CN109651659A - A kind of high-concentration raw substance polysaccharide nanofiber/latex mixed liquor and preparation method thereof, application - Google Patents
A kind of high-concentration raw substance polysaccharide nanofiber/latex mixed liquor and preparation method thereof, application Download PDFInfo
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- CN109651659A CN109651659A CN201811568635.6A CN201811568635A CN109651659A CN 109651659 A CN109651659 A CN 109651659A CN 201811568635 A CN201811568635 A CN 201811568635A CN 109651659 A CN109651659 A CN 109651659A
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- polysaccharide
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- 239000004816 latex Substances 0.000 title claims abstract description 133
- 229920000126 latex Polymers 0.000 title claims abstract description 133
- 239000002121 nanofiber Substances 0.000 title claims abstract description 120
- 229920001282 polysaccharide Polymers 0.000 title claims abstract description 116
- 239000005017 polysaccharide Substances 0.000 title claims abstract description 116
- 150000004676 glycans Chemical class 0.000 title claims abstract description 115
- 239000000126 substance Substances 0.000 title claims abstract description 67
- 238000002360 preparation method Methods 0.000 title claims abstract description 48
- 239000002028 Biomass Substances 0.000 claims abstract description 74
- 239000002002 slurry Substances 0.000 claims abstract description 23
- 239000000463 material Substances 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 8
- 229920002101 Chitin Polymers 0.000 claims description 80
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 19
- 239000000047 product Substances 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 239000001913 cellulose Substances 0.000 claims description 14
- 229920002678 cellulose Polymers 0.000 claims description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 10
- 239000000243 solution Substances 0.000 claims description 10
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 238000005266 casting Methods 0.000 claims description 6
- 239000003153 chemical reaction reagent Substances 0.000 claims description 6
- 239000002070 nanowire Substances 0.000 claims description 6
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 claims description 6
- 239000002174 Styrene-butadiene Substances 0.000 claims description 5
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 claims description 5
- 239000006071 cream Substances 0.000 claims description 5
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methyl-cyclopentane Natural products CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 claims description 5
- 239000011115 styrene butadiene Substances 0.000 claims description 5
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 239000007853 buffer solution Substances 0.000 claims description 4
- 230000008859 change Effects 0.000 claims description 4
- 235000019441 ethanol Nutrition 0.000 claims description 4
- 239000011521 glass Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 229920001084 poly(chloroprene) Polymers 0.000 claims description 4
- 238000013019 agitation Methods 0.000 claims description 3
- 229920005549 butyl rubber Polymers 0.000 claims description 3
- 238000007598 dipping method Methods 0.000 claims description 3
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 3
- 229910000397 disodium phosphate Inorganic materials 0.000 claims description 3
- 230000035800 maturation Effects 0.000 claims description 3
- 150000002825 nitriles Chemical class 0.000 claims description 3
- 238000007254 oxidation reaction Methods 0.000 claims description 3
- 229920002635 polyurethane Polymers 0.000 claims description 3
- 239000004814 polyurethane Substances 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- UKLNMMHNWFDKNT-UHFFFAOYSA-M sodium chlorite Chemical compound [Na+].[O-]Cl=O UKLNMMHNWFDKNT-UHFFFAOYSA-M 0.000 claims description 3
- 229960002218 sodium chlorite Drugs 0.000 claims description 3
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 3
- 239000006228 supernatant Substances 0.000 claims description 3
- 239000004033 plastic Substances 0.000 claims description 2
- 229920003023 plastic Polymers 0.000 claims description 2
- 238000012545 processing Methods 0.000 claims description 2
- 239000005708 Sodium hypochlorite Substances 0.000 claims 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims 1
- 239000005864 Sulphur Substances 0.000 claims 1
- 238000005119 centrifugation Methods 0.000 claims 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims 1
- 239000006185 dispersion Substances 0.000 abstract description 10
- 238000002604 ultrasonography Methods 0.000 abstract description 10
- 239000002131 composite material Substances 0.000 abstract description 8
- 238000011065 in-situ storage Methods 0.000 abstract description 7
- 238000011049 filling Methods 0.000 abstract description 6
- 229920002521 macromolecule Polymers 0.000 abstract description 3
- 238000005516 engineering process Methods 0.000 description 9
- 230000000694 effects Effects 0.000 description 7
- 238000003860 storage Methods 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 238000011068 loading method Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 5
- 230000002787 reinforcement Effects 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 4
- 239000000945 filler Substances 0.000 description 4
- 239000003292 glue Substances 0.000 description 4
- 230000004936 stimulating effect Effects 0.000 description 4
- LGZDNJBUAAXEMN-UHFFFAOYSA-N 1,2,2,3-tetramethyl-1-oxidopiperidin-1-ium Chemical compound CC1CCC[N+](C)([O-])C1(C)C LGZDNJBUAAXEMN-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 230000003068 static effect Effects 0.000 description 3
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 239000001110 calcium chloride Substances 0.000 description 2
- 229910001628 calcium chloride Inorganic materials 0.000 description 2
- 150000001720 carbohydrates Chemical class 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 238000007759 kiss coating Methods 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 210000003739 neck Anatomy 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000012744 reinforcing agent Substances 0.000 description 2
- 230000003014 reinforcing effect Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- -1 carboxylic acid ion Chemical class 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 235000021186 dishes Nutrition 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000000844 transformation Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L7/00—Compositions of natural rubber
- C08L7/02—Latex
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/16—Applications used for films
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
- C08L2205/16—Fibres; Fibrils
Abstract
The present embodiments relate to macromolecule new material and biomedical materials fields, and in particular to a kind of high-concentration raw substance polysaccharide nanofiber/latex mixed liquor and preparation method thereof, application.High-concentration raw substance polysaccharide nanofiber/latex mixed liquor provided in an embodiment of the present invention, raw material includes: modified biomass polysaccharide slurry and latex；Preparation method includes: that modified biomass polysaccharide slurry is added in latex, and ultrasonic disperse obtains mixed liquor.By the way that by the modified biomass polysaccharide slurry of high concentration, ultrasound is removed directly inside latex, the modified biomass nanofiber of in-situ preparation high concentration simultaneously realizes its fine dispersion in latex, biomass polysaccharides class nanofiber/latex mixed liquor that the filling of high-concentration raw substance polysaccharide nanofiber high-content can be obtained, to increase substantially the mechanical property of latex composite material.
Description
Technical field
The present invention relates to macromolecule new material biomedical materials fields, and in particular to a kind of high-concentration raw substance polysaccharide
Nanofiber/latex mixed liquor and preparation method thereof, application.
Background technique
The advantages that latex product has elasticity high, and intensity is big, and wearing property is good, and orthopaedic function is good, and biological property is good, in work
Industry, agricultural, health care, culture and sports, daily life, defence and military etc. suffer from extensive purposes.At present both at home and abroad
Preparing latex elastomeric article, there are many method, such as blow molding, injection moldings and dip forming etc..Wherein dip forming is
Prepare the very universal method of film product (such as polybag, gloves, sheath etc.).However latex film is thinner, mechanical performance
Inevitably decline, therefore the reinforcement of latex film product is vital using playing the role of to it is widened.
Traditional filler, such as carbon black, silica and clay etc., reinforcing effect is bad, and it is non-renewable resources,
Certain pollution can also be generated to environment；Novel reinforcing agent, such as carbon nanotube, graphene etc., though there is preferable reinforcing effect,
It is expensive, is unfavorable for industrialized production, and it easily reunites in water-based latex system.
Biomass polysaccharides class (including chitin, cellulose) is the day that content is high, renewable, biodegradable in nature
Right macromolecule.Biomass polysaccharides class nanofiber is one obtained from handling biomass polysaccharides class as physics or chemical method
Dimension nano material.Biomass polysaccharides class nanofiber with big draw ratio, high Young's modulus and biocompatibility, this
It becomes a kind of ideal reinforcing agent and can be applied to biomedical materials field.Utilize biomass polysaccharides class nanofiber
Carrying out reinforcement latex, (latex here can refer to Heveatex and anionic synthetic latex, such as: polychloroprene latex, butyl latex, fourth
Benzene latex, NBR latex and water-soluble polyurethane latex etc.) while impart composite material biodegradability and biology again
Histocompatbility can widen the application of traditional latex product.But it is existing research be chitin or cellulose are first prepared into it is low
The finely dispersed nanofiber of concentration or nanocrystalline dispersion liquid, then it is compound with Heveatex.In this way the problem is that 1. is above-mentioned
Method can consume large quantity of moisture, be unfavorable for sustainable production, and preparation process is also complex, increase production cost；2. if into one
Step prepares film, the addition of low concentration nanofiber or nanocrystalline dispersion liquid (0.3wt%-3wt%) using dip forming technology
The concentration of Heveatex is greatly reduced, causes kiss-coating difficult, it is difficult to using industrial common dip forming technology, limit
The additional amount of low concentration nanofiber or nanocrystalline dispersion liquid, to limit biomass polysaccharides class nanofiber in practical application
Reinforcement ability.
The information disclosed in the background technology section is intended only to increase the understanding to general background of the invention, without answering
When being considered as recognizing or imply that the information constitutes the prior art already known to those of ordinary skill in the art in any form.
Summary of the invention
Goal of the invention
To solve the above problems, the purpose of the present invention is to provide a kind of high-concentration raw substance polysaccharide nanofiber/glue
Newborn mixed liquor and preparation method thereof, application.The preparation of high-concentration raw substance nanofiber/latex composite material provided by the invention
Method, by the modified biomass polysaccharide slurry of high concentration, ultrasound is removed directly inside latex, and in-situ preparation high concentration changes
Property biomass nano fiber (modified biomass polysaccharide slurry generate modified biomass nanofiber conversion ratio be about 95% with
On) and realize that its fine dispersion in latex, this method can be obtained high-concentration raw substance polysaccharide nanofiber high-content and fill out
The biomass polysaccharides class nanofiber/latex mixed liquor filled, to increase substantially the mechanical property of latex composite material.It obtains
High-concentration raw substance polysaccharide nanofiber/latex mixed liquor can further by dip forming technology or casting preparation birth
Substance nanofiber/latex product.
Solution
Purpose to realize the present invention, the embodiment of the invention provides a kind of high-concentration raw substance polysaccharide nanofiber/glue
Newborn mixed liquor, raw material include: modified biomass polysaccharide slurry and latex；Wherein, change in modified biomass polysaccharide slurry
Property biomass polysaccharides class concentration be 10wt%-30wt%, be optionally 20wt%-30wt%.
The weight ratio of modified biomass polysaccharide slurry and latex can be adjusted arbitrarily according to actual needs.
Above-mentioned high-concentration raw substance polysaccharide nanofiber/latex mixed liquor is in one possible implementation, modified
Biomass polysaccharides class includes the biomass polysaccharides class negatively charged in alkaline condition lower surface；Optionally, modified biomass polysaccharide
Class includes biomass polysaccharides class of the surface with carboxyl or sulfonate radical.
Above-mentioned high-concentration raw substance polysaccharide nanofiber/latex mixed liquor is in one possible implementation, modified
Biomass polysaccharides class includes modified chitin or modified cellulose.
Above-mentioned high-concentration raw substance polysaccharide nanofiber/latex mixed liquor is in one possible implementation, described
Modified chitin includes that surface had not only had carboxyl but also had the double electrical chitins or chitin of the surface with carboxyl of amino.
Above-mentioned high-concentration raw substance polysaccharide nanofiber/latex mixed liquor is in one possible implementation, described
Modified cellulose includes the cellulose that cellulose or surface of the surface with sulfonate radical have carboxyl.
Above-mentioned high-concentration raw substance polysaccharide nanofiber/latex mixed liquor is in one possible implementation, described
Latex includes: Heveatex, pre-vulcanized natural latex, presulfurization NBR latex, presulfurization carboxylated nitrile latex, presulfurization fourth
Benzene latex, presulfurization carboxylated styrene-butadiene latex, presulfurization polychloroprene latex, pre-vulcanized butyl rubber cream or water-soluble polyurethane latex in
It is at least one.
The embodiment of the invention also provides a kind of preparation sides of high-concentration raw substance polysaccharide nanofiber/latex mixed liquor
Method includes the following steps: for modified biomass polysaccharide slurry to be added in latex, and ultrasonic disperse obtains mixed liquor；Wherein, change
Property biomass polysaccharides class slurry in modified biomass polysaccharide concentration be 10wt%-30wt%, be optionally 20wt%-
30wt%.During ultrasonic disperse, about 95% or more modified biomass polysaccharide can in-situ preparation modified biomass polysaccharide
Class nanofiber.
The weight ratio of modified biomass polysaccharide slurry and latex can be adjusted arbitrarily according to actual needs.
The preparation method of above-mentioned high-concentration raw substance polysaccharide nanofiber/latex mixed liquor is in a kind of possible realization side
In formula, ultrasonic disperse instrument is cell crushing instrument.
The preparation method of above-mentioned high-concentration raw substance polysaccharide nanofiber/latex mixed liquor is in a kind of possible realization side
In formula, ultrasonic 5-20min.
The preparation method of above-mentioned high-concentration raw substance polysaccharide nanofiber/latex mixed liquor is in a kind of possible realization side
In formula, modified biomass polysaccharide includes the biomass polysaccharides class negatively charged in alkaline condition lower surface；Optionally, modified life
Substance polysaccharide includes biomass polysaccharides class of the surface with carboxyl or sulfonate radical.
The preparation method of above-mentioned high-concentration raw substance polysaccharide nanofiber/latex mixed liquor is in a kind of possible realization side
In formula, modified biomass polysaccharide includes modified chitin or modified cellulose.
The preparation method of above-mentioned high-concentration raw substance polysaccharide nanofiber/latex mixed liquor is in a kind of possible realization side
In formula, the modified chitin includes that surface had not only had carboxyl but also the double electrical chitins for having amino or surface are with carboxyl
Chitin.
The preparation method of above-mentioned high-concentration raw substance polysaccharide nanofiber/latex mixed liquor is in a kind of possible realization side
In formula, the modified cellulose includes the cellulose that cellulose or surface of the surface with sulfonate radical have carboxyl.
The preparation method of above-mentioned high-concentration raw substance polysaccharide nanofiber/latex mixed liquor is in a kind of possible realization side
In formula, the latex includes: Heveatex, pre-vulcanized natural latex, presulfurization NBR latex, presulfurization carboxylated nitrile glue
Cream, presulfurization styrene-butadiene latex, presulfurization carboxylated styrene-butadiene latex, presulfurization polychloroprene latex, pre-vulcanized butyl rubber cream or aqueous poly-
At least one of urethane latex.
Above-mentioned high-concentration raw substance polysaccharide nanofiber/latex mixed liquor or high-concentration raw substance polysaccharide Nanowire
In one possible implementation, surface had not only had carboxyl but also had had double electricity of amino dimension/latex mixed liquor preparation method
The preparation method of property chitin size includes the following steps:
The chitin of purifying is added in sodium hydroxide solution, is stirred under 60-120 DEG C of oil bath, during washing to pH is
Property；Drying；By the powder of above-mentioned drying, TEMPO reagent (tetramethyl hexahydropyridine oxide), sodium chlorite and Na2HPO4/
NaH2PO4Buffer solution is added sequentially in round-bottomed flask, mixture is placed under 50-70 DEG C of oil bath and is stirred；By secondary chlorine
Sour sodium is added drop-wise in above-mentioned round-bottomed flask；It stands or is centrifuged, remove supernatant, obtain double electrical chitin sizes.
Above-mentioned high-concentration raw substance polysaccharide nanofiber/latex mixed liquor or high-concentration raw substance polysaccharide Nanowire
In one possible implementation, surface has the preparation of the chitin size of carboxyl to dimension/latex mixed liquor preparation method
Method includes the following steps:
Chitin, TEMPO reagent (tetramethyl hexahydropyridine oxide), water, sodium bromide are added to dry three
In neck flask, magnetic agitation obtains mixed liquor at room temperature, and then liquor natrii hypochloritis is added in above-mentioned mixed liquor again, adjusts
The pH value of section system is 9-11；It is stirred at room temperature, ethyl alcohol is added and eliminates oxidation reaction；System pH is transferred to 7, is centrifuged, washing,
Obtain the chitin size that surface has carboxyl.
The embodiment of the invention also provides a kind of specifically answering for high-concentration raw substance polysaccharide nanofiber/latex mixed liquor
With mode, it may be assumed that a kind of biomass nano fiber/latex product, by above-mentioned high-concentration raw substance polysaccharide nanofiber/latex
Mixed liquor is made.
The embodiment of the invention also provides a kind of preparation methods of biomass nano fiber/latex product, including following steps
It is rapid: above-mentioned high-concentration raw substance polysaccharide nanofiber/latex mixed liquor is made by dip forming technology or casting.
The preparation method of above-mentioned biomass nano fiber/latex product in one possible implementation, dip forming
Processing step includes:
The mold of drying is cooled to 50-70 DEG C, soaks coagulator, upper and lower whipping until drop down, drying down without coagulator；
The mold of drying is cooled to 40-60 DEG C, then goes to impregnate above-mentioned high-concentration raw substance polysaccharide with the speed of 10-15mm/s and receive
Rice fiber/latex mixed liquor, double swerve, until being dropped down without liquid；Finally the glass mold after having soaked is put into
Vulcanize 30-50min at 100-120 DEG C and by its maturation 3-5d.
In one possible implementation, coagulator is the preparation method of above-mentioned biomass nano fiber/latex product
The mixing aqueous emulsion of calcium chloride, interleaving agent and lubricant three.
The preparation method of above-mentioned biomass nano fiber/latex product in one possible implementation, casting step
It include: to topple over above-mentioned high-concentration raw substance polysaccharide nanofiber/latex mixed liquor in plastic petri dishes with certain mass,
48-72h is first placed at room temperature, film is taken off and is placed in 100-120 DEG C of air dry oven vulcanizes 60-90min.
Beneficial effect
(1) traditional to be usually first prepared into chitin or cellulose with the method for biomass nano fibrous reinforcement latex
Low concentration, finely dispersed nanofiber or nanocrystalline dispersion liquid, then it is compound with Heveatex.It is asked existing for this preparation method
Topic is: 1. above methods can consume large quantity of moisture, be unfavorable for sustainable production, and preparation process is also complex, and increase is produced into
This；2. prepare film according to dip forming technology, low concentration nanofiber or nanocrystalline dispersion liquid (0.3wt%-3wt%)
The concentration of Heveatex is greatly reduced in addition, causes kiss-coating difficult, it is difficult to using industrial common dip forming technology, limit
The additional amount of low concentration nanofiber or nanocrystalline dispersion liquid is made, to limit biomass polysaccharides class nanometer in practical application
The reinforcement ability of fiber.
And the high-concentration raw substance polysaccharide nanofiber/latex mixed liquor provided in the embodiment of the present invention, with modified life
Substance polysaccharide slurry is filler, is added in latex, cell crushing instrument ultrasonic disperse is directly more by high concentration modified biomass
Carbohydrate slurry ultrasound in situ can be obtained highly concentrated at high concentration modified biomass polysaccharide nanofiber (conversion ratio up to 95% or more)
The biomass polysaccharides class nanofiber/latex mixed liquor for spending the filling of biomass polysaccharides class nanofiber high-content, overcomes tradition
Series of problems existing for low concentration nanofiber or nanocrystalline dispersion liquid and Heveatex compound tense.
(2) the high-concentration raw substance polysaccharide nanofiber/latex mixed liquor provided in the embodiment of the present invention, modification used
Biomass polysaccharides class slurry is the modified negatively charged biomass polysaccharides class slurry in surface, and the biomass with surface with carboxyl is more
For carbohydrate slurry, under the alkaline condition of Heveatex, carboxyl can be ionized into carboxylic acid ion and negatively charged, by power compared with
Big cell crushing instrument can be by its ultrasound at electronegative biomass polysaccharides class nanofiber, and latex particle itself is with negative
Electricity, the content of negative electrical charge is high in system, and the repulsive force between like charges can prevent biomass polysaccharides class to a certain extent
Nanofiber aggregation.Ultrasound disperses biomass nano fiber more evenly in Heveatex.Biomass nano fiber
As soon as generating, surrounding is surrounded by latex particle, so that biomass nano fibril aggregation is effectively prevented, so that biomass nano
Fiber can in Heveatex stable dispersion in situ.
(3) the high-concentration raw substance polysaccharide nanofiber/latex mixed liquor provided in the embodiment of the present invention, uses for the first time
The modified biomass slurry of high concentration is raw material, adds it in latex, obtains a kind of high-concentration raw substance nanofiber/glue
Newborn mixed liquor.Using the mixed liquor as raw material, flexibly, simply, both can choose dip forming technology can also be with for subsequent technique selection
Casting molding process etc. is selected, is saved water, it can be achieved that biomass polysaccharides class nanofiber high-content inside Heveatex is filled out
It fills, to increase substantially the mechanical property of Heveatex nanocomposite.
(4) the high-concentration raw substance polysaccharide nanofiber/latex mixed liquor preparation side provided in the embodiment of the present invention
Method, step is simple, is suitble to industrialized production.
(5) raw made from the high-concentration raw substance polysaccharide nanofiber/latex mixed liquor provided in the embodiment of the present invention
Substance nanofiber/latex product has apparent water stimulating responsive, and mixed liquor loading is bigger, this water stimuli responsive
Property is more obvious.This material with water-responsive can be used as biomaterial and apply in adaptivity medical graft.
Detailed description of the invention
One or more embodiments are illustrated by the picture in corresponding attached drawing, these exemplary theorys
The bright restriction not constituted to embodiment.Dedicated word " exemplary " means " being used as example, embodiment or illustrative " herein.
Here as any embodiment illustrated by " exemplary " should not necessarily be construed as preferred or advantageous over other embodiments.
Fig. 1 is double electrical chitin sizes that the embodiment of the present invention 1 uses.
Fig. 2 is the typical stress-strain of chitin nano fiber/Heveatex laminated film in effect example 1 of the present invention
Curve.
Fig. 3 is chitin nano fiber/Heveatex laminated film 50%, 200%, 300% in effect example 1 of the present invention
The relational graph of stress at definite elongation and double electrical chitin size filler numbers.
Fig. 4 is chitin nano fiber/Heveatex laminated film storage modulus and temperature pass in effect example 1 of the present invention
System's figure.
Fig. 5 be in effect example 1 of the present invention chitin nano fiber/Heveatex laminated film at 25 DEG C storage modulus and
The relational graph of time.
Fig. 6 is chitin nano fiber/Heveatex laminated film energy storage mould under dry and wet state in effect example 1 of the present invention
The relational graph of amount and double electrical chitin size filling numbers.
Specific embodiment
It in order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below will be in the embodiment of the present invention
Technical solution be clearly and completely described, it is clear that described embodiments are some of the embodiments of the present invention, rather than
Whole embodiments.Based on the embodiments of the present invention, those of ordinary skill in the art are not making creative work premise
Under every other embodiment obtained, shall fall within the protection scope of the present invention.Unless otherwise explicitly stated, otherwise whole
In a specification and claims, it is to include that the term " include " or its transformations will be understood as
The element or component stated, and do not exclude other elements or other components.
In addition, in order to better illustrate the present invention, numerous details is given in specific embodiment below.
It will be appreciated by those skilled in the art that without certain details, the present invention equally be can be implemented.In some embodiments, right
It is not described in detail in raw material well known to those skilled in the art, element, method, means etc., in order to highlight master of the invention
Purport.
Pre-vulcanized natural latex is provided by Shandong Xing Yu gloves Co., Ltd.
Embodiment 1
A kind of high-concentration raw substance polysaccharide nanofiber/latex mixed liquor, raw material includes following components in parts by weight:
Surface had not only had carboxyl but also had had double electrical chitin sizes of amino (surface had not only had carboxyl but also had amino in the slurry
The concentration of double electrical property chitins is 30wt%) 1 part and solid content be 60wt% 100 parts of pre-vulcanized natural latex；I.e. double electrical property
Chitin size additive amount is 1phr.
Pre-vulcanized natural latex additional amount is constant, and the additional amount for adjusting double electrical chitin sizes is respectively 2,3,4,5,7,
10,20,30 parts to get the high-concentration raw for double electrical chitin size additive amounts being respectively 2,3,4,5,7,10,20,30phr
Substance polysaccharide nanofiber/latex mixed liquor.
Above-mentioned high-concentration raw substance polysaccharide nanofiber/latex mixed liquor the preparation method comprises the following steps:
Above-mentioned surface had not only been had into carboxyl according to the above ratio but also the double electrical chitin sizes for having amino are added to stirring
In uniform pre-vulcanized natural latex (solid content 60wt%), ultrasound 10min is carried out using cell crushing instrument, obtains mixed liquor.
Surface, which had not only had carboxyl but also had the preparation methods of double electrical chitin sizes of amino, to be included the following steps:
By the chitin of purifying be added to mass concentration be 35wt% sodium hydroxide solution in, under 100 DEG C of oil baths into
Row stirring 3h, then by it, with alcohol and water, 1:1 carries out repeatedly washing suction filtration until pH is neutral by volume；Again 50~70
DEG C convection oven in dry；
By the chitin powder of the above-mentioned drying of 20g, 0.32g TEMPO reagent (tetramethyl hexahydropyridine oxide), 22.6g
Sodium chlorite, 1800mL Na2HPO4/NaH2PO4Buffer solution (pH=6.5) is added sequentially in round-bottomed flask, by mixture
It is placed under 60 DEG C of oil bath and stirs 2h；10.64g liquor natrii hypochloritis and 200mL buffer solution after mixing, then by one
Be added to dripping in the round-bottomed flask containing said mixture, drip off beginning timing, stood 20h or directly carry out from
The heart 5 times, supernatant is outwelled, finally obtains double electrical chitin sizes.Obtained double electrical chitin sizes are shown in Fig. 1.
Embodiment 2
A kind of high-concentration raw substance polysaccharide nanofiber/latex mixed liquor, raw material include: the first that surface has carboxyl
20 parts of shell element slurry (concentration of chitin of the surface with carboxyl is 20wt% in the slurry) and solid content are the pre- of 60wt%
100 parts of vulcanized natural rubber cream；
Wherein, surface with carboxyl chitin size the preparation method comprises the following steps:
The chitin of 10g purifying, 0.16gTEMPO reagent, 1000g water, 1g sodium bromide are added to a three dry necks
In flask, magnetic agitation 10min or so obtains mixed liquor at room temperature, is then again added to the liquor natrii hypochloritis of 53.2g
In above-mentioned mixed liquor, is titrated while stirring with the NaOH solution of 0.5mol/L, the pH value of system is made to be maintained at 10 or so；In room temperature
After lower stirring 20h, a small amount of ethyl alcohol is added and eliminates oxidation reaction；The system pH after reaction is transferred to 7 with the HCl of 0.5mol/L, most
Obtained suspension is centrifuged and is used deionized water repeated flushing at least 5 times in 8000r/15min afterwards, obtains surface with carboxylic
The chitin size of base.
Above-mentioned high-concentration raw substance polysaccharide nanofiber/latex mixed liquor the preparation method comprises the following steps:
According to the above ratio by surface with carboxyl chitin size be added to stir evenly pre-vulcanized natural latex (Gu
Content is 60wt%) in, ultrasound 15min is carried out using cell crushing instrument, obtains mixed liquor.
Effect example 1
1. the preparation of chitin nano fiber/Heveatex laminated film:
It is respectively 1,2,3,4,5,7,10,20,30phr using double electrical property chitin size additive amount made from embodiment 1
High-concentration raw substance polysaccharide nanofiber/latex mixed liquor, pass through dip forming technology prepare chitin nano fiber/day
Right latex laminated film, the specific steps are as follows:
By teat glass die surface wash clean, then it is baked in 80 DEG C or so baking ovens；
The mold of above-mentioned drying is cooled to 60 DEG C or so leaching coagulators, and (coagulator is calcium chloride, interleaving agent and lubricant
Mixing aqueous emulsion), and up and down whipping until being dropped down down without coagulator, and be put into baking oven and dry；
The mold of drying is cooled to 50 DEG C or so, the mixed liquor for then going dipping ultrasound complete with the speed of 10mm/s, so
Glass mold after having soaked finally is put at 100 DEG C until dropping down without liquid and vulcanizes 40min simultaneously by double swerve afterwards
By its maturation 4d.
2. pair chitin nano fiber/Heveatex laminated film static mechanical property is tested, steps are as follows:
Static stretch survey has been carried out to chitin nano fiber/Heveatex laminated film with the program in ASTM standard
Examination, is cut into cyclic annular batten (thickness: 60-200 μm for film；Width: 20 μm), every group of 5 battens, for the uniformity of thickness,
Each batten cuts intermediate position, and rate of extension is 500mm/s at room temperature.
As a result see Fig. 2 and Fig. 3, known by Fig. 2, Fig. 3 with high-concentration raw substance polysaccharide nanofiber/latex mixed liquor
In double electrical chitin size additional amounts increase, chitin nano fiber/Heveatex nano compound film 50%,
200%, 300% stress at definite elongation gradually increases.After double electrical chitin size loadings are greater than 7phr, 50%, 200%,
The equal conspicuousness of 300% stress at definite elongation improves；When double electrical chitin size loadings are greater than 30phr, stress at definite elongation is improved
Original 10 times or so are arrived.This explanation can using the method for the double electrical chitin sizes of direct in-situ ultrasound in Heveatex
Realize: what is mixed with latex is double electrical chitin nano fibers of high concentration.And double electrical chitin Nanowires of high concentration
Its high-content filling in latex can be achieved in dimension, fills the chitin nano fiber of high-content to the nano combined material of Heveatex
The raising of the static mechanical properties of material has better effect.
3. studying chitin nano fiber/Heveatex laminated film temperature-storage modulus, steps are as follows:
The Q800 of TA company is under stretch mode, frequency 1.0Hz, and straining is 0.25%, to chitin nano fiber/day
Right latex composite material carries out the DMA test under temperature scanning, and temperature range is -90-60 DEG C.
As a result Fig. 4 is seen, as shown in Figure 4, at -30 DEG C or more, with the increase of double electrical chitin size loadings, first
Shell element nanofiber/natural latex composite material storage modulus successively increases, and increasing degree is clearly, in elastomeric state
Under, it is minimum that two orders of magnitude are differed with highest storage modulus.This sufficiently shows using the direct in-situ ultrasound pair in Heveatex
The method of electrical chitin size can be realized: what is mixed with latex is double electrical chitin nano fibers of high concentration.And it is highly concentrated
Double electrical chitin nano fibers of degree can realize its high-content filling in latex, the height of double electrical property chitin nano fibers
Content filling can greatly improve chitin nano fiber/natural latex composite material mechanical property.
4. studying chitin nano fiber/Heveatex laminated film water stimulating responsive, steps are as follows:
The sample of different content first impregnates 18h or so with ionized water at room temperature, is then stretching in the Q800 of TA company
Under mode, frequency 1.0Hz, straining is 0.5%, 25 DEG C of temperature, is carried out to chitin nano fiber/natural latex composite material
DMA test, sample is cut into dumbbell shaped, width 4mm, thickness is in 60-200 μ m.
As a result Fig. 5, Fig. 6 are seen, by Fig. 5, Fig. 6 it is found that pure NR (not adding the laminated film of chitin nano fiber) is dry
Under wet condition, modulus change is little；But with the increase of double electrical chitin size loadings, chitin nano fiber/day
Storage modulus variation is increasing under right latex laminated film dry and wet state.Under double electrical property chitin size high-contents (30phr),
Storage modulus differs about three times under chitin nano fiber/Heveatex laminated film dry and wet state, this illustrates water to chitin
The destruction (in a wet state) and reconstruction (in a dry state) of hydrogen bond action between nanofiber are in dynamic equilibrium,
Show certain water stimulating responsive, under the high filler loading capacity of especially double electrical chitin nano fibers, water stimulating responsive
Clearly.
Finally, it should be noted that the above embodiments are merely illustrative of the technical solutions of the present invention, rather than its limitations；Although
Present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that: it still may be used
To modify the technical solutions described in the foregoing embodiments or equivalent replacement of some of the technical features；
And these are modified or replaceed, technical solution of various embodiments of the present invention that it does not separate the essence of the corresponding technical solution spirit and
Range.
Claims (10)
1. a kind of high-concentration raw substance polysaccharide nanofiber/latex mixed liquor, raw material include: modified biomass polysaccharide plasmoid
Material and latex；Wherein, the concentration of modified biomass polysaccharide is 10wt%-30wt% in modified biomass polysaccharide slurry, can
Selection of land is 20wt%-30wt%.
2. a kind of preparation method of high-concentration raw substance polysaccharide nanofiber/latex mixed liquor, includes the following steps: to be modified
Biomass polysaccharides class slurry is added in latex, and ultrasonic disperse obtains mixed liquor；Wherein, change in modified biomass polysaccharide slurry
Property biomass polysaccharides class concentration be 10wt%-30wt%, be optionally 20wt%-30wt%.
3. described in high-concentration raw substance polysaccharide nanofiber/latex mixed liquor according to claim 1 or claim 2
High-concentration raw substance polysaccharide nanofiber/latex mixed liquor preparation method, it is characterised in that: modified biomass polysaccharide
Including the biomass polysaccharides class negatively charged in alkaline condition lower surface；Optionally, modified biomass polysaccharide includes surface band
The biomass polysaccharides class of carboxyl or sulfonate radical；
And/or modified biomass polysaccharide includes modified chitin or modified cellulose；
And/or modified biomass polysaccharide includes that surface had not only had carboxyl but also had the double electrical chitins or surface band of amino
There are the chitin or surface of carboxyl cellulose or surface with sulfonate radical to have the cellulose of carboxyl.
4. described in high-concentration raw substance polysaccharide nanofiber/latex mixed liquor according to claim 1 or claim 2
High-concentration raw substance polysaccharide nanofiber/latex mixed liquor preparation method, it is characterised in that: the latex includes: day
Right latex, pre-vulcanized natural latex, presulfurization NBR latex, presulfurization carboxylated nitrile latex, presulfurization styrene-butadiene latex, pre- sulphur
Carboxylated styrene-butadiene latex, presulfurization polychloroprene latex, at least one of pre-vulcanized butyl rubber cream or water-soluble polyurethane latex.
5. the preparation method of high-concentration raw substance polysaccharide nanofiber/latex mixed liquor according to claim 2, special
Sign is: ultrasonic disperse instrument is cell crushing instrument；
And/or ultrasonic 5-20min.
6. described in high-concentration raw substance polysaccharide nanofiber/latex mixed liquor according to claim 3 or claim 3
High-concentration raw substance polysaccharide nanofiber/latex mixed liquor preparation method, it is characterised in that: surface not only had carboxyl but also
The preparation method of double electrical chitin sizes with amino includes the following steps:
The chitin of purifying is added in sodium hydroxide solution, is stirred under 60-120 DEG C of oil bath, washing to pH is neutrality；It dries
It is dry；By the powder of above-mentioned drying, TEMPO reagent, sodium chlorite and Na2HPO4/NaH2PO4Buffer solution is added sequentially to round bottom
In flask, mixture is placed under 50-70 DEG C of oil bath and is stirred；Sodium hypochlorite is added drop-wise in above-mentioned round-bottomed flask；It stands
Or centrifugation, supernatant is removed, double electrical chitin sizes are obtained；
And/or the preparation method of chitin size of the surface with carboxyl includes the following steps:
Chitin, TEMPO reagent, water, sodium bromide are added in a dry three-neck flask, magnetic agitation obtains at room temperature
To mixed liquor, then liquor natrii hypochloritis is added in above-mentioned mixed liquor again, the pH value of regulation system is 9-11；At room temperature
Stirring is added ethyl alcohol and eliminates oxidation reaction；System pH is transferred to 7, is centrifuged, washing obtains the Chitin pulp that surface has carboxyl
Material.
7. a kind of biomass nano fiber/latex product, by high-concentration raw substance polysaccharide Nanowire described in claim 1
The preparation method of dimension/latex mixed liquor or high-concentration raw substance polysaccharide nanofiber/latex mixed liquor as claimed in claim 2
High-concentration raw substance polysaccharide nanofiber/latex mixed liquor obtained is made.
8. a kind of preparation method of biomass nano fiber/latex product, includes the following steps: height described in claim 1
Concentration biomass polysaccharides class nanofiber/latex mixed liquor or high-concentration raw substance polysaccharide Nanowire as claimed in claim 2
High-concentration raw substance polysaccharide nanofiber/latex mixed liquor made from dimension/latex mixed liquor preparation method by dipping at
Type technique or casting are made.
9. the preparation method of biomass nano fiber/latex product according to claim 8, it is characterised in that: dipping at
Type processing step includes:
The mold of drying is cooled to 50-70 DEG C, soaks coagulator, upper and lower whipping until drop down, drying down without coagulator；It will dry
Dry mold is cooled to 40-60 DEG C, then goes to impregnate above-mentioned high-concentration raw substance polysaccharide Nanowire with the speed of 10-15mm/s
Dimension/latex mixed liquor, double swerve, until being dropped down without liquid；The glass mold after having soaked finally is put into 100-120
Vulcanize 30-50min at DEG C and by its maturation 3-5d.
10. the preparation method of biomass nano fiber/latex product according to claim 8, it is characterised in that: casting step
It suddenly include: that above-mentioned high-concentration raw substance polysaccharide nanofiber/latex mixed liquor is poured over plastic culture dish with certain mass
In, 48-72h is first placed at room temperature, film is taken off and is placed in 100-120 DEG C of air dry oven vulcanizes 60-90min.
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| CN113214549A (en) * | 2020-12-24 | 2021-08-06 | 青岛科技大学 | Natural latex/chitin nano-fiber composite membrane and preparation method thereof |
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