CN110483832A - The natural rubber and agar compound mesoporous film and preparation method of more characteristics - Google Patents
The natural rubber and agar compound mesoporous film and preparation method of more characteristics Download PDFInfo
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- CN110483832A CN110483832A CN201910844008.9A CN201910844008A CN110483832A CN 110483832 A CN110483832 A CN 110483832A CN 201910844008 A CN201910844008 A CN 201910844008A CN 110483832 A CN110483832 A CN 110483832A
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- natural rubber
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- 229920001817 Agar Polymers 0.000 title claims abstract description 95
- 239000008272 agar Substances 0.000 title claims abstract description 95
- 244000043261 Hevea brasiliensis Species 0.000 title claims abstract description 59
- 229920003052 natural elastomer Polymers 0.000 title claims abstract description 59
- 229920001194 natural rubber Polymers 0.000 title claims abstract description 59
- 150000001875 compounds Chemical class 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title abstract description 11
- 239000000243 solution Substances 0.000 claims abstract description 101
- 239000004094 surface-active agent Substances 0.000 claims abstract description 77
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 35
- 238000000034 method Methods 0.000 claims abstract description 22
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 20
- 150000001413 amino acids Chemical class 0.000 claims abstract description 20
- 239000006185 dispersion Substances 0.000 claims abstract description 18
- 230000001804 emulsifying effect Effects 0.000 claims abstract description 18
- 239000007788 liquid Substances 0.000 claims abstract description 18
- 239000002131 composite material Substances 0.000 claims abstract description 15
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 10
- 238000004108 freeze drying Methods 0.000 claims abstract description 9
- 239000012670 alkaline solution Substances 0.000 claims abstract description 5
- 239000002245 particle Substances 0.000 claims description 22
- 238000009835 boiling Methods 0.000 claims description 21
- 235000001014 amino acid Nutrition 0.000 claims description 19
- 229940024606 amino acid Drugs 0.000 claims description 19
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 16
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims description 12
- 229910021529 ammonia Inorganic materials 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 239000012153 distilled water Substances 0.000 claims description 7
- 239000004471 Glycine Substances 0.000 claims description 6
- MTJZWYHTZFVEGI-INIZCTEOSA-N (2s)-2-(tetradecanoylamino)pentanedioic acid Chemical group CCCCCCCCCCCCCC(=O)N[C@H](C(O)=O)CCC(O)=O MTJZWYHTZFVEGI-INIZCTEOSA-N 0.000 claims description 5
- 238000012545 processing Methods 0.000 claims description 5
- UYTOHYBIBPDOKX-ZDUSSCGKSA-N (2s)-2-(dodecanoylamino)propanoic acid Chemical compound CCCCCCCCCCCC(=O)N[C@@H](C)C(O)=O UYTOHYBIBPDOKX-ZDUSSCGKSA-N 0.000 claims description 4
- DXDTUQXKMVJYAM-UHFFFAOYSA-N 2-aminoacetic acid;potassium Chemical compound [K].NCC(O)=O DXDTUQXKMVJYAM-UHFFFAOYSA-N 0.000 claims description 4
- YBESMQHGHZRDRO-TYOUJGAFSA-N N[C@@H](C)C(=O)O.C(CCCCCCCCCCC)(=O)[Na] Chemical compound N[C@@H](C)C(=O)O.C(CCCCCCCCCCC)(=O)[Na] YBESMQHGHZRDRO-TYOUJGAFSA-N 0.000 claims description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- -1 myristoyl sodium glutamate Chemical compound 0.000 claims description 4
- 229910052700 potassium Inorganic materials 0.000 claims description 4
- 239000011591 potassium Substances 0.000 claims description 4
- 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 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 238000009826 distribution Methods 0.000 claims description 3
- 235000013923 monosodium glutamate Nutrition 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 229940073490 sodium glutamate Drugs 0.000 claims description 3
- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical class OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 claims description 2
- 150000007513 acids Chemical class 0.000 claims description 2
- 150000001295 alanines Chemical class 0.000 claims description 2
- 235000009508 confectionery Nutrition 0.000 claims description 2
- 150000002333 glycines Chemical class 0.000 claims description 2
- 125000000400 lauroyl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 235000013162 Cocos nucifera Nutrition 0.000 claims 1
- 244000060011 Cocos nucifera Species 0.000 claims 1
- 239000004519 grease Substances 0.000 claims 1
- 239000012528 membrane Substances 0.000 abstract description 14
- 230000035699 permeability Effects 0.000 abstract description 5
- 239000003814 drug Substances 0.000 abstract description 3
- 239000000758 substrate Substances 0.000 abstract description 2
- 229940079593 drug Drugs 0.000 abstract 1
- 229920001971 elastomer Polymers 0.000 description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 239000000203 mixture Substances 0.000 description 7
- 229920000936 Agarose Polymers 0.000 description 6
- 238000005259 measurement Methods 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 101000952180 Morus alba Mulatexin Proteins 0.000 description 4
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 3
- 235000019864 coconut oil Nutrition 0.000 description 3
- 239000003240 coconut oil Substances 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- JWGGSJFIGIGFSQ-UHFFFAOYSA-N N-dodecanoylglycine Chemical compound CCCCCCCCCCCC(=O)NCC(O)=O JWGGSJFIGIGFSQ-UHFFFAOYSA-N 0.000 description 2
- 239000000908 ammonium hydroxide Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000010494 dissociation reaction Methods 0.000 description 2
- 230000005593 dissociations Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005189 flocculation Methods 0.000 description 2
- 230000016615 flocculation Effects 0.000 description 2
- 238000007710 freezing Methods 0.000 description 2
- 230000008014 freezing Effects 0.000 description 2
- 150000004676 glycans Chemical class 0.000 description 2
- 239000000693 micelle Substances 0.000 description 2
- 229920001282 polysaccharide Polymers 0.000 description 2
- 239000005017 polysaccharide Substances 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 235000018102 proteins Nutrition 0.000 description 2
- 108090000623 proteins and genes Proteins 0.000 description 2
- 102000004169 proteins and genes Human genes 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- DWNBOPVKNPVNQG-LURJTMIESA-N (2s)-4-hydroxy-2-(propylamino)butanoic acid Chemical compound CCCN[C@H](C(O)=O)CCO DWNBOPVKNPVNQG-LURJTMIESA-N 0.000 description 1
- 241001474374 Blennius Species 0.000 description 1
- 229920001661 Chitosan Polymers 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 239000003519 biomedical and dental material Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 229920001002 functional polymer Polymers 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 239000003349 gelling agent Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000005213 imbibition Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000010977 jade Substances 0.000 description 1
- 235000015110 jellies Nutrition 0.000 description 1
- 239000008274 jelly Substances 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
- C08J3/05—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media from solid polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/28—Treatment by wave energy or particle radiation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2305/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2301/00 or C08J2303/00
- C08J2305/12—Agar-agar; Derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2307/00—Characterised by the use of natural rubber
- C08J2307/02—Latex
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2405/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2401/00 or C08J2403/00
- C08J2405/12—Agar-agar; Derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2407/00—Characterised by the use of natural rubber
- C08J2407/02—Latex
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/20—Carboxylic acid amides
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Dispersion Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
The natural rubber and agar compound mesoporous film and preparation method of more characteristics disclosed by the invention, method particularly includes: Heveatex solution is handled respectively first with high shear emulsifying dispersion machine, agar solution, then stablize Heveatex solution with amino acid surfactant, agar solution, and pH value is adjusted to 10 ~ 11 respectively with alkaline solution, then Heveatex-surfactant solution is blended with agar-surfactant solution, mixed liquor at least 3min is handled with microwave irradiation again, then pre-freeze handles mixed liquor 30min in liquid nitrogen, finally by mixed liquor in -50 DEG C of freeze-drying at least 12h, obtain natural rubber and agar compound mesoporous film.The method of the present invention is skillfully constructed, technique and easy to operate, natural rubber and agar composite membrane, which is made, has uniform meso-hole structure, with good moisture pick-up properties, water lock performance, permeability, tensile stress-strain performance and softness, both it may be used as wound dressing, the substrate that may be used as drug loading again, has a wide range of application.
Description
Technical field
The invention belongs to Material Fields, and in particular to the natural rubber and agar compound mesoporous film of a kind of more characteristics and preparation
Method.
Background technique
Agar is the polysaccharide body extracted from seaweed, and main component is agarose, is hydrophilic colloid, does not dissolve in cold water,
It needs to be heated in water just to start to melt at 95 DEG C, 20 times of volume of water itself can be absorbed, and be lower than 40 DEG C of Shi Huifa in temperature
Raw solidification remains to form stable gel when concentration is down to 1%.Currently, agar is widely used as gelling agent, it to be used for field of food
With microculture field.However, single agar membrane shows brittleness, ductility is poor, limits it in medical domain
Using.
Heveatex is a kind of sticky milky white liquid, and main component is cis- Isosorbide-5-Nitrae-polyisoprene rubber particle.It
Right rubber particles have hydrophobic property, in the solution by lipids such as adsorption protein, phosphatide, to be formed steady
Fixed rubber-aqua type dispersion.At normal temperature, natural rubber has excellent elasticity, filming performance, mechanical property, soft
Toughness.Currently, natural rubber is widely used as gloves, sheath as protective materials.However, single natural rubber film is in
Reveal strong-hydrophobicity and high compactness, permeability, vapor pervious performance are poor, limit it in the application of medical domain.
Summary of the invention
The purpose of the present invention is single natural rubber material and agar material there are aiming at the problem that, a kind of more characteristics are provided
Natural rubber and agar compound mesoporous film preparation method and natural rubber obtained by this method and agar compound mesoporous film.
To achieve the object of the present invention, base of the present inventor in the preparation method of disclosed natural rubber film or agar membrane
On plinth, the azeotropic nature of Heveatex and agar solution is explored, is found rubber particles after agar solution addition Heveatex
Flocculation is precipitated rapidly, thus cannot directly be blended.In order to promote coexisting for Heveatex and agar solution, the present inventor is deeply ground
The compositing characteristic and stably dispersing characteristic of Heveatex and agar solution are studied carefully.Since the isoelectric point pI of natural latex proteins matter exists
(Pan Suhua protein and rubber particles protective layer tropical agricultural science, 1985, (1): 22-27.), In between pH4 ~ 5
In high ammonia alkaline environment, the latex protein band negative charge of dissociation, and rubber particles surface is adsorbed on by Van der Waals force and is formed
Rubber particles outermost layer protects structure, this is the main reason for Heveatex is stablized.Since agarose is non-ionic polysaccharide, base
This structure is the long-chain that the β-D- galactolipin of 1,3 connections and 3, the 6- inner ether-L- galactolipin of Isosorbide-5-Nitrae connection alternately connect, because
This agarose can form stronger interaction of hydrogen bond with latex protein.Agar solution is added in the Heveatex of room temperature
When, since sharp temperature drop causes the agar solution being added to solidify rapidly, so that occurring with agarose in agar mutual
The latex protein of effect is easy to peel off from rubber particles surface, causes rubber particles surface charge quantity to decline, Heveatex
Dispersion stabilization be deteriorated, show as rubber particles flocculation be precipitated.To solve rubber in Heveatex and agar solution Blending Processes
The problem of micelle flocculates, the present inventor explores again pre-processes Heveatex solution using high shear emulsifying dispersion machine
Or agar solution, followed by amino acid surfactant stable Heveatex solution or agar solution respectively, then by day
The method that right latex-surfactant solution is blended with agar-surfactant solution, finally found that this process combination
It can guarantee the homogeneous blend of Heveatex and agar solution under room temperature, and exist steadily in the long term.
Due to the molecular size and structure difference of rubber particles and agarose, form a film in Heveatex and agar blend solution
During, rubber particles, the mobile performance difference of agarose are big, cause in natural rubber and agar composite membrane rubber particles and
The phenomenon that agar molecule is clearly separated, the material composition of different location is uneven in film.To solve this problem, the present inventor
It further explores mixed using microwave irradiation processing Heveatex-surfactant solution and agar-surfactant solution
After closing liquid, is sharply cooled down using liquid nitrogen and the method for frozen drying, finally found that this process combination can guarantee natural rubber
Glue and agar composite membrane form is complete, aperture size is uniform, and rubber particles are staggeredly uniformly distributed with agar molecule in film.
The natural rubber and agar compound mesoporous film of more characteristics provided by the invention, it is characterised in that natural in the mesoporous film
The mass ratio of rubber particles and agar is 1:1 ~ 10:1, and amino acid surfactant is at least 161mg in every gram of mesoporous film, should
The pore-size distribution of mesoporous film porosity of=55.0% in 10 ~ 50nm, film, hygroscopic capacity >=8.9g of every gram of film, the water lock performance of film
Value≤8.5cm, evaporated quantity of water >=6.9g.h of film-1.cm-2, tensile strength >=5.7MPa of film, the elongation at break of film >=
473%, softness values≤185mN of film.
In order to solve the above technical problems, the technical scheme is that the natural rubber and agar composite mesopore of more characteristics
The preparation method of film, the processing step and condition of this method are as follows:
1) prepare Heveatex-surfactant solution: 20 DEG C, speed of agitator be 20r/min under conditions of, 150g is distilled
After water is added to 300g Heveatex, high shear emulsifying disperses under conditions of speed of agitator is 3000 ~ 4000r/min
Machine handles 10 ~ 20min of Heveatex solution, and 20 ~ 30g ammonia is then added under conditions of speed of agitator is 2000 ~ 3000r/min
Base acids surfactant, then Heveatex-surfactant solution pH value is adjusted to 10~11 with alkaline solution；
2) it prepares agar-surfactant solution: boiling 1000mL distilled water, keeping solution boiling, speed of agitator 20r/
Under conditions of min be added 20 ~ 40g agar, continue keep solution boiling 30min after, 50 DEG C, speed of agitator be 8000 ~
10 ~ 20min of agar solution is handled with high shear emulsifying dispersion machine under conditions of 12000r/min, is then in speed of agitator
20 ~ 30g amino acid surfactant is added under conditions of 2000 ~ 3000r/min, then with alkaline solution that agar-surface is living
The pH value of property agent solution is adjusted to 10~11；
3) natural rubber and agar compound mesoporous film are prepared:, will be natural under conditions of speed of agitator is 2000 ~ 3000r/min
After latex-surfactant solution is 1:2 ~ 1:10 mixing 20min according to mass ratio with agar-surfactant solution, with frequency
The microwave irradiation that rate is 2450MHz, power is 1 ~ 2kW handles at least 3min, then the rapid pre-freeze mixed liquor in liquid nitrogen
Mixed liquor is finally obtained the natural rubber and agar composite mesopore of more characteristics in -50 DEG C of freeze-drying at least 12h by 30min
Film.
The natural rubber of more characteristics and the preparation method of agar compound mesoporous film, it is characterised in that the step 1)
It is at least one of glutamic acid series, glycine series, alanine series with amino acid surfactant in step 2.
The natural rubber of more characteristics and the preparation method of agar compound mesoporous film, it is characterised in that the step 1)
It is that myristoyl glutamic acid, myristoyl sodium glutamate, lauroyl are sweet with amino acid surfactant in step 2
Propylhomoserin, cocoyl glycine potassium, positive decoyl glycine, lauroyl Sodium L-alaninate, lauroyl alanine potassium, N- coconut oil
At least one of fatty acid-l-Alanine sodium.
The natural rubber of more characteristics provided by the invention and the technology of preparing scheme of agar compound mesoporous film, dexterously utilize
Amino acid surfactant with foaming characteristic and salt-resistance, first with amino acid surfactant can form micella
Characteristic, will be by the agar molecule or aggregation, natural rubber particle or micelle point of high shear emulsifying dispersion machine processing
Not carry out encapsulated package, to promote latex uniformly to mix with agar；Secondly amino and carboxylic in amino acid surfactant are utilized
Electrically charged property, supplements the amount of charge of rubber particles adsorption, is blended with alleviating Heveatex with agar after base dissociation
In the process the problem of the decline of rubber particles surface charge quantity, bad stability, to guarantee that Heveatex can be steady with agar
Surely it coexists, provides uniform solution for the preparation of natural rubber and agar composite membrane；Followed by the rapid cold of ultra-low temperature liquid nitrogen
Jelly effect makes to form tiny ice crystal in Heveatex and agar blend solution, to promote ice crystal in subsequent freezing dry process
Distillation forms meso-hole structure；Finally, the action principle of solution surface tension can be reduced using amino acid surfactant, realize
Protective effect of the surfactant to rubber particles, agar molecule in freezing dry process, to maintain natural rubber after freeze-drying
With the integrality of agar compound mesoporous film mode of appearance and the uniformity of microcosmic composition.
It also have the advantage that
1, method concept provided by the invention is ingenious, technique and easy to operate, and capital equipment used is agitating device, high shear
Emulsifying dispersion machine and microwave treater, these are all common laboratory equipments, are not necessarily to additional investment.
2, the natural rubber made from method provided by the invention and agar compound mesoporous film set natural rubber and fine jade
The advantage of rouge both may be used as wound and applied so that mesoporous film has good mechanical property, water imbibition and water lock, gas permeability
Material, and may be used as the substrate of carrying medicament, have a wide range of application, thus natural rubber and agar compound mesoporous film have preferably
Market prospects.
3, it is using material Heveatex, agar and amino acid surfactant by method institute provided by the invention
Conventional chemical materials, and from natural plants or further processing product, thus material source is extensive, green safe.
Specific embodiment
Embodiment is given below so that the present invention will be described in more detail, it is necessary to be pointed out that following embodiment cannot manage
Solution is limiting the scope of the invention, and the person skilled in the art in the field makes the present invention according to aforementioned present invention content
Some nonessential modifications and adaptations still fall within protection scope of the present invention.
Embodiment 1
1) prepare Heveatex-surfactant solution: 20 DEG C, speed of agitator be 20r/min under conditions of, 150g is distilled
After water is added to 300g Heveatex, under conditions of speed of agitator is 3000r/min at high shear emulsifying dispersion machine
Heveatex solution 20min is managed, 20g myristoyl glutamic acid is then added under conditions of speed of agitator is 3000r/min
Natrium surfactant, then be adjusted to Heveatex-surfactant solution pH value with the ammonia spirit that mass fraction is 10%
10；
2) it prepares agar-surfactant solution: boiling 1000mL distilled water, keeping solution boiling, speed of agitator 20r/
20g agar is added under conditions of min, continues after keeping solution boiling 30min, in 50 DEG C, the item that speed of agitator is 8000r/min
Agar solution 10min is handled with high shear emulsifying dispersion machine under part, then under conditions of speed of agitator is 2000r/min
20g myristoyl sodium glutamate surfactant is added, then the ammonia spirit for being 10% with mass fraction is living by agar-surface
The pH value of property agent solution is adjusted to 10；
3) natural rubber and agar compound mesoporous film are prepared: under conditions of speed of agitator is 2000r/min, by Heveatex-
After surfactant solution is 1:2 mixing 20min according to mass ratio with agar-surfactant solution, it is with frequency
2450MHz, the microwave irradiation that power is 1kW handle 3min, and then the rapid pre-freeze mixed liquor 30min in liquid nitrogen, will finally mix
Liquid is closed in -50 DEG C of freeze-drying 12h, obtains the natural rubber and agar compound mesoporous film of more characteristics.Natural rubber grain in the film
The mass ratio of son and agar is 10:1, and amino acid surfactant content is 161mg in every gram of film.
Embodiment 2
1) prepare Heveatex-surfactant solution: 20 DEG C, speed of agitator be 20r/min under conditions of, 150g is distilled
After water is added to 300g Heveatex, under conditions of speed of agitator is 4000r/min at high shear emulsifying dispersion machine
Manage Heveatex solution 10min, then speed of agitator be 2000r/min under conditions of be added 15g lauroyl glycine and
10g cocoyl glycine potassium surfactant, then the ammonia spirit for being 5% with mass fraction is by Heveatex-surfactant
The pH value of solution is adjusted to 11；
2) it prepares agar-surfactant solution: boiling 1000mL distilled water, keeping solution boiling, speed of agitator 20r/
40g agar is added under conditions of min, continues after keeping solution boiling 30min, is 12000r/min's in 50 DEG C, speed of agitator
Under the conditions of with high shear emulsifying dispersion machine handle agar solution 20min, then speed of agitator be 3000r/min condition
The positive decoyl glycine of lower addition 15g and 15g lauroyl Sodium L-alaninate surfactant, then it is molten with the ammonium hydroxide that mass fraction is 5%
Agar-surfactant solution pH value is adjusted to 11 by liquid；
3) natural rubber and agar compound mesoporous film are prepared: under conditions of speed of agitator is 3000r/min, by Heveatex-
After surfactant solution is 1:10 mixing 20min according to mass ratio with agar-surfactant solution, it is with frequency
2450MHz, the microwave irradiation that power is 2kW handle 6min, and then the rapid pre-freeze mixed liquor 30min in liquid nitrogen, will finally mix
Liquid is closed in -50 DEG C of freeze-drying 16h, obtains the natural rubber and agar compound mesoporous film of more characteristics.Natural rubber grain in the film
The mass ratio of son and agar is 1:1, and amino acid surfactant content is 307mg in every gram of film.
Embodiment 3
1) prepare Heveatex-surfactant solution: 20 DEG C, speed of agitator be 20r/min under conditions of, 150g is distilled
After water is added to 300g Heveatex, under conditions of speed of agitator is 3500r/min at high shear emulsifying dispersion machine
Heveatex solution 15min is managed, the positive decoyl glycine of 14g and 14g are then added under conditions of speed of agitator is 2500r/min
Lauroyl Sodium L-alaninate surfactant, then the sodium hydroxide solution for being 1% with mass fraction is by Heveatex-surface-active
The pH value of agent solution is adjusted to 10.5；
2) it prepares agar-surfactant solution: boiling 1000mL distilled water, keeping solution boiling, speed of agitator 20r/
30g agar is added under conditions of min, continues after keeping solution boiling 30min, is 10000r/min's in 50 DEG C, speed of agitator
Under the conditions of with high shear emulsifying dispersion machine handle agar solution 16min, then speed of agitator be 2300r/min condition
Lower addition 15g lauroyl glycine and 10g cocoyl glycine potassium surfactant, then the hydrogen-oxygen for being 1% with mass fraction
Change sodium solution and agar-surfactant solution pH value is adjusted to 10.5；
3) natural rubber and agar compound mesoporous film are prepared: under conditions of speed of agitator is 2500r/min, by Heveatex-
After surfactant solution is 1:5 mixing 20min according to mass ratio with agar-surfactant solution, it is with frequency
2450MHz, the microwave irradiation that power is 1.8kW handle 5min, then the rapid pre-freeze mixed liquor 30min in liquid nitrogen, finally will
Mixed liquor obtains the natural rubber and agar compound mesoporous film of more characteristics in -50 DEG C of freeze-drying 15h.Natural rubber in the film
The mass ratio of particle and agar is 2.7:1, and amino acid surfactant content is 254mg in every gram of film.
Embodiment 4
1) prepare Heveatex-surfactant solution: 20 DEG C, speed of agitator be 20r/min under conditions of, 150g is distilled
After water is added to 300g Heveatex, under conditions of speed of agitator is 3800r/min at high shear emulsifying dispersion machine
Heveatex solution 13min is managed, 10g lauroyl alanine potassium is then added under conditions of speed of agitator is 2200r/min
With 20gN- coco-nut oil fatty acid-l-Alanine natrium surfactant, then with mass fraction be 2% sodium hydroxide solution will be natural
Latex-surfactant solution pH value is adjusted to 10.5；
2) prepare agar-surfactant solution: boiling 1000mL distilled water, keep solution boiling, speed of agitator be 20r/
25g agar is added under conditions of min, continues after keeping solution boiling 30min, in 50 DEG C, the item that speed of agitator is 9000r/min
Agar solution 14min is handled with high shear emulsifying dispersion machine under part, then under conditions of speed of agitator is 2600r/min
10g lauroyl alanine potassium and 16gN- coco-nut oil fatty acid-l-Alanine natrium surfactant is added, then uses mass fraction
Agar-surfactant solution pH value is adjusted to 10.5 for 2% sodium hydroxide solution；
3) natural rubber and agar compound mesoporous film are prepared: under conditions of speed of agitator is 2800r/min, by Heveatex-
After surfactant solution is 1:4 mixing 20min according to mass ratio with agar-surfactant solution, it is with frequency
2450MHz, the microwave irradiation that power is 1.5kW handle 4min, then the rapid pre-freeze mixed liquor 30min in liquid nitrogen, finally will
Mixed liquor obtains the natural rubber and agar compound mesoporous film of more characteristics in -50 DEG C of freeze-drying 14h.Natural rubber in the film
The mass ratio of particle and agar is 4:1, and amino acid surfactant content is 255mg in every gram of film.
Embodiment 5
1) prepare Heveatex-surfactant solution: 20 DEG C, speed of agitator be 20r/min under conditions of, 150g is distilled
After water is added to 300g Heveatex, under conditions of speed of agitator is 3300r/min at high shear emulsifying dispersion machine
Heveatex solution 18min is managed, the positive decoyl glycine of 13g and 10g are then added under conditions of speed of agitator is 2400r/min
Myristoyl glutamic acid surfactant, then it is with the ammonia spirit that mass fraction is 5% that Heveatex-surfactant is molten
The pH value of liquid is adjusted to 10.5；
2) it prepares agar-surfactant solution: boiling 1000mL distilled water, keeping solution boiling, speed of agitator 20r/
35g agar is added under conditions of min, continues after keeping solution boiling 30min, is 11000r/min's in 50 DEG C, speed of agitator
Under the conditions of with high shear emulsifying dispersion machine handle agar solution 18min, then speed of agitator be 2700r/min condition
The positive decoyl glycine of lower addition 14g and 14g myristoyl glutamic acid surfactant, then it is molten with the ammonium hydroxide that mass fraction is 5%
Agar-surfactant solution pH value is adjusted to 10.5 by liquid；
3) natural rubber and agar compound mesoporous film are prepared: under conditions of speed of agitator is 2300r/min, by Heveatex-
After surfactant solution is 1:3 mixing 20min according to mass ratio with agar-surfactant solution, it is with frequency
2450MHz, the microwave irradiation that power is 1.2kW handle 3min, then the rapid pre-freeze mixed liquor 30min in liquid nitrogen, finally will
Mixed liquor obtains the natural rubber and agar compound mesoporous film of more characteristics in -50 DEG C of freeze-drying 13h.Natural rubber in the film
The mass ratio of particle and agar is 3.8:1, and amino acid surfactant content is 210mg in every gram of film.
In order to investigate characteristic possessed by natural rubber and agar composite membrane of the present invention, above embodiments preparation is randomly selected
Natural rubber and agar composite membrane, the performance of measurement is as shown in table 1.Utilize pore-size distribution in scanning electron microscope measurement film
Situation, aperture is distributed in 10 ~ 50nm in all films, belongs to mesopore size.Using the porosity (Liu Wen of liquid method of substitution measurement film
Brightness, Liu Xiaoya, Chen Mingqing wait the chitosan-based bio-medical material of and its application study progress Journal of Functional Polymers,
2001,14 (4): 493-496.), the numerical value of porosity is bigger, shows that film Hole structure is more.The porosity of=of all films
55.0%, show that natural rubber and agar composite membrane have good hole open structure.Using the hygroscopicity of gravimetric detemination film
Can, the numerical value of hygroscopic capacity is bigger, shows that the moisture pick-up properties of film is better.The moisture absorption magnitude of all films >=8.9 g water .g-1Film shows
Natural rubber and agar composite membrane have good moisture pick-up properties.Using water lock performance (Xia Shichun, the Huang of diffusion method measurement film
Wen Xiang, Chen Jiong wait two kinds of different foam dressing of ventilative, water suction and water lock performance to compare base, China medicine, and 2017,
24 (13): 1946-1949.), the numerical value of diffusion diameter is lower, shows that the water lock performance of film is better.The diffusion diameter of all films
Value≤8.5cm shows that natural rubber and agar composite membrane have good water lock performance.Pass through measurement evaporated quantity of water evaluated for film
(Chen Jiong, Su Guoliang, Li Qiang wait difference dressing combination to the shadow of fire victim's thickness skin donor wound microenvironment to permeability
Ring China burn magazine, 2009,25 (3): 218-221.), the numerical value of evaporated quantity of water is bigger, shows the permeability of film
Better.Water evaporation magnitude >=6.9g.h of all films-1.cm-2, it is good ventilative to show that natural rubber and agar composite membrane have
Performance.According to the tensile strength and elongation at break of GB/T 528-2009 standard test film.The tensile strength of all films >=
5.7MPa, elongation at break >=473% show that natural rubber and agar composite membrane have good tensile stress-strain performance.It presses
According to the flexibility of GB/T 8942-2016 standard test film, the numerical value of pliability is lower, shows that the flexibility of film is better.All films
Softness values≤185mN, show that natural rubber and agar composite membrane have good flexibility.
The characteristic of table 1 natural rubber and agar compound mesoporous film
Claims (4)
1. the natural rubber and agar compound mesoporous film of a kind of more characteristics, it is characterised in that: natural rubber particle in the mesoporous film
Mass ratio with agar is 1:1 ~ 10:1, and amino acid surfactant is at least 161mg in every gram of mesoporous film, the mesoporous film
Pore-size distribution porosity of=55.0% in 10 ~ 50nm, film, hygroscopic capacity >=8.9g of every gram of film, the water lock performance number of film≤
8.5cm, evaporated quantity of water >=6.9g.h of film-1.cm-2, tensile strength >=5.7MPa of film, elongation at break >=473% of film, film
Softness values≤185mN.
2. a kind of method of the natural rubber for preparing more characteristics described in claim 1 and agar compound mesoporous film, this method
Processing step and condition are as follows:
1) prepare Heveatex-surfactant solution: 20 DEG C, speed of agitator be 20r/min under conditions of, 150g is distilled
After water is added to 300g Heveatex, high shear emulsifying disperses under conditions of speed of agitator is 3000 ~ 4000r/min
Machine handles 10 ~ 20min of Heveatex solution, and 20 ~ 30g ammonia is then added under conditions of speed of agitator is 2000 ~ 3000r/min
Base acids surfactant, then Heveatex-surfactant solution pH value is adjusted to 10~11 with alkaline solution；
2) it prepares agar-surfactant solution: boiling 1000mL distilled water, keeping solution boiling, speed of agitator 20r/
Under conditions of min be added 20 ~ 40g agar, continue keep solution boiling 30min after, 50 DEG C, speed of agitator be 8000 ~
10 ~ 20min of agar solution is handled with high shear emulsifying dispersion machine under conditions of 12000r/min, is then in speed of agitator
20 ~ 30g amino acid surfactant is added under conditions of 2000 ~ 3000r/min, then with alkaline solution that agar-surface is living
The pH value of property agent solution is adjusted to 10~11；
3) natural rubber and agar compound mesoporous film are prepared:, will be natural under conditions of speed of agitator is 2000 ~ 3000r/min
After latex-surfactant solution is 1:2 ~ 1:10 mixing 20min according to mass ratio with agar-surfactant solution, with frequency
The microwave irradiation that rate is 2450MHz, power is 1 ~ 2kW handles at least 3min, then the rapid pre-freeze mixed liquor in liquid nitrogen
Mixed liquor is finally obtained the natural rubber and agar composite mesopore of more characteristics in -50 DEG C of freeze-drying at least 12h by 30min
Film.
3. the method for the natural rubber for preparing more characteristics and agar compound mesoporous film according to claim 2, feature exist
In: the amino acid surfactant is at least one of glutamic acid series, glycine series, alanine series.
4. the method for the natural rubber for preparing more characteristics and agar compound mesoporous film according to claim 3, feature exist
In: the amino acid surfactant is myristoyl glutamic acid, myristoyl sodium glutamate, the sweet ammonia of lauroyl
Acid, cocoyl glycine potassium, positive decoyl glycine, lauroyl Sodium L-alaninate, lauroyl alanine potassium, N- coconut grease
At least one of fat acid-l-Alanine sodium.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS564673A (en) * | 1979-06-25 | 1981-01-19 | Showa Denko Kk | Adhesive composition for carpet backing |
| JPH05117431A (en) * | 1991-10-31 | 1993-05-14 | Snow Brand Milk Prod Co Ltd | Fiber-chitosan porous composite, and absorbent pad and pad prepared therefrom |
| CN1116085A (en) * | 1993-02-12 | 1996-02-07 | 菲迪亚高级生物聚合物公司 | Multilayer nonwoven tissue containing a surface layer comprising at least one hyaluronic acid ester |
| CN102256694A (en) * | 2008-12-17 | 2011-11-23 | 花王株式会社 | Method for producing hydrogel particles |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JP5117431B2 (en) * | 2009-03-09 | 2013-01-16 | 株式会社日立製作所 | CO2 recovery type gas turbine plant |
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2019
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS564673A (en) * | 1979-06-25 | 1981-01-19 | Showa Denko Kk | Adhesive composition for carpet backing |
| JPH05117431A (en) * | 1991-10-31 | 1993-05-14 | Snow Brand Milk Prod Co Ltd | Fiber-chitosan porous composite, and absorbent pad and pad prepared therefrom |
| CN1116085A (en) * | 1993-02-12 | 1996-02-07 | 菲迪亚高级生物聚合物公司 | Multilayer nonwoven tissue containing a surface layer comprising at least one hyaluronic acid ester |
| CN102256694A (en) * | 2008-12-17 | 2011-11-23 | 花王株式会社 | Method for producing hydrogel particles |
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