CN103772878B - Biodegradable Materials and preparation method thereof and cosmetic packaging box - Google Patents
Biodegradable Materials and preparation method thereof and cosmetic packaging box Download PDFInfo
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Abstract
The invention provides a kind of Biodegradable Materials and preparation method thereof and cosmetic packaging box.A kind of Biodegradable Materials, the content of its component and component is: complete biodegradable polymer 100 weight portion；Nucleator 0.1～10 weight portion；Radical initiator 0～0.2 weight portion；Maleic anhydride 0～2 weight portion；Other auxiliary agent 0.5～10 weight portions.Owing to the Biodegradable Materials of the present invention has excellent mechanical property, the heat-resisting and feature of low cost.Using this material to can substitute for PE, PP, PVC etc., make various environmental protection plastic products, especially at high-grade cosmetic packaging box (including eye shadow, foundation emulsion, muffin and lip gloss etc.), packaging for foodstuff, household electrical appliances, there is wide market prospect in the field such as automobile.
Description
Technical field
The present invention relates to plastic material field, particularly relate to a kind of Biodegradable Materials and preparation side thereof
Method and cosmetic packaging box.
Background technology
It is raw-material polypropylene (PP), polyethylene (PE), polystyrene with fossil resources such as oil
(PS), polrvinyl chloride (PVC), lucite and Merlon etc. are widely used in packaging for foodstuff, electricity
Change the field such as goods, industry equipment.It is difficult to after this kind of materials'use recycle, causes the tightest
" white pollution " problem of weight, and this class resource of oil is non-renewable, and substantial amounts of unreasonable use is given
The mankind bring serious shortage of resources problem.The appearance of biodegradation material, especially degradable material former
The recyclability of material provides effective means for solving this problem.Wherein, raw material sources are in biomass
Complete biodegradable resin, such as polylactic acid (PLA), poly-succinic fourth diester (PBS), poly-hydroxyl fat
Fat acid esters (PHA) etc. is more paid close attention to by people.
PLA be a class with renewable biological source as raw material, by biofermentation and chemical synthesis process system
Standby, it is thus achieved that wide variety of bio-based degradation material.PLA has good mechanical property, nontoxic, the closeest
Spend low, under room temperature, be easily worked molding, can all biological degraded, the good characteristic such as relative low price, existing
Become the kind that growth rate in bio-based plastics is the fastest, yield is maximum, new product development enlivens the most,
Can be widely applied to chemical industry, light industry, household electrical appliances, packaging material etc..But it is logical with conventional PE, PP, PS etc.
Comparing with plastics, there is poor heat resistance (heat distortion temperature 55～58 DEG C), crystallization rate relatively in pure PLA plastics
Slowly, processing and forming cycle length, goods gloss and the bad shortcoming of the transparency, this makes its range of application necessarily
It is restricted in degree.
PBS resin is creamy white, odorless tasteless, easily by the multiple-microorganism of nature or animal and plant body
Enzyme decomposes, and is typical fully biodegradable polymeric material.Its synthesis source both can be petroleum resources,
Can also be obtained by living resources fermentation.But PBS relative molecular mass is low, melt index is high, mechanical property
Can be poor.
PHA compounds is directed to biofermentation.When the alkyl side chain in PHA is methyl,
This material is referred to as poly 3-hydroxy butyrate (PHB).It is PHA family exists the widest, find the earliest and
Study the most deep one.PHB is hard and crisp thermoplastic polymer, at normal temperatures its mechanical property with
PP and PS is suitable.Compared with PP, PHB have similar ambient temperature mechanical properties, close melt temperature,
Relatively low solvent resistance and preferable anti-ultraviolet ageing performance.But there is also obvious shortcoming: first it melts
Melting temperature (about 170～180 DEG C) close with decomposition temperature (205 DEG C), machine-shaping can only be attached at 190 DEG C
Carry out in a nearly narrow temperature range.The more important thing is, its impact strength is low, and elongation at break is several
Low two orders of magnitude than PP.Therefore, PHB is often modified with other plastic blends.
Summary of the invention
It is an object of the present invention to provide a kind of heat-resist Biodegradable Materials.
The present invention one further objective is that the preparation method providing this material a kind of.
The present invention another further objective is that a kind of cosmetic packaging box to be provided.
On the one hand, the invention provides a kind of Biodegradable Materials, the content of its component and component is:
Complete biodegradable polymer 100 weight portion；
Nucleator 0.1～10 weight portion；
Radical initiator 0～0.2 weight portion；
Maleic anhydride 0～2 weight portion；
Other auxiliary agent 0.5～10 weight portions.
In one embodiment, described complete biodegradable polymer can include or selected from polylactic acid, poly-
One or more in succinic acid fourth diester and polyhydroxyalkanoate.Here " multiple " includes poly-breast
Acid, poly-succinic fourth diester and the blend of polyhydroxyalkanoate or the situation of copolymer.
In one embodiment, described nucleator can include or selected from hydrazide kind compound, with amide
The compound of functional group, Pulvis Talci, silicon dioxide, attapulgite, hexagonal boron nitride, poly-fumaric acid fourth two
One or more in fat, preferably hydrazide kind compound, more preferably Shanxi chemical institute is developed
TMC-300 and TMC-306.
In one embodiment, the content of described nucleator can be 0.1～5 weight portions, further preferably
It is 0.1～2 weight portions.
In one embodiment, described radical initiator can be organic peroxide；Alternatively, institute
Stating organic peroxide is benzoyl peroxide, benzoyl peroxide acetyl, di-tert-butyl peroxide or peroxidating
In diisopropylbenzene (DIPB) one or more.
In one embodiment, other auxiliary agents described can include or selected from antioxidant, heat stabilizer, increase
Mould agent, chain extender, one or more in lubricant；Wherein,
Described antioxidant can include or be selected from Hinered phenols antioxidant or phosphite ester kind antioxidant
Planting or multiple, the content of described antioxidant is 0.5～1 weight portion；And/or
Described plasticizer can include or selected from Polyethylene Glycol, 1,2-cyclohexane dicarboxylic acid diisopropyl ester, the last of the ten Heavenly stems two
Acid two ester the most, dibutyl maleate, DOTP, citrate, aliphatic polyester or poly-
One or more in urethane, preferably citrate and aliphatic polyester；Alternatively, described plasticizer
Content is 5～10 weight portions；And/or
Described lubricant can include or selected from one or more in white oil, stearic acid or EBS.
In one embodiment, described polylactic acid can be L-type polylactic acid, D type polylactic acid, LD mix
Mould assembly polylactic acid, the copolymer of polylactic acid or the mixture of copolymer of poly lactic acid；Alternatively, described poly-breast
The molecular weight of acid is 5～300,000.
On the other hand, the invention provides a kind of method preparing aforesaid Biodegradable Materials, including
Following steps:
A. described complete biodegradable polymer and nucleator are dried process respectively；
B. dried complete biodegradable polymer and nucleator are blended with remaining component melts, are mixed
Charge-coupled point；
C. by the molding by the way of injection, mold pressing or extrusion-blown modling of described blending ingredients；
Alternatively, in step a, the temperature of described complete biodegradable polymer dried can be
60～100 DEG C, the time of dried can be 8～12 hours；The temperature of the dried of described nucleator
Can be 80～120 DEG C, the time of dried can be 2～5 hours；
Still optionally further, in stepb, use banbury or extruder that each component is carried out melt blending,
The temperature of banbury or extruder can be set as 170～220 DEG C, and preferably 180～210 DEG C, rotating speed is permissible
It is 10～200rmp.
Another aspect, the invention provides a kind of cosmetic packaging box, and it is by aforesaid totally biodegradable
Material is made.
Another further aspect, the invention provides a kind of cosmetic packaging box, and it is made up of aforesaid method.
The material of the present invention has completely biodegradable, and material environmental protection, in natural environment and compost
Fully biodegradable, is converted into CO2And water, environmentally friendly.
The present invention is by carrying out preferably the consumption of nucleator and function additive and limiting so that the most biological fall
The crystallization rate of depolymerization compound and degree of crystallinity improve, and the thermostability of material is significantly improved, heat distortion temperature
Up to more than 80 DEG C, it is possible to the high temperature bearing transport by sea is suitable for transport by sea or the field of other experience high temperature
Close.
In the present invention, the initiation reaction in polymer Blending Processes of radical initiator and maleic anhydride is formed
Graft copolymer, becomes bulking agent, improves the compatibility between polymer, thus improves the performance of material.
Meanwhile, goods crystallization refinement, it is ensured that plastics have the preferable transparency.
The method of the present invention is simple to operate, it is easy to control, and preparation cost reduces.
Owing to the Biodegradable Materials of the present invention has excellent mechanical property, the heat-resisting and spy of low cost
Point.Use this material to can substitute for PE, PP, PVC etc., make various environmental protection plastic products, especially exist
High-grade cosmetic packaging box (including eye shadow, foundation emulsion, muffin and lip gloss etc.), packaging for foodstuff,
Household electrical appliances, there is wide market prospect in the field such as automobile.
Detailed description of the invention
Being described in detail present disclosure below in conjunction with embodiment, those skilled in the art will be more
Understand above-mentioned and other purposes, advantage and the feature of the present invention.
The Biodegradable Materials of the present invention includes: the complete biodegradable polymer of 100 weight portions；
The nucleator of 0.1～10 weight portions；The radical initiator of 0～0.2 weight portion；The maleic anhydride of 0～2 weight portions；
And 0.5～10 other auxiliary agents of weight portion.Wherein, complete biodegradable polymer comprise PLA, PBS,
One or more in PHA.PLA is L-type polylactic acid or D type polylactic acid or LD mixed type is gathered
Lactic acid or the copolymer of polylactic acid or the mixture of copolymer of poly lactic acid.In the present invention, PLA is permissible
Comprise PLB.The molecular weight of PLA can be between 5～300,000.PBS be with succinic acid and butanediol be common
Poly-unit, by with different copolymer diacid and/or the copolymerization of different copolymer diol monomer, finally give without gage line
Property copolyesters.Wherein, copolymerization diacid can be in the range of 0.01～99.99% with the molar percentage of succinic acid
Regulation；Wherein, copolymer glycols can regulate with the molar percentage of butanediol in the range of 0.01～99.99%.
Owing to being partially compatible between the polymer such as PLA, PBS, PHA, therefore, if will polymerization
Thing and the direct melt blending of auxiliary agent, the material obtained is in the structure being separated, and affects material property with saturating
Lightness.Present inventor makes polymer melt be blended by adding radical initiator and maleic anhydride
During in situ reactive compatibilization, to reach to increase polymer compatibility and the purpose of interfacial adhesion, thus carry
The high performance of material.Radical initiator can be benzoyl peroxide, di-tert-butyl peroxide, mistake
Oxidation diisopropylbenzene (DIPB) or other organic peroxides.
The present invention adds the main purpose of nucleator and is to provide nucleus, reduces the surface free energy of nucleation, at height
Crystallization is promoted under rate of cooling.Nucleator can be selected from hydrazide kind compound, chemical combination with amide functional group
One in thing, Pulvis Talci, silicon dioxide, attapulgite, hexagonal boron nitride, poly-fumaric acid fourth two fat or
Multiple, preferably hydrazide kind compound is as nucleator, and it is special that further preferred Shanxi chemical institute is developed
Nucleator TMC-300 and TMC-306.The present invention has relatively strict requirements to the consumption of nucleator.For
The complete biodegradable polymer of 100 weight portions, if the adding proportion of nucleator is less than 0.1 weight portion, institute
The nucleus amount formed is not enough, so that promoting the poor effect of crystallization；If the addition of nucleator is higher than 10
Weight portion, obtained plastic, transparent will be poor.Therefore, the weight portion of nucleator is 0.1～10
Part both can guarantee that the effect of crystallization, and plastics can be made again to maintain the preferably transparency.The weight portion of nucleator is excellent
Elect 0.1～5 weight portions as, 0.1～2 weight portions can be preferably further.
Other auxiliary agents can include antioxidant, heat stabilizer, plasticizer, chain extender, the one in lubricant
Or it is multiple.Wherein, plasticizer can improve the migration performance of polymer chain, improves by reducing chain migration energy
Crystallization rate, additionally, plasticizer is conducive to the molding of plastics.Plasticizer can be selected for Polyethylene Glycol, 1,2-ring
Hexane dicarboxylic acid's diisopropyl ester, decanedioic acid two ester the most, dibutyl maleate, DOTP,
Citrate, aliphatic polyester or polyurethane, preferably citrate and aliphatic polyester.The use of plasticizer
Amount preferably 5～10 weight portions (based on complete biodegradable polymer 100 weight portion).
The main purpose adding antioxidant is to stop PLA that thermal degradation occurs in modifying process.Can be selected for being subject to
One or more in resistance phenolic antioxidant or phosphite ester kind antioxidant, the consumption of antioxidant preferably 0.1～0.5
Weight portion (based on complete biodegradable polymer 100 weight portion).
Lubricant can be selected from one or more in white oil, stearic acid or EBS.The present invention is by adding
Crystallization nucleating agent and auxiliary agent, hence it is evident that improve the degree of crystallinity of complete biodegradable plastics, crystalline rate and resistance to
Hot property, heat distortion temperature is up to more than 80 DEG C, it is possible to bear the high temperature of transport by sea.
The preparation method of the Biodegradable Materials of the present invention may comprise steps of:
A. complete biodegradable polymer and nucleator are dried process respectively；
B. dried complete biodegradable polymer and nucleator are blended with remaining component melts, are mixed
Charge-coupled point；
C. by blending ingredients molding by the way of injection, mold pressing or extrusion-blown modling.
In step a, the temperature of complete biodegradable polymer dried can be 60～100 DEG C, is dried
The time processed can be 8～12 hours.The temperature of the dried of nucleator can be 80～120 DEG C, dry
The time of dry process can be 2～5 hours.In stepb, banbury or extruder can be used each group
Divide the temperature carrying out melt blending, extruder or banburying to set and can be 170～220 DEG C, be preferably
180～210 DEG C, rotating speed can be 10～200rmp.In step c, can be by selecting suitable mould
It is directly formed to cosmetic packaging box.
In order to be further appreciated by the present invention, below in conjunction with more specifically embodiment to the preferred embodiment of the invention
It is described, but the present invention is not limited to these embodiments.
Embodiment 1
Raw material and consumption are respectively as follows: 50 grams of PLA(4032D, LD mixed types, Mn=127, and 000, Nature
Works), 0.25 gram of TMC-300 nucleator (Shanxi chemical institute), 2.5 grams of acetyl tributyl citrates three
Butyl ester plasticizer, 0.25 gram of antioxidant 1010,1.25 grams of lubricant stearic acid aluminum.True at 80 DEG C of PLA
Empty baking oven is dried 12 hours；TMC-300 nucleator is dried 2 hours in the vacuum drying oven of 80 DEG C.So
After will add melting mixing in banbury after raw material mix homogeneously, the temperature of banbury three part is respectively
190 DEG C, 195 DEG C and 190 DEG C, rotating speed is 35rmp, and the banburying time is 10 minutes.Tree after melting mixing
Fat is the most hot-forming, preheats 5 minutes；Upper and lower mould hot pressing temperature is 190 DEG C, and pressure is 10MPa；
Hot pressing time is 5 minutes.The performance of the material obtained: hot strength is 47MPa, heat distortion temperature is
80℃。
Embodiment 2
Raw material and consumption are respectively as follows: 25 grams of PBS, 25 grams of PLA(4032D, LD mixed types, Mn=127, and 000,
Nature Works), 0.25 gram of TMC-306 nucleator (Shanxi chemical institute), 0.025 gram of peroxide
Change diisopropylbenzene (DIPB), 0.25 gram of maleic anhydride, 2.5 grams of tributyl 2-acetylcitrate plasticizers, 0.25 gram of antioxygen
Agent 1010,1.25 grams of lubricant stearic acid aluminum.PBS and PLA is dried 12 in the vacuum drying oven of 80 DEG C
Hour；TMC-306 nucleator is dried 2 hours in the vacuum drying oven of 80 DEG C.Then by raw material mixing all
Adding melting mixing in banbury after even, the temperature of banbury three part is respectively 190 DEG C, 195 DEG C and
190 DEG C, rotating speed is 35rmp, and the banburying time is 10 minutes.The hot pressing in a mold of resin after melting mixing
Molding, preheats 5 minutes；Upper and lower mould hot pressing temperature is 190 DEG C, and pressure is 10Mpa；Hot pressing time is
5 minutes.The performance of the material obtained: hot strength 41MPa, heat distortion temperature 95 DEG C.
Embodiment 3
Raw material and consumption are respectively as follows: 15 grams of PHB, 15 grams of PBS, and 25 grams of PLA(4032D, LD are mixed
Mould assembly, Mn=127,000, Nature Works), 0.025 gram of cumyl peroxide, 0.25 Rana nigromaculata is come
Anhydride, 0.25 gram of TMC-306 nucleator (Shanxi chemical institute), 2.5 grams of tributyl 2-acetylcitrates
Plasticizer, 0.25 gram of antioxidant 1010,1.25 grams of lubricant stearic acid aluminum.PHB, PBS and PLA exist
The vacuum drying oven of 80 DEG C is dried 12 hours；TMC-306 nucleator is dried 2 in the vacuum drying oven of 80 DEG C
Hour.To add melting mixing in banbury after raw material mix homogeneously, the temperature of banbury three part is respectively
190 DEG C, 195 DEG C and 190 DEG C, rotating speed is 35rmp, and the banburying time is 10 minutes.Tree after melting mixing
Fat is the most hot-forming, preheats 5 minutes.Upper and lower mould hot pressing temperature is 190 DEG C, and pressure is 10MPa.
Hot pressing time is 5 minutes.Anneal 30 minutes at 110 DEG C after hot pressing.The performance of the material obtained: stretching
Intensity 38MPa, heat distortion temperature 98 DEG C.
Embodiment 4
Raw material and consumption are respectively as follows: 15 grams of PHB, 15 grams of PBS, and 15 grams of PLA(4032D, LD are mixed
Mould assembly, Mn=127,000, Nature Works), 0.025 gram of cumyl peroxide, 0.25 Rana nigromaculata is come
Anhydride, 0.25 gram of TMC-306 nucleator (Shanxi chemical institute), 0.1 gram of attapulgite, 2.5 grams
Tributyl 2-acetylcitrate plasticizer, 0.25 gram of antioxidant 1010,1.25 grams of lubricant stearic acid aluminum.PHB,
PBS and PLA is dried 12 hours in the vacuum drying oven of 80 DEG C；True at 80 DEG C of TMC-306 nucleator
Empty baking oven is dried 2 hours.Melting mixing in banbury, banbury three will be added after raw material mix homogeneously
The temperature divided is respectively 190 DEG C, and 195 DEG C and 190 DEG C, rotating speed is 35rmp, and the banburying time is 10 minutes.
Compression molding in mould put into by resin after melting mixing, preheats 5 minutes.Upper and lower mould hot pressing temperature: note
Penetrating is 190 DEG C, and pressure is 10MPa；Hot pressing time is 5 minutes.The performance of the material obtained: stretching
Intensity 43MPa, heat distortion temperature 105 DEG C.
Embodiment 5
Raw material and consumption are respectively as follows: 50 grams of PLA(4032D, LD mixed types, Mn=127, and 000, Nature
Works), 0.25 gram of antioxidant 1010,1.25 grams of lubricant stearic acid aluminum, 0.1 gram of nucleator six side's nitrogen
Change boron, 0.1 gram of nucleator Pulvis Talci.PLA is dried 12 hours in the vacuum drying oven of 80 DEG C.By raw material
Adding melting mixing in banbury after mix homogeneously, the temperature of banbury three part is respectively 190 DEG C, 195 DEG C
With 190 DEG C, rotating speed is 35rmp, and the banburying time is 10 minutes.Resin after melting mixing is the warmmest
Molded, preheat 5 minutes.Upper and lower mould hot pressing temperature is 190 DEG C, and pressure is 10MPa, hot pressing time
It it is 5 minutes.The performance of the material obtained: hot strength 45MPa, heat distortion temperature 79 DEG C.
Embodiment 6
Raw material and consumption are respectively as follows: 15 grams of PHB, 15 grams of PBS, and 15 grams of PLA(4032D, LD are mixed
Mould assembly, Mn=127,000, Nature Works), 2.5 grams of tributyl 2-acetylcitrate plasticizers, 0.25
Gram antioxidant 1010,1.25 grams of lubricant stearic acid aluminum, 0.5 gram of nucleator poly-fumaric acid fourth two fat.PHB,
PBS and PLA is dried 12 hours in the vacuum drying oven of 80 DEG C；Nucleator poly-fumaric acid fourth two fat is at 80 DEG C
Vacuum drying oven in be dried 2 hours.Melting mixing in banbury, banbury will be added after raw material mix homogeneously
The temperature of three parts is respectively 190 DEG C, 195 DEG C and 190 DEG C, and rotating speed is 35rmp, and the banburying time is 10
Minute.Resin after melting mixing is the most hot-forming, preheats 5 minutes.Upper and lower mould hot pressing temperature
Being 190 DEG C, pressure is 10Mpa, and hot pressing time is 5 minutes.Hot pressing after annealing 30 minutes, annealing temperature
Spend 110 DEG C.The performance of the material obtained: hot strength 38MPa, heat distortion temperature 108 DEG C.
Embodiment 7
Raw material and consumption are respectively as follows: 15 grams of PHB, 15 grams of PBS, and 15 grams of PLA(4032D, LD are mixed
Mould assembly, Mn=127,000, Nature Works), 2.5 grams of tributyl 2-acetylcitrate plasticizers, 0.25
Gram antioxidant 1010,1.25 grams of lubricant stearic acid aluminum, 0.5 gram of nucleator poly-fumaric acid fourth two fat, 0.1 gram
Nucleator attapulgite.PHB, PBS and PLA are dried 12 hours in the vacuum drying oven of 80 DEG C；Nucleation
Agent poly-fumaric acid fourth two fat and attapulgite are dried 2 hours in the vacuum drying oven of 80 DEG C.By raw material mixing all
Adding melting mixing in extruder after even, barrel temperatures set 190～200 DEG C, extruded material is through injection moulding.
The performance of the material obtained: hot strength 38MPa, heat distortion temperature 110 DEG C.
Embodiment 8
Raw material and consumption are respectively as follows: 20 grams of PHB, and (adipic acid contains 20 grams of poly-succinic adipic acid fourth diester
Amount 5%), 10 grams of PLA(4032D, LD mixed types, Mn=127,000, Nature Works),
2.5 grams of tributyl 2-acetylcitrate plasticizers, 0.25 gram of antioxidant 1010,0.5 gram of epoxies chain extender.PHB,
Poly-succinic adipic acid fourth diester and PLA are dried 12 hours in the vacuum drying oven of 80 DEG C, then with plasticising
Agent, chain extender, antioxidant mixing, through double screw extruder extrusion thickening, increase-volume, the material obtained
Performance: hot strength 40MPa, heat distortion temperature 92 DEG C.
Embodiment 9
Raw material and consumption are respectively as follows: 50 grams of PLA(4032D, LD mixed types, Mn=127, and 000, Nature
Works), 2.5 grams of TMC-306 nucleators (Shanxi chemical institute), 2.5 grams of acetyl tributyl citrates three
Butyl ester plasticizer, 0.25 gram of antioxidant 1010,1.25 grams of lubricant stearic acid aluminum.True at 80 DEG C of PLA
Empty baking oven is dried 12 hours；TMC-306 nucleator is dried 2 hours in the vacuum drying oven of 80 DEG C.So
After will add melting mixing in banbury after raw material mix homogeneously, the temperature of banbury three part is respectively
190 DEG C, 195 DEG C and 190 DEG C, rotating speed is 35rmp, and the banburying time is 10 minutes.Tree after melting mixing
Fat is the most hot-forming, preheats 5 minutes；Upper and lower mould hot pressing temperature is 190 DEG C, and pressure is 10Mpa；
Hot pressing time is 5 minutes.The performance of the material obtained: hot strength 46MPa, heat distortion temperature 85 DEG C.
Embodiment 10
Raw material and consumption are respectively as follows: 25 grams of PBS, 25 grams of PLA(4032D, LD mixed types, Mn=127, and 000,
Nature Works), 0.25 gram of TMC-306 nucleator (Shanxi chemical institute), 2.5 grams of acetyl lemons
Lemon acid tributyl plasticizer, 0.25 gram of antioxidant 1010,1.25 grams of lubricant stearic acid aluminum.PBS and PLA
The vacuum drying oven of 80 DEG C is dried 12 hours；TMC-306 nucleator is dry in the vacuum drying oven of 80 DEG C
Dry 2 hours.To add melting mixing in banbury after raw material mix homogeneously, the temperature of banbury three part is divided
Not being 190 DEG C, 195 DEG C and 190 DEG C, rotating speed is 35rmp, and the banburying time is 10 minutes.Melting mixing
After resin the most hot-forming, preheat 5 minutes.Upper and lower mould hot pressing temperature is 190 DEG C, pressure
For 10MPa.Hot pressing time is 5 minutes.Anneal 30 minutes at 110 DEG C after hot pressing.The material obtained
Performance: hot strength 40MPa, heat distortion temperature 90 DEG C.
Embodiment 11
Raw material and consumption are respectively as follows: 50 grams of PLA(4032D, LD mixed types, Mn=127, and 000, Nature
Works), 2.5 grams of tributyl 2-acetylcitrate plasticizers, 0.25 gram of antioxidant 1010,1.25 grams of lubrications
Agent aluminium stearate.PLA is dried 12 hours in the vacuum drying oven of 80 DEG C.To add after raw material mix homogeneously
Melting mixing in banbury, the temperature of banbury three part is respectively 190 DEG C, 195 DEG C and 190 DEG C, rotating speed
For 35rmp, the banburying time is 10 minutes.Resin after melting mixing is the most hot-forming, preheats 5
Minute.Upper and lower mould hot pressing temperature is 190 DEG C, and pressure is 10MPa.Hot pressing time is 5 minutes.Hot pressing
After 110 DEG C anneal 30 minutes.The performance of the material obtained: hot strength 46MPa, thermal deformation temperature
Spend 60 DEG C.
Embodiment 12
Raw material and consumption are respectively as follows: 50 grams of PLA(4032D, LD mixed types, Mn=127, and 000, Nature
Works), 0.25g calcium carbonate, 2.5 grams of tributyl 2-acetylcitrate plasticizers, 0.25 gram of antioxidant 1010,
1.25 grams of lubricant stearic acid aluminum.PLA is dried 12 hours in the vacuum drying oven of 80 DEG C.Raw material is mixed
Adding melting mixing in banbury after uniformly, the temperature of banbury three part is respectively 190 DEG C, 195 DEG C and
190 DEG C, rotating speed is 35rmp, and the banburying time is 10 minutes.The hot pressing in a mold of resin after melting mixing
Molding, preheats 5 minutes.Upper and lower mould hot pressing temperature is 190 DEG C, and pressure is 10MPa.Hot pressing time is
5 minutes.Anneal 30 minutes at 110 DEG C after hot pressing.The performance of the material obtained: hot strength 47MPa,
Heat distortion temperature 62 DEG C.
As can be seen from the above embodiments, the heat distortion temperature of the Biodegradable Materials of the present invention is higher,
And there is excellent mechanical property.Comparative example 2 and embodiment 10, it can be seen that add maleic anhydride and
After radical initiator (cumyl peroxide), materials hot deformation temperature substantially increases.Comparative example
1 and embodiment 11 understand, the heat distortion temperature of the material adding nucleator is greatly improved.
So far, although those skilled in the art will appreciate that and the most detailed illustrate and describing the present invention's
Multiple exemplary embodiments, but, without departing from the spirit and scope of the present invention, still can be according to this
Disclosure of invention directly determines or derives other variations or modifications of many meeting the principle of the invention.Cause
This, the scope of the present invention is it is understood that and regard as covering other variations or modifications all these.
Claims (19)
1. a Biodegradable Materials, the content of its component and component is:
Complete biodegradable polymer 100 weight portion；
Nucleator 0.1～10 weight portion；
Radical initiator is more than 0 and less than or equal to 0.2 weight portion；
Maleic anhydride is more than 0 and less than or equal to 2 weight portions；And
Other auxiliary agent 0.5～10 weight portions,
Wherein said complete biodegradable polymer includes polylactic acid, multiple in poly-succinic fourth diester and polyhydroxyalkanoate.
Biodegradable Materials the most according to claim 1, it is characterized in that, described nucleator includes one or more in hydrazide kind compound, compound with amide functional group, Pulvis Talci, silicon dioxide, attapulgite, hexagonal boron nitride, poly-fumaric acid fourth diester.
Biodegradable Materials the most according to claim 2, it is characterised in that described nucleator is hydrazide kind compound.
Biodegradable Materials the most according to claim 3, it is characterised in that described nucleator is TMC-300 and TMC-306 that Shanxi chemical institute is developed.
Biodegradable Materials the most according to claim 1 and 2, it is characterised in that the content of described nucleator is 0.1～5 weight portions.
Biodegradable Materials the most according to claim 5, it is characterised in that the content of described nucleator is 0.1～2 weight portions.
Biodegradable Materials the most according to claim 1, it is characterised in that described radical initiator is organic peroxide.
Biodegradable Materials the most according to claim 7, it is characterised in that described organic peroxide is one or more in benzoyl peroxide, benzoyl peroxide acetyl, di-tert-butyl peroxide or cumyl peroxide.
Biodegradable Materials the most according to claim 1, it is characterised in that other auxiliary agents described include antioxidant, heat stabilizer, plasticizer, chain extender, one or more in lubricant；Wherein
Described antioxidant includes that one or more in Hinered phenols antioxidant or phosphite ester kind antioxidant, the content of described antioxidant are 0.5～1 weight portion；And/or
Described plasticizer includes one or more in Polyethylene Glycol, 1,2-cyclohexane dicarboxylic acid diisopropyl ester, decanedioic acid two ester the most, dibutyl maleate, DOTP, citrate, aliphatic polyester or polyurethane；And/or
Described lubricant includes one or more in white oil, stearic acid or EBS.
Biodegradable Materials the most according to claim 9, it is characterised in that described plasticizer is citrate and aliphatic polyester.
11. Biodegradable Materials according to claim 9, it is characterised in that the content of described plasticizer is 5～10 weight portions.
12. Biodegradable Materials according to claim 1, it is characterised in that described polylactic acid is L-type polylactic acid, D type polylactic acid, LD mixed type polylactic acid, the copolymer of polylactic acid or the mixture of copolymer of poly lactic acid.
13. Biodegradable Materials according to claim 1, it is characterised in that the molecular weight of described polylactic acid is 5～300,000.
The method of 14. 1 kinds of Biodegradable Materials prepared as according to any one of claim 1～13, comprises the following steps:
A. described complete biodegradable polymer and nucleator are dried process respectively；
B. dried complete biodegradable polymer and nucleator are blended with remaining component melts, obtain blending ingredients；
C. by the molding by the way of injection, mold pressing or extrusion-blown modling of described blending ingredients.
15. methods according to claim 14, it is characterised in that in step a,
The temperature of described complete biodegradable polymer dried is 60～100 DEG C, and the time of dried is 8～12 hours；
The temperature of the dried of described nucleator is 80～120 DEG C, and the time of dried is 2～5 hours.
16. methods according to claim 14, it is characterised in that in stepb, the temperature using banbury or extruder that each component carries out melt blending, banbury or extruder is set as 170～220 DEG C, and rotating speed is 10～200rmp.
17. methods according to claim 16, it is characterised in that in stepb, the temperature using banbury or extruder that each component carries out melt blending, banbury or extruder is set as 180～210 DEG C.
18. 1 kinds of cosmetic packaging boxes, it is made up of the Biodegradable Materials according to any one of claim 1-13.
19. 1 kinds of cosmetic packaging boxes, it is made up of the method according to any one of claim 14-17.
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Families Citing this family (19)
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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 |
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| CN115627559B (en) * | 2022-11-18 | 2023-05-16 | 北京微构工场生物技术有限公司 | Degradable filament and special material thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1544525A (en) * | 2003-11-27 | 2004-11-10 | 中国科学院长春应用化学研究所 | Method for preparing biodegradable poly-lactic acid foam plastic |
| CN101475735A (en) * | 2008-12-15 | 2009-07-08 | 山东省意可曼科技有限公司 | Completely biodegradable polyhydroxyalkanote / poly(butylene succinate) blending alloy |
| CN101544813A (en) * | 2009-04-30 | 2009-09-30 | 上海大学 | Rapid crystallization polylactic acid composite material and preparation method thereof |
| CN101641409A (en) * | 2007-06-29 | 2010-02-03 | 尤尼吉可株式会社 | Crystalline polylactic acid resin composition and molded body made of the same |
-
2014
- 2014-01-13 CN CN201410013566.8A patent/CN103772878B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1544525A (en) * | 2003-11-27 | 2004-11-10 | 中国科学院长春应用化学研究所 | Method for preparing biodegradable poly-lactic acid foam plastic |
| CN101641409A (en) * | 2007-06-29 | 2010-02-03 | 尤尼吉可株式会社 | Crystalline polylactic acid resin composition and molded body made of the same |
| CN101475735A (en) * | 2008-12-15 | 2009-07-08 | 山东省意可曼科技有限公司 | Completely biodegradable polyhydroxyalkanote / poly(butylene succinate) blending alloy |
| CN101544813A (en) * | 2009-04-30 | 2009-09-30 | 上海大学 | Rapid crystallization polylactic acid composite material and preparation method thereof |
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