CN108948614A - A kind of lignin/polyvinyl alcohol composite material and preparation method thereof - Google Patents
A kind of lignin/polyvinyl alcohol composite material and preparation method thereof Download PDFInfo
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- CN108948614A CN108948614A CN201810788263.1A CN201810788263A CN108948614A CN 108948614 A CN108948614 A CN 108948614A CN 201810788263 A CN201810788263 A CN 201810788263A CN 108948614 A CN108948614 A CN 108948614A
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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
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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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
- C08J2329/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
- C08J2329/02—Homopolymers or copolymers of unsaturated alcohols
- C08J2329/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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Abstract
The invention belongs to technical field of polymer materials, a kind of lignin/polyvinyl alcohol composite material and preparation method thereof is disclosed.Composite material of the present invention includes the component of following mass percent: polyvinyl alcohol 70~99.4%；Lignin 0.5~30%；Additive 0.1~10%；The additive includes 3- amino -1,2,4 triazoles, 4-aminopyridine, 1- (3- aminopropyl) imidazoles, 4- (2- ethylamino-) benzene -1,2- diphenol, 2- amino -3- imidazole radicals propionic acid, tannic acid, 3,3,3', 3'- tetramethyl -1,1- spiral biindolyl -5,5', at least one of 6,6'- tetrol, zinc chloride, zinc acetate, iron chloride, calcium chloride, copper chloride, iron oxide, sodium chloride.The present invention also provides the preparation methods of above-mentioned composite material.For lignin of the present invention/polyvinyl alcohol composite material tensile strength up to 140MPa, elongation at break may be up to 800%.
Description
Technical field
The invention belongs to technical field of polymer materials, in particular to a kind of lignin/polyvinyl alcohol composite material and its
Preparation method.
Background technique
Polyvinyl alcohol (PVA) is a kind of water soluble polymer, has excellent mechanical performance, the good transparency, hyperoxia
The advantages that gas barrier property, biodegradable, is widely used in various products packaging [Polym.Int2009；58:97–104.].Together
When, polyvinyl alcohol has no toxic and side effect to human body, and is a kind of good bio-medical material.Contain a large amount of hydroxyls on polyvinyl alcohol backbones
Base, intermolecular and intramolecular form a large amount of hydrogen bonds, and physical crosslinking point is more, and density is high, leads to (200 DEG C of polyvinyl alcohol melting temperature
~250 DEG C) it is very close with decomposition temperature, fiber and plastic products cannot be processed into using melt molding, and solution is processed into
Type complex process, at high cost, environmental pollution is big, it is difficult to prepare the complex-shaped product of heavy wall pipe.Therefore melting temperature is reduced, it improves
Thermal stability is to realize the molding necessary condition of PVA melt-processed.
In recent years, most of to prepare although having much by the research report that blending and modifying prepares PVA composite material
The composite property come is bad, and cost of material is higher, is unfavorable for industrial production and application.For example, Chao Zhang etc.
People [J.Mater.Chem., 2012,22,2427.] is used for using the multi-slice carbon nanotube dispersed graphite alkene lamella of acid processing
The enhancing of PVA film, the compound film strength of PVA improve, and toughness is but substantially reduced, and cost of material is high, and process is cumbersome.
QipengGuo et al. [ACS Macro Lett.2013,2,1100-1104.] is enhanced by melamine and PVA blending and modifying
The mechanical property of PVA composite membrane, cost of material is higher, and reinforcing effect is limited.Pingan Song et al. [Adv.Mater.2017,
1704661.] styrene-ethylene/butylene-styrene triblock copolymer (SSEBS) nanosphere for synthesizing sulfonation modifying, with
The compound building hydrogen bond action of PVA, reduces the fusing point of PVA, improves the compound film strength of PVA and toughness.But SSEBS is synthesized
Complex process, cost of material is higher, and not degradable.
Lignin is the second largest biomass resource that cellulose is only second in plant, is the natural polymer with aromatic ring structure
Sub- compound, being known as 21 century can be by one of the most abundant green resource of human use.Lignin is from a wealth of sources, inexpensive easy
It obtains, degradable, nonhazardous, the feature structures such as phenyl ring, phenolic hydroxyl group in molecule make it have excellent anti-ultraviolet radiation and resist
Ageing properties [Green Chem., 2015,17 (1): 320.].Lignin is blended with PVA and prepares composite material, it not only can be with
Cost is reduced, while the excellent anti-ultraviolet radiation of material and anti-aging property can be assigned, for pushing the effective of biomass resource
Using and high molecular material greenization development all have significance.But current research is largely in lignin and PVA
Using formaldehyde or glutaraldehyde as crosslinking agent in Blending Processes.Guanhao Xu et al. by alkali lignin directly and PVA solution
It is blended, the poor compatibility between lignin and PVA, obtained compound film-strength is low, poor toughness；Ling Su et al.
[BioResources.2014,9 (3): 4477-4488.] industrial alkali lignin is blended with PVA, and formaldehyde is added as crosslinking
Agent, the compound film toughness of obtained PVA is not high, and preparation process uses toxic reagent formaldehyde.Therefore, how to further increase wooden
The interface compatibility of element and polyvinyl alcohol realizes that lignin is that current research is badly in need of to the effect of polyvinyl alcohol enhancing and toughening
The significant difficulty of solution.
Summary of the invention
In order to overcome the shortcomings and deficiencies of the prior art described above, the primary purpose of the present invention is that provide a kind of lignin/
Polyvinyl alcohol composite material.
Another object of the present invention is to provide a kind of preparation method of above-mentioned lignin/polyvinyl alcohol composite material.
The purpose of the present invention is realized by following proposal:
A kind of lignin/polyvinyl alcohol composite material, the component including following mass percent: polyvinyl alcohol 70~
99.4%；Lignin 0.5~30%；Additive 0.1~10%.
The additive preferably includes -1,2,4 triazole of 3- amino (ATA), 4-aminopyridine, 1- (3- aminopropyl) miaow
Azoles, 4- (2- ethylamino-) benzene -1,2- diphenol (dopamine), 2- amino -3- imidazole radicals propionic acid (histidine), tannic acid, 3,3,3',
3'- tetramethyl -1,1- spiral biindolyl -5,5', 6,6'- tetrol (TTSBI), zinc chloride, zinc acetate, iron chloride, calcium chloride, chlorine
Change at least one of copper, iron oxide, sodium chloride.
The polyvinyl alcohol is the alcoholysis product of polyvinyl acetate well known in the art, it is preferable that its alcoholysis
85% or more degree, molecular weight is 3000 or more.
The lignin can be but be not limited to the obtained alkali lignin of soda pulping process in paper industry or wood fibre
The organic solvent lignin that the enzymolysis xylogen or organic solvent method that element fermentation ethyl alcohol processed extracts are extracted from lignocellulosic,
Or the by-product lignosulfonates of sulfite pulping (include calcium lignosulfonate, sodium lignin sulfonate, sulfomethylated lignin
At least one of acid).
The present invention also provides a kind of preparation methods of above-mentioned lignin/polyvinyl alcohol composite material, comprising the following steps: will
Polyvinyl alcohol, lignin, additive mixing, are added to the water and are uniformly dispersed, and under heating condition, 1~10h are stirred, then using stream
Prolong film-forming process, obtains lignin/polyvinyl alcohol composite material.
Gained lignin/polyvinyl alcohol composite material can be further used for the processing of downstream melt molding.
The heating condition is preferably 50~100 DEG C, and more preferably 70~90 DEG C.
The stirring is preferably 50~500rpm, more preferably 300rpm.
The casting film-forming process conditions are routinely cast film-forming process condition using this field, for those skilled in the art institute
It is known.
The present invention in polyvinyl alcohol by adding lignin and additive, the structure between lignin and polyvinyl alcohol phase interface
The dynamic crosslinking network of non-covalent bond connection is built, this dynamic crosslinking network can promote dispersion of the lignin in polyvinyl alcohol,
Improve the interface compatibility of lignin and polyvinyl alcohol, moreover it is possible to repeatedly fracture and reconstruct under external force, thus in large quantities
External mechanical energy is consumed, achievees the purpose that activeness and quietness, and adds lignin to reduce the hydrogen bond between polyvinyl alcohol molecule
Effect, thus it is possible to vary the crystallization behavior of polyvinyl alcohol reduces its fusing point, improves its melt-processable, it is subsequent to be conducive to its
Melt-processed molding.
The method of the present invention can obtain different mechanical properties by adjusting the dosage of lignin and additive in composite material
Composite material, tensile strength can be 30~140MPa, reach as high as 140MPa；Elongation at break can be 30~800%, can be high
Up to 800%.
The present invention compared with the existing technology, have the following advantages and the utility model has the advantages that
1, lignin used in the present invention is the obtained alkali lignin of soda pulping process or lignocellulosic hair in paper industry
The lignin or sulphite slurrying that the enzymolysis xylogen or organic solvent method that ferment ethyl alcohol extracts are extracted from lignocellulosic
By-product lignosulfonates, raw material sources have environment friendly and biodegradability, therefore in biomass resource
Composite material of the present invention is a kind of environmentally protective high molecular material, relative to existing polyvinyl alcohol composite material, institute of the present invention
The composite material cost of preparation is lower, and is full-biodegradable material.
2, the present invention constructs non-covalent bond connection by addition lignin and additive between lignin and polyvinyl alcohol
Dynamic crosslinking network, this dynamic crosslinking network can not only promote dispersion of the lignin in polyvinyl alcohol, improve lignin
With the interface compatibility of polyvinyl alcohol, moreover it is possible to repeatedly fracture and reconstruct under external force, to consume external machine in large quantities
Tool energy improves the intensity and toughness of composite material.
3, the present invention changes the crystallization behavior of polyvinyl alcohol, reduces the fusing point of polyvinyl alcohol by addition lignin, improves
Its melt-processable.
4, the lignin itself used in the present invention has the function of excellent anti-ultraviolet radiation and anti-aging, imparts composite wood
Expect better anti-ultraviolet radiation and anti ageing property.
Detailed description of the invention
Fig. 1 is lignin sulfonic acid in the intracorporal distribution situation of PVA base.
Fig. 2 is the sulfomethylated lignin acid particles that more than ten nanometers of size of lignin sulfonic acid nanoparticle is agglomerated into about 300 nanometers.
Fig. 3 is dumbbell shape batten and its major parameter.
Specific embodiment
Below with reference to embodiment, the present invention is described in further detail, and embodiments of the present invention are not limited thereto.
Material involved in the following example can be obtained from commercial channel.
Embodiment 1
Quality parts by volume, g/mL take 4.975 mass parts polyvinyl alcohol and 0.025 mass parts lignin, 0.025 mass parts
The water of 100 parts by volume is added in sodium chloride；Under the conditions of 90 DEG C of heating temperature, 50rpm mechanical stirring 3h, the mixing that will sufficiently dissolve
After being evaporated completely moisture naturally at room temperature, lignin/polyvinyl alcohol composite material is can be obtained in solution cast film formation.Wherein, selected
Polyvinyl alcohol Mw=130000g/mol, degree of hydrolysis 99%.Selected lignin is the by-product wood of sulfite pulping
Quality sulfonic acid.
Embodiment 2
Quality parts by volume, g/mL take 4.95 mass parts polyvinyl alcohol and 0.05 mass parts lignin, 0.05 mass parts chlorination
The water of 100 parts by volume is added in sodium；Under the conditions of 80 DEG C of heating temperature, 100rpm mechanical stirring 2h, the mixed solution that will sufficiently dissolve
After being evaporated completely moisture naturally at room temperature, lignin/polyvinyl alcohol composite material is can be obtained in casting film-forming.Wherein, selected
Polyvinyl alcohol Mw=30000g/mol, degree of hydrolysis 99%.Selected lignin is the by-product lignin of sulfite pulping
Sulfonic acid.
Embodiment 3
Quality parts by volume, g/mL take 4.90 mass parts polyvinyl alcohol and 0.10 mass parts lignin, 0.5 mass parts 1- (3-
Aminopropyl) imidazoles, the water of 100 parts by volume is added；Under the conditions of 70 DEG C of heating temperature, 300rpm mechanical stirring 5h will be sufficiently molten
After being evaporated completely moisture naturally at room temperature, lignin/polyvinyl alcohol composite material is can be obtained in the mixed solution casting film-forming of solution.
Wherein, selected polyvinyl alcohol Mw=89000g/mol, degree of hydrolysis 99%.Selected lignin is sulfite pulping
By-product lignin sulfonic acid.
Embodiment 4
Quality parts by volume, g/mL take 4.75 mass parts polyvinyl alcohol and 0.25 mass parts lignin, 0.005 mass parts chlorine
Change copper, the water of 100 parts by volume is added；Under the conditions of 90 DEG C of heating temperature, 500rpm mechanical stirring 3h is molten by the mixing sufficiently dissolved
After being evaporated completely moisture naturally at room temperature, lignin/polyvinyl alcohol composite material is can be obtained in liquid casting film-forming.Wherein, selected
Polyvinyl alcohol Mw=130000g/mol, degree of hydrolysis 99%.Selected lignin is that the by-product of sulfite pulping is wooden
Plain sulfonic acid.
Embodiment 5
Quality parts by volume, g/mL take 4.50 mass parts polyvinyl alcohol and 0.50 mass parts lignin, 0.25 mass parts chlorination
The water of 100 parts by volume is added in sodium；Under the conditions of 90 DEG C of heating temperature, 100rpm mechanical stirring 3h, the mixed solution that will sufficiently dissolve
After being evaporated completely moisture naturally at room temperature, lignin/polyvinyl alcohol composite material is can be obtained in casting film-forming.Wherein, selected
Polyvinyl alcohol Mw=130000g/mol, degree of hydrolysis 99%.Selected lignin is the by-product lignin of sulfite pulping
Sulfonic acid.
Embodiment 6
Quality parts by volume, g/mL take 4.00 mass parts polyvinyl alcohol and 1.00 mass parts lignin, 0.5 mass parts acetic acid
The water of 100 parts by volume is added in zinc；Under the conditions of 30 DEG C of heating temperature, 50rpm mechanical stirring 10h, the mixed solution that will sufficiently dissolve
After being evaporated completely moisture naturally at room temperature, lignin/polyvinyl alcohol composite material is can be obtained in casting film-forming.Wherein, selected
Polyvinyl alcohol Mw=130000g/mol, degree of hydrolysis 99%.Selected lignin is the by-product lignin of sulfite pulping
Sulfonic acid.
Embodiment 7
Quality parts by volume, g/mL take 3.50 mass parts polyvinyl alcohol and 1.50 mass parts lignin, 0.5 mass parts chlorination
The water of 100 parts by volume is added in sodium；Under the conditions of 90 DEG C of heating temperature, 100rpm mechanical stirring 3h, the mixed solution that will sufficiently dissolve
After being evaporated completely moisture naturally at room temperature, lignin/polyvinyl alcohol composite material is can be obtained in casting film-forming.Wherein, selected
Polyvinyl alcohol Mw=130000g/mol, degree of hydrolysis 99%.Selected lignin is the by-product lignin of sulfite pulping
Sulfonic acid.
Embodiment 8
Quality parts by volume, g/mL take 4.975 mass parts polyvinyl alcohol and 0.025 mass parts lignin, 0.05 mass parts chlorine
Change calcium, the water of 100 parts by volume is added；Under the conditions of 80 DEG C of heating temperature, 200rpm mechanical stirring 3h is molten by the mixing sufficiently dissolved
After being evaporated completely moisture naturally at room temperature, lignin/polyvinyl alcohol composite material is can be obtained in liquid casting film-forming.Wherein, selected
Polyvinyl alcohol Mw=130000g/mol, degree of hydrolysis 99%.Selected lignin is that the by-product of sulfite pulping is wooden
Plain sulfonic acid.
Embodiment 9
Quality parts by volume, g/mL take 4.75 mass parts polyvinyl alcohol and 0.25 mass parts lignin, 0.05 mass parts chlorination
The water of 100 parts by volume is added in copper；Under the conditions of 90 DEG C of heating temperature, 300rpm mechanical stirring 3h, the mixed solution that will sufficiently dissolve
After being evaporated completely moisture naturally at room temperature, lignin/polyvinyl alcohol composite material is can be obtained in casting film-forming.Wherein, selected
Polyvinyl alcohol Mw=30000g/mol, degree of hydrolysis 99%.Selected lignin is the by-product lignin of sulfite pulping
Sulfonic acid.
Embodiment 10
Quality parts by volume, g/mL take 4.00 mass parts polyvinyl alcohol, 1.00 mass parts lignin and 0.01 mass parts DOPA
The water of 100 parts by volume is added in amine (4- (2- ethylamino-) benzene -1,2- diphenol)；Under the conditions of 90 DEG C of heating temperature, 300rpm machinery is stirred
3h is mixed, after being evaporated completely moisture naturally at room temperature, lignin/poly- second is can be obtained in the mixed solution casting film-forming that will sufficiently dissolve
Enol composite material.Wherein, selected polyvinyl alcohol Mw=130000g/mol, degree of hydrolysis 89%.Selected lignin is Asia
The by-product lignin sulfonic acid of sulfate pulping.
Embodiment 11
Quality parts by volume, g/mL take 3.50 mass parts polyvinyl alcohol, 1.50 mass parts lignin and 0.5 mass parts chlorination
The water of 100 parts by volume is added in calcium；Under the conditions of 50 DEG C of heating temperature, 300rpm mechanical stirring 5h, the mixed solution that will sufficiently dissolve
After being evaporated completely moisture naturally at room temperature, lignin/polyvinyl alcohol composite material is can be obtained in casting film-forming.Wherein, selected
Polyvinyl alcohol Mw=3000g/mol, degree of hydrolysis 99%.Selected lignin is the by-product sulfomethylated lignin of sulfite pulping
Acid.
Embodiment 12
Quality parts by volume, g/mL take 4.75 mass parts polyvinyl alcohol and 0.25 mass parts lignin, 0.05 mass parts chlorination
The water of 100 parts by volume is added in iron；Under the conditions of 90 DEG C of heating temperature, 300rpm mechanical stirring 3h, the mixed solution that will sufficiently dissolve
After being evaporated completely moisture naturally at room temperature, lignin/polyvinyl alcohol composite material is can be obtained in casting film-forming.Wherein, selected
Polyvinyl alcohol Mw=130000g/mol, degree of hydrolysis 99%.Selected lignin is the by-product lignin of sulfite pulping
Sulfonic acid.
Embodiment 13
Quality parts by volume, g/mL take 4.00 mass parts polyvinyl alcohol, 1.00 mass parts lignin and 0.1 mass parts 3- ammonia
The water of 100 parts by volume is added in base -1,2,4-triazoles (ATA)；Under the conditions of 90 DEG C of heating temperature, 300rpm mechanical stirring 3h will fill
The mixed solution casting film-forming for dividing dissolution, after being evaporated completely moisture naturally at room temperature, can be obtained lignin/polyvinyl alcohol composite wood
Material.Wherein, selected polyvinyl alcohol Mw=130000g/mol, degree of hydrolysis 99%.Selected lignin is sulphite legal system
The by-product lignin sulfonic acid of slurry.
Embodiment 14
Quality parts by volume, g/mL take 3.50 mass parts polyvinyl alcohol, 1.50 mass parts lignin and 0.5 mass parts chlorination
The water of 100 parts by volume is added in zinc；Under the conditions of 100 DEG C of heating temperature, 300rpm mechanical stirring 1h is molten by the mixing sufficiently dissolved
After being evaporated completely moisture naturally at room temperature, lignin/polyvinyl alcohol composite material is can be obtained in liquid casting film-forming.Wherein, selected
Polyvinyl alcohol Mw=89000g/mol, degree of hydrolysis 99%.Selected lignin is that the by-product of sulfite pulping is wooden
Plain sulfonic acid.
Embodiment 15
Quality parts by volume, g/mL take 4.975 mass parts polyvinyl alcohol, 0.025 mass parts lignin and 0.025 mass parts
The water of 100 parts by volume is added in zinc chloride；Under the conditions of 90 DEG C of heating temperature, 300rpm mechanical stirring 1h, the mixing that will sufficiently dissolve
After being evaporated completely moisture naturally at room temperature, lignin/polyvinyl alcohol composite material is can be obtained in solution cast film formation.Wherein, selected
Polyvinyl alcohol Mw=130000g/mol, degree of hydrolysis 99%.Selected lignin is obtained by soda pulping process in paper industry
Alkali lignin.
Embodiment 16
Quality parts by volume, g/mL take 4.75 mass parts polyvinyl alcohol, 0.25 mass parts lignin and 0.025 mass parts 3-
The water of 100 parts by volume is added in amino -1,2,4-triazoles (ATA)；Under the conditions of 90 DEG C of heating temperature, 300rpm mechanical stirring 3h will
After being evaporated completely moisture naturally at room temperature, it is compound that lignin/polyvinyl alcohol is can be obtained in the mixed solution casting film-forming sufficiently dissolved
Material.Wherein, selected polyvinyl alcohol Mw=30000g/mol, degree of hydrolysis 99%.Selected lignin is in paper industry
The obtained alkali lignin of soda pulping process.
Embodiment 17
Quality parts by volume, g/mL take 3.50 mass parts polyvinyl alcohol, 1.50 mass parts lignin and 0.025 mass parts 3,
The water of 100 parts by volume is added in 3,3', 3'- tetramethyl -1,1- spiral biindolyl -5,5', 6,6'- tetrols (TTSBI)；Heating temperature
Under the conditions of 90 DEG C of degree, 300rpm mechanical stirring 3h, the mixed solution casting film-forming that will sufficiently dissolve is evaporated completely water naturally at room temperature
After point, lignin/polyvinyl alcohol composite material can be obtained.Wherein, selected polyvinyl alcohol Mw=130000g/mol, water
Xie Du is 99%.Selected lignin is the obtained alkali lignin of soda pulping process in paper industry.
Embodiment 18
Quality parts by volume, g/mL take 4.975 mass parts polyvinyl alcohol, 0.025 mass parts lignin and 0.5 mass parts tan
The water of 100 parts by volume is added in acid；Under the conditions of 90 DEG C of heating temperature, 300rpm mechanical stirring 3h, the mixed solution that will sufficiently dissolve
After being evaporated completely moisture naturally at room temperature, lignin/polyvinyl alcohol composite material is can be obtained in casting film-forming.Wherein, selected
Polyvinyl alcohol Mw=130000g/mol, degree of hydrolysis 99%.Selected lignin is the by-product lignin of sulfite pulping
Sodium sulfonate.
Embodiment 19
Quality parts by volume, g/mL take 4.75 mass parts polyvinyl alcohol, 0.25 mass parts lignin and 0.025 mass parts chlorine
Change copper, the water of 100 parts by volume is added；Under the conditions of 90 DEG C of heating temperature, 300rpm mechanical stirring 3h is molten by the mixing sufficiently dissolved
After being evaporated completely moisture naturally at room temperature, lignin/polyvinyl alcohol composite material is can be obtained in liquid casting film-forming.Wherein, selected
Polyvinyl alcohol Mw=130000g/mol, degree of hydrolysis 99%.Selected lignin is that the by-product of sulfite pulping is wooden
Plain sodium sulfonate.
Embodiment 20
Quality parts by volume, g/mL take 3.50 mass parts polyvinyl alcohol, 1.50 mass parts lignin and 0.025 mass parts 1-
The water of 100 parts by volume is added in (3- aminopropyl) imidazoles；Under the conditions of 90 DEG C of heating temperature, 300rpm mechanical stirring 3h will be abundant
After being evaporated completely moisture naturally at room temperature, lignin/polyvinyl alcohol composite wood is can be obtained in the mixed solution casting film-forming of dissolution
Material.Wherein, selected polyvinyl alcohol Mw=130000g/mol, degree of hydrolysis 99%.Selected lignin is sulphite legal system
The by-product sodium lignin sulfonate of slurry.
Embodiment 21
Quality parts by volume, g/mL take 4.975 mass parts polyvinyl alcohol, 0.025 mass parts lignin and 0.025 mass parts
The water of 100 parts by volume is added in 1- (3- aminopropyl) imidazoles；Under the conditions of 60 DEG C of heating temperature, 300rpm mechanical stirring 8h will fill
The mixed solution casting film-forming for dividing dissolution, after being evaporated completely moisture naturally at room temperature, can be obtained lignin/polyvinyl alcohol composite wood
Material.Wherein, selected polyvinyl alcohol Mw=30000g/mol, degree of hydrolysis 70%.Selected lignin is sulphite legal system
The by-product calcium lignosulfonate of slurry.
Embodiment 22
Quality parts by volume, g/mL take 4.75 mass parts polyvinyl alcohol, 0.25 mass parts lignin and 0.025 mass parts vinegar
The water of 100 parts by volume is added in sour zinc；Under the conditions of 90 DEG C of heating temperature, 300rpm mechanical stirring 9h is molten by the mixing sufficiently dissolved
Lignin/polyvinyl alcohol composite material can be obtained in liquid casting film-forming.Wherein, selected polyvinyl alcohol Mw=130000g/
Mol, degree of hydrolysis 99%.Selected lignin is the by-product calcium lignosulfonate of sulfite pulping.
Embodiment 23
Quality parts by volume, g/mL take 3.50 mass parts polyvinyl alcohol, 1.50 mass parts lignin and 0.05 mass parts chlorination
The water of 100 parts by volume is added in copper；Under the conditions of 70 DEG C of heating temperature, 300rpm mechanical stirring 3h, the mixed solution that will sufficiently dissolve
After being evaporated completely moisture naturally at room temperature, lignin/polyvinyl alcohol composite material is can be obtained in casting film-forming.Wherein, selected
Polyvinyl alcohol Mw=130000g/mol, degree of hydrolysis 85%.Selected lignin is the by-product lignin of sulfite pulping
Sulfoacid calcium.
Embodiment 24
Quality parts by volume, g/mL take 4.975 mass parts polyvinyl alcohol, 0.025 mass parts lignin and 0.5 mass parts tan
The water of 100 parts by volume is added in acid；Under the conditions of 90 DEG C of heating temperature, 300rpm mechanical stirring 1h, the mixed solution that will sufficiently dissolve
After being evaporated completely moisture naturally at room temperature, lignin/polyvinyl alcohol composite material is can be obtained in casting film-forming.Wherein, selected
Polyvinyl alcohol Mw=130000g/mol, degree of hydrolysis 99%.Selected lignin is the obtained alkali of soda pulping process in paper industry
Lignin.
Embodiment 25
Quality parts by volume, g/mL take 4.975 mass parts polyvinyl alcohol, 0.025 mass parts lignin and 0.5 mass parts 3,
The water of 100 parts by volume is added in 3,3', 3'- tetramethyl -1,1- spiral biindolyl -5,5', 6,6'- tetrols (TTSBI)；Heating temperature
Under the conditions of 90 DEG C of degree, 300rpm mechanical stirring 1h, the mixed solution casting film-forming that will sufficiently dissolve is evaporated completely water naturally at room temperature
After point, lignin/polyvinyl alcohol composite material can be obtained.Wherein, selected polyvinyl alcohol Mw=130000g/mol, water
Xie Du is 99%.Selected lignin is the obtained alkali lignin of soda pulping process in paper industry.
Embodiment 26
Quality parts by volume, g/mL take 4.975 mass parts polyvinyl alcohol, 0.025 mass parts lignin and 0.1 mass parts 1-
The water of 100 parts by volume is added in (3- aminopropyl) imidazoles；Under the conditions of 60 DEG C of heating temperature, 300rpm mechanical stirring 8h will be abundant
After being evaporated completely moisture naturally at room temperature, lignin/polyvinyl alcohol composite wood is can be obtained in the mixed solution casting film-forming of dissolution
Material.Wherein, selected polyvinyl alcohol Mw=30000g/mol, degree of hydrolysis 70%.Selected lignin is sulphite legal system
The by-product calcium lignosulfonate of slurry.
Embodiment 27: performance test
(1) frozen section is carried out to composite sample, is observed using transmission electron microscope, to observe lignin in matrix
In distribution situation.Fig. 1 and Fig. 2 is respectively the composite material TEM figure of embodiment 26.Fig. 1 is lignin sulfonic acid in PVA matrix
Distribution situation, Fig. 2 is the lignin sulfonic acid nanoparticle that more than ten nanometers of lignin sulfonic acid nanoparticle is agglomerated into several hundred nanometers
Son.It can be seen from the figure that the lignin sulfonic acid of addition is uniformly dispersed in PVA matrix, lignin sulfonic acid partial size is small, rounding is advised
Then, lignin sulfonic acid nanoparticle is assembled to form nanosphere, and lignin sulfonic acid nanoparticle is coated by matrix, not existing exposed
Sulfomethylated lignin granulates.For this explanation under the action of additive, lignin and matrix have good interface compatibility, promote
Lignin particle it is evenly dispersed.
(2) embodiment product is made to the batten for meeting GBT 1040-2006 standard, is tested using MTS universal testing machine
The mechanical performance datas such as tensile strength, break-draw rate, the results are shown in Table 1.
The dumbbell shape batten tailored is put into drying in a vacuum drying oven for 24 hours, being subsequently placed into temperature is 30 DEG C ± 0.5 DEG C,
Humidity is 72h in the climatic chamber of RH 25% ± 5%, is used for Mechanics Performance Testing.Dumbbell shape batten and its major parameter are shown in
Fig. 3.
The Mechanics Performance Testing of lignin/PVA laminated film is according to GB/T 1040.3-2006 standard, with electron number video card
It is averaged after the thickness of random 10 positions between ruler measurement composite membrane interlude, then uses universal testing machine with 10mm/
The tensile speed of min measures the mechanical property of composite membrane.
Lignin/PVA laminated film (about 6~7mg) after taking a small amount of vacuum drying for 24 hours, is placed in Single-use crucible
DSC test is carried out, entire test process is in N2It is carried out in atmosphere.Test program are as follows: heating for the first time (eliminates thermal history): heating
30 DEG C to 240 DEG C, 10 DEG C/min of heating rate, after keeping 3min, it is cooled to 30 DEG C.Second of heating: 30 DEG C to 240 of heating
DEG C, 10 DEG C/min of heating rate.DSC data takes the test data of secondary temperature elevation.
Take 5~6mg sample in N2Thermogravimetric test is carried out in atmosphere, heating rate is 10 DEG C/min, temperature range 30~700
℃。
1 lignin polyvinyl alcohol composite material performance of table
As seen from Table 1, relative to pure PVA blank sample, it is wooden that embodiment 4,19,22 and 24 adds 5wt% respectively
Plain sulfonic acid, sodium lignin sulfonate, calcium lignosulfonate and lignin, elongation at break and tensile strength and toughness have bright
It is aobvious to improve；The addition for illustrating variety classes lignin is remarkably improved the tensile strength of composite material, elongation at break and disconnected
Split absorption energy；Embodiment the result shows that, by addition lignin and additive, composite material can be played effective enhancing and
Toughening effect.Meanwhile by addition lignin, the fusing point of polyvinyl alcohol is reduced, the thermal decomposition temperature of polyvinyl alcohol is improved,
To improve its melt-processable.
Due to other embodiments use raw material and blending technology all have the characteristics that with embodiment 4 it is similar, it is after tested, other
The performance of composite material obtained by embodiment has similar feature with the above results, therefore does not repeat one by one.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present invention,
It should be equivalent substitute mode, be included within the scope of the present invention.
Claims (7)
1. a kind of lignin/polyvinyl alcohol composite material, it is characterised in that the component including following mass percent: polyvinyl alcohol
70~99.4%；Lignin 0.5~30%；Additive 0.1~10%；
The additive includes -1,2,4 triazole of 3- amino, 4-aminopyridine, 1- (3- aminopropyl) imidazoles, 4- (2- ethamine
Base) benzene -1,2- diphenol, 2- amino -3- imidazole radicals propionic acid, tannic acid, 3,3,3', 3'- tetramethyl -1,1- spiral biindolyl -5,5',
At least one of 6,6'- tetrol, zinc chloride, zinc acetate, iron chloride, calcium chloride, copper chloride, iron oxide, sodium chloride.
2. lignin/polyvinyl alcohol composite material according to claim 1, it is characterised in that: the polyvinyl alcohol,
85% or more alcoholysis degree, molecular weight is 3000 or more.
3. lignin/polyvinyl alcohol composite material according to claim 1, it is characterised in that: the lignin includes
The enzymolysis xylogen that the obtained alkali lignin of soda pulping process or lignocellulose for fermentation ethyl alcohol extract in paper industry, or
The by-product sulfomethylated lignin of organic solvent lignin or sulfite pulping that organic solvent method is extracted from lignocellulosic
At least one of hydrochlorate.
4. a kind of preparation method of the described in any item lignin/polyvinyl alcohol composite materials of claims 1 to 3, feature exist
In the following steps are included: by polyvinyl alcohol, lignin, additive mix, be added to the water and be uniformly dispersed, under heating condition, stirring 1
Then~10h uses casting film-forming technique, obtains lignin/polyvinyl alcohol composite material.
5. the preparation method of lignin/polyvinyl alcohol composite material according to claim 4, it is characterised in that: described
Heating condition is 50~100 DEG C.
6. the preparation method of lignin/polyvinyl alcohol composite material according to claim 4, it is characterised in that: described to stir
It mixes as 50~500rpm.
7. the preparation method of lignin/polyvinyl alcohol composite material according to claim 4, it is characterised in that: gained wood
Quality/polyvinyl alcohol composite material is further used for the processing of downstream melt molding.
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| CN114539696A (en) * | 2022-01-07 | 2022-05-27 | 华南理工大学 | Lignin synergistic plasticizing polyvinyl alcohol and melt processing method thereof |
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| CN116462927B (en) * | 2023-05-17 | 2024-05-07 | 广州白云美湾产业发展有限公司 | Lignin sulfonic acid/polyvinyl alcohol composite film, preparation method thereof and application thereof in facial mask |
| CN118165321A (en) * | 2024-03-15 | 2024-06-11 | 中国林业科学研究院林产化学工业研究所 | Preparation method of self-assembled lignin/copper ion nanoparticle reinforced polyvinyl alcohol film |
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