CN101974230B - Sisal hemp microfiber/ gelatin composite material - Google Patents
Sisal hemp microfiber/ gelatin composite material Download PDFInfo
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- CN101974230B CN101974230B CN2010102947277A CN201010294727A CN101974230B CN 101974230 B CN101974230 B CN 101974230B CN 2010102947277 A CN2010102947277 A CN 2010102947277A CN 201010294727 A CN201010294727 A CN 201010294727A CN 101974230 B CN101974230 B CN 101974230B
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Abstract
The invention discloses a sisal hemp fiber/ gelatin composite material which belongs to the technical field of material and is mainly prepared from 20-90 parts by weight of gelatin and 10-80 parts by weight of sisal hemp microfiber, wherein the diameter of the sisal hemp microfiber is 3-20 mu m, the draw ratio is 1-150, and the gelatin can be successively modified by a plasticizer and a cross-linking agent. The invention uses plasticized and cross-linking modified gelatin as a polymer matrix and uses micrometer-level sisal hemp microfiber split from nature sisal hemp fiber as a reinforcement; the prepared novel composite material has low cost, good performance and environment protection and is an excellent biodegradable material. After the composite material is abandoned, gelatin and sisal hemp fiber therein both can be completely degraded by microorganism in a natural environment and naturalized, which conforms to the requirement of low-carbon cycling economic growth. Thus, the invention performs an active promotion action on alleviating resource, energy and environment crisis.
Description
Technical field
The invention belongs to the material technology field, be specifically related to a kind of sisal hemp primitive fiber/gelatin composite material.
Background technology
When the mankind were born, our ancestors were just utilizing various natural macromolecular materials by the light of nature.20 beginnings of the century, the important chapter on the material history has been write in the appearance of synthesized polymer material.Yet; Severe resource, energy and environment crisis make people again sight turned to natural macromolecular material; Hope can be obtained environmental friendliness, high-performance, natural materials cheaply from the Nature, for the Sustainable development of national economy provides strong support and guarantee.At present, countries in the world have all received people's especially concern at research work, the especially Biodegradable material carried out energetically aspect the degradation material.Wherein, the natural materials that derive from nature, in physical environment, can degrade voluntarily becomes the key player in the biodegradable material.People will use natural biological fiber (mainly comprise with the Mierocrystalline cellulose be the vegetable fibre of main body and be the animal fibre of main body with protein) to be called Biocomposite material (biocomposite) as the polymer composite that strengthens body.In natural fiber, vegetable fibre receives investigator's favor because of characteristics such as its wide material sources, cheap, specific tenacity height.Compare with enhancing bodies such as spun glass, thomels; Natural plant fibre has remarkable advantages; It is cheap, specific tenacity is high and characteristic such as environmental friendliness makes its weighting material that is widely used as macromolecular material, and natural fibers such as sisal hemp, jute, flax, banana and coconut all can be used for the filled high polymer material.Because the vegetable fibre heat resisting temperature is lower, can select the lower polymkeric substance of processing temperatures such as polyolefine, unsaturated polyester as matrix usually.Though these are that the synthetic polymer of raw material is the characteristic that the matrix material of matrix preparation has multiple excellence with non-renewable petroleum resources, do not meet the requirement of green preparation and Sustainable development.In recent years; When selecting body material; People have turned to the degradable polymer matrix with sight gradually; Like POLYACTIC ACID, polycaprolactone, gather beta-hydroxy-butanoic acid ester etc., this is that to strengthen body, biodegradable polymers be that the matrix material of matrix preparation is a kind of material of fully biodegradable with the natural fiber, is called as green matrix material.The most noticeable part of green matrix material be the equal environmental friendliness of its each component, renewable, can degrade fully, all meet the requirement of " green " in every respect, will make huge contribution for the Sustainable development and the environment protection of economy.
The natural macromolecular material that gelatin is made up of multiple amino acids, wide material sources, cheap, its molecular chain top has kept its distinctive triple helix chain structure.It is orderly that gelatin does not structurally present tangible inside, therefore in the aqueous solution, when temperature raises, presents random conformation.Gelatin possesses many good performances, like the reversible transition property of gelation, gel-sol, polyelectrolyte property, colloid protectiveness, surfactivity, water-swelling property and fabulous film-forming properties etc.Contain a large amount of hydroxyls, carboxyl, amino isoreactivity group on the gelatin chains, be prone to it is carried out chemical modification, give its particular performances.Yet pure having property of gelatin is crisp, to water sensitive, be subject to shortcomings such as microbial attack, ining all sorts of ways, it is carried out modification is the important means of giving its new features, widening its Application Areas.The method of modifying of gelatin mainly contains physically modified, chemical modification, enzyme modification and blend and composite modified.Wherein, gelatin can with other macromolecular materials (chitosan, starch, POLYACTIC ACID, polycaprolactone, silk fibroin etc.) blend, the material that processability is different.Gelatin also can be mutually compound with particle, fiber, the laminal filler of organic or inorganic, and this is one of important method of the novel gelatin materials of preparation.Gelatin is mutually compound with thomel, can make the good matrix material of mechanical property, is being expected to be able to application aspect the fracture fixation material.Can prepare gelatin/Nano composite material of montmorillonite with the intercalation complex method, the adding of polynite can improve the tensile strength and the modulus of material greatly, and can significantly improve its wet tenacity, reduces its swelling behavior.Gelatin can be processed trielement composite material with polynite and Mierocrystalline cellulose, as the tissue recovery support material.Win 40350, chitosan and gelatin added in the aqueous solution step by step stir; Add LUTARALDEHYDE and make it crosslinked; Solution is freezing down at-40 ℃; Induce solid-liquid to be separated, have the three-dimensional netted matrix material of vesicular structure then with the Freeze Drying Technique preparation, can be used for bone tissue engineer.Yet, the matrix material of gelatin and vegetable fibre is not appeared in the newspapers as yet.
Summary of the invention
The objective of the invention is for a kind of sisal hemp primitive fiber/gelatin composite material is provided.
Based on this purpose, the present invention has adopted following technical scheme: sisal hemp primitive fiber/gelatin composite material, mainly process by the gelatin of 20-90 weight part and the sisal hemp primitive fiber of 10-80 weight part.
The diameter of said sisal hemp primitive fiber is that 3-20 μ m, length-to-diameter ratio are 1-150.
Gelatin successively through plasticization and modification and cross-linking modified after directly carry out blend with the sisal hemp primitive fiber, or first the sisal hemp primitive fiber is processed felt, and then with modification after gelatin solution to flood blend compound, promptly get sisal hemp primitive fiber/gelatin composite material.
Used linking agent is formaldehyde, LUTARALDEHYDE or dialdehyde starch when cross-linking modified.
The used softening agent of plasticization and modification is glycerine, sorbyl alcohol or Macrogol 200～800 (PEG200～800).
Said softening agent is PEG 400 (PEG400), and consumption is 20～40% of a gelatin dry weight.
The present invention utilizes through plasticising, gelatin after cross-linking modified as polymeric matrix, utilizes the micron order sisal hemp primitive fiber that from natural sisal fibers, splits out as strengthening body, cheap, the excellent performance of the advanced composite material of preparing.Wherein, have a large amount of hydroxyls, carboxyl and amino on the gelatin chains, and the sisal hemp primitive fiber has a large amount of hydroxyls as cellulose materials, so both has fabulous consistency.The intensity of vegetable fibre is mainly provided by the Mierocrystalline cellulose fibril; But Mierocrystalline cellulose always with impurity associations mutually such as semicellulose, xylogen, wax and pectin; Selecting suitable surface treatment to remove the non-cellulose composition in the vegetable fibre, is the basis of improving the fiber reinforcement effect.In addition, natural plant fibre has complicated multilevel hierarchy, can be split as the primitive fiber and even the nano level whisker of different scale under certain condition.As toughener, the original fiber degree of vegetable fibre and fiber form are to the performance of composites influence greatly.Therefore, for specific polymeric matrix, the primitive fiber of selecting suitable length-to-diameter ratio for use is the key of decision composite property.
Simultaneously, sisal hemp primitive fiber/gelatin composite material of the present invention is environmentally friendly, is Biodegradable material completely.After this matrix material went out of use, gelatin and sisal fibers all can be degraded by mikrobe in physical environment fully, and back to nature meets the needs that low-carbon circular economy develops, and will play positive pushing effect to alleviating resource, the energy and ecocrisis.
This matrix material also has the advantage that preparation technology is simple, structural controllability is good.The sisal hemp primitive fiber can prepare through following step: impurity such as the wax in (1) removal sisal fibers, semicellulose, xylogen, pectin, and isolate cellulosic fibre: the mixed solvent with absolute ethyl alcohol and toluene, DMSO 99.8MIN., sherwood oil, THF or YLENE preparation carries out boiling and extracting to sisal fibers; With sodium hydroxide sisal fibers is carried out alkaline purification; With Youxiaolin sisal fibers is bleached.(2) sisal fibers is split and fibrillation: make sisal fibers generation partly hydrolysed or make sisal fibers generation part enzymolysis with enzyme with sulfuric acid.
Description of drawings
Fig. 1 is the variation diagrams of different elasticizer plasticizing gelatin film 60min solubility rates with plasticizer consumption;
Fig. 2 is the swelling curve of gelatin film in frozen water after difference amount GTA is cross-linking modified;
Fig. 3 is the swelling curve of gelatin film in frozen water after difference amount DAS is cross-linking modified;
Fig. 4 is that the sisal hemp fento strengthens the variation diagram of the tensile strength of DAS cross-linked gelatin matrix material with fento content;
Fig. 5 is that the sisal hemp fento strengthens the variation diagram of the tensile strength of GTA cross-linked gelatin matrix material with fento content;
Fig. 6 is that the sisal hemp fento strengthens the variation diagram of the elongation at break of DAS cross-linked gelatin matrix material with fento content;
Fig. 7 is that the sisal hemp fento strengthens the variation diagram of the elongation at break of GTA cross-linked gelatin matrix material with fento content;
Fig. 8 is that the sisal hemp fento strengthens the variation diagram of the degradation rate of DAS cross-linked gelatin matrix material with fento content;
Fig. 9 is that the sisal hemp fento strengthens the variation diagram of the degradation rate of GTA cross-linked gelatin matrix material with fento content.
Embodiment
Below in conjunction with concrete test main technical details of the present invention is elaborated.It is to be noted; The consumption percentage ratio of softening agent, linking agent and sisal hemp fento is meant the weight percent of softening agent, linking agent, sisal hemp fento and gelatin dry weight in this patent; For example: the 20%PEG400 plasticization and modification is meant and has added 20 parts softening agent in 100 parts of gelatin butts.
1, the modification of gelatin
1.1 the selection of softening agent
Consider that the sorbyl alcohol price is relatively costly, emphasis of the present invention select glycerine (Glycerin, GLY), PEG200, PEG400 and PEG800 do further test.
(1) plasticization and modification of gelatin: gelatin is soluble in water; Be mixed with uniform solution (gelatin: water=1: 4), respectively with softening agent (glycerine, the PEG200 of different mass; PEG400; PEG800) add in the gelatin solution, after thorough mixing is even gelatin solution is poured in the polypropylene board mould, take off after the seasoning film forming (about thickness 0.7mm).
(2) solubility rate of softening agent in the mensuration gelatin film: gelatin film is cut into 1cm * 1cm fritter, puts into and fill P
2O
5Moisture eliminator in thorough drying to constant weight (quality is designated as m
0); Take out after dried gelatin film put into frozen water 60min; Fully (quality is designated as m to constant weight more than the oven dry 24h to put into vacuum drying oven
1).The softening agent solubility rate calculates according to formula (1):
With the plasticizer consumption is X-coordinate, and the softening agent solubility rate is the ordinate zou mapping, and is as shown in Figure 1.As can beappreciated from fig. 1, along with the increase of plasticizer consumption, the solubility rate of glycerine and PEG200 plasticising gelatin film raises gradually, and rising by a relatively large margin after plasticizer consumption is greater than 30wt%, all occurred.It is thus clear that glycerine and PEG200 below the 30wt% consumption are stronger to the plastification of gelatin film, most of softening agent and gelatin molecule have formed hydrogen bonded, help the motion of gelatin chains; And along with plasticizer consumption further increases, it is saturated that the hydrogen bonded between softening agent and the gelatin molecule has been tending towards, and unnecessary softening agent is free in the gelatin system, and very fast stripping causes the softening agent solubility rate significantly to increase when meeting water.When plasticizer consumption higher (＞30%), the solubility rate of PEG400 and PEG800 plasticising gelatin film descends with the increase of plasticizer consumption to some extent.This possibly be because of the increase along with the PEG molecular weight, and its molecular polarity reduces, and the solubleness of softening agent in water reduces; And because the dimensional effect of molecular chain, along with the increase of PEG400 and PEG800 consumption, plasticizer molecule chain and gelatin chains are twined each other, have hindered the motion of plasticizer molecule chain, thereby have hindered the migration and the stripping of plasticizer molecule.
It can also be seen that from Fig. 1 the solubility rate of glycerine plasticising gelatin film is apparently higher than all PEG plasticising gelatin films.And along with the increase of PEG molecular weight, the solubility rate of its plasticising gelatin film reduces.Thus it is clear that, the plasticising stability of the dimensional effect remarkably influenced softening agent of plasticizer molecule.
(3) mechanical property of plasticising gelatin film
It is that one week of 65% environment damping is above to constant weight that gelatin film is placed relative humidity; Batten is cut into the standard batten that effective dimensions is 50.0mm * 6.0mm, and with its mechanical property of CMT5140 microcomputer control electronics universal testing machine research, rate of extension is 50mm/min, and the mechanics data of acquisition are seen table 1.
The mechanical property of the dissimilar elasticizer plasticizing gelatin films of table 1
Can find out that from table 1 to the various softening agent of being investigated, with the increase of plasticizer loading, the tensile strength of modified gelatin film reduces, elongation at break raises, and meets the mechanical property rule of general plastification material.Under the identical plasticizer loading, the tensile strength of PEG plasticising gelatin film all is higher than glycerine plasticising gelatin film, and the softening agent of visible higher molecular weight helps improving the mechanical strength of gelatin film.For different molecular weight PEG plastifying gelatin film; When plasticizer loading is identical; The mechanical strength of PEG400 plasticising gelatin film all is higher than corresponding PEG200 and PEG800 plasticising gelatin film, shows not to be the big more mechanical property that helps improving gelatin film more of molecular weight of PEG.This possibly be because when the PEG molecular weight was big, the degree that the PEG molecular chain takes place to tangle increased; With gelatin molecule binding ability variation; When the concentration of softening agent exceed its compatible with gelatin to greatest extent after, two are separated mutually, cause PEG from the gelatin system, to ooze out.
In addition,, find that the transparency of PEG800 plasticising gelatin film is poor, show that the consistency of system reduces through observing the outward appearance of gelatin film.Can infer that from the mechanical property result polyoxyethylene glycol of molecular-weight average more than 800 is inappropriate for the softening agent as gelatin.
Therefore, the preferred PEG400 of softening agent of the present invention, consumption is preferably 20～40wt%.
1.2 the selection of linking agent
On the basis of above physically modified (plasticization and modification), comprehensively compare the solubility rate of softening agent and the mechanical property of plasticising gelatin film, the present invention selects PEG400 to do to carry out in the softening agent adding gelatin system discussion of cross-linking modified (chemical modification).Because formaldehyde has certain bio-toxicity, the present invention discusses dialdehyde starch (DAS) and LUTARALDEHYDE (GTA) as linking agent.
(1) gelatin is cross-linking modified
Gelatin is soluble in water, be mixed with uniform solution (gelatin: water=1: 4), add 20wt%PEG400; The alkaline aqueous solution (pH=10) of DAS or GTA are slowly dripped wherein, dropwise the back with the aqueous solution of 10%NaOH with system pH regulator to 8～9, in 60～65 ℃ fully react down after, solution is poured in the polypropylene board mould, take off after the seasoning film forming.
(2) swelling ratio of cross-linked gelatin film
Gelatin film is cut into 1cm * 1cm fritter, puts into and fill P
2O
5Moisture eliminator in thorough drying to constant weight (quality is designated as m
2); Dried gelatin film is put into frozen water, take out after for some time, wipe away the moisture on dry film surface, the quality after accurate its swelling of weighing on the electronic balance with filter paper.Respectively at interval different time claim the quality of gelatin film after the swelling, be designated as m
t, measure constantly basically up to the swelling quality of film, promptly gelatin film reaches swelling equilibrium.Calculate the swelling ratio of different time gelatin film according to formula (2):
With swelling ratio the time is mapped, the swelling curve figure of acquisition as shown in Figures 2 and 3.Because unmodified gelatin film very easily breaks in water, does not provide the swelling ratio data of pure gelatin in water here.
As can beappreciated from fig. 2, in 5h, gelatin film suction back is swelling rapidly, and the swelling ratio increase is very fast; Rate of growth slows down behind the 5h, and curve is gradually in gently; Basically reach balance about 40h.Along with dosage of crosslinking agent increases, the swelling ratio of modified gelatin film reduces gradually, and the crosslinked gelatin film of 1.7% GTA just reaches swelling equilibrium about 35min.This is because intermolecular chemically crosslinked can form stable network structure effectively in system, has limited the motion of gelatin chains, thereby has reduced the swelling capacity of material.Dosage of crosslinking agent hour, less with the cross-linking set of gelatin molecule chain formation, network structure is comparatively loose.Along with dosage of crosslinking agent increases, linking agent and gelatin chains point of application increase, and form fine and close cross-linked network.Along with water molecules soaks into sample, gelatin film is swelling gradually, and size increases.Along with the entering of moisture, also there is reactive force in gelatin chains to water molecules, trends towards water molecules is discharged cross-linking system.When the moisture of the absorption moisture of system and discharge equated, system promptly reached swelling equilibrium.It is limited in one's ability that fine and close cross-linked network absorbs the moisture swelling, and bigger to the water molecules repulsive interaction.So when dosage of crosslinking agent was big, the modified gelatin film formed fine and close cross-linked network, can reach swelling equilibrium quickly, and swelling ratio (degree) is smaller.
Fig. 3 shows that when the DAS consumption was 4.0%, 5.0% and 7.4%, the swelling ratio of gelatin film increased very fast at preceding 8h, and curve tends towards stability behind the 8h, reaches swelling equilibrium about 15h basically.DAS belongs to macromole poly aldehyde cross-linking agent, and molecular chain is longer, and a DAS molecular chain can interact with some gelatin chains, forms more fine and close cross-linked network.Fig. 2 compares with Fig. 3, and when dosage of crosslinking agent was identical, the swelling ratio of DAS cross-linked gelatin film all was lower than corresponding GTA cross-linked gelatin film.When the DAS consumption reached 10% and 15%, the swelling rule of gelatin film changed: preceding 4h, swelling ratio increases sharply, and descends slightly afterwards, reaches swelling equilibrium about 15h, and the swelling ratio during balance is suitable basically with 7.4%DAS modified gelatin membrane swelling ratio.This maybe since amount of starch when too high gelatin and dialdehyde starch be separated and cause.Along with the raising of DAS consumption, gelatin and DAS are separated.After meeting water, the DAS that does not play crosslinked action separates out from system, and film quality is reduced, and shows as membrane swelling ratio and reduces.Along with the prolongation of time, the gelatin system crosslinked through DAS can reach swelling equilibrium.The DAS consumption is higher than at 7.4% o'clock, and all near 245%, visible too high DAS consumption can't further improve the crosslinking degree of gelatin system to the swelling ratio when system reaches balance.
(3) mechanical property of cross-linked gelatin film
With gelatin film relative humidity be in 65% the environment more than one week of damping to constant weight; Batten is cut into the standard batten that effective dimensions is 50.0mm * 6mm, and with its mechanical property of CMT5140 universal testing machine research, the chuck draw speed is 50mm/min.The mechanical property parameters of gained is as shown in table 2.
The mechanical property of the different linking agent cross-linked gelatin of table 2 film
| Linking agent type and consumption | Tensile strength (MPa) | Elongation at break (%) |
| GTA0.4％ | 3.93 | 203.4 |
| GTA0.7％ | 4.70 | 174.0 |
| GTA?1％ | 5.43 | 150.0 |
| GTA?1.5％ | 5.79 | 154.6 |
| GTA?1.7％ | 4.64 | 128.9 |
| DAS4％ | 4.10 | 181.2 |
| DAS5％ | 4.24 | 156.3 |
| DAS7％ | 5.29 | 140.2 |
| DAS10％ | 3.93 | 135.9 |
| DAS15％ | 3.77 | 127.0 |
| Control?films | 3.87 | 122.0 |
(Control films is meant the 20%PEG400 plasticising gelatin film of Non-crosslinked modification)
Table 2 shows that compare with the gelatin film that does not add linking agent, the tensile strength of GTA, DAS modified gelatin film all is improved, and its elongation at break also has raising in various degree.For GTA cross-linked gelatin film, the GTA consumption is 1.5% when following, and along with the increase of dosage of crosslinking agent, the tensile strength of gelatin film improves gradually, and elongation at break reduces gradually.The GTA consumption was at 1.7% o'clock, and tensile strength begins to descend.The autohemagglutination phenomenon be prone to take place in GTA, after its consumption is increased to a certain degree, in gelatin solution, block gel in various degree can occur, and these blocks will exert an influence as defective or the focal point of stress mechanical property to gelatin film, thereby reduce its tensile strength.
Along with the DAS dosage of crosslinking agent increases, the tensile strength of gelatin film is the trend that raises and afterwards reduce earlier, and the mechanical property that the DAS consumption is higher than 7.4% back gelatin film reduces gradually.As a kind of poly aldehyde cross-linking agent, the molecular dimension effect of DAS and macromole segmental in gelatin solution distributes and all can have influence on the mechanical property of gelatin film.The mechanical property of contrast GTA and two kinds of cross-linked gelatin films of DAS can be known; The tensile strength of the GTA cross-linked gelatin film of less consumption is equivalent to or the tensile strength of the DAS cross-linked gelatin film of a little higher than more consumption basically, and DAS does not make gelatin form cross-linked network as small molecule aldehyde efficiently.The limited compatibility of DAS and gelatin makes when the DAS consumption is too high, and system produces and is separated, and the starch microcell that gathers will impact with focal point of stress or the defective form mechanical property to gelatin film.In addition, DAS has certain hydrophilic macromole, and its consumption increases, and also will absorb more moisture and remains in the gelatin film.Water molecules is a kind of effective softening agent for the protein film.In addition, the elongation at break of DAS cross-linked gelatin film all is higher than the gelatin film that does not add linking agent, and when the DAS consumption is too high, because and be separated between the gelatin, the elongation at break of modified gelatin film is descended.
(4) IR spectroscopy of gelatin film
Gelatin film is ground powdered, in filling P
2O
5Moisture eliminator in thorough drying; Sample adopts the preparation of KBr pressed disc method, utilizes Fourier infrared spectrograph (Thermo Nicolet IR200) comparative analysis gelatin at the infrared spectrum through LUTARALDEHYDE, dialdehyde starch crosslinked front and back, finds through the crosslinked gelatin of 1.5%GTA at 1103cm
-1Strong C-O absorption peak has appearred in the place, and this is because after the aldehyde radical of GTA and the reaction of the amino in the gelatin, the two keys of C=O become singly-bound, cause the C-O absorption peak to strengthen, and have confirmed between GTA and the gelatin crosslinking reaction to have taken place.And the infrared spectrum of 7.4%DAS cross-linked gelatin is compared with pure gelatin, pure DAS, at 1102cm
-1Strong C-O absorption peak has also appearred in the place, explains that reaction has to a certain degree taken place aldehyde radical and the gelatin on the DAS molecular chain.While 2932cm
-1Stronger aldehyde radical absorption peak has appearred in the place, and the aldehyde radical unreacted in the explanation system on the DAS molecular chain is complete.
Take all factors into consideration the mechanical property and the swelling ratio of cross-linked gelatin film, when adopting GTA crosslinked, the preferred 1.0-1.7% of its consumption, further preferred 1.5%, if linking agent is used DAS instead, then its consumption is preferred 5～10%, and further preferred 7～7.4%.
2, blend form and blending amount are to the influence of composite property
(1) preparation of sisal fibers felt
With pretreated sisal hemp primitive fiber machinery beat wad a quilt with cotton after; After fiber and the water of getting certain mass mixes, evenly pour in the B that the bottom is covered with non-wetting ability filter cloth (should guarantee the homogeneity when fiber is poured into), carry out decompress filter then; Remove moisture, obtain sisal hemp primitive fiber felt.The primitive fiber felt is trimmed to and becomes film die area identical size.
(2) preparation of sisal hemp primitive fiber felt/gelatin composite material
The primitive fiber felt is layered in the film forming mould, then the 1.5%GTA and the gelatin solution after the 7.4%DAS modification (plasticizer P EG400,20%) of certain mass is slowly poured in the mould equably, the primitive fiber felt is soaked into by gelatin solution.After to be dried, composite package is taken off, obtained sisal hemp primitive fiber felt/gelatin-compounded film respectively through LUTARALDEHYDE and dialdehyde starch modification.
(3) preparation of sisal hemp primitive fiber/gelatin composite material
Gelatin solution is behind the 20%PEG400 plasticization and modification; With 1.5%GTA and 7.4%DAS system is carried out modification respectively; The Powdered sisal fibers of handling through 0.25% enzyme of certain mass is joined in the gelatin solution, mix fully, then mixed solution is poured into in the film die; Take off after the drying, promptly get sisal hemp primitive fiber/gelatin-compounded film through LUTARALDEHYDE and dialdehyde starch modification.
(4) mechanical property of matrix material
With above sisal hemp primitive fiber felt/gelatin-compounded film of processing and sisal hemp primitive fiber/gelatin-compounded film relative humidity be in 65% the environment more than two weeks of damping to constant weight; Sample is cut into the standard batten that effective dimensions is 50.0mm * 6.0mm, and with its mechanical property of CMT5140 universal testing machine research, the chuck draw speed is 50mm/min.
Gelatin film with 7.4%DAS and 1.5%GTA modification is a matrix, serves as to strengthen body with sisal hemp primitive fiber and sisal hemp primitive fiber felt, and preparation sisal hemp primitive fiber/gelatin composite material carries out the test of mechanical property, and the result is shown in Fig. 4-7.
Figure 4 and 5 are respectively the tensile strengths that sisal hemp primitive fiber and primitive fiber felt strengthen DAS and the cross-linking modified gelatin composite material of GTA, and the tensile strength of matrix material presents similar Changing Pattern with the adding of sisal hemp fento among these two figure.In the primitive fiber reinforced composite, when sisal hemp primitive fiber add-on was 5%, tensile strength of material slightly reduced.This possibly be because primitive fiber content more after a little while, the primitive fiber distribution density is lower, the load that primitive fiber is born is limited, this moment primitive fiber be prone to become focal point of stress at the gelatin matrix, reduce the tensile strength of matrix material on the contrary; Along with the raising of primitive fiber add-on, receiving external force to do the time spent, fiber can play the effect of carry load effectively, and material has been played enhancement, thereby the tensile strength of matrix material is improved.When the primitive fiber add-on was 15%, the tensile strength of matrix material reached peak; Yet along with the continuation of fibre weight increases, the tensile strength of material reduces.Analyzing reason, possibly be that too much sisal hemp primitive fiber can produce reunion outside gelatin network because Fiber Distribution reaches capacity in the gelatin cross-linked network; When fibre content is higher, the fiber accumulations phenomenon occurs, make matrix material the time spent all be unfavorable for the transmission of load, cause the reduction of material mechanical performance stressed the work.In primitive fiber felt enhancing system, along with the increase of primitive fiber felt consumption, the tensile strength of matrix material rises significantly.When the fibre felt amount is 17.9%, be that the tensile strength of the matrix material of matrix reaches 15.3MPa with the DAS modified gelatin; When the fibre felt amount is 16.9%, be that the tensile strength of the matrix material of matrix reaches 14.8MPa with the GTA modified gelatin, demonstrate excellent reinforced effects.Can find out; When the enhancing body is the felt form; Network and gelatin cross-linked network that fento forms run through each other, are receiving external force to do the time spent, and the formed network of fento has stopped the diffusion of tiny crack in the gelatin matrix effectively; The sisal hemp fento that forms network can be born more load, plays significant reinforced effects.
Fig. 6 and 7 is respectively the elongation at break that sisal hemp primitive fiber and primitive fiber felt strengthen DAS and the cross-linking modified gelatin composite material of GTA.The adding of sisal hemp fento reduces the elongation at break of system.The elongation at break that the primitive fiber felt strengthens system is lower than corresponding primitive fiber enhancing system.
(5) degradation property of matrix material
Material is cut into the sample of 0.5cm * 0.5cm size dimension, at P
2O
5Thorough drying is claimed to such an extent that quality is designated as W0 up to steady quality in the moisture eliminator.Preparation PBS buffered soln (pH=5.2) adds 0.1% (w/v) N,O-Diacetylmuramidase.Sample is immersed in the buffered soln, in 37 ℃ of water baths, places after the 12h, take out sample.After the zero(ppm) water washing, be dried to constant weight, this moment, quality was designated as W
1, the degradation rate of material calculates by formula (3):
Fig. 8 and 9 is respectively to be sisal hemp primitive fiber/gelatin composite material degradation rate behind the 12h in 37 ℃ lysozyme soln of matrix preparation with DAS and GTA modified gelatin.Compare with the gelatin that does not add the sisal hemp fento, the adding of sisal hemp fento has significantly reduced the degradation rate of matrix material, serves as that to strengthen the degradation rate of matrix material of body lower with the primitive fiber felt wherein, explains that the interaction between primitive fiber felt and the cross-linked gelatin is stronger.The adding of sisal hemp fento has slowed down the degradation rate of gelatin in enzyme solution, has improved the ability of the anti-mikrobe of matrix material, to playing positive effect the work-ing life of improving matrix material.
In sum, the preferred primitive fiber felt of sisal hemp primitive fiber/gelatin composite material of the present invention type is compound, and fento content is when 15～20wt%, and material has mechanical property and lower degradation rate preferably.
Embodiment 1
1) dewax: get absolute ethyl alcohol and DMSO 99.8MIN. and be mixed with mixed solvent according to 2: 1 volume ratio; Sisal fibers is tied up, immersed and be equipped with in the container of mixed solvent, heating in water bath to 60 ℃ processing 6h, the sisal fibers of acquisition dewax.
2) soda boiling: it is dry that the sisal fibers behind the dewax is put into baking oven, is cut into then about 5cm, and soda boiling 2h in the NaOH solution of input 10wt%, bath raio is 1: 30,80 ℃ of temperature (changing alkali lye therebetween a time), continuously stirring in the process of boiling.After soda boiling is handled, use zero(ppm) water repeated water washing fiber to be neutrality to pH.
3) being split as the sisal hemp primitive fiber: the sisal fibers after dewax-soda boiling is put in the NaClO solution that concentration is 4g/L stirred 6h; bath raio is 1: 30; 40 ℃ of bath temperatures (changing liquid once after handling 4h), bleaching processing, is neutral with the sisal fibers repeated water washing to pH then.And then sisal fibers is placed concentration is the H of 35wt%
2SO
4In the aqueous solution (bath raio 1: 25), at 45 ℃ of following acidolysis 1h, make sisal fibers fibrillation, the sisal hemp primitive fiber diameter of acquisition is 5-20 μ m, and length-to-diameter ratio is 80-150.
4) gelatin modified: it is soluble in water to get the 100g gelatin, is mixed with uniform solution (gelatin: water=1: 4); 35g glycerine is added in the gelatin solution, and thorough mixing is even; Get the alkaline aqueous solution (pH=10) that 7.4g DAS is mixed with, it slowly be added drop-wise in the gelatin, dropwise the back with the NaOH aqueous solution of 10wt% with system pH regulator to 8～9, under 65 ℃, fully react.
5) compound: it is extremely neutral with the zero(ppm) water repeated water washing to get 15g sisal hemp primitive fiber, and suction filtration is laid in the polypropylene board mould after becoming felt; Pour the gelatin solution after the modification into and make gelatin solution with primitive fiber felt dipping in the mould, seasoning film forming then promptly gets gelatin/sisal fibers felt composite material.
Embodiment 2
1) dewax: getting absolute ethyl alcohol and toluene, to be made into volume ratio be 2: 1 mixed solvent; Put into the extraction tube that capacity is the Soxhlet extractor of 500mL after sisal fibers is tied up, the 100g mixed solvent is poured in the extraction flask.Begin to clock after being heated to azeotropic point, obtain the sisal fibers of dewax behind the processing 6h.
2) soda boiling: it is dry to put into baking oven through the sisal fibers that dewax is handled, and is cut into the segment about 5cm then, joins the NaOH solution soda boiling 2h of 10wt%, and bath raio is 1: 30,80 ℃ of bath temperatures (changing alkali lye therebetween a time), continuously stirring in the alkali cooking process.After soda boiling finishes, the sisal fibers repetitive scrubbing is neutral to pH with zero(ppm) water.
3) be split as the sisal hemp primitive fiber: putting into concentration to the sisal fibers after dewax-soda boiling is that the NaClO solution of 4g/L is bleached processing, and bath raio is 1: 30,40 ℃ of temperature, stir process 6h (changing liquid once during 4h).After the bleaching that the sisal fibers repeated water washing is neutral to pH, join the H that concentration is 40wt% again
2SO
4In the aqueous solution (bath raio 1: 25), at 35 ℃ of following acidolysis 1.5h, make sisal fibers fibrillation, the sisal hemp primitive fiber diameter of acquisition is 5-20 μ m, and length-to-diameter ratio is 100-150.
4) gelatin modified: as to get the 100g gelatin uniform solution (gelatin: water=1: 4) that is mixed with soluble in water; The sorbyl alcohol of 30g is added in the gelatin solution, and thorough mixing is even; Feed 1.5g LUTARALDEHYDE steam to system, use then concentration as the NaOH aqueous solution of 10wt% with system pH regulator to 8～9, under 60 ℃, fully react.
5) compound: it is extremely neutral with the zero(ppm) water repeated water washing to get 400g sisal hemp primitive fiber, and suction filtration is laid in the polypropylene board mould after becoming felt; Gelatin solution after the modification is poured in the polypropylene board mould, treated that gelatin solution fully floods back seasoning film forming with the primitive fiber felt, promptly gets sisal hemp primitive fiber felt/gelatin composite material.
Embodiment 3
1) dewax: getting absolute ethyl alcohol and THF, to be made into volume ratio be 2: 1 mixed solvent; The extraction tube that capacity is the Soxhlet extractor of 500mL is tied up and put into to sisal fibers, get the 80g mixing solutions and add in the extraction flask, begin to clock after being heated to azeotropic point, handle the sisal fibers that obtains dewax behind the 6h.
2) soda boiling: the sisal fibers behind the dewax is carried out drying, and it is cut into the segment about 5cm, put into concentration then and be soda boiling 2h in the NaOH aqueous solution of 10wt%, bath raio is 1: 30,80 ℃ of temperature (changing alkali lye therebetween a time).It is neutral to pH with zero(ppm) water repetitive scrubbing sisal fibers that soda boiling finishes the back.
3) be split as the sisal hemp primitive fiber: the sisal fibers to after dewax-soda boiling is bleached processing: fiber is joined stir process 6h (changing liquid once during 4h) in the NaClO solution of 4g/L, bath raio is 1: 30,40 ℃ of temperature.After bleaching finishes that the sisal fibers repeated water washing is neutral to pH, and then to be added to concentration be 63.5wt%H
2SO
4In the aqueous solution (bath raio 1: 25), at 45 ℃ of following acidolysis 25min, make sisal fibers fibrillation, the sisal hemp primitive fiber diameter of acquisition is 5-20 μ m, length-to-diameter ratio 100-150.With zero(ppm) water that sisal hemp primitive fiber repeated water washing is extremely neutral.
4) gelatin modified: it is soluble in water to get the 100g gelatin, is mixed with uniform solution (gelatin: water=1: 4); 20gPEG200 is added in the gelatin solution, and thorough mixing is even; Get the alkaline aqueous solution (pH=10) that 10g DAS is mixed with, slowly be added drop-wise in the gelatin solution, dropwise the back with the 10%NaOH aqueous solution with system pH regulator to 8～9, under 65 ℃, fully react.
5) compound: as to get 12g sisal hemp primitive fiber and modified gelatin solution thorough mixing, pour seasoning film forming in the polypropylene board mould into, promptly get sisal hemp primitive fiber/gelatin composite material.
1) dewax: it is 2: 1 mixed solvent that absolute ethyl alcohol and sherwood oil are made into volume ratio; Put into the extraction tube that capacity is the Soxhlet extractor of 500mL after sisal fibers is tied up, get the 100g mixing solutions and join in the extraction flask, begin to clock after being heated to azeotropic point, handle the sisal fibers that obtains dewax behind the 6h.
2) soda boiling: the sisal fibers behind the dewax is carried out drying, and it is cut into the segment about 5cm, put into concentration then and be soda boiling 2h in the NaOH aqueous solution of 10wt%, bath raio is 1: 30,80 ℃ of temperature (changing alkali lye therebetween a time).It is neutral to pH with zero(ppm) water repetitive scrubbing sisal fibers that soda boiling finishes the back.
3) be split as the sisal hemp primitive fiber: the sisal fibers to after dewax-soda boiling is bleached processing: fiber is joined stir process 6h (changing liquid once during 4h) in the NaClO solution of 4g/L, bath raio is 1: 30,40 ℃ of temperature.After bleaching finishes that the sisal fibers repeated water washing is neutral to pH.Be equipped with the NaAc/HAc buffered soln of pH=4.8, getting a certain amount of β-1,4 NCE5, in buffered soln, to become to prepare massfraction be 0.25% enzyme liquid.Sisal fibers after the bleaching processing is joined in β-1, the 4 NCE5 liquid (bath raio 1: 25), at 50 ℃ of following enzymolysis 2h, make sisal fibers fibrillation, the sisal hemp primitive fiber diameter of acquisition is 3-20 μ m, length-to-diameter ratio 1-80.With zero(ppm) water the enzyme in the sisal hemp primitive fiber is washed out.
4) gelatin modified: as to get the 100g gelatin uniform solution (gelatin: water=1: 4) that is mixed with soluble in water; 40gPEG400 is added in the gelatin solution, and thorough mixing is even; Get the alkaline aqueous solution (pH=10) that 5g DAS is mixed with, slowly be added drop-wise in the gelatin solution, dropwise the back with the 10%NaOH aqueous solution with system pH regulator to 8～9, under 65 ℃, react fully.
5) compound: as to get 40g sisal hemp primitive fiber and modified gelatin solution thorough mixing, pour seasoning film forming in the polypropylene board mould into, promptly get sisal hemp primitive fiber/gelatin composite material.
1) dewax: get absolute ethyl alcohol and YLENE and be mixed with mixed solvent according to 2: 1 volume ratio; Put into the extraction tube that capacity is the Soxhlet extractor of 500ml after sisal fibers tied up, get the 100g mixing solutions and add in the extraction flask, begin to clock after being heated to azeotropic point, handle the sisal fibers that obtains dewax behind the 6h.
2) soda boiling: the sisal fibers behind the dewax is carried out drying, and it is cut into the segment about 5cm, put into concentration then and be soda boiling 2h in the NaOH aqueous solution of 10wt%, bath raio is 1: 30,80 ℃ of temperature (changing alkali lye therebetween a time).It is neutral to pH with zero(ppm) water repetitive scrubbing sisal fibers that soda boiling finishes the back.
3) be split as the sisal hemp primitive fiber: the sisal fibers to after dewax-soda boiling is bleached processing: fiber is joined stir process 6h (changing liquid once during 4h) in the NaClO solution of 4g/L, bath raio is 1: 30,40 ℃ of temperature.After bleaching finishes that the sisal fibers repeated water washing is neutral to pH.Be equipped with the NaAc/HAc buffered soln of pH=4.8, getting a certain amount of β-1,4 NCE5, in buffered soln, to become to prepare massfraction be 3% enzyme liquid.Sisal fibers after the bleaching processing is joined in β-1, the 4 NCE5 liquid (bath raio 1: 25), at 55 ℃ of following enzymolysis 1h, make sisal fibers fibrillation, the sisal hemp primitive fiber diameter of acquisition is 3-20 μ m, length-to-diameter ratio 1-80.With zero(ppm) water the enzyme in the sisal hemp primitive fiber is washed out.
4) gelatin modified: as to get the 100g gelatin uniform solution (gelatin: water=1: 4) that is mixed with soluble in water; 28g PEG800 is added in the gelatin solution, and thorough mixing is even; Get formaldehyde solution (containing formaldehyde 5g) and slowly be added drop-wise in the gelatin solution, dropwise the back use concentration as the NaOH aqueous solution of 10wt% with system pH regulator to 8～9, under 65 ℃, fully react.
5) compound: as to get 100g sisal hemp primitive fiber and modified gelatin solution thorough mixing, pour seasoning film forming in the polypropylene board mould into, promptly get sisal hemp primitive fiber/gelatin composite material.
Claims (5)
1. sisal hemp primitive fiber/gelatin composite material is mainly processed by the gelatin of 20-90 weight part and the sisal hemp primitive fiber of 10-80 weight part, and the diameter of said sisal hemp primitive fiber is 3-20 μ m, and length-to-diameter ratio is 1-150; Described sisal hemp primitive fiber prepares through following step: wax, semicellulose, xylogen, the pectin impurity in the sisal fibers is removed in (1), isolates cellulosic fibre: the mixed solvent with absolute ethyl alcohol and toluene, DMSO 99.8MIN., sherwood oil, THF or YLENE preparation carries out boiling and extracting to sisal fibers; With sodium hydroxide sisal fibers is carried out alkaline purification; With Youxiaolin sisal fibers is bleached; (2) sisal fibers is split and fibrillation: make sisal fibers generation partly hydrolysed or make sisal fibers generation part enzymolysis with enzyme with sulfuric acid.
2. sisal hemp primitive fiber/gelatin composite material as claimed in claim 1; It is characterized in that; Gelatin successively through plasticization and modification and cross-linking modified after, directly carry out blend, or first the sisal hemp primitive fiber processed felt with the sisal hemp primitive fiber; And then with modification after gelatin solution to flood blend compound, promptly get sisal hemp primitive fiber/gelatin composite material.
3. according to claim 1 or claim 2 sisal hemp primitive fiber/gelatin composite material is characterized in that used linking agent is formaldehyde, LUTARALDEHYDE or dialdehyde starch when cross-linking modified.
4. sisal hemp primitive fiber/gelatin composite material as claimed in claim 3 is characterized in that, the used softening agent of plasticization and modification is glycerine, sorbyl alcohol or Macrogol 200～800.
5. sisal hemp primitive fiber/gelatin composite material as claimed in claim 4 is characterized in that, when softening agent was PEG 400, consumption was 20～40% of a gelatin dry weight.
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| CN106245153B (en) * | 2016-07-28 | 2019-01-29 | 湖南帝星智能科技有限公司 | Medical fiber mixed by gelatin and bamboo fiber and preparation method thereof |
| CN108440974A (en) * | 2018-01-25 | 2018-08-24 | 四川大学 | A kind of high intensity glutin plastic packaging film and preparation method thereof |
| CN109395061A (en) * | 2018-12-12 | 2019-03-01 | 广州汇朗无纺制品有限公司 | A kind of composite membrane for the nursing of skin lesions of pemphigus vulgaris position |
| CN110591390B (en) * | 2019-09-19 | 2021-09-17 | 广东工业大学 | Dialdehyde starch crosslinked fiber/cottonseed protein composite material and preparation method and application thereof |
| CN116023794A (en) * | 2022-09-14 | 2023-04-28 | 于博雅 | Degradable material, preparation method and application |
| CN115678117B (en) * | 2022-12-16 | 2023-09-19 | 湖南师范大学 | Preparation method of sisal fiber reinforced nano hydroxyapatite/chitosan composite material |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| GB1149257A (en) * | 1965-07-22 | 1969-04-23 | Ibe Ltd | Emulsions |
| CN1168316A (en) * | 1997-06-12 | 1997-12-24 | 中山大学 | Preparation method of sisal fibre-resin base composite material |
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