CN112375265A - Low-protein natural rubber and preparation method thereof - Google Patents
Low-protein natural rubber and preparation method thereof Download PDFInfo
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- CN112375265A CN112375265A CN202011268694.9A CN202011268694A CN112375265A CN 112375265 A CN112375265 A CN 112375265A CN 202011268694 A CN202011268694 A CN 202011268694A CN 112375265 A CN112375265 A CN 112375265A
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- 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
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/43—Compounds containing sulfur bound to nitrogen
- C08K5/435—Sulfonamides
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- 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
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
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- 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
- C08K5/17—Amines; Quaternary ammonium compounds
- C08K5/18—Amines; Quaternary ammonium compounds with aromatically bound amino groups
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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Abstract
The invention provides a low-protein natural rubber and a preparation method thereof. Relates to the technical field of rubber materials. The preparation method of the low-protein natural rubber provided by the invention comprises the following steps: providing a dispersion comprising a rubber antioxidant; mixing deproteinized natural latex with the rubber antioxidant-containing dispersoid to obtain a mixed material; and sequentially solidifying, washing, pressing and winching, granulating and drying the mixed material to obtain the low-protein natural rubber. The method provided by the invention can prevent the phenomena of stickiness and half-cooked of the rubber material during drying, improve the drying efficiency and simultaneously improve the ageing resistance and the mechanical property of the low-protein natural rubber.
Description
Technical Field
The invention relates to the technical field of rubber materials, in particular to low-protein natural rubber and a preparation method thereof.
Background
The low-protein natural rubber has the characteristics of low water absorption, creep resistance, low heat generation and the like, and the conventional preparation process comprises the following steps: mixing deproteinizing agent (such as protease, sodium dodecyl sulfate, urea, fumed silica or metal hydroxide) with natural rubber latex, reacting for a period of time, coagulating the latex to obtain coagulum, washing the coagulum, pressing, creping, granulating and drying to obtain the low-protein natural rubber. However, the low-protein natural rubber prepared by the process is easy to cause the phenomena of sizing material stickiness and half-cooked in the drying process, and the drying time needs to be prolonged; and the aging resistance and the mechanical property of the low-protein natural rubber are easily deteriorated due to the extension of the drying time.
Disclosure of Invention
The invention aims to provide a low-protein natural rubber and a preparation method thereof, and the method provided by the invention can prevent the phenomena of stickiness and half-cooked phenomenon of rubber materials during drying, improve the drying efficiency and simultaneously improve the aging resistance and the mechanical property of the low-protein natural rubber.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of low-protein natural rubber, which comprises the following steps:
providing a dispersion comprising a rubber antioxidant;
mixing deproteinized natural latex with the rubber antioxidant-containing dispersoid to obtain a mixed material;
and sequentially solidifying, washing, pressing and winching, granulating and drying the mixed material to obtain the low-protein natural rubber.
Preferably, the rubber antioxidant is a natural antioxidant and/or a synthetic antioxidant.
Preferably, the natural antioxidant is a natural phenolic antioxidant; the synthetic anti-aging agent is at least one of synthetic phenol anti-aging agent, synthetic amine anti-aging agent and synthetic heterocyclic anti-aging agent.
Preferably, the natural phenolic antioxidant is at least one of tocopherol and tocotrienol;
the synthetic phenol antioxidant comprises at least one of antioxidant 1010, antioxidant 264, antioxidant 2246 and antioxidant DOD;
the synthetic amine antioxidant comprises at least one of an antioxidant H, an antioxidant D, an antioxidant RD, an antioxidant DNP, an antioxidant KY-405, an antioxidant 4010 and an antioxidant 4010 NA;
the synthetic heterocyclic antioxidant comprises at least one of antioxidant DBH and antioxidant MB.
Preferably, the dispersion containing the rubber antioxidant comprises the following components in parts by mass:
3-50 parts of a rubber antioxidant;
0-5 parts of a stabilizer;
0-5 parts of a dispersing agent;
40-97 parts of water.
Preferably, the stabilizer is at least one of a diffusant NF, casein and sodium pyrophosphate; the dispersant is at least one of ammonium oleate, ammonium laurate and triethanolamine oleate.
Preferably, the deproteinized natural rubber latex is obtained by deproteinizing natural rubber latex, and the dry rubber content of the natural rubber latex is 20-50 wt%.
Preferably, the mass of the natural rubber latex is calculated by dry rubber, and the mass of the rubber antioxidant in the mixed material is 0.01-1% of the mass of the natural rubber latex.
Preferably, the drying temperature is 80-130 ℃, and the drying time is 2-10 h.
The invention provides the low-protein natural rubber prepared by the preparation method in the technical scheme, the low-protein natural rubber contains a rubber anti-aging agent, and the nitrogen content in the low-protein natural rubber is less than or equal to 0.2 wt%.
The invention provides a preparation method of low-protein natural rubber, which comprises the following steps: providing a dispersion comprising a rubber antioxidant; mixing deproteinized natural latex with the rubber antioxidant-containing dispersoid to obtain a mixed material; and sequentially solidifying, washing, pressing and winching, granulating and drying the mixed material to obtain the low-protein natural rubber. The deproteinized natural latex and the rubber antioxidant are mixed and then subjected to operations such as solidification, the rubber antioxidant can be adsorbed on the surface of deproteinized rubber particles, the protein loss caused by deproteinization treatment is compensated, the antioxidant capacity of the rubber particles can be improved, the oxidative degradation of rubber molecular chains is reduced, the phenomena of stickiness and half-growth of rubber materials during drying are prevented, the drying efficiency is improved, and meanwhile, the aging resistance and the mechanical property of the low-protein natural rubber can be improved. The results of the examples show that compared with the low-protein natural rubber prepared without adding the rubber antioxidant, the plasticity retention rate (PRI) of the low-protein natural rubber prepared by the method provided by the invention is improved by at least 20%, the tensile strength is improved by at least 15%, and the tensile strength retention rate after aging is improved by at least 25%.
Detailed Description
The invention provides a preparation method of low-protein natural rubber, which comprises the following steps:
providing a dispersion comprising a rubber antioxidant;
mixing deproteinized natural latex with the rubber antioxidant-containing dispersoid to obtain a mixed material;
and sequentially solidifying, washing, pressing and winching, granulating and drying the mixed material to obtain the low-protein natural rubber.
In the present invention, unless otherwise specified, all the starting materials for the preparation are commercially available products well known to those skilled in the art.
The invention provides a dispersion containing a rubber antioxidant. In the present invention, the rubber antioxidant is specifically a natural antioxidant and/or a synthetic antioxidant, and preferably a natural antioxidant or a synthetic antioxidant. In the present invention, the natural antioxidant is preferably a natural phenolic antioxidant, and the natural phenolic antioxidant is preferably at least one of tocopherol and tocotrienol, and more preferably tocopherol or tocotrienol. In the present invention, the synthetic antioxidant is preferably at least one of a synthetic phenol antioxidant, a synthetic amine antioxidant and a synthetic heterocyclic antioxidant, and more preferably a synthetic phenol antioxidant, a synthetic amine antioxidant or a synthetic heterocyclic antioxidant. In the present invention, the synthetic phenolic antioxidant preferably comprises at least one of antioxidant 1010, antioxidant 264, antioxidant 2246 and antioxidant DOD, more preferably antioxidant 1010, antioxidant 264, antioxidant 2246 or antioxidant DOD; the synthetic amine antioxidant preferably comprises at least one of antioxidant H, antioxidant D, antioxidant RD, antioxidant DNP, antioxidant KY-405, antioxidant 4010 and antioxidant 4010NA, and more preferably comprises antioxidant H, antioxidant D, antioxidant RD, antioxidant DNP, antioxidant KY-405, antioxidant 4010 or antioxidant 4010 NA; the synthetic heterocyclic antioxidant comprises at least one of antioxidant DBH and antioxidant MB, and is more preferably antioxidant DBH or antioxidant MB.
In the present invention, the rubber antioxidant-containing dispersion preferably includes the following components in parts by mass:
3-50 parts of a rubber antioxidant;
0-5 parts of a stabilizer;
0-5 parts of a dispersing agent;
40-97 parts of water.
The dispersion provided by the invention comprises 3-50 parts of rubber antioxidant, preferably 3-35 parts by mass.
Based on the mass part of the rubber antioxidant, the dispersion provided by the invention comprises 0-5 parts of a stabilizer, preferably 3-5 parts. In the invention, the stabilizer is preferably at least one of a dispersing agent NF, casein and sodium pyrophosphate, more preferably the dispersing agent NF and casein, and the mass ratio of the dispersing agent NF to the casein is preferably 6: (7-9). In the invention, the stabilizer can improve the stability of the dispersion containing the rubber antioxidant, and is beneficial to the uniform distribution of the rubber antioxidant in the latex.
Based on the mass part of the rubber antioxidant, the dispersion provided by the invention comprises 0-5 parts of a dispersing agent, preferably 0.5-2 parts. In the present invention, the dispersant is preferably at least one of ammonium oleate, ammonium laurate and triethanolamine oleate, and more preferably ammonium oleate, ammonium laurate or triethanolamine oleate. In the invention, the dispersant can reduce the interfacial tension between the rubber antioxidant and water, so that the rubber antioxidant particles are uniformly dispersed in the aqueous solution, and the dispersion state of the rubber antioxidant is favorably maintained.
Based on the mass portion of the rubber antioxidant, the dispersion provided by the invention comprises 40-97 parts of water, preferably 45-80 parts of water. In the present invention, the water is preferably deionized water.
In the invention, the preparation method of the dispersion containing the rubber antioxidant takes the uniform mixing of the components as a reference; in the present invention, the dispersion containing a rubber antioxidant is preferably used in either of the following two ways:
the first method is as follows: and mixing the components of the dispersion, and homogenizing to obtain the dispersion. In the invention, the rotation speed of the homogenization treatment is preferably 8000-12000 r/min, and more preferably 10000 r/min; the time of the homogenization treatment is preferably 5-15 min, and more preferably 10 min; the homogenization treatment is preferably carried out in a high shear homogenizer.
The second method comprises the following steps: the components of the dispersion were mixed with glass sand with stirring, and then the glass sand was removed by filtration to obtain a dispersion. In the invention, the particle size of the glass sand is preferably 2-3 mm; the mass ratio of the stacking volume of the glass sand to the rubber antioxidant is preferably (180-220) mL: 100g, more preferably 200 mL: 100g of the total weight of the mixture; the invention uses glass sand as grinding medium. In the invention, the rotation speed of stirring and mixing is preferably based on fast speed without splashing of liquid drops, and can be 1500r/min specifically; the stirring and mixing time is preferably 10-15 h, and more preferably 12 h. The invention preferably uses a screen to filter and remove the glass sand.
In the embodiment of the present invention, when the rubber antioxidant is tocopherol or tocotrienol, the dispersion containing the rubber antioxidant may be prepared in a first manner; when the rubber antioxidant is antioxidant 4010NA or antioxidant 264, a dispersion containing the rubber antioxidant can be specifically prepared by the second method.
After the dispersoid containing the rubber antioxidant is obtained, the deproteinized natural latex is mixed with the dispersoid containing the rubber antioxidant to obtain a mixed material. In the present invention, the deproteinized natural rubber latex is preferably obtained by deproteinizing natural rubber latex. In the invention, the natural rubber latex is preferably fresh natural rubber latex, and the dry rubber content of the natural rubber latex is preferably 20-50 wt%, and more preferably 30 wt%.
In the present invention, the deproteinizing agent used for the deproteinizing treatment preferably includes at least one of protease, sodium dodecyl sulfate, urea, fumed silica and metal hydroxide, and the protease is preferably at least one of papain and 2709 alkaline protease; in the invention, the deproteinization treatment agent is preferably protease and sodium dodecyl sulfate, and the mass ratio of the protease to the sodium dodecyl sulfate is preferably (3-9): 5, more preferably 6: 5. in the present invention, the sodium dodecyl sulfate is preferably used in the form of an aqueous sodium dodecyl sulfate solution, and the concentration of the aqueous sodium dodecyl sulfate solution is preferably 8 to 12 wt%, and more preferably 10 wt%. In the present invention, the mass ratio of the natural rubber latex to the deproteinizing treatment agent is preferably 30: (0.10 to 0.13), more preferably 30: 0.11.
according to the invention, the deproteinized natural latex is preferably obtained by mixing natural rubber latex, ammonia water and a deproteinizing agent and then performing deproteinization treatment. In the invention, the concentration of the ammonia water is preferably 22-28 wt%, and more preferably 25 wt%; the mass of the natural rubber latex is calculated by dry rubber, and the mass ratio of the natural rubber latex to ammonia water is preferably 30: (0.35 to 0.45), more preferably 30: 0.4. the invention is beneficial to improving the stability of the natural rubber latex through ammonia water.
In the invention, the deproteinization treatment temperature is preferably 30-40 ℃, and more preferably 35 ℃; the time is preferably 8-12 h, and more preferably 10 h.
In the present invention, the mass of the rubber antioxidant in the mixture is preferably 0.01 to 1%, more preferably 0.02 to 0.5%, and even more preferably 0.05 to 0.2% of the mass of the natural rubber latex, in terms of dry rubber. The mixing mode of the deproteinized natural latex and the rubber antioxidant-containing dispersion is not particularly limited, and the components are uniformly mixed by adopting a mode well known by the technical personnel in the field.
After the mixed material is obtained, the mixed material is sequentially coagulated, washed, creped, granulated and dried to obtain the low-protein natural rubber. In the present invention, the coagulating agent used for the coagulation is preferably formic acid, acetic acid or hydrochloric acid, and more preferably formic acid. The invention preferably mixes the mixed material with a coagulating reagent for coagulation to obtain a clot; the mass of the coagulating reagent is preferably 1.5-2.5% of the mass of the mixed material, and more preferably 2%.
After the coagulum is obtained, the coagulum is washed and pressed and creped in sequence to obtain the film. In the present invention, the washing reagent is preferably water; the thickness of the film obtained after the creping is preferably 2-3 mm; the washing and creping are preferably carried out in a creper.
After the rubber sheet is obtained, the rubber sheet is sequentially granulated and dried to obtain the low-protein natural rubber. In the invention, the grain diameter of the colloidal particles obtained after granulation is preferably 2-5 mm; the granulation is preferably carried out in a granulator, and the granules obtained by granulation are dried after dripping water. In the invention, the drying temperature is preferably 80-130 ℃, and more preferably 115 ℃; the time is preferably 2-10 h, and more preferably 3-4 h; the drying is preferably carried out in a hot air drying oven.
The invention provides the low-protein natural rubber prepared by the preparation method in the technical scheme. In the invention, the nitrogen content in the low-protein natural rubber is less than or equal to 0.2 wt%, the low-protein natural rubber contains the rubber anti-aging agent, and the rubber anti-aging agent can capture free radicals in a system in the process of preparing the low-protein natural rubber, thereby playing a role in protecting colloidal particles.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Taking 100kg of fresh natural rubber latex, and measuring the dry rubber content to be 30.0 wt%; mixing the fresh natural rubber latex with 0.4kg of ammonia water with the concentration of 25 wt%, 0.5kg of sodium dodecyl sulfate aqueous solution with the concentration of 10 wt% and 60g of papain, and reacting for 10 hours at 35 ℃ to obtain deproteinized natural rubber latex;
adding 15g of tocopherol, 2g of ammonium oleate and 300mL of deionized water into a beaker, and treating for 10min at 10000r/min by using a high-shear homogenizer to obtain a stable tocopherol dispersion;
mixing the deproteinized natural latex with a tocopherol dispersion to obtain a mixed material;
mixing the mixed material with formic acid for coagulation to obtain a coagulum; the mass of the formic acid is 2% of that of the mixed material;
washing and pressing the coagulum by using clean water through a creper to obtain a film with the thickness of 2-3 mm, granulating by using a grain tearing machine to obtain colloidal particles with the particle size of 2-5 mm, and drying the colloidal particles in a hot air drying oven at 115 ℃ for 4 hours after dripping water to obtain the low-protein natural rubber.
Example 2
Taking 100kg of fresh natural rubber latex, and measuring the dry rubber content to be 30.0 wt%; mixing the fresh natural rubber latex with 0.4kg of ammonia water with the concentration of 25 wt%, 0.5kg of sodium dodecyl sulfate aqueous solution with the concentration of 10 wt% and 60g of papain, and reacting for 10 hours at 35 ℃ to obtain deproteinized natural rubber latex;
placing 100g of anti-aging agent 4010NA and 6g of dispersing agent NF into an enamel cup, adding 80mL of casein solution with the concentration of 10 wt% (the solvent is water), 64mL of deionized water and glass sand with the accumulation volume of 200mL (the granularity is 2-3 mm), stirring, covering, stirring for 12h by using an electric stirrer with stainless steel stirring slurry (the stirring speed is 1500rpm), and filtering out the glass sand by using a screen mesh to obtain a stable anti-aging agent 4010NA dispersoid;
mixing the deproteinized natural latex with 75g of the age inhibitor 4010NA dispersoid to obtain a mixed material;
mixing the mixed material with formic acid for coagulation to obtain a coagulum; the mass of the formic acid is 2% of that of the mixed material;
washing and pressing the coagulum by using clean water through a creper to obtain a film with the thickness of 2-3 mm, granulating by using a grain tearing machine to obtain colloidal particles with the particle size of 2-5 mm, and drying the colloidal particles in a hot air drying oven at 115 ℃ for 3.5 hours after dripping water to obtain the low-protein natural rubber.
Example 3
Taking 100kg of fresh natural rubber latex, and measuring the dry rubber content to be 30.0 wt%; mixing the fresh natural rubber latex with 0.4kg of ammonia water with the concentration of 25 wt%, 0.5kg of sodium dodecyl sulfate aqueous solution with the concentration of 10 wt% and 60g of 2709 alkaline protease, and reacting for 10 hours at the temperature of 35 ℃ to obtain deproteinized natural rubber latex;
placing 100g of age resister 264 and 6g of diffusant NF into an enamel cup, adding 80mL of casein solution with the concentration of 10 wt% (the solvent is water), 64mL of deionized water and 200mL of glass sand (the granularity is 2-3 mm) in bulk volume, stirring, covering, stirring for 12h by using an electric stirrer with stainless steel stirring slurry (the stirring speed is 1500rpm), and filtering out the glass sand by using a screen to obtain a stable age resister 264 dispersion;
mixing the deproteinized natural latex with 150g of the antioxidant 264 dispersion to obtain a mixed material;
mixing the mixed material with formic acid for coagulation to obtain a coagulum; the mass of the formic acid is 2% of that of the mixed material;
washing and pressing the coagulum by using clean water through a creper to obtain a film with the thickness of 2-3 mm, granulating by using a grain tearing machine to obtain colloidal particles with the particle size of 2-5 mm, and drying the colloidal particles in a hot air drying oven at 115 ℃ for 3 hours after dripping water to obtain the low-protein natural rubber.
Comparative example 1
Taking 100kg of fresh natural rubber latex, and measuring the dry rubber content to be 30.0 wt%; mixing the fresh natural rubber latex with 0.4kg of ammonia water with the concentration of 25 wt%, 0.5kg of sodium dodecyl sulfate aqueous solution with the concentration of 10 wt% and 60g of papain, and reacting for 10 hours at 35 ℃ to obtain deproteinized natural rubber latex;
mixing the deproteinized natural latex with formic acid for coagulation to obtain a coagulum; the mass of the formic acid is 2% of that of the deproteinized natural latex;
and washing and pressing the coagulum by using clear water through a creper, granulating by using a granule tearing machine, and drying the coagulum in a hot air drying box at 115 ℃ for 8 hours after dripping water to obtain the low-protein natural rubber.
And (3) performance testing:
performing performance tests on the low-protein natural rubber prepared in the examples 1 to 3 and the comparative example 1, wherein the test samples of the drying condition, ash content, volatile matter, nitrogen content, impurities, plastic initial value and plastic retention rate are raw rubber, namely the low-protein natural rubber prepared in the examples 1 to 3 and the comparative example 1; the test samples of tensile strength and tensile strength retention rate are vulcanized rubber obtained after the raw rubber is subjected to vulcanization treatment, and the vulcanized rubber adopts an ACS1 formula. The test results are shown in table 1.
TABLE 1 results of Performance testing of Low protein Natural rubber prepared in examples 1-3 and comparative example 1
As can be seen from Table 1, the method provided by the invention can prevent the sizing material from being sticky and undercooked; compared with the comparative example 1, the low-protein natural rubber prepared by the method provided by the invention has more excellent performance, the plasticity retention rate (PRI) is increased by at least 20%, the tensile strength is increased by at least 15%, and the tensile strength retention rate after aging is increased by at least 25%.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A preparation method of low-protein natural rubber comprises the following steps:
providing a dispersion comprising a rubber antioxidant;
mixing deproteinized natural latex with the rubber antioxidant-containing dispersoid to obtain a mixed material;
and sequentially solidifying, washing, pressing and winching, granulating and drying the mixed material to obtain the low-protein natural rubber.
2. The production method according to claim 1, wherein the rubber antioxidant is a natural antioxidant and/or a synthetic antioxidant.
3. The production method according to claim 2, wherein the natural antioxidant is a natural phenolic antioxidant; the synthetic anti-aging agent is at least one of synthetic phenol anti-aging agent, synthetic amine anti-aging agent and synthetic heterocyclic anti-aging agent.
4. The production method according to claim 3, wherein the natural phenolic antioxidant is at least one of tocopherol and tocotrienol;
the synthetic phenol antioxidant comprises at least one of antioxidant 1010, antioxidant 264, antioxidant 2246 and antioxidant DOD;
the synthetic amine antioxidant comprises at least one of an antioxidant H, an antioxidant D, an antioxidant RD, an antioxidant DNP, an antioxidant KY-405, an antioxidant 4010 and an antioxidant 4010 NA;
the synthetic heterocyclic antioxidant comprises at least one of antioxidant DBH and antioxidant MB.
5. The production method according to any one of claims 1 to 4, wherein the dispersion containing the rubber antioxidant comprises the following components in parts by mass:
3-50 parts of a rubber antioxidant;
0-5 parts of a stabilizer;
0-5 parts of a dispersing agent;
40-97 parts of water.
6. The method according to claim 5, wherein the stabilizer is at least one of a diffusing agent NF, casein and sodium pyrophosphate; the dispersant is at least one of ammonium oleate, ammonium laurate and triethanolamine oleate.
7. The preparation method according to claim 1, wherein the deproteinized natural rubber latex is obtained by deproteinizing natural rubber latex, and the dry rubber content of the natural rubber latex is 20-50 wt%.
8. The production method according to claim 7, wherein the mass of the natural rubber latex is 0.01 to 1% by mass of the rubber antioxidant in the mixture based on dry rubber.
9. The method according to claim 1, wherein the drying temperature is 80-130 ℃ and the drying time is 2-10 h.
10. The low-protein natural rubber prepared by the preparation method of any one of claims 1 to 9, wherein the low-protein natural rubber contains a rubber anti-aging agent, and the nitrogen content in the low-protein natural rubber is less than or equal to 0.2 wt%.
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| CN202011268694.9A CN112375265A (en) | 2020-11-13 | 2020-11-13 | Low-protein natural rubber and preparation method thereof |
| PCT/CN2020/139735 WO2022099883A1 (en) | 2020-11-13 | 2020-12-26 | Low-protein natural rubber and method for preparation thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114276476A (en) * | 2021-12-31 | 2022-04-05 | 中国热带农业科学院橡胶研究所 | Method for improving plasticity retention index of natural rubber |
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