CN105462196B - A kind of preparation method of the high tough polymeric lactic acid compound film with barrier - Google Patents
A kind of preparation method of the high tough polymeric lactic acid compound film with barrier Download PDFInfo
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- CN105462196B CN105462196B CN201510216265.XA CN201510216265A CN105462196B CN 105462196 B CN105462196 B CN 105462196B CN 201510216265 A CN201510216265 A CN 201510216265A CN 105462196 B CN105462196 B CN 105462196B
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Abstract
The present invention relates to a kind of preparation method of the high intensity polymeric lactic acid compound film with barrier, its process is to be dissolved in dichloromethane solution and obtain clear solution PLA, PLA grafted maleic anhydride, polycaprolactone, maleic anhydride isobutyl group grafting POSS, solution is moved afterwards in groove as bottom liquid, electrostatic spinning nylon nano fiber is introduced in the solution, after be cast in Teflon mould, after standing dry evaporation solution obtain composite membrane.The composite membrane has excellent intensity, toughness, and has good barrier to oxygen, can be applied to environment-protective packaging film field.
Description
Technical field
The present invention relates to a kind of polymeric lactic acid compound film, more particularly to a kind of excellent strong, toughness and high barrier PLA
Composite membrane and preparation method thereof.
Background technology
Although plastic material possesses more excellent performance and wide applicability, but it derives from oil product and cannot drop
Solution, in crisis of resource and environmental pollution today serious all the more, finds function admirable and reproducible alternative materials then turns into mesh
The most important thing of preceding Material Field research.
In current degradation material, starch is furtherd investigate and passed through because of its cheap price and extensive source
It is modified to be prepared for various lives and industrial goods, such as starch basement membrane, starch dishware with compound.But starch has its natural to lack
Fall into, its poor mechanical property, unstable properties can only apply to the field low to mechanical property requirements.And the appearance of PLA
Change this present situation.PLA (PLA) is aliphatic polyester, with lactic acid (2 hydroxy propanoic acid) as basic structural unit.PLA can
It is obtained by natural materials such as fermented maizes, can be also obtained using lactic acid polycondensation.PLA and its end product can be under composting conditionses
Natural decomposition turns into CO2And water, solid waste discharge amount is reduced, it is a kind of biogenic material of environmental protection.
Although PLA is with good biodegradability, machinability, excellent mechanical property, its property is crisp easily
It is broken, lack flexibility and pliability, the application of PLA is largely limited, and, it is packaging in the main application of film
Using upper, its barrier is poor, it is impossible to be applied to the packaging field of preferable barrier.Change for PLA film strength
Property, certain research is there has been at present, during different materials adds PLA by way of blending or chemical modification.As such as grandson
(Sun Zhidan, Xu Yang, the Chen Xiaolang, Zhang Zhibin such as Zhidan；Polymer material science and engineering .2013.2,29 (2):54-57.) with
PLA-PEG-PLA block copolymer is plasticized modifier and polylactic acid blend, has obtained being broken at 80 DEG C and has prolonged
Stretching rate increases by 15% lactic acid composite material, and toughness obtains improvement to a certain extent, but its preparation process is complex, phase
Increase consuming energy and cost value；Open big grade (Wei Zhang, Long Chen, Yu Zhang, Polymer.2009,50:
1311-1315.) by polyamide elastomer and the blending of PLA, PLA pliability is substantially improved, but causes compound
The degradation of material mechanical performance.Chen Zhize etc. has invented a kind of its preparation method of transparent high-toughness polylactic acid film
(201310393192.2), it forms the common molten film of PLA and methyl MQ silicones, effectively raises the toughness of film.And
The method for being related to PLA barrier to improve is included therein introducing laminar nano particle such as nano imvite and realizes intercalation or common
Other barrier materials are mixed, but its barrier improves still limited, and it is highly dependent on processing conditions.
The content of the invention
The invention aims to overcome polylactic acid membrane material fragility big, the defect of barrier difference, there is provided one kind has
The preparation method of the polylactic acid membrane composite of excellent toughness and intensity.
The purpose of the present invention is achieved through the following technical solutions：
A kind of preparation method of the high intensity polymeric lactic acid compound film with barrier, the composite membrane is with PLA, PLA
Grafted maleic anhydride, polycaprolactone, maleic anhydride-isobutyl group grafting POSS and electrostatic spinning nylon nano fiber are raw material, with
Solvent method is obtained；
Its preparation process is：
(1)：PLA, PLA grafted maleic anhydride, polycaprolactone, maleic anhydride-isobutyl group are grafted POSS in 60
After the lower vacuum drying 24h of degree, in input dichloromethane, after 70 degree of lower high-speed stirred 1-2h, solution obtains clear solution, wherein,
PLA mass concentration in the solution is 15-25wt%, and the mass concentration of polycaprolactone is 5-15wt%, PLA grafting horse
Carry out the mass concentration of acid anhydrides for 3-6wt%, the mass concentration of maleic anhydride-isobutyl group grafting POSS is 1-3wt%；
(2)：Solution prepared by (1) is moved in groove as electrostatic spinning bottom liquid, is introduced in the solution by electrostatic spinning
Nylon nano fiber, stands 4 hours, wherein, the nylon nano fiber quality for introducing solution is the 20-40% of PLA；
(3)：Evaporation solution is dried during the solution that (2) obtain moved into Teflon mould, after standing and obtains composite membrane.
Further, the PLA is Pfansteihl, D-ALPHA-Hydroxypropionic acid or L, D-ALPHA-Hydroxypropionic acid composition, and the molecular weight of the PLA is situated between
Optimal in 100,000-30 ten thousand, selection molecular weight is between 150,000-25 ten thousand.
Further, between 1.2%-2%, molecular weight is between 12 for the grafting degree of the PLA grafted maleic anhydride
Between ten thousand -24 ten thousand.
Further, maleic anhydride involved in the present invention-isobutyl group grafting POSS is a kind of polyhedral oligomeric silsesquioxane
(POSS) derivative, POSS is the silica structure with octahedra cage structure, and POSS has 8 on the corner of cage structure
The group R that can be modified.R group is isobutyl group in the present invention, and its molecular structural formula is as follows：
Further, the solvent used by the nylon nano fiber electrostatic spinning is dichloromethane/formic acid mixed solution, both
Volume ratio is between 2：1-1：Between 2, nylon mass fraction wherein is 20-35wt%.
Further, the condition of the electrostatic spinning is：Solution flow rate between 0.7-1ml/h, voltage between 20-30kV it
Between, spinning distance is set as 15-20cm, and humidity is between 25%-35%.
Further, the diameter of the nylon nano fiber is between 20-200nm.
Further, excellent effect of the invention is that the addition of PLA grafted maleic anhydride effectively causes maleic acid
Acid anhydride-isobutyl group grafting POSS can be good be scattered in PLA matrix, and be closely connected with PLA matrix, so as to improve material
On the one hand the barrier of material, adding for electrostatic spinning nylon greatly improved the mechanical property of material, another aspect nylon plus
Enter to be also beneficial to the raising of film barrier.
Specific embodiment
Illustrative embodiment of the invention described in detail below.But these implementations are only exemplary purpose, and
The invention is not restricted to this.
Embodiment 1
A kind of high intensity polymeric lactic acid compound film with barrier, with PLA, PLA grafted maleic anhydride, gathers in oneself
Ester, maleic anhydride-isobutyl group grafting POSS and electrostatic spinning nylon nano fiber are raw material, are obtained with solvent method；
Its preparation process is：
PLA, PLA grafted maleic anhydride, polycaprolactone, maleic anhydride-isobutyl group grafting POSS are lower true in 60 degree
After sky dries 24h, it is dissolved in dichloromethane solution and obtains clear solution, wherein, PLA concentration in the solution is 22wt%,
The concentration of polycaprolactone is 12wt%, and the concentration of PLA grafted maleic anhydride is 4.5wt%, maleic anhydride-isobutyl group grafting
The concentration of POSS is 1.3wt%；Solution is moved in groove as bottom liquid, electrostatic spinning introduces nylon nano fiber in the solution,
After be placed in Teflon mould, after standing dry evaporation solution obtain composite membrane.Wherein, the nylon nano for introducing solution is fine
Dimension quality is the 25% of PLA.
The PLA is Pfansteihl, and the molecular weight of the PLA is between 150,000-20 ten thousand.
The grafting degree of the PLA grafted maleic anhydride is 1.4%, and molecular weight is between 140,000-20 ten thousand.
Further, the solvent used by the nylon nano fiber electrostatic spinning is dichloromethane/formic acid mixed solution, both
Volume ratio is 2: 1.5, and nylon mass fraction wherein is 30wt%.
The condition of the electrostatic spinning is：Between 0.8ml/h, voltage is 25kV to solution flow rate, and spinning distance is set as
18cm, humidity is 30%.
The diameter of the nylon nano fiber is between 50-100nm.
Specific performance is as shown in table 1.
Embodiment 2
A kind of high intensity polymeric lactic acid compound film with barrier, with PLA, PLA grafted maleic anhydride, gathers in oneself
Ester, maleic anhydride-isobutyl group grafting POSS and electrostatic spinning nylon nano fiber are raw material, are obtained with solvent method；By PLA,
PLA grafted maleic anhydride, polycaprolactone, maleic anhydride-isobutyl group grafting POSS dissolve in after 60 degree of lower vacuum drying 24h
Clear solution is obtained in dichloromethane solution, wherein, PLA concentration in the solution is 20wt%, and the concentration of polycaprolactone is
10wt%, the concentration of PLA grafted maleic anhydride is 4wt%, and the concentration of maleic anhydride-isobutyl group grafting POSS is 2wt%；
Solution is moved in groove as bottom liquid, electrostatic spinning nylon nano fiber is introduced in the solution, after be placed in Teflon mould
In, evaporation solution is dried after standing and obtains composite membrane, wherein, it is PLA to introduce the nylon nano fiber quality of solution
30%.
The PLA is D-ALPHA-Hydroxypropionic acid, and the molecular weight of the PLA is between 150,000-20 ten thousand.
The grafting degree of the PLA grafted maleic anhydride is 1.8%, and molecular weight is between 160,000-20 ten thousand.
Further, the solvent of the nylon nano fiber electrostatic spinning is dichloromethane/formic acid mixed solution, both volumes
Than being 1: 1, nylon mass fraction wherein is 25wt%.
The condition of the electrostatic spinning is：Between 0.9ml/h, voltage is 25kV to solution flow rate, and spinning distance is set as
16cm, humidity is 30%.
The diameter of the nylon nano fiber is between 50-150nm.
Specific performance is as shown in table 1.
The performance of composite membrane in the embodiment 1,2 of table 1
| Composite property | Embodiment 1 | Embodiment 2 |
| Fracture elongation (%) | 94±10 | 102±10 |
| Fracture strength (Mpa) | 86.4±3.21 | 88.7±2.45 |
| 25±4 | 30±5 |
Claims (5)
1. a kind of preparation method of the high intensity polymeric lactic acid compound film with barrier, the composite membrane is connect with PLA, PLA
Branch maleic anhydride, polycaprolactone, maleic anhydride-isobutyl group grafting POSS and electrostatic spinning nylon nano fiber are raw material, with molten
Agent method is obtained；Its preparation process is：
(1)：By PLA, PLA grafted maleic anhydride, polycaprolactone, the grafting of maleic anhydride-isobutyl group, POSS is Celsius in 60
After the lower vacuum drying 24h of degree, in input dichloromethane, after 70 degrees Celsius of lower high-speed stirred 1-2h, clear solution is obtained, wherein,
PLA mass concentration in the solution is 15-25wt%, and the mass concentration of polycaprolactone is 5-15wt%, PLA grafting horse
Carry out the mass concentration of acid anhydrides for 3-6wt%, the mass concentration of maleic anhydride-isobutyl group grafting POSS is 1-3wt%；
(2)：The solution prepared in (1) is moved in groove as electrostatic spinning bottom liquid, Buddhist nun is introduced by electrostatic spinning in the solution
Imperial nanofiber, stands 4 hours, wherein, the nylon nano fiber quality for introducing solution is the 20-40% of PLA；
(3)：Evaporation solution is dried during the solution that (2) obtain moved into Teflon mould, after standing and obtains composite membrane.
2. a kind of preparation method of the high intensity polymeric lactic acid compound film with barrier as claimed in claim 1, its feature exists
In, solvent used by the electrostatic spinning nylon nano fiber be dichloromethane/formic acid mixed solution, dichloromethane and formic acid
Volume ratio is between 2：1-1：Between 2, nylon mass fraction wherein is 20-35wt%.
3. a kind of preparation method of the high intensity polymeric lactic acid compound film with barrier as claimed in claim 1, its feature exists
In the condition of the electrostatic spinning is：Between 0.7-1ml/h, between 20-30kV, spinning distance sets voltage solution flow rate
It is set to 15-20cm, humidity is between 25%-35%.
4. a kind of preparation method of the high intensity polymeric lactic acid compound film with barrier as claimed in claim 1, its feature exists
In the diameter of the nylon nano fiber is between 20-200nm.
5. a kind of preparation method of the high intensity polymeric lactic acid compound film with barrier as claimed in claim 1, its feature exists
In the grafting degree of the PLA grafted maleic anhydride is between 1.2%-2%.
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Inventor after: Zhang Xuhua Inventor after: Chen Yi Inventor before: Chen Yi |
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Effective date of registration: 20170818 Address after: 411400 No. 7, Golden Road, Xiangxiang Economic Development Zone, Hunan Patentee after: Hunan Lihua New Material Co., Ltd. Address before: 412008 No. 88 West Taishan Road, Tianyuan District, Hunan, Zhuzhou Patentee before: Hunan University of Technology |
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