embodiment, described complete biodegradable polymkeric substance can comprise or be selected from poly(lactic acid), one or more in poly-succinic fourth diester and polyhydroxyalkanoate.Here " multiple " comprises poly(lactic acid), the blend of poly-succinic fourth diester and polyhydroxyalkanoate or the situation of multipolymer.
In one embodiment, described nucleator can comprise or be selected from one or more in hydrazide kind compound, compound with amide functional group, talcum powder, silicon-dioxide, attapulgite, hexagonal boron nitride, poly-fumaric acid fourth two fat, be preferably hydrazide kind compound, more preferably TMC-300 and the TMC-306 of the development of Shanxi chemical institute.
In one embodiment, the content of described nucleator can be 0.1～5 weight part, more preferably 0.1～2 weight part.
In one embodiment, described radical initiator can be organo-peroxide; Alternatively, described organo-peroxide be in benzoyl peroxide, benzoyl peroxide acetyl, ditertiary butyl peroxide or dicumyl peroxide one or more.
In one embodiment, described other auxiliary agents can comprise or be selected from oxidation inhibitor, thermo-stabilizer, softening agent, chainextender, one or more in lubricant; Wherein,
Described oxidation inhibitor can comprise or be selected from one or more in Hinered phenols antioxidant or phosphite ester kind antioxidant, and the content of described oxidation inhibitor is 0.5～1 weight part; And/or
Described softening agent can comprise or be selected from polyoxyethylene glycol, 1,2-cyclohexane dicarboxylic acid diisopropyl ester, sebacic acid two be one or more in ester, dibutyl maleinate, dioctyl terephthalate, citrate, aliphatic polyester or urethane just, are preferably citrate and aliphatic polyester; Alternatively, the content of described softening agent is 5～10 weight parts; And/or
Described lubricant can comprise or be selected from one or more in white oil, stearic acid or EBS.
In one embodiment, described poly(lactic acid) can be L-type poly(lactic acid), D type poly(lactic acid), LD mixed type poly(lactic acid), the multipolymer of poly(lactic acid) or the mixture of copolymer of poly lactic acid; Alternatively, the molecular weight of described poly(lactic acid) is 5～300,000.
On the other hand, the invention provides a kind of method of preparing aforesaid Biodegradable Materials, comprise the following steps:
A. described complete biodegradable polymkeric substance and nucleator are carried out respectively to drying treatment;
B. by dried complete biodegradable polymkeric substance and nucleator and all the other component melts blend, obtain blending ingredients;
C. by described blending ingredients by the mode moulding of injection, mold pressing or extrusion-blown modling;
Alternatively, in step a, the dry temperature of processing of described complete biodegradable polymkeric substance can be 60～100 ℃, and the time of drying treatment can be 8～12 hours; The temperature of the drying treatment of described nucleator can be 80～120 ℃, and the time of drying treatment can be 2～5 hours;
Further alternatively, in step b, adopt Banbury mixer or forcing machine to carry out melt blending to each component, the temperature of Banbury mixer or forcing machine can be set as 170～220 ℃, is preferably 180～210 ℃, and rotating speed can be 10～200rmp.
Another aspect, the invention provides a kind of cosmetic packaging box, and it is made up of aforesaid totally biodegradable material.
On the one hand, the invention provides a kind of cosmetic packaging box again, it is made up of aforesaid method.
Material of the present invention has completely biodegradable, material environmental protection, and fully biodegradable in physical environment and compost, is converted into CO
2and water, environmentally friendly.
The present invention is by carrying out the consumption of nucleator and functional agent preferably and limiting, crystallization velocity and the degree of crystallinity of complete biodegradable polymkeric substance are improved, the thermotolerance of material is significantly improved, heat-drawn wire can reach more than 80 ℃, and the high temperature that can bear seagoing transport is applicable to the occasion of seagoing transport or other experience high temperature.
In the present invention, the initiation reaction in polymer blending process of radical initiator and maleic anhydride forms graft copolymer, becomes expanding material, has improved the consistency between polymkeric substance, thereby has improved the performance of material.Meanwhile, goods crystallization refinement, guarantees that plastics have the good transparency.
Method of the present invention is simple to operate, be easy to control, and preparation cost reduces.
Because Biodegradable Materials of the present invention has good mechanical property, heat-resisting and feature cheaply.Adopt this material can replace PE, PP, PVC etc., make various environmental protection plastic products, especially at high-grade cosmetic packaging box (comprising eye shadow, foundation emulsion, muffin and lip gloss etc.), food product pack, household electrical appliances, there are wide market outlook in the fields such as automobile.
Embodiment
Below in conjunction with embodiment, content of the present invention is described in detail, those skilled in the art will understand above-mentioned and other objects, advantage and feature of the present invention more.
Biodegradable Materials of the present invention comprises: the complete biodegradable polymkeric substance of 100 weight parts; The nucleator of 0.1～10 weight part; The radical initiator of 0～0.2 weight part; The maleic anhydride of 0～2 weight part; And other auxiliary agents of 0.5～10 weight part.Wherein, complete biodegradable polymkeric substance comprises one or more in PLA, PBS, PHA.PLA is L-type poly(lactic acid) or D type poly(lactic acid) or the multipolymer of LD mixed type poly(lactic acid) or poly(lactic acid) or the mixture of copolymer of poly lactic acid.In the present invention, PLA can comprise PLB.The molecular weight of PLA can be between 5～300,000.PBS is take succinic acid and butyleneglycol as copolymerization units, by with the copolymerization of different copolymer diacid and/or different copolymer diol monomer, finally obtain random linear copolyester.Wherein, the molar percentage of copolymerization diacid and succinic acid can regulate in 0.01～99.99% scope; Wherein, the molar percentage of copolymerization glycol and butyleneglycol can regulate in 0.01～99.99% scope.
Owing to being that part is compatible between the polymkeric substance such as PLA, PBS, PHA, therefore, if by polymkeric substance and the direct melt blending of auxiliary agent, the material obtaining is the structure in being separated, and affects material property and transparency.Present inventor, by adding radical initiator and maleic anhydride to make the process situ increasing reaction of polymer melt blend, to reach the object that increases polymer phase capacitive and interfacial adhesion, thereby has improved the performance of material.Radical initiator can be benzoyl peroxide, ditertiary butyl peroxide, dicumyl peroxide or other organo-peroxides.
The present invention adds the main purpose of nucleator to be to provide the surface free energy of nucleus, reduction nucleation, under high speed of cooling, promotes crystallization.Nucleator can be selected from one or more in hydrazide kind compound, compound with amide functional group, talcum powder, silicon-dioxide, attapulgite, hexagonal boron nitride, poly-fumaric acid fourth two fat, preferably hydrazide kind compound is as nucleator, further preferably special nucleator TMC-300 and the TMC-306 of the development of Shanxi chemical institute.The present invention has stricter requirement to the consumption of nucleator.For the complete biodegradable polymkeric substance of 100 weight parts, if the nucleus quantity not sufficient that the adding proportion of nucleator, lower than 0.1 weight part, forms, so that promote the poor effect of crystallization; If the addition of nucleator is higher than 10 weight parts, prepared plastic, transparent will be poor.Therefore, the weight part of nucleator, 0.1～10 part of effect that can guarantee crystallization, can make again plastics maintain the good transparency.The weight part of nucleator is preferably 0.1～5 weight part, further can be preferably 0.1～2 weight part.
Other auxiliary agents can comprise oxidation inhibitor, thermo-stabilizer, softening agent, chainextender, one or more in lubricant.Wherein, softening agent can improve the migration performance of polymer chain, improves crystallization velocity by reducing chain migration energy, and in addition, softening agent is conducive to the moulding of plastics.Softening agent can be selected polyoxyethylene glycol, 1, and 2-cyclohexane dicarboxylic acid diisopropyl ester, sebacic acid two ester, dibutyl maleinate, dioctyl terephthalate, citrate, aliphatic polyester or urethane just, is preferably citrate and aliphatic polyester.The consumption of softening agent is 5～10 weight parts (with respect to complete biodegradable polymkeric substance 100 weight part meters) preferably.
The main purpose of adding oxidation inhibitor is to stop PLA that thermal destruction occurs in modifying process.Can select one or more in Hinered phenols antioxidant or phosphite ester kind antioxidant, the consumption of oxidation inhibitor is 0.1～0.5 weight part (with respect to complete biodegradable polymkeric substance 100 weight part meters) preferably.
Lubricant can be selected from one or more in white oil, stearic acid or EBS.The present invention, by adding crystallization nucleating agent and auxiliary agent, has obviously improved the degree of crystallinity of complete biodegradable plastics, crystallization rate and resistance toheat, and heat-drawn wire can reach more than 80 ℃, can bear the high temperature of seagoing transport.
The preparation method of Biodegradable Materials of the present invention can comprise the following steps:
A. complete biodegradable polymkeric substance and nucleator are carried out respectively to drying treatment;
B. by dried complete biodegradable polymkeric substance and nucleator and all the other component melts blend, obtain blending ingredients;
C. by blending ingredients by the mode moulding of injection, mold pressing or extrusion-blown modling.
In step a, the dry temperature of processing of complete biodegradable polymkeric substance can be 60～100 ℃, and the time of drying treatment can be 8～12 hours.The temperature of the drying treatment of nucleator can be 80～120 ℃, and the time of drying treatment can be 2～5 hours.In step b, can adopt Banbury mixer or forcing machine to carry out melt blending to each component, the Temperature Setting of forcing machine or banburying can be 170～220 ℃, is preferably 180～210 ℃, rotating speed can be 10～200rmp.In step c, can be by selecting suitable mould to be directly formed to cosmetic packaging box.
In order further to understand the present invention, below in conjunction with embodiment more specifically, the preferred embodiment of the invention is described, but the present invention is not limited to these embodiment.
Embodiment 1
Raw material and consumption are respectively: 50 grams of PLA(4032D, LD mixed type, Mn=127,000, NatureWorks), 0.25 gram of TMC-300 nucleator (Shanxi chemical institute), 2.5 grams of tributyl acetylcitrate softening agent, 0.25 gram of antioxidant 1010,1.25 grams of lubricant stearic acid aluminium.PLA is dried 12 hours in the vacuum drying oven of 80 ℃; TMC-300 nucleator is dried 2 hours in the vacuum drying oven of 80 ℃.Then after raw material being mixed, add melting mixing in Banbury mixer, the temperature of Banbury mixer three parts is respectively 190 ℃, and 195 ℃ and 190 ℃, rotating speed is 35rmp, and the banburying time is 10 minutes.Resin after melting mixing is hot-forming in mould, preheating 5 minutes; Upper and lower mould hot pressing temperature is 190 ℃, and pressure is 10MPa; Hot pressing time is 5 minutes.The performance of the material obtaining: tensile strength is 47MPa, heat-drawn wire is 80 ℃.
Embodiment 2
Raw material and consumption are respectively: 25 grams of PBS, 25 grams of PLA(4032D, LD mixed type, Mn=127,000, Nature Works), 0.25 gram of TMC-306 nucleator (Shanxi chemical institute), 0.025 gram of dicumyl peroxide, 0.25 gram of maleic anhydride, 2.5 grams of tributyl acetylcitrate softening agent, 0.25 gram of antioxidant 1010,1.25 grams of lubricant stearic acid aluminium.PBS and PLA are dried 12 hours in the vacuum drying oven of 80 ℃; TMC-306 nucleator is dried 2 hours in the vacuum drying oven of 80 ℃.Then after raw material being mixed, add melting mixing in Banbury mixer, the temperature of Banbury mixer three parts is respectively 190 ℃, and 195 ℃ and 190 ℃, rotating speed is 35rmp, and the banburying time is 10 minutes.Resin after melting mixing is hot-forming in mould, preheating 5 minutes; Upper and lower mould hot pressing temperature is 190 ℃, and pressure is 10Mpa; Hot pressing time is 5 minutes.The performance of the material obtaining: tensile strength 41MPa, 95 ℃ of heat-drawn wires.
Embodiment 3
Raw material and consumption are respectively: 15 grams of PHB, 15 grams of PBS, 25 grams of PLA(4032D, LD mixed type, Mn=127,000, Nature Works), 0.025 gram of dicumyl peroxide, 0.25 gram of maleic anhydride, 0.25 gram of TMC-306 nucleator (Shanxi chemical institute), 2.5 grams of tributyl acetylcitrate softening agent, 0.25 gram of antioxidant 1010,1.25 grams of lubricant stearic acid aluminium.PHB, PBS and PLA are dried 12 hours in the vacuum drying oven of 80 ℃; TMC-306 nucleator is dried 2 hours in the vacuum drying oven of 80 ℃.After raw material is mixed, add melting mixing in Banbury mixer, the temperature of Banbury mixer three parts is respectively 190 ℃, and 195 ℃ and 190 ℃, rotating speed is 35rmp, and the banburying time is 10 minutes.Resin after melting mixing is hot-forming in mould, preheating 5 minutes.Upper and lower mould hot pressing temperature is 190 ℃, and pressure is 10MPa.Hot pressing time is 5 minutes.After hot pressing, anneal 30 minutes at 110 ℃.The performance of the material obtaining: tensile strength 38MPa, 98 ℃ of heat-drawn wires.
Embodiment 4
Raw material and consumption are respectively: 15 grams of PHB, 15 grams of PBS, 15 grams of PLA(4032D, LD mixed type, Mn=127,000, Nature Works), 0.025 gram of dicumyl peroxide, 0.25 gram of maleic anhydride, 0.25 gram of TMC-306 nucleator (Shanxi chemical institute), 0.1 gram of attapulgite, 2.5 grams of tributyl acetylcitrate softening agent, 0.25 gram of antioxidant 1010,1.25 grams of lubricant stearic acid aluminium.PHB, PBS and PLA are dried 12 hours in the vacuum drying oven of 80 ℃; TMC-306 nucleator is dried 2 hours in the vacuum drying oven of 80 ℃.After raw material is mixed, add melting mixing in Banbury mixer, the temperature of Banbury mixer three parts is respectively 190 ℃, and 195 ℃ and 190 ℃, rotating speed is 35rmp, and the banburying time is 10 minutes.Resin after melting mixing is put into mould compression molding, preheating 5 minutes.Upper and lower mould hot pressing temperature: injection is 190 ℃, pressure is 10MPa; Hot pressing time is 5 minutes.The performance of the material obtaining: tensile strength 43MPa, 105 ℃ of heat-drawn wires.
Embodiment 5
Raw material and consumption are respectively: 50 grams of PLA(4032D, LD mixed type, Mn=127,000, NatureWorks), 0.25 gram of antioxidant 1010,1.25 grams of lubricant stearic acid aluminium, 0.1 gram of nucleator hexagonal boron nitride, 0.1 gram of nucleator talcum powder.PLA is dried 12 hours in the vacuum drying oven of 80 ℃.After raw material is mixed, add melting mixing in Banbury mixer, the temperature of Banbury mixer three parts is respectively 190 ℃, and 195 ℃ and 190 ℃, rotating speed is 35rmp, and the banburying time is 10 minutes.Resin after melting mixing is hot-forming in mould, preheating 5 minutes.Upper and lower mould hot pressing temperature is 190 ℃, and pressure is 10MPa, and hot pressing time is 5 minutes.The performance of the material obtaining: tensile strength 45MPa, 79 ℃ of heat-drawn wires.
Embodiment 6
Raw material and consumption are respectively: 15 grams of PHB, 15 grams of PBS, 15 grams of PLA(4032D, LD mixed type, Mn=127,000, Nature Works), 2.5 grams of tributyl acetylcitrate softening agent, 0.25 gram of antioxidant 1010,1.25 grams of lubricant stearic acid aluminium, 0.5 gram of poly-fumaric acid fourth two fat of nucleator.PHB, PBS and PLA are dried 12 hours in the vacuum drying oven of 80 ℃; Poly-fumaric acid fourth two fat of nucleator are dried 2 hours in the vacuum drying oven of 80 ℃.After raw material is mixed, add melting mixing in Banbury mixer, the temperature of Banbury mixer three parts is respectively 190 ℃, and 195 ℃ and 190 ℃, rotating speed is 35rmp, and the banburying time is 10 minutes.Resin after melting mixing is hot-forming in mould, preheating 5 minutes.Upper and lower mould hot pressing temperature is 190 ℃, and pressure is 10Mpa, and hot pressing time is 5 minutes.Hot pressing after annealing 30 minutes, 110 ℃ of annealing temperatures.The performance of the material obtaining: tensile strength 38MPa, 108 ℃ of heat-drawn wires.
Embodiment 7
Raw material and consumption are respectively: 15 grams of PHB, 15 grams of PBS, 15 grams of PLA(4032D, LD mixed type, Mn=127,000, Nature Works), 2.5 grams of tributyl acetylcitrate softening agent, 0.25 gram of antioxidant 1010,1.25 grams of lubricant stearic acid aluminium, 0.5 gram of poly-fumaric acid fourth two fat of nucleator, 0.1 gram of nucleator attapulgite.PHB, PBS and PLA are dried 12 hours in the vacuum drying oven of 80 ℃; Poly-fumaric acid fourth two fat of nucleator and attapulgite are dried 2 hours in the vacuum drying oven of 80 ℃.After raw material is mixed, add melting mixing in forcing machine, barrel zone temperature is set 190～200 ℃, and extruded material is through injection molding.The performance of the material obtaining: tensile strength 38MPa, 110 ℃ of heat-drawn wires.
Embodiment 8
Raw material and consumption are respectively: 20 grams of PHB, 20 grams of poly-succinic hexanodioic acid fourth diester (hexanodioic acid content 5%), 10 grams of PLA(4032D, LD mixed type, Mn=127,000, Nature Works), 2.5 grams of tributyl acetylcitrate softening agent, 0.25 gram of antioxidant 1010,0.5 gram of epoxies chainextender.PHB, poly-succinic hexanodioic acid fourth diester and PLA are dried 12 hours in the vacuum drying oven of 80 ℃, then mix with softening agent, chainextender, oxidation inhibitor, extrude tackify, increase-volume through twin screw extruder, the performance of the material obtaining: tensile strength 40MPa, 92 ℃ of heat-drawn wires.
Embodiment 9
Raw material and consumption are respectively: 50 grams of PLA(4032D, LD mixed type, Mn=127,000, NatureWorks), 2.5 grams of TMC-306 nucleators (Shanxi chemical institute), 2.5 grams of tributyl acetylcitrate softening agent, 0.25 gram of antioxidant 1010,1.25 grams of lubricant stearic acid aluminium.PLA is dried 12 hours in the vacuum drying oven of 80 ℃; TMC-306 nucleator is dried 2 hours in the vacuum drying oven of 80 ℃.Then after raw material being mixed, add melting mixing in Banbury mixer, the temperature of Banbury mixer three parts is respectively 190 ℃, and 195 ℃ and 190 ℃, rotating speed is 35rmp, and the banburying time is 10 minutes.Resin after melting mixing is hot-forming in mould, preheating 5 minutes; Upper and lower mould hot pressing temperature is 190 ℃, and pressure is 10Mpa; Hot pressing time is 5 minutes.The performance of the material obtaining: tensile strength 46MPa, 85 ℃ of heat-drawn wires.
Embodiment 10
Raw material and consumption are respectively: 25 grams of PBS, 25 grams of PLA(4032D, LD mixed type, Mn=127,000, Nature Works), 0.25 gram of TMC-306 nucleator (Shanxi chemical institute), 2.5 grams of tributyl acetylcitrate softening agent, 0.25 gram of antioxidant 1010,1.25 grams of lubricant stearic acid aluminium.PBS and PLA are dried 12 hours in the vacuum drying oven of 80 ℃; TMC-306 nucleator is dried 2 hours in the vacuum drying oven of 80 ℃.After raw material is mixed, add melting mixing in Banbury mixer, the temperature of Banbury mixer three parts is respectively 190 ℃, and 195 ℃ and 190 ℃, rotating speed is 35rmp, and the banburying time is 10 minutes.Resin after melting mixing is hot-forming in mould, preheating 5 minutes.Upper and lower mould hot pressing temperature is 190 ℃, and pressure is 10MPa.Hot pressing time is 5 minutes.After hot pressing, anneal 30 minutes at 110 ℃.The performance of the material obtaining: tensile strength 40MPa, 90 ℃ of heat-drawn wires.
Embodiment 11
Raw material and consumption are respectively: 50 grams of PLA(4032D, LD mixed type, Mn=127,000, NatureWorks), 2.5 grams of tributyl acetylcitrate softening agent, 0.25 gram of antioxidant 1010,1.25 grams of lubricant stearic acid aluminium.PLA is dried 12 hours in the vacuum drying oven of 80 ℃.After raw material is mixed, add melting mixing in Banbury mixer, the temperature of Banbury mixer three parts is respectively 190 ℃, and 195 ℃ and 190 ℃, rotating speed is 35rmp, and the banburying time is 10 minutes.Resin after melting mixing is hot-forming in mould, preheating 5 minutes.Upper and lower mould hot pressing temperature is 190 ℃, and pressure is 10MPa.Hot pressing time is 5 minutes.After hot pressing, anneal 30 minutes at 110 ℃.The performance of the material obtaining: tensile strength 46MPa, 60 ℃ of heat-drawn wires.
Embodiment 12
Raw material and consumption are respectively: 50 grams of PLA(4032D, LD mixed type, Mn=127,000, NatureWorks), 0.25g calcium carbonate, 2.5 grams of tributyl acetylcitrate softening agent, 0.25 gram of antioxidant 1010,1.25 grams of lubricant stearic acid aluminium.PLA is dried 12 hours in the vacuum drying oven of 80 ℃.After raw material is mixed, add melting mixing in Banbury mixer, the temperature of Banbury mixer three parts is respectively 190 ℃, and 195 ℃ and 190 ℃, rotating speed is 35rmp, and the banburying time is 10 minutes.Resin after melting mixing is hot-forming in mould, preheating 5 minutes.Upper and lower mould hot pressing temperature is 190 ℃, and pressure is 10MPa.Hot pressing time is 5 minutes.After hot pressing, anneal 30 minutes at 110 ℃.The performance of the material obtaining: tensile strength 47MPa, 62 ℃ of heat-drawn wires.
As can be seen from the above embodiments, the heat-drawn wire of Biodegradable Materials of the present invention is higher, and has good mechanical property.Comparative example 2 and embodiment 10, can find out and add after maleic anhydride and radical initiator (dicumyl peroxide), materials hot deformation temperature obviously increases.Comparative example 1 and embodiment 11 are known, and the heat-drawn wire of adding the material of nucleator significantly improves.
So far, those skilled in the art will recognize that, illustrate and described of the present invention multiple exemplary embodiment although detailed herein, but, without departing from the spirit and scope of the present invention, still can directly determine or derive many other modification or the modification that meet the principle of the invention according to content disclosed by the invention.Therefore, scope of the present invention should be understood and regard as and cover all these other modification or modifications.
Claims (10)
1. a Biodegradable Materials, the content of its component and component is:
Complete biodegradable polymkeric substance 100 weight parts;
Nucleator 0.1～10 weight part;
Radical initiator 0～0.2 weight part;
Maleic anhydride 0～2 weight part;
Other auxiliary agent 0.5～10 weight parts.
2. Biodegradable Materials according to claim 1, is characterized in that, described complete biodegradable polymkeric substance comprises poly(lactic acid), one or more in poly-succinic fourth diester and polyhydroxyalkanoate.
3. Biodegradable Materials according to claim 1 and 2, it is characterized in that, described nucleator comprises one or more in hydrazide kind compound, compound with amide functional group, talcum powder, silicon-dioxide, attapulgite, hexagonal boron nitride, poly-fumaric acid fourth two fat, be preferably hydrazide kind compound, more preferably TMC-300 and the TMC-306 of the development of Shanxi chemical institute.
4. according to the Biodegradable Materials described in any one in claim 1～3, it is characterized in that, the content of described nucleator is 0.1～5 weight part, more preferably 0.1～2 weight part.
5. according to the Biodegradable Materials described in any one in claim 1～4, it is characterized in that, described radical initiator is organo-peroxide; Alternatively, described organo-peroxide be in benzoyl peroxide, benzoyl peroxide acetyl, ditertiary butyl peroxide or dicumyl peroxide one or more.
6. according to the Biodegradable Materials described in any one in claim 1～5, it is characterized in that,
Described other auxiliary agents comprise oxidation inhibitor, thermo-stabilizer, softening agent, chainextender, one or more in lubricant; Wherein,
Described oxidation inhibitor comprises one or more in Hinered phenols antioxidant or phosphite ester kind antioxidant, and the content of described oxidation inhibitor is 0.5～1 weight part; And/or
Described softening agent comprises polyoxyethylene glycol, 1,2-cyclohexane dicarboxylic acid diisopropyl ester, sebacic acid two be one or more in ester, dibutyl maleinate, dioctyl terephthalate, citrate, aliphatic polyester or urethane just, are preferably citrate and aliphatic polyester; Alternatively, the content of described softening agent is 5～10 weight parts; And/or
Described lubricant comprises one or more in white oil, stearic acid or EBS.
7. Biodegradable Materials according to claim 2, is characterized in that, described poly(lactic acid) is L-type poly(lactic acid), D type poly(lactic acid), LD mixed type poly(lactic acid), the multipolymer of poly(lactic acid) or the mixture of copolymer of poly lactic acid; Alternatively, the molecular weight of described poly(lactic acid) is 5～300,000.
8. a method of preparing the Biodegradable Materials as described in any one in claim 1～7, comprises the following steps:
A. described complete biodegradable polymkeric substance and nucleator are carried out respectively to drying treatment;
B. by dried complete biodegradable polymkeric substance and nucleator and all the other component melts blend, obtain blending ingredients;
C. by described blending ingredients by the mode moulding of injection, mold pressing or extrusion-blown modling;
Alternatively, in step a, the dry temperature of processing of described complete biodegradable polymkeric substance is 60～100 ℃, and the time of drying treatment is 8～12 hours; The temperature of the drying treatment of described nucleator is 80～120 ℃, and the time of drying treatment is 2～5 hours;
Further alternatively, in step b, adopt Banbury mixer or forcing machine to carry out melt blending to each component, the Temperature Setting of Banbury mixer or forcing machine is 170～220 ℃, is preferably 180～210 ℃, and rotating speed is 10～200rmp.
9. a cosmetic packaging box, it is made up of the totally biodegradable material described in any one in claim 1-7.
10. a cosmetic packaging box, it is made up of method claimed in claim 8.
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| CN104448737A (en) * | 2014-10-17 | 2015-03-25 | 济南大学 | Carboxylic acid rare earth cross-linked PLA biodegradable plastic and preparation thereof |
| CN104530669A (en) * | 2014-12-18 | 2015-04-22 | 陈梓煜 | Modified polylactic material for 3D (three dimensional) printing and preparation method thereof |
| CN104830035A (en) * | 2015-05-18 | 2015-08-12 | 夏世勇 | Biodegradable composite with barrier property and preparation method and applications thereof |
| CN105255122A (en) * | 2015-10-19 | 2016-01-20 | 福建师范大学 | PBS (poly butylenes succinate) 3D printing wire and preparation method thereof |
| CN107150398A (en) * | 2017-04-28 | 2017-09-12 | 无锡市锡佳印刷包装有限公司 | Environment-friendly type commodity packaging paper and preparation method thereof |
| CN107698714A (en) * | 2017-11-01 | 2018-02-16 | 宁波家联科技股份有限公司 | A kind of itaconic anhydride grafted polylactic acid copolymer and its preparation method and application |
| CN107759990A (en) * | 2017-11-01 | 2018-03-06 | 宁波家联科技股份有限公司 | A kind of full biological poly lactic acid composite and preparation method thereof |
| CN107805377A (en) * | 2017-11-17 | 2018-03-16 | 梁乔保 | A kind of antibacteria degradation packing box and preparation method thereof |
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| CN108338482A (en) * | 2018-02-09 | 2018-07-31 | 浙江正庄实业有限公司 | Environmentally friendly high rigidity antistatic single tube eyebrow pencil and preparation method thereof |
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| CN108976729A (en) * | 2018-08-16 | 2018-12-11 | 孙世华 | A kind of preparation method of cosmetics plastic package material |
| CN110194306A (en) * | 2019-06-06 | 2019-09-03 | 浙江正庄实业有限公司 | Antibacterial degradable cream bottle and its material preparation method |
| CN110577751A (en) * | 2019-07-18 | 2019-12-17 | 广州市明顿包装制品有限公司 | ingredient formula process of cosmetic packaging material |
| CN112341650A (en) * | 2020-11-03 | 2021-02-09 | 漳州新迪新材料科技有限公司 | Compostable fully-degradable film and preparation method thereof |
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| CN104530669A (en) * | 2014-12-18 | 2015-04-22 | 陈梓煜 | Modified polylactic material for 3D (three dimensional) printing and preparation method thereof |
| CN104830035A (en) * | 2015-05-18 | 2015-08-12 | 夏世勇 | Biodegradable composite with barrier property and preparation method and applications thereof |
| CN105255122A (en) * | 2015-10-19 | 2016-01-20 | 福建师范大学 | PBS (poly butylenes succinate) 3D printing wire and preparation method thereof |
| CN107150398A (en) * | 2017-04-28 | 2017-09-12 | 无锡市锡佳印刷包装有限公司 | Environment-friendly type commodity packaging paper and preparation method thereof |
| CN107698714B (en) * | 2017-11-01 | 2020-10-16 | 宁波家联科技股份有限公司 | Itaconic anhydride grafted polylactic acid copolymer and preparation method and application thereof |
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| CN107759990B (en) * | 2017-11-01 | 2020-10-16 | 宁波家联科技股份有限公司 | Full-bio-based polylactic acid composite material and preparation method thereof |
| CN107805377A (en) * | 2017-11-17 | 2018-03-16 | 梁乔保 | A kind of antibacteria degradation packing box and preparation method thereof |
| CN108456408A (en) * | 2018-02-09 | 2018-08-28 | 浙江正庄实业有限公司 | Environmentally friendly high rigidity antistatic lipstick tube and preparation method thereof |
| CN108338482A (en) * | 2018-02-09 | 2018-07-31 | 浙江正庄实业有限公司 | Environmentally friendly high rigidity antistatic single tube eyebrow pencil and preparation method thereof |
| CN108264745A (en) * | 2018-02-09 | 2018-07-10 | 浙江正庄实业有限公司 | Environmentally friendly high heat proof material single tube lip gloss of high rigidity and preparation method thereof |
| CN108338482B (en) * | 2018-02-09 | 2023-09-01 | 浙江正庄实业有限公司 | Environment-friendly high-rigidity antistatic single-tube eyebrow pencil and preparation method thereof |
| CN108456408B (en) * | 2018-02-09 | 2023-10-13 | 浙江正庄实业有限公司 | Environment-friendly high-rigidity antistatic lipstick tube and preparation method thereof |
| CN108976729A (en) * | 2018-08-16 | 2018-12-11 | 孙世华 | A kind of preparation method of cosmetics plastic package material |
| CN110194306A (en) * | 2019-06-06 | 2019-09-03 | 浙江正庄实业有限公司 | Antibacterial degradable cream bottle and its material preparation method |
| CN110577751A (en) * | 2019-07-18 | 2019-12-17 | 广州市明顿包装制品有限公司 | ingredient formula process of cosmetic packaging material |
| CN112341650A (en) * | 2020-11-03 | 2021-02-09 | 漳州新迪新材料科技有限公司 | Compostable fully-degradable film and preparation method thereof |
| CN112341649A (en) * | 2020-11-03 | 2021-02-09 | 漳州新迪新材料科技有限公司 | Fully biodegradable paper packaging waterproof film and preparation method thereof |
| CN113105731A (en) * | 2021-04-15 | 2021-07-13 | 山东道恩高分子材料股份有限公司 | Biodegradable foamed sheet |
| CN113684557A (en) * | 2021-08-26 | 2021-11-23 | 海南赛诺实业有限公司 | Polylactic acid melt-spraying material and preparation method and application thereof |
| CN115627559A (en) * | 2022-11-18 | 2023-01-20 | 北京微构工场生物技术有限公司 | Degradable filament and special material thereof |
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