CN105936675B - A kind of preparation method of nylon CS blend film - Google Patents
A kind of preparation method of nylon CS blend film Download PDFInfo
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- CN105936675B CN105936675B CN201610406630.8A CN201610406630A CN105936675B CN 105936675 B CN105936675 B CN 105936675B CN 201610406630 A CN201610406630 A CN 201610406630A CN 105936675 B CN105936675 B CN 105936675B
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L5/00—Compositions of polysaccharides or of their derivatives not provided for in groups C08L1/00 or C08L3/00
- C08L5/08—Chitin; Chondroitin sulfate; Hyaluronic acid; Derivatives thereof
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- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
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- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
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- C08J2305/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2301/00 or C08J2303/00
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
- C08J2377/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
- C08J2377/06—Polyamides derived from polyamines and polycarboxylic acids
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- C—CHEMISTRY; METALLURGY
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Abstract
The present invention relates to a kind of preparation methods of nylon CS blend film, this method is without doing subsequent processing to nylon and chitosan surface, it does not need that solubilizer is added in the blend yet, but apply stable DC electrostatic field simultaneously in inversion of phases film forming procedure, the distribution of charges between CS segment can be stablized during the inversion of phases of DC electric field auxiliary, utilize the electrostatic repulsion between charge, moreover it is possible to lure that dipole orientation occurs for polar functional group into, stretch CS conformation；Phenomena such as controlling dipole orientation by DC electric field, inhibit the formation in CS strand with molecule interchain hydrogen bond, on the one hand avoiding the reunion, sedimentation and migration of CS strand；On the other hand the crystallization behavior for inhibiting strand to be caused by hydrogen bond, strengthen the interface interaction between nylon and CS molecule segment, so that CS and PA is formed the interaction such as more chain entanglements, so as to improve the compatibility of blend, the tensile property of blend is improved, and whole preparation process is low in cost, efficient.
Description
Technical field
The present invention relates to a kind of preparation methods of nylon CS blend film.
Background technique
Chitosan (CS) is a kind of highly important natural macromolecular material, because its is cheap and easy to get, biocompatibility is excellent
And the features such as degradable and be widely used in the fields such as UF membrane, food packaging and drug release.However, CS is lower mechanical strong
Degree but limits its application range.Nylon is blended with CS, the hydrophily, antibiotic property, stability of CS can be greatly improved.But
It is, it is past after it is blended with nylon (PA) due to the substantive characteristics such as polar functional group and polycation a large amount of on CS strand
Toward there are the mutually separation of macro-scale, cause the mechanical strength of blend low, or even the mechanical strength no more than CS itself.
Phase inversion is one of the main method for preparing polymer blended film.It is with chitosan-formic acid-nylon system
Example, formic acid can with the polar functional group on PA strand formed hydrogen bond so that around strand formed connected by hydrogen bond it is molten
Agent layer promotes the dissolution and stable dispersion of PA strand.- NH under the action of formic acid, on CS strand2It is protonated
For-NH3+, form the high polymer main chain of polycation, strand internal cause-NH2The electrostatic repulsion that protonation is formed makes CS segment exist
The conformation (J.Am.Chem.Soc.2015,137,13024-13030) of stretching, extension is formed in formic acid solution.However, due to the matter of CS
Sub-ization degree is very sensitive to solution concentration, with the continuous volatilization of formic acid ,-NH2Protonation decline rapidly, cause point
Electrostatic repulsion weakens between subchain, or even disappears, and segment conformation becomes to crimp.At this point, a large amount of-OH and-NH on CS main chain2Meeting exists
In strand and molecule interchain forms hydrogen bond, so that CS chain amount of crimp is aggravated, and lures that strand is reunited into, this leads to PA
Strand hardly enters CS molecule interchain, it is difficult to realize the uniform mixing on strand scale, the boundary strength of blend is extremely low.
When film forming, due to density (the ρ ≈ 1.75g/cm of CS3) it is higher than PA (ρ ≈ 0.89g/cm3), it has eventually led to PA and has been enriched on film
Layer, and CS is deposited on film lower layer, prolong film thickness direction there are the mutually separation of apparent phase interface and macro-scale (Polymer,
1999,40,1657-1666)。
Patent CN104975504A discloses a kind of method for preparing CS Yu PA blend, by nylon section hydrolysis and it is right
The modification of nylon molecules chain progress carboxyl and amino；Then chitosan is carried out amino modified；Finally, utilizing amide condensed reaction
Uniformly mixed nylon/the chitosan mixed film of preparation.Antibacterial, the gas permeability of composite membrane are obviously improved.However, this method technique is multiple
Miscellaneous, graft modification process be easy to cause the chain rupture behavior of CS strand, has lost the original characteristic of natural polymer significantly.
Summary of the invention
The technical problem to be solved by the invention for the present situation of prior art is to provide one kind can effectively improve blend
Compatibility, improve blend tensile property nylon CS blend film preparation method.
The technical scheme of the invention to solve the technical problem is: a kind of preparation method of nylon CS blend film,
Characterized by the following steps:
(1) nylon is dissolved in organic solvent, prepares mother liquor；
(2) it is added chitosan into mother liquor, the weight ratio of chitosan and nylon is 10%~90%, after stirring 24~72h,
Static 4~8h, obtains blended liquid；
(3) blended liquid is placed on conduction film forming plate, is applied on conduction film forming plate perpendicular to the conductive plate that forms a film
DC electrostatic field, which promotes solvent release mother liquor and volatilizees, until obtaining nylon/chitosan mixed film.
In the above scheme, conductive film forming upper plate, the conductive film forming are provided with above the conductive film forming plate
Plate ground connection, the conductive film forming upper plate connect power cathode；The electrostatic field applies to be formed by DC power supply, described straight
The voltage in galvanic electricity source is 0.01~10MV/m.
Preferably, the organic solvent is anhydrous formic acid, in the blended liquid nylon and formic acid dose than for
0.001~1g/mL.
Preferably, the nylon is selected from nylon 6, nylon66 fiber, nylon 1010 and its mixture.
Preferably, the deacetylation of the chitosan is 70%~100%.
Preferably, the molecular weight of the nylon is 1000~100000g/mol, the molecular weight of the CS is 2000~
200000g/mol。
Compared with the prior art, the advantages of the present invention are as follows: the present invention is without doing subsequent place to nylon and chitosan surface
Reason, does not need that solubilizer is added in the blend yet, but applies stable DC static simultaneously in inversion of phases film forming procedure
, the distribution of charges between CS segment can be stablized during the inversion of phases of DC electric field auxiliary, denounceed using the electrostatic between charge
Power, moreover it is possible to it lures that dipole orientation occurs for polar functional group into, destroys the hydrogen bond environment in system inner macromolecule interchain and macromolecular chain,
Strengthen interface interaction between nylon and CS molecule segment, stretches CS conformation；With the volatilization of formic acid, when protonation declines
When, electrostatic repulsion fades away, at this point, the dipole orientation of polar functional group is to the respondent behavior of electric field in CS segment in strand
Conformation transition in will play a significant role, by DC electric field control dipole orientation, inhibit CS strand in and molecule interchain
The formation of hydrogen bond, phenomena such as on the one hand avoiding the reunion of CS strand, sedimentation and migration；On the other hand inhibit strand by hydrogen bond
The crystallization behavior of initiation strengthens the interface interaction between nylon and CS molecule segment, CS and PA is made to form the phases such as more chain entanglements
Interaction improves the tensile property of blend so as to improve the compatibility of blend, and whole preparation process is low in cost, high
Effect.
Detailed description of the invention
Fig. 1 is the Total Reflection Infrared comparison diagram of blend film prepared by the embodiment of the present invention 1 and comparative example 1；
Fig. 2 is that the SEM of blend film prepared by the embodiment of the present invention 1 and comparative example 1 schemes.
Specific embodiment
The present invention will be described in further detail below with reference to the embodiments of the drawings.
Embodiment 1:
The nylon 6 that 0.5g molecular weight is 10000g/mol is dissolved in 10ml formic acid, film forming mother liquor is obtained.Add into mother liquor
Enter molecular weight be 10000g/mol chitosan, deacetylation 95%, the weight ratio 50% of chitosan and nylon, stirring for 24 hours after, it is quiet
Only 8h；Mother liquor is placed on conductive film forming plate；Film forming plate is placed in parallel-plate electric field, applies electricity in surface plate two sides
, wherein conductive film forming plate upper plate is negatively charged, plate earthing under conduction film forming plate, DC voltage field strength is 0.3MV/m.To molten
After agent volatilization, nylon/chitosan mixed film is obtained.Gained blend film tensile strength reaches 80MPa, and elongation at break is up to 85%.
Comparative example 1:
The nylon 6 that 0.5g molecular weight is 10000g/mol is dissolved in 10ml formic acid, film forming mother liquor is obtained.Add into mother liquor
Enter molecular weight be 10000g/mol chitosan, deacetylation 95%, the weight ratio 50% of chitosan and nylon, stirring for 24 hours after,
Static 8h；Mother liquor is placed on conductive film forming plate；Do not apply voltage and it is total to obtain nylon/chitosan after band solvent volatilizees naturally
Mixed film.The tensile strength 34MPa of gained blend film, elongation at break 1.5%.
As seen from Figure 1,3300cm-1Place is the stretching vibration peak of PA6 strand N-H key, 3080cm-1Place is the face N-H
Internal vibration peak, 1640cm-1Place is C=O stretching vibration peak.1540cm-1Place is the vibration peak of CO-N-H.3300cm-1The broad peak at place
For the NH of CS strand2Stretching vibration peak, 898cm-1And 1150cm-1The peak at place corresponds to the sugared structure of CS.As seen from the figure, right
In the CS/PA blend that ratio 1 is prepared under gravitational field, upper surface is mostly the infrared signature peak of PA6, and lower surface is mostly CS
Infrared signature peak.CS is deposited on film lower surface after showing mutually separation, and PA is more enriched in film upper surface.And embodiment 1 is applied
After the direct current flat field for adding 0.3MV/m, upper and lower surfaces 898cm-1And 1150cm-1The feature peak intensity of place CS is decreased obviously,
Lower surface 3300cm-1The broad peak at place disappears.1540cm-1Place is the vibration peak and 3300cm of CO-N-H-1The flexible vibration of the N-H key at place
Dynamic peak intensity obviously increases, and shows the hydrogen bond action enhancing between CS and PA.Upper and lower surface infrared line is similar, illustrates CS's and PA
Macro-scale phenomenon of phase separation is obviously inhibited.
CS/PA cross-section diagram a) prepared in Fig. 2 for comparative example 1；B) the CS/PA cross-section diagram prepared for embodiment 1, voltage
0.3MV/m；C) the CS/PA upper surface figure prepared for comparative example 1；D) the CS/PA upper surface figure prepared for embodiment 1, voltage
0.3MV/m.As seen from the figure, there are apparent phase interfaces for the blend film section that comparative example 1 is prepared under gravitational field, and upper surface is very
It is coarse, and have many kicks.This shows that blend mixed effect is very poor, and there are the mutually separation of macro-scale in film.And implement
After example 1 applies the direct current flat field of 0.3MV/m, blend film cross-section morphology is uniform, surfacing, illustrates to act in electric field force
Under, CS and PA be blended effect be improved significantly.
Embodiment 2:
The nylon66 fiber that 0.5g molecular weight is 100000g/mol is dissolved in 500ml formic acid, film forming mother liquor is obtained.To mother liquor
Middle addition molecular weight is 200000g/mol chitosan, deacetylation 80%, the weight ratio 10% of chitosan and nylon, stirring 72h
Afterwards, static 4h；Mother liquor is placed on conductive film forming plate；Film forming plate is placed in parallel-plate electric field, is applied in surface plate two sides
Added electric field, wherein conductive film forming plate upper plate is negatively charged, plate earthing under conduction film forming plate, DC voltage field strength is 10MV/m.
After the solvent is volatilized, nylon/chitosan hybrid films are obtained.The tensile strength of gained composite membrane reaches 195MPa, and elongation at break reaches
115%.
Embodiment 3:
The nylon 1010 that 0.5g molecular weight is 1000g/mol is dissolved in 0.5ml formic acid, film forming mother liquor is obtained.To mother liquor
Middle addition molecular weight is 2000g/mol chitosan, deacetylation 70%, the weight ratio 90% of chitosan and nylon, stirring 72h
Afterwards, static 6h；(3) mother liquor is placed on conductive film forming plate；(4) film forming plate is placed in parallel-plate electric field, in surface plate
Two sides apply electric field, wherein conduction forms a film, plate upper plate is negatively charged, plate earthing under conduction film forming plate, and DC voltage field strength is
0.01MV/m.After the solvent is volatilized, nylon/chitosan hybrid films are obtained.The tensile strength of gained composite membrane reaches 65MPa, fracture
Elongation is up to 135%.
Embodiment 4:
The nylon 5 that 0.5g molecular weight is 5000g/mol is dissolved in 20ml formic acid, film forming mother liquor is obtained.Add into mother liquor
Enter molecular weight be 10000g/mol chitosan, deacetylation 90%, the weight ratio 70% of chitosan and nylon, stir 48h after, it is quiet
Only 8h；(3) mother liquor is placed on conductive film forming plate；(4) film forming plate is placed in parallel-plate electric field, is applied in surface plate two sides
Added electric field, wherein conductive film forming plate upper plate is negatively charged, plate earthing under conduction film forming plate, DC voltage field strength is 6MV/m.To
After solvent volatilization, nylon/chitosan hybrid films are obtained.The tensile strength of gained composite membrane reaches 95MPa, and elongation at break reaches
95%.
Embodiment 5:
The nylon 5 that 0.5g molecular weight is 5000g/mol is dissolved in 20ml formic acid, film forming mother liquor is obtained.Add into mother liquor
Enter molecular weight be 8000g/mol chitosan, deacetylation 100%, the weight ratio 30% of chitosan and nylon, stir 48h after, it is quiet
Only 8h；(3) mother liquor is placed on conductive film forming plate；(4) film forming plate is placed in parallel-plate electric field, is applied in surface plate two sides
Added electric field, wherein conductive film forming plate upper plate is negatively charged, plate earthing under conduction film forming plate, DC voltage field strength is 0.1MV/m.
After the solvent is volatilized, nylon/chitosan hybrid films are obtained.The tensile strength 905MPa of gained composite membrane, elongation at break reach
75%.
Claims (6)
1. a kind of preparation method of nylon CS blend film, it is characterised in that the following steps are included:
(1) nylon is dissolved in organic solvent, prepares mother liquor；
(2) it is added chitosan into mother liquor, the weight ratio of chitosan and nylon is 10%~90%, static after stirring 24~72h
4~8h obtains blended liquid；
(3) blended liquid is placed on conductive film forming plate, is applied on conductive film forming plate perpendicular to the straight of conductive film forming plate
Electrostatic field is flowed, which promotes solvent release mother liquor and volatilize, until obtaining nylon/chitosan mixed film.
2. the preparation method of nylon CS blend film according to claim 1, it is characterised in that: the conductive film forming plate
Top is provided with conductive film forming upper plate, the conductive film forming plate ground connection, and the conductive film forming upper plate connects power cathode；Institute
The electrostatic field stated applies to be formed by DC power supply, and the voltage of the DC power supply is 0.01~10MV/m.
3. the preparation method of nylon CS blend film according to claim 1, it is characterised in that: the organic solvent is nothing
Water beetle acid, nylon and formic acid doses than for 0.001~1g/mL in the blended liquid.
4. the preparation method of nylon CS blend film according to claim 1, it is characterised in that: the nylon be selected from nylon 6,
Nylon66 fiber, nylon 1010 and its mixture.
5. the preparation method of nylon CS blend film according to claim 1, it is characterised in that: the chitosan it is deacetylated
Degree is 70%~100%.
6. the preparation method of nylon CS blend film according to claim 1, it is characterised in that: the molecular weight of the nylon is
The molecular weight of 1000~100000g/mol, the CS are 2000~200000g/mol.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112225829A (en) * | 2020-10-29 | 2021-01-15 | 江南大学 | Polysaccharide with charged tail end and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106513703B (en) * | 2016-11-22 | 2018-05-15 | 宁波工程学院 | A kind of preparation method of chitosan Ag nano composite membranes |
| CN106832436A (en) * | 2016-12-26 | 2017-06-13 | 华东理工大学 | A kind of polybutyrolactam/chitosan blend thing and preparation method thereof |
| CN108795029B (en) * | 2018-06-28 | 2020-09-04 | 宁波工程学院 | Method for preparing polyamide/chitosan blend membrane and application |
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| CN103755984A (en) * | 2013-12-30 | 2014-04-30 | 宁波工程学院 | Method for preparing macromolecular nano composite membrane enriching inorganic filler on surface |
| CN104744715A (en) * | 2015-04-03 | 2015-07-01 | 宁波工程学院 | Method for preparing hydrophilic nylon film |
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|---|---|---|---|---|
| CN103755984A (en) * | 2013-12-30 | 2014-04-30 | 宁波工程学院 | Method for preparing macromolecular nano composite membrane enriching inorganic filler on surface |
| CN104744715A (en) * | 2015-04-03 | 2015-07-01 | 宁波工程学院 | Method for preparing hydrophilic nylon film |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112225829A (en) * | 2020-10-29 | 2021-01-15 | 江南大学 | Polysaccharide with charged tail end and preparation method thereof |
| CN112225829B (en) * | 2020-10-29 | 2021-08-24 | 江南大学 | Polysaccharide with charged tail end and preparation method thereof |
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