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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- CN103772878A CN103772878A CN201410013566.8A CN201410013566A CN103772878A CN 103772878 A CN103772878 A CN 103772878A CN 201410013566 A CN201410013566 A CN 201410013566A CN 103772878 A CN103772878 A CN 103772878A
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- 239000000463 material Substances 0.000 title claims abstract description 55
- 239000002537 cosmetic Substances 0.000 title claims abstract description 12
- 238000002360 preparation method Methods 0.000 title abstract description 6
- 239000002667 nucleating agent Substances 0.000 claims abstract description 48
- 229920002988 biodegradable polymer Polymers 0.000 claims abstract description 21
- 239000004621 biodegradable polymer Substances 0.000 claims abstract description 21
- -1 Polyethylene Polymers 0.000 claims abstract description 17
- 239000003999 initiator Substances 0.000 claims abstract description 10
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000004626 polylactic acid Substances 0.000 claims description 57
- 229920000747 poly(lactic acid) Polymers 0.000 claims description 56
- 238000002156 mixing Methods 0.000 claims description 29
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- 238000001035 drying Methods 0.000 claims description 21
- 239000000314 lubricant Substances 0.000 claims description 17
- 239000003963 antioxidant agent Substances 0.000 claims description 16
- 238000002844 melting Methods 0.000 claims description 15
- 230000008018 melting Effects 0.000 claims description 15
- 150000001875 compounds Chemical class 0.000 claims description 11
- 239000000126 substance Substances 0.000 claims description 10
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- GQIDSVPVVYHXAP-UHFFFAOYSA-N dihexyl decanedioate Chemical compound CCCCCCOC(=O)CCCCCCCCC(=O)OCCCCCC GQIDSVPVVYHXAP-UHFFFAOYSA-N 0.000 claims description 3
- OEIWPNWSDYFMIL-UHFFFAOYSA-N dioctyl benzene-1,4-dicarboxylate Chemical compound CCCCCCCCOC(=O)C1=CC=C(C(=O)OCCCCCCCC)C=C1 OEIWPNWSDYFMIL-UHFFFAOYSA-N 0.000 claims description 3
- HFVJRYILMUSLFV-UHFFFAOYSA-N dipropan-2-yl cyclohexane-1,2-dicarboxylate Chemical compound CC(C)OC(=O)C1CCCCC1C(=O)OC(C)C HFVJRYILMUSLFV-UHFFFAOYSA-N 0.000 claims description 3
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- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 3
- 239000003921 oil Substances 0.000 claims description 3
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 3
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- 239000000454 talc Substances 0.000 claims description 3
- 229910052623 talc Inorganic materials 0.000 claims description 3
- 238000007723 die pressing method Methods 0.000 claims description 2
- FKGFBYXUGQXYKX-UHFFFAOYSA-N phenyl ethaneperoxoate Chemical compound CC(=O)OOC1=CC=CC=C1 FKGFBYXUGQXYKX-UHFFFAOYSA-N 0.000 claims description 2
- 229920003023 plastic Polymers 0.000 abstract description 12
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- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 12
- QZCLKYGREBVARF-UHFFFAOYSA-N Acetyl tributyl citrate Chemical compound CCCCOC(=O)CC(C(=O)OCCCC)(OC(C)=O)CC(=O)OCCCC QZCLKYGREBVARF-UHFFFAOYSA-N 0.000 description 11
- CEGOLXSVJUTHNZ-UHFFFAOYSA-K aluminium tristearate Chemical compound [Al+3].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CEGOLXSVJUTHNZ-UHFFFAOYSA-K 0.000 description 11
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- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 4
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- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 1
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Landscapes
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- Compositions Of Macromolecular Compounds (AREA)
- Blow-Moulding Or Thermoforming Of Plastics Or The Like (AREA)
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 invention relates to the field of plastic materials, in particular to a completely biodegradable material, a preparation method thereof and a cosmetic packaging box.
Background
Polypropylene (PP), Polyethylene (PE), Polystyrene (PS), polyvinyl chloride (PVC), organic glass, polycarbonate and the like, which use stone resources such as petroleum and the like as raw materials, are widely used in the fields of food packaging, electrochemical products, industrial equipment and the like. The materials are difficult to recycle after being used, so that the current serious 'white pollution' problem is caused, petroleum resources are non-renewable, and a large amount of unreasonable use brings serious resource shortage problem to human beings. The advent of biodegradable materials, especially the renewability of raw materials for the degradable materials, provides an effective means for solving this problem. Among them, fully biodegradable resins whose raw materials are derived from biomass, such as polylactic acid (PLA), polybutylene succinate (PBS), Polyhydroxyalkanoate (PHA), and the like, have received much attention.
PLA is a bio-based degradable material which is prepared by taking renewable biological resources as raw materials through biological fermentation and chemical synthesis methods and is widely applied. PLA has the excellent characteristics of good mechanical property, no toxicity, low relative density, easy processing and forming at normal temperature, complete biodegradation, relatively low price and the like, is the variety with the fastest growth speed, the largest yield and the most active development of new products in bio-based plastics, and can be widely used for chemical industry, light industry, household appliances, packaging materials and the like. However, compared with common plastics such as PE, PP, PS and the like, pure PLA plastics have the defects of poor heat resistance (the heat distortion temperature is 55-58 ℃), slow crystallization speed, long molding processing period and poor product gloss and transparency, so that the application range of the PLA plastics is limited to a certain extent.
The PBS resin is milky white, odorless and tasteless, is easily decomposed by various microorganisms or enzymes in animals and plants in the nature, and is a typical completely biodegradable polymer material. The synthetic source of the compound can be petroleum resources and can also be obtained by fermentation of biological resources. But PBS has low relative molecular mass, high melt index and poor mechanical property.
PHA compounds are directly originated from biological fermentation. When the n-alkyl side chain in PHA is methyl, the material is referred to as poly-3-hydroxybutyrate (PHB). It is the most widely existing, the earliest and most deeply studied one of the PHA families. PHB is a hard and brittle thermoplastic polymer, and the mechanical properties of PHB are equivalent to those of PP and PS at normal temperature. Compared with PP, PHB has similar normal-temperature mechanical properties, similar melting temperature, lower solvent resistance and better ultraviolet aging resistance. But there are also significant disadvantages: firstly, the melting temperature (about 170-180 ℃) is close to the decomposition temperature (205 ℃), and the processing and molding can be carried out only in a narrow temperature range near 190 ℃. More importantly, it has low impact strength and elongation at break almost two orders of magnitude lower than PP. Therefore, PHB is often modified by blending with other plastics.
Disclosure of Invention
An object of the present invention is to provide a completely biodegradable material having good heat resistance.
It is a further object of the present invention to provide a method for preparing such a material.
It is another further object of the present invention to provide a cosmetic product package.
On one hand, the invention provides a completely biodegradable material, which comprises the following components in percentage by weight:
100 parts by weight of completely biodegradable polymer;
0.1-10 parts by weight of a nucleating agent;
0-0.2 parts by weight of a free radical initiator;
0-2 parts by weight of maleic anhydride;
0.5-10 parts of other auxiliary agents.
In one embodiment, the fully biodegradable polymer may comprise or be selected from one or more of polylactic acid, polybutylene succinate and polyhydroxyalkanoates. The "plurality" herein includes the case of a blend or copolymer of polylactic acid, polybutylene succinate, and polyhydroxyalkanoate.
In one embodiment, the nucleating agent may comprise or be selected from one or more of hydrazide type compounds, amide functional group-containing compounds, talc, silica, attapulgite, hexagonal boron nitride, polybutylene fumarate, preferably hydrazide type compounds, and more preferably TMC-300 and TMC-306 developed by Shanxi chemical research institute.
In one embodiment, the content of the nucleating agent may be 0.1 to 5 parts by weight, and more preferably 0.1 to 2 parts by weight.
In one embodiment, the free radical initiator may be an organic peroxide; optionally, the organic peroxide is one or more of benzoyl peroxide, phenylacetyl peroxide, di-t-butyl peroxide, or dicumyl peroxide.
In one embodiment, the other auxiliary agents may include or be selected from one or more of antioxidants, heat stabilizers, plasticizers, chain extenders, lubricants; wherein,
the antioxidant can comprise or be selected from one or more of hindered phenol antioxidants or phosphite antioxidants, and the content of the antioxidant is 0.5-1 part by weight; and/or
The plasticizer may comprise or be selected from one or more of polyethylene glycol, diisopropyl 1, 2-cyclohexanedicarboxylate, di-n-hexyl sebacate, dibutyl maleate, dioctyl terephthalate, citrate esters, aliphatic polyesters or polyurethanes, preferably citrate esters and aliphatic polyesters; optionally, the plasticizer is contained in an amount of 5 to 10 parts by weight; and/or
The lubricant may comprise or be selected from one or more of white oil, stearic acid or EBS.
In one embodiment, the polylactic acid may be L-type polylactic acid, D-type polylactic acid, LD-mixed polylactic acid, a copolymer of polylactic acid, or a mixture of polylactic acid copolymers; optionally, the polylactic acid has a molecular weight of 5 to 30 ten thousand.
In another aspect, the present invention provides a method for preparing the aforementioned completely biodegradable material, comprising the steps of:
a. respectively drying the completely biodegradable polymer and the nucleating agent;
b. melting and blending the dried completely biodegradable polymer and the nucleating agent with the rest components to obtain a mixed component;
c. molding the mixed components by injection, die pressing or extrusion blow molding;
optionally, in the step a, the temperature of the drying treatment of the completely biodegradable polymer can be 60-100 ℃, and the time of the drying treatment can be 8-12 hours; the temperature of the drying treatment of the nucleating agent can be 80-120 ℃, and the time of the drying treatment can be 2-5 hours;
further optionally, in the step b, an internal mixer or an extruder is used for melt blending of the components, the temperature of the internal mixer or the extruder can be set to be 170-220 ℃, preferably 180-210 ℃, and the rotation speed can be 10-200 rmp.
In a further aspect, the present invention provides a cosmetic product packaging made from the aforementioned fully biodegradable material.
In yet another aspect, the present invention provides a cosmetic product packaging made by the aforementioned method.
The material of the invention has complete biodegradability, is environment-friendly, can be completely biodegraded in natural environment and compost, and is converted into CO2And water, and is environmentally friendly.
The invention optimizes and limits the dosage of the nucleating agent and the functional assistant, so that the crystallization speed and the crystallinity of the completely biodegradable polymer are improved, the heat resistance of the material is obviously improved, the heat distortion temperature can reach more than 80 ℃, and the material can bear the high temperature of ocean transportation and is suitable for ocean transportation or other occasions experiencing high temperature.
In the invention, the free radical initiator and the maleic anhydride initiate reaction in the polymer blending process to form a graft copolymer which becomes a compatibilizer, and the compatibility among polymers is improved, so that the performance of the material is improved. Meanwhile, the product is crystallized and refined, and the plastic is ensured to have better transparency.
The method is simple to operate, easy to control and low in preparation cost.
The completely biodegradable material has the characteristics of excellent mechanical property, heat resistance and low cost. The material can replace PE, PP, PVC and the like to be made into various environment-friendly plastic products, and particularly has wide market prospect in the fields of high-grade cosmetic packaging boxes (including eye shadow, foundation liquid, pressed powder, lip gloss and the like), food packaging, household appliances, automobiles and the like.
Detailed Description
The above and other objects, advantages and features of the present invention will become more apparent to those skilled in the art from the following detailed description of the invention taken in conjunction with the accompanying examples.
The completely biodegradable material of the present invention comprises: 100 parts by weight of a fully biodegradable polymer; 0.1-10 parts by weight of a nucleating agent; 0 to 0.2 parts by weight of a radical initiator; 0 to 2 parts by weight of maleic anhydride; and 0.5-10 parts by weight of other additives. Wherein the completely biodegradable polymer comprises one or more of PLA, PBS and PHA. PLA is L-type polylactic acid or D-type polylactic acid or LD mixed polylactic acid or a copolymer of polylactic acid or a mixture of polylactic acid copolymers. In the present invention, the PLA may comprise PLB. The molecular weight of the PLA can be between 5 and 30 ten thousand. PBS takes succinic acid and butanediol as copolymerization units, and random linear copolyester is finally obtained by copolymerization of the PBS and different copolymerization diacid and/or different copolymerization diol monomers. Wherein, the mol percentage of the copolymerized diacid and the succinic acid can be adjusted within the range of 0.01 to 99.99 percent; wherein, the mol percentage of the copolymerization diol and the butanediol can be adjusted within the range of 0.01-99.99%.
Because polymers such as PLA, PBS, PHA and the like are partially compatible with each other, if the polymers and the additives are directly melt-blended, the obtained material is in a phase-separated structure, and the material performance and the transparency are influenced. The inventor of the application adds the free radical initiator and the maleic anhydride to ensure that the polymer is subjected to in-situ reaction compatibilization in the process of melt blending so as to achieve the aim of increasing the compatibility and the interfacial adhesion of the polymer, thereby improving the performance of the material. The free radical initiator may be benzoyl peroxide, di-t-butyl peroxide, dicumyl peroxide or other organic peroxides.
The main purpose of adding the nucleating agent is to provide crystal nuclei, reduce the surface free energy of nucleation and promote crystallization at a high cooling speed. The nucleating agent can be one or more selected from hydrazide compounds, compounds with amide functional groups, talcum powder, silicon dioxide, attapulgite, hexagonal boron nitride and polybutylene fumarate, the hydrazide compounds are preferably used as the nucleating agent, and the special nucleating agents TMC-300 and TMC-306 developed by Shanxi chemical research are further preferably selected. The invention has stricter requirements on the dosage of the nucleating agent. If the nucleating agent is added in an amount of less than 0.1 part by weight per 100 parts by weight of the completely biodegradable polymer, the amount of formed crystal nuclei is insufficient, so that the effect of promoting crystallization is not good; if the amount of the nucleating agent added is more than 10 parts by weight, the resulting plastic tends to be poor in transparency. Therefore, the nucleating agent with the weight portion of 0.1-10 parts can ensure the crystallization effect and maintain better transparency of the plastic. The amount of the nucleating agent is preferably 0.1 to 5 parts by weight, and more preferably 0.1 to 2 parts by weight.
Other auxiliaries may include one or more of antioxidants, heat stabilizers, plasticizers, chain extenders, lubricants. Among them, the plasticizer can improve the migration property of polymer chains, increase the crystallization speed by reducing the chain migration property, and in addition, the plasticizer is advantageous for the molding of plastics. The plasticizer can be selected from polyethylene glycol, diisopropyl 1, 2-cyclohexanedicarboxylate, di-n-hexyl sebacate, dibutyl maleate, dioctyl terephthalate, citrate, aliphatic polyester or polyurethane, preferably citrate and aliphatic polyester. The plasticizer is preferably used in an amount of 5 to 10 parts by weight (relative to 100 parts by weight of the completely biodegradable polymer).
The primary purpose of the antioxidant is to prevent thermal degradation of the PLA during modification. One or more of hindered phenol antioxidants or phosphite antioxidants can be selected, and the using amount of the antioxidants is preferably 0.1-0.5 part by weight (relative to 100 parts by weight of the completely biodegradable polymer).
The lubricant may be selected from one or more of white oil, stearic acid or EBS. The invention obviously improves the crystallinity, crystallization rate and heat resistance of the completely biodegradable plastic by adding the crystallization nucleating agent and the auxiliary agent, the heat distortion temperature can reach more than 80 ℃, and the invention can bear the high temperature of ocean transportation.
The preparation method of the completely biodegradable material of the present invention may comprise the steps of:
a. respectively drying the completely biodegradable polymer and the nucleating agent;
b. melting and blending the dried completely biodegradable polymer and the nucleating agent with the rest components to obtain a mixed component;
c. the mixed components are formed by means of injection, compression molding or extrusion blow molding.
In the step a, the temperature of the drying treatment of the completely biodegradable polymer can be 60-100 ℃, and the time of the drying treatment can be 8-12 hours. The temperature of the drying treatment of the nucleating agent can be 80-120 ℃, and the time of the drying treatment can be 2-5 hours. In the step b, an internal mixer or an extruder can be adopted to melt and blend the components, the temperature of the extruder or the internal mixer can be set to be 170-220 ℃, preferably 180-210 ℃, and the rotating speed can be 10-200 rmp. In step c, the cosmetic packaging box can be directly formed by selecting a proper mold.
For a further understanding of the present invention, preferred embodiments of the present invention will be described below with reference to more specific examples, but the present invention is not limited to these examples.
Example 1
The raw materials and the dosage are respectively as follows: 50 grams of PLA (4032D, LD mixed, Mn =127,000, NatureWorks), 0.25 grams of TMC-300 nucleating agent (Shanxi chemical research institute), 2.5 grams of acetyl tributyl citrate plasticizer, 0.25 grams of antioxidant 1010, 1.25 grams of lubricant aluminum stearate. Drying PLA in a vacuum oven at 80 ℃ for 12 hours; TMC-300 nucleating agent was dried in a vacuum oven at 80 ℃ for 2 hours. Then the raw materials are evenly mixed and then added into an internal mixer for melting and mixing, the temperature of the three parts of the internal mixer is 190 ℃, 195 ℃ and 190 ℃, the rotating speed is 35rmp, and the internal mixing time is 10 minutes. Hot-pressing the melted and mixed resin in a mould, and preheating for 5 minutes; the hot-pressing temperature of the upper die and the lower die is 190 ℃, and the pressure is 10 MPa; the hot pressing time was 5 minutes. Properties of the obtained material: the tensile strength is 47MPa, and the heat distortion temperature is 80 ℃.
Example 2
The raw materials and the dosage are respectively as follows: 25 grams of PBS, 25 grams of PLA (4032D, LD mixed, Mn =127,000, Nature Works), 0.25 grams of TMC-306 nucleating agent (shanxi chemical research institute), 0.025 grams of dicumyl peroxide, 0.25 grams of maleic anhydride, 2.5 grams of acetyl tributyl citrate plasticizer, 0.25 grams of antioxidant 1010, 1.25 grams of lubricant aluminum stearate. PBS and PLA were dried in a vacuum oven at 80 ℃ for 12 hours; the TMC-306 nucleating agent was dried in a vacuum oven at 80 ℃ for 2 hours. Then the raw materials are evenly mixed and then added into an internal mixer for melting and mixing, the temperature of the three parts of the internal mixer is 190 ℃, 195 ℃ and 190 ℃, the rotating speed is 35rmp, and the internal mixing time is 10 minutes. Hot-pressing the melted and mixed resin in a mould, and preheating for 5 minutes; the hot-pressing temperature of the upper die and the lower die is 190 ℃, and the pressure is 10 Mpa; the hot pressing time was 5 minutes. Properties of the obtained material: tensile strength 41MPa, and thermal deformation temperature 95 ℃.
Example 3
The raw materials and the dosage are respectively as follows: 15 grams of PHB, 15 grams of PBS, 25 grams of PLA (4032D, LD mixed type, Mn =127,000, Nature Works), 0.025 grams of dicumyl peroxide, 0.25 grams of maleic anhydride, 0.25 grams of TMC-306 nucleating agent (Shanxi chemical research institute), 2.5 grams of acetyl tributyl citrate plasticizer, 0.25 grams of antioxidant 1010, 1.25 grams of lubricant aluminum stearate. Drying PHB, PBS and PLA in a vacuum oven at 80 ℃ for 12 hours; the TMC-306 nucleating agent was dried in a vacuum oven at 80 ℃ for 2 hours. The raw materials are evenly mixed and then added into an internal mixer for melting and mixing, the temperature of the three parts of the internal mixer is 190 ℃, 195 ℃ and 190 ℃, the rotating speed is 35rmp, and the internal mixing time is 10 minutes. The melted and mixed resin is hot-pressed in a mould and preheated for 5 minutes. The hot-pressing temperature of the upper die and the lower die is 190 ℃ and the pressure is 10 MPa. The hot pressing time was 5 minutes. Annealing at 110 ℃ for 30 minutes after hot pressing. Properties of the obtained material: tensile strength 38MPa, and heat distortion temperature 98 ℃.
Example 4
The raw materials and the dosage are respectively as follows: 15 grams of PHB, 15 grams of PBS, 15 grams of PLA (4032D, LD mixed type, Mn =127,000, Nature Works), 0.025 grams of dicumyl peroxide, 0.25 grams of maleic anhydride, 0.25 grams of TMC-306 nucleating agent (Shanxi chemical research institute), 0.1 grams of attapulgite, 2.5 grams of acetyl tributyl citrate plasticizer, 0.25 grams of antioxidant 1010, 1.25 grams of lubricant aluminum stearate. Drying PHB, PBS and PLA in a vacuum oven at 80 ℃ for 12 hours; the TMC-306 nucleating agent was dried in a vacuum oven at 80 ℃ for 2 hours. The raw materials are evenly mixed and then added into an internal mixer for melting and mixing, the temperature of the three parts of the internal mixer is 190 ℃, 195 ℃ and 190 ℃, the rotating speed is 35rmp, and the internal mixing time is 10 minutes. The melted and mixed resin is put into a mould for compression molding and is preheated for 5 minutes. Hot pressing temperature of upper and lower dies: the injection temperature is 190 ℃, and the pressure is 10 MPa; the hot pressing time was 5 minutes. Properties of the obtained material: tensile strength 43MPa, heat distortion temperature 105 ℃.
Example 5
The raw materials and the dosage are respectively as follows: 50 grams of PLA (4032D, LD mixed, Mn =127,000, NatureWorks), 0.25 grams of antioxidant 1010, 1.25 grams of lubricant aluminum stearate, 0.1 grams of nucleating agent hexagonal boron nitride, 0.1 grams of nucleating agent talc. The PLA was dried in a vacuum oven at 80 ℃ for 12 hours. The raw materials are evenly mixed and then added into an internal mixer for melting and mixing, the temperature of the three parts of the internal mixer is 190 ℃, 195 ℃ and 190 ℃, the rotating speed is 35rmp, and the internal mixing time is 10 minutes. The melted and mixed resin is hot-pressed in a mould and preheated for 5 minutes. The hot-pressing temperature of the upper die and the lower die is 190 ℃, the pressure is 10MPa, and the hot-pressing time is 5 minutes. Properties of the obtained material: tensile strength of 45MPa and heat distortion temperature of 79 ℃.
Example 6
The raw materials and the dosage are respectively as follows: 15 grams of PHB, 15 grams of PBS, 15 grams of PLA (4032D, LD mixed, Mn =127,000, Nature Works), 2.5 grams of acetyl tributyl citrate plasticizer, 0.25 grams of antioxidant 1010, 1.25 grams of lubricant aluminum stearate, 0.5 grams of nucleating agent polybutylene fumarate. Drying PHB, PBS and PLA in a vacuum oven at 80 ℃ for 12 hours; the nucleating agent polybutylene fumarate was dried in a vacuum oven at 80 ℃ for 2 hours. The raw materials are evenly mixed and then added into an internal mixer for melting and mixing, the temperature of the three parts of the internal mixer is 190 ℃, 195 ℃ and 190 ℃, the rotating speed is 35rmp, and the internal mixing time is 10 minutes. The melted and mixed resin is hot-pressed in a mould and preheated for 5 minutes. The hot pressing temperature of the upper die and the lower die is 190 ℃, the pressure is 10Mpa, and the hot pressing time is 5 minutes. Annealing is carried out for 30 minutes after hot pressing, and the annealing temperature is 110 ℃. Properties of the obtained material: tensile strength 38MPa, heat distortion temperature 108 ℃.
Example 7
The raw materials and the dosage are respectively as follows: 15 grams of PHB, 15 grams of PBS, 15 grams of PLA (4032D, LD blend, Mn =127,000, Nature Works), 2.5 grams of acetyl tributyl citrate plasticizer, 0.25 grams of antioxidant 1010, 1.25 grams of lubricant aluminum stearate, 0.5 grams of nucleating agent polybutylene fumarate, 0.1 grams of nucleating agent attapulgite. Drying PHB, PBS and PLA in a vacuum oven at 80 ℃ for 12 hours; the nucleating agents polybutylene fumarate and attapulgite were dried in a vacuum oven at 80 ℃ for 2 hours. The raw materials are uniformly mixed and then added into an extruder for melt mixing, the temperature of a machine barrel is set to be 190-200 ℃, and the extrusion material is subjected to injection molding. Properties of the obtained material: tensile strength 38MPa, and heat distortion temperature 110 ℃.
Example 8
The raw materials and the dosage are respectively as follows: 20 g of PHB, 20 g of polybutylene succinate adipate (5% of adipic acid), 10 g of PLA (4032D, LD mixed type, Mn =127,000, Nature Works), 2.5 g of acetyl tributyl citrate plasticizer, 0.25g of antioxidant 1010 and 0.5 g of epoxy chain extender. PHB, polybutylene succinate adipate and PLA are dried for 12 hours in a vacuum oven at 80 ℃, then mixed with a plasticizer, a chain extender and an antioxidant, and extruded by a double-screw extruder for tackifying and increasing the capacity, and the obtained material has the following properties: tensile strength of 40MPa and heat distortion temperature of 92 ℃.
Example 9
The raw materials and the dosage are respectively as follows: 50 grams of PLA (4032D, LD mixed, Mn =127,000, NatureWorks), 2.5 grams of TMC-306 nucleating agent (Shanxi chemical research institute), 2.5 grams of acetyl tributyl citrate plasticizer, 0.25 grams of antioxidant 1010, 1.25 grams of lubricant aluminum stearate. Drying PLA in a vacuum oven at 80 ℃ for 12 hours; the TMC-306 nucleating agent was dried in a vacuum oven at 80 ℃ for 2 hours. Then the raw materials are evenly mixed and then added into an internal mixer for melting and mixing, the temperature of the three parts of the internal mixer is 190 ℃, 195 ℃ and 190 ℃, the rotating speed is 35rmp, and the internal mixing time is 10 minutes. Hot-pressing the melted and mixed resin in a mould, and preheating for 5 minutes; the hot-pressing temperature of the upper die and the lower die is 190 ℃, and the pressure is 10 Mpa; the hot pressing time was 5 minutes. Properties of the obtained material: tensile strength of 46MPa and heat distortion temperature of 85 ℃.
Example 10
The raw materials and the dosage are respectively as follows: 25 grams of PBS, 25 grams of PLA (4032D, LD mixed, Mn =127,000, Nature Works), 0.25 grams of TMC-306 nucleating agent (shanxi chemical research institute), 2.5 grams of acetyl tributyl citrate plasticizer, 0.25 grams of antioxidant 1010, 1.25 grams of lubricant aluminum stearate. PBS and PLA were dried in a vacuum oven at 80 ℃ for 12 hours; the TMC-306 nucleating agent was dried in a vacuum oven at 80 ℃ for 2 hours. The raw materials are evenly mixed and then added into an internal mixer for melting and mixing, the temperature of the three parts of the internal mixer is 190 ℃, 195 ℃ and 190 ℃, the rotating speed is 35rmp, and the internal mixing time is 10 minutes. The melted and mixed resin is hot-pressed in a mould and preheated for 5 minutes. The hot-pressing temperature of the upper die and the lower die is 190 ℃ and the pressure is 10 MPa. The hot pressing time was 5 minutes. Annealing at 110 ℃ for 30 minutes after hot pressing. Properties of the obtained material: tensile strength of 40MPa and thermal deformation temperature of 90 ℃.
Example 11
The raw materials and the dosage are respectively as follows: 50 grams of PLA (4032D, LD mixed, Mn =127,000, NatureWorks), 2.5 grams of acetyl tributyl citrate plasticizer, 0.25 grams of antioxidant 1010, 1.25 grams of lubricant aluminum stearate. The PLA was dried in a vacuum oven at 80 ℃ for 12 hours. The raw materials are evenly mixed and then added into an internal mixer for melting and mixing, the temperature of the three parts of the internal mixer is 190 ℃, 195 ℃ and 190 ℃, the rotating speed is 35rmp, and the internal mixing time is 10 minutes. The melted and mixed resin is hot-pressed in a mould and preheated for 5 minutes. The hot-pressing temperature of the upper die and the lower die is 190 ℃ and the pressure is 10 MPa. The hot pressing time was 5 minutes. Annealing at 110 ℃ for 30 minutes after hot pressing. Properties of the obtained material: tensile strength of 46MPa and heat distortion temperature of 60 ℃.
Example 12
The raw materials and the dosage are respectively as follows: 50 grams of PLA (4032D, LD mixed, Mn =127,000, NatureWorks), 0.25 grams of calcium carbonate, 2.5 grams of acetyl tributyl citrate plasticizer, 0.25 grams of antioxidant 1010, 1.25 grams of lubricant aluminum stearate. The PLA was dried in a vacuum oven at 80 ℃ for 12 hours. The raw materials are evenly mixed and then added into an internal mixer for melting and mixing, the temperature of the three parts of the internal mixer is 190 ℃, 195 ℃ and 190 ℃, the rotating speed is 35rmp, and the internal mixing time is 10 minutes. The melted and mixed resin is hot-pressed in a mould and preheated for 5 minutes. The hot-pressing temperature of the upper die and the lower die is 190 ℃ and the pressure is 10 MPa. The hot pressing time was 5 minutes. Annealing at 110 ℃ for 30 minutes after hot pressing. Properties of the obtained material: tensile strength 47MPa, heat distortion temperature 62 ℃.
As can be seen from the above examples, the completely biodegradable material of the present invention has a high heat distortion temperature and excellent mechanical properties. Comparing example 2 with example 10, it can be seen that the heat distortion temperature of the material increases significantly with the addition of maleic anhydride and a free radical initiator (dicumyl peroxide). Comparing example 1 and example 11, it is seen that the heat distortion temperature of the material with the added nucleating agent is greatly increased.
Thus, it should be appreciated by those skilled in the art that while a number of exemplary embodiments of the invention have been illustrated and described in detail herein, many other variations or modifications consistent with the principles of the invention may be directly determined or derived from the disclosure of the present invention without departing from the spirit and scope of the invention. Accordingly, the scope of the invention should be understood and interpreted to cover all such other variations or modifications.
Claims (10)
1. A completely biodegradable material comprises the following components in percentage by weight:
100 parts by weight of completely biodegradable polymer;
0.1-10 parts by weight of a nucleating agent;
0-0.2 parts by weight of a free radical initiator;
0-2 parts by weight of maleic anhydride;
0.5-10 parts of other auxiliary agents.
2. The completely biodegradable material according to claim 1, characterized in that said completely biodegradable polymer comprises one or more of polylactic acid, polybutylene succinate and polyhydroxyalkanoates.
3. The completely biodegradable material according to claim 1 or 2, characterized in that the nucleating agent comprises one or more of hydrazide type compounds, amide functional group-containing compounds, talc, silica, attapulgite, hexagonal boron nitride, polybutylene fumarate, preferably hydrazide type compounds, and further preferably TMC-300 and TMC-306 developed by shanxi chemical research institute.
4. A completely biodegradable material according to any of claims 1-3, characterized in that the nucleating agent is present in an amount of 0.1-5 parts by weight, more preferably 0.1-2 parts by weight.
5. The completely biodegradable material according to any one of claims 1 to 4, characterized in that the radical initiator is an organic peroxide; optionally, the organic peroxide is one or more of benzoyl peroxide, phenylacetyl peroxide, di-t-butyl peroxide, or dicumyl peroxide.
6. Completely biodegradable material according to any of claims 1 to 5, characterized in that,
the other auxiliary agents comprise one or more of an antioxidant, a heat stabilizer, a plasticizer, a chain extender and a lubricant; wherein,
the antioxidant comprises one or more of hindered phenol antioxidant or phosphite antioxidant, and the content of the antioxidant is 0.5-1 part by weight; and/or
The plasticizer comprises one or more of polyethylene glycol, diisopropyl 1, 2-cyclohexanedicarboxylate, di-n-hexyl sebacate, dibutyl maleate, dioctyl terephthalate, citrate, aliphatic polyester or polyurethane, preferably citrate and aliphatic polyester; optionally, the plasticizer is contained in an amount of 5 to 10 parts by weight; and/or
The lubricant comprises one or more of white oil, stearic acid, or EBS.
7. The completely biodegradable material according to claim 2, characterized in that the polylactic acid is L-type polylactic acid, D-type polylactic acid, LD mixed polylactic acid, copolymer of polylactic acid, or mixture of polylactic acid copolymers; optionally, the polylactic acid has a molecular weight of 5 to 30 ten thousand.
8. A method for preparing a fully biodegradable material according to any of claims 1-7, comprising the steps of:
a. respectively drying the completely biodegradable polymer and the nucleating agent;
b. melting and blending the dried completely biodegradable polymer and the nucleating agent with the rest components to obtain a mixed component;
c. molding the mixed components by injection, die pressing or extrusion blow molding;
optionally, in the step a, the temperature of the drying treatment of the completely biodegradable polymer is 60-100 ℃, and the time of the drying treatment is 8-12 hours; the temperature of the drying treatment of the nucleating agent is 80-120 ℃, and the time of the drying treatment is 2-5 hours;
further optionally, in the step b, an internal mixer or an extruder is used for melt blending of the components, wherein the temperature of the internal mixer or the extruder is set to be 170-220 ℃, preferably 180-210 ℃, and the rotation speed is 10-200 rmp.
9. A cosmetic package made from a completely biodegradable material according to any one of claims 1-7.
10. A cosmetic package made by the method of 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 |
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