CN101851302B - Method for improving oxygen aging resistance of protein-removed natural rubber - Google Patents
Method for improving oxygen aging resistance of protein-removed natural rubber Download PDFInfo
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- CN101851302B CN101851302B CN 201010183070 CN201010183070A CN101851302B CN 101851302 B CN101851302 B CN 101851302B CN 201010183070 CN201010183070 CN 201010183070 CN 201010183070 A CN201010183070 A CN 201010183070A CN 101851302 B CN101851302 B CN 101851302B
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- natural rubber
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- 238000000034 method Methods 0.000 title claims abstract description 23
- 230000032683 aging Effects 0.000 title claims abstract description 21
- 244000043261 Hevea brasiliensis Species 0.000 title claims abstract description 13
- 229920003052 natural elastomer Polymers 0.000 title claims abstract description 13
- 229920001194 natural rubber Polymers 0.000 title claims abstract description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title abstract description 15
- 229910052760 oxygen Inorganic materials 0.000 title abstract description 15
- 239000001301 oxygen Substances 0.000 title abstract description 15
- 229920006173 natural rubber latex Polymers 0.000 claims abstract description 30
- 150000001413 amino acids Chemical class 0.000 claims abstract description 19
- 229920000126 latex Polymers 0.000 claims abstract description 18
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract 3
- 229940024606 amino acid Drugs 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 239000004816 latex Substances 0.000 claims description 17
- QNAYBMKLOCPYGJ-REOHCLBHSA-N L-alanine Chemical compound C[C@H](N)C(O)=O QNAYBMKLOCPYGJ-REOHCLBHSA-N 0.000 claims description 4
- DCXYFEDJOCDNAF-REOHCLBHSA-N L-asparagine Chemical compound OC(=O)[C@@H](N)CC(N)=O DCXYFEDJOCDNAF-REOHCLBHSA-N 0.000 claims description 4
- COLNVLDHVKWLRT-QMMMGPOBSA-N L-phenylalanine Chemical compound OC(=O)[C@@H](N)CC1=CC=CC=C1 COLNVLDHVKWLRT-QMMMGPOBSA-N 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- COLNVLDHVKWLRT-UHFFFAOYSA-N phenylalanine Natural products OC(=O)C(N)CC1=CC=CC=C1 COLNVLDHVKWLRT-UHFFFAOYSA-N 0.000 claims description 2
- 235000001014 amino acid Nutrition 0.000 claims 8
- DCXYFEDJOCDNAF-UHFFFAOYSA-N Asparagine Natural products OC(=O)C(N)CC(N)=O DCXYFEDJOCDNAF-UHFFFAOYSA-N 0.000 claims 1
- 235000004279 alanine Nutrition 0.000 claims 1
- 229910021529 ammonia Inorganic materials 0.000 claims 1
- 230000003078 antioxidant effect Effects 0.000 claims 1
- 235000009582 asparagine Nutrition 0.000 claims 1
- 229960001230 asparagine Drugs 0.000 claims 1
- 235000018417 cysteine Nutrition 0.000 claims 1
- XUJNEKJLAYXESH-UHFFFAOYSA-N cysteine Natural products SCC(N)C(O)=O XUJNEKJLAYXESH-UHFFFAOYSA-N 0.000 claims 1
- 102000004169 proteins and genes Human genes 0.000 abstract description 7
- 108090000623 proteins and genes Proteins 0.000 abstract description 7
- 230000003647 oxidation Effects 0.000 abstract description 4
- 238000007254 oxidation reaction Methods 0.000 abstract description 4
- 125000003172 aldehyde group Chemical group 0.000 abstract 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 abstract 1
- 230000002401 inhibitory effect Effects 0.000 abstract 1
- 239000006185 dispersion Substances 0.000 description 16
- -1 aldehyde radical Chemical class 0.000 description 9
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 8
- 239000000047 product Substances 0.000 description 7
- 239000000839 emulsion Substances 0.000 description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 239000012467 final product Substances 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- RKQOSDAEEGPRER-UHFFFAOYSA-L zinc diethyldithiocarbamate Chemical compound [Zn+2].CCN(CC)C([S-])=S.CCN(CC)C([S-])=S RKQOSDAEEGPRER-UHFFFAOYSA-L 0.000 description 4
- 239000011787 zinc oxide Substances 0.000 description 4
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 3
- 206010002198 Anaphylactic reaction Diseases 0.000 description 2
- XUJNEKJLAYXESH-REOHCLBHSA-N L-Cysteine Chemical compound SC[C@H](N)C(O)=O XUJNEKJLAYXESH-REOHCLBHSA-N 0.000 description 2
- DYUQAZSOFZSPHD-UHFFFAOYSA-N Phenylpropyl alcohol Natural products CCC(O)C1=CC=CC=C1 DYUQAZSOFZSPHD-UHFFFAOYSA-N 0.000 description 2
- 230000036783 anaphylactic response Effects 0.000 description 2
- 208000003455 anaphylaxis Diseases 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 238000010525 oxidative degradation reaction Methods 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- 206010010741 Conjunctivitis Diseases 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 1
- 108091005804 Peptidases Proteins 0.000 description 1
- 101710093543 Probable non-specific lipid-transfer protein Proteins 0.000 description 1
- 239000004365 Protease Substances 0.000 description 1
- 102100037486 Reverse transcriptase/ribonuclease H Human genes 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 208000006673 asthma Diseases 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N ferric oxide Chemical compound O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229940051841 polyoxyethylene ether Drugs 0.000 description 1
- 229920000056 polyoxyethylene ether Polymers 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
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- Adhesives Or Adhesive Processes (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a method for improving oxygen aging resistance of protein-removed natural rubber, which comprises the following steps of: adding amino acid into protein-removed natural rubber latex, mixing the amino acid and the rubber latex uniformly, then adjusting the pH value of the protein-removed natural rubber latex to be between 8.1 and 8.3 by adopting aqueous ammonia, protecting aldehyde groups produced after natural rubber protein removal, and inhibiting the oxidation of the aldehyde groups so as to improve the oxygen aging resistance of the protein-removed natural rubber.
Description
[technical field]
The present invention relates to the control techniques of oxygen aging resistance of protein-removed natural rubber.
[background technology]
The natural rubber latex naturally synthetic by Brazilian para ruber has excellent elasticity, film-forming properties and mechanical property, therefore, up to the present, at medical assistance apparatuses such as the widely used surgical gloves of medical field, medical catheter, tube for blood transfusion,latex, latex examination glovess, and family planning articles for use condom etc., mainly adopt concentrated natural latex production.
Along with being widely used of medical emulsion products, the safety issue of medical emulsion products obtains all the more paying close attention to.Some hospitalized patients the anaphylaxis such as fash, nose, eye conjunctivitis, asthma can occur using even contacting in the process of medical emulsion products, may cause hospitalized patients shock to occur when serious, even threat to life safety.Studies show that, the anaphylaxis of medical emulsion products mainly is that the soluble protein that is present in the natural rubber latex Ruzhong causes, therefore, reduce the protein content in natural rubber latex Ruzhong, in order to reduce medical emulsion products supersensitivity risk from the starting material angle, it is the research emphasis of this area always.Domestic and international many scientific research personnel are studied this, mainly be by: (1) is the centrifugal soluble protein that removes the natural rubber latex Ruzhong repeatedly; (2) hydrolysis by novo is removed the soluble protein (CN 1246485A, CN 1865292A, CN 1376720A) in natural rubber latex Ruzhong; (3) adopt the mode of urea complexation to remove the soluble protein (CN 1930191A) in natural rubber latex Ruzhong.Wherein, the method for hydrolysis by novo deproteination matter is for the production of deproteinized natural rubber latex.Above method respectively has its advantages and disadvantages part, such as centrifuging, needs to use heavy equipment, and production cost is higher.Low protein natural rubber latex stability, oxygen aging resistance and mechanical property that protease hydrolysis obtains are relatively poor.Wyler's process is recently a kind of new technology of invention of Japanese scientific research personnel, there is not yet the report of practical application.
Adopt the DPNR aging resistance of hydrolysis by novo preparation obviously to descend, had a strong impact on the application of DPNR.The scientific research personnel once attempted adopting various oxidation inhibitor to improve the oxygen aging resistance of DPNR, can't produce a desired effect all the time.This mainly is to have little understanding for the reason that oxygen aging resistance of protein-removed natural rubber descends.We show result of study in recent years, in the process that the protein that adopts Sumizyme MP to the natural rubber latex Ruzhong is hydrolyzed, have produced aldehyde radical functional group (concrete reason it be unclear that) at the natural rubber molecular chain simultaneously.Because aldehyde radical is unstable, oxidizing reaction easily occurs in heating and storage process, cause the oxygen aging resistance of deproteinizing rubber to descend.Because the thermal-oxidative degradation of the natural rubber molecular chain that the oxidizing reaction of aldehyde radical causes is not identical with the thermal-oxidative degradation mechanism of natural rubber traditional sense, adopts traditional free radical capture formulation oxidation inhibitor naturally can't reach re-set target.
[summary of the invention]
The present invention aims to provide a kind of method that improves oxygen aging resistance of protein-removed natural rubber, thereby improves the oxygen aging resistance of various latex products.
The method of raising oxygen aging resistance of protein-removed natural rubber of the present invention; it is characterized in that in DPNR, adding one or more amino acid; make the aldehyde radical generation condensation reaction on amino acid whose amino and the rubber chain chain; aldehyde radical is protected, can be improved the oxygen aging resistance of DPNR.
The preferred phenylpropyl alcohol amino acid of wherein said amino acid, L-Ala, half Guang amino acid or l-asparagine.
In a preferred embodiment, amino acid whose consumption is 0.05～0.5% of the dried glue weight of deproteinated natural rubber latex.
In a preferred embodiment, to adopt deionized water to be mixed with mass concentration before adding latex be 10% the aqueous solution to described amino acid.
In another preferred embodiment, in deproteinated latex, add behind the amino acid namely with ammoniacal liquor the pH value of deproteinated natural rubber latex is adjusted to 8.1～8.3.
DPNR of the present invention is to adopt Sumizyme MP that the fresh latex that is derived from Brazilian para ruber is carried out deproteinated to process resulting protein content and be lower than 0.03% natural rubber latex.A kind for the treatment of process of routine may further comprise the steps: add fatty alcohol-polyoxyethylene ether or Sodium dodecylbenzene sulfonate in fresh natural rubber latex, make fresh natural rubber latex keep stable, then add the basic protein enzyme aqueous solution, in 37 ℃ of insulations 24 hours.It is centrifugal to adopt supercentrifuge that latex is carried out after reaction finishes, and can obtain deproteinated natural rubber latex (CN 1246485A, CN 1865292A, CN 1376720A).
[key problem in technology point]
The present invention utilizes the aldehyde radical on amino acid whose amino and the DPNR molecule to carry out condensation, suppresses the oxidation of aldehyde radical, thereby improves the oxygen aging resistance of DPNR.
The optimal ph of the aldehyde radical generation condensation reaction on amino acid whose amino and the DPNR molecular chain is 8.1～8.3.
[beneficial effect]
Adopt the deproteinated natural rubber latex of the technology of the present invention processing, do not affect characteristic and the processing characteristics of latex itself, can production technology routinely produce various medical emulsion products, its oxygen aging resistance significantly improves.
[embodiment]
The present invention will be described hereinafter to adopt indefiniteness embodiment.Except as otherwise noted, the umber that hereinafter adopts is weight part.
Embodiment 1
Take by weighing 200 parts of drcs and be the deproteinated natural rubber latex of 50% fresh preparation, add the L-Ala aqueous solution of 1.2 part 10% (mass concentration), stirring gets final product afterwards with the pH regulator to 8.2 of ammoniacal liquor with the deproteinated natural rubber latex.After the deproteinated natural rubber latex that will contain L-Ala at room temperature leaves standstill 24 hours, add successively 2.0 parts of mass concentrations and be 50.0% Sulfur water dispersion, 2.5 parts of mass concentrations and be 40.0% zinc diethyldithiocarbamate water dispersion and 1.0 parts of mass concentrations and be 50.0% Zinc oxide water dispersion, technique is routinely vulcanized, and cure conditions is 60 ℃ * 60 minutes.After room temperature is parked 24 hours, add 2.0 parts of mass concentrations and be 50% 2,6 di tert butyl 4 methyl phenol water dispersion, gained mechanics performance of latex film tensile strength 26.3MPa, elongation rate of tensile failure 890.Aging tensile strength after 72 hours is 21.0MPa in 70 ℃ warm air, and elongation rate of tensile failure is 720.
Embodiment 2
Take by weighing 200 parts of drcs and be the deproteinated natural rubber latex of 50% fresh preparation, add the phenylpropyl alcohol amino acid solution of 1.0 part 10% (mass concentration), stirring gets final product afterwards with the pH regulator to 8.2 of ammoniacal liquor with latex.After the deproteinated natural rubber latex that will contain phenylalanine at room temperature leaves standstill 24 hours, add successively 2.0 parts of mass concentrations and be 50.0% Sulfur water dispersion, 2.5 parts of mass concentrations and be 40.0% zinc diethyldithiocarbamate water dispersion and 1.0 parts of mass concentrations and be 50.0% Zinc oxide water dispersion, technique is routinely vulcanized, and cure conditions is 60 ℃ * 60 minutes.After room temperature is parked 24 hours, add 2.0 parts of mass concentrations and be 50% 2,2 '-methylene-bis (4-methyl-6-tert-butylphenol) water dispersion, gained mechanics performance of latex film tensile strength 28.6MPa, elongation rate of tensile failure 870.Aging tensile strength after 72 hours is 22.1MPa in 70 ℃ warm air, and elongation rate of tensile failure is 730.
Embodiment 3
Take by weighing 200 parts of drcs and be 50% deproteinated natural rubber latex, add the halfcystine aqueous solution of 1.3 part 10% (mass concentration), stirring gets final product afterwards with the pH regulator to 8.2 of ammoniacal liquor with latex.After the deproteinated natural rubber latex that will contain halfcystine at room temperature leaves standstill 72 hours, add successively 2.0 parts of mass concentrations and be 50.0% Sulfur water dispersion, 2.5 parts of mass concentrations and be 40.0% zinc diethyldithiocarbamate water dispersion and 1.0 parts of mass concentrations and be 50.0% Zinc oxide water dispersion, technique is routinely vulcanized, and cure conditions is 60 ℃ * 60 minutes.After room temperature is parked 24 hours, add 2.0 parts of mass concentrations and be 50% 2,2 '-methylene-bis (4-methyl-6-tert-butylphenol) water dispersion, gained mechanics performance of latex film tensile strength 26.8MPa, elongation rate of tensile failure 830.Aging tensile strength after 72 hours is 21.3MPa in 70 ℃ warm air, and elongation rate of tensile failure is 710.
Embodiment 4
Take by weighing 200 parts of drcs and be 50% deproteinated natural rubber latex, add the l-asparagine aqueous solution of 1.0 part 10% (mass concentration), stirring gets final product afterwards with the pH regulator to 8.2 of ammoniacal liquor with latex.After the deproteinated natural rubber latex that will contain l-asparagine at room temperature leaves standstill 72 hours, add successively 2.0 parts of mass concentrations and be 50.0% Sulfur water dispersion, 2.5 parts of mass concentrations and be 40.0% zinc diethyldithiocarbamate water dispersion and 1.0 parts of mass concentrations and be 50.0% Zinc oxide water dispersion, technique is routinely vulcanized, and cure conditions is 60 ℃ * 60 minutes.After room temperature is parked 24 hours, add 2.0 parts of mass concentrations and be 50% 2,2 '-methylene-bis (4-methyl-6-tert-butylphenol) water dispersion, gained mechanics performance of latex film tensile strength 26.0MPa, elongation rate of tensile failure 840.Aging tensile strength after 72 hours is 19.1MPa in 70 ℃ warm air, and elongation rate of tensile failure is 640.
Claims (5)
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| Application Number | Priority Date | Filing Date | Title |
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| CN 201010183070 CN101851302B (en) | 2010-05-20 | 2010-05-20 | Method for improving oxygen aging resistance of protein-removed natural rubber |
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| CN 201010183070 CN101851302B (en) | 2010-05-20 | 2010-05-20 | Method for improving oxygen aging resistance of protein-removed natural rubber |
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| CN101851302B true CN101851302B (en) | 2013-02-20 |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102850585A (en) * | 2012-09-25 | 2013-01-02 | 中国热带农业科学院农产品加工研究所 | Application of phenylalanine in vulcanization and aging prevention of rubber |
| CN106279467A (en) * | 2016-09-21 | 2017-01-04 | 云南师范大学 | A kind of method utilizing tannic extract to fix natural rubber latex proteins matter |
| CN111333881B (en) * | 2020-04-17 | 2023-03-21 | 田晓慧 | Prevulcanization method and application of deproteinized natural latex |
| CN119241926A (en) * | 2024-10-29 | 2025-01-03 | 中国热带农业科学院农产品加工研究所 | Vulcanized rubber and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1692128A (en) * | 2002-12-06 | 2005-11-02 | 株式会社普利司通 | Natural rubber latex, natural rubber, rubber composition containing the same, and tire |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1692128A (en) * | 2002-12-06 | 2005-11-02 | 株式会社普利司通 | Natural rubber latex, natural rubber, rubber composition containing the same, and tire |
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