CN109721978A - A kind of polylactic acid biodegradable composite material and preparation method thereof - Google Patents
A kind of polylactic acid biodegradable composite material and preparation method thereof Download PDFInfo
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- CN109721978A CN109721978A CN201910028186.4A CN201910028186A CN109721978A CN 109721978 A CN109721978 A CN 109721978A CN 201910028186 A CN201910028186 A CN 201910028186A CN 109721978 A CN109721978 A CN 109721978A
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- polylactic acid
- composite material
- biodegradable composite
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- bamboo fibre
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Abstract
The present invention relates to the technical fields of degradable composite material, and in particular to a kind of polylactic acid biodegradable composite material and preparation method thereof.Component including following parts by weight: 40-60 parts of polylactic acid, 30-50 parts of bamboo fibre, 10-15 parts of crosslinking agent, 0.2-1.5 parts of surfactant, 0.2-1 parts of levelling agent, 0.1-0.5 parts of antioxidant.The present invention is enough so that bamboo fibre and the interface compatibility of polylactic acid greatly improve, to reduce polylactic acid glass transition temperature, enhancing polylactic acid toughness makes it be more suitable for footwear processing.
Description
Technical field
The present invention relates to the technical fields of degradable composite material, and in particular to a kind of polylactic acid biodegradable composite wood
Material and preparation method thereof.
Background technique
With the continuous improvement of people's living standards, some articles for daily use shoes that for example we wear usually are lived to us
Also caused a series of problem while bringing convenient, due to the main component plastics of shoes materials, conventional plastic its due to
Its degradation time is too long, will cause such as environmental pollution, and petroleum resources are exhausted and endanger ecological environment etc..With the hair of technology
Exhibition, some degradation materials are employed in footwear production.Such as the composite material of poly-lactic acid material and bamboo fibre is since it comes
Derived from natural resources, have the characteristics that complete biodegradable, therefore becomes the preferred material of novel environment friendly shoes.But polylactic acid material
Material is maximum with bamboo fiber composite material the disadvantage is that brittleness is big, toughness is poor and flexible difference, therefore in footwear with receiving
To certain restrictions.
Summary of the invention
For this reason, it may be necessary to provide a kind of polylactic acid biodegradable composite material and preparation method thereof, the object of the invention is intended to
Improve the toughness and flexibility of polylactic acid biodegradable composite material.
To achieve the above object, the present invention provides a kind of polylactic acid biodegradable composite materials, it is characterised in that: packet
Include the component of following parts by weight:
Comprehensive above-mentioned each component is 100 parts by weight；The polylactic acid molecule amount is 110000-150000, and melt index is
7-9g/min (170 DEG C, 2.15kg), density 1.25-1.3g/cm3。
Preferably, the bamboo fibre uses moso bamboo fiber, and specification is 30~70 mesh.
Preferably, the crosslinking agent is lysine triisocyanate, benzoyl peroxide, tetraalkyl butyl acrylate, titanium
One of sour four butyl esters.
Preferably, the surfactant be one of magnesium stearate, fatty glyceride, lauryl sodium sulfate or
It is several.
Preferably, the levelling agent is ternary polymerization type polyacrylate.
Preferably, the preparation method of the ternary polymerization type polyacrylate is, is basic monomer, first with butyl acrylate
Base methyl acrylate and 2-Hydroxy ethyl acrylate are functional comonomer, with isopropanol are molten under the action of initiator
Agent carries out free radical polymerization, obtains ternary polymerization type polyacrylate.
Preferably, the antioxidant is phosphite ester antioxidant.
The present invention also provides a kind of polylactic acid biodegradable composite material preparation methods, which is characterized in that including following
Step:
(1) bamboo fibre is subjected to alkali process；
(2) bamboo fibre, crosslinking agent, surfactant, levelling agent, the antioxidant after polylactic acid, alkali process are dried in proportion
It is uniformly mixed after dry, 10~14h is placed in sealing at normal temperature；
(3) it is kneaded using open type dual-roller kneading machine,
(4) it is blended by super power crusher to graininess, drying after cooling.
Preferably, which is characterized in that in step (1), bamboo fibre is put under 12%NaOH aqueous solution room temperature (20 DEG C) and is soaked
After steeping 36h, it is sent into electronic thermostatic drying cabinet with strainer sub-department bamboo fibre and with after tap water repeated flushing to neutrality 75
It dries at a temperature of DEG C to constant mass.
Preferably, melting temperature is 165~180 DEG C, 12~20min of mixing time.
It is different from the prior art, above-mentioned technical proposal has the advantages that
1. the present invention uses lysine triisocyanate, benzoyl peroxide, tetraalkyl butyl acrylate, butyl titanate
One of esterification is carried out to polylactic acid and graft modification is handled, ternary polymerization type polyacrylate of the invention can after being added
So that bamboo fibre and the interface compatibility of polylactic acid greatly improve, to reduce polylactic acid glass transition temperature, enhance poly- cream
Sour toughness makes it be more suitable for footwear processing.
2. the present invention is handled bamboo fibre using sodium hydroxide, which can improve bamboo fibre and polylactic acid
Between interface compatibility so that the elongation at break of composite material greatly improves, tensile strength is increased to from 40MPa
80MPa, degree of drawing improve by about one time again, and thermal stability also significantly improves.
Specific embodiment
Technology contents, construction feature, the objects and the effects for detailed description technical solution, below in conjunction with specific reality
Example is applied to be explained in detail.
Polylactic acid molecule amount in the present embodiment is 110000-150000, melt index be 7-9g/min (170 DEG C,
2.15kg), density 1.25g-1.3/cm3。
Bamboo fibre in the present embodiment uses moso bamboo fiber, and specification is 30~70 mesh.
The preparation of ternary polymerization type polyacrylate:
It is basic monomer with butyl acrylate, methyl methacrylate and 2-Hydroxy ethyl acrylate are functional copolymerization
Monomer carries out free radical polymerization by solvent of isopropanol under the action of initiator, obtains ternary polymerization type polyacrylate.
Embodiment 1
(1) bamboo fibre is put into after impregnating 36 under 12%%NaOH aqueous solution room temperature (20 DEG C), it is fine with strainer sub-department bamboo
It ties up and uses to be sent into electronic thermostatic drying cabinet after tap water repeated flushing to neutrality and dry at a temperature of 75 DEG C to constant mass.
(2) by 60 parts of polylactic acid, 32 parts of bamboo fibres, 5 parts of lysine triisocyanate, 1.5 parts of magnesium stearates, 1 part of ternary
It is uniformly mixed after copolymerized type propene polymer acid esters, 0.5 part of phosphite ester antioxidant drying, 10h is placed in sealing at normal temperature；It is above-mentioned
Comprehensive each component is 100 parts by weight；The polylactic acid molecule amount be 110000, melt index be 7g/min (170 DEG C,
2.15kg), density 1.25g/cm3.
(3) it is kneaded using open type dual-roller kneading machine, melting temperature is 165 DEG C, mixing time 12min；
(4) it is blended by super power crusher to graininess after cooling, then imports hot pressing die (specification 200mm*120mm*
5mm), piling height is more than mold 1mm, and one layer of masking foil is enclosed on surface, and mold is put into hot press, and hot pressing time 25 minutes,
160 DEG C of hot pressing temperature, pressure 12MPa, composite material drying pack sealing after hot pressing.
Embodiment 2
(1) bamboo fibre is put into after impregnating 40h under 15%NaOH aqueous solution room temperature (24 DEG C), with strainer sub-department bamboo fibre
And it is dried at a temperature of 80 DEG C to constant mass with being sent into after tap water repeated flushing to neutrality in electronic thermostatic drying cabinet.
(2) by 40 parts of polylactic acid, 48 parts of bamboo fibres, 11 parts of benzoyl peroxides, 0.1 part of benzoyl peroxide, 0.8 part three
It is uniformly mixed after first copolymerized type propene polymer acid esters, 0.1 part of phosphite ester antioxidant drying, 14h is placed in sealing at normal temperature；On
It is 100 parts by weight that it is comprehensive, which to state each component,；The polylactic acid molecule amount be 150000, melt index be 9g/min (170 DEG C,
2.15kg), density 1.3/cm3.
(3) it is kneaded using open type dual-roller kneading machine, melting temperature is 180 DEG C, mixing time 20min；
(4) it is blended by super power crusher to graininess after cooling, then imports hot pressing die (specification 200mm*120mm*
5mm), piling height is more than mold 1mm, and one layer of masking foil is enclosed on surface, and mold is put into hot press, and hot pressing time 25 minutes,
160 DEG C of hot pressing temperature, pressure 12MPa, composite material drying pack sealing after hot pressing.
Embodiment 3
(1) bamboo fibre is put into after impregnating 38h under 13%NaOH aqueous solution room temperature (23 DEG C), with strainer sub-department bamboo fibre
And it is dried at a temperature of 78 DEG C to constant mass with being sent into after tap water repeated flushing to neutrality in electronic thermostatic drying cabinet.
(2) by 50 parts of polylactic acid, 34 parts of bamboo fibres, 15 parts of tetraalkyl butyl acrylates, 0.2 part of lauryl sodium sulfate,
It is uniformly mixed after 0.5 part of ternary polymerization type polyacrylate, 0.3 part of phosphite ester antioxidant drying, sealing is put at normal temperature
Set 12h；Comprehensive above-mentioned each component is 100 parts by weight；The polylactic acid molecule amount is 130000, and melt index is 8g/min (170
DEG C, 2.15kg), density 1.28g/cm3。
(3) it is kneaded using open type dual-roller kneading machine, melting temperature is 175 DEG C, mixing time 18min；
(4) it is blended by super power crusher to graininess after cooling, then imports hot pressing die (specification 200mm*120mm*
5mm), piling height is more than mold 1mm, and one layer of masking foil is enclosed on surface, and mold is put into hot press, and hot pressing time 25 minutes,
160 DEG C of hot pressing temperature, pressure 12MPa, composite material drying pack sealing after hot pressing.
Embodiment 4
(1) bamboo fibre is put into after impregnating 37h under 14%NaOH aqueous solution room temperature (22 DEG C), with strainer sub-department bamboo fibre
And it is dried at a temperature of 76 DEG C to constant mass with being sent into after tap water repeated flushing to neutrality in electronic thermostatic drying cabinet.
(2) by 55 parts of polylactic acid, 50 parts of bamboo fibres, 10 parts of lysine triisocyanate, 0.5 part of fatty glyceride, 0.2
It is uniformly mixed after part ternary polymerization type polyacrylate, 0.3 part of phosphite ester antioxidant drying, sealing is placed at normal temperature
11h；Comprehensive above-mentioned each component is 100 parts by weight；The polylactic acid molecule amount is 140000, and melt index is 9g/min (170
DEG C, 2.15kg), density 1.25g/cm3.
(3) it is kneaded using open type dual-roller kneading machine, melting temperature is 170 DEG C, mixing time 15min；
(4) it is blended by super power crusher to graininess after cooling, then imports hot pressing die (specification 200mm*120mm*
5mm), piling height is more than mold 1mm, and one layer of masking foil is enclosed on surface, and mold is put into hot press, and hot pressing time 25 minutes,
160 DEG C of hot pressing temperature, pressure 12MPa, composite material drying pack sealing after hot pressing.
Embodiment 5
(1) bamboo fibre is put into after impregnating 36h under 12%NaOH aqueous solution room temperature (20 DEG C), with strainer sub-department bamboo fibre
And it is dried at a temperature of 75 DEG C to constant mass with being sent into after tap water repeated flushing to neutrality in electronic thermostatic drying cabinet.
(2) by 52 parts of polylactic acid, 31 parts of bamboo fibres, 14 parts of lysine triisocyanate, 1.5 parts of lauryl sodium sulfate, 1
It is uniformly mixed after part ternary polymerization type polyacrylate, 0.5 part of phosphite ester antioxidant drying, sealing is placed at normal temperature
14h；Comprehensive above-mentioned each component is 100 parts by weight；The polylactic acid molecule amount is 150000, and melt index is 9g/min (170
DEG C, 2.15kg), density 1.3/cm3.
(3) it is kneaded using open type dual-roller kneading machine, melting temperature is 180 DEG C, mixing time 20min；
(4) it is blended by super power crusher to graininess after cooling, then imports hot pressing die (specification 200mm*120mm*
5mm), piling height is more than mold 1mm, and one layer of masking foil is enclosed on surface, and mold is put into hot press, and hot pressing time 25 minutes,
160 DEG C of hot pressing temperature, pressure 12MPa, composite material drying pack sealing after hot pressing.
Comparative example 1 not could be used without that crosslinking agent and ternary polymerization type polyacrylate is added, and the bamboo for not carrying out alkali process is fine
Tie up material.
By above-described embodiment 1-5, comparative example 1 is cut into 100mm*100mm*1mm size, with the rate of extension of 60mm/min
Test its elongation at break.
It can be seen that specific experiment data through this embodiment from above-described embodiment and comparative example to show, the present invention is logical
Cross polylactic acid and the reasonable combination and accurate proportioning of other material mixture ratios, the mechanical performance of the product of acquisition, crystal property and resistance to
Hot property greatly improves.
It should be noted that, in this document, relational terms such as first and second and the like are used merely to a reality
Body or operation are distinguished with another entity or operation, are deposited without necessarily requiring or implying between these entities or operation
In any actual relationship or order or sequence.Moreover, the terms "include", "comprise" or its any other variant are intended to
Non-exclusive inclusion, so that the process, method, article or the terminal device that include a series of elements not only include those
Element, but also including other elements that are not explicitly listed, or further include for this process, method, article or end
The intrinsic element of end equipment.In the absence of more restrictions, being limited by sentence " including ... " or " including ... "
Element, it is not excluded that there is also other elements in process, method, article or the terminal device for including the element.This
Outside, herein, " being greater than ", " being less than ", " being more than " etc. are interpreted as not including this number；" more than ", " following ", " within " etc. understand
Being includes this number.
Although the various embodiments described above are described, once a person skilled in the art knows basic wounds
The property made concept, then additional changes and modifications can be made to these embodiments, so the above description is only an embodiment of the present invention,
It is not intended to limit scope of patent protection of the invention, it is all to utilize equivalent structure or equivalent made by present specification
Process transformation, being applied directly or indirectly in other relevant technical fields, similarly includes in patent protection model of the invention
Within enclosing.
Claims (10)
1. a kind of polylactic acid biodegradable composite material, it is characterised in that: the component including following parts by weight:
Comprehensive above-mentioned each component is 100 parts by weight；The polylactic acid molecule amount is 110000-150000, melt index 7-9g/
Min (170 DEG C, 2.15kg), density 1.25g-1.3/cm3。
2. a kind of polylactic acid biodegradable composite material according to claim 1, it is characterised in that: the bamboo fibre is adopted
With moso bamboo fiber, specification is 30~70 mesh.
3. a kind of polylactic acid biodegradable composite material according to claim 1, it is characterised in that: the crosslinking agent is
One of lysine triisocyanate, benzoyl peroxide, tetraalkyl butyl acrylate.
4. a kind of polylactic acid biodegradable composite material according to claim 1, it is characterised in that: the surface-active
Agent is one or more of magnesium stearate, fatty glyceride, lauryl sodium sulfate.
5. a kind of polylactic acid biodegradable composite material according to claim 1, it is characterised in that: the levelling agent is
Ternary polymerization type polyacrylate.
6. a kind of polylactic acid biodegradable composite material according to claim 4, it is characterised in that: the ternary polymerization
The preparation method of type polyacrylate is, is basic monomer, methyl methacrylate and acrylic acid -2- hydroxyl with butyl acrylate
Ethyl ester is functional comonomer, carries out free radical polymerization by solvent of isopropanol under the action of initiator, and it is total to obtain ternary
Poly- type polyacrylate.
7. a kind of polylactic acid biodegradable composite material according to claim 1, it is characterised in that: the antioxidant is
Phosphite ester antioxidant.
8. a kind of polylactic acid biodegradable composite material preparation method, which comprises the following steps:
(1) bamboo fibre is subjected to alkali process；
(2) after bamboo fibre, crosslinking agent, surfactant, levelling agent, the antioxidant after polylactic acid, alkali process being dried in proportion
It is uniformly mixed, 10~14h is placed in sealing at normal temperature；
(3) it is kneaded using open type dual-roller kneading machine,
(4) it is blended by super power crusher to graininess, drying after cooling.
9. a kind of polylactic acid biodegradable composite material preparation method according to claim 8, which is characterized in that step
(1) in, bamboo fibre is put into after impregnating 36-40h under 12%-15%NaOH aqueous solution room temperature (20 DEG C -24 DEG C), with strainer sub-argument
Locate bamboo fibre and is dried at a temperature of 75-80 DEG C to matter with being sent into after tap water repeated flushing to neutrality in electronic thermostatic drying cabinet
It measures constant.
10. a kind of polylactic acid biodegradable composite material preparation method according to claim 8, which is characterized in that mixed
Refining temperature is 165~180 DEG C, 12~20min of mixing time.
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| CN201910028186.4A CN109721978A (en) | 2019-01-11 | 2019-01-11 | A kind of polylactic acid biodegradable composite material and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113045836A (en) * | 2019-12-28 | 2021-06-29 | 合肥杰事杰新材料股份有限公司 | Degradable high impact polystyrene resin and preparation method thereof |
| CN113881208A (en) * | 2021-11-22 | 2022-01-04 | 中南林业科技大学 | Functionalized modified straw/polylactic acid composite material and preparation method thereof |
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| CN105623219A (en) * | 2016-03-28 | 2016-06-01 | 东莞市恒丰高新技术开发有限公司 | Full-degradable injection product and preparation method therefor |
| CN108117729A (en) * | 2018-01-31 | 2018-06-05 | 浙江明江新材料科技有限公司 | A kind of bamboo fibre/lactic acid composite material and preparation method thereof |
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Patent Citations (3)
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| US20090288667A1 (en) * | 2008-05-21 | 2009-11-26 | R. J. Reynolds Tobacco Company | Apparatus for Forming a Filter Component of a Smoking Article, and Associated Method |
| CN105623219A (en) * | 2016-03-28 | 2016-06-01 | 东莞市恒丰高新技术开发有限公司 | Full-degradable injection product and preparation method therefor |
| CN108117729A (en) * | 2018-01-31 | 2018-06-05 | 浙江明江新材料科技有限公司 | A kind of bamboo fibre/lactic acid composite material and preparation method thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113045836A (en) * | 2019-12-28 | 2021-06-29 | 合肥杰事杰新材料股份有限公司 | Degradable high impact polystyrene resin and preparation method thereof |
| CN113045836B (en) * | 2019-12-28 | 2023-11-03 | 合肥杰事杰新材料股份有限公司 | Degradable high-impact polystyrene resin and preparation method thereof |
| CN113881208A (en) * | 2021-11-22 | 2022-01-04 | 中南林业科技大学 | Functionalized modified straw/polylactic acid composite material and preparation method thereof |
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