CN106317960A - Method for immobilizing proteins in natural rubber latex by aid of modified tannin extract - Google Patents
Method for immobilizing proteins in natural rubber latex by aid of modified tannin extract Download PDFInfo
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- CN106317960A CN106317960A CN201610837533.4A CN201610837533A CN106317960A CN 106317960 A CN106317960 A CN 106317960A CN 201610837533 A CN201610837533 A CN 201610837533A CN 106317960 A CN106317960 A CN 106317960A
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- tannin extract
- natural rubber
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- 239000000284 extract Substances 0.000 title claims abstract description 86
- 235000018553 tannin Nutrition 0.000 title claims abstract description 57
- 239000001648 tannin Substances 0.000 title claims abstract description 57
- 229920001864 tannin Polymers 0.000 title claims abstract description 57
- 229920006173 natural rubber latex Polymers 0.000 title claims abstract description 43
- 238000000034 method Methods 0.000 title claims abstract description 41
- 102000004169 proteins and genes Human genes 0.000 title abstract description 27
- 108090000623 proteins and genes Proteins 0.000 title abstract description 27
- 230000003100 immobilizing effect Effects 0.000 title abstract 3
- 229920001971 elastomer Polymers 0.000 claims abstract description 56
- 244000043261 Hevea brasiliensis Species 0.000 claims abstract description 23
- 229920003052 natural elastomer Polymers 0.000 claims abstract description 23
- 229920001194 natural rubber Polymers 0.000 claims abstract description 23
- 229920000126 latex Polymers 0.000 claims abstract description 22
- 239000004816 latex Substances 0.000 claims abstract description 18
- 230000008569 process Effects 0.000 claims abstract description 12
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 11
- 238000012545 processing Methods 0.000 claims abstract description 11
- 238000002386 leaching Methods 0.000 claims abstract description 9
- 239000007787 solid Substances 0.000 claims abstract description 8
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 22
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 20
- 101000952180 Morus alba Mulatexin Proteins 0.000 claims description 19
- 238000003756 stirring Methods 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 238000009472 formulation Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 238000007598 dipping method Methods 0.000 claims description 5
- 238000009413 insulation Methods 0.000 claims description 5
- 239000006228 supernatant Substances 0.000 claims description 5
- 239000003292 glue Substances 0.000 claims description 4
- 238000005987 sulfurization reaction Methods 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 1
- 239000003607 modifier Substances 0.000 claims 1
- 230000032683 aging Effects 0.000 abstract description 6
- 206010016946 Food allergy Diseases 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 238000001035 drying Methods 0.000 abstract 1
- 238000005755 formation reaction Methods 0.000 abstract 1
- 238000005470 impregnation Methods 0.000 abstract 1
- 230000005486 microgravity Effects 0.000 abstract 1
- 238000005580 one pot reaction Methods 0.000 abstract 1
- 238000004073 vulcanization Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 15
- 238000012986 modification Methods 0.000 description 9
- 230000004048 modification Effects 0.000 description 9
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 8
- 241000220479 Acacia Species 0.000 description 7
- 235000010643 Leucaena leucocephala Nutrition 0.000 description 7
- 239000000834 fixative Substances 0.000 description 7
- 239000004215 Carbon black (E152) Substances 0.000 description 5
- 229930195733 hydrocarbon Natural products 0.000 description 5
- 150000002430 hydrocarbons Chemical class 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 230000008859 change Effects 0.000 description 4
- 229960002163 hydrogen peroxide Drugs 0.000 description 4
- 230000002209 hydrophobic effect Effects 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 235000013824 polyphenols Nutrition 0.000 description 4
- 241000196324 Embryophyta Species 0.000 description 3
- 206010020751 Hypersensitivity Diseases 0.000 description 3
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 3
- 108010013296 Sericins Proteins 0.000 description 3
- 208000026935 allergic disease Diseases 0.000 description 3
- 230000007815 allergy Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 150000008442 polyphenolic compounds Chemical class 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 206010070834 Sensitisation Diseases 0.000 description 2
- -1 amino, carboxyl Chemical group 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000005486 sulfidation Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 1
- 102100034613 Annexin A2 Human genes 0.000 description 1
- 108090000668 Annexin A2 Proteins 0.000 description 1
- 229920001661 Chitosan Polymers 0.000 description 1
- ZNZYKNKBJPZETN-WELNAUFTSA-N Dialdehyde 11678 Chemical compound N1C2=CC=CC=C2C2=C1[C@H](C[C@H](/C(=C/O)C(=O)OC)[C@@H](C=C)C=O)NCC2 ZNZYKNKBJPZETN-WELNAUFTSA-N 0.000 description 1
- 241000219433 Myrica Species 0.000 description 1
- 108091005804 Peptidases Proteins 0.000 description 1
- 239000004365 Protease Substances 0.000 description 1
- 102100037486 Reverse transcriptase/ribonuclease H Human genes 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical class OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 230000003679 aging effect Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000000172 allergic effect Effects 0.000 description 1
- 230000003026 anti-oxygenic effect Effects 0.000 description 1
- 208000010668 atopic eczema Diseases 0.000 description 1
- 230000001851 biosynthetic effect Effects 0.000 description 1
- 238000001246 colloidal dispersion Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000001934 delay Effects 0.000 description 1
- 238000004925 denaturation Methods 0.000 description 1
- 230000036425 denaturation Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000003752 hydrotrope Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000001524 infective effect Effects 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000008267 milk Substances 0.000 description 1
- 210000004080 milk Anatomy 0.000 description 1
- 235000013336 milk Nutrition 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- BHZRJJOHZFYXTO-UHFFFAOYSA-L potassium sulfite Chemical compound [K+].[K+].[O-]S([O-])=O BHZRJJOHZFYXTO-UHFFFAOYSA-L 0.000 description 1
- 235000019252 potassium sulphite Nutrition 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 235000010413 sodium alginate Nutrition 0.000 description 1
- 229940005550 sodium alginate Drugs 0.000 description 1
- 239000000661 sodium alginate Substances 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- QUCDWLYKDRVKMI-UHFFFAOYSA-M sodium;3,4-dimethylbenzenesulfonate Chemical compound [Na+].CC1=CC=C(S([O-])(=O)=O)C=C1C QUCDWLYKDRVKMI-UHFFFAOYSA-M 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011240 wet gel Substances 0.000 description 1
- 210000004885 white matter Anatomy 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
-
- 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
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09F—NATURAL RESINS; FRENCH POLISH; DRYING-OILS; OIL DRYING AGENTS, i.e. SICCATIVES; TURPENTINE
- C09F1/00—Obtaining purification, or chemical modification of natural resins, e.g. oleo-resins
- C09F1/04—Chemical modification, e.g. esterification
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Gloves (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
The invention discloses a method for immobilizing proteins in natural rubber latex by the aid of modified tannin extract. The method is characterized by comprising steps of adding, by weight, more than 0.2 part of solid modified tannin extract into 100 parts of natural rubber latex and carrying out film formation, leaching, drying and vulcanization processing on rubber products according to conventional proportions and processes for the rubber products. The contents of extractable water-soluble proteins in the prepared rubber products are lower than 100 micro-g/dm<2>; the rubber products are natural rubber glove products manufactured by means of impregnation; the natural rubber latex is high-ammonia concentrated latex; the modified tannin extract is a modified product of powdery tannin extract which is a commercially available commodity. The method has the advantages that the modified tannin extract prepared by means of one-step reaction is used as a protein immobilizing agent, accordingly, the problem of protein allergy of existing natural rubber products can be solved, the mechanical properties, the ageing resistance and the hydrophilic performance of the rubber products can be improved, and the application range of tannin extract can be expanded.
Description
Technical field
The invention belongs to the processing technology field of rubber, be specifically related to one and utilize modified tannin extract to fix natural rubber latex
Method of protein.
Background technology
Nature rubber latex is a kind of biosynthetic high polymer aqua type colloidal dispersion, is mainly composed of rubber hydrocarbon (poly-
Isoprene), water, non-rubber substance, wherein non-rubber substance includes the molten thing of protein, lipoid, acetone, the hydrotrope, inorganic salt etc..
Heveatex has technological operation and the physical property of excellence, and its wet gel strength is high, elastic greatly, creep is little, is widely used in
Produce dipped article, including medical gloves, core industry special type protection glove, balloon etc..For versatility, there is no other at present
Material can substitute completely, and natural rubber remains being preferably selected of virus-isolating, infective micro-organisms and protection.
Natural rubber latex contains two proteinoid, and a class is and the hmw protein of rubber hydrocarbon particle strong bonded,
The low molecule water soluble protein that one class is present in milk surum.In natural rubber dipped article, protein is commonly present distribution not
Uniform phenomenon, as in natural emulsion glove, the protein of about 95% is distributed in glove interior surface, the water solublity egg wherein remained
White matter is to cause the sensitization source of protein I type allergy.It is even dead that severe allergy person there will be shock.Natural for overcoming
The allergic problem of rubber latex proteins matter, the scheme of solution is divided three classes.One is, removes isolating protein, including repeatedly leaching rubber
Goods, latex is centrifuged, utilize protease acid or basic hydrolysis protein, radiation cured latex after carry out centrifugal treating,
Adsorbent protein, this scheme is utilized to be disadvantageous in that, along with the decline of protein content in latex, latex glue
Body system stability declines, and the mechanical property of the dry rate of rubber and antioxygenic property, rubber also can be by bad
Impact.Two are, chloridized makes protein denaturation, but this can make the percentage elongation of rubber decline, and affects the use of goods.Three
It is to utilize fixative stable protein, fixative used to include dialdehyde sodium alginate (Chinese invention patent, application number
200910041291.8, authorized announcement date on July 6th, 2011), chitosan/sericin (Chinese invention patent, application number
200910198482.5, authorized announcement date on July 20th, 2011), sericin compositions (Chinese invention patent, application number
200910197790.6, authorized announcement date on May 30th, 2012), sericin grafting aqueous polyurethane (Chinese invention patent, application
Numbers 201210470393.3, June 4 2014 Shen Qing Publication day), this scheme can not only effectively reduce natural rubber latex or
Content of soluble protein in natural rubber products, moreover it is possible to the physical and mechanical properties of natural rubber products is produced favourable work
With, but the deficiency of the program is, fixative is both needed to prepare beforehand through complex reaction, and the productivity of fixative is low, reacts bar
Part difficulty controls so that the cost of these fixatives is high, and is difficult to real in natural rubber latex processing factory or natural rubber products factory
Now it is prepared in situ and uses.Therefore, a kind of side utilizing wide material sources, inexpensive fixative to stablize natural rubber protein is developed
Method, has become as the urgent needs of this area.
Summary of the invention
It is an object of the invention to for the deficiencies in the prior art, it is provided that one utilizes modified tannin extract to fix natural rubber latex
Method of protein, to solve protein allergy problem in natural rubber products.
For completing the task of the present invention, applicant has analysed in depth existing natural rubber latex proteins matter fixing means
Feature.On this basis, in conjunction with natural rubber latex proteins matter and the feature of afforestation product tannic extract, propose to utilize modified tannin extract solid
The method determining natural rubber latex proteins matter.
What the present invention provided utilizes the method that modified tannin extract fixes natural rubber latex proteins matter, it is characterised in that: will change
Property tannic extract add natural rubber latex Ruzhong, then according to the conventional formulations of rubber and technique, complete rubber film forming,
Leaching, dry, sulfuration processing, can extract water-soluble protein content less than 100 μ g/dm in prepared rubber2;Described
Rubber be dipping manufacture natural rubber gloves goods;Described natural rubber latex is high ammonia concentrated latex.
For achieving the above object, what the present invention proposed utilizes the method that modified tannin extract fixes natural rubber latex proteins matter,
According to following steps, modified tannin extract is added in latex successively:
1) preparation of modified tannin extract: the mass percentage content of 1 weight portion be 10~25% ammonia spirit in, 30
~under the stirring condition of 60 revs/min, add the mass percentage content of 1~3 weight portions be 20~30% modifying agent water-soluble
Liquid, is subsequently adding the aqueous solution of commercial goods powdered extracts that the mass percentage content of 15~25 weight portions is 20~30%,
After stirring 15~30 minutes, 30~60 DEG C of insulation reaction 1 hour, it is thus achieved that the solution of modified tannin extract;
2) the pure process of the increasing of modified tannin extract: modified tannin extract solution is placed after 30~90 minutes in room temperature, 6000~
It is centrifuged 15~30 minutes under the conditions of 8000 revs/min, collects the supernatant, obtain increasing pure modified tannin extract solution;
3) being blended of modified tannin extract solution and natural rubber latex: at ambient temperature, natural according to every 100 weight portions
Rubber latex adds the ratio of the Solid Modified tannic extract of more than 0.2 weight portion, by above-mentioned 2) modified tannin extract solution add sky
So in rubber latex, stirring makes modified tannin extract mix homogeneously with latex, and mixing speed is 60~120 revs/min.
One or more in sulphite, hydrogen peroxide of modifying agent described in said method.
What the present invention provided utilizes the method that modified tannin extract fixes natural rubber latex proteins matter, make use of modification dexterously
H-bonding capability between amino, carboxyl and modification in phenolic hydroxyl group and natural rubber latex proteins matter molecule in tannic extract molecule
Hydrophobic bond binding ability between tannic extract molecule and protein molecule.Low point is made by the interaction of modified tannin extract Yu protein
Sub-water soluble protein molecular change is big.In natural rubber film forming procedure, the diffusion of the protein molecule that these changes are big and migration
Be obstructed, it is intended to rest on the inside of rubber, it is to avoid protein water-soluble go out rear sensitisation problems.Modified tannin extract has hydrophilic
And non-oxidizability, in the range of molecular weight concentrates on 500~3000, less than natural rubber latex proteins matter.For with the addition of modification
For the natural rubber latex of tannic extract, in its film forming procedure, not yet there is that combine and that molecular weight is little modification with protein
Tannic extract molecular diffusion rates is fast, it is easy to migrate to rubber article, and by modified tannin extract molecule and rubber hydrocarbon (poly-isoamyl
Diene) hydrophobic bond between molecule interacts, and rests on rubber article, and these tannic extract molecules can not only effectively capture rubber
The protein molecule of glue product surface, but also natural rubber products hydrophilic and ageing resistace can be improved.Poly-isoamyl two
Alkene molecule contains a large amount of unsaturated double-bond, and in sulfidation, these double bonds crosslink chemical reaction after opening and form solid
Network structure, gives rubber intensity, elasticity, dimensional stability and application.Rubber chain and modified tannin extract molecule it
Between there is hydrophobic bond binding ability, there is hydrogen bond, hydrophobic bond binding ability between modified tannin extract molecule and protein molecule, therefore,
Modified tannin extract, as the bridge between rubber hydrocarbon and protein, in natural rubber products sulfidation, helps lend some impetus to rubber
Hydrocarbon, modified tannin extract, protein three component further combined with, form the bigger network structure of crosslink density, improve rubber
The mechanical property such as hot strength.What the present invention provided utilizes the method that modified tannin extract fixes natural rubber latex proteins matter, no
Be only capable of solving the protein allergy problem of natural rubber products, overcome traditional latex protein fixative preparation process complicated,
The shortcoming that process conditions difficulty controls, cost is high, moreover it is possible to improve mechanical property and the ageing resistace of rubber, has the most
The feature obtained.
Tannic extract be mainly composed of plant polyphenol, oxidizable, this can make the rubber that with the addition of tannic extract present necessarily
Color.For overcoming this problem, the present invention utilizes alkaline environment sulfite salt and/or the reproducibility of hydrogen peroxide, and protection is planted
Thing polyphenol, delays the oxidation of plant polyphenol self in the course of processing after tannic extract is blended with natural rubber latex, in certain journey
The color of blend film is controlled on degree.What applicant completed experimental results demonstrate, with being blended of modified tannin extract and natural rubber latex
Thing compares, and the modified tannin extract prepared according to the common process of dipped article and natural rubber latex are blended the colourity of goods color
Amplitude of variation is less than 4 grades, the tannic extract method of modifying proposed by the present invention is described, controls the oxidation stain of modified tannin extract, from
And control modified tannin extract and Heveatex and the color of goods is blended.
Advantages of the present invention:
1) environmental friendliness, low cost: tannic extract is a kind of natural product deriving from plant, has wide material sources, price low
Feature honest and clean, eco-friendly.What the present invention provided utilizes the method that modified tannin extract fixes natural rubber latex proteins matter, it is only necessary to right
Tannic extract carries out a step modification, and reaction condition gentleness is easy to control, and the response time is short, does not use organic solvent, will not be to environment
Have a negative impact, be a kind of method of environmental friendliness and economy.
2) feasible process, easily popularization: the modified tannin extract that utilizes that the present invention provides fixes the side of natural rubber latex proteins matter
Method, is directly to add in natural rubber latex Ruzhong to increase pure modified tannin extract solution, then according to natural rubber products conventional formulations
And technique, complete to impregnate film forming, leaching, vulcanize, be dried processing, it is not necessary to change the processing technique of rubber and condition, also
Need not increase new equipment.The modification of tannic extract, increase pure and modified tannin extract is simple with the blending operations of latex, easy to control, can be
Rubber mill scene completes, easy popularization and application.
3) tannic extract range of application is expanded: tannic extract is a kind of traditional afforestation product, is mainly used as at process hides tanning agent, boiler water
Reason agent, timber work glue.Being affected by factors such as petrochemical industry low costs, the application market of tannic extract is significantly shunk.This
Bright being developed for by tannic extract fixes natural latex proteins matter, is a kind of new opplication to tannic extract, contributes to expanding afforestation product
Utilize scope.
Detailed description of the invention
Embodiment is given below so that the present invention will be described in more detail, it is necessary to be pointed out that following example can not be managed
Solve as limiting the scope of the invention, the person skilled in the art in this field according to present invention, the present invention is made one
A little nonessential improvement and adjustment still belong to protection scope of the present invention.
Embodiment 1
In the ammonia spirit that mass percentage content is 10% of 1 weight portion, under the stirring condition of 60 revs/min,
Adding the sodium sulfite aqueous solution that mass percentage content is 20% of 1 weight portion, the mass percent adding 15 weight portions contains
Amount is the aqueous solution of the commodity powdery Acacia mangiumwilld tannic extract of 20%, stirs 15 minutes, then 60 DEG C of insulation reaction 1 hour, obtains
Obtain modified Acacia mangiumwilld solution.Modification Acacia mangiumwilld solution is placed 90 minutes in room temperature, then under the conditions of 8000 revs/min
Centrifugal 15 minutes, collect the supernatant, obtain increasing pure modified Acacia mangiumwilld solution.At ambient temperature, according to every 100 weight
The natural rubber latex Ruzhong of part adds the ratio of the Solid Modified Acacia mangiumwilld of 1 weight portion, and by increasing, pure modified Acacia mangiumwilld is molten
Liquid adds in high ammonia concentrated natural rubber latex, and stirring makes modified Acacia mangiumwilld mix homogeneously with latex, and mixing speed is 60 turns/
Minute.The conventional formulations of natural rubber gloves goods manufactured according to dipping and technique, complete to impregnate film forming, leaching, be dried, sulfur
Change processing.Detect the extracted water-soluble protein content of these goods, hot strength, elongation at break and this product surface
Hydrophilic, and the rubber obtained with the common process that processes without modified tannin extract makees the comparison of respective performances.
Embodiment 2
In the ammonia spirit that mass percentage content is 25% of 1 weight portion, under the stirring condition of 30 revs/min,
Add the hydrogenperoxide steam generator that mass percentage content is 30% of 3 weight portions, add the mass percentage content of 20 weight portions
It is the aqueous solution of the commodity powdery rubber tannic extract of 20%, stirs 30 minutes, then 30 DEG C of insulation reaction 1 hour, it is thus achieved that modified
Rubber solution.Modification rubber solution is placed 60 minutes in room temperature, is then centrifuged 30 minutes under the conditions of 6000 revs/min, receive
The collection supernatant, obtains increasing pure modified rubber solution.At ambient temperature, according to the natural rubber latex of every 100 weight portions
The ratio of the Solid Modified rubber of middle addition 0.2 weight portion, adds high ammonia concentrated natural rubber by increasing pure modified rubber solution
In latex, stirring makes modified rubber mix homogeneously with latex, and mixing speed is 120 revs/min.The natural rubber manufactured according to dipping
The conventional formulations of Rubber gloves goods and technique, complete to impregnate film forming, leaching, dry, sulfuration processing.Detect extracting of these goods
The hydrophilic of water-soluble protein content, hot strength, elongation at break and this product surface, and with without modified tannin extract
The rubber that the common process processed obtains makees the comparison of respective performances.
Embodiment 3
In the ammonia spirit that mass percentage content is 15% of 1 weight portion, under the stirring condition of 45 revs/min,
The mass percentage content of the potassium sulfite aqueous solution that mass percentage content is 20% and 1 weight portion that add 1 weight portion is
The hydrogenperoxide steam generator of 20%, adds the commodity powdery myrica extract that mass percentage content is 30% water-soluble of 25 weight portions
Liquid, stirs 30 minutes, then 50 DEG C of insulation reaction 1 hour, it is thus achieved that modified Fructus Myricae rubrae solution.Modification Fructus Myricae rubrae solution is put in room temperature
Put 30 minutes, be then centrifuged 30 minutes under the conditions of 8000 revs/min, collect the supernatant, obtain increasing pure modified Fructus Myricae rubrae molten
Liquid.At ambient temperature, the ratio of the Solid Modified Fructus Myricae rubrae of 2 weight portions is added according to the natural rubber latex Ruzhong of every 100 weight portions
Example, adds in high ammonia concentrated natural rubber latex by increasing pure modified Fructus Myricae rubrae solution, and stirring makes modified Fructus Myricae rubrae mix all with latex
Even, mixing speed is 90 revs/min.The conventional formulations of natural rubber gloves goods manufactured according to dipping and technique, complete leaching
Stain film forming, leaching, dry, sulfuration processing.Detect the extracted water-soluble protein content of these goods, hot strength, pull apart and stretch
Long rate and the hydrophilic of this product surface, and make corresponding to the rubber that the common process processed without modified tannin extract obtains
Performance comparision.
The extracted water-soluble protein content of rubber of embodiment 1~3 acquisition, hot strength, elongation at break
As shown in table 1 with the hydrophilic on surface (contact angle) test result.Rubber embodiment 1~3 obtained is empty 70 DEG C of heat
After aging 168 hours of gas, rubber can extract water-soluble protein content, hot strength, elongation at break and contact angle
Test result is as shown in table 2.Modified tannin extract is added natural rubber latex Ruzhong, effectively secures latex protein, natural rubber
Goods and the extracted water-soluble protein content after heat ageing processes thereof are respectively less than 100 μ g/dm2, meet ASTM D
3577-2009 international standard and the limitation requirement of GB 24788-2009 domestic standard, solve natural rubber latex proteins matter allergy
Problem.Modified tannin extract is added natural rubber latex Ruzhong, is effectively increased hot strength and the elongation at break of rubber, and
Improve the heat aging property of rubber.Modified tannin extract is added natural rubber latex Ruzhong, reduces rubber article
Contact angle, improve the hydrophilic of rubber article.
The extracted water-soluble protein content of rubber of table 1 embodiment 1~3, hot strength, elongation at break and
Contact angle
Table 2 after hot air aging processes, the extracted water-soluble protein content of the rubber of embodiment 1~3,
Hot strength, elongation at break and contact angle
Claims (2)
1. one kind utilizes the method that modified tannin extract fixes natural rubber latex proteins matter, it is characterised in that: modified tannin extract is added
Natural rubber latex Ruzhong, then according to the conventional formulations of rubber and technique, complete the film forming of rubber, leaching, be dried,
Sulfuration processing, can extract water-soluble protein content less than 100 μ g/dm in prepared rubber2;Described rubber
The natural rubber gloves goods manufactured for dipping;Described natural rubber latex is high ammonia concentrated latex.
The method utilizing modified tannin extract to fix natural rubber latex proteins matter the most according to claim 1, it is characterised in that
According to following steps, modified tannin extract is added in latex successively:
1) preparation of modified tannin extract: in the ammonia spirit that mass percentage content is 10 ~ 25% of 1 weight portion, 30 ~ 60 turns/
Minute stirring condition under, add 1 ~ 3 weight portion the modifier aqueous solution that mass percentage content is 20 ~ 30%, be subsequently adding
The mass percentage content of 15 ~ 25 weight portions is the aqueous solution of the commercial goods powdered extracts of 20 ~ 30%, stirs 15 ~ 30 minutes
After, 30 ~ 60 DEG C of insulation reaction 1 hour, it is thus achieved that the solution of modified tannin extract;Modifying agent used is selected from sulphite, peroxidating
One or more in hydrogen;
2) the pure process of the increasing of modified tannin extract: by modified tannin extract solution after room temperature is placed 30 ~ 90 minutes, at 6000 ~ 8000 revs/min
It is centrifuged 15 ~ 30 minutes under the conditions of clock, collects the supernatant, obtain increasing pure modified tannin extract solution;
3) being blended of modified tannin extract solution and natural rubber latex: at ambient temperature, according to the natural rubber of every 100 weight portions
Latex adds the ratio of the Solid Modified tannic extract of more than 0.2 weight portion, by above-mentioned 2) modified tannin extract solution add natural rubber
In glue latex, stirring makes modified tannin extract mix homogeneously with latex, and mixing speed is 60 ~ 120 revs/min.
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